JPS6141258B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an underwater antifouling coating method. More specifically, the present invention relates to an underwater antifouling coating method applicable to ship bottoms, marine structures, seawater introduction pipes, and the like. In general, the antifouling property of a coating film is exerted by the gradual elution and diffusion of the antifouling agent contained in the coating material or its separation product from the coating film into the sea or water. The elution mechanism can be roughly divided into the following two modes. One embodiment is to mix cuprous oxide as an antifouling agent in a high concentration in a paint that uses a water-resistant resin that does not contain rosin and can form a film (for example, vinyl chloride resin) as a color vehicle. This is a so-called isosoluble type in which cuprous oxide is continuously eluted from the paint film over a long period of time by utilizing its solubility in water. In this type, when the content of cuprous oxide in the paint is low, the amount of cuprous oxide eluted during immersion in seawater decreases in a short period of time, and the sustainability of the antifouling effect is extremely reduced. In other words, this type of paint generally requires a large amount of antifouling agent to be incorporated into the paint, and as a result, for example, cuprous oxide tends to precipitate during storage and cause hard caking, and also makes it difficult to apply during the painting process. In addition to impairing the properties of the paint, it also has defects such as a brittle paint film, poor adhesion, and is prone to cracking and peeling.Coupled with the cost of the paint, it is rarely used these days. Another embodiment is a paint having a so-called soluble matrix type elution mechanism, which is made by using rosin as the main film-forming component and adding an antifouling agent such as cuprous oxide to the rosin. In this type of paint, rosin gradually dissolves from the surface of the paint film in seawater as a matrix component, and as a result, the antifouling agent is constantly exposed on the surface of the paint film, dissolves into the seawater, and exhibits antifouling properties. do. However, although this method can also be expected to improve the durability of the antifouling effect to some extent compared to the former, it will only last for about a year at most. However, all of the above-mentioned conventional antifouling coatings contain an antifouling agent and exhibit antifouling properties by elution of the antifouling agent, and therefore, dissolution and diffusion of the antifouling agent into water is unavoidable. It is. Such dissolution and diffusion of antifouling agents into water is not preferable from the viewpoint of preventing pollution of oceans and the like. In addition, with conventional antifouling coatings, the antifouling effect decreases and oyster shells, barnacles, etc. adhere to the coating.
Once attached, barnacles, etc. will burrow into the paint film,
It was something that could not be easily peeled off. Furthermore, in conventional antifouling coatings, there was a problem in that the coating film in the areas exposed to sunlight near the water line deteriorated due to ultraviolet rays, resulting in a decrease in the antifouling effect. The purpose of the present invention is to improve the above-mentioned defects of conventional antifouling coatings, and to prevent the adhesion of aquatic organisms without using any antifouling agent, and even if aquatic organisms adhere to The object of the present invention is to provide an underwater antifouling coating method that forms a coating film that can be peeled off with a small amount of force and has excellent weather resistance. That is, the present invention provides the following methods: (a) 40 to 60 mol % of fluoroolefin, 5 to 45 mol % of cyclohexyl vinyl ether, 5 to 45 mol % of alkyl vinyl ether, and 3 to 15 mol % of hydroxyalkyl vinyl ether on an article having an anticorrosive coating layer; % and other comonomers from 0 to 30 mol%, or a composition containing 200 parts by weight or less of a lubricant per 100 parts by weight of the fluorinated copolymer. (b) An underwater antifouling coating method characterized by applying an antifouling paint containing a polyvalent isocyanate and drying it at room temperature. In the method of the present invention, the anticorrosive coating layer is, for example, (i) a coating layer obtained from a wash primer, a zinc-rich paint, an oil-based primer, or a synthetic resin-based primer paint; (ii) a coating layer obtained from a wash primer, a zinc-rich paint, or an oil-based primer paint; Examples include a coating layer obtained by applying a synthetic resin paint onto an anticorrosive coating such as a primer, and (iii) a coating layer obtained from a synthetic resin paint. The wash primer used as the anti-corrosion coating layer of the present invention includes polyvinyl butyral resin or the resin and phenol resin as the main color vehicle, phosphoric acid, chromic anhydride, zinc chromate,
Compositions containing alcohol and the like are generally exemplified, but non-polluting compositions using condensed phosphate pigments, borate pigments, and molybdate pigments in addition to the zinc chromate pigments are also included. Ru. The wash primer is also called an etching primer, and a short exposure type is used when the period until topcoating is short, and a long exposure type is used when the period is long. Further, as the oil-based paint used for the anti-corrosion coating layer, those prepared by adding various anti-corrosion pigments to oil or boiled oil, and those specified in JIS K5621 to 5628 are exemplified. The zinc-rich paint used as the anticorrosive coating layer is an organic or inorganic paint containing 75 to 95% by weight, preferably 80 to 90% by weight of zinc dust in the dry coating. The vehicle for organic zinc-rich paint is a combination of epoxy resin and polyamide resin.
Examples include chlorinated rubber, polystyrene resin, silicone resin, etc. Vehicles for inorganic zinc-rich paint include ethyl silicate, sodium silicate, lithium silicate, potassium silicate, ammonium silicate, etc. Preferred vehicles, particularly for purposes such as the present invention, are epoxy resin-polyamide resin combinations, ethyl silicates, potassium silicates, lithium silicates. The synthetic resin paint used in the method of the present invention preferably includes epoxy resins (including tar-modified and urethane-modified resins), vinyl resins (including tar-modified resins and acrylic resins), chlorinated rubber,
At least one synthetic resin selected from polyurethane resins and phenolic resins, commonly used coloring pigments, extender pigments, anticorrosion pigments, anti-settling agents,
It is a paint obtained by kneading a dispersant, curing agent, curing accelerator, diluent, solvent, etc. The epoxy resin is a resin that has two or more epoxy groups in its molecule and is commonly used for paints. Examples of the epoxy resin include bisphenol type epoxy resins such as Epicote 828, a commercially available product manufactured by Ciel Kagaku Co., Ltd.;
834, 836, 1001, 1004, DX-255: Araldite GY-260, manufactured by Ciba Geigy Corporation; DER 330, 331, DER 331, manufactured by Dow Chemical Co., Ltd.
337: Trade name Epicron 800 manufactured by Dainippon Ink and Chemicals Co., Ltd., etc.: Dow Chemical Co., Ltd., which is generally commercially available as a phenol novolak type epoxy resin.
Commercially available polyglycol type epoxy resins are DEN 431 and DEN 438, manufactured by Ciba Geigy Co., Ltd.; Araldite CT-508, manufactured by Dow Chemical Co.; DER-732 and DER-736, manufactured by Dow Chemical Co.; Ester-type epoxy resins include, for example, Epiclon 200 and 400 manufactured by Dainippon Ink and Chemicals; linear aliphatic epoxy resins include epoxidized products such as BF-1000, manufactured by Nippon Soda Co., Ltd. Examples include polybutadiene. Furthermore, epoxy compounds that are easily analogous to these resins and derivatives of the above-mentioned epoxy resins can be similarly used and are included within the technical scope of the present invention. Examples include polyol type epoxy resins, alicyclic epoxy resins, halogen-containing epoxy resins, and the like. The epoxy resin includes natural asphalt, asphaltite, asphaltic pyrobitumen, tar, coal tar, artificial asphalt,
Bituminous substances such as pitch and swelling coal can be mixed. Furthermore, as the curing agent for the epoxy resin, those commonly used for paints, such as amine adduct and polyamide resin, can be used. Examples of the curing agent include Tomide Y-25, 245, 2400, and 2500, manufactured by Fuji Kasei Kogyo Co., Ltd., which are generally commercially available as polyamide resin; and Zenamide 2000, manufactured by Daiichi General Co., Ltd. Versamide
115, 125: Sanwa Chemical Co., Ltd. product name Sanmide
320, 330, and X2000: manufactured by Ciel Kagaku Co., Ltd. under the trade name Epicure 3255, 4255; as amine adduct resin manufactured by Fuji Chemical Industry Co., Ltd. under the trade name Tomide 238, Fujikyure 202: manufactured by Asahi Denka Co., Ltd. under the trade name ADEKA Hardener EH-531; Sanwa Chemical as aliphatic polyamine
Product names: Sunmide T-100, Sunmide D-100, Sunmide P manufactured by Co., Ltd.
−100; Ajinomoto Co., Inc. as a heterocyclic diamine derivative
Examples include Epomate B-002, Epomate C-002, and Epomate S-005. The amount of the curing agent added to the epoxy resin is around the equivalent, that is, 0.7 to 1.3 per equivalent of the epoxy resin.
It is in the equivalent range. Polyisocyanates can also be used as curing agents for the epoxy resins. The polyisocyanate is a polyisocyanate having two or more isocyanate groups in one molecule, such as ethylene diisocyanate,
Propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1.
5-Naphthylene diisocyanate, 4.4'.
4″-Triphenylmethane triisocyanate,
4,4'-diphenylmethane-diisocyanate,
Polyisocyanates such as 3,3'-dimethyl-4,4'-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, lysine isocyanate and excess of the above isocyanate compounds, such as ethylene glycol, propylene Low molecules such as glycol, 1,3-butylene glycol, neopentyl glycol, 2,2,4-trimethyl 1,3-pentanediol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, etc. Examples include polyisocyanates having two or more functionalities obtained by an addition reaction with a polyol, polyisocyanates having a Biuret structure, and polyisocyanates having an allophanate bond. The mixing ratio of the epoxy resin and polyisocyanate is (hydroxyl group in epoxy resin)/(isocyanate group in polyisocyanate) = 1/1.3 ~
A range of 1/0.5 (equivalent ratio) is preferred. Vinyl resins used in the present invention include vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, styrene, vinyl toluene, vinyl alcohol, acrylic acid, methacrylic acid, maleic anhydride, acrylic acid alkyl ester, and methacrylic acid. It is a copolymer of one or more monomers such as alkyl esters, vinyl chloride resin,
Examples include vinyl chloride-vinyl acetate copolymer resin and acrylic resin. Further, the chlorinated rubber resin used in the present invention is a chlorinated product of natural rubber and usually has a chlorine content of 65 to 68%. Chlorinated rubber is rosin, coumaron-indene resin,
It can be used in combination with phenolic resin, vinyl chloride resin, petroleum resin, nitrile rubber, chloroprene rubber, and alkyd resin. It is also used in combination with a plasticizer such as chlorinated paraffin, diphenyl chloride, dioctyl phthalate, and tricresyl phosphate. Furthermore, the polyurethane resin used in the present invention refers to compounds having two or more active hydrogens in the molecule, such as polyester polyols obtained from polybasic acids and polyhydric alcohols, polyether polyols, polyoxyalkylene glycols, This is a composition containing an acrylic polyol as a main ingredient and a curing agent containing the aforementioned polyisocyanate having two or more isocyanate groups in the molecule. The fluorine-containing copolymer used as the antifouling paint used in the coating method of the present invention contains fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether as essential constituents of 40 to 60 mol% and 5 to 5 mol%, respectively.
~45 mol%, 5-45 mol% and 3-15 mol%, preferably 45-55 mol%, 10-30 respectively
It is important that the content is 10 to 35 mol% and 5 to 13 mol%. Too low a fluoroolefin content is not only unfavorable from the viewpoint of weather resistance, but also causes problems in production. Also, those containing too high a fluoroolefin content are also difficult to manufacture. On the other hand, if the cyclohexyl vinyl ether content is too low, the hardness when formed into a coating film is undesirable, and if the alkyl vinyl ether content is too low, the flexibility will be reduced, and if the hydroxyalkyl vinyl ether content is too high, the coating film will be hard to coat. The solubility of the polymer changes and it becomes soluble only in certain substances such as alcohols, which not only limits its applicability as a base for solution-based paints, but also reduces the flexibility of the cured coating. This is undesirable because it reduces the gelation time (pot life) in the presence of a hardening agent and significantly impairs the workability of the paint. If the content is too low, the effect of improving curability will be lost, resulting in an increase in curing time, a decrease in solvent resistance, stain resistance, etc. of the cured coating film, and furthermore, the adhesion with the anticorrosion coating layer may be reduced. This is not preferable because it causes disadvantages such as loss of quality. In the fluorine-containing copolymer, perhaloolefin, particularly chlorotrifluoroethylene or tetrafluoroethylene, is preferably employed as the fluoroolefin. Moreover, as the alkyl vinyl ether, those containing a linear or branched alkyl group having 2 to 8 carbon atoms, particularly those in which the alkyl group has 2 to 4 carbon atoms, are preferably employed. Note that the fluoroolefin and the alkyl vinyl ether are not limited to being used alone, but may also be used in the form of a mixture of two or more types. The fluorine-containing copolymer may contain units based on comonomers other than the above four essential components in an amount not exceeding 30 mol %. Such comonomers include olefins such as ethylene, propylene, and isobutylene, haloolefins such as vinyl chloride and vinylidene chloride, unsaturated carboxylic acid esters such as methyl methacrylate, vinyl acetate, vinyl n-butyrate, etc. Examples include vinyl carboxylates. As the fluorine-containing copolymer, one having an intrinsic viscosity of about 0.05 to 2.0 dl/g, particularly about 0.07 to 0.8 dl/g, as measured in an uncured state in tetrahydrofuran at 30° C., can be preferably employed. If the viscosity is too low, the mechanical strength will decrease, while if it is too high, when applied as a solution-type paint, the solution concentration will have to be lowered due to the viscosity, and the workability will be impaired. Both are undesirable. The above-mentioned fluorine-containing copolymers are produced by polymerization using a polymerization initiator such as a water-soluble initiator or an oil-soluble initiator or ionizing radiation in the presence or absence of a polymerization medium in a monomer mixture of a predetermined ratio. It can be produced by causing a copolymerization reaction by applying an initiating source. Another embodiment of the present invention includes a composition in which 200 parts by weight or less, preferably 0.1 parts by weight or more of a lubricant is added to 100 parts by weight of the fluorine-containing copolymer. In the above range, if the lubricant is added in an amount exceeding 200 parts by weight per 100 parts by weight of the fluorine-containing copolymer, the adhesion of the resulting coating film may be impaired, which is not preferable. Such lubricants include various additives or various surface-active substances collectively known as so-called solid lubricants, and various conventionally known or well-known ones can be used. Typical examples include perfluoropolymers, chlorotrifluoroethylene polymers, graphite fluoride, graphite,
Examples include molybdenum disulfide, metal soaps, perfluoroalkyl group-containing compounds, and silicone compounds, but perfluoropolymers can be preferably employed from the viewpoint of anticorrosion effects. Such suitable perfluoropolymers include polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropene, copolymers of tetrafluoroethylene and perfluoro(vinyl ether), tetrafluoroethylene-
Examples include hexafluoropropene-perfluoro(vinyl ether) terpolymer and perfluoropolyether, but polytetrafluoroethylene, especially those lowered in molecular weight by heat treatment or radiation irradiation, or those with chain transfer agents Low molecular weight polytetrafluoroethylene produced by polymerization in a polymerization medium such as an existing aqueous medium or a chlorofluorocarbon solvent, and polytetrafluoroethylene produced by an emulsion polymerization method are preferably employed. The fluorine-containing copolymer contains a solvent, and if necessary, a colored pigment, an extender pigment, a flat filler such as flake glass, and other dispersants, a suspending agent, a viscosity modifier, a leveling agent, and an antigelation agent. , an ultraviolet absorber, etc. can be added as appropriate. In the coating method of the present invention, a polyvalent isocyanate is mixed with the fluorine-containing copolymer solution obtained as described above or a composition in which a lubricant and the like are added and dissolved or dispersed at the time of use and applied. The polyvalent isocyanate is a polyvalent isocyanate having two or more isocyanate groups in one molecule, for example, ethylene diisocyanate,
Propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1.
5-Naphthylene diisocyanate, 4.4'.
4″-Triphenylmethane triisocyanate,
4,4'-diphenylmethane-diisocyanate,
Polyvalent isocyanates such as 3,3'-dimethyl-4,4'-diphenylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, lysine isocyanate, and an excess of the above-mentioned isocyanate compounds, for example, ethylene glycol, Propylene glycol, 1,3-butylene glycol, neopentyl glycol, 2,2,4-trimethyl 1,3-pentanediol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, etc. Examples include polyvalent isocyanates having two or more functionalities obtained by an addition reaction with a molecular polyol, polyvalent isocyanates having a Biuret structure, and polyvalent isocyanates having an allophanate bond. Among the polyvalent isocyanates, non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and adducts thereof are particularly useful. The mixing ratio of the fluorine-containing copolymer and the polyvalent isocyanate is (hydroxyl groups in the fluorine-containing copolymer)/
(Isocyanate group in polyvalent isocyanate)=
The range of 1/1.3 to 1/0.5 (equivalent ratio) is preferable. In addition, in order to promote the reaction between the fluorine-containing copolymer and the polyvalent isocyanate, it is also possible to add a known catalyst such as dibutyltin dilaurate. Next, an example of the coating method of the present invention will be shown. First, the zinc-rich paint is applied by spraying or brushing onto a steel surface that has been sufficiently rust-removed by sandblasting or shotblasting. In the present invention, the thickness of the dry film of the zinc-rich paint is usually 10 to 150 microns, preferably 15 to 75 microns. After applying the synthetic resin paint onto the zinc-rich paint film obtained by drying the zinc-rich paint at room temperature using a brush, spray coating machine, roller, etc. to a dry film thickness of about 25 to 300 microns, Dry at room temperature. A synthetic resin coating film is usually formed in about 1 to 7 days. Next, an antifouling paint consisting of the fluorine-containing copolymer or a composition containing the copolymer and a polyvalent isocyanate is applied onto the synthetic resin coating using a brush, a spray coating machine, a roller, etc., usually to a dry film thickness. is 10~
Apply to a thickness of about 200 microns and finish by drying at room temperature. Thus, the antifouling coating film obtained by the method of the present invention has excellent underwater antifouling properties, and even if aquatic organisms adhere to it, it can be easily removed, and the coating film shows little deterioration and has excellent weather resistance. Become something. The details of the present invention will be explained below with reference to Examples.
"Part" or "%" indicates "part by weight" or "% by weight". First, prior to the Examples, each paint was prepared using the following formulations. [Formulation 1] Ethyl silicate solution 25 parts Zinc powder 75 The ethyl silicate solution is manufactured by Nippon Colcoat Co., Ltd. under the trade name Colcoat 40 [40% solids alcohol solution;
A condensate mixture of linear and branched tetraethyl orthosilicate] having an average degree of condensation of about 4 to 5 was used. [Formulation 2] (Main ingredient) Epoxy resin 6 parts xylol 10 methyl isobutyl ketone 9 Zinc powder 65 (hardening agent) Polyamide resin 4 parts xylol 4 isobutanol 2 The above epoxy resin is manufactured by Ciel Chemical Co., Ltd. under the trade name Epicote #1001. The polyamide resin used was Tomide #210 (trade name, manufactured by Fuji Kasei Co., Ltd.) [amine value 95±5]. The above formulations 1 and 2 are formulations of zinc-rich paint, and each is mixed with zinc dust or zinc dust and a curing agent at the time of use. [Formulation 3] (Main ingredient) Phenol resin 11 parts Polyvinyl butyral resin 9 Iron oxide yellow 3 Carbon black 0.3 Phthalocyanine blue 0.3 Zinc chromate 5 Anti-settling agent 1 Aluminum powder paste 5 Butyl alcohol 11 Isopropyl alcohol 25 Toluene 29.4 (Additives) 85% Phosphoric acid 9.4 Chromic anhydride 0.2 Water 4.5 Isopropyl alcohol 85.9 After kneading the main ingredients except for the aluminum powder paste in a pot mill for a day and night, a specified amount of aluminum powder paste was added to the kneaded mixture and lightly dispersed so as to be uniform. . A wash primer (formulation 3) was obtained by mixing 80 parts of the main agent and 20 parts of the additive. [Formulation 4] (Main ingredient) Bisphenol type epoxy resin [Product name Epicote 828 manufactured by Ciel Kagaku Co., Ltd.: Epoxy equivalent 184 ~
194] 25 parts Titanium oxide pigment 20 Talc 15 Precipitated barium sulfate 15 Anti-settling agent (organic bentonite) 2 Methyl isobutyl ketone 13 Xylol 10 The above composition was kneaded with a roller to obtain a main ingredient. (Curing agent) Polyamide resin [trade name Tomide #245 manufactured by Fuji Kasei Kogyo Co., Ltd.; active hydrogen equivalent: 90] 60 parts isobutanol 40 The above formulation was stirred with a disper to prepare a curing agent. Immediately before use, 80 parts of the base agent and 20 parts of the curing agent were mixed to obtain a coating composition of Formulation 4. [Formulation 5] Soybean oil modified medium oil type alkyd resin (oil length 50%, acid value 5) 15 parts Chlorinated rubber 15 Chlorinated paraffin 40% 7 Titanium oxide 15 Metal dryer 2 Anti-skinning agent 0.5 Anti-settling agent 1 Xylol 44.5 [ Formulation 6] Acrylic resin [manufactured by Dainippon Ink and Chemicals Co., Ltd., trade name Acrydik A-169, non-volatile content 50%] 40 parts Titanium oxide 20 Anti-settling agent 1 Xylol 39 [Formulation 7] Vinyl chloride resin (Union Carbide Co., Ltd.) Product name: VYHH) 20 parts dibutyl phthalate (DBP) 9 Titanium oxide 10 Anti-settling agent 1 Methyl isobutyl ketone 30 Xylol 20 Butyl acetate 10 [Formulation 8] Phenol resin [Product name: Hytanol 1131, manufactured by Hitachi Chemical Co., Ltd.] 20 parts soybean oil modified medium oil type alkyd resin (same as formulation 5)
15 Toluene 20 Ethyl acetate 15 Titanium oxide 30 [Formulation 9] (Main ingredient) Polyester resin (Bayer product name: Desmofene 1100) 14.1 parts Polyester resin (Bayer product name: Desmofene 800) 14.1 Titanium oxide 10 Xylol 6 Ethyl acetate 6 Butyl acetate 6 Cellosolve acetate 4.8 In addition to the above-mentioned main agent, a polyvalent isocyanate is added as a curing agent [trade name Mitek GP101A manufactured by Mitsubishi Chemical Corporation:
75% non-volatile content] is mixed at the time of painting. [Formulation 10] 51.2 mol%, 17.1 mol%, 22.5 mol% of units based on chlorotrifluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether and hydroxybutyl vinyl ether, respectively.
Contains at a ratio of 22.5 mol% and 9.1 mol%,
Intrinsic viscosity (30℃ in tetrahydrofuran) ([η])
is 0.21dl/g, glass transition temperature (DSC 10℃/m
100 parts of a fluorine-containing quaternary copolymer (A) having a temperature increase (Tg) of 45°C was dissolved in a mixed solvent of 40 parts of xylene and 120 parts of methyl isobutyl ketone to obtain a main ingredient for an antifouling paint. . Immediately before use, add 8 parts of hexamethylene diisocyanate and 15x dibutyltin dilaurate to the main ingredient.
Mix a curing agent consisting of 10 ^-7 parts and apply the antifouling paint (formulated
10). [Formulation 11] 50.8 mol%, 16.9 mol%, 22.8 mol% and 9.5 mol% of units based on tetrafluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether and hydroxybutyl vinyl ether, respectively
Contained in mol%, [η] is 0.23 dl/g, [T
Antifouling paint (formulation 11) using the same formulation as formulation 10 using the fluorine-containing quaternary copolymer (B) whose temperature is 27°C
I got it. [Blend 12] To 100 parts of the fluorine-containing quaternary copolymer (A), polytetrafluoroethylene (manufactured by ICI, UK: Fluon L) was added.
An antifouling paint (formulation 12) was obtained using the same formulation as formulation 10, except that 20 parts of 171) were mixed. [Formulation 13] An antifouling paint (Formulation 13) was obtained using the same formulation as other Formulation 11 except that the amount of polytetrafluoroethylene added was 40 parts. [Formulation 14] An antifouling paint was prepared using the same formulation as Formulation 10, except that 5 parts of tetrafluoroethylene low polymer (Asahi Glass: AG Lube) was mixed with 100 parts of the fluorine-containing quaternary copolymer (A). (Formulation 14) was obtained. [Formulation 15] Antifouling paint (Formulation 15) was prepared using the same formulation as Formulation 10, except that 20 parts of tetrafluoroethylene-hexafluoropropene copolymer was mixed with 100 parts of the fluorine-containing quaternary copolymer (A). I got it. [Formulation 16] Rosin 30 parts Polymerized linseed oil 10 Petals 10 Cuprous oxide 30 Talc 20 Mineral spirits 20 The above mixture was kneaded in a pot mill for 24 hours to obtain an antifouling paint (Formulation 16). [Formulation 17] Rosin 30 parts Chlorinated rubber 10 Chlorinated paraffin 5 Cuprous oxide 30 Talc 20 Mineral spirits 20 A paint was prepared in the same manner as Formulation 16 to obtain an antifouling paint (Formulation 17). Examples 1 to 6 A 150 x 50 x 1.6 mm mild steel plate (JIS G 3141) was shot blasted to completely remove black scale, rust, and oil, and then a primer was applied according to the coating system shown in Table 1. Air spray painted. For wash primer, paint to a dry film thickness of 20 ± 2 microns and dry for 3 days at 20°C and 75% RH. For zinc-rich paint, paint to a dry film thickness of 35 ± 5 microns. and dried at 20°C and 75% RH for 7 days. Next, a synthetic resin paint was applied on top of it using an air sprayer to a dry film thickness of 100±10 microns, and dried at 20℃ and 75%RH for 7 days to obtain a synthetic resin film. Apply the dirty paint using air spray so that the dry film thickness is 50 ± 10 microns, and
It was dried at 75% RH for 7 days. Each of the obtained test pieces was subjected to a comparative test described below.

【table】

[Table] Comparative Examples 1-2 Test pieces were obtained based on the coating systems shown in Table 2 in the same manner as in the above examples, and then subjected to comparative tests.

【table】

[Table] It is clear from the comparative test result table that the coating film obtained from the antifouling coating method of the present invention has better antifouling properties than the coating film obtained from the conventionally known antifouling paint composition. It is as good as it gets, and even if aquatic organisms get attached, they can be easily removed.
There was no damage to the top coating film.

Claims (1)

[Scope of Claims] 1. On an article having an anticorrosion coating layer, (a) 40 to 60 mol% of fluoroolefin, 5 to 45 mol% of cyclohexyl vinyl ether, 5 to 45 mol% of alkyl vinyl ether, and 3 to 45 mol% of hydroxyalkyl vinyl ether. An antifouling paint containing a fluorine-containing copolymer consisting of 15 mol% and 0 to 30 mol% of other comonomers, and (b) a polyvalent isocyanate is applied and dried at room temperature. Underwater antifouling coating method. 2. The underwater antifouling coating method according to claim 1, wherein the anticorrosion coating layer is at least one layer of a wash primer, a zinc-rich primer, an oil-based paint, or a synthetic resin-based paint. 3. The underwater antifouling coating method according to claim 1, wherein the fluoroolefin is chlorotrifluoroethylene and/or tetrafluoroethylene. 4. On the coated object having the anticorrosive coating layer, (a) 40 to 60 mol% of fluoroolefin, 5 to 45 mol% of cyclohexyl vinyl ether, 5 to 45 mol% of alkyl vinyl ether, 3 to 15 mol% of hydroxyalkyl vinyl ether, and others. (b) an antifouling composition containing a polyvalent isocyanate; An underwater antifouling coating method characterized by applying paint and drying it at room temperature. 5. The underwater antifouling coating method according to claim 4, wherein the anticorrosive coating layer is at least one layer of a wash primer, a zinc-rich primer, an oil-based paint, or a synthetic resin-based paint. 6. The underwater antifouling coating method according to claim 4, wherein the fluoroolefin is chlorotrifluoroethylene and/or tetrafluoroethylene. 7. The underwater antifouling coating method according to claim 4, wherein the lubricant is a perfluoropolymer.