WO2021186760A1 - Paint and base material with coating film - Google Patents

Abstract

Provided are a paint which can form an antifouling coating film with excellent hot water resistance, and a base material with the coating film.　The paint according to the present invention includes a fluorine-containing polymer, polydimethyl silicone having a first crosslinking group, acrylic silicone having a second crosslinking group, and a curing agent having a reactive group which can react with the first crosslinking group and the second crosslinking group.

Description

Base material with paint and coating

The present invention relates to a paint and a base material with a coating film.

A paint containing a fluorine-containing polymer can form a coating film having excellent weather resistance. Patent Document 1 describes a coating material containing a fluorine-containing polymer containing a unit based on a fluoroolefin, a unit based on a cyclohexyl vinyl ether, a unit based on an alkyl vinyl ether and a unit based on a hydroxyalkyl vinyl ether, a curing agent, and an organic solvent. It is disclosed.

Tokusho 57-34107

In recent years, since paints containing a fluorine-containing polymer are used in various fields, antifouling properties may be required for a coating film formed by using the paint.
When the present inventors evaluated the coating film described in Patent Document 1, they found that there was room for improvement in the antifouling property of the coating film. Further, it has been found that in order to put a coating film having antifouling property into practical use in various fields, it is necessary to maintain the antifouling property even when immersed in warm water for a certain period of time.

An object of the present invention is to provide a paint and a base material with a coating film capable of forming an antifouling coating film having excellent temperature and water resistance.

As a result of diligent studies, the present inventors have found that the above problems can be solved by the following configuration.
[1] A fluoropolymer, a polydimethyl silicone having a first cross-linking group, an acrylic silicone having a second cross-linking group, the first cross-linking group and the second cross-linking group. A coating material comprising, and a curing agent having a reactive group capable of reacting.
[2] The coating material of [1], wherein the polydimethylsilicone has a kinematic viscosity of 30 to 150 mm ^{2 / s.}
[3] The coating material of [1] or [2], wherein the fluorine-containing polymer contains a unit having a third crosslinkable group.
[4] The coating material of [3], wherein the first crosslinkable group, the second crosslinkable group, and the third crosslinkable group are all hydroxy groups.
[5] The coating material according to any one of [1] to [4], wherein the reactive group is an isocyanate group or a blocked isocyanate group.
[6] The coating material according to any one of [1] to [5], wherein the hydroxyl value of the polydimethylsilicone is 150 mgKOH / g or less.
[7] The coating material according to any one of [1] to [6], wherein the polydimethylsilicone has a dimethylsiloxane unit and the number of repetitions of the dimethylsiloxane unit is 10 or more.
[8] Any of [1] to [7], wherein the content of the polydimethylsilicone is 2.0 to 10 parts by mass with respect to a total of 100 parts by mass of the fluorine-containing polymer and the curing agent. Paint.
[9] The coating material according to any one of [1] to [8], wherein the acrylic silicone has a hydroxyl value of 5 to 200 mgKOH / g.
[10] The coating material according to any one of [1] to [9], wherein the content of the acrylic silicone is 20 parts by mass or more with respect to 100 parts by mass in total of the fluorine-containing polymer and the curing agent.
[11] Further, [1] to [10], further comprising a liquid medium, wherein the liquid medium contains a liquid medium S1 having a relative evaporation rate of less than 0.50 when the evaporation rate of butyl acetate is 1. Either paint.
[12] The coating material of [11], wherein the content ratio of the liquid medium S1 is 15% by mass or more with respect to the total mass of the liquid medium.
[13] The coating material according to any one of [1] to [12], further containing colloidal silica.
[14] A fluoropolymer, a polydimethyl silicone having a first cross-linking group, an acrylic silicone having a second cross-linking group, the first cross-linking group and the second cross-linking group. A method for producing a coating material, wherein a curing agent having a reactive group capable of reacting and an organosilica sol in which colloidal silica is dispersed in an organic solvent are mixed to obtain the coating material of [13].
[15] A coated base material having a base material and a coating film formed from any of the paints [1] to [13] arranged on the base material.

According to the present invention, it is possible to provide a paint capable of forming an antifouling coating film having excellent temperature and water resistance and a base material with a coating film.

The terms in the present invention will be described below.
The numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
(Meta) acrylate is a general term for acrylate and methacrylate. Similarly, (meth) acrylic acid is a general term for acrylic acid and methacrylic acid. Further, the (meth) acrylic polymer is a polymer mainly composed of a unit based on (meth) acrylate, and the (meth) acrylic resin is composed of a polymer mainly composed of a unit based on (meth) acrylate. Means resin.
The reactive silyl group is a general term for a hydrolyzable silyl group and a silanol group (-Si-OH). The hydrolyzable silyl group means a group capable of forming a silanol group by a hydrolyzing reaction.
The unit is a general term for an atomic group based on one molecule of the monomer, which is directly formed by polymerizing a monomer, and an atomic group obtained by chemically converting a part of the atomic group. The content ratio (mol%) of each unit to all the units contained in the polymer is determined by analyzing the polymer by a nuclear magnetic resonance spectrum (NMR) method.
The hydroxyl value is a value measured according to the method of JIS K 0070-3 (1992), respectively.
The glass transition temperature (Tg) is the intermediate glass transition temperature of the polymer as measured by the differential scanning calorimetry (DSC) method.
The minimum film-forming temperature (MFT) is the lowest temperature at which a uniform coating film without cracks is formed when the fluorine-containing polymer is dried. For example, the film-forming temperature measuring device IMC-1535 (Imoto Co., Ltd.) Can be measured using (manufactured by Mfg. Co., Ltd.).
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by gel permeation chromatography using polystyrene as a standard substance.
The film thickness of the coating film is a value measured using an eddy current type film thickness meter, and can be measured using, for example, "EDY-5000" manufactured by Sanko Denshi Co., Ltd.
The water fall angle is the inclination of the coating film with respect to the horizontal plane of the coating film surface when the water droplets move by 1 mm by gradually tilting the coating film surface after attaching about 20 μL of water droplets to the horizontally arranged coating film surface. It is a value obtained by measuring the angle using a contact angle meter. In the examples of the present invention, the measurement was performed using DMo-501SA (trade name of Kyowa Interface Science Co., Ltd.) as a contact angle meter.
The water contact angle is obtained by measuring the angle formed by a water droplet and the surface of the coating film when about 2 μL of distilled water placed on the surface of the coating film is placed using a contact angle meter, and calculating by the 2θ method. The value. In the examples of the present invention, the measurement was performed using DMo-501SA (trade name of Kyowa Interface Science Co., Ltd.) as a contact angle meter.
The kinematic viscosity is a value measured according to the method of JIS Z 8803 (2011).
The relative evaporation rate means the relative evaporation rate when the evaporation rate of butyl acetate is 1, and is a value measured according to the method of ASTM D3539.
The solid content mass of the paint is the mass obtained by removing the solvent from the paint when the paint contains a solvent. It should be noted that the components constituting the solid content of the composition other than the solvent are regarded as the solid content even if the properties are liquid. The solid content mass of the coating material is determined as the mass remaining after heating 1 g of the coating material at 130 ° C. for 20 minutes.

The coating material of the present invention comprises a fluorine-containing polymer, polydimethylsilicone having a first crosslinkable group, acrylic silicone having a second crosslinkable group, the first crosslinkable group and the second crosslinkable group. Includes a curing agent having a reactive group capable of reacting with the sex group.
The paint of the present invention (hereinafter, also referred to as the present paint) can form an antifouling coating film having excellent heat resistance and water resistance. The reason for this is not always clear, but it can be considered as follows.
The present coating contains a polydimethylsilicone having a first crosslinkable group and an acrylic silicone having a second crosslinkable group. As a result, the effect of improving the water repellency of the coating film by polydimethylsilicone and the effect of improving the durability of the coating film by acrylic silicone work synergistically to have excellent antifouling property. It is considered that a coating film having a long-lasting antifouling property was obtained even after the hot water resistance test.

The fluorine-containing polymer in the present invention is a polymer containing a fluorine atom, and is preferably a polymer containing a unit based on a fluoroolefin (hereinafter, also referred to as a unit F).
A fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with fluorine atoms. In the fluoroolefin, one or more hydrogen atoms which are not substituted with fluorine atoms may be substituted with chlorine atoms. The number of carbon atoms of the fluoroolefin is preferably 2 to 8, and particularly preferably 2 to 4.

Specific examples of fluoroolefins include CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CHF, CH ₂ = CF ₂ , CF ₂ = CFCF ₃ , CF ₂ = CHCF ₃ , CF ₃ CH = CHF, CF ₃ CF = CH ₂ , formula CH ₂ = CX ^f1 (CF ₂ ) _n1 Y ^f1 (In the formula, X ^f1 and Y ^f1 are independently hydrogen atoms or fluorine atoms, and n1 is an integer of 2 to 10. ) Can be mentioned. _{As the fluoroolefin, CF 2} = CF ₂ , CH ₂ = CF ₂ , CF ₂ = CFCl, CF ₃ CH = CHF and CF ₃ CF = CH ₂ are preferable, and CF ₂ is preferable from the viewpoint of excellent antifouling property of the coating film. = CFCl is particularly preferable. Two or more kinds of fluoroolefins may be used in combination.

The content ratio of the unit F is preferably 20 to 100 mol%, more preferably 30 to 70 mol%, and more preferably 40 to 60, based on all the units contained in the fluorine-containing polymer, from the viewpoint of antifouling property of the coating film. Mol% is particularly preferred.

The fluorine-containing polymer preferably further contains a unit having a third crosslinkable group (hereinafter, also referred to as unit C). Examples of the crosslinkable group include a hydroxy group, a carboxy group, an amino group, an epoxy group, an oxetanyl group, a reactive silyl group and the like, and a hydroxy group or a carboxy group is preferable, and a hydroxy group is particularly preferable.

The unit C is preferably a unit having no fluorine atom. The unit C may be a unit based on a monomer having a third crosslinkable group (hereinafter, also referred to as monomer C), and a unit having a group convertible into a third crosslinkable group may be used. In the fluorine-containing polymer containing, it may be a unit obtained by converting the group into a third crosslinkable group. As such a unit, for example, a fluorine-containing polymer containing a unit having a hydroxy group is reacted with a polycarboxylic acid, an acid anhydride thereof, or the like to convert at least a part of the hydroxy group into a carboxy group. The unit to be used is mentioned.
The unit C is preferably a unit based on a monomer having a hydroxy group from the viewpoint of reactivity with polydimethylsilicone and acrylic silicone in the present invention.

Examples of the monomer having a hydroxy group include vinyl ether, vinyl ester, allyl ether, allyl ester or (meth) acrylate having a hydroxy group, allyl alcohol and the like. The monomer having a hydroxy group is preferably vinyl ether from the viewpoint of polymerizability with fluoroolefin.
Specific examples of the monomer having a hydroxy group include CH ₂ = CHO-CH _2- cycloC ₆ H _10- CH ₂ OH, CH ₂ = CHCH ₂ O-CH _2- cycloC ₆ H _10- CH ₂ OH, CH. _{2 = CHOCH 2 -cycloC 6 H 10} -CH 2 - (OCH 2 CH 2) 15 OH, CH 2 = CHOCH 2 CH 2 OH, CH 2 = CHCH 2 OCH 2 CH 2 OH, CH 2 = CHOCH 2 CH ₂ CH ₂ CH ₂ OH and CH ₂ = _{CH CH 2} OCH ₂ CH ₂ CH ₂ CH ₂ OH can be mentioned. As the monomer having a hydroxy group, CH ₂ = CHCH ₂ OCH ₂ CH ₂ OH and CH ₂ = CHOCH ₂ CH ₂ CH ₂ CH ₂ OH are preferable from the viewpoint of copolymerizability with a fluoroolefin.
In addition, "-cycloC ₆ H _10- " represents a cyclohexylene group, and the binding site of " _{-cycloC 6} H _{10-" is usually 1,4-.}

Examples of the monomer having a carboxy group include unsaturated carboxylic acid, (meth) acrylic acid, and a monomer obtained by reacting a hydroxy group of the above-mentioned monomer having a hydroxy group with a carboxylic acid anhydride. ..
Specific examples of the monomer having a carboxy group include CH ₂ = CHCOOH, CH (CH ₃ ) = CHCOOH, CH ₂ = C (CH ₃ ) COOH, HOOCCH = CHCOOH, CH ₂ = CH (CH ₂ ) _n11 COOH. (However, n11 represents an integer of 1 to 10) and a monomer represented by CH ₂ = CHO (CH ₂ ) _n12 OC (O) CH ₂ CH ₂ COOH (where n11 is represented by). , N12 indicates an integer of 1 to 10). Examples of the monomer having a carboxy group include a monomer _{represented by CH 2} = CH (CH ₂ ) _n11 COOH and CH ₂ = CHO (CH ₂ ) _n12 OC (from the viewpoint of copolymerizability with a fluoroolefin. O) CH ₂ A monomer represented by CH _{2 COOH is preferable.}

Two or more types of monomer C may be used in combination.
The content ratio of the unit C is 0.5 to 40 mol% with respect to all the units contained in the fluorine-containing polymer because the crosslink density of the coating film is high and the coating film is excellent in antifouling property and heat resistance. It is preferably, more preferably 10 to 35 mol%, and particularly preferably 15 to 30 mol%.

The fluorine-containing polymer may further contain a unit (hereinafter, also referred to as unit D) based on a monomer other than the fluoroolefin and the monomer C (hereinafter, also referred to as monomer D). The unit D is preferably a unit having no fluorine atom.

Examples of the monomer D include alkene, vinyl ether, vinyl ester, allyl ether, allyl ester, (meth) acrylate and the like, which do not have a third crosslinkable group. As the monomer D, vinyl ether and vinyl ester are preferable, and vinyl ether is particularly preferable, from the viewpoint of copolymerizability with fluoroolefin and weather resistance of the fluorine-containing polymer.
Two or more types of monomer D may be used in combination.

Specific examples of the monomer D include ethylene, propylene, 1-butene, ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl pivalate, and vinyl neononanoate (manufactured by HEXION). Name "Beova 9" etc.), Vinyl neodecanoate (manufactured by HEXION, trade name "Beova 10" etc.), Vinyl Versaticate, Vinyl benzoate, vinyl tert-butyl benzoate, tert-butyl (meth) acrylate, benzyl ( Meta) acrylate can be mentioned.
When the fluorine-containing polymer contains the unit D, the content ratio of the unit D is preferably 5 to 60 mol%, preferably 10 to 50 mol%, based on all the units contained in the fluorine-containing polymer. Especially preferable.

The fluorine-containing polymer contains units F, unit C, and unit D in this order of 30 to 70 mol%, 0.5 to 40 mol%, and 5 to 60 mol% with respect to all the units contained in the fluorine-containing polymer. It is preferable to include it.

The Tg of the fluorine-containing polymer is preferably 0 to 120 ° C., more preferably 10 to 100 ° C., and particularly preferably 30 to 80 ° C. When the Tg of the fluorine-containing polymer is within the above range, the antifouling property of the coating film is improved.
The MFT of the fluorine-containing polymer is preferably 0 to 100 ° C, particularly preferably 10 to 40 ° C.
The Mn of the fluorine-containing polymer is preferably 1,000 to 100,000, more preferably 2,000 to 30,000, and particularly preferably 2,000 to 10,000. When the Mn of the fluorine-containing polymer is within the above range, the temperature and water resistance of the coating film is improved.

The fluorine-containing polymer preferably has a hydroxyl value in a specific range. The hydroxyl value is preferably 1 to 200 mgKOH / g, more preferably 10 to 100 mgKOH / g, and particularly preferably 20 to 80 mgKOH / g.
From the viewpoint of the durability of the coating film, the fluorine-containing polymer preferably has a hydroxyl value in the above range.

The fluorine-containing polymer is produced by a known method. For example, the fluorine-containing polymer can be obtained by copolymerizing each monomer in the presence of a solvent and a radical polymerization initiator. Examples of the method for producing a fluorine-containing polymer include solution polymerization and emulsion polymerization. If necessary, a polymerization stabilizer, a polymerization inhibitor, a surfactant, or the like may be used during or after the production of the fluorine-containing polymer.

As the fluorine-containing polymer, a commercially available product may be used, and specific examples thereof include "Lumiflon" series (manufactured by AGC), "Fluon" series (manufactured by AGC), "Kynar" series (manufactured by Arkema), and the like. Examples include the "Zeffle" series (manufactured by Daikin Industries, Ltd.), the "Eterflon" series (manufactured by Eternal), and the "Zendura" series (manufactured by Honeywell).
As the fluorine-containing polymer, two or more kinds may be used in combination.

The present coating material preferably contains a fluorine-containing polymer in an amount of 5 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 60% by mass, based on the solid content mass of the present coating material. ..

A polydimethylsilicone having a first crosslinkable group (hereinafter, also referred to as a specific polydimethylsilicone) is a siloxane compound having a number of repetitions of 2 or more dimethylsiloxane units and having a first crosslinkable group.
The specific polydimethylsilicone is excellent in the effect of imparting water repellency to the coating film, and can form a coating film having a particularly large water contact angle and a small water fall angle. When the water contact angle of the coating film is large and the water fall angle is small, dirt does not easily adhere to the coating film, and the adhered dirt easily flows off, which is more excellent in the stain resistance of the coating film.
The polydimethylsilicone is preferably in an oily state at room temperature (25 ° C.).

The first crosslinkable group is preferably a hydroxy group, a carboxy group, an amino group, an epoxy group, an oxetanyl group, or a reactive silyl group, and a hydroxy group is particularly preferable, from the viewpoint of curability of the coating material.

The dimethylsiloxane unit is a unit represented by- _{(Si (CH 3} ) _{2 O)-.} The number of repetitions of the dimethylsiloxane unit contained in the specific polydimethylsilicone is 2 or more, preferably 10 or more, more preferably 30 or more, and particularly preferably 50 or more. When the number of repetitions of the dimethylsiloxane unit is 10 or more, the kinematic viscosity of the specific polydimethylsilicone is improved, and a coating film having a large water contact angle and a small water rolling angle can be obtained.
The number of repetitions of the dimethylsiloxane unit is preferably 300 or less, more preferably 200 or less, and particularly preferably 100 or less, from the viewpoint of handleability of the polydimethylsilicone.

The specific polydimethylsilicone is preferably a compound represented by the following formula (1) from the viewpoint that the effect of the present invention is more excellent.

In formula (1), n represents two or more integers arbitrarily selected so that the number average molecular weight of the specific polydimethylsilicone is 500 to 40,000. As n, 10 to 300 is preferable, 30 to 200 is more preferable, and 50 to 100 is particularly preferable.
In the formula (1), the two R ¹ each independently represents a divalent group having 1 to 30 carbon atoms having an alkylene group of 1 to 30 carbon atoms, or, an ether bond. Two of R ¹ is preferably the same groups.
Specific examples of the alkylene group having 1 to 30 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene and octylene.
Specific examples of the divalent group having 1 to 30 carbon atoms having an ether _{bond, -C 3 H 6 -O-C} 2 H 4 -, - C 3 H 6 - (OC 2 H 4) m -, - _{C 2 H 4 -O-C 2} H 4 -, - C 3 H 6 -O-C 3 H 6 - and the like. In the formula, m represents an integer from 1 to 30.
When ^{the carbon number of R 1} is 30 or less, the handleability and heat resistance of the specific polydimethylsilicone are excellent.
R ¹ is a propylene group, _{or, -C 3 H 6 -O-C} 2 H 4 - is preferable.

The compound represented by the formula (1) is preferably the compound represented by the following formula (1A) from the viewpoint that the effect of the present invention is more excellent.

In formula (1A), the definition of na is synonymous with n in formula (1).
Each of the two ps independently represents an integer of 0 to 9, and 1 to 5 is preferable, and 1 to 3 is particularly preferable, from the viewpoint that the effect of the present invention is more excellent. It is preferable that the two ps have the same value.
Each of the two qs independently represents an integer of 3 to 9, and 3 to 7 is preferable, and 3 to 5 is particularly preferable, because the effect of the present invention is more excellent. The two qs are preferably the same value.

As the specific polydimethyl silicone, a commercially available product may be used, and as a specific example, DMS-C16 (trade name of Gelest Co., Ltd., number average molecular weight: about 700. In formula (1A), p = 0, q = 3 A compound.), FM-4411 (trade name of Chisso Co., Ltd. Mn: about 1,000. A compound having p = 1 and q = 3 in the formula (1A)), FM-4421 (trade name of Chisso Co., Ltd. Mn). : Approximately 5,000. Compound with p = 1, q = 3 in formula (1A)), FM-4425 (trade name of Chisso Co., Ltd. Mn: Approximately 10,000. In formula (1A), p = 1, Q = 3 compound.), KF-6000 (trade name of Shin-Etsu Chemical Industry Co., Ltd. Mn: about 1,000. In formula (1A), p = 1, q = 3 compound), KF-6001 ( Shin-Etsu Chemical Industry Co., Ltd. Product name. Mn: Approximately 1,700. Compounds having p = 1 and q = 3 in the formula (1A)), KF-6002 (Shin-Etsu Chemical Industry Co., Ltd. product name. Mn: Approximately 3,000. In formula (1A), p = 1, q = 3), KF-6003 (trade name of Shin-Etsu Chemical Industry Co., Ltd. Mn: about 5,500. In formula (1A), p = 1, q = 3), X-22-4952 (trade name of Shin-Etsu Chemical Industry Co., Ltd. Mn: about 4,000. In formula (1A), p≈5, q = 3).
Two or more kinds of specific polydimethyl silicones may be used in combination.

The Mn of the specific polydimethylsilicone is preferably 500 to 20,000, more preferably 1,000 to 20,000, and particularly preferably 4,000 to 7,000.

The kinematic viscosity of a particular polydimethyl silicone is preferably from 30 ~ 150mm ² / s, particularly preferably 100 ~ 120mm ² / s. When the kinematic viscosity is 30 mm ² / s or more, a coating film having a large water contact angle and a small water fall angle can be obtained. When the kinematic viscosity is 150 mm ² / s or less, the handleability of the specific polydimethylsilicone is excellent.

The hydroxyl value of the specific polydimethylsilicone is preferably 150 mgKOH / g or less, more preferably less than 100 mgKOH / g, and particularly preferably 50 mgKOH / g or less, from the viewpoint that the water roll angle becomes smaller.
The hydroxyl value of the specific polydimethylsilicone is particularly preferably 10 mgKOH / g or more from the viewpoint of obtaining a coating film capable of maintaining antifouling property even when immersed in warm water.

The content of the specific polydimethyl silicone is preferably 1.0 to 20 parts by mass, more preferably 2.0 to 10 parts by mass, and 2.5 to 25 parts by mass with respect to 100 parts by mass of the total of the fluorine-containing polymer and the curing agent. 8.0 parts by mass is particularly preferable. When the content of the specific polydimethylsilicone is 1.0 part by mass or more, a coating film having a small water fall angle and capable of maintaining antifouling property even when immersed in warm water can be obtained. When the content of the specific polydimethylsilicone is 20 parts by mass or less, a transparent coating film that is easily compatible with the fluorine-containing polymer can be obtained.

Acrylic silicone having a second crosslinkable group (hereinafter, also referred to as specific acrylic silicone) means a (meth) acrylic polymer having a second crosslinkability and modified with silicone.
The specific acrylic silicone has excellent film properties and can improve the durability of the obtained coating film. As a result, the temperature and water resistance of the coating film is further improved.

The specific acrylic silicone preferably contains a unit based on (meth) acrylate.
Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl. Examples thereof include (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate.
The (meth) acrylate includes a (meth) acrylate having a branch in the side chain, a (meth) acrylate having a cyclic hydrocarbon group in the side chain, and a (meth) acrylate having an aromatic ring in the side chain from the viewpoint of excellent filmability. Is preferable, and (meth) acrylate having a branch in the side chain or (meth) acrylate having an aromatic ring in the side chain is particularly preferable. Examples of such (meth) acrylate include isopropyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate, and isobutyl (meth) acrylate. , 2-Ethylhexyl (meth) acrylate, benzyl (meth) acrylate is particularly preferable.
The specific acrylic silicone contains a unit based on (meth) acrylate having a branch in the side chain or a unit based on (meth) acrylate having an aromatic ring in the side chain in an amount of more than 40 mol% with respect to all the units contained in the specific acrylic silicone. It is preferable, it is more preferable to contain more than 50 mol%, and it is particularly preferable to contain more than 80 mol%.
Further, the specific acrylic silicone preferably contains a unit based on (meth) acrylate having a branch in the side chain and a unit based on (meth) acrylate having an aromatic ring in the side chain. In that case, the content ratio of the two types of units is a molar ratio, a unit based on (meth) acrylate having a branch in the side chain: a unit based on (meth) acrylate having an aromatic ring in the side chain = 1: 9 to. It is preferably 9: 1, and particularly preferably 6: 4 to 4: 6.
The unit based on the (meth) acrylate contained in the specific acrylic silicone may further have a second crosslinkable group in the side chain, or may be silicone-modified.

As the second crosslinkable group, a hydroxy group, a carboxy group, an amino group, an epoxy group, an oxetanyl group and a reactive silyl group are preferable, and a hydroxy group is particularly preferable, from the viewpoint of curability of the coating material.
The second crosslinkable group is preferably introduced into the side chain of the specific acrylic silicone.

As the specific acrylic silicone, a commercially available product may be used, and specific examples thereof include BYK-SILCLEAN 3700 (trade name of BYK) and ZX-28-G (trade name of T & K TOKA).
Two or more kinds of specific acrylic silicones may be used in combination.

The hydroxyl value of the specific acrylic silicone is preferably 5 to 200 mgKOH / g, more preferably 10 to 100 mgKOH / g, and particularly preferably 20 to 50 mgKOH / g. When the hydroxyl value is 5 mgKOH / g or more, a coating film capable of maintaining antifouling property even when immersed in warm water can be obtained. When the hydroxyl value is 200 mgKOH / g or less, the water fall angle of the coating film can be made smaller.

The Mn of the specific acrylic silicone is preferably 5,000 to 30,000, more preferably 7,000 to 20,000, and particularly preferably 10,000 to 15,000 from the viewpoint of the durability of the obtained coating film. ..
The Mw of the specific acrylic silicone is preferably 10,000 to 50,000, more preferably 12,000 to 30,000, and particularly preferably 15,000 to 20,000 from the viewpoint of the durability of the obtained coating film. ..

The content of the specific acrylic silicone is preferably 20 parts by mass or more, more preferably 35 parts by mass or more, and particularly preferably 50 parts by mass or more with respect to 100 parts by mass of the total of the fluorine-containing polymer and the curing agent. When the content of the specific acrylic silicone is 20 parts by mass or more, a coating film capable of maintaining antifouling property even when immersed in warm water can be obtained.
The content of the specific acrylic silicone is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and particularly preferably 100 parts by mass or less, based on 100 parts by mass of the total of the fluorine-containing polymer and the curing agent. When the content of the specific acrylic silicone is 200 parts by mass or less, the scratch property of the coating film surface can be sufficiently maintained.

The curing agent has a first crosslinkable group and a reactive group capable of reacting with the second crosslinkable group. As a result, the crosslink density of the main coating film is increased, and the durability of the main coating film is excellent. The reactive group is preferably a reactive group that can also react with the third crosslinkable group from the viewpoint of maintaining the antifouling property of the coating film.

The curing agent preferably has two or more reactive groups in one molecule, and particularly preferably 2 to 30 reactive groups.
When the reactive group of the curing agent reacts with the first crosslinkable group of the specific polydimethyl silicone and the second crosslinkable group of the acrylic silicone, the specific polydimethyl silicone and the specific acrylic silicone are crosslinked by the curing agent. do.
When the fluorine-containing polymer has a crosslinkable group, when the reactive group of the curing agent reacts with the crosslinkable group of the fluorine-containing polymer, the fluorine-containing polymer is crosslinked by the curing agent. In particular, when the first to third crosslinkable groups are the same group, the effect of the present invention is more excellent by cross-linking the fluorine-containing polymer, the specific polydimethyl silicone, and the specific acrylic silicone.

Specific examples of the reactive group contained in the curing agent include an isocyanate group, a blocked isocyanate group, an epoxy group, an oxazolinyl group, and a β-hydroxyalkylamide group. In particular, when two or more of the first to third crosslinkable groups are hydroxy groups, isocyanate groups and blocked isocyanate groups are preferable as the reactive groups of the curing agent. In this case, as the curing agent, polyisocyanate, which is a curing agent having two or more isocyanate groups or blocked isocyanate groups in one molecule, is preferable.

As the polyisocyanate, a polyisocyanate monomer and a polyisocyanate derivative are preferable.
As the polyisocyanate monomer, alicyclic polyisocyanate, aliphatic polyisocyanate, and aromatic polyisocyanate are preferable. As the polyisocyanate derivative, a multimer or a modified form of the polyisocyanate monomer (adduct form, allophanate form, biuret form, isocyanurate form, etc.) is preferable.

Specific examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, and lysine diisocyanate, and lysine triisocyanate. , 4-Isocyanatomethyl-1,8-octamethylene diisocyanate, bis (2-isocyanatoethyl) 2-isocyanatoglutarate.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylylene diisocyanate. Can be mentioned.
Specific examples of the aromatic polyisocyanate include aromatic diisocyanates such as xylylene diisocyanate.

The polyisocyanate may be a compound in which two or more isocyanate groups of the above-mentioned polyisocyanate monomer or polyisocyanate derivative are blocked by a blocking agent.
The blocking agent is a compound having active hydrogen, and specific examples thereof include alcohol, phenol, active methylene, amine, imine, acid amide, lactam, oxime, pyrazole, imidazole, imidazoline, pyrimidine, and guanidine.

The content of the curing agent is preferably 2 to 50 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the fluorine-containing polymer.
Two or more kinds of curing agents may be used in combination.

Since this paint is particularly excellent in temperature and water resistance and water resistance of the coating film due to the interaction of each component, a fluorine-containing polymer, a specific polydimethyl silicone, a specific acrylic silicone, and a curing agent are used in this paint. It is preferable to contain 10 to 90% by mass, 0.1 to 10% by mass, 1 to 50% by mass, 5 to 35% by mass, and 30 to 50% by mass, 1 to 5% by mass, respectively, with respect to the solid content mass. %, 20-40% by mass, 10-30% by mass is particularly preferable. In particular, when the fluorine-containing polymer, the specific polydimethyl silicone, and the specific acrylic silicone all have a hydroxy group and the curing agent is a polyisocyanate, the effect of the present invention is more excellent due to cross-linking between each component.

The present coating material may further contain a liquid medium, and may be a coating material in which a fluorine-containing polymer, polydimethyl silicone and acrylic silicone are dissolved or dispersed in the liquid medium, and the coating material does not substantially contain the liquid medium (). It may be a powder paint or the like).
Examples of the liquid medium include an organic solvent and water, and a mixed solvent of water and an organic solvent may be used. Examples of the paint dissolved or dispersed in the liquid medium include paints dissolved in organic solvents and the like (solvent-type paints and the like) and paints dispersed in water (water-based paints and the like). This paint is preferably a solvent-based paint from the viewpoint of being able to form a dense coating film and having excellent weather resistance.
When the liquid medium is a mixed solvent of water and an organic solvent, the content ratio of water is preferably 1 to 99% by mass, more preferably 70 to 95% by mass, based on the total mass of the liquid medium.
The fact that the liquid medium is substantially not contained means that the content of the liquid medium is 0.1% by mass or less with respect to the total mass of the present coating material.

Examples of the organic solvent include a ketone solvent, an ester solvent, a hydrocarbon solvent, an alcohol solvent, a glycol ether solvent, and a glycol ester solvent.
Specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and diacetone alcohol.
Specific examples of the ester solvent include ethyl acetate and butyl acetate.
Specific examples of the hydrocarbon solvent include hexane, heptane, and cyclohexane.
Specific examples of the alcohol solvent include butyl alcohol.
Specific examples of the glycol ether solvent include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monopropyl ether.
Specific examples of the glycol ester solvent include 1-methoxypropyl-2-acetate.

When the present coating material contains a liquid medium, the content ratio of the liquid medium is preferably 10 to 95% by mass, particularly preferably 60 to 90% by mass, based on the total mass of the present coating material.

When the present coating material contains a liquid medium, the liquid medium preferably contains a liquid medium S1 having a relative evaporation rate of less than 0.50 when the evaporation rate of butyl acetate is 1. As a result, a coating film having an excellent appearance can be obtained. The reason for this is that since the liquid medium S1 evaporates slowly, the fluorine-containing polymer and the acrylic silicone are easily layer-separated during the formation of the coating film, and the coating film becomes turbid due to the mixture of the fluorine-containing polymer and the acrylic silicone. It is presumed that it can be suppressed.
The relative evaporation rate of the liquid medium S1 is more preferably 0.40 or less, and particularly preferably 0.35 or less, from the viewpoint of improving the appearance of the coating film.
The smaller the relative evaporation rate of the liquid medium S1, the more preferable it is, and the lower limit is usually more than 0.

When the present coating material contains the liquid medium S1, the content ratio of the liquid medium S1 is preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more, based on the total mass of the liquid medium. When the content of the liquid medium S1 is 15% by mass or more, the appearance of the coating film is more excellent.
The higher the content of the liquid medium S1 in the liquid medium, the more preferable, and the upper limit value is usually 100% by mass.

Specific examples of the liquid medium S1 include cyclohexanone (relative evaporation rate: 0.32), butyl alcohol (relative evaporation rate: 0.47), diisobutyl ketone (relative evaporation rate: 0.20), and diacetone alcohol (relative evaporation rate: 0.20). Rate: 0.15), ethylene glycol monoethyl ether (relative evaporation rate: 0.38), ethylene glycol monobutyl ether (relative evaporation rate: 0.08), 1-methoxypropyl-2-acetate (relative evaporation rate: 0) .44), propylene glycol monopropyl ether (relative evaporation rate: 0.22), and cyclohexanone is particularly preferable because the appearance of the coating film is more excellent.

The present paint may contain components other than the above. Examples of the component include a fluorine-containing polymer, a resin other than the specific polydimethylsilicone and the specific acrylic silicone, and additives.
Examples of such a resin include a thermoplastic resin, a curable resin, a crosslinkable resin, and the like, and a curable resin and a crosslinkable resin are preferable. Specific examples thereof include curable or crosslinkable (meth) acrylic resins, polyester resins, urethane resins, epoxy resins, specific polydimethyl silicones, and silicone resins other than specific acrylic silicones.
Additives include curing catalysts, fillers (inorganic fillers such as silica, organic fillers such as resin beads), colorants (dye, organic pigments, inorganic pigments, bright pigments using metal or mica, etc.), UV absorption. Agents, light stabilizers, matting agents, surface conditioners, degassing agents, fillers, heat stabilizers, thickeners, dispersants, surfactants, antistatic agents, rust preventives, silane coupling agents, antifouling Examples include agents, decontamination treatment agents, plasticizers, adhesives and the like.

The present coating material preferably contains a silicone oligomer from the viewpoint of further improving the antifouling property of the coating film. However, the silicone oligomer does not include the specific polydimethyl silicone and the specific acrylic silicone in the present invention.
The silicone oligomer preferably has an alkoxy group that is directly bonded to the Si atom. Examples of the alkoxy group include a methoxy group and an ethoxy group, and a methoxy group is preferable.
The silicone oligomer further preferably has at least one of an alkyl group and a phenyl group that are directly bonded to the Si atom, and more preferably has both an alkyl group and a phenyl group that are directly bonded to the Si atom. Examples of the alkyl group include a methyl group and an ethyl group, and a methyl group is preferable.

Commercially available products may be used as the silicone oligomer, and specific examples thereof include KC-89S, KR-515, KR-500, X-40-9225, X-40-9246, X-40-9250, and KR-. Examples thereof include 401N, X-40-9227, KR-510, KR-9218, KR-213, K-400, X-40-2327, and KR-401 (all of which are trade names of Shin-Etsu Chemical Co., Ltd.).

The content ratio of the silicone oligomer in the present coating material is preferably 1 to 100% by mass, particularly preferably 10 to 40% by mass, based on the total solid content mass of the present coating material.

The present paint preferably contains colloidal silica from the viewpoint of further improving the antifouling property of the coating film and improving the strength of the coating film. Colloidal silica is a colloidal particle of _{SiO 2} or _{a hydrate of SiO 2.}
The average primary particle size of colloidal silica measured by the dynamic scattering method is preferably 5 to 200 nm, and particularly preferably 5 to 30 nm.
The average primary particle size of the colloidal silica is calculated by the formula D (nm) = 2720 / S based on the ^{specific surface area S (m 2} / g) obtained by the nitrogen adsorption method (BET method). Is.
The particle shape of colloidal silica may be spherical or non-spherical, and is preferably spherical. Examples of the non-spherical colloidal silica include an elongated shape in which silica particles having a shape close to a spherical shape are connected in a chain or a bead shape.
The content of colloidal silica in the present paint is preferably 1 to 100 parts by mass, more preferably 5 to 30 parts by mass, and 10 to 10 to 100 parts by mass with respect to 100 parts by mass of the paint solid content other than colloidal silica. It is particularly preferably 25 parts by mass.

The present coating material comprises a fluorine-containing polymer, polydimethylsilicone having a first crosslinkable group, acrylic silicone having a second crosslinkable group, the first crosslinkable group and the second crosslinkable group. It is preferably produced by mixing a curing agent having a reactive group capable of reacting with, and an organosilica sol in which colloidal silica is dispersed in an organic solvent.
Organic solvents in the organosilica sol include methanol, ethylene glycol, isopropyl alcohol, dimethylacetamide, methylethylketone, methylisobutylketone, ethyl acetate, toluene, cyclohexanone, propylene glycol monomethyl ether, ethylene glycol monon-propyl ether, and propylene glycol monomethyl ether acetate. Etc., and from the viewpoint of uniform mixing with the liquid medium S1 in the present invention, methyl ethyl ketone is preferable.
The colloidal silica content in the organosilica sol is preferably 10 to 60% by mass, particularly preferably 15 to 50% by mass, based on the total mass of the organosilica sol.

Commercially available products may be used as the organosilica sol, and specific examples thereof include EG-ST-XL30, NMP-ST, PGM-ST-UP, MA-ST-M, MA-ST-L, and MA-ST-. ZL, MA-ST-UP, IPA-ST-L, DMAC-ST-ZL, EG-ST-ZL, EAC-ST, TOR-ST, MEK-ST-40, MEK-ST-L, MIBK-SD, MIBK-SD-L, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, MEK-EC-2130Y, CHO-ST-M, PGM-AC-2140Y, PGM-AC-4130Y, MIBK- AC-2140Z, IPA-ST, IPA-ST-ZL, EG-ST, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, PMA-ST, PGM-ST (all of which are Nissan Chemicals) Company product name).

The coating film of the present invention (hereinafter, also referred to as the present coating film) may be formed by applying the present coating film on a substrate, drying the coating film if necessary, and heat-curing the coating film.
When this paint is a water-based paint or solvent-based paint, the coating methods include spray coating method, squeegee coating method, flow coating method, bar coating method, spin coating method, dip coating method, screen printing method, and gravure printing method. Examples include a die coating method, an inkjet method, a curtain coating method, and a method using a brush or spatula.
When this paint is a powder paint, the coating methods include electrostatic coating method, electrostatic spraying method, electrostatic immersion method, spraying method, flow immersion method, spraying method, spraying method, thermal spraying method, plasma spraying method, etc. Can be mentioned.
When the present coating material contains a liquid medium, it is preferable to dry it after application to remove the solvent. The drying temperature is usually 0 to 50 ° C., and the drying time is usually 1 minute to 2 weeks.
When the present coating material contains a curing agent, it is preferably heat-cured after application. The heat curing temperature is usually 50 ° C. to 300 ° C., and the heat curing time is usually 1 minute to 24 hours.

The film thickness of the main coating film is preferably 1 to 1,000 μm, more preferably 25 to 500 μm, and particularly preferably 50 to 100 μm from the viewpoint of weather resistance of the main coating film. In the present coating film, the film thickness of the coating film formed by one coat using the present coating film, which is a solvent type coating film, is preferably 50 to 100 μm from the viewpoint of reducing the process of forming the coating film.

When this paint is used, a base material with a coating film having a base material and the main coating film arranged on the base material can be obtained. An article containing a coated substrate of the present invention is also referred to as a coated article.
Specific examples of the material of the base material in the present invention include inorganic substances, organic substances, and organic-inorganic composite materials.
Specific examples of inorganic substances include concrete, natural stone, glass, and metal materials.
Specific examples of organic substances include plastics, rubbers, adhesives, and wood.
Specific examples of the organic-inorganic composite material include fiber reinforced plastic, resin reinforced concrete, and fiber reinforced concrete.
The base material may be subjected to a known surface treatment. Examples of the surface treatment include metal film treatment and chemical conversion treatment. Examples of the metal film treatment include electroplating, hot-dip plating, and thin-film plating. Examples of the chemical conversion treatment include chromate treatment and phosphate treatment.

The base material is preferably made of metal from the viewpoint that the effects of the present invention are more exerted. Examples of the metal include materials containing metals such as iron, aluminum, zinc, tin, titanium, lead, copper, magnesium, manganese, silicon, chromium, zirconium, vanadium, nickel and bismuth. As the metal, iron and aluminum are particularly suitable. The metal may be an alloy containing two or more kinds of metals.
As the metal, iron alloys (steel, stainless steel, etc.) and aluminum alloys are preferable, and steel is particularly preferable.

The base material with a coating film in the present invention may have another coating film such as an intermediate coating film or an undercoat (primer) coating film between the base material and the main coating film.
Examples of the paint for forming the undercoat coating film include paints containing (meth) acrylic resin, polyester resin, urethane resin, epoxy resin, silicone resin and the like.
The undercoat coating may contain a crosslinkable resin, a prepolymer having a crosslinkable group, a curable resin, or the like.
When drying, heat curing, or the like is required to form each coating film, the order of application, drying, and heat curing of the paint forming each coating film is not limited. That is, each coating film may be dried or heat-cured, or may be performed at the same time.

Hereinafter, the present invention will be described in detail with reference to an example. Examples 1 to 5 and 8 to 17 are examples, and examples 6 to 7 are comparative examples. However, the present invention is not limited to these examples. The blending amount of each component in the table described later indicates a mass standard.

<Abbreviation of ingredients used>
[Monomer]
CTFE: Chlorotrifluoroethylene CHVE: Cyclohexyl vinyl ether HBVE: 4-Hydroxybutyl vinyl ether

<Paint component>
The following ingredients were obtained or manufactured and used by the following methods.

[Polydimethylsilicone]
Polydimethyl Silicone 1: Shin-Etsu Chemical Co., Ltd. Brand name KF-6003 (Polydimethyl silicone having 68 repetitions of dimethylsiloxane unit, Mn: about 5,500, kinematic viscosity: 110 mm ² / s, hydroxyl value: 22 mgKOH / g )
Polydimethyl Silicone 2: Shin-Etsu Chemical Co., Ltd. Brand name KF-6000 (Polydimethyl silicone having 12 repetitions of dimethylsiloxane unit, Mn: about 1,000, kinematic viscosity: 35 mm ² / s, hydroxyl value: 120 mgKOH / g )

[Acrylic silicone]
Acrylic Silicone Solution 1: BYK Trade Name BYK-SILCLEAN 3700 (Hydroxy group, silicone modified (meth) containing about equimolar units of benzyl (meth) acrylate and units based on isobutyl (meth) acrylate. ) 25% by mass solution of acrylic polymer, hydroxyl value: 30 mgKOH / g)

[Curing agent]
Hardener 1: Asahi Kasei Corporation Brand name Duranate TPA-100 (isocyanurate form of hexamethylene diisocyanate)

[Liquid medium]
Cyclohexanone (relative evaporation rate: 0.32)
Methyl ethyl ketone (relative evaporation rate: 3.70)

[Organosilica sol]
Organosilica sol 1: Nissan Chemical Industries, Ltd. Brand name MEK-ST-40 (Spherical organosilica sol in which colloidal silica is dispersed in methyl ethyl ketone. Solid content concentration 40% by mass, average primary particle size 10 to 15 nm)
Organosilica sol 2: Nissan Chemical Industries, Ltd. Brand name MEK-ST-UP (Non-spherical (elongated shape) organosilica sol in which colloidal silica is dispersed in methyl ethyl ketone. Solid content concentration 20% by mass, average primary particle size 40-100 nm)

[Silicone oligomer]
Silicone oligomer 1: Shin-Etsu Chemical Co., Ltd. Product name KR-400 (Silicone oligomer having an alkoxy group and a methyl group directly bonded to a Si atom)
Silicone oligomer 2: Shin-Etsu Chemical Co., Ltd. Trade name KR-401 (Silicone oligomer having an alkoxy group, a methyl group and a phenyl group directly bonded to a Si atom)

[Production of Fluorine-Containing Polymer F1]
Potassium carbonate (12.3 g) and Kyoward KW500SH (trade name of Kyowa Chemical Industry Co., Ltd., hereinafter also referred to as an adsorbent) (4.5 g) were charged in an autoclave and degassed by vacuum. Next, xylene (503 g), ethanol (142 g), CTFE (387 g), CHVE (326 g) and HBVE (84.9 g) were introduced into the autoclave to raise the temperature, and tert-butylperoxypivarate as a polymerization initiator. The 50% by mass xylene solution (20 mL) of the above was continuously added to carry out the polymerization. After 11 hours, the autoclave was cooled with water to stop the polymerization, and the solution in the autoclave was filtered to obtain a solution containing the fluorine-containing polymer F1.
The obtained solution was vacuum dried at 65 ° C. for 24 hours to remove the solvent, and further vacuum dried at 130 ° C. for 20 minutes to obtain a block-shaped fluorine-containing polymer F1.
The fluorine-containing polymer F1 contains CTFE-based units, CHVE-based units, and HBVE-based units in this order of 50 mol%, 39 mol%, and 11 mol, respectively, with respect to all the units contained in the fluorine-containing polymer F1. It was a polymer containing%. The Tg of the fluorine-containing polymer F1 was 52 ° C., the Mn was 10,000, and the hydroxyl value was 50 mgKOH / g.

[Examples 1 to 17]
<Manufacturing of paint>
The components shown in Tables 1 and 2 were mixed to obtain paints 1 to 17.

<Manufacturing of base material with coating film>
After applying paint 1 with a spin coater on one surface of a 7.5 cm square glass plate (Corning's brand name "Eagle Glass") (application conditions: rotation speed 1,000 rpm, slope-up time 10 seconds, rotation) Heat treatment was carried out in an oven at 80 ° C. for 1 hour at a time of 30 seconds and a dropping amount of the paint of 1.5 mL) to obtain a substrate 1 with a coating film.
Substrates 2 to 17 with a coating film were obtained in the same manner except that the type of paint used was changed as shown in Table 1.

<Evaluation of substrate with coating film>
(Initial antifouling property)
[Mud 1]
A drop of muddy water (prepared by mixing 71.4 g of yellow oak, 23.6 g of 8 types of calcined Kanto loam, 5 g of silica powder, and 166 g of pure water) was dropped on the surface of the coating film, and the mixture was allowed to stand at 25 ° C. for 12 hours. After drying, it was washed with water. The degree of mud stain on the coating film after cleaning was visually confirmed, and the initial antifouling property of the coating film was evaluated according to the following criteria.
S: No mud stains. Also, the mud will fall off immediately when washed with water.
A: No mud stains. However, it takes time for the mud to come off when washed with water.
B: Mud stains have been removed, but there are traces of mud on the coating film.
C: Mud stains are visible.

[Mud 2]
Spray muddy water (71.4 g of yellow oak, 23.6 g of 8 types of calcined Kanto loam, 5 g of silica powder, and 166 g of pure water) sprayed on the surface of the coating film and let stand at 80 ° C. for 1 hour. After drying, it was washed with 50 mL of water in a liquid separation funnel. The degree of mud stain on the coating film after cleaning was visually confirmed, and the initial antifouling property of the coating film was evaluated according to the following criteria.
S: No mud stains. Also, when washed with water, the mud can be removed simply by tilting the coating film.
A: No mud stains. However, it takes a shock to remove the mud when washed with water.
B: Fine mud marks remain, but dirt is almost removed.

[Bird droppings]
Two drops of bird droppings (prepared by mixing 20 g of water and 6 g of pancreatin) were added dropwise to the surface of the coating film with a dropper, and the mixture was allowed to stand at 25 ° C. for 12 hours to dry. After that, the work of wiping with a cloth once, letting it stand for another 15 minutes, and then wiping with a cloth once is repeated several times to visually check the degree of bird droppings stain on the coating film, and the initial antifouling of the coating film. Gender was evaluated according to the following criteria.
A: Most of the dirt is removed by the first dry wipe.
B: Almost all stains are removed by dry wiping more than once and not more than 4 times.

[insect]
A drop of insect solution (prepared by mixing 47 g of formic acid, 24 g of tannic acid, 5 g of albumin acid, and 24 g of honey) is dropped on the surface of the coating film with a dropper, and allowed to stand at 80 ° C. for 1 hour to dry. I let you. Then, it was wiped dry with a cloth 10 times, the degree of insect stain on the coating film was visually confirmed, and the initial antifouling property of the coating film was evaluated according to the following criteria.
S: No dirt.
A: A slight mark remains at the dropping point, but the dirt is almost removed.
B: A mark remains at the dropping point, but the dirt is almost removed.

[Rain streaks]
Drop 2 drops of the test solution for rain streaks (prepared by mixing 30 g of carbon black, 10 g of silica, 20 g of 8 kinds of calcined Kanto loam, and 40 g of yellow oak) on the surface of the coating film with a dropper to make the coating film. The tilted dropping liquid was spread on the coating film. After allowing to stand at 25 ° C. for 30 minutes to dry, 50 mL of water was added dropwise at 2 drops / sec to the dropping site of the test solution on the coating film, and the mixture was further allowed to stand at 25 ° C. for 15 minutes to dry. Then, it was wiped dry with Bencot (trade name, manufactured by Asahi Kasei Corporation), the degree of rain streak stain on the coating film was visually confirmed, and the initial stain resistance of the coating film was evaluated according to the following criteria.
S: No dirt.
A: A few traces remain, but the dirt is almost removed.
B: Traces remain, but dirt is almost removed.

[Scale]
A few drops of tap water were dropped on the surface of the coating film, and the mixture was allowed to stand at room temperature for 1 hour and then allowed to stand at 80 ° C. for 45 minutes to dry. Then, it was wiped dry with Bencot (trade name, manufactured by Asahi Kasei Corporation) 10 times, the degree of water stain on the coating film was visually confirmed, and the initial antifouling property of the coating film was evaluated according to the following criteria.
A: No dirt.
B: Slight marks remain, but dirt is almost removed.

(Anti-fouling property after hot water test)
After immersing the coated substrate in warm water at 98 ° C. for 6 hours, the coated substrate is taken out from the warm water, water droplets on the surface of the coating film are wiped off, and then the same as the mud 1 in the above initial antifouling property. Was evaluated.

(Initial water fall angle)
In an environment of 25 ° C. and 40% RH, when about 20 μL of distilled water was dropped on the surface of the coating film and tilted at a tilting speed of 1 degree / sec, the angle at which the water moved by 1 mm was defined as the initial water fall angle. DMo-501SA (trade name of Kyowa Interface Science Co., Ltd.) was used for measuring the water fall angle.

(Initial water contact angle)
The contact angle of about 2 μL of distilled water placed on the surface of the coating film was measured using DMo-501SA (trade name of Kyowa Interface Science Co., Ltd.). Measurements were performed at five different points on the surface-treated surface of the base material, and the average value was calculated and used as the initial water contact angle. The 2θ method was used to calculate the contact angle.

(Appearance of coating film)
The appearance of the coating film immediately after the coating film was formed was visually confirmed and evaluated according to the following criteria.
A: The coating film is transparent without turbidity.
B: The coating film is slightly white and turbid.
C: The coating film is white and turbid.

(Coating film strength)
The surface of the coating film was rubbed with Bencot (trade name, manufactured by Asahi Kasei Corporation) or a nail, and it was visually judged whether or not a mark remained on the coating film.
A: No trace is left even if the coating film is rubbed with a nail.
B: When the coating film is rubbed with a nail, a mark remains, but when rubbed with Bencot (trade name, manufactured by Asahi Kasei Co., Ltd.), no mark remains.
C: When the coating film is rubbed with Bencot (trade name, manufactured by Asahi Kasei Corporation), a mark remains, but the coating film does not peel off.

The results of the above evaluation tests are shown in Tables 1 and 2.
In Table 1, "polydimethylsilicone / fluorine-containing polymer + curing agent" means the content (parts by mass) of polydimethylsilicone with respect to a total of 100 parts by mass of the fluorine-containing polymer and the curing agent.
In Table 1, "acrylic silicone / fluorine-containing polymer + curing agent" means the content (parts by mass) of acrylic silicone with respect to a total of 100 parts by mass of the fluorine-containing polymer and the curing agent.
In Table 1, "cyclohexanone / liquid medium" means the content (mass%) of cyclohexanone with respect to the total mass of the liquid medium in the coating material.
In Table 1, "coloidal silica / other solid content" means the content (parts by mass) of colloidal silica with respect to a total of 100 parts by mass of the solid content other than colloidal silica in the coating material.
In all of Examples 8 to 17 in Table 2, the initial water fall angle was 14 degrees or less, the initial water contact angle was 103 degrees or more, and the antifouling property after the hot water resistance test was B or more. ..

As shown in Tables 1 and 2, a fluorine-containing polymer, a polydimethyl silicone having a first crosslinkable group, an acrylic silicone having a second crosslinkable group, a first crosslinkable group and a second crosslinkable group. It has been shown that when a coating material having a curing agent having a reactive group capable of reacting with a crosslinkable group is used, an antifouling coating film having excellent heat resistance and water resistance can be formed (Examples 1 to 5 and Examples 8 to 17). ).

In the present invention, it is possible to provide a painted article having an antifouling coating film having excellent temperature and water resistance. The article of the present invention is attached to an automobile window glass, an automobile, a motorcycle, a painted surface of a bicycle, a head lamp cover, a sensor cover, an outdoor antenna receiver or its cover, a signal lamp cover, kitchen equipment, kitchen utensils, and kitchen equipment. It can be used for fins and filters of air conditioners such as exhaust devices and air conditioners, home appliances, bathing facilities, washbasin facilities, medical facilities, medical machinery and equipment, mirrors, eyeglasses, inkjet printer parts, toilet bowls, etc. ..

In particular, equipment, devices, appliances, parts, etc. that are washed with water, such as refrigerators, freezers, fins and filters of air conditioning equipment, adhere with water droplets, ice, frost, etc. in order to improve drainage after washing with water. A function that makes it difficult to do is required. The coating film formed from this paint can also be used as an icing prevention film for fins and filters of freezers and air conditioning equipment. Since the surface-treated layer having excellent water-sliding property is less likely to have water droplets attached to it, the painted article of the present invention can be used for equipment, devices, appliances, parts and the like in which water cleaning is performed.
The painted surfaces of vehicles such as automobiles, bicycles, motorcycles, and trains, exteriors of buildings, and equipment that may be installed outdoors such as vending machines and guardrails are prone to mud due to rainfall, etc. Depending on the area where it is used, it may be exposed to a hot and humid environment for a long time. The coating film formed from the present paint is less likely to adhere to mud even after being immersed in warm water for a long time, and once adhered mud can be easily removed by washing with water. Therefore, the painted article of the present invention can be used for the vehicle exterior.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2020-045596 filed on March 16, 2020 are cited here and incorporated as disclosure of the specification of the present invention. Is.

Claims (15)

1. A fluorine-containing polymer, a polydimethyl silicone having a first cross-linking group, an acrylic silicone having a second cross-linking group, and the first cross-linking group and the second cross-linking group can react with each other. A coating material comprising, and a curing agent having a reactive group.
2. The coating material according to claim 1, wherein the polydimethylsilicone has a kinematic viscosity of 30 to 150 mm ^{2 / s.}
3. The coating material according to claim 1 or 2, wherein the fluorine-containing polymer contains a unit having a third crosslinkable group.
4. The coating material according to claim 3, wherein the first crosslinkable group, the second crosslinkable group, and the third crosslinkable group are all hydroxy groups.
5. The coating material according to any one of claims 1 to 4, wherein the reactive group is an isocyanate group or a blocked isocyanate group.
6. The coating material according to any one of claims 1 to 5, wherein the polydimethylsilicone has a hydroxyl value of 150 mgKOH / g or less.
7. The polydimethyl silicone has a dimethylsiloxane unit and
   The coating material according to any one of claims 1 to 6, wherein the number of repetitions of the dimethylsiloxane unit is 10 or more.
8. The method according to any one of claims 1 to 7, wherein the content of the polydimethylsilicone is 2.0 to 10 parts by mass with respect to a total of 100 parts by mass of the fluorine-containing polymer and the curing agent. paint.
9. The paint according to any one of claims 1 to 8, wherein the acrylic silicone has a hydroxyl value of 5 to 200 mgKOH / g.
10. The coating material according to any one of claims 1 to 9, wherein the content of the acrylic silicone is 20 parts by mass or more with respect to 100 parts by mass in total of the fluorine-containing polymer and the curing agent.
11. In addition, it contains a liquid medium,
    The coating material according to any one of claims 1 to 10, wherein the liquid medium contains a liquid medium S1 having a relative evaporation rate of less than 0.50 when the evaporation rate of butyl acetate is 1.
12. The coating material according to claim 11, wherein the content ratio of the liquid medium S1 is 15% by mass or more with respect to the total mass of the liquid medium.
13. The paint according to any one of claims 1 to 12, further containing colloidal silica.
14. A fluorine-containing polymer, a polydimethyl silicone having a first cross-linking group, an acrylic silicone having a second cross-linking group, and the first cross-linking group and the second cross-linking group can react with each other. The method for producing a coating material, wherein the curing agent having a reactive group and an organosilica sol in which colloidal silica is dispersed in an organic solvent are mixed to obtain the coating material according to claim 13.
15. A base material with a coating film, which comprises a base material and a coating film formed from the coating material according to any one of claims 1 to 13 arranged on the base material.