JP2002338872A - Fluororubber coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluororubber coating composition which can directly form a rubber coating layer on a metal surface without using a primer, has an improved resistance to an antifreezing fluid, and gives a coating film improved in permanent set under high-temperature long-time compression. SOLUTION: This coating composition contains a liquid carrier, a fluororubber dissolved or dispersed in the liquid carrier, a polyol-based vulcanizing agent, and an amino-group-containing metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluororubber coating composition, and more particularly, to a fluororubber coating composition comprising a fluorocopolymer, a polyol vulcanizing agent, an amino group-containing metal compound and a liquid carrier. About things.

[0002]

2. Description of the Related Art Fluororubber is molded or coated by utilizing its excellent heat resistance, oil resistance, solvent resistance, and chemical resistance, and is, for example, woven fabric, fiber, metal, plastic, rubber, and various other substrates. It has been widely used as an industrial material by being applied or impregnated, especially in the field of engine gaskets, a fluororubber-coated metal gasket has begun to be used as an alternative to asbestos material,
Further development is expected in the future.

[0003] Coating materials for metal gaskets are not affected by gaseous fluids under high temperature and high pressure conditions.
It must maintain sufficient elasticity and flexibility against pressure, maintain the required tightening pressure so as not to cause leakage from the joint surface, and satisfy antifreeze liquid resistance and engine oil resistance Must. As a fluororubber paint used for metal gaskets, a polyol vulcanization-based paint that generally has excellent sealing properties is used. In this case, it is necessary to use a primer for adhesion to the base material, thus forming a primer layer. And the formation of a fluororubber layer. Looking at the settability of the coating film during compression, in the case of polyol vulcanization, the double bond is not involved in the crosslinking during vulcanization. It tends to be easy.

On the other hand, when a polyamine vulcanization-based coating material in which a primer component can be internally added to a curing agent is used, the coating process can be simplified, but the compression set, which is the most important physical property as a sealing material, is reduced by polyol addition. Since it is larger than the sulfur-based paint, it is necessary to increase the tightening pressure so as not to cause leakage from the joint surface.

[0005]

An object of the present invention is to provide a material capable of forming a rubber coating layer directly on a metal surface without using a primer. An object of the present invention is to provide a fluororubber coating composition having improved settling of a coating film.

[0006]

According to the present invention, the above object comprises a liquid carrier, a fluororubber dissolved or dispersed in the liquid carrier, a polyol vulcanizing agent, and an amino group-containing metal compound. The problem is solved by a fluororubber coating composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Each component contained in the composition of the present invention will be specifically described below. Fluorine rubber Fluorine rubber, the main chain -CH ₂ - is preferably a fluorine-containing copolymer comprising a repeating unit represented by. A typical example thereof is an elastic fluorinated copolymer containing vinylidene fluoride, specifically, a copolymer having a main chain containing a repeating unit having the following structure. : -CF ₂ -CH _2- , -CH
₂ -CH ₂ -, and -CH ₂ -CH (CH ₃₎ - at least one repeating unit selected from, and, -CF ₂ -CF (CF _{3)
-, - CF 2 -CF 2 -} , - CF 2 -CFCl -, - CF 2 -CF (CF 2
H) - and -CF ₂ -CF (ORf) - (wherein, Rf is 1 to 9 carbon atoms
Is a fluoroalkyl group. At least one type of repeating unit selected from).

More specifically, a copolymer of vinylidene fluoride and hexafluoropropylene, a copolymer of vinylidene fluoride and tetrafluoroethylene and hexafluoropropylene, a copolymer of ethylene and hexafluoropropylene, and a copolymer of tetrafluoroethylene And a propylene copolymer. Such elastic fluorinated copolymers include "Daiel" (trademark) (Daikin Industries, Ltd.), "Viton Frome" (trademark) (EI DuPont), "Afras" (trademark) (Asahi Glass) It is marketed under the trade name such as Co., Ltd.). The molecular weight of fluororubber is 50
It is preferably from 00 to 200,000. In addition, a vinylidene difluoride-based copolymer is preferable from the viewpoint of crosslinkability.

Polyol vulcanizing agent As the vulcanizing agent used in the fluororubber composition, a vulcanizing agent for a polyol vulcanized fluororubber which is usually used can be used. Examples of preferred vulcanizing agents are shown below. In the present invention, the polyol-based vulcanizing agent includes a compound having at least two hydroxyl groups, particularly a phenolic hydroxyl group in a molecule, and a high molecular compound having vulcanization performance.

For example,

Embedded image Phenolic compounds, such as

[0011]

Embedded image (Where Y is a hydrogen atom, a halogen atom, R ⁵ , CH ₂ OR
⁵ or OR ⁵ , Z is —CH ₂ — or —CH ₂ OCH
₂ -, R ⁵ is an alkyl group having 1 to 4 carbon atoms, n represents 0 to 100
Represents an integer. )) And / or their salts with basic compounds.

Preferred basic compounds include the following ammonium salts or tertiary amines. Ammonium salts: trimethylbenzylammonium, triethylbenzylammonium, dimethyldecylbenzylammonium, triethylbenzylammonium, myristylbenzyldimethylammonium, dodecyltrimethylammonium, dimethyltetradecylbenzylammonium, trimethyltetradecylammonium, coconut trimethylammonium, stearyltrimethylammonium, di Stearyl dimethyl ammonium,
Tetrabutylammonium, 1,4-phenylenedimethylenebistrimethylammonium, 1,4-phenylenedimethylenebistriethylammonium, ethylenebistriethylammonium and the like.

Tertiary amine: 1,8-diaza-bicyclo [5.4.
0] -Undecene-7, 8-methyl-1,8-diaza-bicyclo [5.4.
0] -undecene-7, 8-propyl-1,8-diaza-bicyclo [5.
4.0] -undecene-7,8-dodecyl-1,8-diaza-bicyclo
[5.4.0] -undecene-7, 8-eicosyl-1,8-diaza-bicyclo [5.4.0] -undecene-7, 8-tetracosyl-1,8-diaza-bicyclo [5.4.0] -undecene- 7,8-benzyl-1,8-diaza-bicyclo [5.4.0] -undecene-7,8-phenethyl-1,
8-diaza-bicyclo [5.4.0] -undecene-7, 8- (3-phenylpropyl) -1,8-diaza-bicyclo [5.4.0] -undecene-
7, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, triisobutylamine, methyldiethylamine, dimethylethylamine,
Dimethyl-n-propylamine, dimethyl-n-butylamine, dimethylisobutylamine, dimethylisopropylamine, dimethyl-sec-butylamine, dimethyl-tert-
Butylamine, triallylamine, diallylmethylamine, allyldimethylamine, benzyldimethylamine,
Benzyldiethylamine, N-allylpiperidine, N-ethylpiperidine, N-butylpiperidine, N-methylpyrrolidine, N-cyclohexylpyrrolidine, Nn-butylpyrrolidine, N-ethylpyrrolidine, N-benzylpyrrolidine, 2,4,
6-trimethylpyridine and the like.

Among them, phenol derivatives such as bisphenol A, bisphenol AF, hydroquinone and / or
Or a salt thereof; a polyhydroxy compound having two or more enol-type hydroxyl groups in the molecule, such as a phenol resin, and / or a salt thereof; a formula: Rf (CH ₂ OH) ₂ (where Rf is
Perfluoroalkyl polyether group. And the like.

In addition, any commercially available polyol vulcanizing agent for fluororubber can be used.
When the medium is an organic solvent, it is preferable to use a solvent which can be dissolved or dispersed in the organic solvent when the medium is water, and when the medium is water.

Amino Group-Containing Metal Compound The amino group-containing metal compound used in the present invention acts on an interface between an organic material, fluororubber, and an inorganic material, and forms a strong bridge between the two materials by a chemical bond or a physical bond. A compound which functions as a vulcanizing agent for fluororubber and can be used safely for liquid carriers.

In the present invention, preferably, Si, Al, Ti
And at least one metal selected from the group consisting of Zr and Zr. Preferred amino group-containing metal compounds include amino group-containing silane compounds and their monomers and oligomers, amino group-containing aluminum compounds and these monomers and oligomers, and amino group-containing titanium compounds and these monomers and oligomers. Zirconium compounds and their monomers and oligomers.

Preferred amino group-containing silane compounds include N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrisilane. Methoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N-β-aminoethyl-γ-
Aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, β-aminoethyl-β-
Monomer or oligomer such as aminoethyl-γ-aminopropyltrimethoxysilane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane.

The compounding of the polyol vulcanizing agent and the amino group-containing metal compound is, for example, 0.1 to 20 parts by weight of the polyol vulcanizing agent and 0.5 to 30 parts by weight of the amino group-containing metal compound per 100 parts by weight of fluororubber. A range of parts by weight is preferred,
The composition ratio of the vulcanizing agent to the amino group-containing metal compound is 1 / 1.2.
It is preferably selected from the range of 1/30 (weight). If the amount of the polyol vulcanizing agent is small, the LLC (long life coolant) resistance and the like may become a problem, and if the amount of the amino group-containing metal compound is small, the adhesion may be deteriorated. It is preferable that the total of at least the polyol vulcanizing agent and the amino group-containing metal compound is 5 parts by weight or more. Preferably, 0.5 to 5 parts by weight of the polyol vulcanizing agent and 6 to 15 parts by weight of the amino group-containing metal compound can be selected.

Vulcanization Aid A vulcanization aid may be used to promote vulcanization. As the vulcanizing aid, the following compounds can be used: trimethylbenzylammonium chloride, triethylbenzylammonium chloride, dimethyldecylbenzylammonium chloride, triethylbenzylammonium chloride, myristylbenzyldimethylammonium chloride, dodecyltrimethylammonium chloride, Dimethyltetradecylbenzylammonium chloride, trimethyltetradecylammonium chloride, coconut trimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, tetrabutylammonium hydroxide,
Alkyl and aralkyl quaternary ammonium salts such as 1,4-phenylenedimethylenebistrimethylammonium dichloride, 1,4-phenylenedimethylenebistriethylammonium dichloride, ethylenebistriethylammonium dibromide;

8-methyl-1,8-diaza-bicyclo [5.4.0] -7-
Undecenium chloride, 8-methyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium iodide, 8-methyl
-1,8-diaza-bicyclo [5.4.0] -7-undecenium hydroxide, 8-methyl-1,8-diaza-bicyclo [5.4.0]-
7-undecenium-methyl sulfate, 8-methyl-1,8-
Diaza-bicyclo [5.4.0] -7-undecenium bromide, 8-propyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium bromide, 8-dodecyl-1,8-diaza- Bicyclo
[5.4.0] -7-undecenium chloride, 8-dodecyl-1,8
-Diaza-bicyclo [5.4.0] -7-undecenium hydroxide, 8-eicosyl-1,8-diaza-bicyclo [5.4.0]-
7-undecenium chloride, 8-tetracosyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium chloride, 8
-Benzyl-1,8-diaza-bicyclo [5.4.0] -7-undecenium chloride, 8-benzyl-1,8-diaza-bicyclo [5.
4.0] -7-Undecenium hydroxide, 8-phenethyl-1,8-diaza-bicyclo [5.4.0] -7-Undecenium chloride, 8- (3-phenylpropyl) -1,8-diaza- Quaternary 1,8- such as bicyclo [5.4.0] -7-undecenium chloride
Quaternary ammonium salts such as diaza-bicyclo [5.4.0] -7-undecenium salt;

Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, triisobutylamine, methyldiethylamine, dimethylethylamine, dimethyln-propylamine, dimethyln-butylamine, dimethylisobutylamine, dimethylisopropylamine, dimethyl-sec -Butylamine, dimethyl-tert
-Butylamine, triallylamine, diallylmethylamine, allyldimethylamine, benzyldimethylamine, benzyldiethylamine, N-allylpiperidine, N-
Ethyl piperidine, N-butylpiperidine, N-methylpyrrolidine, N-cyclohexylpyrrolidine, Nn-butylpyrrolidine, N-ethylpyrrolidine, N-benzylpyrrolidine,
Tertiary amines such as 2,4,6-trimethylpyridine;

Benzyltriphenylphosphonium, methyltriphenylphosphonium, 2,4-dichlorobenzyltriphenylphosphonium, 4-methylbenzyltriphenylphosphonium, 4-chlorobenzyltriphenylphosphonium, m-trifluoromethylbenzyltriphenylphosphonium, 2 -Cyanobenzyltriphenylphosphonium, α-carbethoxybenzyltriphenylphosphonium, diphenylmethyltriphenylphosphonium, 1-
Naphthylmethyltriphenylphosphonium, carbethoxymethyltriphenylphosphonium, methoxymethyltriphenylphosphonium, allyloxymethyltriphenylphosphonium, 1-carbethoxyethyltriphenylphosphonium, isobutyltriphenylphosphonium, 4-
Cyanobutyltriphenylphosphonium, 2-pentyltriphenylphosphonium, allyltriphenylphosphonium, tetraphenylphosphonium, methyltrioctylphosphonium, benzyltrioctylphosphonium,
Methoxyethoxyethyltrioctylphosphonium, butyltrioctylphosphonium, m-trifluoromethylbenzyltrioctylphosphonium, 2,2,3,3-tetrafluoropropyltrioctylphosphonium, 2,2,3,3,4,
Quaternary phosphonium salts such as 4,5,5-octafluoropentyltrioctylphosphonium, tetraoctylphosphonium, and tetrabutylphosphonium.

Although some physical properties can be ensured without using a vulcanization aid, the addition of a vulcanization aid improves the physical properties. The amount of the vulcanization aid used is 100
0 to 10 parts by weight, preferably 0.1 to 10 parts by weight based on parts by weight
Parts by weight, more preferably in the range of 0.3 to 5 parts by weight, are employed.

Adhesion Aid An adhesion aid may be added in order to make the composition of the present invention more firmly adhere to the substrate or to increase the affinity with the substrate. For example, when the substrate is a metal or glass, a silane compound, a zirconium compound, a titanium compound, an aluminum compound, or the like can be used as an adhesion aid. When using an adhesion aid, the amount used is 0.5 to 100 parts by weight of the fluororubber.
30 parts by weight.

Stabilizer A stabilizer can be added for the purpose of improving the storage stability of the fluororubber coating composition. As a stabilizer,
An organic acid having 1 to 12 carbon atoms, preferably an organic acid having 1 to 4 carbon atoms is used. Examples of preferred organic acids are monocarboxylic acids such as formic acid, acetic acid and propionic acid, and dicarboxylic acids such as oxalic acid, malonic acid and succinic acid.

Polyamine Vulcanizing Agent For the purpose of improving the mechanical strength, a polyamine vulcanizing agent can be added to the composition of the present invention in addition to the polyol vulcanizing agent. Examples of the polyamine vulcanizing agent include triethylenetetramine, tetraethylenepentamine, ethylenediamine, triethylenediamine, ethanolamine, 3,9-bis (3-aminopropyl) -2,4,8,1.
Aliphatic polyamines such as 0-tetraoxa-2-spiro [5,5] -undecane and salts thereof, aromatic amines such as diaminodiphenylmethane, xylylenediamine, phenylenediamine, diaminodiphenylsulfone and diaminodiphenylether and salts thereof, and modified polyamines ,
And polyamidoamine.

Liquid Carrier As used herein, a liquid carrier is a liquid capable of dissolving or dispersing other components of the composition of the present invention. Examples of the organic solvent include ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as butyl acetate and isopentyl acetate; ethers such as diethylene glycol dimethyl ether; hydrocarbons such as toluene and xylene; N, N-dimethylacetamide; -Methyl-2
Amides such as -pyrrolidone; The organic solvent is
It is used in an amount of 40 to 90% by weight based on the total weight of the coating composition.

When water is used, a dispersant is used to disperse the fluororubber or fluororesin in water. Examples of the dispersant include anionic surfactants such as lauryl sulfate, perfluoroalkyl carboxylate, and ω-hydroperfluoroalkyl carboxylate; and nonionic surfactants such as polyethylene glycol derivatives and polyethylene glycol / polypropylene glycol derivatives. And resin-based dispersants such as alkyl polyethylene glycol ether, alkyl phenyl polyethylene glycol ether, alkyl polyethylene glycol ester, ethylene glycol / propylene glycol copolymer, polyethylene glycol alkyl ester, and polycarboxylate.

Water is used in an amount of 30 to 90% by weight based on the total weight of the coating composition. The dispersant is used in an amount of 0.1 to 10% by weight based on the total weight of the composition.

The fluororubber coating composition of the present invention may contain, in addition to the above-mentioned components, various additives usually added to the fluororubber coating composition, for example, a filler, a colorant, and an acid acceptor. .

Examples of the filler include carbon black, molybdenum disulfide, white carbon, calcium carbonate, barium sulfate, talc and calcium silicate.
Examples of the coloring agent include an inorganic pigment and a composite oxide pigment.

Examples of the acid acceptor include double salts such as magnesium oxide, lead oxide, zinc oxide, lead carbonate, zinc carbonate and hydrotalcite. Usually, the acid acceptor is used in an amount of 1 to 100 parts by weight of the fluorine-containing copolymer depending on the activity.
40 parts by weight can be blended.

The fluororubber coating composition of the present invention can be prepared by the same method as that for preparing a conventional fluororubber coating composition. Specifically, the following method can be adopted.

When the liquid carrier is an organic solvent, the fluororubber base polymer obtained by emulsion polymerization is coagulated.
By drying, a raw fluororubber is obtained. A filler, an acid acceptor, and a colorant, which are optional components, are kneaded with an open roll or a kneader to obtain a compound. This compound is dissolved or dispersed in an organic solvent, and a stabilizer is added as necessary to obtain a liquid A. On the other hand, a polyol vulcanizing agent and, if necessary, a vulcanizing aid are dissolved or dispersed in an organic solvent to obtain a liquid B. In the case of the two-pack type, the liquid A and the liquid B are mixed and prepared from the beginning. In addition, an amino group-containing metal compound and, if necessary, an adhesion aid and / or a polyamine vulcanizing agent as a liquid C are dissolved or dispersed in an organic solvent.

When the liquid carrier is water, a fluororubber concentrate is prepared by dispersing fluororubber in water in the presence of a dispersant. Fluoro rubber latex may be used as it is. A filler, an acid acceptor, and a colorant, which are optional components, are also pre-mill-dispersed using a dispersant. These liquids are mixed, a stabilizer is added if necessary, and further adjusted to an appropriate concentration and viscosity with water to obtain a liquid A. On the other hand, an aqueous solution of a polyol vulcanizing agent (when the vulcanizing agent is water-soluble) or an aqueous dispersion using a dispersing agent (when the vulcanizing agent is water-insoluble)
Is prepared, and if necessary, a vulcanization aid is dissolved or dispersed in water to obtain a liquid B. In the case of the two-pack type, the liquid A and the liquid B are mixed and prepared from the beginning.

As the liquid C, an aqueous solution containing an amino group-containing metal compound and, if necessary, an adhesion aid and / or a polyamine vulcanizing agent (when the vulcanizing agent is water-soluble), or an aqueous dispersion using a dispersing agent. A liquid (when the vulcanizing agent is insoluble in water) is used.

Fluororesin A fluorine resin which can be melt-processed can be added to the coating composition of the present invention. The meltable fluororesin is a fluororesin having a melting point of 320 ° C. or lower, and specific examples thereof include the following fluororesins. Tetrafluoroethylene / hexafluoropropylene copolymer (FE
P), tetrafluoroethylene / perfluoroalkyl vinyl ether (PFVE) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer (EPA),
Tetrafluoroethylene / chlorotrifluoroethylene copolymer (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVdF), tetrafluoroethylene having a molecular weight of 300,000 or less (LMW-PTFE), and the like.

Here, examples of the PFVE include compounds represented by the following formulas (1) to (5).

Formula (1): CF ₂ = CFO (CF ₂ ) _n CF ₃ (n = 1 to 9) Formula (2): CF ₂ = CFO (CF ₂ CF ₂ CF ₂ O) _m −CF ₂ CF ₂ CF ₃ (1 ≦ m ≦ 5) Formula (3): CF ₂ = CFO [CF ₂ CF (CF ₃ )] _m −CF ₂ CF ₂ CF ₃ (1 ≦ m ≦ 5) Formula (4): CF ₂ = CFO [CF ₂ CF (CF ₃ )] _m -CF ₂ CF ₂ CH ₂ I (1 ≦ m ≦ 5) Equation (5): CF ₂ = CFOCFOCH ₂ (CF ₂ ) _k X (k = 1 to 12, X = H, F or Cl)

Of these fluororesins, FEP, P
FA or EPA is preferred in terms of non-adhesion and surface smoothness. These fluororesins can be added to the liquid A as an aqueous dispersion using a dispersion obtained by emulsion polymerization using a medium such as water and a dispersant, or as an organosol after phase inversion to an organic solvent.

When a fluororesin is used, the weight ratio of the fluororubber to the fluororesin (fluororubber: fluororesin) is usually 95: 5 to 20:80, preferably 90:10 to 3
0:70. If the proportion of the fluororubber exceeds the above upper limit, the effect of adding the fluororesin (non-adhesiveness, abrasion resistance, etc.) cannot be obtained, and if it is less than the above lower limit, the elasticity of the fluororubber is only lost. In addition, defects such as cracks occur in the coating.

The coating composition of the present invention can be applied to a substrate by a usual coating method such as brush coating, spray coating, dip coating, flow coating, dispenser coating, screen coating, etc., and is sufficiently dried. When subsequently heated and fired, a film is formed.

Examples of the article substrate (object to be coated) coated with the coating composition of the present invention include metals such as iron, stainless steel, copper, aluminum, and brass; glass plates, woven and non-woven fabrics of glass fibers, and the like. Glass products; general-purpose and heat-resistant resin molded products and coatings such as polypropylene, polyoxymethylene, polyimide, polyamideimide, polysulfone, polyethersulfone, and polyetheretherketone; general-purpose rubbers such as SBR, butyl rubber, NBR, and EPDM Moldings and coatings of heat-resistant rubbers such as silicone rubber and fluororubber; woven and non-woven fabrics of natural and synthetic fibers; and the like. Excellent in nature.

An example (coating of a coating composition) of the film forming method of the present invention will be described. First, it is preferable that the surface of the object to be coated is sufficiently degreased and washed before applying the composition. The fluororubber coating composition is applied to the object by spray coating, flow coating, dispenser coating, screen coating, etc.
In order to evaporate the medium, it is sufficiently dried in an atmosphere at about 100 ° C. Thereafter, for example, at 150 to 250 ° C for 0.5 to
Bake for 24 hours. Thereby, the fluororubber in the composition is sufficiently vulcanized, and the reaction gas and water vapor are expelled out of the system.

The coating formed from the composition of the present invention has excellent antifreeze resistance and improved surface settability during long-term compression at high temperatures, and is therefore suitable for metal gaskets. In addition, by forming a film on the other substrate, it can be used in fields where heat resistance, solvent resistance, lubricity, and non-adhesiveness are required. Specific applications include sheets and belts; -Rings, diaphragms, chemical resistant tubes, fuel hoses,
Valve seals, gaskets for chemical plants, engine gaskets; OA for copiers, printers, facsimile machines, etc.
Rolls for equipment (for example, fixing rolls, pressure rolls) and transport belts are included.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Example 1 Preparation of main agent: First, 20 parts by weight of MT carbon black and 100 parts by weight of fluorocarbon rubber (Daiel G-801 manufactured by Daikin Industries, Ltd.) and an acid acceptor (hydrotalcite DHT-
4A. 5 parts by weight of Kyowa Chemical Industry Co., Ltd.) were kneaded with an open roll to obtain a compound. This compound is mixed with 400 parts by weight of butyl acetate and 40 parts of methyl isobutyl ketone.
It was dissolved in 0 parts by weight of the mixed solvent.

On the other hand, 2 parts by weight of bisphenol AF as a polyol vulcanizing agent and DBU-b (8-
Benzyl-1,8-diazabicyclo [5.4.0] -7-
0.5 parts by weight of undecenium chloride were dissolved in 17.5 parts by weight of ethanol, and 2 parts by weight of acetic acid and 4 parts by weight of xylene were added thereto. This solution was mixed with the previously dissolved compound solution by a disper to prepare a main ingredient.

Preparation of curing agent: metal compound containing amino group H
15 parts by weight of ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ (manufactured by Chisso Corporation) were dissolved in 85 parts by weight of butanol to prepare a curing agent.

Preparation of paint: The above-mentioned main agent and curing agent were mixed by a disper to prepare a paint. Preparation of coating film: 25 g of the above coating material is placed in a fluorine-coated hand-size tray, spread over the entire surface, and then allowed to stand at room temperature for 3 days. Next, after drying at 100 ° C. for 24 hours, baking was performed at 200 ° C. for 60 minutes. After firing, the film was taken out and its thickness was measured to be about 300 μm. Preparation of painted board: SUS301 which has been washed with acetone beforehand
The paint was applied to the board with a 16 mil applicator. After air drying, after drying at 80-100 ° C for 30 minutes,
It baked at 200 degreeC for 30 minutes.

Comparative Example 1 Preparation of paint: The procedure of Example 1 was repeated except that the curing agent was omitted in Example 1. Preparation of coating film: 25 g of the above coating material is placed in a fluorine-coated hand-size tray, spread over the entire surface, and then allowed to stand at room temperature for 3 days. Next, after drying at 100 ° C. for 24 hours, baking was performed at 200 ° C. for 60 minutes. After firing, the film was taken out and its thickness was measured to be about 300 μm.

Preparation of a coated plate: A SUS301 plate which had been washed with acetone in advance was dipped with a commercially available primer for fluororubber, and was preliminarily dried at 80 to 100 ° C. for 30 minutes. After returning to room temperature, apply the paint to a 16 mil applicator.
Painted. After air-drying, it was dried at 80 to 100 ° C for 30 minutes, and then fired at 200 ° C for 30 minutes.

Comparative Example 2 Fluoro rubber (Daikin G-801 manufactured by Daikin Industries, Ltd.) 1
Twenty parts by weight of MT carbon black and 5 parts by weight of an acid acceptor (hydrotalcite DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) were kneaded with an open roll with respect to 00 parts by weight to obtain a compound. This compound was dissolved in a mixed solvent of 400 parts by weight of butyl acetate and 400 parts by weight of methyl isobutyl ketone.

Preparation of curing agent: amino group-containing metal compound H
15 parts by weight of ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ (manufactured by Chisso) were dissolved in 85 parts by weight of butanol to prepare a curing agent.

Preparation of paint: The above-mentioned fluororubber solution and a curing agent were mixed with a disper to prepare a paint. Preparation of coating film: 25 g of the above coating material is placed in a fluorine-coated hand-size tray, spread over the entire surface, and then allowed to stand at room temperature for 3 days. Next, after drying at 100 ° C. for 24 hours, baking was performed at 200 ° C. for 60 minutes. After firing, the film was taken out and its thickness was measured to be about 300 μm. Preparation of painted board: SUS301 which has been washed with acetone beforehand
The paint was painted on a board with a 16 mil applicator. After the preliminary drying, it was dried at 80 to 100 ° C. for 30 minutes, and then baked at 200 ° C. for 30 minutes.

With respect to the coated plates prepared in Examples and Comparative Examples, the antifreeze solution resistance and the settling of the coating film were evaluated as follows. <Anti-freeze resistant> Toyota genuine long life coolant (L
LC) in water to prepare a 50% (by volume) aqueous solution,
The coated plate is immersed in this aqueous solution at 120 ° C. for 500 hours. After immersion, the presence or absence of blisters on the coating film surface is visually observed and evaluated.も の indicates that the coating film appearance did not change, Δ indicates that partial blisters were generated, and X indicates that blisters were generated on the entire surface.

<Falling (missing part) of coating film> A coated plate is sandwiched between jigs for measuring compression set without using a spacer.
After maintaining at 200 ° C. for 5 hours, the presence or absence of a missing end of the coating film was visually observed and evaluated. When the coating film protruded and did not have any missing portions, it was evaluated as ○, and when the coating film protruded and was missing, it was evaluated as x. Table 1 shows the results.

<Seal property (compression set; JIS K)
6262-5)> The above coating films are superimposed so as to be about 10 mm, and the thickness is measured with a dial gauge. Next, the sample was placed in a furnace at a temperature of 175 ° C. for 72 hours under 25% compression and pressurization, then taken out of the furnace, allowed to cool at room temperature for 30 minutes, measured with a dial gauge, and calculated according to the following equation.

[0058]

## EQU1 ## Compression set (rate) = 100 × (t ₀ −
t ₁ ) / (t ₀ −t ₂ ) where t ₀ : thickness before compression (mm) t ₁ : thickness after compression (mm) t ₂ : thickness of spacer (mm) Compression set is 50% The following are ○, 51% to 89
%, And 90% or more were evaluated as x.

[0059]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) F16J 15/08 F16J 15/08 Q F term (Reference) 3J040 EA48 FA01 FA06 HA17 4H017 AA03 AA27 AA29 AB12 AC01 AC03 AC14 AC17 AD01 AE02 4J038 CD111 DA032 DL082 DM022 GA09 JA64 JC35 JC38 KA04 KA06 NA04 NA11 PB06 PB07 PB11 PC02

Claims (10)

[Claims] A fluororubber coating composition comprising a liquid carrier, a fluororubber dissolved or dispersed in the liquid carrier, a polyol-based vulcanizing agent, and an amino group-containing metal compound. 2. The fluororubber coating composition according to claim 1, comprising a polyol vulcanizing agent and an amino group-containing metal compound in an amount of 5 to 50 parts by weight based on 100 parts by weight of the fluororubber. 3. The fluororubber coating composition according to claim 1, wherein the ratio of the polyol vulcanizing agent to the amino group-containing metal compound is from 1: 1.2 to 1:30. 4. The fluororubber paint according to claim 1, wherein the metal in the amino group-containing metal compound is at least one metal selected from the group consisting of Si, Al, Ti and Zr. Composition. 5. An amount of 0.1 to 100 parts by weight of fluororubber.
1-20 parts by weight of a polyol vulcanizing agent, and 0.5-3
2. The composition of claim 1, wherein the metal compound contains 0 parts by weight of the amino group-containing metal compound.
5. The fluororubber coating composition according to any one of items 1 to 4. 6. The fluororubber coating composition according to claim 1, further comprising 0.1 to 10 parts by weight of a vulcanization aid per 100 parts by weight of the fluororubber. 7. The method according to claim 1, further comprising a fluororesin.
7. The fluororubber coating composition according to any one of items 6 to 6. 8. The group consisting of a fluororesin comprising a tetrafluoroethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer and a tetrafluoroethylene-hexafluoropropylene-perfluoroalkylvinyl ether copolymer. The fluororubber coating composition according to claim 7, which is at least one fluororesin selected from the group consisting of: 9. The method according to claim 1, wherein one or both sides of the metal plate are provided.
A coated article having a coating film formed from the fluororubber coating composition according to any one of the above. 10. The coated article according to claim 9, which is a material for an automobile engine gasket.