JPH10101985A - Coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition which can give a coating film which is excellent in staining resistance, removal of contaminants and weather resistance, has good water resistance, chemical resistance and appearance, and is excellent in environmental protection and safety. SOLUTION: This composition is prepared by adding a metal oxide sol (C) to a curable composition containing a fluorocopolymer (A) comprising structural fluoroolefin units represented by the formula: -CF2 -CFX- (wherein X is fluorine, chlorine, hydrogen or trifluoromethyl), structural β-methyl-substituted α-olefin units represented by the formula (wherein R is a 1-8C alkyl), structural units derived from a monomer having a chemically curable group, and structural units derived from another copolymerizable monomer and having a number- average molecular weight of 1,000-500,000 and a curing agent (B). The metal oxide sol is desirable a silicon oxide sol surface-treated with a silane coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a coating composition. More specifically, the present invention relates to a coating composition containing, as essential components, a specific fluorinated copolymer which can be chemically bonded to a resin component, a curing agent, and a metal oxide sol. The present invention relates to a coating composition which gives a cured coating film having excellent decontamination properties, weather resistance, chemical resistance, moisture resistance and appearance, and has high environmental preservation and safety.

[0002]

2. Description of the Related Art In recent years, oil droplets and dust contained in the air have increased due to environmental changes such as air pollution, and as a result, coatings applied to buildings and automobiles have become more contaminated than before. However, there is a problem that the stain becomes difficult to remove. Therefore, the coating film has good gloss, appearance, water resistance, and chemical resistance as well as resistance to contamination, that is, stain resistance, and removal of contaminants from the contaminated coating film. It has been desired to also have a property, that is, a decontamination property. There is also a demand for a paint composition having excellent environmental preservation and safety as a paint. By the way, the stain-resistant paint which has been conventionally used has a fluorine-containing resin as a main component, and the stain resistance is due to the weather resistance of the fluorine-containing resin. The fluororesin has (1) stability due to a large bond energy between a fluorine atom and a carbon atom, and (2) a fluorine atom having a larger atomic radius than a hydrogen atom and a polarizability between fluorine molecules. Low (0.68 × 10 ^-24 CC)
Water repellency due to low surface free energy,
Its function is expressed by oil repellency. In order to use a fluororesin for coatings, a copolymer of a fluoroolefin and a vinyl ether monomer such as cyclohexyl vinyl ether is used for the purpose of improving the solubility in a solvent (JP-A-57-34107). JP-A No. 61-12760), a resin mixture of a fluorine-containing copolymer and an acrylic copolymer.
No.). However, at present, the portion based on the fluorine-containing monomer is reduced, and the high weather resistance and stain resistance inherent to the fluorine-containing resin are not sufficiently exhibited at present. In addition, as a material for improving the weather resistance and stain resistance of a fluorine-containing resin for coating, a fluoroolefin, a β-methyl-substituted α-olefin, a monomer having a chemically curing reactive group, and an ester group in a side chain. Copolymers with such monomers have been proposed (JP-A-4-279612). However, the decontamination property is not yet sufficient. On the other hand, with respect to improvement of stain resistance, a coating composition comprising a partial condensate of an organosilicon compound and specific silica fine particles has been proposed (JP-A-2-3468).
No.). However, this publication does not describe in detail the resin component used in the coating composition. Further, a coating composition containing an acrylic polyol resin, a binder, an inorganic organosol and a solvent has been proposed (JP-A-4-173882). However, this coating composition has the drawback that the stain resistance and weather resistance are improved to some extent, but the stain removal properties are insufficient. At present, there is no coating composition which gives a coating film having excellent stain resistance, stain removal properties and weather resistance.

[0003]

Under such circumstances, the present invention provides a coating film having excellent stain resistance, stain removal properties and weather resistance and having good water resistance, chemical resistance and appearance. Another object of the present invention is to provide a coating composition having excellent environmental preservation and safety.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to develop a coating composition having the above-mentioned properties.
It has been found that a coating composition containing a specific fluorinated copolymer (A), a curing agent (B) and a metal oxide sol (C) can be suitable for the purpose. It was completed. That is, the present invention provides [1] (1), a formula (I): -CF ₂ -CFX- (I) wherein X is a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group. Fluoroolefin structural units (1) and (2) represented by the formula (II):

[0005]

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(Wherein R is an alkyl group having 1 to 8 carbon atoms) β-methyl-substituted α-olefin structural unit (2), (3) a monomer having a chemically curing reactive group (3) Structural unit based on a body, (4) Structural unit based on a monomer having an ester group in a side chain, (4), and (5) Structural unit based on another copolymerizable monomer (5) A curable composition comprising a fluorine-containing copolymer (A) having a number average molecular weight of 1,000 to 500,000 and a curing agent (B), comprising a metal oxide sol (C). [2] The coating composition according to the above [1], wherein the metal oxide sol is a dispersion of a silicon oxide sol, and [3] the dispersion of the silicon oxide sol is a silane coupling agent. The above [1] or [2], which is surface-treated. It is a coating composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing copolymer (A) used in the coating composition of the present invention is as described in the above (1) to (5).
Is a copolymer containing a structural unit of Hereinafter, each structural unit constituting the fluorinated copolymer (A) will be described.

The monomers giving the structural unit (1) are tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene and hexafluoropropylene. The content ratio of the structural unit (1) in the fluorinated copolymer (A) is 20 to 60 mol%. If it is less than 20 mol%, the weather resistance of the coating film is poor, and if it is more than 60 mol%, the solubility of the fluorine-containing copolymer (A) in the solvent is poor.

The monomers giving the structural unit (2) are isobutylene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene and the like, and the fluorine-containing copolymer ( The content ratio in A) is 5 to 45 mol%. If it is less than 5 mol%, the weather resistance of the coating film is inferior,
If it exceeds 45 mol%, it becomes difficult to synthesize the fluorinated copolymer (A). The content of the total amount of the structural units (1) and (2) in the fluorinated copolymer (A) is 40 to 40%.
It is 90 mol%, preferably 50 to 85 mol%. 40
If it is less than 90 mol%, the weather resistance, stain resistance, heat yellowing resistance, and chemical resistance of the coating film are poor. If it exceeds 90 mol%, the solubility of the fluorocopolymer (A) is poor. Is also inferior in optical properties.

The structural unit (3) includes a hydroxyl group, a hydroxyl group blocked with vinyl ether, an epoxy group, a carboxyl group, a carboxyl group blocked with vinyl ether,
It is based on a monomer having a chemically curing reactive group such as an amino group, an isocyanate group, a blocked isocyanate group, and a silyl group. Among these chemically curing reactive groups, a preferred one is a hydroxyl group. The content ratio of the structural unit (3) in the fluorocopolymer (A) is from 1 to 45 mol%, preferably from 1 to 30 mol%, particularly preferably from 5 to 5 mol%.
If the amount is less than 1%, the curability becomes insufficient. If the amount exceeds 45% by mole, gelation of the fluorine-containing copolymer (A) is liable to occur, storage stability is poor, and the resulting coating composition is poor. The membrane becomes brittle. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl vinyl ether and 3-hydroxyethyl vinyl ether.
Hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2- Examples thereof include vinyl ethers such as hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, and allyl ethers.

Examples of the monomer having an epoxy group include glycidyl vinyl ether, glycidyl allyl ether, glycidyl (meth) acrylate, 1,4-pentadiene monoepoxide and the like.

Examples of the monomer having a silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, trimethoxysilylethyl vinyl ether, and γ- (meth) acryloyloxy. And propyltrimethoxysilane. Other monomers that give the structural unit (3) are disclosed in
-279612.

The monomer having an ester group in the side chain to give the structural unit (4) may be any monomer having a polymerizable unsaturated group and an ester group, but is preferably a vinyl carboxylate. Esters and diesters of dicarboxylic acids. Examples of vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate,
Vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, p-tert-butyl vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate, vinyl hexafluoropropionate, vinyl trichloroacetate, and the like. As the diester, for example, dimethyl of maleic acid or fumaric acid, diethyl, dipropyl, dibutyl, diphenyl, dibenzyl, ditrityl, ditrifluoromethyl,
Examples thereof include ditrifluoroethyl and dihexafluoropropyl ester.

The fluorine-containing copolymer (A) of the structural unit (4)
The content thereof is 1 to 45 mol%, preferably 5 to 40 mol%, particularly preferably 10 to 30 mol%. 1 mol%
If it is less than 1, the solubility and compatibility of the fluorinated copolymer (A) are poor, and the glass transition temperature is undesirably low. On the other hand, if it exceeds 45 mol%, the weather resistance of the coating film is poor, which is not preferable. The structural unit (4) contributes to the improvement of the compatibility of the copolymer (A), the glass transition temperature, the dispersibility of the pigment, and the gloss, stain resistance, hardness and adhesion of the obtained coating film to the substrate.

In addition to the structural units (1) to (4), a structural unit (5) based on another copolymerizable monomer is contained in the fluorine-containing copolymer (A) in an amount of 45 mol% or less, preferably Is 1 to 1
By adding 5 mol%, other properties of the other monomer can be imparted without impairing the properties provided by the structural units (1) to (4). Other monomers include, for example, methyl vinyl ether, ethyl vinyl ether, n-
Propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, 2-acetoxyethyl vinyl ether, 2-chloroethyl vinyl ether Alkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, methyl cyclohexyl vinyl ether,
Cycloalkyl vinyl ethers such as cyclooctyl vinyl ether; vinyl ethers having an aromatic group such as benzyl vinyl ether, phenethyl vinyl ether, phenyl vinyl ether, 2-phenoxyethyl vinyl ether, and 2-vinyloxyethyl benzoate;
2,2-trifluoroethyl vinyl ether, 2,2
3,3-tetrafluoropropyl vinyl ether, 2,
2,3,3,3-pentafluoropropyl vinyl ether, 2,2,3,3,4,4,5,5-octafluoropentyl vinyl ether, 2,2,3,3,4,4
Fluoroalkyl vinyl ethers such as 5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether and perfluoropropyl vinyl ether; fluoroalkyl ethylene And the like are typical examples. In addition, esters of acrylic or methacrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate,
Isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, methacrylic acid C1-C18 alkyl esters of acrylic acid or methacrylic acid such as lauryl and trityl methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxy methacrylate C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid such as butyl; vinyl aromatic compounds such as styrene and α-methylstyrene Vinyl toluene, may also be copolymerized, such as p- chlorostyrene.

Further, among the other monomers giving the structural unit (5), when the structural unit (1) is the structural unit (1a) based on tetrafluoroethylene, the structural unit based on the monomer having a carboxyl group is preferred. It is particularly effective to include the unit (5a). The carboxyl group-containing monomer may be any carboxylic acid compound having a polymerizable unsaturated group, such as acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, and 3-allyl. Oxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitate and the like.
Preferred are acrylic acid, methacrylic acid, vinyl acetic acid and crotonic acid. The structural unit (5a) based on a monomer having a carboxyl group improves dispersibility in water, curing reactivity and dispersibility of a pigment in the copolymer solution, and provides a gloss, hardness, Improves adhesion to materials. In this case, the structural units (1a) / (2) / (3) / (4) /
The molar ratio of (5) / (5a) is 30 to 60/5 to 45/1.
~ 45/1 ~ 45/0 ~ 45 / 0.1 ~ 15 (however,
(1) + (2) is preferably 40 to 90 mol%). When the structural unit (5a) is less than 0.1 mol%, the above properties are deteriorated, and when it exceeds 15 mol%, storage stability may be poor. Structural units (1) to (5) and (5)
a) may be of two or more types.

The fluorine-containing copolymer (A) of the present invention comprising these structural units has a number average molecular weight of 1,000 to 1,000.
500,000, preferably 3,000 to 100,000, and a glass transition temperature of -40 to 90 ° C, preferably -1.
0-70 ° C. When the number average molecular weight is less than 1,000, the curing of the coating film becomes insufficient. When the number average molecular weight exceeds 500,000, the viscosity of the coating material increases and handling becomes difficult.

The fluorinated copolymer (A) can be obtained by copolymerizing the above monomer components by an emulsion, suspension or solution polymerization method. Specific polymerization conditions such as polymerization temperature, polymerization solvent, polymerization initiator and the like can be the methods described in JP-A-4-279612. In addition, a resin form such as an aqueous dispersion type or a powder type can be used as necessary.

The coating composition of the present invention uses a curing agent (B) together with the above-mentioned fluorine-containing copolymer (A). Curing agent (B)
Is reacted with the curing reactive group in the fluorinated copolymer (A) to be crosslinked, so that there is no particular limitation as long as the compound has two or more functional groups in one molecule. Examples of the curing agent (B) used in the present invention include ordinary curing agents used in paints, such as isocyanate group- or blocked or adducted isocyanate-containing compounds, amino resins, hydroxyl- or vinyl-ether-blocked hydroxyl-containing compounds, and carboxyl groups. Alternatively, a carboxyl group-containing compound, an acid anhydride, a polysilane compound, a polyepoxy compound, an isocyanate group-containing silane compound, or the like blocked with vinyl ether can be used as it is. The amount of the curing agent (B) used is 0.1 to 5 equivalents, preferably 0.5 to 1.5 equivalents, relative to 1 equivalent of the chemically curing reactive group in the fluorinated copolymer (A). It is. The composition of the present invention can be usually cured at 0 to 200 ° C. for several minutes to about 10 days.

Specific examples of the isocyanates include:
For example, 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4 Diisocyanates, their trimers,
These adducts and burettes, these polymers containing two or more isocyanate groups, and further blocked isocyanates are exemplified, but not limited thereto.

Specific examples of the amino resins include, for example, urea resins, melamine resins, benzoguanamine resins,
In addition to glycoluril resins, methylolated melamine resins obtained by converting melamine to methylol, alkyl etherified melamine resins obtained by etherifying methylolated melamine with alcohols such as methanol, ethanol, and butanol, and the like, include, but are not limited to, is not.

[0022] Specific examples of the acid anhydride, for example phthalic anhydride, do not pyromellitic anhydride, the like anhydrous trimellitic acid as being limited thereto.

The polysilane compound is a compound having two or more groups selected from a hydrolyzable group and a SiO ₂ group directly bonded to a silicon atom or a condensate thereof, for example, Japanese Patent Application Laid-Open No. Hei 4-279612. Can be used. Specific examples include dimethyldimethoxysilane, dibutyldimethoxysilane, diisopropyldipropoxysilane, diphenyldibutoxysilane, diphenylethoxysilane, diethyldisilanol, dihexyldisilanol, methyltriethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, Phenyltriethoxysilane, phenyltributoxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraacetoxysilane, diisopropoxyvaleroxysilane, tetrasilanol, etc. can give.

Examples of the polyepoxy compound and the isocyanate group-containing silane compound are described in, for example, JP-A-4-2796.
No. 12, JP-A-2-232250, JP-A-2-232250
Those described in JP-A-232251 can be used. Preferred examples include, for example, ethylene glycol diglycidyl ether, triglycidyl isocyanurate, bisphenol A diglycidyl ether, and the like.

The metal oxide sol (C) used in the present invention is obtained by dispersing metal oxide fine particles in water or an organic solvent to form a fluid, and the metal is not particularly limited. And at least one dispersion selected from sols of oxides of silicon, zirconium and antimony. Among these oxide sols, a particularly preferred one is a silicon oxide sol. These oxide sols generally have a particle size of 5 to 10 μm.
Often supplied as an aqueous dispersion of If the coating is an aqueous coating, the aqueous dispersion can be used as it is, and if it is an organic solvent, there is no problem if the aqueous dispersion is converted to an organic solvent and used. As an example of the phase inversion, there is a method in which a water-soluble organic solvent is added to the aqueous dispersion, water is distilled off, and the same operation is repeated to perform phase inversion into a desired organic solvent.

Among these metal oxide sols, silicon oxide sol can be easily surface-modified with a silane coupling agent. Since various organic functional groups can be introduced into the surface of the silicon oxide sol particles by this surface modification, a chemical bond can be formed between the silicon oxide sol and organic components such as a resin and a curing agent. As described above, when the metal oxide sol (C) and the organic component are bonded via a chemical bond, the coating film becomes stronger than when the metal oxide sol (C) is not bonded, and the stain resistance, stain removal property, and weather resistance are improved. I do. Examples of commercially available silicon oxide sols include Snowtex-O and Snowtex-N (trade names of Nissan Chemical Industries, Ltd.) as aqueous dispersions, and Snowtex MIBK-ST (Nissan Chemical) as organic solvent dispersions. (Trade name, manufactured by K.K.). One of these oxide sols may be used,
Two or more kinds may be used in combination. The metal oxide sol (C) component is used in an amount of 5 to 60% by weight, preferably 5 to 40% by weight, based on the total solid content of the paint. If the amount is less than 5% by weight in the solid content of the paint, the effect of adding the oxide sol is not sufficiently exhibited, and the stain resistance, stain removal property, and weather resistance are not improved. On the other hand, if it exceeds 60% by weight, the ratio of the metal oxide sol is too large, and disadvantages such as loss of flexibility of the coating film occur, which is not preferable.

In order to efficiently produce the coating composition of the present invention, the metal oxide sol (C) is dispersed and stabilized in a solvent for synthesizing the fluorocopolymer (A), and then the fluorocopolymer (C) is dispersed. A) is synthesized or a fluorinated copolymer (A)
Can be obtained by adding the metal oxide sol (C) with or without heating to stabilize the dispersion. Resin solution obtained by dispersing and stabilizing the obtained metal oxide sol (C) and curing agent (B)
Can be mixed to produce a coating composition. Also,
The coating composition of the present invention may contain a solvent, another organic resin, a reaction catalyst, a curing accelerator, if necessary, in addition to the fluorocopolymer (A), the curing agent (B), and the metal oxide sol (C). Agents, pigments,
Dyes, pigment dispersants, leveling agents, flow regulators, ultraviolet stabilizers, ultraviolet absorbers, radical scavengers, defoamers, gelling inhibitors, antioxidants and other additives can be used.

As the solvent, a solvent usually used for a coating material can be used as it is. Esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate; acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as toluene and xylene; propylene glycol Alcohols such as methyl ether; hydrocarbons such as hexane and heptane; mixed solvents thereof.

As the organic resin, for example, a (meth) acrylic resin which may contain styrene, a polyester resin, an alkyd resin, a melamine-formaldehyde resin, a polyisocyanate resin, an epoxy resin, a vinyl chloride resin ( For example, vinyl chloride-vinyl acetate copolymers), ketone resins, petroleum resins, chlorinated products of polyolefins such as polyethylene and polypropylene, inorganic resins such as silica sol and silicic acid, and the fluorine-containing copolymer (A ) Can be blended with one or more kinds of fluororesins other than the above (for example, a homopolymer of tetrafluoroethylene or chlorotrifluoroethylene or a copolymer of these with other monomers). It is not limited. Among these resins, a mixed system with an acrylic polymer having particularly excellent compatibility is preferable, and gives high gloss, high hardness, and good finished appearance to the obtained coating film.

Examples of the acrylic polymer include those conventionally used for paints. In particular, (i) a homopolymer or copolymer of an alkyl ester of (meth) acrylic acid having 1 to 10 carbon atoms, And (ii) a (meth) acrylate copolymer having a curable functional group at the side chain and / or main chain terminal can be preferably used. For example, a copolymer obtained by copolymerizing an acrylic monomer described in JP-A-4-279612 or a commercial product can be preferably used.

Examples of the curing accelerator include an organic tin compound, an acidic phosphate, a reaction product of an acidic phosphate with an amine, a saturated or unsaturated polycarboxylic acid or an acid anhydride thereof, an organic titanate compound, and an amine. Series compounds, lead octylate and the like. The curing accelerator is used as needed, and one kind may be used or two or more kinds may be used in combination. The compounding ratio of the curing accelerator is preferably about 1.0 × 10 ^{−6 to} 1.0 × 10 ⁻² parts by weight based on 100 parts by weight of the copolymer, and is preferably 5.0 × 10 ^{−5 to} 1.0 × 10. ^{About -3} parts by weight is more preferable.

Specific examples of the organotin compound include dibutyltin dilaurate, dibutyltin maleate, dioctyltin malate, dibutyltin diacetate, dibutyltin phthalate, tin octylate, tin naphthenate, dibutyltin methoxide, and the like.

The acidic phosphoric acid ester is not particularly limited as long as it is a monoalkyl or dialkyl ester of orthophosphoric acid. Preferably, the alkyl group is a methyl group,
1 selected from ethyl, isopropyl, and butyl groups
Mono- or di-alkyl orthophosphates of one or more species. Examples of the organic titanate compound include tetrabutyl titanate,
Examples include titanates such as tetraisopropyl titanate and triethanolamine titanate.

Further, specific examples of the amine compound include, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine,
Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N -Methylmorpholine, 1,8-diazabicyclo (5.4.
0) amine compounds such as undecene-7 (DBU);
Further examples thereof include salts of such carboxylic acids, low molecular weight polyamide resins obtained from excess polyamine and polybasic acid, and reaction products of excess polyamine and epoxy compound.

Specific examples of the pigment include inorganic pigments such as titanium oxide, calcium carbonate and carbon black; organic pigments such as phthalocyanine, quinacridone and azo; luminous agents such as glass flakes and mica flakes and fillers. But not limited to these. The amount of pigment added is usually up to about 200% by weight, based on the copolymer.

[0036] The form of the paint can be appropriately selected as required, such as a water-dispersible paint, a non-hydroacid paint, a powder paint, and an electrodeposition paint, in addition to the solvent paint.

The coating composition of the present invention is excellent in solvent solubility, and the formed coating film has a high degree of weather resistance, stain resistance, chemical resistance, optical properties, mechanical properties, and Adhesion,
It is excellent in heat-resistant yellowing, etc., as well as ordinary curing compositions, for building materials, interior materials and other indoor or outdoor use, for automotive parts such as bodies, bumpers, spoilers, mirrors, wheels, etc. For painting, and for exterior or interior of aircraft, ships, trains, etc., the material of the object to be coated is not particularly limited, for example, metal, concrete, plastic, wood, etc. directly or wash primer, rust preventive paint, epoxy It can be applied over an undercoat such as paint, acrylic resin paint, or polyester resin paint. further,
It can also be used as a sealing agent and a film forming agent. Furthermore, it can be used not only for paints but also for inks, adhesives, molded products and the like.

[0038]

The present invention will be described in more detail with reference to the following examples. In addition, the analysis of the resin, the preparation of the test plate, and the evaluation of the coating film performance were performed as follows. (1) Analysis of resin The number average molecular weight was measured for the molecular weight by the GPC method. The glass transition temperature was measured by a DSC method. (2) Preparation of test plate On a SUS-304 or SPV-HL plate, a baking type epoxy resin paint (Epico Primer No. 1000 BF)
2: Nippon Oil & Fats Co., Ltd.) was applied to a dry film thickness of 20 μm and baked at 160 ° C. for 20 minutes. Further, a urethane resin paint (High Urethane No. 5000 (white) 51HA, trade name of Nippon Oil & Fats Co., Ltd.) was applied thereon so that the dry film thickness became 25 μm.
Forcibly dried at 0 ° C. for 30 minutes. What was left overnight was used as a test plate.

(3) Evaluation method of coating film (a) Gloss at 60 °: JIS Z8741, 60-degree specular gloss (Gs60 °) was determined. (B) Sharpness: Evaluated by visual observation according to the following criteria. ；: The fluorescent light is clearly seen when the fluorescent light is transferred to the coating film. Δ: When a fluorescent lamp is transferred to the coating film, the periphery (outline) of the fluorescent lamp is slightly blurred. ×: When a fluorescent lamp is transferred to the coating film, the periphery (outline) of the fluorescent lamp is significantly blurred. (C) Pencil hardness: determined in accordance with JIS K5400 8.4.2. (D) Adhesion: determined in accordance with JIS K5400 8.5.1. (E) Xylene rubbing resistance: The surface of the test piece was rubbed 100 times with a flannel impregnated with xylene, and the change in the surface state was visually observed, and the xylene rubbing resistance was evaluated according to the following criteria. ；: There is no change in the gloss of the test specimen as compared to the original test specimen. Δ: There is a slight change in the gloss of the test piece as compared to the original test piece. ×: The gloss of the test piece is remarkably changed compared to the original test piece. (F) Oil resistance marker stain: A line is drawn on the coating film of the test piece with an oily marker, and after heating at 80 ° C. for 5 hours, After wiping the line with a flannel impregnated with xylene, a change in the surface state was visually observed, and the oily marker contamination was evaluated according to the following criteria. ；: The line of the oily marker on the test piece was completely wiped off, and no trace was left. Δ: Trace of oily marker on test piece slightly left. ×: Marks of the oily marker on the test piece clearly remain. (G) Outdoor stain resistance: After exposing the coated plate to the outdoors for one month, the L value after exposure was measured using an SM color computer SM-4-MCH (trade name, manufactured by Suga Test Instruments Co., Ltd.), and the exposure was performed. The value obtained by subtracting the pre-exposure L value from the subsequent L value was determined as ΔL and evaluated. (H) Accelerated weathering test: JIS D 0205 5.4
Of a 60 ° gloss by a test using a sunshine carbon arc lamp type weather resistance tester (JISK-5)
400 (1990) 7.6). (I) Acid resistance: An acid resistance test was performed according to JIS K5400 8.22, and the acid resistance was evaluated according to the following criteria. ；: There is no change or discoloration in the gloss of the test specimen as compared to the original test specimen. Δ: The test specimen has a slight change or discoloration compared to the original test specimen. X: The gloss and the color tone of the test piece are significantly different from those of the original test piece. (J) Alkali resistance: An alkali resistance test was performed according to JIS K5400 8.21, and the alkali resistance was evaluated according to the following criteria. ；: There is no change or discoloration in the gloss of the test specimen as compared to the original test specimen. Δ: The test specimen has a slight change or discoloration compared to the original test specimen. X: The gloss and the color tone of the test piece are significantly different from those of the original test piece. (K) Moisture resistance: After exposure for 240 hours at 40 ± 1 ° C. at a relative humidity of 95% or more, the surface state 2 hours after removal was visually observed and evaluated according to the following criteria. ；: There is no change in the gloss and the surface condition of the test piece as compared with the original test piece. Δ: There is a slight change in gloss and blistering of the test piece as compared to the original test piece. ×: The test specimen has a marked change in gloss and blisters as compared to the original test specimen.

Production Example 1 (Production of Silicon Oxide Sol Treated with Silane Coupling Agent) A Snowtex MIBK-ST (silicon oxide) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux tube equipped with a Dean-Stark trap, and a dropping funnel. Organic solvent dispersion of sol, average particle size: 30 nm, Nissan Chemical Co., Ltd. product name) 1
80 parts by weight and 40 parts by weight of A-163 (silane coupling agent, trade name, manufactured by Nippon Unicar Co., Ltd.)
By heating and holding at 8 ° C. for 8 hours, 1020 parts by weight of a silicon oxide sol treated with a silane coupling agent was obtained. The solids content is 45% by weight.

Production Example 2 (Production of Fluorine-Containing Copolymer Resin Solution) According to the method for producing and analyzing a fluorine-containing copolymer described in JP-A-4-279612, monomers are appropriately selected, and Fluorine-containing copolymer F-1 containing the structural units (1) to (5) and (5a) of the present invention in a predetermined ratio
~ F-9 were synthesized. Table 1 shows the monomers used for synthesizing each resin, the content ratio of each structural unit in the obtained fluorocopolymer, and the properties of the obtained resin.
Next, each of the fluorocopolymer resin solutions F-1 to F-9 was diluted with cyclohexanone, and the resin solid content was uniformly 5%.
FS-1 to FS-9 adjusted to 0% by weight were obtained and used in the following experiments.

Test Example 1 (Mixing test of fluorine-containing resin solution and silica sol) The FS-1 to FS-9 obtained in Production Example 2 and the silane-treated silicon oxide sol obtained in Production Example 1 were weighed. 8 by ratio
/ 1 (4/1 with respect to the resin itself) to obtain a silica sol mixed resin solution. The mixed resin solution was flow-coated on a glass plate and heated at 80 ° C. for 30 minutes to obtain a dried film. From the observation of the obtained dried film, the compatibility, transparency and heat-resistant yellowing of both components were visually evaluated. The results are shown in Table 1.

[0043]

[Table 1]

Example 1 (Manufacture of clear paint) Using the FS-1 obtained in Production Example 2, raw materials were mixed and stirred according to the formulation shown in Table 2 to obtain a clear paint. Solvent paint # 100 (trade name, manufactured by Esso Corporation)
No./cyclohexanone=50/50 (weight ratio) mixed solvent with Ford Cup No. Has a viscosity of 1 at 20 ° C.
Dilute to 5 seconds. This diluted paint was applied on the test plate with an air atomizing spray (atomizing pressure 5 kg / cm ² ) so that the dry film pressure became 30 μm.
After being forcibly dried for 0 minutes and left at room temperature for 3 days, the coating film performance was evaluated. Table 2 shows the composition of the paint and the properties of the paint.
Table 3 shows the evaluation results of the coating films.

Examples 2 to 9 (Manufacture of clear paint) Hereinafter, the same procedures as in the case of FS-1 except that FS-1 in Example 1 was replaced with FS-2 to FS-9, respectively. 2 to 9 clear paints were produced and coated in the same manner to obtain coating films. Table 2 shows the formulation of paint production and the properties of each paint for each of the above examples, and Table 3 shows the evaluation results of the coating films.

[0046]

[Table 2]

Notes in Table 2 (* 1) Solvesso # 100 / cyclohexanone = 50
/ 50 (weight ratio) (* 2) Acrylic copolymer, trade name manufactured by Mitsubishi Rayon Co., Ltd. (* 3) Trimethylolpropane adduct of isophorone diisocyanate, trade name manufactured by Takeda Pharmaceutical Co., Ltd. (* 4) Production Example 1 (* 5) UV absorber, trade name of Ciba-Geigy (* 6) Hindered amine antioxidant, trade name of Ciba-Geigy (* 7) Surface conditioner, BYK Chemie Product name (* 8) Defoamer, trade name of Big Chemie (* 9) Defoamer, trade name of Big Chemie

[0048]

[Table 3]

Example 10 (Production of an enamel paint) Using the FS-1 obtained in Production Example 2, the raw material A was mixed in the composition shown in Table 4, and then mixed with a motor mill (manufactured by Eiger Japan) at 3000 rpm. For 40 minutes to obtain a pigment-dispersed resin solution. Next, the raw material B was mixed with the pigment-dispersed resin solution in the composition shown in Table 4 to obtain an enamel paint. The obtained paint was dissolved in Solvesso # 100 / cyclohexanone = 50.
/ 50 (weight ratio) mixed solvent with Ford Cup No.
4 was diluted so that the viscosity at 20 ° C. was 15 seconds. This diluted paint is sprayed with an air atomizer (atomizing pressure 5kg /
After coating on the test plate so as to have a dry film thickness of 30 μm in cm ² ), it was forcibly dried at 80 ° C. for 30 minutes to obtain a test plate for evaluation. After leaving the obtained test plate at room temperature for 3 days, the coating film performance was evaluated. Table 4 shows the composition of the paint and the properties of the paint, and Table 5 shows the evaluation results of the paint film.

Examples 11 to 18 (Production of enamel paints) Examples 11 to 18 were carried out in exactly the same manner as in the case of FS-1, except that FS-1 was replaced with FS-2 to 9, respectively.
Was manufactured and further painted to obtain a test plate for evaluation. Table 4 shows the coating composition and coating properties, and Table 5 shows the evaluation results of the coating film.

[0051]

[Table 4]

[0052]

[Table 5]

Comparative Production Example (Production of Fluorine-Containing Copolymer Resin Solution) According to the production method and analysis method of a fluorine-containing copolymer described in JP-A-4-279612, monomers are appropriately selected, and Copolymers FH-1 to FH-3 lacking a part of the structural units (1) to (5) according to the invention were synthesized. Table 6 shows the monomers used for synthesizing each resin, the content ratio of each structural unit in the resin of the obtained fluorinated copolymer, and the properties of the obtained resin. Next, each of the fluorinated copolymer resin solutions FH-1 to FH-3 was diluted with cyclohexanone to adjust the resin solid content to 50% by weight uniformly.
S-1 to FHS-3 were obtained. Test Example 1 using this
Table 6 shows the results of a mixing test with silica sol by the method shown in Table 1.

[0054]

[Table 6]

Comparative Examples 1 to 8 Fluorine-containing copolymer resin solution FHS-1 obtained in Comparative Production Example
Using FHS-4 to FS-6 and FS-4 to FS-6 obtained in Production Example 2, a clear paint was prepared in the same manner as in Examples 1 and 10.
An enamel paint was obtained. Further, a test plate for evaluation was obtained in the same manner as in the examples. Tables 7 and 8 show the composition and characteristics of the paint, and Tables 9 and 10 show the evaluation results of the coating film.

[0056]

[Table 7]

[0057]

[Table 8]

[0058]

[Table 9]

[0059]

[Table 10]

Comparative Examples 1, 2, 3, and 5, 6, and 7 used a fluorine-containing resin lacking any of the structural units of the present invention, so that clear paint and enamel paint were inferior in sharpness.
In addition, the stain resistance is reduced, which is not preferable. Comparative Examples 4 and 8 are the cases of the coating compositions containing no metal oxide sol of the present invention. Both the clear coating and the enamel coating have reduced coating film hardness, and have reduced stain removal properties, stain resistance, and weather resistance. And the result is not preferable.

[0061]

Industrial Applicability The coating composition of the present invention is a coating composition containing a metal oxide sol component, and is excellent in weather resistance, stain resistance and stain removal properties, and has good appearance and water resistance. It has excellent features such as providing a coating film having chemical resistance and high environmental preservation and stability.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 175/04 C09D 175/04 // C08G 18/62 C08G 18/62

Claims (3)

[Claims] 1. A fluoro compound represented by the formula (I): —CF ₂ —CFX— (I) wherein X is a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group. Olefin structural unit (1), (2), formula (II): (Wherein, R is an alkyl group having 1 to 8 carbon atoms) represented by the formula (2):
(3) a structural unit (3) based on a monomer having a chemical curing reactive group, (4) a structural unit (4) based on a monomer having an ester group in a side chain, and (5) other structural units. Contains a structural unit (5) based on a polymerizable monomer, and has a number average molecular weight of 1
A coating composition comprising a metal oxide sol (C) in a curable composition containing a fluorinated copolymer (A) having a molecular weight of 000 to 500,000 and a curing agent (B). 2. The coating composition according to claim 1, wherein the metal oxide sol is a dispersion of a silicon oxide sol. 3. The coating composition according to claim 1, wherein the dispersion of the silicon oxide sol, which is a metal oxide sol, is surface-treated with a silane coupling agent.