CN111194340A

CN111194340A - Fluorine-containing coating

Info

Publication number: CN111194340A
Application number: CN201880064521.XA
Authority: CN
Inventors: 斋藤俊; 尾知修平; 由上刊; 杉田翼
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2017-10-02
Filing date: 2018-09-28
Publication date: 2020-05-22
Also published as: WO2019069822A1; JPWO2019069822A1

Abstract

Provided is a fluorine-based coating material which can form a coating film having excellent water repellency, appropriate hardness, and excellent durability. A fluorine-based paint, characterized by comprising: a fluorine-containing non-block copolymer, a fluorine-containing block copolymer, and an organic solvent, wherein the mass ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0001 to 10, the fluorine-containing non-block copolymer comprises a fluoroolefin-based unit, and the fluorine-containing block copolymer comprises: a fluorine-containing segment comprising a unit based on a monomer having a perfluoroalkyl group, and a non-fluorine segment containing no fluorine atom.

Description

Fluorine-containing coating

Technical Field

The present invention relates to a fluorine-based coating material capable of forming a coating film excellent in water repellency, hardness and durability.

Background

Coating with a coating film having excellent weather resistance and stain resistance is required for wall materials in residential buildings, surface materials for furniture, vehicle exterior, and the like, from the viewpoint of maintaining the appearance for a long period of time. In contrast, a coating material containing a fluorine-containing polymer containing a fluoroolefin has been proposed (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-208043

Disclosure of Invention

Problems to be solved by the invention

The present inventors have evaluated a coating film formed from the thermosetting resin composition described in patent document 1, and as a result, have found that the durability of the coating film is problematic because the contamination resistance, particularly the water repellency, is insufficient. Further, when an attempt is made to impart water repellency to the coating film of patent document 1, it is found that the hardness of the coating film is not appropriate.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a fluorine-based coating material capable of forming a coating film having excellent water repellency, appropriate hardness, and excellent durability.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the following means.

[1] A fluorine-based paint, characterized by comprising: a fluorine-containing non-block copolymer, a fluorine-containing block copolymer, and an organic solvent, wherein the mass ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0001 to 10, wherein the fluorine-containing non-block copolymer comprises a fluoroolefin-based unit, and the fluorine-containing block copolymer comprises: a fluorine-containing segment comprising a unit based on a monomer having a perfluoroalkyl group, and a non-fluorine segment containing no fluorine atom.

[2] The fluorine-based coating material according to [1], wherein the fluorine atom content is 5 to 40% by mass based on the total mass of solid components contained in the fluorine-based coating material.

[3] The fluorine-containing coating material according to [1] or [2], wherein the fluorine-containing non-block copolymer further contains a unit having a crosslinkable group.

[4] The fluorine-containing coating material according to any one of [1] to [3], wherein the fluorine-containing block copolymer contains: a unit having a crosslinkable group, and a unit based on an alkyl (meth) acrylate.

[5] The fluorine-based coating material according to [3] or [4], wherein the unit having a crosslinkable group is a unit based on a monomer having a crosslinkable group.

[6] The fluorine-based coating material according to any one of [3] to [5], wherein the crosslinkable group is a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group or an amino group.

[7] The fluorine-containing coating material according to any one of [1] to [6], wherein the fluorine-containing non-block copolymer and the fluorine-containing block copolymer each contain a unit having a crosslinkable group, and the crosslinkable group is a hydroxyl group.

[8] The fluorine-based paint according to any one of [1] to [7], further comprising a curing agent.

[9] The fluorine-based paint according to any one of [1] to [8], further comprising an amide wax.

[10] The fluorine-based paint according to [9], wherein the amide wax is a carboxylic acid amide.

[11] The fluorine-containing coating material according to [9] or [10], wherein the amide wax is an aliphatic carboxylic acid amide having an alkyl group with an average carbon number of 20 to 40.

[12] The fluorine-containing coating material according to any one of [9] to [11], wherein the amide wax is contained in an amount of 0.01 to 15 mass% based on the total mass of the fluorine-containing non-block copolymer and the fluorine-containing block copolymer.

[13] The fluorine-containing coating material according to any one of [9] to [12], wherein the mass ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0005 to 0.01.

[14] A method for producing a substrate with a coating film, comprising applying the fluorine-based coating material according to any one of [1] to [13] to the surface of a substrate to form a coating layer, and drying the coating layer to form a coating film.

[15] A coating film formed from the fluorine-based coating material according to any one of [1] to [13], wherein the pencil hardness of the coating film is HB or more, the static contact angle of water to the coating film is 100 ° or more, and the static contact angle of oil to the coating film is 65 ° or more.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide a fluorine-based coating material which can form a coating film having excellent water repellency, appropriate hardness, and excellent durability.

Detailed Description

The meanings of the terms of the present invention are as follows.

The numerical range represented by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.

"(meth) acrylate" is a generic term for both acrylate and methacrylate, and "(meth) acrylic acid" is a generic term for both acrylic acid and methacrylic acid.

The "unit" is a general term for a radical formed directly by polymerization of a monomer and based on the molecule of the monomer 1 and a radical obtained by chemical conversion of a part of the radical. The content (% by mole) of each unit in the polymer relative to the total units may be determined by analyzing the polymer by nmr spectroscopy, or may be determined according to the amount of the components to be used in the production of the polymer.

The "acid value" and the "hydroxyl value" are values measured by the methods according to JIS K0070-3 (1992), respectively.

The "number average molecular weight" and the "weight average molecular weight" are values measured by gel permeation chromatography using polystyrene as a standard substance. The number average molecular weight is also referred to as Mn and the weight average molecular weight is also referred to as Mw.

"glass transition temperature" is a value of an intermediate glass transition temperature measured by a Differential Scanning Calorimetry (DSC) method. The glass transition temperature is also referred to as Tg.

The "fluorine-containing block copolymer" is a polymer compound composed of a plurality of segments containing different types of units, or composed of a plurality of segments containing different types of units in the same type, and at least 1 segment has a fluorine atom.

The "fluorine-containing non-block copolymer" is a polymer compound having a fluorine atom in the molecule, and means a copolymer other than the above-mentioned "fluorine-containing block copolymer", and specific examples thereof include polymers in which the bonding order of different units is random or alternating.

The "fluorine atom content" refers to the proportion (mass%) of fluorine atoms to all atoms constituting all solid components contained in the coating material. The fluorine atom content was measured under the following conditions for the solid content contained in the fluorine-based paint by an automatic test burner-ion chromatography (AQF-IC method).

< analysis conditions >

Automatic test combustion apparatus

The device comprises the following steps: mitsubishi Chemical Analytech Co., Ltd., manufactured by Ltd., AQF-100

The combustion conditions are as follows: solid sample mode, sample amount: 2 to 20mg of

Ion chromatograph

The device comprises the following steps: manufactured by Thermo Fisher SCIENTIFIC

Column: IonpacAG11HC + IonpacAS11HC

Eluent: KOH10mN (0-9 min), 10-16mN (9-11 min), 16mN (11-15 min), 16-61mN (15-20 min), 60mN (20-25 min), flow rate: 1.0 mL/min, suppressor: ASRS, detector: conductivity detector, injection amount: 5 μ L

The mass of the solid content of the coating material is the mass after the solvent is removed from the coating material when the coating material contains the solvent. The components constituting the solid components of the coating material other than the solvent may be in a liquid state or may be regarded as solid components. The mass of the solid content of the coating material was determined as the mass remaining after heating the coating material at 130 ℃ for 20 minutes.

The fluorine-containing coating material (hereinafter, also referred to as the present coating material) of the present invention has a fluorine-containing non-block copolymer (hereinafter, also referred to as a polymer a)) and a fluorine-containing block copolymer (hereinafter, also referred to as a polymer B)) dissolved or dispersed in an organic solvent, wherein the ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0001 to 10, the fluorine-containing non-block copolymer contains a fluoroolefin-based unit (hereinafter, also referred to as a unit F), and the fluorine-containing block copolymer has: a fluorine-containing segment (hereinafter, also referred to as segment 1) containing a unit (hereinafter, also referred to as unit B1) based on a monomer having a perfluoroalkyl group (hereinafter, also referred to as monomer B1), and a non-fluorine segment (hereinafter, also referred to as segment 2) containing no fluorine atom.

In the present specification, the polymer a and the polymer B are also collectively referred to simply as a polymer.

The coating material can form a coating film formed from the coating material (hereinafter, also referred to as the present coating film) having excellent water repellency, appropriate hardness, and excellent durability. The reason is not clear, but is considered as follows.

The coating material is obtained by mixing a specific fluorine-containing non-block copolymer and a specific fluorine-containing block copolymer at a predetermined ratio in the presence of an organic solvent. Therefore, the fluorinated non-block copolymer and the fluorinated block copolymer, which are generally difficult to be compatible, are easily compatible with each other by the organic solvent, and the respective copolymers are easily uniformly dispersed in the organic solvent. Further, when a coating film is formed from the present coating material, it is considered that the perfluoroalkyl group of the fluorinated block copolymer is oriented on the surface of the coating film, and the influence of the fluorine atom of the perfluoroalkyl group is adjusted, so that the fluorine atom contained in the fluorinated non-block copolymer is stably arranged. Therefore, the coating film is considered to have appropriate hardness, excellent water repellency, and durability.

In the present specification, the durability of the coating film means that the stain resistance of the coating film is maintained.

The polymer A will be described in detail below.

The fluoroolefin is an olefin in which 1 or more hydrogen atoms are replaced by fluorine atoms. In the case of the fluoroolefin, 1 or more of the hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.

As examples of the fluoroolefin, CF may be mentioned₂＝CF₂、CF₂＝CFCl、CF₂＝CHF、CH₂＝CF₂、CF₂＝CFCF₃、CF₂＝CHCF₃、CF₃-CH＝CHF、CF₃-CF＝CH₂. As the fluoroolefin, CF is more preferable from the viewpoint of weather resistance of the present coating film₂＝CF₂Or CF₂CFCl. The fluoroolefin may be used in combination of 2 or more.

The content of the unit F is preferably 20 to 70 mol%, more preferably 30 to 60 mol%, and particularly preferably 45 to 55 mol% based on the total units contained in the polymer a, from the viewpoints of dispersion stability of the polymer a and weather resistance of the present coating film.

The polymer a preferably contains a unit having a crosslinkable group (hereinafter, also referred to as a unit a 1.) from the viewpoint of durability of the present coating film. The unit a1 may be a unit based on a monomer having a crosslinkable group (hereinafter, also referred to as a monomer a 1), or may be a unit obtained by converting a crosslinkable group of a fluoropolymer containing the unit a1 into a different crosslinkable group. Examples of such units include units obtained by reacting a fluoropolymer containing a unit having a hydroxyl group with a polycarboxylic acid, an anhydride thereof, or the like to convert a part or all of the hydroxyl groups into carboxyl groups. The unit A1 is preferably a unit having no fluorine atom from the viewpoint of polymerizability with the unit F.

The crosslinkable group of the unit a1 is preferably a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group or an amino group, and from the viewpoint of curability of the polymer a, a hydroxyl group or a carboxyl group is preferred.

Examples of the monomer having a carboxyl group include unsaturated carboxylic acids, (meth) acrylic acids, and the like. The monomer having a carboxyl group is preferably represented by the general formula: x¹¹-Y¹¹The monomer shown (hereinafter, also referred to as monomer a 11.).

Examples of the monomer having a hydroxyl group include allyl alcohol; a vinyl ether having a hydroxyl group, a vinyl ester having a hydroxyl group, an allyl ether having a hydroxyl group, an allyl ester having a hydroxyl group, or a (meth) acrylate having a hydroxyl group. As the monomer having a hydroxyl group, allyl alcohol is preferred, or a compound represented by the general formula: x¹²-Y¹²The monomer shown (hereinafter, also referred to as monomer a 12.).

The monomer A1 may be used in combination of 2 or more.

The symbols in the formula represent the following meanings.

X¹¹Is CH₂＝CH-、CH(CH₃) CH-or CH₂＝C(CH₃) -, preferably CH₂CH-or CH (CH)₃)＝CH-。

Y¹¹The carboxyl group or 1-valent saturated hydrocarbon group having 1-12 carbon atoms and having a carboxyl group, preferably a carboxyl group or carboxyalkyl group having 1-10 carbon atoms.

X¹²Is CH₂＝CHO-、CH₂＝CHCH₂O-、CH₂＝CHOC(O)-、CH₂CHCOO-or CH₂＝C(CH₃)COO-。

Y¹²The hydrocarbon group is a C2-12 saturated hydrocarbon group having a hydroxyl group. The 1-valent saturated hydrocarbon group may be linear or branched. The 1-valent saturated hydrocarbon group may be formed of a ring structure, or may include a ring structure.

The 1-valent saturated hydrocarbon group is preferably an alkyl group having 2 to 6 carbon atoms or an alkyl group containing a cycloalkylene group having 6 to 8 carbon atoms.

Specific examples of the monomer A11 include CH₂＝CHCOOH、CH(CH₃)＝CHCOOH、CH₂＝C(CH₃)COOH、CH₂＝CH(CH₂)_n2COOH (wherein n2 represents an integer of 1 to 10).

Specific examples of the monomer A12 include CH₂＝CHO-CH₂-cycloC₆H₁₀-CH₂OH、CH₂＝CHCH₂O-CH₂-cycloC₆H₁₀-CH₂OH、CH₂＝CHOCH₂CH₂OH、CH₂＝CHCH₂OCH₂CH₂OH、CH₂＝CHOCH₂CH₂CH₂CH₂OH、CH₂＝CHCH₂OCH₂CH₂CH₂CH₂OH、CH₂＝CHCOOCH₂CH₂OH、CH₂＝C(CH₃)COOCH₂CH₂And (5) OH. Note that, "-CycloC₆H₁₀- "denotes cyclohexylene," -CycloC₆H₁₀The bonding site of the- "is usually 1, 4-.

When the polymer a contains a curing agent, the crosslinkable group of the unit a1 becomes a crosslinking point, and crosslinking reactions between the polymers a, between the polymers B, and between the polymer a and the polymer B proceed via the curing agent, so that the hardness of the present coating film becomes appropriate, and the durability thereof is improved.

The content of the unit a1 is preferably 0.5 to 35 mol%, more preferably 3 to 25 mol%, particularly preferably 5 to 20 mol%, most preferably 5 to 15 mol% based on the total units contained in the polymer a.

The polymer a may further contain a unit other than the unit F and the unit a1 (hereinafter, also referred to as a unit a 2.) in view of flexibility of the present coating film. Examples of the unit A2 include units based on a vinyl ether having no crosslinkable group and no fluorine atom, a vinyl ester having no crosslinkable group and no fluorine atom, an allyl ether having no crosslinkable group and no fluorine atom, an allyl ester having no crosslinkable group and no fluorine atom, a (meth) acrylic ester having no crosslinkable group and no fluorine atom, and the like.

The unit A2 is preferably based on the general formula: x²-Z²A unit of the monomer shown (hereinafter, also referred to as a monomer a 2).

X²Is CH₂＝CHC(O)O-、CH₂＝C(CH₃)C(O)O-、CH₂＝CHOC(O)-、CH₂＝CHCH₂OC(O)-、CH₂CHO-or CH₂＝CHCH₂O-CH is preferred because the coating film has excellent weather resistance₂＝CHOC(O)-、CH₂＝CHCH₂OC(O)-、CH₂CHO-or CH₂＝CHCH₂O-。

Z²Is a C1-24 hydrocarbon group. The 1-valent hydrocarbon group may be linear or branched. The 1-valent hydrocarbon group may be formed of a ring structure, or may include a ring structure. The 1-valent hydrocarbon group may be a 1-valent saturated hydrocarbon group or a 1-valent unsaturated hydrocarbon group.

The 1-valent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and more preferably an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 12 carbon atoms.

Specific examples of the alkyl group include methyl, ethyl, tert-butyl, hexyl, nonyl, decyl and dodecyl.

Specific examples of the cycloalkyl group include cyclohexyl groups.

Specific examples of the aralkyl group include a benzyl group.

Specific examples of the aryl group include a phenyl group and a naphthyl group.

The monomer A2 may be used in combination of 2 or more.

Specific examples of the monomer A2 include ethyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl pivalate, vinyl neononanoate (trade name "VeoVa 9" from HEXION), vinyl neodecanoate (trade name "VeoVa 10" from HEXION), vinyl benzoate, methyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate.

When the polymer a contains the unit a2, the content of the unit a2 is preferably 1 to 70 mol%, particularly preferably 10 to 50 mol%, based on the total units contained in the polymer a.

The polymer A preferably comprises 20 to 70 mol% of the unit F, 0.5 to 35 mol% of the unit A1, and 1 to 70 mol% of the unit A2, respectively, in this order, based on the total units of the polymer A, and is particularly preferably composed of the unit F, the unit A1, and the unit A2.

The Tg of the polymer A is preferably 25 to 120 ℃ and more preferably 30 to 100 ℃ in view of the hardness of the coating film.

The Mn of the polymer A is preferably 3,000 to 30,000, more preferably 5,000 to 20,000, and particularly preferably 8,000 to 18,000 in view of the impact resistance of the present coating film.

When the polymer A is a polymer having a carboxyl group, the acid value of the polymer A is preferably 1 to 150mgKOH/g, more preferably 3 to 100mgKOH/g, and particularly preferably 10 to 60mgKOH/g, from the viewpoint of durability of the coating film.

When the polymer A is a polymer having a hydroxyl group, the hydroxyl value of the polymer A is preferably 1 to 150mgKOH/g, more preferably 3 to 100mgKOH/g, and particularly preferably 10 to 60mgKOH/g, from the viewpoint of the durability of the coating film.

The polymer a may have either a hydroxyl value or an acid value, or both.

From the viewpoint of weather resistance of the coating film, the content of the polymer a is preferably 20 to 95% by mass, and particularly preferably 30 to 90% by mass, based on the total solid content mass of the coating material. The polymer A may be used in combination of 2 or more.

The polymer a is obtained by polymerizing the above-mentioned monomers in the presence of a polymerization solvent and a polymerization initiator, for example. In the production of the polymer a, a light stabilizer, a pH adjuster, and the like may be added as necessary.

The polymer B will be described in detail below.

Segment 1 is preferably composed of a homopolymer of monomer B1, a copolymer of 2 or more monomers B1, or a copolymer of at least 1 monomer B1 and at least 1 non-fluorine-containing monomer, more preferably a homopolymer of monomer B1 or a copolymer of 2 or more monomers B1, and particularly preferably a homopolymer of monomer B1.

As monomers B1, preference is given to using monomers of the formula: x³-L³-R^FThe monomer shown (hereinafter, also referred to as monomer B11.).

X³Is CH₂＝C(R¹)C(O)O-、CH₂＝C(R¹)OCO-、CH₂CHO-or CH₂＝CHCH₂O-, preferably CH₂＝C(R¹) C (O) O-. R is as defined above¹Is a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom, preferably a hydrogen atom.

L³Is a single bond or a 2-valent linking group. The 2-valent linking group is preferably a 2-valent hydrocarbon group, more preferably a 2-valent aliphatic hydrocarbon group, and particularly preferably a 2-valent alkylene group. The number of carbons in the 2-valent hydrocarbon group is preferably 1 to 10, more preferably 1 to 5. The 2-valent hydrocarbon group may be linear or branched. The 2-valent hydrocarbon group may be formed of a ring structure, or may include a ring structure. The ring structure may be aromatic. The 2-valent linking group may be a group in which a 2-valent hydrocarbon group and-O-are combined.

R^FIs a perfluoroalkyl group. The number of carbons in the perfluoroalkyl group is preferably 1 to 30, particularly preferably 1 to 6, from the viewpoint of the antifouling property of the present coating film. The perfluoroalkyl group may be linear or branched.

Specific examples of the monomer B11 include CH₂＝C(R¹)C(O)O(CH₂)₂(CF₂)₆F、CH₂＝C(R¹)C(O)O(CH₂)₂(CF₂)₈F、CH₂＝C(R¹)C(O)O(CH₂)₂(CF₂)₁₀F、CH₂＝C(R¹)C(O)O(CH₂)₂(CF₂)₆CF(CF₃)₂、CH₂＝C(R¹)C(O)O(CH₂)₂(CF₂)₈CF(CF₃)₂、CH₂＝C(R¹)OCOCH₂-Ph-O-(CF₂)₈F (Ph represents an optionally substituted phenylene group). In the above formula, R represents¹Is as defined above.

The segment 1 may have a unit based on a non-fluorine-based monomer (hereinafter, also referred to as a monomer B2.) in view of compatibility with the polymer a.

The monomer B2 is preferably an alkyl (meth) acrylate having an alkyl group with 12 to 20 carbon atoms (hereinafter, also referred to as a monomer B22.).

Specific examples of the monomer B22 include dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, and behenyl (meth) acrylate.

The content of the unit constituting the segment 1 in the polymer B is preferably 2 to 40 mol%, more preferably 3 to 20 mol%, and particularly preferably 5 to 15 mol% based on the total units contained in the polymer B, from the viewpoint of water repellency of the present coating film.

From the viewpoint of water repellency of the present coating film, the content of the unit B1 in the segment 1 is preferably 80 mol% or more, more preferably 85 mol% or more, and particularly preferably 95 mol% or more, based on the total units contained in the segment 1.

The segment 2 is preferably composed of a homopolymer of the monomer B2 or a copolymer of 2 or more monomers B2, as long as it does not have a fluorine atom, and in view of the ease with which the polymer B is held on the surface of the present coating film.

Examples of monomers B2 include (meth) acrylates, preferably those of the formula: x⁴-Y⁴The monomer shown (hereinafter, also referred to as monomer B21.).

X⁴Is CH₂CHC (O) O-or CH₂＝C(CH₃)C(O)O-。

Y⁴Is alkyl or substituted alkyl having 1 to 22 carbon atoms, cycloalkyl or substituted cycloalkyl having 3 to 15 carbon atoms, or phenyl or substituted phenyl.

Specific examples of the substituent include an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, an ester group, a ketone group, an amino group, an amide group, an imide group, a nitro group, a carboxylic acid group, a mercapto group, and an ether group.

Specific examples of the monomer B21 include alkyl (meth) acrylates ((methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc.), hydroxyl-containing (meth) acrylates ((hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, hydroxypropyl (meth) acrylate, dipropylene glycol mono (meth) acrylate, etc.), (glycidyl (meth) acrylate, nitrogen-containing (meth) acrylates ((dimethylaminoethyl (meth) acrylate, ethylene glycol mono (meth) acrylate, etc.), Diethylaminoethyl (meth) acrylate, 4- (meth) acryloyloxy-2, 2,6, 6-tetramethylpiperidine, 4- (meth) acryloylamino-2, 2,6, 6-tetramethylpiperidine, etc.).

Among the monomers B2, alkyl (meth) acrylates are preferable from the viewpoint of maintaining the water repellency of the present coating film.

The segment 2 preferably has a crosslinkable group in view of durability of the present coating film. That is, the segment 2 preferably contains a unit having a crosslinkable group. Specific examples and suitable embodiments of the unit having a crosslinkable group are the same as those described for the unit A1.

As the monomer having a crosslinkable group, a hydroxyl group-containing vinyl monomer such as the compound exemplified above as the hydroxyl group-containing (meth) acrylate is preferable.

As the segment 2, a segment containing an alkyl (meth) acrylate-based unit and a hydroxyalkyl (meth) acrylate-based unit is preferable, and a segment containing a methyl (meth) acrylate-based unit, a butyl (meth) acrylate-based unit, and a hydroxyethyl (meth) acrylate-based unit, or a segment containing a hydroxyethyl (meth) acrylate-based unit and an octadecyl (meth) acrylate-based unit is particularly preferable.

The content of the unit constituting the segment 2 in the polymer B is preferably 60 to 98 mol%, more preferably 80 to 97 mol%, and particularly preferably 85 to 95 mol% based on the total units contained in the polymer B.

From the viewpoint of durability of the present coating film, the content of the unit based on the monomer having a crosslinkable group in the polymer B is preferably 1 to 25 mol%, more preferably 5 to 20 mol%, based on the total units of the polymer B.

When the polymer B has a hydroxyl value, the hydroxyl value of the polymer B is preferably 10 to 100mgKOH/g, more preferably 15 to 90mgKOH/g, and particularly preferably 30 to 70mgKOH/g, from the viewpoint of durability of the present coating film.

The Mn of the polymer B is preferably 5,000 to 1,000,000, more preferably 10,000 to 300,000, and particularly preferably 10,000 to 100,000 in view of the flexibility of the coating film.

From the viewpoint of water repellency of the present coating film, the mass ratio of the polymer B to the total mass of the polymer a (mass of the polymer B/mass of the polymer a) is 0.0001 to 10, preferably 0.001 to 10, more preferably 0.01 to 0.1, and particularly preferably 0.02 to 0.09.

The polymer B may be used in combination of 2 or more.

Specific examples of the polymer B include MODIPER F206, MODIPER F246, MODIPER F906, MODIPER F3636, MODIPER F226 and MODIPER F606 (all of which are trade names of japan oil co.

From the viewpoint of water repellency of the coating film, the content of the polymer B is preferably 0.01 to 10% by mass based on the total solid content of the coating material.

The coating material preferably contains 1 to 99 mass%, more preferably 40 to 80 mass%, and particularly preferably 50 to 70 mass% of the mass of the solid content, based on the total mass of the coating material.

The coating contains an organic solvent as a coating solvent.

Specific examples of the organic solvent include petroleum-based mixed solvents (toluene, xylene, Solvesso 100 manufactured by Exxon Mobil Corporation, Solvesso 150 manufactured by Exxon Mobil Corporation, etc.), aromatic hydrocarbon solvents (mineral spirits, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and alcohol solvents (ethanol, t-butyl alcohol, isopropyl alcohol, etc.). The organic solvent may be used in combination of 2 or more.

The content of the organic solvent in the coating material is preferably 1 to 99 mass%, more preferably 20 to 60 mass%, and particularly preferably 30 to 50 mass% based on the total mass of the coating material.

The present coating preferably comprises a curing agent.

The curing agent is a compound having 2 or more groups reactive with the crosslinkable group in 1 molecule. The polymer is crosslinked by the reaction of the curing agent with the crosslinkable group contained in the polymer. The curing agent generally has 2 to 30 groups capable of reacting with the crosslinkable group.

The curing agent in the case where the polymer has a hydroxyl group is preferably a compound having 2 or more isocyanate groups or blocked isocyanate groups in 1 molecule.

the curing agent in the case where the polymer has a carboxyl group is preferably a compound having 2 or more epoxy groups, carbodiimide groups, oxazoline groups, or β -hydroxyalkylamide groups in 1 molecule.

when the polymer has both a hydroxyl group and a carboxyl group, it is preferable to use a compound having 2 or more isocyanate groups or blocked isocyanate groups in 1 molecule and a compound having 2 or more epoxy groups, carbodiimide groups, oxazoline groups, or β -hydroxyalkylamide groups in 1 molecule in combination.

The compound having 2 or more isocyanate groups in 1 molecule is preferably a polyisocyanate monomer or a polyisocyanate derivative.

The polyisocyanate monomer is preferably an alicyclic polyisocyanate, an aliphatic polyisocyanate or an aromatic polyisocyanate. The polyisocyanate derivative is preferably a polymer or a modified product (biuret, isocyanurate or adduct) of a polyisocyanate monomer.

Specific examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2, 4-trimethyl-1, 6-diisocyanatohexane and lysine diisocyanate, lysine triisocyanate, 4-isocyanatomethyl-1, 8-octamethylene diisocyanate and bis (2-isocyanatoethyl) 2-isocyanatoglutamate.

Specific examples of the alicyclic polyisocyanate include alicyclic diisocyanates such as isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) -cyclohexane, 4' -dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylylene diisocyanate.

Specific examples of the aromatic polyisocyanate include aromatic diisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, naphthalene diisocyanate, and xylylene diisocyanate.

The curing agent is preferably a modified polyisocyanate monomer, more preferably an adduct of a polyisocyanate monomer, and particularly preferably an adduct of hexamethylene diisocyanate, in view of obtaining a coating film having elasticity and less occurrence of cracks.

The compound having 2 or more blocked isocyanate groups in 1 molecule is preferably a compound in which 2 or more isocyanate groups of the polyisocyanate monomer or the polyisocyanate derivative are blocked with a blocking agent.

The blocking agent is a compound having an active hydrogen, and specific examples thereof include alcohols, phenols, active methylene groups, amines, imines, acid amides, lactams, oximes, pyrazoles, imidazoles, imidazolines, pyrimidines, and guanidines.

Specific examples of the compound having 2 or more epoxy groups in 1 molecule include bisphenol type epoxy compounds (a type, F type, S type, etc.), diphenyl ether type epoxy compounds, hydroquinone type epoxy compounds, naphthalene type epoxy compounds, biphenyl type epoxy compounds, fluorene type epoxy compounds, hydrogenated bisphenol a type epoxy compounds, bisphenol a core-containing polyhydric alcohol type epoxy compounds, polypropylene glycol type epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, glyoxal type epoxy compounds, alicyclic type polyfunctional epoxy compounds, heterocyclic type epoxy compounds (triglycidyl isocyanurate, etc.).

Specific examples of the compound having 2 or more carbodiimide groups in 1 molecule include alicyclic carbodiimide, aliphatic carbodiimide, and aromatic carbodiimide, and multimers and modifications thereof.

Specific examples of the compound having 2 or more oxazoline groups in 1 molecule include addition-polymerizable oxazoline having 2-oxazoline groups and polymers of the addition-polymerizable oxazoline.

specific examples of the compound having 2 or more β -hydroxyalkylamide groups in 1 molecule include N, N, N ', N' -tetrakis- (2-hydroxyethyl) -adipamide (PrimidXL-552, trade name of EMS) and N, N, N ', N' -tetrakis- (2-hydroxypropyl) -adipamide (PrimidQM 1260, trade name of EMS).

When the coating material contains a curing agent, the content of the curing agent is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 50 to 100 parts by mass, based on 100 parts by mass of the polymer a in the coating material.

The present coating may comprise a curing catalyst. The curing catalyst is a compound which promotes a curing reaction when a curing agent is used, and may be selected from known curing catalysts depending on the kind of the curing agent.

The present coating material preferably contains 1 or more selected from the group consisting of an ultraviolet absorber and a light stabilizer. That is, the present coating material may contain both an ultraviolet absorber and a light stabilizer, or may contain only either one.

The ultraviolet absorber is a compound that protects the present coating film from ultraviolet rays.

As the ultraviolet absorber, a salicylate-based compound, a benzotriazole-based compound, a benzophenone-based compound, a triazine-based compound, and a cyanoacrylate-based compound are preferable.

Specific examples of the ultraviolet absorber include "Tinuvin 326" (molecular weight: 315.8, melting point: 139 ℃), "Tinuvin 400" (molecular weight: 647), "Tinuvin 405" (molecular weight: 583.8, melting point: 74 to 77 ℃), "Tinuvin 460" (molecular weight: 629.8, melting point: 93 to 102 ℃), "Tinuvin 900" (molecular weight: 447.6, melting point: 137 to 141 ℃), "Tinuvin 928" (molecular weight: 441.6, melting point: 109 to 113 ℃), "Sanduvor VSU powder" (molecular weight: 312.0, melting point: 123 to 127 ℃) manufactured by Clariant, and "HastavinPR-25 Gran" (molecular weight: 250.0, melting point: 55 to 59 ℃) manufactured by Clariant.

The ultraviolet absorber may be used in combination of 2 or more.

When the coating material contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 to 10% by mass, particularly preferably 0.01 to 5% by mass, based on the mass of the solid content of the polymer, from the viewpoint of the weather resistance of the coating film.

Light stabilizers are compounds that improve the light resistance of the present coatings.

As the light stabilizer, a hindered amine compound is preferable. Specific examples of the hindered amine compound include Tinuvin 111FDL (molecular weight: 2,000 to 4,000, melting point: 63 ℃ C.) commercially available from BASF corporation, "Tinuvin 144 (molecular weight: 685, melting point: 146 to 150 ℃ C.)," Tinuvin 152 (molecular weight: 756.6, melting point: 83 to 90 ℃ C.), "Tinuvin 292 (molecular weight: 508.8)," Sanduvor3051powder (molecular weight: 364.0, melting point: 225 ℃ C.) manufactured by Clariant, "Sanduvor 3070powder (molecular weight: 1,500, melting point: 148 ℃ C.) manufactured by Clariant, and" SanVPduvor PR-31 (molecular weight: 529: 125, melting point: 120 to 125 ℃ C.) manufactured by Clariant.

The light stabilizer may be used in combination of 2 or more.

When the coating material contains a light stabilizer, the content of the light stabilizer is preferably 0.01 to 15% by mass, particularly preferably 0.1 to 5% by mass, based on the total solid content of the coating material.

The present coating preferably comprises an amide wax. When the coating material contains an amide wax, the coating film has excellent water repellency, and particularly the slip angle of water to the coating film can be reduced.

Examples of the amide wax include a carboxylic acid amide which is in the form of a powder or a wax at 25 ℃. Examples of the carboxylic acid amide include aliphatic carboxylic acid amides such as aliphatic carboxylic acid amides, N-substituted aliphatic carboxylic acid amides, and N-substituted ureas, aromatic carboxylic acid amides, and hydroxyamides further having a hydroxyl group.

The carboxylic acid amide is preferably an aliphatic carboxylic acid amide having an alkyl group with an average carbon number of 20 to 40, and particularly preferably an aliphatic carboxylic acid amide having an alkyl group with an average carbon number of 25 to 35. The alkyl group is preferably linear. If the carboxylic acid amide has the alkyl group, the combination with the fluoropolymer can reduce the slip angle of water to a coating film formed from the present coating material.

The amide wax may be used in combination of 2 or more.

When the coating material contains an amide wax, the content of the amide wax is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 5% by mass, based on the total mass of the polymer a and the polymer B, from the viewpoint of water repellency and durability of the coating film.

When the coating material contains an amide wax, the mass ratio of the polymer B to the polymer a (mass of polymer B/mass of polymer a) is more preferably 0.0005 to 0.01 from the viewpoint of the water repellency and the durability of the coating film. When the polymer a and the polymer B are contained in the above ratio, the effect of the amide wax is particularly remarkable.

The coating material may contain a silane compound in view of water repellency of the coating film. As the silane compound, an alkoxysilane is preferable. Examples of the alkoxysilane include alkylalkoxysilane, alkylphenylalkoxysilane, and phenylalkoxysilane.

The silane compound may be used in combination of 2 or more.

The coating material may contain a silicone resin in view of the water repellency of the coating film. The fluorine-containing non-block copolymer of the present invention is not included in the silicone resin.

Examples of the silicone resin include modified silicone oils or modified silicone resins such as dialkylpolysiloxanes such as dimethylpolysiloxane, polyarylsiloxanes such as polydiphenylsiloxane, and polyalkylarylsiloxanes such as methylphenylpolysiloxane, amino-modified silicones, epoxy-modified silicones, carboxyl-modified silicones, alcohol-modified silicones, and polyether-modified silicones, and silicone oligomers.

The silicone resin may be used in combination of 2 or more.

The coating composition may contain components other than those described above, for example, a filler (inorganic filler such as silica, organic filler such as resin beads, etc.) agent, a matting agent, a leveling agent, a surface conditioner, a degassing agent, a filler, a heat stabilizer, a thickener, a dispersant, a surfactant, an antistatic agent, a rust preventive, a silane coupling agent, an antifouling agent, and a pollution reduction treatment agent, as necessary.

The content of fluorine atoms based on the total solid content of the coating material is preferably 5 to 40 mass%, more preferably 10 to 30 mass%, and particularly preferably 13 to 20 mass%. When the content is 5% by mass or more, the weather resistance of the coating film is excellent. When the content is 40% by mass or less, the flexibility of the coating film is excellent. When the content is 5 to 40 mass% and the content of the organic solvent in the coating material is within the above range, the compatibility between the polymer a and the polymer B is excellent, and the durability of the coating film is improved.

The present coating material can be produced by mixing, for example, the polymer a, the polymer B, an organic solvent, and optional components (for example, a curing agent, an ultraviolet absorber, and a light stabilizer). The organic solvent may be a polymerization solvent in the production of the polymer a.

The base material with a coating film of the present invention comprises: a substrate, and a coating film (the present coating film) formed on the substrate by the present coating material.

Specific examples of the base material include organic materials such as resin, rubber, and wood, inorganic materials such as concrete, glass, ceramics, and stone, iron alloys, aluminum, and aluminum alloys.

The film thickness of the coating film is preferably 10 to 200 μm, more preferably 20 to 100 μm. When the film thickness is 10 μm or more, the blocking resistance of the coating film is improved, and when the film thickness is 200 μm or less, the weather resistance of the coating film is improved.

The static contact angle of water with respect to the present coating film is preferably 100 ° or more, more preferably 105 ° or more, from the viewpoint of more excellent stain resistance of the present coating film.

The static contact angle of the oil to the present coating film is preferably 65 ° or more, more preferably 70 ° or more, from the viewpoint of more excellent stain resistance of the present coating film.

The present coating film preferably has a static contact angle of water of 100 ° or more and a static contact angle of oil of 65 ° or more.

The static contact angle of water and the static contact angle of oil in the coating film can be particularly suitably adjusted by the ratio of the polymer B to the polymer a in the coating material, and the like.

The slip angle of water to the present coating film is preferably 60 ° or less, more preferably 35 ° or less, from the viewpoint of more excellent stain resistance of the present coating film.

The hardness of the present coating film is preferably HB or more, and preferably H or more, in view of the difficulty in cracking the present coating film and the excellent wear resistance.

The hardness of the coating film can be particularly suitably adjusted by the kind of each unit contained in the polymer a and the polymer B in the coating material.

The method for producing a substrate with a coating film of the present invention is a method for forming a coating film by applying the present coating material on the surface of a substrate and drying the coating film. When the present coating material contains a curing agent, it is preferable to cure the coating material by heating after the drying.

The coating material may be applied directly to the surface of the substrate, or may be applied after subjecting the surface of the substrate to a known surface treatment (e.g., a primer treatment). Further, an undercoat layer may be formed on the substrate and then applied to the undercoat layer.

Specific examples of the method for applying the coating material include a method using a coating apparatus such as a brush, a roll, a dip coater, a spray coater, a roll coater, a die coater, an applicator, or a spin coater. The drying temperature and the curing temperature after coating are preferably 20 to 300 ℃, and more preferably 20 to 250 ℃.

As described above, the coating material is excellent in stain resistance, and therefore, can be suitably used for wall materials in residential buildings, surface materials for furniture, exterior materials for vehicles, and the like.

Examples

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples for explanation.

The amounts of the components in the table described later are based on mass. Examples 6 to 9, 11 to 14 and 16 to 24 are examples, and examples 5, 10 and 15 are comparative examples.

(abbreviation of Compound, etc.)

Chlorotrifluoroethylene (CTFE)

4-hydroxybutyl vinyl ether (HBVE)

Cyclohexyl vinyl ether (CHVE)

Ethyl Vinyl Ether (EVE)

Curing agent 1: STABiO D-370N (trade name of Mitsui chemical Co., Ltd.)

Curing agent 2: desmodur N3300(Bayer trade name)

Curing catalyst: 10,000 fold diluted solution of dibutyltin dilaurate

Wax 1: amide wax comprising carboxylic acid amide having alkyl group with average carbon number 28

Wax 2: wax comprising modified polyethylene

Wax 3: amide wax comprising carboxylic acid amide having alkyl group with average carbon number 27

Wax 4: amide wax comprising carboxylic acid amide having oleyl group with average carbon number 18

Diluting the solvent: solvesso 150 (trade name of Exxon Mobil Corporation) and xylene (ratio of xylene to Solvesso 150: 9)

(Polymer B)

Polymer B1: a fluorine-containing block copolymer having the following fluorine-containing segment and non-fluorine-containing segment

Fluorine-containing segment: a segment comprising perfluorohexylethyl methacrylate-based units.

Non-fluorine segments: a segment comprising hydroxyethyl methacrylate-based units, butyl methacrylate-based units, and methyl methacrylate-based units.

The content of the perfluorohexylethylmethacrylate-based unit, the hydroxyethyl methacrylate-based unit, the butyl methacrylate-based unit, and the methyl methacrylate-based unit was 10 mol%, 15 mol%, 33 mol%, and 42 mol%, respectively, based on all the units contained in the polymer B1.

[ example 1]

A50 mass% xylene solution (20mL) of xylene (503g), ethanol (142g), CTFE (387g), CHVE (326g), HBVE (84.9g), potassium carbonate (12.3g) and tert-butyl peroxypivalate was introduced into the autoclave, and polymerization was carried out at 65 ℃ for 11 hours. Next, the autoclave solution was filtered to obtain a solution containing polymer a1 as a fluorine-containing non-block copolymer, and then the solvent was removed to obtain polymer a 1.

Polymer a1 was a polymer containing 50 mol%, 39 mol%, and 11 mol% of units based on CTFE, units based on CHVE, and units based on HBVE, respectively, with respect to the total units contained in polymer a 1. Polymer A1 had a hydroxyl value of 50mgKOH/g, a Tg of 52 ℃ and an Mn of 10,000.

[ example 2]

A polymer a2 was obtained as a fluorine-containing non-block copolymer in the same manner as above except that the amount of the monomer used was changed.

Polymer a2 was a polymer containing 50 mol%, 25 mol%, and 25 mol% of units based on CTFE, units based on CHVE, and units based on HBVE, respectively, with respect to the total units contained in polymer a 2. Polymer A2 had a hydroxyl value of 118mgKOH/g, a Tg of 45 ℃ and an Mn of 7,000.

[ example 3]

A solution containing polymer A3 as a fluorine-containing non-block copolymer was obtained in the same manner except that the kind and amount of the monomer used were changed, and then the solvent was removed to obtain polymer A3.

Polymer A3 was a polymer that contained 50 mol%, 15 mol%, 20 mol% of units based on CTFE, units based on CHVE, units based on EVE, and units based on HBVE, respectively, with respect to all units contained in polymer A3. Polymer A3 had a hydroxyl value of 100mgKOH/g, a Tg of 35 ℃ and an Mn of 7,000.

[ example 4]

The components described in the column of "components of fluorine-based coating material" in tables 1 and 2 described later were mixed in the air by using a rocking mill (rolling mill) to obtain fluorine-based coating materials 1 to 20. In the mixing of the components, the polymer B is uniformly dissolved or dispersed in butyl acetate, methyl ethyl ketone, or a diluent solvent in advance, and then components other than the above are mixed and used. The details of the amounts of the respective components are shown in tables 1 and 2.

< production of substrate with coating film >

[ examples 5 to 24 ]

The fluorine-based paint 1 was applied to the surface of an aluminum plate (200 mm in vertical direction, 125mm in horizontal direction, and 0.8mm in plate thickness) with an applicator so that the dry film thickness became 40 μm, and the plate was dried at room temperature (25 ℃) for 1 week to form a coating film, thereby obtaining a substrate 1 with a coating film formed of the fluorine-based paint 1 as a test piece 1.

The same procedure as in the case of the test piece 1 was carried out for each of the fluorine-based paints 2 to 20, and test pieces 2 to 20 were obtained.

The obtained test pieces 1 to 20 were subjected to the following evaluations.

< evaluation >

[ Water repellency a1]

For each test piece, the static contact angle of water to the coating film of the test piece was measured.

Pure water having a diameter of 1 to 2mm was dropped on the surface of the coating film of the test piece using a contact angle measuring apparatus (trade name of FACE corporation, CA-X type), and the drop 30 seconds after dropping was photographed with a camera to analyze the image. The angle of a straight line connecting the end point and the apex of the droplet to the test piece was 2 times as measured as the static contact angle. The measurement was performed 3 times, and the average value of the obtained measurement values was used as the value of the static contact angle, and evaluated as follows. The larger the static contact angle, the more excellent the water repellency of the coating film.

And SS: the static contact angle of water is 105 degrees or more.

S: the static contact angle of water is 100 degrees or more and less than 105 degrees.

A: the static contact angle of water is 90 degrees or more and less than 100 degrees.

B: the static contact angle of water is 80 degrees or more and less than 90 degrees.

C: the static contact angle of water is less than 80 degrees.

[ oil repellency a1]

For each test piece, the static contact angle of the liquid paraffin to the coating film of the test piece was measured.

A contact angle measuring device (trade name of FACE corporation, CA-X type) was used to drop liquid paraffin having a diameter of 1-2 mm on the surface of the coating film of the test piece, and the liquid droplets 30 seconds after dropping were photographed by a camera to analyze the image. The angle of a straight line connecting the end point and the apex of the droplet to the test piece was 2 times as measured as the static contact angle. The measurement was performed 3 times, and the average value of the obtained measurement values was used as the value of the static contact angle, and evaluated as follows. The larger the static contact angle, the more excellent the oil repellency of the coating film.

A: the static contact angle of the liquid paraffin is 70 degrees or more.

B: the static contact angle of the liquid paraffin is 40 degrees or more and less than 70 degrees.

C: the static contact angle of the liquid paraffin is less than 40 degrees.

[ Water repellency a2]

The static contact angle of water to the coating film of the test piece was measured and evaluated in the same manner as the water repellency a1 described above except that the test piece was immersed in warm water at 23 ℃ for 2 hours and then dried.

[ oil repellency a2]

The static contact angle of liquid paraffin to the coating film of the test piece was measured and evaluated in the same manner as the oil-repellent property a1 described above, except that the test piece was dried after being immersed in warm water at 23 ℃ for 2 hours.

[ Water repellency a3]

The static contact angle of water to the coating film of the test piece was measured and evaluated in the same manner as the water repellency a1 described above except that the test piece was immersed in warm water at 23 ℃ for 24 hours and then dried.

[ Water repellency a4]

The static contact angle of water to the coating film of the test piece was measured and evaluated in the same manner as the water repellency a1 described above except that the test piece was dried after being immersed in warm water at 23 ℃ for 72 hours.

[ oil repellency a4]

The static contact angle of liquid paraffin to the coating film of the test piece was measured and evaluated in the same manner as the oil-repellent property a1 described above, except that the test piece was dried after being immersed in warm water at 23 ℃ for 72 hours.

[ Water repellency b1]

The slip angle of water to the coating film of each test piece was measured as follows.

Pure water having a diameter of 1 to 2mm was dropped on the surface of the test piece, the test piece was gently tilted, the tilt angle at which the droplet started to slide was measured, and the average value obtained by performing the measurement 3 times was taken as the value of the landing angle.

S: the slip angle is 35 degrees or less.

A: the slip angle exceeds 35 degrees and is 60 degrees or less.

B: the slip angle exceeds 60 degrees.

[ Water repellency b3]

The same procedure as for the water repellency b1 was carried out except that a test piece dried after being immersed in warm water at 23 ℃ for 24 hours was used as the test piece, and the slip angle of water on the coating film of the test piece was measured and evaluated.

[ Pencil hardness of coating film ]

The pencil hardness of the coating film in the test piece was measured on 4 grades of H, HB, B and F in accordance with JIS K5600-5-4. The pencil used was a uni manufactured by Mitsubishi Pencil corporation.

[ compatibility ]

50g of the fluorine-based paint was sealed in a colorless and transparent vial, and the appearance of the fluorine-based paint was visually evaluated. When the fluorine-based coating material is clouded, the compatibility between the polymer a and the polymer B is insufficient.

A: no cloudiness was observed in the fluorine-based coating material.

B: although white turbidity was observed in the fluorine-based paint, the rear side was clearly seen through the vial.

C: the fluorine-based paint was clouded and the back side was not seen through the vial.

[ contamination resistance ]

The test piece was placed horizontally on the ground, sprayed with water by spraying, and then, about 0.5mL of a contaminated liquid obtained by suspending 5 mass% of carbon black and 95 mass% of liquid paraffin was dropped into the tube. Next, the test piece was placed vertically with respect to the ground, and spraying of tap water was started within 10 seconds by spraying, and spraying was continued until the contaminated liquid did not flow down with the upper limit of 60 seconds. The appearance of the coated plate surface after completion of spraying was visually evaluated according to the following criteria.

A: more than 90% of the contaminated liquid runs down.

B: more than 50% and less than 90% of the contaminated liquid flows down.

C: more than 50% of the contaminated liquid remained without flowing down.

The evaluation results are shown in tables 1 and 2. In the evaluation column in the table, "-" means that no evaluation was performed.

In tables 1 and 2, "polymer B/polymer a" is the ratio of the mass of polymer B to the mass of polymer a in the fluorine-based coating material, and "fluorine atom content" is the mass ratio (%) of fluorine atoms to the total solid content mass of the fluorine-based coating material.

[ Table 1]

[ Table 2]

The entire contents of the specification, claims, and abstract of japanese patent application No. 2017-192880 filed on day 10/2 in 2017 and japanese patent application No. 2018-147957 filed on day 8/6 in 2018 are incorporated herein as disclosure of the specification of the present invention.

Claims

1. A fluorine-based paint, characterized by comprising:

a fluorine-containing non-block copolymer, a fluorine-containing block copolymer, and an organic solvent, and

the mass ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0001 to 10,

wherein the fluorine-containing non-block copolymer comprises a fluoroolefin-based unit,

the fluorine-containing block copolymer has: a fluorine-containing segment comprising a unit based on a monomer having a perfluoroalkyl group, and a non-fluorine segment containing no fluorine atom.

2. The fluorine-based paint according to claim 1, wherein the fluorine atom content is 5 to 40% by mass based on the total mass of solid components contained in the fluorine-based paint.

3. The fluorine-containing coating material according to claim 1 or 2, wherein the fluorine-containing non-block copolymer further comprises a unit having a crosslinkable group.

4. The fluorine-containing coating material according to any one of claims 1 to 3, wherein the fluorine-containing block copolymer comprises: a unit having a crosslinkable group, and a unit based on an alkyl (meth) acrylate.

5. The fluorine-based coating material according to claim 3 or 4, wherein the unit having a crosslinkable group is a unit based on a monomer having a crosslinkable group.

6. The fluorine-based coating material according to any one of claims 3 to 5, wherein the crosslinkable group is a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group or an amino group.

7. The fluorine-containing coating material according to any one of claims 1 to 6, wherein each of the fluorine-containing non-block copolymer and the fluorine-containing block copolymer comprises a unit having a crosslinkable group, and each of the crosslinkable groups is a hydroxyl group.

8. The fluorine-based coating material according to any one of claims 1 to 7, further comprising a curing agent.

9. The fluorine-based coating material according to any one of claims 1 to 8, further comprising an amide wax.

10. The fluorine-based paint according to claim 9, wherein the amide wax is a carboxylic acid amide.

11. The fluorine-based paint according to claim 9 or 10, wherein the amide wax is an aliphatic carboxylic acid amide having an alkyl group with an average carbon number of 20 to 40.

12. The fluorine-containing coating material according to any one of claims 9 to 11, wherein the amide wax is contained in an amount of 0.01 to 15 mass% based on the total mass of the fluorine-containing non-block copolymer and the fluorine-containing block copolymer.

13. The fluorine-containing coating material according to any one of claims 9 to 12, wherein the mass ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0005 to 0.01.

14. A method for producing a substrate with a coating film, comprising applying the fluorine-based coating material according to any one of claims 1 to 13 to the surface of a substrate to form a coating layer, and drying the coating layer to form a coating film.

15. A coating film formed from the fluorine-based paint according to any one of claims 1 to 13, wherein the pencil hardness of the coating film is HB or more, the static contact angle of water to the coating film is 100 ° or more, and the static contact angle of oil to the coating film is 65 ° or more.