JP6994864B2 - Fluorine-based paints, substrates with coating films, and methods for manufacturing them - Google Patents

Description

The present invention relates to a fluorine-based paint, a substrate with a coating film, and a method for producing the same.

A paint containing a coloring pigment is widely used in order to impart designability to a coating film formed by using the paint.
Among such colored pigments, bright pigments are known from the viewpoint of imparting metallic luster to the coating film, and Patent Document 1 discloses a paint containing a mica pigment coated with iron oxide or the like. There is.

Japanese Unexamined Patent Publication No. 2001-316632

In recent years, the performance required for a coating film formed by using a paint has become high, and specifically, a coating film having excellent designability and processability is required. Here, the coating film having excellent processability means a coating film in which cracks and peeling are unlikely to occur when the base material on which the coating film is formed is bent.
The present inventors have found that the coating film obtained by using the mica pigment coated with iron oxide described in Patent Document 1 is excellent in designability but may be inferior in processability.

In view of the above problems, it is an object of the present invention to provide a fluorine-based paint capable of forming a coating film having excellent designability and processability, a base material with a coating film, and a method for producing the same.

As a result of diligent studies on the above problems, the present inventors can use a fluorine-based paint containing a fluorine-containing polymer having a hydrophilic group and an iron oxide-coated aluminum pigment having a predetermined average particle size. We have found that a desired effect can be obtained, and have reached the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

[1] A fluorine-based paint comprising a fluorine-containing polymer having a hydrophilic group and an aluminum pigment coated with iron oxide having an average particle size of 5 to 50 μm.
[2] The fluorine-based paint according to [1], wherein the content of the aluminum pigment coated with iron oxide with respect to the total mass of the fluorine-based paint is 0.1 to 50% by mass.
[3] The hydrophilic group is at least one selected from a hydroxyl group and a carboxy group, and the total hydroxyl value and acid value of the fluorine-containing polymer is 1 to 200 mgKOH / g, [1] or [2]. ] Fluorine-based paint described in.
[4] Further, according to any one of [1] to [3], which contains a fatty acid amide and the content of the fatty acid amide with respect to the total mass of the fluorine-based paint is 0.1 to 30% by mass. Fluorine-based paint.
[5] Further, any one of [1] to [4], which contains an ultraviolet absorber and the content of the ultraviolet absorber with respect to the total mass of the fluorine-based paint is 0.01 to 20% by mass. Fluorine-based paint described in.
[6] The fluorine-based paint according to [5], wherein the ultraviolet absorber is at least one selected from a compound having a benzotriazole structure and a compound having a triazine structure and a hydroxyphenyl group.
[7] The fluorine-based paint according to [6], wherein the content of the compound having a triazine structure and a hydroxyphenyl group is 20 to 40% by mass with respect to the total mass of the ultraviolet absorber.
[8] A method for producing a substrate with a coating film, which has an undercoat layer, an intermediate coat layer, and a topcoat layer on the surface of the substrate in this order, according to any one of [1] to [7]. A method for producing a base material with a coating film, which forms the intermediate coating layer or the top coating layer using a paint.
[9] A base material with a coating film having at least a base material and a coating film formed from the fluorine-based paint according to any one of [1] to [7].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a fluorine-based paint capable of forming a coating film having excellent designability and processability, a substrate with a coating film, and a method for producing the same.

It is a schematic diagram for demonstrating the 180 degree bending test in an Example.

The meanings of the terms in the present invention are as follows.
The numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
"(Meta) acrylate" is a general term for acrylate and methacrylate, and "(meth) acrylic" is a general term for "acrylic" and "methacrylic".
The "unit" is a general term for an atomic group derived from one molecule of the monomer, which is directly formed by polymerizing a monomer, and an atomic group obtained by chemically converting a part of the atomic group. be. The "monomer-based unit" is also simply referred to as "unit" below. The content (mol%) of each unit with respect to all the units contained in the polymer can be determined from the amount of the components used in the production of the polymer.
For the "average particle size", the volume average is calculated from the particle size distribution measured using a known particle size distribution measuring device (manufactured by Symbolec, trade name "Hellos-Rodos", etc.) based on the laser diffraction method. It is a value of 50% diameter obtained.
The "acid value" and the "hydroxyl value" are values measured according to the method of JIS K 0070-3 (1992), respectively.
"Number average molecular weight" and "mass 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 "mass average molecular weight" is also referred to as "Mw".
"Aspect ratio" means the ratio of the longest length to the thickness of the substrate particles (longest length / thickness), and "average aspect ratio" is 50 randomly selected substrate particles. It is the average value of the aspect ratio. The thickness of the substrate particles is measured by an atomic force microscope, and the longest length of the substrate particles is measured by a transmission electron microscope.

The fluorine-based paint of the present invention (hereinafter, also referred to as “the paint”) is a fluorine-containing polymer having a hydrophilic group and an iron oxide-coated aluminum pigment having an average particle size of 5 to 50 μm (hereinafter, also referred to as “paint”). , Also referred to as "iron oxide-coated Al pigment").
The coating film formed by using the present coating film (hereinafter, also referred to as "the present coating film") is excellent in designability, processability and the like. The reason why the processability of this coating film is excellent is that the hydrophilic group of the fluorine-containing polymer interacts with the iron oxide portion in the iron oxide-coated Al pigment, and the aluminum pigment portion in the iron oxide-containing polymer and the iron oxide-coated A1 pigment. It is considered that by appropriately maintaining the arrangement of the iron oxide-containing polymer and the iron oxide-coated Al pigment, partial free movement is possible and the flexibility is improved.
Further, it is considered that the reason why the present coating film is excellent in designability is that the particle size of the iron oxide-coated A1 pigment is suitable. As described above, the fluorine-containing polymer interacts with the iron oxide-coated A1 pigment. Therefore, if the particle size of the iron oxide-coated A1 pigment is suitable, it is considered that the above interaction is effectively exhibited and the iron oxide-coated A1 pigment can be uniformly dispersed in the fluorine-containing polymer. Further, if the particle size of the iron oxide-coated Al pigment is suitable, the interaction between the iron oxide-coated A1 pigment and the fluorine-containing polymer even when a part of the iron oxide-coated A1 pigment precipitates during long-term storage. Is easy to occur again, and it is considered that the redispersibility is excellent. As described above, if the dispersibility of the iron oxide-coated A1 pigment in the fluorine-containing polymer is excellent, the iron oxide-coated Al pigment can be easily uniformly arranged even when the present coating film is formed by the present coating material. It is presumed that the design of the film has improved.

The fluorine-containing polymer is a polymer having a hydrophilic group and a fluorine atom.
The fluorine atom is preferably introduced into the fluorine-containing polymer by a unit based on a fluoroolefin (hereinafter, also referred to as “unit F”).
A fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with a fluorine atom. In the fluoroolefin, one or more hydrogen atoms which are not substituted with a fluorine atom may be substituted with a chlorine atom.
Specific examples of fluoroolefins include CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CHF, CH ₂ = CF ₂ , CF ₂ = CFCF ₃ , CF ₂ = CHCF ₃ , CF ₃ CH = CHF, CF ₃ . CF = CH ₂ is mentioned, and CF ₂ = CFCl, CF ₃ CH = CHF, and CF ₃ CF = CH ₂ are preferable from the viewpoint of copolymerizability. As the fluoroolefin, one type may be used alone, or two or more types may be used in combination.
The content of the unit F is preferably 20 to 70 mol%, more preferably 40 to 60 mol%, with respect to all the units contained in the fluorine-containing polymer, from the viewpoint of weather resistance of the present coating film.

The hydrophilic group is introduced into the fluorine-containing polymer by a unit (hereinafter, also referred to as “unit 1”) based on a monomer having a hydrophilic group (hereinafter, also referred to as “monomer 1”). Is preferable.
Specific examples of the hydrophilic group include a hydroxyl group, a carboxy group, and an amino group, and at least one selected from the hydroxyl group and the carboxy group is preferable from the viewpoint of further improving the processability of the present coating film.

The monomer 1 is a monomer represented by the formula X ¹¹ -Y ¹¹ (hereinafter, also referred to as "monomer 11") and a monomer represented by the formula X ¹² -Y ¹² (hereinafter, "monomer 11"). Also referred to as "monomer 12") or allyl alcohol is preferred.
The symbols in the formula have the following meanings.
X ¹¹ is CH ₂ = CH-, CH (CH ₃ ) = CH- or CH ₂ = C (CH ₃ )-, and CH ₂ = CH- or CH (CH ₃ ) = CH- is preferable.
Y ¹¹ is a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms having a carboxy group or a carboxy group, and a carboxy group or a carboxyalkyl group having 1 to 10 carbon atoms is preferable.
X ¹² is CH ₂ = CHO- or CH ₂ = CHCH ₂ O-.
Y ¹² is a monovalent saturated hydrocarbon group having 2 to 12 carbon atoms and having a hydroxyl group. The monovalent saturated hydrocarbon group may be linear or branched. Further, the monovalent saturated hydrocarbon group may have a ring structure or may contain a ring structure.
The monovalent 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 11 include CH ₂ = CHCOOH, CH (CH ₃ ) = CHCOOH, CH ₂ = C (CH ₃ ) COOH, and the formula CH ₂ = CH (CH ₂ ) _n2 COOH. However, n2 indicates an integer of 1 to 10).
Specific examples of the monomer 12 include CH ₂ = CHO-CH ₂ -cycloC ₆ H ₁₀ -CH ₂ OH, CH ₂ = CHCH ₂ O-CH ₂ -cycloC ₆ H ₁₀ -CH ₂ OH, CH ₂ = CHOCH. ₂ CH ₂ OH, CH ₂ = CHCH ₂ OCH ₂ CH ₂ OH, CH ₂ = CHOCH ₂ CH ₂ CH ₂ CH ₂ OH, CH ₂ = CH CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OH. In addition, "-cycloC ₆ H _10- " represents a cyclohexylene group, and the binding site of "-cycloC ₆ H _10- " is usually 1,4-.
As the monomer 1, one type may be used alone, or two or more types may be used in combination.

When the present coating material contains a curing agent, the hydrophilic group of unit 1 serves as a crosslinking point, the crosslinking reaction between the fluoropolymers proceeds via the curing agent, and the hardness of the present coating film is improved. The physical properties of the coating film such as weather resistance, water resistance, chemical resistance, and heat resistance are improved.
The content of unit 1 is preferably 1 to 25 mol%, more preferably 5 to 25 mol%, based on all the units contained in the fluorine-containing polymer, from the viewpoint of interaction with the iron oxide-coated A1 pigment. -20 mol% is particularly preferred.

The fluorine-containing polymer contains a unit (hereinafter, also referred to as “unit ^{2”) based on a monomer represented by the formula X2-Z 2 (} hereinafter, also referred to as “monomer 2”). May be good.
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 O-, and from the viewpoint of excellent weather resistance of this coating film, CH ₂ = CHOC (O)-, CH ₂ = CHCH ₂ OC (O)-, CH ₂ = CHO -Or CH ₂ = CHCH ₂ O-is preferable.

Z ² is a monovalent hydrocarbon group having 1 to 24 carbon atoms. The monovalent hydrocarbon group may be linear or branched. Further, the monovalent hydrocarbon group may have a ring structure or may contain a ring structure. Further, 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, an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Alternatively, an aralkyl group having 7 to 12 carbon atoms is more preferable.
Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a hexyl group, a nonyl group, a decyl group and a dodecyl group.
Specific examples of the cycloalkyl group include a cyclohexyl group.
Specific examples of the aralkyl group include a benzyl group.
Specific examples of the aryl group include a phenyl group and a naphthyl group.

As the monomer 2, one type may be used alone, or two or more types may be used in combination.
Specific examples of the monomer 2 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, pivalic acid vinyl ester, and neononanoic acid vinyl ester (manufactured by HEXION, trade name "Beova 9"). , Neodecanoic acid vinyl ester (manufactured by HEXION, trade name "Beova 10"), benzoic acid vinyl ester tert-butyl (meth) acrylate, benzyl (meth) acrylate.
When the fluorinated polymer contains the unit 2, the content of the unit 2 is preferably 1 to 70 mol%, more preferably 10 to 50 mol%, based on all the units contained in the fluorinated polymer.

The fluorine-containing polymer contains the unit F, the unit 1 and the unit 2 in this order of 20 to 70 mol%, 1 to 25 mol%, and 0 to 70 mol% with respect to all the units of the fluorine-containing polymer. Is preferable.
The Mn of the fluorine-containing polymer is preferably 2000 to 40,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000, from the viewpoint of processability of the present coating film.
When the fluorine-containing polymer is a fluorine-containing polymer having an acid value, the acid value of the fluorine-containing polymer is preferably 1 to 150 mgKOH / g, preferably 3 to 100 mgKOH, from the viewpoint of interaction with the iron oxide-coated A1 pigment. / G is more preferable, and 5 to 50 mgKOH / g is particularly preferable.
When the fluorinated polymer is a fluorinated polymer having a hydroxyl value, the hydroxyl value of the fluorinated polymer is preferably 1 to 200 mgKOH / g, preferably 20 to 150 mgKOH from the viewpoint of interaction with the iron oxide-coated A1 pigment. / G is more preferable, and 40 to 100 mgKOH / g is particularly preferable.
The fluorine-containing polymer may have at least one of a hydroxyl value and an acid value, and may have both. When the fluorine-containing polymer has both a hydroxyl value and an acid value, the total of the hydroxyl value and the acid value is preferably 1 to 200 mgKOH / g, preferably 40 to 100 mgKOH / g.
The content of the fluorine-containing polymer is preferably 10 to 70% by mass with respect to the total mass of the present coating material.

The iron oxide-coated Al pigment is preferably a pigment obtained by forming a thin film of iron oxide on the surface of a flake-shaped aluminum base material obtained by pulverizing an aluminum base material.
Iron oxide may cover at least a part of the surface of the aluminum base material.
The flake shape means a flaky shape, and is a concept including a shape such as a scale shape or a flat plate shape.
The aluminum base material means a base material containing an aluminum atom. Specific examples of the material constituting the aluminum base material include aluminum alone, an aluminum alloy, and a mixture of aluminum or an aluminum alloy and another inorganic oxide (for example, tin oxide, silica). The aluminum atom may be contained in the aluminum base material in the form of aluminum oxide.
The iron oxide content in the iron oxide-coated A1 pigment is preferably 10 to 60% by mass, more preferably 20 to 55% by mass, from the viewpoint of suitable interaction with the fluorine-containing polymer.
The content of aluminum contained in the aluminum base material in the iron oxide-coated A1 pigment is preferably 10 to 40% by mass, more preferably 20 to 30% by mass, from the viewpoint of suitable interaction with the fluorine-containing polymer.

The average particle size of the iron oxide-coated Al pigment is 5 to 50 μm and 5 to 50 μm from the viewpoint that the interaction with the fluorine-containing polymer is suitable and the dispersibility of the iron oxide-coated A1 pigment in the fluorine-containing polymer is excellent. 30 μm is preferable, and 10 to 25 μm is particularly preferable. When the average particle size is 5 μm or more, aggregation of the iron oxide-coated Al pigment can be suppressed, and as a result, the iron oxide-coated Al pigment is uniformly arranged on the substrate, and as a result, the design of the coating film is improved. Further, when the average particle size is 50 μm or less, the redispersibility of the iron oxide-coated Al pigment precipitated during storage of the present paint is improved, so that the storage stability of the present paint and the design of the present coating film are improved. ..
The average aspect ratio of the iron oxide-coated Al pigment is preferably 1 to 200, more preferably 1 to 100, particularly preferably 5 to 70, and most preferably 10 to 50.

As the iron oxide-coated Al pigment, a commercially available product may be used, for example, Palochrom L2020, Palochrome L2050, Palochrome L2800, Palochrome L2850, Palochrome L3505 (all of which are trade names manufactured by BASF), Mexal F120-30CWT, Mexal F120-30CWT. Examples thereof include 58CWT and Mexican F121-51CWT (all of which are trade names manufactured by Merck Group).
One type of iron oxide-coated Al pigment may be used alone, or two or more types may be used in combination.
The content of the iron oxide-coated Al pigment is preferably 0.1 to 50% by mass, more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass with respect to the total mass of the present coating material. When the content of the iron oxide-coated Al pigment is 0.1% by mass or more, the design of the present coating film is more excellent. When the content of the iron oxide-coated Al pigment is 50% by mass or less, the storage stability of the present paint is excellent.

The present paint preferably contains a fatty acid amide from the viewpoint of improving storage stability.
The fatty acid amide regulates the affinity between the fluorine-containing polymer and the iron oxide-coated Al pigment. As a result, the iron oxide-coated Al pigment whose affinity has been improved by the fatty acid amide is suitably arranged on the surface of the fluorine-containing polymer. As a result, it is presumed that the dispersibility of the iron oxide-coated Al pigment in the present paint is improved and the storage stability of the present paint is improved.

Specific examples of fatty acid amides include saturated fatty acid monoamides (eg, lauric acid amides, stearic acid amides, palmitic acid amides, caproic acid amides, capric acid amides, capric acid amides, myristic acid amides, behenic acid amides, hydroxystearic acid amides). ), Unsaturated fatty acid monoamide (oleic acid amide, erucic acid amide, ricinoleic acid amide, brushzic acid amide, esulic acid amide, linoleic acid amide, linolenic acid amide, rice sugar fatty acid amide, coconut fatty acid amide, etc.), saturated fatty acid bisamide ( Methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbechenic acid amide , Hexamethylenebishydroxystearic acid amide, N, N'-distealyl adipic acid amide, N, N'-distealyl sebasic acid amide, methylenebispalmitic acid amide, ethylene bispalmitic acid amide, methylenebisbechenic acid amide, ethylene Bisbechenic acid amide, hexaethylene bispalmitic acid amide, etc.), unsaturated fatty acid bisamide (ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'-diorail adipic acid amide, N, N'-diorail Sevacinic acid amide, etc.), Substituent amides (N-stearyl steayl amide, N-oleyl oleate amide, N-stearyl oleate amide, N-oleyl steayl amide, N-stearyl erucate amide, N-oleyl palmitate amide) Etc.), aromatic bisamides (N, N'-distearylisophthalic acid amides, metaxylylene bisstearic acid amides, etc.), branched amides (N, N'-2-hydroxyethylstearic acid amides, N, N'- Ethylenebisoleic acid amide, N, N'-xylene bisstearic acid amide, N, N'-diorail adipic acid amide, N, N'-diorail sevacinic acid amide, N, N'-distearylisophthalic acid amide, etc. ), Alkanol amide (palm oil fatty acid monoethanolamide, lauric acid monoethanolamide, myristic acid monoethanolamide, oleic acid monoethanolamide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, myristic acid diethanolamide) Examples thereof include amides, oleic acid diethanolamides, coconut oil fatty acid monopropanol amides, lauric acid monopropanol amides, myristic acid monopropanol amides, oleic acid monopropanol amides, polyoxyalkylene alkanol amides, etc.).

As the fatty acid amide, a commercially available product may be used, and specific examples thereof include Disparon 6300, Disparon 6500, Disparon 6600, Disparon 6650, Disparon 6700, Disparon 6900-10X, Disparon 6900-20X, Disparon 6810-20X, Disparon 6820-. 10X, Disparon 6820-20X, Disparon 6850-20X, Disparon F-9050, Disparon FS-6010, Disparon PFA-220, Disparon PFA-231, Disparon PFA-131, Disparon A603-10X, Disparon A603-20X, Disparon A650 20X, Disparon A670-20M, Disparon A671-EZ, Disparon NS-5010, Disparon NS-5025, Disparon NS-5810, Disparon NS-5210, Disparon NS-5310 (all manufactured by Kusumoto Kasei Co., Ltd.), Tarren 7200-20, Turen 8200-20, Taren 8300-20, Taren 8700-20, Taren BA-600, Tarren RCM-220, Tarren M-1020XFS, Tarren M-1021B, Floren RCM-210, Floren SP-1000, Floren SP-1000, Examples include Floren SP-1000AF, Floren RCM-230AF, Floren SH-290, Floren SH-295S, Floren SH-350, Floren HR-2, Floren HR-2G, and Floren HR-4AF (all manufactured by Kyoeisha Chemical Co., Ltd.). ..

Further, the fatty acid amide and a compound other than the fatty acid amide may be mixed in advance and used. In this case, the stability of the fatty acid amide itself is improved, and the fatty acid amide promotes the effect of increasing the affinity between the fluoropolymer and the iron oxide-coated pigment A1.
Examples of the compound include polymers other than the fluorine-containing polymer, and preferred is polyolefin oxide, and more preferably polyethylene oxide. That is, when the present coating material contains a fatty acid amide, it is preferable that both the fatty acid amide and the fatty acid amide contain polyethylene oxide.
Specific examples of commercially available products containing fatty acid amides and oxidized polyolefins include Disparon NS-5010, Disparon NS-5025, Disparon NS-5810, Disparon NS-5210, and Disparon NS-5310 (all manufactured by Kusumoto Kasei Co., Ltd.). Be done.
One type of fatty acid amide may be used alone, or two or more types may be used in combination.

The content of the fatty acid amide is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass with respect to the total mass of the present coating material. When the content of fatty acid amide is 0.1% by mass or more, the storage stability of the present coating material is further improved. When the content of the fatty acid amide is 30% by mass or less, the coating workability and the weather resistance of the coating film are further improved.

The present coating material preferably contains an ultraviolet absorber from the viewpoint of protecting the present coating film from ultraviolet rays.
Specific examples of the ultraviolet absorber include a compound having a benzotriazole structure, a compound having a triazine structure and a hydroxyphenyl group, a compound having a benzophenone structure, and a compound having a dicyanoacrylate structure.
The ultraviolet absorber may be used alone or in combination of two or more, but the ultraviolet absorber is a compound having a benzotriazole structure and a compound having a triazine structure and a hydroxyphenyl group. It is preferable that it is at least one selected from.
Above all, from the viewpoint of maintaining the excellent design property of the present coating film for a long period of time (that is, the design sustainability of the present coating film is excellent), the ultraviolet absorber includes a compound having a benzotriazole structure, a triazine structure and a hydroxyphenyl. It is preferably a compound having a group. That is, the ultraviolet absorber is preferably a mixture of a compound having a benzotriazole structure and a compound having a triazine structure and a hydroxyphenyl group. The reason for this is not always clear, but it can be considered as follows.
When a compound having a benzotriazole structure and a compound having a triazine structure and a hydroxyphenyl group are mixed, the structures of the above two compounds are in a state in which they interact with each other and have a suitable hydrophobicity. Be retained. Since the mixture in this state is arranged so as to protect the interaction between the iron oxide-coated A1 pigment and the fluorine-containing polymer due to the hydrophobicity, it is considered that the mixture preferably acts on the design sustainability of the present coating film.

As the compound having a benzotriazole structure, a commercially available product may be used, and specific examples thereof include Tinuvin P, Tinuvin PS, Tinuvin 99-2, Tinuvin 234, Tinuvin 326, Tinuvin 326FL, Tinuvin 328, Tinuvin 384-2, and Tin. 329, Tinuvin 329FL, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin CarboProtect, Tinuvin 99-DW, UVA-1700, UVA-1935LH, Tinuvin 5050, Tinuvin 5160
As the compound having a triazine structure and a hydroxyphenyl group, a commercially available product may be used, and specific examples thereof include Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 400-DW, Tinuvin 477-DW, and Tinuvin. 479-DW, Tinuvin 1577-ED, (all manufactured by BASF) can be mentioned.

The content of the ultraviolet absorber is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 5% by mass with respect to the total mass of the present coating material. When the content of the ultraviolet absorber is within the above range, the design durability of the present coating film is further improved.
When the ultraviolet absorber is a mixture of a compound having a benzotriazole structure and a compound having a triazine structure and a hydroxyphenyl group, the content of the compound having a triazine structure and a hydroxyphenyl group is the content of the ultraviolet absorber (that is, the above. 5 to 90% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass, based on the total mass of the mixture). When the content of the triazine structure and the compound having a hydroxyphenyl group is within the above range, the design durability of this coating film is more excellent.

The present paint may contain a curing agent. As the curing agent, various curing agents known as curing agents for paints can be used, and a compound having two or more groups capable of reacting with a hydroxyl group and a carboxy group in one molecule is preferable. When the curing agent reacts with the group having active hydrogen contained in the fluorine-containing polymer, the fluorine-containing polymer is crosslinked and the present coating film is cured. The curing agent usually has 2 to 30 of the above-mentioned reactive groups.
When the fluorine-containing 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 fluorine-containing polymer has a carboxy group, the curing agent preferably has a compound having two or more epoxy groups, carbodiimide groups, oxazoline groups or β-hydroxyalkylamide groups in one molecule.
When the fluorine-containing 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 an epoxy group, a carbodiimide group, an oxazoline group or a β-hydroxyalkylamide group are used. It is preferable to use in combination with a compound having two or more in one molecule.

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, and an aromatic polyisocyanate. The polyisocyanate derivative is preferably a multimer or a modified polyisocyanate monomer.

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

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

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, and biphenyl type. Epoxy compound, fluorene type epoxy compound, hydrogenated bisphenol A type epoxy compound, bisphenol A nucleated polyol type epoxy compound, polypropylene glycol type epoxy compound, glycidyl ester type epoxy compound, glycidylamine type epoxy compound, glioxal type epoxy compound, alicyclic Examples thereof include type epoxy compounds, alicyclic polyfunctional epoxy compounds, and heterocyclic epoxy compounds (triglycidyl isocyanate and the like).

Specific examples of compounds 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 addition-polymerizable oxazoline having a 2-oxazoline group and a polymer of this 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 (PrimidXL-552, manufactured by EMS). , N, N, N', N'-Tetrakis- (2-Hydroxypropyl) -adipamide (Primid QM 1260 Primid XL-552, manufactured by EMS).

The curing agent is not limited to the above-mentioned curing agent, and may be an amino-based curing agent such as aminoplast or urea resin. As the curing agent, one type may be used alone, or two or more types may be used in combination.
When the present coating material contains a curing agent, the content of the curing agent is preferably 1 to 100% by mass, particularly preferably 1 to 50% by mass, based on the total mass of the fluoropolymer in the present coating.
When a self-curing resin is used, a curing agent is not essential.
The present coating material is not limited to the curing method, and may be any curing type such as a thermosetting type, a thermoplastic type, a room temperature drying type, or a room temperature curing type.

The present paint may be any of a water-based paint mainly containing water as a paint solvent, a solvent-type paint mainly containing an organic solvent as a paint solvent, and a powder paint containing no paint solvent such as water and an organic solvent. A solvent-based paint is preferable from the viewpoint of effectively exhibiting the design of the coating film.
Specific examples of the organic solvent include petroleum-based mixed solvents (toluene, xylene, Solbesso 100 manufactured by Exxon Mobile, Solbesso 150 manufactured by Exxon Mobile, etc.), aromatic hydrocarbon solvents (mineral spirit, etc.), ester solvents (ethyl acetate, etc.). (Butyl acetate, etc.), ketone solvent (methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) can be mentioned. As the organic solvent, one type may be used alone, or two or more types may be used in combination.
When the present coating material contains a coating material solvent, the content of the coating material solvent is preferably 1 to 99% by mass, more preferably 3 to 60% by mass, and particularly preferably 5 to 40% by mass, based on the total mass of the present coating material. ..

The present coating material may contain a polymer other than the fluorine-containing polymer in the present invention from the viewpoint of adhesion of the coating film and the like. Examples of the polymer other than the fluoropolymer in the present invention include fluororesins (polyvinylidene fluoride, etc.) containing fluoropolymers other than the fluoropolymers in the present invention, alkyd resins, aminoalkyd resins, polyester resins, and epoxy resins. , Urethane resin, epoxy polyester resin, polyvinylidene acetate resin, acrylic resin, vinyl chloride resin, phenol resin, modified polyester resin, acrylic silicone resin, silicone resin and the like.

The present paint may contain components other than the above (hereinafter, referred to as "other additives"), if necessary. Specific examples of other additives include fillers (inorganic fillers such as silica, organic fillers such as resin beads), light stabilizers (hindered amine-based light stabilizers, etc.), leveling agents, and surface conditioners (of this coating film). Improves surface smoothness.), Surface active agents, curing catalysts, degassing agents, plastics, fillers, heat stabilizers, viscosity modifiers, anti-dripping agents, rust inhibitors, dispersants, antistatic agents, silanes. Coupling agents, antifouling agents, low-contamination treatment agents, inorganic coloring pigments, organic coloring pigments, rust preventive pigments, extender pigments, bright pigments other than iron oxide-coated Al pigments in the present invention, gloss adjusters and matting agents. Agents are mentioned. Further, in order to give a color tone to the coating film, an enamel paint or the like may be mixed.

The substrate with a coating film of the present invention has at least a substrate and a coating film formed from the present coating film (the present coating film). Since the base material with a coating film of the present invention has the present coating film, it is excellent in designability and processability.
The substrate with a coating film of the present invention can be produced by applying the present paint on the substrate to form the present coating film. The present paint may be applied directly to the surface of the base material, or may be applied after applying a known surface treatment to the surface of the base material.
Specific examples of the surface treatment include polishing of the surface of the base material, sanding treatment, sealing treatment, blast treatment, chemical conversion treatment, primer treatment, and application of an undercoat agent.
Further, after forming the undercoat layer on the base material, the present paint may be applied on the undercoat layer. Further, after forming the undercoat layer and the intermediate coat layer on the base material, the present paint may be applied on the intermediate coat layer. That is, when the base material with a coating film of the present invention has a multi-layer film, the present coating film may form any layer in the above-mentioned multi-layer film.

As an example of the method for producing a substrate with a coating film of the present invention, a method for producing a substrate with a coating film, which has a multi-layer film having an undercoat layer, an intermediate coat layer and a topcoat layer in this order on the surface of the substrate (hereinafter, Also referred to as “the manufacturing method of the present embodiment”), a method in which the intermediate coating layer or the top coating layer is formed by using the present coating material will be described.

The material of the base material is not particularly limited, and specific examples thereof include an inorganic base material composed of cement concrete, natural stone, glass, iron, steel, stainless steel, aluminum, copper, brass, titanium, etc., acrylic resin, and polycarbonate. , FRP, organic base material composed of resin reinforced concrete and the like.
In particular, for exterior member applications such as home appliances, furniture, building materials and automobile parts, metal plates (metal base materials) such as iron, steel, stainless steel, aluminum, copper, brass and titanium are preferable as the base material. Aluminum is more preferred.
Specific examples of steel sheets include galvanized steel sheets (electric galvanized steel sheets, hot-dip galvanized steel sheets, etc.), alloyed galvanized steel sheets (alloyed hot-dip galvanized steel sheets that have been alloyed after hot-dip galvanized plating, etc.), and zinc alloy-plated steel sheets (hot-dip galvanized steel sheets, etc.). -Magnetic plating, hot-dip galvanized-aluminum-magnesium plating, hot-dip galvanized steel sheet, hot-dip galvanized steel sheet, hot-dip galvanized steel sheet, electric galvanized steel sheet, electric galvanized steel sheet, electric zinc-chrome Galvanized steel sheets, multi-layer plated steel sheets and stainless steel sheets in combination thereof can be mentioned.
When a metal plate (aluminum or the like) is used as a base material, a metal plate having a chemical conversion treatment film formed on its surface is preferable from the viewpoint of coating film adhesion and corrosion resistance. Specific examples of the chemical conversion treatment include coating chromate treatment, electrolytic chromate treatment, chromium-free treatment and phosphate treatment.

The undercoat layer has a function of improving the adhesion, corrosion resistance or rust resistance of the present coating film. Specific examples of the method for forming the undercoat layer include a method of applying an undercoat paint (primer paint) to the surface of a base material or a chemical conversion treatment film and curing the undercoat layer.
The intermediate coating layer has a function of improving the design of the base material with a coating film and the interlayer adhesion of the main coating film. As a specific example of the method for forming the intermediate coating layer, the present coating material or a coating material other than the present coating material is used as the intermediate coating material, and the above intermediate coating material is applied to the surface of the undercoat layer to form a coating film, and the formed coating film is formed. There is a method of curing.
The topcoat layer has a function of protecting the intermediate coat layer and improving the design of the base material with a coating film. As a specific example of the method for forming the topcoat layer, this paint or a paint other than this paint is used as the topcoat paint, and the above topcoat paint is applied to the surface of the intermediate coat layer to form a coating film, and the formed coating film is cured. There is a way to make it.
Specific examples of the application method of the undercoat paint, the intermediate coat paint, or the top coat paint include electrostatic coating method, brush coating method, roller coating method, dip coating method, cast coating method, spray coating method, spinner coating method, and bead coating method. Examples thereof include a wire bar coating method, a blade coating method, a roller coating method, a curtain coating method, a slit die coater method, a gravure coater method, a slit reverse coater method, a microgravure method, an inkjet method, and a comma coater method.

As a curing method when an undercoat paint, an intermediate coat paint, or a top coat paint is applied to form a coating layer and the coating layer is cured to form a coating film, the heat resistance of the base material used and the type of curing agent are used. Therefore, normal temperature drying, forced drying, baking drying and the like can be appropriately adopted.
The film thickness of the undercoat layer, the intermediate coat layer, or the topcoat layer is usually 0.5 to 200 μm, more preferably 0.5 to 100 μm, and particularly preferably 1 to 60 μm.
Specific examples of the components that can be contained in the undercoat paint, the intermediate coat paint, or the top coat paint include the fluoropolymer in the present invention and a fluororesin (polyvinylidene fluoride) containing a fluoropolymer other than the fluoropolymer in the present invention. Etc.), alkyd resin, amino alkyd resin, polyester resin, epoxy resin, urethane resin, epoxy polyester resin, polyvinylidene acetate resin, acrylic resin, vinyl chloride resin, phenol resin, modified polyester resin, acrylic silicone resin, silicone resin. Be done. In addition, rust-preventive pigments (zinc phosphate, lead tan, zinc powder, lead phosphite, calcium leadate, cyanamide lead, basic lead chromate, basic lead sulfate, etc.), scaly pigments (iron oxide, mica, aluminum) , Glass flakes, etc.), and preferably contains a rust-preventive pigment from the viewpoint of enhancing rust-preventive power. In particular, in the undercoat paint, a zinc rich primer may be used. The above components may be used alone or in combination of two or more. Further, the components listed in the present paint may be contained.

In the production method of the present embodiment, in the substrate with a coating film of the present invention, another layer may be formed between each layer of the undercoat layer, the intermediate coat layer, and the topcoat layer and on the layer. Further, the undercoat layer, the intermediate coat layer, and the topcoat layer may be formed by applying the undercoat paint, the intermediate coat paint, and the topcoat paint a plurality of times, and each layer may have a multi-layer structure.

As described above, since the present coating film is excellent in design and processability, the substrate with a coating film of the present invention can be suitably used in applications of ceramic building materials that require an excellent appearance.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. The blending amount of each component in the table described later indicates a mass standard. Examples 16 and 22 to 27 are examples, and examples 17 to 21, 28 and 29 are comparative examples.

[Manufacturing of fluorinated polymer]
In an autoclave, cyclohexyl vinyl ether (CHVE) (18.9 g), ethyl vinyl ether (18.2 g), 4-hydroxybutyl vinyl ether (HBVE) (11.6 g), xylene (55.8 g), ethanol (15.7 g), A 50% by mass xylene solution (0.7 g) of potassium carbonate (1.1 g), tert-butyl peroxypivalate (PBPV), and chlorotrifluoroethylene (CTFE) (58.2 g) were introduced and stirred. Polymerization was carried out at 65 ° C. for 15 hours. The solution in the autoclave was filtered, and the obtained filtrate was distilled off under reduced pressure to obtain a solution containing the fluorine-containing polymer 1 (fluorine-containing polymer concentration 60% by mass).
The fluorine-containing polymer 1 contains 50 mol% and 15 mol% of CTFE-based units, CHVE-based units, EVE-based units, and HBVE-based units in this order with respect to all the units contained in the fluorine-containing polymer 1. , 25 mol%, 10 mol% was a polymer. The fluorine-containing polymer 1 had a hydroxyl value of 52 mgKOH / g and a Mn of 20000.

[Manufacturing of topcoat bright paint]
(Examples 1 to 10)
The components shown in Table 1 were added to the fluorine-containing polymer 1 with stirring, and then the mixture was further stirred for 15 to 30 minutes to obtain topcoat bright paints 1 to 10. Details of each component are described later.

[Manufacturing of intermediate coating bright paint]
(Examples 11 to 13)
The components shown in Table 2 were added to the fluorine-containing polymer 1 with stirring, and then the mixture was further stirred for 15 to 30 minutes to obtain intermediate coating bright paints 1 to 3. Details of each component are described later.

[Manufacturing of top clear paint]
(Examples 14 to 15)
The components shown in Table 2 were added to the fluorine-containing polymer 1 with stirring, and then the mixture was further stirred for 15 to 30 minutes to obtain top clear paints 1 and 2. Details of each component are described later.

(Ingredients used in the manufacture of paint)
Pigment 1: Mexican F120-58CWT (trade name) (Merck, iron oxide-coated aluminum flake pigment (average particle size 17 μm, iron oxide content 39%))
Pigment 2: Friend Color D851YE (trade name) (Made by Toyo Aluminum Co., Ltd., colored resin-coated aluminum flake pigment (average particle diameter 23 μm))
Pigment 3: Iriodin 502 WNT (trade name) (Merck, iron oxide-coated mica flake pigment (average particle size 20 μm))
Pigment 4: Colorstream F20-00 WNT (Merck, iron oxide-coated silica flake pigment (average particle diameter 21 μm))
Pigment 5: Iron oxide-coated aluminum flake pigment (average particle size 4 μm, developed product, iron oxide content 15%)
Pigment 6: Iron oxide-coated aluminum flake pigment (average particle size 55 μm, developed product, iron oxide content 57%)
Dispersant 1: Disparon NS-5210 (trade name) (manufactured by Kusumoto Kasei Co., Ltd., dispersant containing fatty acid amide)
Dispersant 2: DISPERBYK-2152 (trade name) (manufactured by Big Chemie, dispersant containing polyester)
Dispersant 3: DISPERBYK-2155 (trade name) (manufactured by Big Chemie, dispersant containing block copolymer)
Ultraviolet absorber 1: Tinuvin 1130 (trade name) (manufactured by BASF, a compound having a benzotriazole structure)
Ultraviolet absorber 2: Tinuvin 479 (trade name) (manufactured by BASF, a compound having a triazine structure and a hydroxyphenyl group)
Curing catalyst: Tin-based curing catalyst Curing agent: Compound having two or more blocked isocyanate groups in one molecule Photostabilizer: Hinderedamine-based compound Defoaming agent: Solution containing acrylic polymer and silicone Leveling agent: Polyether-modified poly Solution containing dimethylsiloxane

[Preparation of test piece]
(Example 16)
A primer paint containing a polyester resin and an epoxy resin is applied to a chromate-treated base material (aluminum plate) using a bar coater to obtain a primer plate (dry film thickness 5 μm) having a primer layer as an undercoat layer. Obtained.
Next, an enamel paint containing a fluororesin is applied onto the primer layer of the primer plate using a bar coater, dried at 190 ° C. for 60 seconds, and the enamel plate having an enamel layer as an intermediate coating layer (undercoat). The total dry film thickness of the layer and the intermediate coating layer (25 μm) was obtained.
Next, the topcoat bright paint 1 is applied onto the enamel layer of the enamel plate using a bar coater, dried at 230 ° C. for 60 seconds, and is a coating formed from the topcoat bright paint 1 which is the topcoat layer. A three-layered multi-layer film (undercoat) in which a film is formed and an undercoat layer (primer layer), an intermediate coat layer (enamel layer), and a topcoat layer (a coating film consisting of a topcoat brilliant paint 1) are laminated in this order on a substrate. An enamel-coated aluminum plate 1 having a total dry film thickness of 43 μm) of the layer, the intermediate coating layer and the top coating layer was obtained. The aluminum plate 1 with a coating film was used as a test piece 1 and evaluated as described later. The results are shown in Table 3.

(Examples 17 to 25)
Test pieces 2 to 10 were obtained in the same manner as in Example 14 except that the topcoat bright paint 1 was changed to the topcoat bright paints 2 to 10, and evaluated as described later. The results are shown in Table 3.

(Example 26)
A primer coating material containing a polyester resin and an epoxy resin was applied to a chromate-treated aluminum plate using a bar coater to obtain a primer plate (dry film thickness 5 μm) having a primer layer as an undercoat layer.
Next, the intermediate coating bright paint 1 is applied onto the primer layer of the primer plate using a bar coater, dried at 190 ° C. for 60 seconds, and formed from the intermediate coating bright paint 1 which is an intermediate coating layer. A metallic plate having a coating film (total dry film thickness of 19 μm for the undercoat layer and the intermediate coat layer) was obtained.
Next, the top clear paint 1 is applied onto the intermediate coating layer of the metallic plate using a bar coater and dried at 230 ° C. for 60 seconds to form the top clear layer which is the top coating layer on the substrate. A multi-layer film (undercoat layer, intermediate coat layer and topcoat layer) in which an undercoat layer (primer layer), an intermediate coat layer (a coating film composed of an intermediate coat bright paint 1) and a topcoat layer (top clear layer) are laminated in this order. An aluminum plate 11 with a coating film having a total dry film thickness of 33 μm) was obtained. The aluminum plate 11 with a coating film was used as a test piece 11 and evaluated as described later. The results are shown in Table 4.

(Examples 27-29)
The test piece 12 was obtained in the same manner as in Example 26 except that the top clear paint 1 was changed to the top clear paint 2. Further, test pieces 13 and 14 were obtained in the same manner as in Example 26 except that the intermediate coating bright paint 1 was changed to the intermediate coating bright paint 2 or 3. The obtained test pieces 12 to 14 were evaluated as described later. The results are shown in Table 4.

[Evaluation of coating film]
(Processability of coating film)
Judgment was made by the 180 degree bending test shown in FIG. The test piece X is immersed in ice water and cooled to 5 ° C., and a spacer 20 having a plate thickness of 1T (spacer 20A in FIG. 1B) and a spacer 20 having a thickness of 2T (spacer 20B in FIG. 1C) are placed on a load base 30. The test piece X was bent 180 ° C. perpendicular to the rolling direction of the base material while being sandwiched between the two (see FIG. 1 (A)). After bending, the bent portion Xc of the coating film surface was observed, and whether or not deformation such as cracking or peeling occurred was evaluated by enlarging the loupe. The plate thickness T of the spacer 20 is 0.5 mm per 1T.
◯: Even if the bending diameter X1 is 0.5 mm (plate thickness 1T), cracks and peeling do not occur in the bent portion Xc.
X: When the bending diameter X1 is 0.5 mm (plate thickness 1T), cracks and peeling occur in the bent portion Xc, but when the bending diameter X1 is 1.0 mm (plate thickness 2T), cracks and peeling occur in the bent portion Xc. Does not occur.

(Design of coating film 1)
The design of the appearance of the coating film surface on the test piece was visually evaluated.
◯: The appearance of the coating film is even, there is a consistent metallic luster, and the color tone is gorgeous.
X: The appearance of the coating film is uneven, there is no metallic luster, or the color tone is partially dull.

(Design of coating film 2)
An accelerated weathering test was conducted using an accelerated weathering tester conforming to the sunshine weather meter method (JIS B 7753: 2007) with a test time of 8000 hours. The retention rate (gloss retention rate) (%) of the 60-degree mirror surface gloss value of the coating film after the test was determined with the initial value of the 60-degree mirror surface gloss value before the start of the test as 100%, and evaluated according to the following criteria. The 60-degree mirror gloss value was measured with a variable-angle gloss meter (trade name "UGV-6P", incoming reflection angle 60 degrees, manufactured by Suga Test Instruments Co., Ltd.). The higher the gloss retention rate, the higher the durability of the appearance of the coating film and the better the design.
◯: The gloss retention rate at 8000 hours is 80% or more.
X: The gloss retention rate at 8000 hours is less than 80%.

(Design of coating film 3)
Color difference between the coating film after the test and the coating film before the test, which was subjected to the accelerated weathering resistance test with the test time set to 8000 hours using the accelerated weathering resistance tester compliant with the sunshine weather meter method (JIS B 7753: 2007). Was measured using a spectrocolorimeter (trade name "CM-5", manufactured by Konica Minolta Co., Ltd.). The smaller the color difference, the longer the durability of the appearance of the coating film and the better the design.
Color difference (ΔE ^* ab) = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
ΔL ^* = L ^* value of the coating film after the test-L ^* value of the coating film before the test
Δa ^* = a ^* value of the coating film after the test-a ^* value of the coating film before the test
Δb ^* = b ^* value of the coating film after the test-b ^* value of the coating film before the test ◯: The color difference at 8000 hours is less than 5.
Δ: The color difference in 8000 hours is 5 or more and less than 10.
X: The color difference in 8000 hours is 10 or more.

(Paint storage stability)
The storage stability of the bright paint was evaluated from the degree of aggregation of the precipitate generated during storage. 100 g of each of the bright paints was placed in a centrifuge tube and allowed to stand at 23 ° C. for 2 months to evaluate the ease of stirring the resulting precipitate.
⊚: When stirring the bright paint with a glass rod or the like, no resistance due to the precipitate is felt.
◯: When stirring the bright paint with a glass rod or the like, resistance due to the precipitate is felt, but the resistance disappears within 1 minute.
Δ: When the bright paint is stirred with a glass rod or the like, resistance due to the precipitate is felt, but the resistance disappears within more than 1 minute and 3 minutes.
X: When the bright paint is stirred with a glass rod or the like, the resistance due to the precipitate is large and the resistance does not disappear even after more than 3 minutes.

As shown in Tables 3 and 4, a coating film formed of a fluorine-based paint containing a fluorine-containing polymer having a hydrophilic group and an iron oxide-coated aluminum pigment having a predetermined particle size has a design property. And has workability.

X Test piece Xc Bending part X1 Bending diameter 1T, 2T Plate thickness 20, 20A, 20B Spacer 30 Load capacity

Claims (8)

A fluorine-based paint containing a fluorine- containing polymer having a hydrophilic group, an iron oxide-coated aluminum pigment having an average particle size of 5 to 50 μm, and a fatty acid amide .
A fluorine-based paint, wherein the content of the fatty acid amide with respect to the total mass of the fluorine-based paint is 0.1 to 30% by mass . The fluorine-based paint according to claim 1, wherein the content of the aluminum pigment coated with iron oxide is 0.1 to 50% by mass with respect to the total mass of the fluorine-based paint. The fluorine according to claim 1 or 2, wherein the hydrophilic group is at least one selected from a hydroxyl group and a carboxy group, and the total hydroxyl value and acid value of the fluorine-containing polymer is 1 to 200 mgKOH / g. System paint. The fluorine-based product according to any one of claims 1 to 3 , further comprising an ultraviolet absorber, wherein the content of the ultraviolet absorber with respect to the total mass of the fluorine-based paint is 0.01 to 20% by mass. paint. The fluorine-based paint according to claim 4 , wherein the ultraviolet absorber is at least one selected from a compound having a benzotriazole structure and a compound having a triazine structure and a hydroxyphenyl group. The fluorine-based paint according to claim 5 , wherein the content of the compound having a triazine structure and a hydroxyphenyl group is 20 to 40% by mass with respect to the total mass of the ultraviolet absorber. A method for producing a base material with a coating film, which has an undercoat layer, an intermediate coat layer, and a topcoat layer on the surface of the base material in this order.
A method for producing a base material with a coating film, which forms the intermediate coating layer or the top coating layer by using the fluorine-based coating material according to any one of claims 1 to 6 . A base material with a coating film, which comprises at least a base material and a coating film formed from the fluorine-based paint according to any one of claims 1 to 6 .

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