WO2019069822A1

WO2019069822A1 - Fluorine-based coating material

Info

Publication number: WO2019069822A1
Application number: PCT/JP2018/036385
Authority: WO
Inventors: 俊齋藤; 修平尾知; 栞由上; 翼杉田
Original assignee: Ａｇｃ株式会社
Priority date: 2017-10-02
Filing date: 2018-09-28
Publication date: 2019-04-11
Also published as: CN111194340A; JPWO2019069822A1

Abstract

Provided is a fluorine-based coating material which can be formed into a coating film having excellent water repellency, proper hardness and excellent durability. A fluorine-based coating material characterized by containing a fluorinated non-block copolymer containing a unit derived from a fluoroolefin, a fluorinated block copolymer having a fluorinated segment containing a unit derived from a monomer having a perfluoroalkyl group and a non-fluorinated segment containing no fluorine atom, and an organic solvent, wherein the ratio of the mass of the fluorinated block copolymer to the mass of the fluorinated non-block copolymer is 0.0001 to 10.

Description

Fluorine paint

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

From the viewpoint of maintaining the appearance over a long period of time, a coating with a coating film having excellent weather resistance and stain resistance is required for wall materials in household buildings, surface materials of household goods, vehicle exteriors, and the like. On the other hand, the coating material containing the fluorine-containing polymer containing a fluoro olefin is proposed (patent document 1).

Japanese Unexamined Patent Publication 2011-208043

When the present inventors evaluated the coating film formed from the thermosetting resin composition of patent document 1, since stain resistance, especially water repellency, is not enough, the subject of durability of a coating film is carried out. Found out that Furthermore, when it was tried to give water repellency to the coating film of patent document 1, it discovered that the hardness of a coating film was not suitable.

This invention was made in view of the said subject, Comprising: While the hardness of a coating film is excellent while being excellent in the water repellency of a coating film, it aims at provision of the fluorine-type paint which can form the coating film excellent in durability. I assume.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by the following aspect, as a result of earnestly examining in order to solve the said subject.

[1] A fluorine-containing non-block copolymer containing units based on fluoroolefins, a fluorine-containing segment containing units based on a monomer having a perfluoroalkyl group, and a fluorine-containing block comprising non-fluorine segments not containing fluorine atoms A fluorine-based paint comprising: a copolymer, an organic solvent, and a mass ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0001 to 10 .
[2] The fluorine-based paint according to [1], wherein the fluorine atom content relative to the total mass of the solid content contained in the fluorine-based paint is 5 to 40% by mass.
[3] The fluorine-based paint according to [1] or [2], wherein the fluorine-containing non-block copolymer further contains a unit having a crosslinkable group.
[4] The fluorine-based paint 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 a (meth) acrylic acid alkyl ester.
[5] The fluorine-based paint 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 paint according to any one of [3] to [5], wherein the crosslinkable group is a hydroxyl group, a carboxy group, an alkoxysilyl group, an epoxy group or an amino group.
[7] Any of the above [1] to [6], wherein each of the fluorine-containing non-block copolymer and the fluorine-containing block copolymer contains a unit having a crosslinkable group, and the crosslinkable group is both a hydroxyl group Fluorine-based paint described in
[8] The fluorine-based paint according to any one of [1] to [7], further containing a curing agent.
[9] The fluorine-based paint according to any one of [1] to [8], which further contains an amide wax.
[10] The fluorine-based paint according to [9], wherein the amide wax is a carboxylic acid amide.
[11] The fluorine-based paint according to [9] or [10], wherein the amide wax is an aliphatic carboxylic acid amide having an alkyl group having an average carbon number of 20 to 40.
[12] Any one of [9] to [11], which contains 0.01 to 15% by mass of the amide wax based on the total mass of the fluorine-containing non-block copolymer and the fluorine-containing block copolymer The fluorine-based paint described in.
[13] The fluorine 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. Paint system.
[14] A coating film is formed by applying the fluorine-based paint according to any one of [1] to [13] on the surface of a substrate to form a coating layer, and drying the coating layer to form a coating film. Method of producing a coated substrate.
[15] A coating film formed of the fluorine-based paint according to any one of [1] to [13], wherein the pencil hardness of the above-mentioned coating film is HB or more, and the static of water with respect to the above-mentioned coating film Coating film whose contact angle is 100 ° or more and whose static contact angle of oil is 65 ° or more.

According to the present invention, it is possible to provide a fluorine-based paint which is excellent in water repellency of a coating film and suitable in hardness of the coating film and can form a coating film excellent in durability.

The meanings of the terms in the present invention are as follows.
The numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit value and the upper limit value.
"(Meth) acrylate" is a general term for acrylate and methacrylate, and "(Meth) acrylic" is a general term for acryl and methacryl.
The "unit" is a generic term for an atomic group based on one molecule of the above-mentioned monomer, formed directly by polymerization of a monomer, and an atomic group obtained by chemical conversion of a part of the above-mentioned atomic group. . In addition, content (mol%) of each unit with respect to all the units which a polymer contains is calculated | required by analyzing a polymer by nuclear magnetic resonance spectroscopy, and also from the preparation amount of the component used in manufacture of a polymer It can be decided.
The “acid value” and the “hydroxy value” are values measured according to the method of JIS K 0070-3 (1992).
"Number average molecular weight" and "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 the value of the midpoint glass transition temperature measured by differential scanning calorimetry (DSC). The glass transition temperature is also referred to as Tg.

The “fluorine-containing block copolymer” is composed of a plurality of types of segments in which the types of units contained are different or, in the case of the same type, the composition of units is different, and at least one segment has a fluorine atom It means a macromolecular compound.
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 as a specific example, it is different Included are polymers in which the bonding order of the units is random or alternating.

"Fluorine atom content" means the ratio (mass%) of the fluorine atom with respect to the total atoms which comprise the total solid which a coating material contains. The fluorine atom content is obtained by measuring the solid content contained in the fluorine-based paint by an automatic sample combustion device-ion chromatography method (AQF-IC method) under the following conditions.
<Analytical conditions>
-Automatic sample combustion device: AQF-100 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
Combustion conditions: mode for solid sample, sample amount: 2 to 20 mg
・ Ion chromatograph device: Thermo Fisher SCIENTIFIC manufactured column: Ionpac AG11 HC + Ionpac AS 11 HC
Eluent: KOH 10 mN (0-9 min), 10-16 mN (9-11 min), 16 mN (11-15 min), 16-61 mN (15-20 min), 60 mN (20-25 min), flow rate: 1.0 mL / min, Suppressor: ASRS, Detector: Conductivity detector, Injection volume: 5 μL

The mass of the solid content of the paint is the mass of the paint removed of the solvent when the paint contains the solvent. In addition, regarding the component which comprises solid content of coating materials other than a solvent, even if the property is liquid, it is regarded as solid content. The mass of the solid content of the paint is determined as the mass remaining after heating the paint at 130 ° C. for 20 minutes.

The fluorine-based paint of the present invention (hereinafter, also referred to as the present paint) is a fluorine-containing non-block copolymer (hereinafter, also referred to as polymer A) containing a unit based on fluoroolefin (hereinafter, also referred to as unit F). And 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 fluorine atom And a fluorine-containing block copolymer (hereinafter, also referred to as a polymer B) having a non-fluorine segment (hereinafter, also referred to as a segment 2) not containing The ratio of the above-mentioned fluorine-containing block copolymer to the fluorine non-block copolymer is 0.0001 to 10.
In the present specification, the polymer A and the polymer B are collectively referred to simply as a polymer.

The coating is excellent in water repellency of a coating formed of the coating (hereinafter, also referred to as the coating) and has a suitable hardness of the coating, and can form a coating having excellent durability. Can be formed. The reason for this is not necessarily clear, but is considered as follows.

In the paint, a specific fluorine-containing non-block copolymer and a specific fluorine-containing block copolymer are mixed at a constant ratio in the presence of an organic solvent. Therefore, the fluorine-containing non-block copolymer and the fluorine-containing block copolymer, which are generally incompatible, are easily compatible via the organic solvent, and the respective copolymers are uniformly dispersed in the organic solvent. Cheap. Furthermore, when forming a coating film from the present coating, the perfluoroalkyl group possessed by the fluorine-containing block copolymer is oriented on the coating film surface, and the influence of the fluorine atom of the above-mentioned perfluoroalkyl group is adjusted. It is thought that the fluorine atom which a block copolymer contains is arrange | positioned stably. Therefore, while the hardness of this coating film becomes suitable, it is thought that it is excellent in water repellency and equipped with endurance.
In the present specification, the durability of the coating means that the stain resistance of the coating is sustained.

Hereinafter, the polymer A will be described in detail.
Fluoroolefins are olefins in which one or more of the hydrogen atoms have been replaced by fluorine atoms. In the fluoroolefin, at least one hydrogen atom not substituted by a fluorine atom may be substituted by a chlorine atom.
Examples of _{_{_{_{fluoroolefin, 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 is mentioned. Fluoroolefins, from the viewpoint of weather resistance of the coating _film, CF 2 = CF ₂ or _CF 2 = CFCl is more preferable. Two or more fluoroolefins may be used in combination.

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

The polymer A preferably contains a unit having a crosslinkable group (hereinafter, also referred to as a unit A1) from the viewpoint of the 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 A1), and the crosslinkable group of the fluorine-containing polymer containing the unit A1 is different in crosslinkable group It may be a unit obtained by converting into As such a unit, a unit obtained by reacting a fluorine-containing polymer containing a unit having a hydroxyl group with a polycarboxylic acid or an acid anhydride thereof to convert part or all of the hydroxyl groups to a carboxy group is obtained. It can be mentioned. From the viewpoint of the polymerizability with the unit F, the unit A1 is preferably a unit having no fluorine atom.
As a crosslinkable group which unit A1 has, a hydroxyl group, a carboxy group, an alkoxy silyl group, an epoxy group, or an amino group is preferable, and from the viewpoint of the curability of the polymer A, a hydroxyl group or a carboxy group is preferable.

As a monomer which has a carboxy group, unsaturated carboxylic acid, (meth) acrylic acid, etc. are mentioned. The monomer having a carboxy group is preferably a monomer represented by the formula: X ¹¹ -Y ¹¹ (hereinafter also referred to as a monomer A 11).
Examples of the monomer having a hydroxyl group include allyl alcohol, vinyl ether having a hydroxyl group, vinyl ester, allyl ether, allyl ester or (meth) acrylic acid ester. As the monomer having a hydroxyl group, allyl alcohol or a monomer represented by the formula: X ¹² -Y ¹² (hereinafter, also referred to as a monomer A12) is preferable.
Two or more kinds of monomers A1 may be used in combination.

The symbols in the formula have the following meanings.
X ¹¹ is CH ₂ CHCH—, CH (CH ₃ ) = CH— or CH ₂ CC (CH ₃ ) —, preferably CH ₂ CHCH— or CH (CH ₃ ) = CH—.
Y ¹¹ is a carboxy group or a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms having a carboxy group, preferably a carboxy group or a carboxyalkyl group having 1 to 10 carbon atoms.
X ¹² _{_{_{_{is, CH 2 = CHO-, CH 2}}}} = CHCH 2 O-, CH 2 = CHOC (O) -, CH 2 = CHCOO- , or _CH 2 _{= C} (CH 3) a COO-.
Y ¹² is a C 2 to C 12 monovalent saturated hydrocarbon group having a hydroxyl group. The monovalent saturated hydrocarbon group may be linear or branched. The monovalent saturated hydrocarbon group may consist of a ring structure or may contain a ring structure.
The monovalent saturated hydrocarbon group is preferably an alkyl group containing a C 2-6 alkyl group or a C 6-8 cycloalkylene group.

Specific examples of the monomer A11 include CH ₂ CHCHCOOH, CH (CH ₃ ) = CHCOOH, CH ₂ CC (CH ₃ ) COOH, and CH ₂ CHCH (CH ₂ ) _{n 2} COOH (where n2 is 1 to It represents an integer of 10.).
Specific examples of the monomer _{_{A12, CH 2 = CHOCH 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 CH ₂ OH, CH ₂ CHCHCH ₂ OCH ₂ CH ₂ OH, CH ₂ CHO CHOCH ₂ CH ₂ CH ₂ CH ₂ OH, CH ₂ CHCHCH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OH, CH ₂ CHCHCOOCH ₂ CH ₂ OH, CH ₂ CC (CH ₃ ) COOCH ₂ CH ₂ OH. Here, "-cycloC ₆ H _10- " represents a cyclohexylene group, and the bonding site of "-cycloC ₆ H _10- " is usually 1,4-.

When the polymer A contains a curing agent, the crosslinkable group of the unit A1 becomes a crosslinking point, and the crosslinking reaction between the polymers A, B, and A and B is a curing agent. As the hardness of the present coating film becomes suitable, 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%, 5 to 15 mol based on all units contained in the polymer A. % Is most preferred.

The polymer A may further contain units other than the unit F and the unit A1 (hereinafter, also referred to as a unit A2) from the viewpoint of the flexibility of the present coating film. Examples of the unit A2 include units based on vinyl ethers, vinyl esters, allyl ethers, allyl esters, (meth) acrylates, etc. which do not contain a crosslinkable group and a fluorine atom.
The unit A2 is preferably a unit based on a monomer represented by the formula: X ² -Z ² (hereinafter, also referred to as a monomer A2).
X ² _{_{_{is, CH 2 = CHC (O)}}} O-, CH 2 = C (CH 3) C (O) O-, CH 2 = CHOC (O) -, CH 2 = CHCH 2 OC (O) -, CH ₂ = CHO- or _CH 2 = CHCH ₂ is O-, from the viewpoint of excellent weather resistance of the coating _{_{_{film, CH 2 = CHOC (O)}}} -, CH 2 = CHCH 2 OC (O) -, CH 2 = CHO -Or CH ₂ = CHCH ₂ O- is preferred.

Z ² is a monovalent hydrocarbon group having 1 to 24 carbon atoms. The monovalent hydrocarbon group may be linear or branched. The monovalent hydrocarbon group may consist of a ring structure or may contain a ring structure. The monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group.
The monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and is an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms Or an aralkyl group having 7 to 12 carbon atoms is more preferable.
Specific examples of the alkyl group include methyl group, ethyl group, tert-butyl group, hexyl group, nonyl group, decyl group and dodecyl group.
A cyclohexyl group is mentioned as a specific example of a cycloalkyl group.
Specific examples of the aralkyl group include 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 two 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 "Beova 9" by HEXION), Examples thereof include vinyl neodecanoate (trade name “Beova 10” by 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 all units contained in the polymer A.

The polymer A contains 20 to 70% by mole, 0.5 to 35% by mole, and 1 to 70% by mole of the unit F, the unit A1 and the unit A2 with respect to all units included in the polymer A, respectively. It is preferable to include, and it is particularly preferable to consist of the unit F, the unit A1 and the unit A2.
The Tg of the polymer A is preferably 25 to 120 ° C., more preferably 30 to 100 ° C., from the viewpoint of the hardness of the present 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, from the viewpoint of the impact resistance of the present coating film.

When the polymer A is a polymer having a carboxy group, the acid value of the polymer A is preferably 1 to 150 mg KOH / g, more preferably 3 to 100 mg KOH / g from the viewpoint of the durability of the present coating film. -60 mg KOH / g is particularly preferred.
When the polymer A is a polymer having a hydroxyl group, the hydroxyl value of the polymer A is preferably 1 to 150 mg KOH / g, more preferably 3 to 100 mg KOH / g from the viewpoint of the durability of the present coating film. 60 mg KOH / g is particularly preferred.
The polymer A may have either one of a hydroxyl value or an acid value, or may have both.

The content of the polymer A is preferably 20 to 95% by mass, particularly preferably 30 to 90% by mass, with respect to the total solid content mass of the present paint, from the viewpoint of the weather resistance of the present coating film. The polymer A may be used in combination of two or more.
The polymer A is obtained, for example, by polymerizing the above-mentioned monomers in the presence of a polymerization solvent and a polymerization initiator. In the production of the polymer A, light stabilizers, pH adjusters and the like may be added, as necessary.

Hereinafter, the polymer B will be described in detail.
Segment 1 is a homopolymer of monomer B1, a copolymer of two or more monomers B1, or a copolymer of at least one monomer B1 and at least one non-fluorinated monomer. It is preferable to be composed of a combination, more preferably composed of a homopolymer of monomer B1 or a copolymer of two or more monomers B1, and composed of a homopolymer of monomer B1 Are particularly preferred.
The monomer B1, the ^formula: X 3 monomer represented by ^-L 3 -R ^F (. Hereinafter, also referred to as monomer B11) are preferred.
X ³ is CH ₂ CC (R ¹ ) C (O) O—, CH ₂ CC (R ¹ ) OCO—, CH ₂ CHOCHO— or CH ₂ CHCHCH ₂ O—, CH ₂ CC (R ¹ ) C (O) O— is preferred. The above R ¹ is a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, preferably a hydrogen atom.
L ³ is a single bond or a divalent linking group. As a bivalent coupling group, a bivalent hydrocarbon group is preferable, a bivalent aliphatic hydrocarbon group is more preferable, and a bivalent alkylene group is especially preferable. The carbon number of the divalent hydrocarbon group is preferably 1 to 10, and more preferably 1 to 5. The divalent hydrocarbon group may be linear or branched. In addition, the divalent hydrocarbon group may have a ring structure or may contain a ring structure. The ring structure may be an aromatic ring. Further, the divalent linking group may be a combination of a divalent hydrocarbon group and -O-.
R ^F is a perfluoroalkyl group. The carbon number of the perfluoroalkyl group is preferably 1 to 30, and 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, CH 2 = C (R}}}} 1) C (O) O (CH 2) 2 (CF 2) 6 F, CH 2 = C (R 1) C (O) O (CH _{_{_{_{2) 2 (CF 2) 8}}}} F, CH 2 = C (R 1) C (O) O (CH 2) 2 (CF 2) 10 F, CH 2 = C (R 1) C (O) O (CH ₂ ) ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ , CH ₂ (C (R ¹ ) C (O) O (CH ₂ ) ₂ (CF ₂ ) ₈ CF (CF ₃ ) ₂ , CH ₂ CC ( R ¹ ) OCOCH ₂ -Ph-O- (CF ₂ ) ₈ F (Ph represents a phenylene group which may have a substituent). In the above formulae, the definition of R ¹ is as described above.

The segment 1 may have a unit based on a non-fluorinated monomer (hereinafter also referred to as a monomer B2) from the viewpoint of compatibility with the polymer A.
As the monomer B2, an alkyl (meth) acrylate having an alkyl group having 12 to 20 carbon atoms (hereinafter also referred to as a monomer B22) is preferable.
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) And acrylates.

The content of units constituting segment 1 in polymer B is preferably 2 to 40 mol% with respect to all units contained in polymer B from the viewpoint of water repellency of polymer B in the present coating film, 3 to 20 mol% is more preferable, and 5 to 15 mol% is particularly preferable.
The content of the unit B1 in the segment 1 is preferably 80 mol% or more, more preferably 85 mol% or more, 95 mol% or more with respect to all units included in the segment 1 from the viewpoint of water repellency of the present coating film. Is particularly preferred.

The segment 2 preferably has no fluorine atom, and from the viewpoint that the polymer B is easily held on the surface of the present coating film, a homopolymer of the monomer B2 or a co-polymer of two or more monomers B2 It is preferably composed of a polymer.
Examples of the monomer B2 include (meth) acrylates, and a monomer represented by the formula: X ⁴ -Y ⁴ (hereinafter, also referred to as a monomer B21) is preferable.
X ⁴ is CH ₂ CHCHC (O) O— or CH ₂ CC (CH ₃ ) C (O) O—.
Y ⁴ is an alkyl or substituted alkyl group having 1 to 22 carbon atoms, a cycloalkyl or substituted cycloalkyl group having 3 to 15 carbon atoms, or a phenyl group or a substituted phenyl group.
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 amido group, an imide group, a nitro group, a carboxylic acid group, a thiol group and an ether group.

Specific examples of the monomer B21 include alkyl (meth) acrylate (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 group-containing (meth) acrylate (hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, hydroxypropyl (meth) acrylate, dipro Glycol mono (meth) acrylate etc.), glycidyl (meth) acrylate, nitrogen-containing (meth) acrylate (dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 4- (meth) acryloyloxy-2,2, And 6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine and the like.
Among the monomers described above, alkyl (meth) acrylate is preferable as the monomer B2 from the viewpoint that the water repellency of the present coating film is maintained.

The segment 2 preferably has a crosslinkable group from the viewpoint of the durability of the present coating film. That is, segment 2 preferably contains a unit having a crosslinkable group. Specific examples and preferred embodiments of the unit having a crosslinkable group are the same as the specific examples and preferred embodiments described for the unit A1.
As a monomer which has a crosslinkable group, hydroxyl-containing vinyl monomers, such as a compound illustrated previously as a hydroxyl-containing (meth) acrylate, are preferable.

As segment 2, a segment consisting of a unit based on alkyl (meth) acrylate and a unit based on hydroxyalkyl (meth) acrylate is preferable, and a unit based on methyl (meth) acrylate and a unit based on butyl (meth) acrylate and hydroxy Particularly preferred are segments consisting of units based on ethyl (meth) acrylate, or segments consisting of units based on hydroxyethyl (meth) acrylate and units based on octadecyl (meth) acrylate.

The content of the units constituting the segment 2 in the polymer B is preferably 60 to 98 mol%, more preferably 80 to 97 mol%, 85 to 95 mol% with respect to all units contained in the polymer B. Is particularly preferred.
The content of the unit based on the monomer having a crosslinkable group in the polymer B is preferably 1 to 25% by mole, based on the total units of the polymer B, from the viewpoint of the durability of the present coating film, and 20 mol% is more preferable.

When the polymer B has a hydroxyl value, the hydroxyl value of the polymer B is preferably 10 to 100 mg KOH / g, more preferably 15 to 90 mg KOH / g, and more preferably 30 to 70 mg KOH / g from the viewpoint of the durability of the present coating film. Is particularly preferred.
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, from the viewpoint of flexibility of the present coating film. .
The mass ratio of the polymer B to the total mass of the polymer A (mass of polymer B / mass of polymer A) is 0.0001 to 10, from 0.001 to 10, from the point of water repellency of the present coating film. 10 is preferable, 0.01 to 0.1 is more preferable, and 0.02 to 0.09 is particularly preferable.

The polymer B may use 2 or more types together.
Specific examples of the polymer B include Modiper F206, Modiper F246, Modiper F906, Modiper F3636, Modiper F226, and Modiper F606 (all trade names by NOF Corporation).
The content of the polymer B is preferably 0.01 to 10% by mass with respect to the total solid content mass of the present coating material from the viewpoint of water repellency of the present coating film.
The present paint preferably contains 1 to 99% by mass, more preferably 40 to 80% by mass, and particularly preferably 50 to 70% by mass of solid content based on the total mass of the present paint.

The paint contains an organic solvent as a paint solvent.
Specific examples of the organic solvent include petroleum mixed solvents (toluene, xylene, Solvesso 100 manufactured by ExxonMobil, Solvesso 150 manufactured by ExxonMobil, etc.), aromatic hydrocarbon solvents (mineral spirit etc.), ester solvents (ethyl acetate, etc. Examples include butyl acetate and the like, ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like), and alcohol solvents (ethanol, tert-butyl alcohol, isopropyl alcohol and the like). Two or more organic solvents may be used in combination.
The content of the organic solvent in the present coating is preferably 1 to 99% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass, with respect to the total mass of the present coating.

The coating preferably comprises a curing agent.
The curing agent is a compound having two or more groups capable of reacting with the crosslinkable group in one molecule. The polymer is crosslinked by the reaction of the curing agent and the crosslinkable group contained in the polymer. The curing agent usually has 2 to 30 groups capable of reacting with the crosslinkable group.
When the polymer has a hydroxyl group, the curing agent is preferably a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule.
When the polymer has a carboxy group, the curing agent is preferably a compound having two or more of an epoxy group, a carbodiimide group, an oxazoline group or a β-hydroxyalkylamide group in one molecule.
When the polymer has both a hydroxyl group and a carboxy group, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, and one epoxy, carbodiimide, oxazoline or β-hydroxyalkylamide group It is preferable to use two or more compounds in combination.

The compound having two or more isocyanate groups in one 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 multimer or a modified product (biuret, isocyanurate or adduct) of a polyisocyanate monomer.

Specific examples of aliphatic polyisocyanates include aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, and lysine diisocyanate, and lysine tris And isocyanates, 4-isocyanatomethyl-1,8-octamethylene diisocyanate, bis (2-isocyanatoethyl) 2-isocyanatoflate.
Specific examples of the alicyclic polyisocyanate include alicyclic diisocyanates such as 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 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate and xylylene diisocyanate.

The curing agent is preferably a modified product of a polyisocyanate monomer, more preferably an adduct of a polyisocyanate monomer, from the viewpoint that a coating film having elasticity and less generation of cracks is obtained, and hexamethylene diisocyanate is more preferable. An adduct of is particularly preferred.

The compound having two or more blocked isocyanate groups in one molecule is preferably a compound in which two or more isocyanate groups possessed by the aforementioned 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, guanidine and the like.

Specific examples of compounds having two or more epoxy groups in one 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 compound, fluorene type epoxy compound, hydrogenated bisphenol A type epoxy compound, bisphenol A cored polyol type epoxy compound, polypropylene glycol type epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compound, glyoxal type epoxy compound, alicyclic Type epoxy compounds, alicyclic polyfunctional epoxy compounds, heterocyclic type epoxy compounds (eg, triglycidyl isocyanurate).

Specific examples of the compound having two or more carbodiimide groups in one molecule include alicyclic carbodiimides, aliphatic carbodiimides, and aromatic carbodiimides, and multimers and modified products thereof.

Specific examples of the compound having two or more oxazoline groups in one molecule include an addition polymerizable oxazoline having a 2-oxazoline group and a polymer of the addition polymerizable oxazoline.

Specific examples of the compound having two or more β-hydroxyalkylamide groups in one molecule include N, N, N ′, N′-tetrakis- (2-hydroxyethyl) -adipamide (Primid XL-552, trade name of EMS company) And N, N, N ′, N′-tetrakis- (2-hydroxypropyl) -adipamide (Primid QM 1260, trade name of EMS).

When the coating 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, with respect to 100 parts by mass of the polymer A in the coating. 100 parts by weight is particularly preferred.
The coating may comprise a curing catalyst. The curing catalyst is a compound that accelerates the curing reaction when a curing agent is used, and can be selected from known curing catalysts according to the type of the curing agent.

The paint preferably contains one or more selected from the group consisting of ultraviolet light absorbers and light stabilizers. That is, the paint may contain both of the ultraviolet light absorber and the light stabilizer, or may contain only one of them.

An ultraviolet absorber is a compound which protects this coating film from an ultraviolet-ray.
As the ultraviolet absorber, a salicylic acid ester compound, a benzotriazole compound, a benzophenone compound, a triazine compound, and a cyanoacrylate compound are preferable.
Specific examples of the UV absorber include “Tinuvin 326” (molecular weight: 315.8, melting point: 139 ° C.), “Tinuvin 400” (molecular weight: 647) and “Tinuvin 405” (molecular weight: 583.8), which are products of BASF. Melting point: 74-77 ° C), "Tinuvin 460" (molecular weight: 629.8, melting point: 93-102 ° C), "Tinuvin 900" (molecular weight: 447.6, melting point: 137-141 ° C), "Tinuvin 928 (Molecular weight: 441.6, melting point: 109-113 ° C.), Clariant's “Sanduvor VSU powder” (molecular weight: 312.0, melting point: 123-127 ° C.), Clariant's “Hastavin PR-25 Gran” Molecular weight: 250.0, melting point: 55-59 ° C.).
You may use together 2 or more types of ultraviolet absorbers.
When the coating contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 to 10% by mass with respect to the solid content of the polymer from the viewpoint of the weather resistance of the coating, and 0. 01 to 5% by mass is particularly preferred.

A light stabilizer is a compound which improves the light resistance of this paint.
As the light stabilizer, hindered amine compounds are preferred. Specific examples of the hindered amine compound include “Tinuvin 111 FDL” (molecular weight: 2,000 to 4,000, melting point: 63 ° C.) and “Tinuvin 144” (molecular weight: 685, melting point: 146 to 150 ° C.) “Tinuvin 152” (molecular weight: 756.6, melting point: 83-90 ° C.), “Tinuvin 292” (molecular weight: 508.8), “Sanduvor 3051 powder” manufactured by Clariant (molecular weight: 364.0, melting point: 225 ° C. And “Sanduvor 3070 powder” (molecular weight: 1,500, melting point: 148 ° C.) manufactured by Clariant, “VP Sanduvor PR-31” (molecular weight: 529, melting point: 120-125 ° C.) manufactured by Clariant.
The light stabilizer may be used in combination of two or more.
When the paint 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, with respect to the total solid content of the paint.

The paint preferably comprises an amide wax. When the present paint contains an amide wax, the water repellency of the present coating is excellent, and in particular, the sliding angle of water with respect to the present coating can be reduced.

Examples of the amide wax include carboxylic acid amide powdery or waxy at 25 ° C. Examples of carboxylic acid amides include aliphatic carboxylic acid amides, N-substituted aliphatic carboxylic acid amides, aliphatic carboxylic acid amides such as N-substituted ureas, aromatic carboxylic acid amides, and hydroxyamides further having a hydroxyl group. Be

As the carboxylic acid amide, an aliphatic carboxylic acid amide having an alkyl group having an average carbon number of 20 to 40 is preferable, and an aliphatic carboxylic acid amide having an alkyl group having an average carbon number of 25 to 35 is particularly preferable. The alkyl group is preferably linear. When the carboxylic acid amide has the above alkyl group, the sliding angle of water with respect to the coating film formed from the present paint can be reduced in combination with the fluorine-containing polymer.

Amide wax may be used in combination of two or more.
When the paint contains an amide wax, the content of the amide wax is 0.01 to 15 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. % Is preferable, 0.1 to 10% by mass is more preferable, and 0.5 to 5% by mass is particularly preferable.
The mass ratio of the polymer B to the polymer A (the mass of the polymer B / the mass of the polymer A) in the case where the coating contains an amide wax is 0 in view of the water repellency of the coating and the durability thereof. More preferred is .0005 to 0.01. When the polymer A and the polymer B are contained in the above ratio, the effect of the amide wax is particularly remarkable.

The present paint may also contain a silane compound from the viewpoint of water repellency of the present coating film. As a silane compound, alkoxysilane is preferable. Examples of alkoxysilanes include alkylalkoxysilanes, alkylphenylalkoxysilanes and phenylalkoxysilanes.
Two or more silane compounds may be used in combination.

The present paint may contain a silicone resin in view of the water repellency of the present coating. In addition, the fluorine-containing non-block copolymer in this invention is not contained in this silicone resin.
As silicone resins, silicone oils comprising dialkylpolysiloxanes such as dimethylpolysiloxane, polyarylsiloxanes such as polydiphenylsiloxane, polyalkylaryl siloxanes such as methylphenylpolysiloxane, amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, Examples thereof include modified silicone oils such as alcohol-modified silicones and polyether-modified silicones, modified silicone resins, silicone oligomers and the like.
Two or more silicone resins may be used in combination.

The paint may contain other components as necessary, for example, fillers (inorganic fillers such as silica, organic fillers such as resin beads, etc.), matting agents, leveling agents, surface conditioners, degassing agents, fillers, thermal agents Stabilizers, thickeners, dispersants, surfactants, antistatic agents, rust inhibitors, silane coupling agents, antifouling agents, and low-pollution treatments may be included.

The content of fluorine atoms is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 13 to 20% by mass with respect to the total solid content mass of the paint. When the content is 5% by mass or more, the weather resistance of the present coating film is excellent. When the content is 40% by mass or less, the flexibility of the present coating film is excellent. In addition, when the content is 5 to 40% by mass and the content of the organic solvent in the present paint is within the above range, the compatibility of the polymer A and the polymer B is excellent, and It is thought that durability improves.

The present paint can be produced, for example, by mixing polymer A, polymer B, an organic solvent, and optional components (for example, a curing agent, an ultraviolet light absorber, a light stabilizer). The organic solvent may be a polymerization solvent for producing the polymer A.

The coated substrate of the present invention has a substrate and a coated film (present coated film) formed on the above substrate by the present paint.
Specific examples of the substrate include resins, rubber, organic materials such as wood, concrete, glass, ceramics, inorganic materials such as stone, iron, iron alloys, aluminum, and aluminum alloys.
The thickness of the present coating film is preferably 10 to 200 μm, and more preferably 20 to 100 μm. When the film thickness is 10 μm or more, the blocking resistance of the present coating film is improved, and when it is 200 μm or less, the weather resistance of the present coating film is improved.

The static contact angle of water with respect to the present coating film is preferably 100 ° or more, and more preferably 105 ° or more from the viewpoint that the contamination resistance of the present coating film is more excellent.
The static contact angle of the oil with respect to the present coating film is preferably 65 ° or more, and more preferably 70 ° or more from the viewpoint that the contamination resistance of the present coating film is more excellent.
The 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 of the present coating can be particularly preferably adjusted by the ratio of the polymer B to the polymer A, etc. in the present coating.
The sliding angle of water with respect to the present coating film is preferably 60 ° or less, and more preferably 35 ° or less from the viewpoint that the contamination resistance of the present coating film is more excellent.

The hardness of the present coating film is preferably such that the pencil hardness is HB or more, and preferably H or more, from the viewpoint that the present coating film is not easily broken and is excellent in abrasion resistance.
The hardness of the present coating can be particularly suitably adjusted depending on the type of each unit contained in the polymer A and the polymer B in the present coating.

The method for producing a coated substrate of the present invention is a method of applying the present paint on the surface of a substrate to form a coated layer, and drying the coated layer to form the present coated film. When the paint contains a curing agent, it is preferable to heat and cure after the above drying.
The paint may be applied directly to the surface of the substrate, or may be applied after the surface of the substrate has been subjected to known surface treatment (such as base treatment). Furthermore, after forming a subbing layer on a substrate, it may be applied on this subbing layer.
Specific examples of the coating method of the present paint include methods using coating devices such as a brush, a roller, dipping, a spray, a roll coater, a die coater, an applicator, and a spin coater. The drying temperature and the curing temperature after application are preferably 20 to 300 ° C., and more preferably 20 to 250 ° C.

As described above, since the paint is excellent in contamination resistance, it can be suitably used as a wall material in a residential building, a surface material of household goods, a vehicle exterior, and the like.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not interpreted as being limited to these examples.
In addition, the compounding quantity of each component in the table | surface mentioned later shows a mass reference | standard. Further, Examples 6 to 9, Examples 11 to 14, and Examples 16 to 24 are Examples, and Examples 5, 10, and 15 are Comparative Examples.

(Abbreviation of compounds etc.)
Chlorotrifluoroethylene (CTFE)
4-hydroxybutyl vinyl ether (HBVE)
Cyclohexyl vinyl ether (CHVE)
Ethyl vinyl ether (EVE)
Curing agent 1: Stabio D-370N (Mitsui Chemical Co., Ltd. trade name)
Curing agent 2: Desmodur N3300 (Bayer trade name)
Curing catalyst: 10,000-fold diluted solution of dibutyltin dilaurate Wax 1: Amide wax consisting of carboxylic acid amide having an alkyl group having an average of 28 carbon atoms Wax 2: Wax consisting of a modified polyethylene Wax 3: Alkyl having an average carbon number of 27 Amide wax consisting of carboxylic acid amide having a group Wax 4: Amide wax consisting of carboxylic acid amide having an average carbon number of 18 oleyl group Diluted solvent: Mixed solvent of Solvesso 150 (trade name of Exxon Mobil) and xylene (Solvesse 150) The ratio of xylene to is 9)

(Polymer B)
Polymer B1: Fluorine-containing block copolymer having the following fluorine-containing segment and non-fluorine segment: Fluorine-containing segment: A segment composed of units based on perfluorohexylethyl methacrylate.
Non-fluorinated segments: segments consisting of units based on hydroxyethyl methacrylate, units based on butyl methacrylate, and units based on methyl methacrylate.
· The content of the unit based on perfluorohexylethyl methacrylate, the unit based on hydroxyethyl methacrylate, the unit based on butyl methacrylate, the unit based on methyl methacrylate is 10 mol%, 15 mol% in this order relative to all units contained in the polymer B1 , 33 mol%, 42 mol%.

[Example 1]
In an autoclave, 50% by weight of xylene (503 g), ethanol (142 g), CTFE (387 g), CHVE (326 g), HBVE (84.9 g), potassium carbonate (12.3 g), and tert-butyl peroxypivalate A xylene solution (20 mL) was introduced, the temperature was raised, and polymerization was carried out at 65 ° C. for 11 hours. Subsequently, the solution in the autoclave was filtered to obtain a solution containing the polymer A1, which is a fluorine-containing non-block copolymer, and then the solvent was removed to obtain a polymer A1.
The polymer A1 was a polymer containing 50 mol%, 39 mol%, and 11 mol% of a unit based on CTFE, a unit based on CHVE, and a unit based on HBVE in this order relative to all units contained in polymer A1. . The hydroxyl value of the polymer A1 was 50 mg KOH / g, the Tg was 52 ° C., and the Mn was 10,000.

[Example 2]
A fluorine-containing non-block copolymer, polymer A2, was similarly obtained except that the amount of monomers used was changed.
The polymer A2 was a polymer containing 50 mol%, 25 mol%, and 25 mol% of a unit based on CTFE, a unit based on CHVE, and a unit based on HBVE in this order relative to all units contained in polymer A2 . The hydroxyl value of the polymer A2 was 118 mg KOH / g, the Tg was 45 ° C., and the Mn was 7,000.

[Example 3]
A solution containing polymer A3, which is a fluorine-containing non-block copolymer, was obtained in the same manner except that the type and amount of monomers used were changed, and then the solvent was removed to obtain polymer A3.
The polymer A3 is a unit based on CTFE, a unit based on CHVE, a unit based on EVE, a unit based on HBVE in this order 50 mol%, 15 mol%, 15 mol%, based on all units contained in the polymer A3. It was a polymer containing 20 mol%. The hydroxyl value of the polymer A3 was 100 mg KOH / g, the Tg was 35 ° C., and the Mn was 7,000.

[Example 4]
The components described in the “components of the fluorine-based paint” column in Tables 1 and 2 described later were mixed in the air using a rocking mill to obtain fluorine-based paints 1 to 20. In addition, in mixing of each component, the polymer B was uniformly melt | dissolved or disperse | distributed uniformly in butyl acetate, methyl ethyl ketone, or a dilution solvent, and the component except the above was mixed and used after that. The details of the blending amounts of each component are shown in Table 1 and Table 2.

<Manufacture of coated substrate>
[Examples 5 to 24]
Apply fluorine-based paint 1 to the surface of an aluminum plate (200 mm long, 125 mm wide, 0.8 mm thick) with an applicator so that the dry film thickness is 40 μm, and dry it at normal temperature (25 ° C) for 1 week The coated film was formed to obtain a coated film-formed substrate 1 formed of the fluorine-based paint 1 and used as a test piece 1.
Test pieces 2 to 20 were obtained for each of the fluorine-based paints 2 to 20 in the same manner as in the case of producing the test piece 1 above.
The obtained test pieces 1 to 20 were subjected to the following evaluations.

<Evaluation>
[Water repellant a1]
For each test piece, the static contact angle of water to the coating of the test piece was measured.
Pure water with a diameter of 1 to 2 mm is dropped on the coating film surface of the test piece using a contact angle measurement device (trade name: CA-X, trade name of FACE), and a droplet after 30 seconds of droplet deposition is photographed with a video camera The image was analyzed. The static contact angle was measured at twice the angle of the straight line connecting the end point and the apex of the droplet to the test piece. The measurement was performed three times, and the average value of the obtained measurement values was evaluated as the value of the static contact angle as follows. The larger the static contact angle, the better the water repellency of the coating.
SS: Static contact angle of water is 105 degrees or more.
S: Static contact angle of water is 100 degrees or more and less than 105 degrees.
A: Static contact angle of water is 90 degrees or more and less than 100 degrees.
B: Static contact angle of water is 80 degrees or more and less than 90 degrees.
C: Static contact angle of water is less than 80 degrees.

[Oil-repellent a1]
For each test piece, the static contact angle of liquid paraffin to the coating of the test piece was measured.
Using a contact angle measurement device (FACE, trade name CA-X), drop liquid paraffin with a diameter of 1 to 2 mm on the coated surface of the test piece, and shoot the drop 30 seconds after deposition using a video camera The image was analyzed. The static contact angle was measured at twice the angle of the straight line connecting the end point and the apex of the droplet to the test piece. The measurement was performed three times, and the average value of the obtained measurement values was evaluated as the value of the static contact angle as follows. The larger the static contact angle, the better the oil repellency of the coating.
A: The static contact angle of liquid paraffin is 70 degrees or more.
B: The static contact angle of liquid paraffin is 40 degrees or more and less than 70 degrees.
C: The static contact angle of liquid paraffin is less than 40 degrees.

[Water repellant a2]
The static contact angle of water to the coating of the test piece is measured and evaluated in the same manner as the above-described water repellency a1 except that the test piece is a test piece which is immersed in warm water at 23 ° C. for 2 hours and then dried. did.

[Oil-repellent a2]
The static contact angle of the liquid paraffin to the coating of the test piece is measured in the same manner as the oil repellency a1 described above except that the test piece is immersed in warm water at 23 ° C. for 2 hours and then dried. And rated.

[Water repellant a3]
The static contact angle of water to the coating of the test piece is measured and evaluated in the same manner as the water repellency a1 described above except that the test piece is a test piece which is immersed in warm water at 23 ° C. for 24 hours and then dried. did.

[Water repellant a4]
The static contact angle of water to the coating of the test piece is measured and evaluated in the same manner as the above-described water repellency a1 except that the test piece is a test piece soaked in warm water at 23 ° C. for 72 hours and then dried. did.

[Oil-repellent a4]
Measure the static contact angle of liquid paraffin to the coating of the test piece in the same manner as the oil repellency a1 described above, except that the test piece is a test piece soaked in warm water at 23 ° C. for 72 hours and then dried. evaluated.

[Water repellant b1]
For each test piece, the sliding angle of water to the coating of the test piece was measured as follows.
Pure water with a diameter of 1 to 2 mm is dropped on the surface of the test piece, the test piece is gradually inclined, the inclination angle at which the droplet starts to slide is measured, and the average value obtained three times is measured It is a value.
S: The sliding angle is 35 degrees or less.
A: The sliding angle is more than 35 degrees and 60 degrees or less.
B: The sliding angle is over 60 degrees.

[Water repellant b3]
The sliding angle of water with respect to the coating of the test piece was measured and evaluated in the same manner as the above-described water repellency b1 except that the test piece was immersed in warm water of 23 ° C. for 24 hours and then dried.

[Pencil hardness of coating film]
The pencil hardness of the coating film on the test piece was measured in four stages of H, HB, B, and F in accordance with JIS K5600-5-4. The pencil used Mitsubishi pencil company uni.

[Compatibility]
50 g of the fluorine-based paint was enclosed in a colorless and transparent vial, and the appearance of the fluorine-based paint was evaluated visually. When the fluorine-based paint is cloudy, the compatibility between the polymer A and the polymer B is not sufficient.
A: No white turbidity is observed in the fluorine-based paint.
B: The fluorine-based paint shows cloudiness, but the background is visible through the vial.
C: The fluorine-based paint is cloudy, and the background can not be seen through via the vial.

[Stain resistance]
The test piece was placed horizontally to the ground and sprayed with water, and then about 0.5 mL of a contaminated liquid obtained by suspending 5% by mass of carbon black and 95% by mass of liquid paraffin was dropped by a dropper. Next, the test piece was placed vertically to the ground, and spraying of tap water was started by spraying within 10 seconds, and spraying continued for 60 seconds at the upper limit until the contamination did not run off. The appearance of the coated plate surface after the end of spraying was visually evaluated according to the following criteria.
A: More than 90% of the contaminated fluid has run off.
B: 50% or more and less than 90% of the contaminated liquid flowed off.
C: More than 50% of the contaminated liquid did not flow and remained.

The evaluation results are shown in Tables 1 and 2. In addition, "-" in the evaluation column in the table means that the evaluation was not 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 paint, and “fluorine atom content” is a fluorine-based It is the ratio (%) of the mass of the fluorine atom to the total solid mass of the paint.

In addition, the specifications, claims and abstracts of Japanese Patent Application Nos. 2017-192880 filed on Oct. 2, 2017 and Japanese Patent Application No. 2018-147957 filed on August 6, 2018 are disclosed. The entire contents are incorporated herein by reference and incorporated as a disclosure of the specification of the present invention.

Claims

A fluorine-containing non-block copolymer containing units based on fluoroolefin;
A fluorine-containing segment containing a unit based on a monomer having a perfluoroalkyl group, and a fluorine-containing block copolymer having a non-fluorine segment not containing a fluorine atom;
A fluorine-based paint comprising: an organic solvent; and a mass ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0001 to 10.
The fluorine-based paint according to claim 1, wherein the fluorine atom content relative to the total mass of the solid content contained in the fluorine-based paint is 5 to 40% by mass.
The fluorine-based paint according to claim 1, wherein the fluorine-containing non-block copolymer further contains a unit having a crosslinkable group.
The fluorine-based paint 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 (meth) acrylic acid alkyl ester.
The fluorine-based paint according to claim 3 or 4, wherein the unit having a crosslinkable group is a unit based on a monomer having a crosslinkable group.
The fluorine-based paint according to any one of claims 3 to 5, wherein the crosslinkable group is a hydroxyl group, a carboxy group, an alkoxysilyl group, an epoxy group or an amino group.
The method according to any one of claims 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 both a hydroxyl group. Fluorine-based paint.
The fluorine-based paint according to any one of claims 1 to 7, further comprising a curing agent.
The fluorine-based paint according to any one of claims 1 to 8, further comprising an amide wax.
The fluorine-based paint according to claim 9, wherein the amide wax is a carboxylic acid amide.
The fluorine-based paint according to claim 9 or 10, wherein the amide wax is an aliphatic carboxylic acid amide having an alkyl group having an average carbon number of 20 to 40.
The fluorine-based material according to any one of claims 9 to 11, which contains 0.01 to 15% by mass of the amide wax based on the total mass of the fluorine-containing non-block copolymer and the fluorine-containing block copolymer. paint.
The fluorine-based paint according to any one of claims 9 to 12, wherein a mass ratio of the fluorine-containing block copolymer to the fluorine-containing non-block copolymer is 0.0005 to 0.01.
A coated film-coated substrate, wherein the fluorinated paint according to any one of claims 1 to 13 is applied on the surface of a substrate to form a coated layer, and the coated layer is dried to form a coated film. Manufacturing method.
It is a coating film formed from the fluorine-type paint of any one of Claims 1-13, Comprising: The pencil hardness of the said coating film is HB or more, The static contact angle of the water with respect to the said coating film is A coating having a static contact angle of at least 100 ° and a static contact angle of at least 65 °.