JPS58133874A - Underwater corrosion preventive coating method - Google Patents

Abstract

PURPOSE:To form underwater corrosion preventive coating which prevents sticking of aquatic living things by coating anti-fouling paint contg. a fluorocopolymer, polyvalent isocyanate and, if necessary, lubricants on a corrosion preventive coating layer. CONSTITUTION:The anti-fouling paint contg. 40-60mol% fluoroolefin, 5-45% cyclohexyl vinyl ehter, 5-45% alkyl vinyl ether, 3-15% hydroxyalkyl vinyl ether and 0-30% other comonomers and polyvalent isocyanate is coated on a substrate having a corrosion preventive coating layer, and is dried at ordinary temp., whereby an underwater anti-fouling coating is formed. The above-mentioned corrosion preventive coating layer consists preferably of at least 1 layer of a wash primer, a zinc rich primer, oil base paints and synthetic resin paints. The similar underwater anti-fouling coating is obtained by contg. 200pts.wt. lubricants in 100pts.wt. the above-mentioned fluorocopolymer.

Description

[Detailed description of the invention] The present invention relates to an underwater antifouling coating method.

For more details, see 1. Regarding the underwater antifouling coating method applicable to ship bottoms, marine structures, seawater inlet pipes, etc.In general, the antifouling properties of coating films are determined by the antifouling agent contained in the paint or its decomposition products. It is exerted by gradual elution and diffusion from the paint film into the sea or water.

However, its elution mechanism can be broadly divided into the following two types: When cuprous oxide as an antifouling agent is blended at a high concentration in a paint that uses a water-resistant resin (for example, vinyl chloride resin) as a color vehicle, This is a so-called in-luple type in which cuprous oxide is continuously eluted from the coating film over a long period of time by utilizing the solubility of suboxide steel in water.

In this type, when the content of cuprous oxide in the paint is low, the amount of suboxide steel eluted during immersion in seawater decreases in a short period of time, and the sustainability of the antifouling effect is extremely reduced.

That is, in this type of paint, it is generally necessary to incorporate a large amount of antifouling agent into the paint, and as a result, for example, cuprous oxide tends to precipitate during storage and cause hard caking. In addition, it impairs painting workability and is accompanied by defects such as brittle paint films, poor adhesion, easy cracking, and easy peeling, and is rarely used these days due to the cost of the paint. .

Another embodiment is a paint having a so-called lump 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 to the surface of the paint film. demonstrate.

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 - years at most.

However, the conventional antifouling coating film also contains an antifouling agent, and exhibits antifouling properties through its elution. It's something I want. Such dissolution and diffusion of antifouling agents into water is not desirable from the viewpoint of preventing pollution of the ocean and the like.

In addition, with conventional antifouling coatings, as the antifouling effect decreases, oyster shells, fujibo, etc. adhere to the coating, and once attached, fujibo, etc., sink into the inside of the coating and cannot be easily removed. there were.

Furthermore, in conventional antifouling coatings, there is a problem in that the coating film in the area exposed to sunlight near the water line is degraded by 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 applies a fluorine-containing copolymer consisting of (a) 40 to 60 mol of fluoroolefin, 5 mol of cyclohexyl vinyl ether, 5 mol of alkyl vinyl ether, 5 mol of alkyl vinyl ether, and 6 mol of droxyalkyl vinyl ether to a coated article having an anticorrosion coating layer. Apply an antifouling paint containing a composition containing 200 parts by weight or less of a lubricant to 100 parts by weight of the fluorine-containing copolymer, and (b) polyvalent incyanate, and dry at room temperature. 1. In the method of the present invention, the anticorrosive coating layer refers to, for example, (1) a water-resistant coating obtained from a wash primer, a zinc-rich paint, an oil-based primer, or a synthetic resin-based primer paint; (11) A coating layer obtained by applying a synthetic resin paint onto an anticorrosive coating such as a wash primer, a zinc-rich paint or an oil-based primer, and (011) A coating layer obtained from a synthetic resin paint. be done.

The wash primer used as the anticorrosive coating layer of the present invention generally has a composition consisting of polyvinyl butyral resin or polyvinyl butyral resin and phenol resin as the main color vehicle, to which phosphoric acid, chromic anhydride, zinc chromate, alcohol, etc. are added. For example, in addition to the zinc chromate pigment, non-polluting compositions using condensed phosphate pigments, borate pigments, and molybdate pigments are also included.

The wash primer is also called an etching primer, and a short-term exposure type is used when the period until topcoating is short, and a long-term 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 defined in JIS K5621 to 5628 are exemplified.

The zinc-rich paint used as the anti-corrosion coating layer has a dry paint film with a weight ratio of 75 to 95%, preferably 80% by weight.
It is an organic or inorganic paint containing ~90% by weight of zinc dust.

Vehicles for organic zinc-rich paints include epoxy resin-polyamide resin combinations, chlorinated rubber, polystyrene resins, silicone resins, etc. Vehicles for inorganic zinc-rich paints include ethyl silicate, sodium silicate, lithium, etc. silicate,
Examples include potassium silicate and ammonium silicate. Preferred vehicles, particularly for purposes such as the present invention, are Epoquin resin-bolyamide resin combinations, ethyl silicate, potassium heptasilicate, lithium silicate.

The synthetic resin paints used in the method of the present invention include those having good coloring properties (-< means epoxy resins (including tar-modified and urethane-modified resins), vinyl resins (including tar-modified resins and acrylic resins), At least one synthetic resin selected from chloride comb, polyurethane resin, and phenolic resin, commonly used coloring pigments, extender pigments, anticorrosion pigments, sedimentation prevention agents, dispersants, curing agents, and curing accelerators. It is a paint obtained by mixing agents, diluents, solvents, etc.

The epoxy resin is a resin that has two or more epoxy groups in its molecule and is commonly used for paints.

As the epoxy resin, for example, bisphenol type epoxy resin is generally available commercially.
Product names: Epicoat 828, 834, and 836 manufactured by Epicoat Co., Ltd.
, 1001, 1004, DX-255F Ciba-Geigy Co., Ltd. pure product name Araldite 0Y-260: Dow Chemical Co., Ltd. product name DER330, 331
, 337: Trade name Ebichlor 800, manufactured by Dainippon Ink and Chemicals Co., Ltd.; Trade name DEN431, 438, manufactured by Dow Chemical Co., Ltd., which is generally commercially available as a phenol novolak type epoxy resin; Polyglycol type epoxy Ciba Gaiki Co., Ltd. is commercially available as a resin.
Araldite c'r-sos manufactured by Dow Chemical Co., Ltd.; product names DER-732 and DER-736 manufactured by Dow Chemical; ester type epoxy resins such as Dainippon Ink and Chemicals
Product names: Epiclon 20o and 400 manufactured by Nippon Soda Co., Ltd.;
Examples include epoxidized polybutadiene such as F-IQQQ.

Furthermore, epoxy compounds that are easily analogous to these resins, as well as derivatives of the above-mentioned epoxy resins, can also be used and are included within the technical scope of the present invention.

Examples include polyol-type epoxy resins, alicyclic epoxy resins, and halogen-containing epoxy resins.

Bituminous substances such as natural asphalt, asphaltite, asphaltic pyrobitum, tar, coal tar, artificial asphalt, pitch, and swelling coal can be mixed with the epoxy resin.

Furthermore, as the curing agent for the epoxy resin, those commonly used for paints, such as amine adduct and polyamide resin, can be used.

An example of the curing agent is Tomide Y-, a product of Fuji Kasei Kogyo Co., Ltd., which is generally commercially available as a polyamide resin.
25, 245, 2400゜2500, Daiichi General Co., Ltd. Product name on the back: Xenamide 2000, Persamide 11
5. 125: Sanwa Kagaku Co., Ltd. Sanmide 32
o, 330, X2000 Nigel Chemical Co., Ltd. Product name on the back side: Ebicure 3255, 4255; Product name: Tomide 2 manufactured by Fuji Kasei Kogyo Co., Ltd. as amine adduct resin
38, Fuji Cure 202: Mudenka Co., Ltd. Back side Product name: Ateriki Hardener EH-531; As an aliphatic polyamine, Sansho Kagaku Co., Ltd. product name: 7-Fide T-100, Same D-1
00. P-100: Examples of heterocyclic diamine derivatives include Epomate B-002, 40-002, and S-005 manufactured by Ajinomoto Co., Inc. 1゜The amount of the curing agent added to the epoxy resin is equivalent. The amount is approximately 0.7 to 1.3 equivalents per equivalent of the epoxy resin.

Polyincyanate can also be used as a curing agent for the epoxy resin.

The polyinsyanate is a polyinsyanate having two or more incyanate groups in one molecule, and examples thereof include ethylene diycinyanate, propylene diysyanate, tetramethylene diysyanate, hexamethylene diysyanate, tecamethylene diysyanate, m -phenylene diincyanate, p-phenylene diincyanate, 2.6-) lylene diincyanate, 1,5-naphthylene diincyanate, a, 4'
, 4”-)riphenylmethanetriincyane-),
4.4'-diphenylmethane-diincyanate, 3,
Polyincyanates such as 3'-dimethyl-4,4'-diphenylene diincyanate, m-xylylene diincyanate, p-xylylene diincyanate, inphorone diynnyanate, lysine incyanate, and excess of the incyanate compounds , such as ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, 2.2.4-toIJ methyl 1,3-bentanediol, hexamethylene glycol, cyclohexane dimetatool, trimethylolpropane, hexane. Examples include polyinsyanates having two or more functionalities obtained by addition reaction with low-molecular-weight polyols such as triol, glycerin, and pentaerythritol, polyinsyanates having a biuret structure, and polyinsyanates having an allophanate bond.

The mixing ratio of the epoxy resin and polyincyanate is
(Hydroxyl group in epoxy resin)/(Incyanate group in polyincyanate) -1/1.3 to 1/a, S (
(equivalent ratio) range 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 two or more monomers such as alkyl esters, and examples include vinyl chloride resin, 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 can be used in combination with rosin, coumaron-inten resin, phenolic resin, vinyl chloride resin, petroleum resin, nitrile rubber, chloroprene rubber, alkyd resin, chlorinated paraffin, diphenyl chloride, dioctyl phthalate. , tricresyl phosphate and other plasticizers.

Furthermore, the polyurethane resin used in the present invention is a compound having two or more active hydrogens in the molecule, such as a polybasic acid and a polyhydric alcohol, polyester polyol, polyether polyol, polyoxyalkylene, etc. This is a composition that uses glycol, acrylic polyol, etc. as a main ingredient, and uses the aforementioned polyynoneanate having two or more incyanate groups in the molecule as a curing agent.

The fluorine-containing copolymer used as the antifouling paint used in the coating method of the present invention contains fluoroolefin, chlorohexyl vinyl ether, and alkyl vinyl ether and hydroxyalkyl vinyl ether as essential constituents of 40 to 60 mol and 45 mol, respectively. ~45 mol timole and 3 to 15 mol timole, preferably 45 mol timole each
It is important that the content is 55 to 30 moles, 10 to 35 moles, 5 to 13 moles.

Products with a low fluoroolefin content are not only unfavorable from the viewpoint of weather resistance, but also cause problems in production.

Also, products with too high a fluoroolefin content are also difficult to manufacture.3 On the other hand, J-Kyl products with a low cyclohexyl vinyl ether content have a hardness when made into a coating, while those with a too low alkyl vinyl ether content are not flexible. This is undesirable because the copolymer has a high content of hydroxyalkyl vinyl ether, and the solubility of the copolymer changes and it becomes soluble only in certain substances such as alcohols, making it unsuitable for use as a base for solution-type paints. It does not limit its adaptability, but it reduces the flexibility of the cured coating and reduces the gelling time (pot life) in the presence of a hardener, significantly impairing the application properties of the coating. This is not desirable as it may lead to problems. If the content is too low, the effect of improving curability will be lost, and the curing time will increase.
This is not preferred because it causes a decrease in the solvent resistance, stain resistance, etc. of the cured coating film, and also causes drawbacks such as impairing the adhesion with the anticorrosive coating layer.

In the fluorine-containing copolymer, perhaloolefins, particularly chlorotrifluoroethylene or tetrafluoroethylene, are preferably employed as the fluoroolefin. In addition, as alkyl vinyl ethers, those containing a linear or branched alkyl group having 2 to 8 carbon atoms, especially those containing a linear or branched alkyl group having 2 to 4 carbon atoms, are used. Note that the fluoroolefins and alkyl vinyl ethers are not limited to being used alone, but can also be used in the form of a mixture of two or more.

The fluorine-containing copolymer may contain units based on comonomers other than the above four essential components in an amount not exceeding 30 moles.

Examples of such comonomers include olefins such as ethylene, propylene, and imbutylene, haloolefins such as vinyl chloride and vinyl chloride, unsaturated carboxylic acid esters such as methyl methacrylate, vinyl acetate, vinyl n-butyrate, and the like. Examples include vinyl carboxylates.

The fluorine-containing copolymer has an intrinsic viscosity of 0.05 measured at 60°C in tetrahydrofuran in an uncured state.
~2. ohz/r, especially o, 07-0, 8 dll y
It is preferable to adopt a medium-sized one. If the viscosity is too low, the mechanical strength will decrease, and if the blade is too high, when applied as a solution-based paint, the solution concentration will have to be lowered due to viscosity, resulting in poor workability. Both are unfavorable because they cause h.

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 prepared by activating an initiating source to carry out a copolymerization reaction.

In another embodiment of the present invention, the fluorine-containing copolymer 10
0 parts by weight, 2oo parts by weight or less, preferably 0.1 parts by weight
This includes compositions in which more than one part by weight of a lubricant is added.

In the above range, the lubricant contains fluorine-containing copolymer 100
If more than 200 parts by weight is added, the adhesion of the resulting coating film may be impaired, which is undesirable.

Such lubricants include various additives and various surface-active substances collectively referred to 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, molybdenum disulfide, metal soaps, compounds containing perfluoroalkyl groups, silicone compounds, etc. Perfluoropolymers can be preferably employed from the viewpoint of effects and the like.

Such suitable perfluoropolymers include polytetrafluoroethylene, copolymers of tetrafluoroethylene and hexafluoropropene, copolymers of tetrafluoroethylene and perfluoro(vinyl ether), and tetrafluoroethylene-hexafluoropropene. - Examples include perfluoro(vinyl ether) terpolymers and perfluoropolyethers, but polytetrafluoroethylene/, especially those lowered in molecular weight by heat treatment or radiation irradiation, or those with chain transfer agents The aqueous medium (b) that is present is preferably a low molecular weight polytetrafluoroethylene produced by polymerization in a polymerization medium such as a fluorocarbon solvent, or more preferably a polytetrafluoroethylene produced by an emulsion polymerization method. It is possible.

The fluorine-containing copolymer contains a solvent, and if necessary, a colored pigment, an extender pigment, a flat filler such as flake glass, a fine dispersing agent, 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, the polyvalent inanate is mixed with the fluorine-containing copolymer solution obtained as described above or the composition in which a lubricant, etc. is added and dissolved or dispersed, and then applied.

The polyvalent incyanate is a polyvalent incyanate having two or more incyanate groups in one molecule, and includes, for example, ethylene diincyanate, propylene diinocyanate, tetramethylene diincyanate, hexamethylene diincyanate, and decamethylene. Diincyanate, m-phenylene diincyanate, p-phenylene-
Diincyanate, 2,4-tolylene diincyanate, 2,6-tolylene diincyanate, 1,5-naphthylene diincyanate, 4,4', 4"-triphenylmethane triincyanate, 4.4' -diphenylmethane-diincyanate, 5,3'-dimethyl-
Polyvalent incyanate such as 4,4′-diphenylene diincyanate, m-xylylene diincyanate, p-xylylene diincyanate, inphorone diincyanate, lysine incyanate, and an excess of the incyanate compound; For example, ethylene glycol, propylene glycol, 1.5-7'f/glycol, neopentyl glycol, 2°2,4-trimethyl 1,5
- 2 obtained by addition reaction with low-molecular polyols such as penta/diol, hexamethylene glycol, cyclohexane dimetatool, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, etc.
Examples include polyvalent incyanates having a functional or higher functionality, polyvalent incyanates having a biuret structure, and polyvalent incyanates having an allophanate bond.

Among the polyvalent incyanates, non-yellowing diincyanates such as hexamethylene diincyanate and inphorone diincyanate, as well as adducts thereof, are particularly useful.

The mixing ratio of the fluorine-containing copolymer and the polyvalent incyanate is (hydroxyl group in the fluorine-containing copolymer)/(incyanate group in the polyvalent incyanate) = 1/1.3 to 110.
．． The range of s (equivalent ratio) is preferable.

Incidentally, in order to promote the reaction between the fluorine-containing copolymer and the polyvalent in/anate, 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 dried coating film of the zinc-rich paint is usually 10 to 150 microns, preferably 15 microns.
~75 microns.

On the zinc-rich paint film obtained by drying the zinc-rich paint at room temperature, apply the synthetic resin paint with a brush, spray paint machine, roller, etc. to a dry film thickness of 25 to 25 cm.
After coating to a thickness of about 500 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 polyvalent ino/anate is usually dried on the synthetic resin coating using a brush, spray coating machine, roller, etc. It is applied to a film thickness of about 10 to 200 microns and finished by drying at room temperature.

Thus, the antifouling coating film obtained by the method of the present invention has excellent underwater antifouling properties, can be easily removed even if aquatic organisms adhere to it, has minimal deterioration of the coating film, and has excellent weather resistance. becomes.

The details of the present invention will be explained below with reference to Examples.

"Part" or "俤" indicates "part by weight" or "part by weight." First, prior to the Examples, each paint was prepared using the following formulations.

[Formulation 1] Ethyl silicate solution 25 parts zinc
The 75 ethyl silicate solution is manufactured by Nippon Colcoat Co., Ltd. under the trade name Colcoat 40 [
An alcoholic solution with a solid content of 40%; a condensation polymer of linear and branched tetraethyl orne silicate with an average degree of condensation of about 4 to 5 was used.

[Formulation 2] (Main ingredient) Epoxy resin 6 parts xylol
1゜Methyl in butyl ketone 9 Zinc powder 65 (hardening agent) Polyamide resin 4 parts Kinol 4
Inbutanol 2 The above-mentioned epoxy resin is manufactured by Neru Kagaku Co., Ltd., product name on the back side is Ebikotna 1001 [epoxy equivalent weight 450-520],
The polyamide resin is manufactured by Fuji Kasei Co., Ltd. The product name is Tomide φ.
21o [amine value 95±5] was used.

The above formulations 1 and 2 are formulations of zinc-rich paints, 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.

Carbon black 0.3 Phthalocyanine blue 0.6 Zinc chromate
5 Antisettling agent 1 Aluminum powder paste 5 Butyl alcohol 11 Inglobil alcohol 25 Doleol 29.
4 (Additives) 85 Thiphosphoric acid 9.4 Chromic anhydride
0.2 Water 4.5 Inglobil alcohol 85.9 After kneading the main ingredients except the aluminum powder paste in a pot mill for a day and night, add the specified amount of aluminum powder paste to the kneaded mixture12 and lightly disperse it to make it uniform. I let it happen. The main agent 8
A wash primer (formulation 3) was obtained by mixing 0 parts of the additive and 20 parts of the additive.

[Formulation 4] (Main agent) Bisphenol type epoxy resin [Product name: 25 parts Epicoat 828, manufactured by Ciel Kagaku Co., Ltd.: Epoxy equivalent: 184
~194] Titanium oxide pigment 20 Tarri
15 precipitation - barium sulfate 15 precipitation - inhibitor (
Organic bentonite) 2 Methyl in butyl ketone 13 Quizylol
10 The above composition was kneaded with a roller to obtain a main ingredient.

(Curing agent) Polyamide resin [trade name: Tomide φ245, 60 parts, manufactured by Fuji Kasei Kogyo Co., Ltd., active hydrogen equivalent: 90] Inbutanol, 40 parts The above formulation was stirred with a teaper 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] 15 parts of soybean oil modified medium oil type alkyd resin (oil length 50%
, acid value 5) salt, chemical rubber
15 Chlorinated paraffin 40% 7 Titanium oxide 15 Metal dryer 2 Anti-skinning agent 0.5 Anti-settling agent 1 Kijirol 44.5 [Formulation 6] Acrylic resin 40 parts [manufactured by Dainippon Ink & Chemicals Co., Ltd., trade name: Acrylic Tick A-169, non-volatile 9so%) titanium oxide
20 Anti-settling agent 1 kg
39 [Formulation 7] Vinyl chloride resin (Union Carbye) 20 Co., Ltd. Back side name: VYHH) Dibutyl phthalate (DBP) ?Titanium oxide 1゜Anti-sedimentation agent 1 Methyl inbutyl ketone 3゜Kidylol 2゜Butyl acetate 1゜[Formulation 8] Phenol resin 20 parts [Hitachi Chemical Co., Ltd. product name: Hytanol 1131] Soybean oil modified medium oil alkyd resin 15 (Formulation 5
(same as) Drol 2° Ethyl acetate 15 Titanium oxide 3° [Formulation 9] (Main ingredient) Polyester resin 14.1 parts (Bayer product name: Desmofe/1100) Polyester resin 14.1 (Bayer product name :Tesmofen 800) Titanium oxide 10 Quizylol 6 Ethyl acetate 6 Butyl acetate 6 Selonlupe acetate 4.8 In the above main agent, polyvalent incyanate as a hardening agent [Mitsubishi Chemical Industries, Ltd., product name Mitic GP101A: non-volatile content 75%] Mix 39 parts when painting.

[Formulation 10] 51.2 mol t each of units based on chlorotrifluoroethylene, chlorohexyl vinyl ether, ethyl vinyl ether and hydroxy-methyl vinyl ether
Contains lb, 1y, 1 mol, 22.5 mol, 22.5 mol, and 9.1 mol, and has an intrinsic viscosity (in tetrahydrofuran at 50°C (1:v)) of 0.21 d.
i/9, glass transition temperature (DSC under temperature increase of 10℃/m)
A main ingredient for an antifouling paint was obtained by dissolving 100 parts of a fluorine-containing quaternary copolymer (A) having a (Ty) of 45° C. in a mixed solvent of 40 parts of xylene and 120 parts of methyl in butyl ketone.

Immediately before use, a curing agent consisting of 8 parts of hexamethylene diinocyanate and 15 x 10 -7 parts of dibutyltin dilaure was mixed with the base material to obtain an antifouling paint (Formulation 10).

[Formulation 11] Units based on tetrafluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether, and hydroxy-methyl vinyl ether in proportions of 50.8 mol%, 16.9 mol%, 22.8 mol%, and 9.5 mol%, respectively. and [η] is 0.23
An antifouling paint (formulation 11) was obtained using a fluorine-containing quaternary copolymer (B) having a dl/f and [Tf] of 27° C. and a formulation similar to formulation 10.

[Blend 12] 100 parts of the fluorine-containing quaternary copolymer (A) was added with polytetrafluoroethylene (manufactured by IC1, UK: Fluon
An antifouling paint (formulation 12) was obtained using the same formulation as formulation 10, except that 200 parts of L 171 ) was mixed therein.

[Formulation 13] An antifouling paint (Formulation 15) having the same formulation as Formulation 11 was obtained except that the amount of polytetrafluoroethylene added was 40 parts.

[Formulation 14] The same formulation as Formulation 10 was used except that 5 parts of tetrafluoroethylene low polymer (Asahi Glass: AG Loop) was mixed with 100 parts of the fluorine-containing quaternary copolymer (A). A soil paint (formulation 14) was obtained.

[Formulation 15] 100 parts of the fluorine-containing quaternary copolymer (A) and 2 parts of the tetrafluoroethylene-hexafluoropropprope 7 copolymer.
3. [Formulation 16] Rosin
30 parts polymerized linseed oil
10 valve handle
10 pieces Copper oxide 30 pieces
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 Copper nitrous oxide
30 tal
20 parts mineral spirit 2° It was made into a paint 7 in the same manner as Formulation 16 to obtain an antifouling paint (Formulation 17).

Examples 1 to 6 150 x 50 x 1.6m+ mild steel plate (J]'S
() 3141) to black skin by shot blasting,
After completely removing rust and oil, a primer was air sprayed according to the coating system shown in Table 1. In the case of wash primer, paint to a dry film thickness of 20 ± 2 microns and dry for 3 days at 20°C and 7 s% II (H), and in the case of zinc-rich paint, dry film thickness of 35 ±
It was coated to a thickness of 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 air spray so that the dry film thickness was 100±10 microns.
After drying for 7 days at ℃ and 75% RH to obtain a synthetic resin coating, air spray the antifouling paint until the dry film thickness is 50±.
Painted to a thickness of 10 microns, 20℃, 7s%
It was dried in I'll for 7 days.

Each test piece obtained was subjected to the comparative test described below.

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

It is clear from the comparative test results table that the coating film obtained from the antifouling coating method of the present invention is superior in antifouling properties to the coating film obtained from the conventionally known antifouling paint composition. It was of comparable quality, and even if aquatic organisms were attached to it, it could be easily removed, and there was no damage to the top coating.1

Claims (6)

[Claims] (1) On the object to be coated which has an anti-corrosion coating layer, (a)
A fluorine-containing copolymer comprising 40 to 60 moles of fluoroolefin, 5 moles of cyclohexyl vinyl ether, 15 to 30 moles of hydroxyalkyl vinyl ether, and (b)
An underwater antifouling coating method characterized by applying an antifouling paint containing polyvalent incyanate and drying at room temperature. (2) The underwater antifouling coating method according to claim (1), 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. (3) The underwater antifouling coating method according to claim (1), wherein the fluoroolefin is chlorotrifluoroethylene and/or tetrafluoroethylene. (4) On the object to be coated which has an anti-corrosion coating layer, (a)
(b) a composition containing 200 parts by weight or less of a lubricant per 100 parts by weight of a fluorine-containing copolymer consisting of 40 to 60 moles of fluoroolefin and 5 to 30 moles of cyclohexyl vinyl ether; An underwater antifouling coating method characterized by applying an antifouling paint containing incyanate and drying it at room temperature. (5) The underwater antifouling coating method according to claim (4), 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 paint. (6) The underwater antifouling coating method according to claim (4), wherein the fluoroolefin is chlorotrifluoroethylene and/or tetrafluoroethylene. The underwater antifouling coating method according to claim (4), wherein the lubricant is a perfluoropolymer.