JP2008156511A - Stain-proof coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stain-proof coating composition keeping excellent stain-proof effect over a long period of time, while suppressing the consumption rate of a coated film within a definite range. <P>SOLUTION: The stain-proof coating composition comprises (A) a crosslinking type metal salt bond-containing copolymer having a prescribed structure, (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, (C) zinc-2-pyridinethiol-1-oxide and (D) titanium dioxide. The stain-proof coating composition enables remarkable improvement of persistency of stain-proof effect without increasing consumption property of coated film by synergistic effect of combination of these components. It is preferable that the titanium dioxide (D) is contained in a ratio of 5-40 pts.wt. and the 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B) and zinc-2-pyridinethiol-1-oxide (C) are contained in total in a ratio of 0.1-15 pts.wt., based on 100 pts.wt., total solid content of the stain-proof coating composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antifouling coating composition used for preventing the substrate from being soiled by aquatic organisms.

  Various kinds of aquatic organisms such as oysters, mussels, barnacles and other animals, plants such as oysters, mussels and barnacles, and bacteria are likely to adhere to the surface of the base material exposed to water for a long time, such as the bottom of a ship, underwater structures, and fishing nets. . When these aquatic organisms propagate on the substrate surface, the surface roughness of the ship increases, resulting in a decrease in speed and an increase in fuel consumption. There is a risk that damage such as a decrease in the strength and function of the structure and a significant shortening of the service life may occur. Therefore, research and development of various antifouling paint compositions that are used by applying to the surface of the base material in order to prevent adhesion of aquatic organisms has been advanced.

  An organic antifouling agent is a component that is blended in such an antifouling paint composition and is eluted from a hydrolyzable coating film to exert an antifouling action, but has low fish toxicity and is also degradable. It is widely used in antifouling paint compositions because of its high environmental load and low environmental load.

  However, since the antifouling durability with organic antifouling agents tends to be relatively short, the antifouling effect can be achieved by combining with a method that significantly increases the consumption rate of the coating film compared to the case of using conventional antifouling agents. Had been forced to maintain. If the consumption rate of the coating film is high, more frequent maintenance such as anti-fouling coating must be performed, which requires a lot of labor and work time, which is disadvantageous in terms of cost. .

The present applicant has previously disclosed an antifouling coating composition that can contain components such as a hydrolyzable copolymer, titanium oxide, and an organic antifouling agent (see Patent Documents 1 and 2). An antifouling coating composition having a particularly suitable blending composition for solving the above problems has not been pursued.
JP 2004-196957 A Japanese Patent Laying-Open No. 2005-097400

  An object of this invention is to provide the antifouling coating composition from which the antifouling coating film excellent in the antifouling effect is obtained, suppressing the consumption rate of a coating film.

  The inventor has a metal salt bond-containing copolymer (A) having a predetermined structure and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B), which is an organic antifouling agent. And when 2-pyridinethiol-1-oxide zinc (C) and titanium oxide (D) are used in combination, the durability of the antifouling effect is particularly excellent without increasing the coating consumption rate due to the synergistic effect. As a result, the present invention has been completed.

  That is, the antifouling coating composition of the present invention comprises a crosslinked metal salt bond-containing copolymer (A), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B), It contains 2-pyridinethiol-1-oxide zinc (C) and titanium oxide (D).

The titanium oxide (D) is preferably contained in a proportion of 5 to 40 parts by weight in 100 parts by weight of the total solid content of the antifouling coating composition, and 4,5-dichloro-2-n-octyl- 4-isothiazolin-3-one (B) and 2-pyridinethiol-1-oxide zinc (C) are preferably contained in a proportion of 0.1 to 15 parts by weight in total.

Furthermore, the antifouling paint composition of the present invention comprises 10 to 30 parts by weight of zinc oxide and 0.1 to 10 parts by weight of boron based on 100 parts by weight of the total solid content of the antifouling paint composition. It is desirable to contain an organic antifouling agent, an inorganic dehydrating agent in a proportion of 0.02 to 10 parts by weight, or a plasticizer in a proportion of 0.1 to 5 parts by weight. On the other hand, it is desirable that cuprous oxide is not substantially contained in the antifouling coating composition of the present invention.

The metal salt bond-containing copolymer (A) comprises a metal-containing monomer (a1) capable of inducing the structure represented by the formula (I) and a metal non-polymerizable copolymer with these metal-containing monomers. It was obtained by copolymerization with the monomer-containing monomer (a2), the compounding amount of the metal-containing monomer (a1) was 2 to 50% by weight, and the metal-free monomer (a2) The blending amount is preferably 50 to 98% by weight.

  According to the antifouling paint composition of the present invention using the combination of the specific components as described above, the antifouling effect can be maintained over a long period while suppressing the consumption rate of the coating film within a certain range. Since it becomes possible to form a coating film, a base material (such as an ocean-going ship) coated with the antifouling paint composition of the present invention can continuously exhibit antifouling performance without maintenance of the surface for a long period of time. .

  In addition, the antifouling paint composition of the present invention contains titanium oxide, but because of its photocatalytic action, surface renewal by hydrolysis of the antifouling coating surface is performed smoothly, so that the antifouling performance can always be maintained well. It is considered. Therefore, when the anti-fouling paint composition of the present invention is applied to the vicinity of the sea surface of a base material (such as a draft portion of a ship) where aquatic organisms are likely to adhere because the sunshine and temperature conditions are suitable for aquatic organisms, Such antifouling performance due to titanium oxide is particularly effective.

  Furthermore, the antifouling coating composition of the present invention can exhibit excellent antifouling performance without using cuprous oxide, which is an antifouling agent with a high environmental load. Cuprous oxide is a substance that is also used as a dark red pigment, but it is not necessary to add such cuprous oxide to the coating composition, thereby increasing the range of coloring options and increasing the white color. Antifouling paint can also be manufactured. The resulting antifouling coating film is flexible and has good adhesion during recoating, and at the same time has a clear hue and little discoloration after submersion / exposure.

  In the description of the present invention, the “solid content” is a component obtained by removing volatile components such as a polymerization solvent and a solvent from the antifouling coating composition, and refers to a component constituting a dry coating film. In addition, the coating film obtained from the antifouling coating composition of the present invention is sometimes simply referred to as “antifouling coating film”. “(Meth) acrylic acid” means acrylic acid and / or methacrylic acid.

Composition of antifouling paint composition <Resin component>
The antifouling coating composition of the present invention is an acrylic resin-type metal salt bond-containing copolymer having a structure represented by the following formula (I) as a resin having hydrolyzability in an alkaline atmosphere such as in seawater. Contains coalescence (A). Such a structure is sometimes referred to as a “cross-linked” metal salt bond. These polymers may be used alone or in combination of two or more.

In formula (I), M is a zinc atom or a copper atom, and R ¹ independently represents a hydrogen atom or a methyl group.
The crosslinkable metal salt bond represented by the above formula (I) is generally a polymerizable unsaturated monomer (a1) containing a metal represented by the following general formula (II) (hereinafter referred to as “crosslinking”). This is a structure derived from the polymerization reaction of “type metal-containing monomer”.

^{_{CH 2 = C (R 1)}} -COO-M-OCO-C (R 1) = CH 2 ...... (II)
In formula (II), M represents a zinc atom or a copper atom, and R ¹ independently represents a hydrogen atom or a methyl group.

  Specific examples of such a cross-linkable metal-containing monomer (a1) include zinc di (meth) acrylate and copper di (meth) acrylate. In particular, zinc dimethacrylate is obtained. It is suitable in terms of resin viscosity, storage stability of the paint, elution of the resin in the coating film, and the like.

  In addition, the preparation method of the metal containing monomer (a1) mentioned above is well-known (refer Unexamined-Japanese-Patent No. 2005-97400 etc.). For example, an inorganic metal compound (zinc or copper oxide, hydroxide, chloride, etc.) and (meth) acrylic acid or an ester compound thereof in the presence of an alcoholic organic solvent and water, the decomposition temperature of the metal salt The crosslinked metal-containing monomer (a1) can be prepared by heating and stirring below.

  In the present invention, one or two or more kinds of metal-containing monomers (a1) and one or more kinds of polymerizable unsaturated monomers (a2) which can be copolymerized therewith are used. It is preferable to use a metal salt bond-containing copolymer obtained by copolymerizing (hereinafter also referred to as “metal-free monomer”).

  Examples of the metal-free monomer (a2) include alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group and carbons in the alkoxy group, which are also used in the production of general acrylic resins. An alkoxyalkyl (meth) acrylate having 1 to 20 atoms and an alkylene group having 1 to 20 carbon atoms, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 1 to 20 carbon atoms, or the like may be used. it can.

Specifically, for example, alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl Alkoxyalkyl (meth) acrylates such as (meth) acrylate, ethoxyethyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate; 2 -Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate.

Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate are the properties of the resulting coating film and the elution persistence of resin components from the coating film. From this point, it is a preferred metal-free monomer (a2) in the present invention.

  The preparation method of the metal salt bond-containing copolymer (A) used in the present invention is known. For example, the metal-containing monomer (a1) and the metal-free monomer (a2) described above are mixed, It can be prepared by carrying out a copolymerization reaction at a temperature of about 60 to 180 ° C. for about 5 to 14 hours in the presence of a polymerization initiator and a chain transfer agent.

  The compounding ratio of the metal-containing monomer (a1) and the metal-free monomer (a2) used in the preparation of the metal salt bond-containing copolymer (A) is the resin viscosity, paint storage stability, and coating film elution. The antifouling paint composition or the antifouling coating film can be appropriately adjusted in view of the balance between the property and the water resistance, and the crack resistance. In the present invention, the metal-containing monomer (a1) is preferably blended in an amount of 2 to 50% by weight, more preferably 5 to 40% by weight, based on the whole monomer, and the metal-free monomer (a2) is blended. The remaining part, that is, the metal salt bond-containing copolymer (A) obtained by blending preferably 50 to 98% by weight, more preferably 60 to 95% by weight is used.

  In addition, the number average molecular weight (Mn: polystyrene conversion value) and the weight average molecular weight (Mw: polystyrene conversion value) of the metal salt bond-containing copolymer (A) should be adjusted as appropriate in consideration of the same matters as described above. Can do. In the present invention, the Mn of the metal salt bond-containing copolymer (A) is usually 1,000 to 100,000, preferably 1,000 to 50,000, and Mw is usually 1,000 to It is 20,000, preferably 3,000 to 10,000.

<Anti-fouling agent>
The antifouling coating composition of the present invention comprises 4,5-dichloro-2-n-octyl-4-isothiazoline-3-
Contains on (B) and 2-pyridinethiol-1-oxide zinc (C). Both
The organic antifouling agent is a known substance. In addition, 2-pyridinethiol-1-oxide zinc (
C) is also referred to as “zinc pyrithione” and is a metal pyrithione compound represented by the following formula (III) and derivatives thereof, wherein M is Zn.

In formula (III), R ^{1 to} R ⁴ each independently represent hydrogen, an alkyl group, an alkoxy group, or a halogenated alkyl group, and M represents Cu, Na, Mg, Zn, Ca, Ba, Pb, Fe, A metal such as Al is shown, and n is a valence.

In the present invention, the total amount of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B) and 2-pyridinethiol-1-oxide zinc (C) is an antifouling paint composition. In view of the antifouling property of the coating film obtained from the above, the adhesion of the coating film, etc., in the total solid content of 100 parts by weight of the antifouling coating composition, preferably 0.1-15 parts by weight, more preferably The ratio is 15 parts by weight.

The antifouling paint composition of the present invention comprises the above 4,5-dichloro-2-n-octyl- as an organic antifouling agent.
4-isothiazolin-3-one (B) and 2-pyridinethiol-1-oxide zinc (C) are essential components, and further, such as triphenylboranepyridine complex and methyldiphenylborane-4-isopropylpyridine complex A boron organic antifouling agent may be blended. When a boron organic antifouling agent is used, it is usually 0.1 in 100 parts by weight of the total solid content of the antifouling coating composition.
What is necessary is just to mix | blend in the ratio of 10-10 weight part, Preferably 5-10 weight part.

In addition, for example, metal pyrithione compounds represented by the above formula (III) other than zinc pyrithione and derivatives thereof (copper pyrithione, etc.), tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate, 2 , 4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino S triazine, Known organic antifouling agents such as basic copper acetate, copper resinate, and copper naphthenate can be used in combination as required.

  However, cuprous oxide, which has been widely used as an antifouling agent, has been regarded as a problem that it has a large addition to the environment, and the above-mentioned predetermined organic antifouling agent is sufficient without using cuprous oxide. Therefore, it is desirable that the antifouling coating composition of the present invention does not substantially contain cuprous oxide.

<Titanium oxide (D)>
Titanium oxide (titanium dioxide, TiO ₂ ) is known as a material having a photocatalytic function that is harmless, chemically stable, and available at low cost. Titanium oxide includes anatase type, rutile type, and brookite type, and any of them can be used in the present invention. However, using anatase type titanium oxide is more preferable in terms of antifouling performance. In order to improve stability and physical properties, a rutile or brookite type titanium oxide and an anatase type titanium oxide may be used in combination. In addition, the manufacturing method of these titanium oxides is not specifically limited, The titanium oxide manufactured by the well-known general method (a sulfuric acid method, a chlorine method, etc.) can be used.

  The blending amount of titanium oxide (D) in the present invention is 100 parts by weight based on the total solid content of the antifouling coating composition in consideration of the antifouling property of the coating obtained from the antifouling coating composition and the adhesion of the coating. The ratio is preferably 5 to 40 parts by weight, more preferably 10 to 35 parts by weight.

  In addition, since a coating film having further excellent antifouling performance can be produced, the titanium oxide used in the present invention is a compound such as Al, Si, Zr, Sb, Cr, Ti or alcohols (trimethylolpropane, pentane). (Erythritol, ethylene glycol, propylene glycol, ethanol, propanol, butanol, etc.) are preferably subjected to surface treatment.

  Examples of the compounds such as Al include oxides, hydroxides, halides, alkoxides, organosilicon compounds (polysiloxanes such as dimethylpolysiloxane and diphenylpolysiloxane, vinyltrichlorosilane, and glycidoxypropyltrimethoxy. Silane compounds such as silane). Examples of the alcohols include monovalent or divalent or higher alcohols such as trimethylolpropane, pentaerythritol, ethylene glycol, propylene glycol, ethanol, propanol, and butanol.

  Methods for preparing such a surface-treated titanium oxide are known (see, for example, JP-A-2001-2417, JP-A-10-158015, JP-A-6-49388, etc.) Surface-treated titanium oxide is also available on the market.

  The average particle size of titanium oxide is usually 1 nm to 10 μm, but the antifouling performance of the coating film obtained varies depending on the average particle size. Tends to decrease. On the contrary, if it is large, the smoothness of the coating film tends to decrease. Considering these points, the average particle diameter of the titanium oxide used in the present invention is preferably 10 to 5000 nm, more preferably 20 to 4000 nm, and particularly preferably 100 to 300 nm.

  Furthermore, in the antifouling coating composition of the present invention, titanium oxide (D) and a component capable of improving the photocatalytic function may be used in combination. Examples of such components include metals such as V, Fe, Co, Ni, Zn, Ru, Rh, Pd, Ag, Pt, and Au, and compounds of these metals (oxides, hydroxides). Oxyhydroxide, sulfate, halide, nitrate, etc.).

<Other ingredients>
In the antifouling paint composition of the present invention, in addition to the above-mentioned copolymer (A) containing a metal salt bond, a predetermined organic antifouling agent and titanium oxide, zinc oxide, plasticizer, extender pigment, coloring Various components used in general coating compositions such as pigments, inorganic dehydrating agents, discoloring agents, resins other than (A), organic acids, and solvents may be blended as necessary.

Zinc oxide Zinc oxide (ZnO, zinc white) that can be blended in the antifouling paint composition of the present invention is conventionally known as a white pigment, but has an antifouling action and is resistant to coatings. It is a substance that can contribute to improving cracking and adhesion.

  When zinc oxide is used in the present invention, the blending amount thereof is 100% by weight of the total solid content of the antifouling coating composition in consideration of the antifouling property of the coating obtained from the antifouling coating composition and the adhesion of the coating. The ratio is preferably 10 to 30 parts by weight, more preferably 15 to 25 parts by weight.

-Plasticizer Plasticizer is a component that contributes to improving crack resistance and water resistance of antifouling coatings and suppressing discoloration. For example, chlorinated paraffin, terpene phenol, tricresyl phosphate (TCP), Examples thereof include polyvinyl ethyl ether and terpene phenol. Among them, chlorinated paraffin is preferable.

  The chlorinated paraffin used in the present invention may be linear or branched, and may be liquid or solid (powder) at room temperature. Considering the effect of suppressing cracking and peeling of the antifouling coating film, the consumption rate of the coating film, and the like, the average carbon number of the chlorinated paraffin is usually 8 to 30, preferably 10 to 26. The average molecular weight is usually 200 to 1200, preferably 300 to 1100, the viscosity is usually 1 or more (poise / 25 ° C.), preferably 1.2 or more (poise / 25 ° C.), and the specific gravity is usually 1 0.05 to 1.80 / 25 ° C, preferably 1.10 to 1.70 / 25 ° C, and the chlorination rate (chlorine content) is usually 35 to 75%, preferably 35 to 65%.

  When adding a plasticizer typified by such chlorinated paraffin, considering the effect of improving anti-fouling coating crack resistance and water resistance or reducing discoloration, What is necessary is just to mix | blend in 0.1 to 5 weight part normally in 100 weight part of total solid, Preferably it is 1 to 2 weight part.

-Extender pigment, color pigment As extender pigments that can be used in the present invention, for example, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, barium carbonate, alumina white, water used also as an anti-settling agent, water Examples thereof include aluminum oxide, magnesium carbonate, and white carbon used as a matting agent. Such extender pigment is usually 0 to 50 parts by weight in 100 parts by weight of the total solid content of the antifouling coating composition of the present invention, from the viewpoint of adjusting the consumption rate of the coating film, transparency, fleshiness, etc. Preferably, it can be blended at a ratio of 0 to 30 parts by weight. From the viewpoint of appropriately increasing the amount of paint, it is usually 0.0 in the antifouling paint composition of the present invention.
1 to 20% by weight, preferably 0.1 to 8% by weight can be blended.

  Examples of the color pigment that can be used in the present invention include organic pigments such as carbon black, naphthol red, and phthalocyanine blue, and inorganic pigments such as bengara, barite powder, and yellow iron oxide. The pigment may further contain a colorant such as a dye.

-Inorganic dehydrating agent An inorganic dehydrating agent is a component which contributes to the improvement of the storage stability of a coating material. As the inorganic dehydrating agent to be blended in the antifouling coating composition of the present invention, anhydrous gypsum (CaSO ₄ ), synthetic zeolite adsorbent (trade name: molecular sieve, etc.) and the like are preferable. In addition, methyl orthoformate, orthoacetic acid General inorganic dehydrating agents such as orthoesters such as methyl, orthoborate, silicates and isocyanates (trade name: Additive T1) can also be used.

Such an inorganic dehydrating agent is usually blended at a ratio of 0.02 to 10 parts by weight, preferably 0.2 to 5 parts by weight, in 100 parts by weight of the total solid content of the antifouling coating composition of the present invention. be able to.
· Anti-fading agent The anti-fading agent (anti-sagging / precipitating agent) that can be used in the present invention includes, for example, organic clays such as amine salts, stearate salts, lecithin salts, and alkyl sulfonates of Al, Ca, and Zn. Examples thereof include organic waxes such as polyethylene compounds, polyethylene oxide waxes, polyamide waxes, amide waxes, hydrogenated castor oil waxes, and synthetic fine powder silica. Such a discoloring agent can be normally mix | blended in the antifouling coating composition of this invention in the ratio of 0.15 weight%, Preferably 0.1-3 weight%.

Other resins The antifouling coating composition of the present invention contains one or more other resins as desired in addition to the above-mentioned copolymer (A) containing a metal salt bond. Also good.

  For example, acrylic resin, acrylic silicone resin, polyester resin, unsaturated polyester resin, fluorine resin, polybutene resin, silicone rubber, polyurethane resin, epoxy resin, polyamide resin, vinyl resin (vinyl chloride copolymer) that does not contain metal salt bond , Ethylene / vinyl acetate copolymer, etc.), chlorinated rubber, chlorinated olefin resin, styrene / butadiene copolymer resin, ketone resin, alkyd resin, coumarone resin, terpene phenol resin, petroleum resin, etc. These resins can be used.

  In addition, water-soluble resins such as pine tar and rosin (gum rosin, wood rosin, tall oil rosin), organic acids having 9 to 19 carbon atoms such as naphthenic acid and versatic acid, and metal salts thereof (Cu salt, Zn salt) , Ca salts, etc.) can also be used as other resins.

-Solvent The various components as described above contained in the antifouling coating composition of the present invention are usually dissolved or dispersed in a solvent. Examples of the solvent that can be used in the present invention include aliphatic solvents;
Aromatic solvents such as xylene and toluene; Ketone solvents such as MIBK and cyclohexanone; Ester solvents; Ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (PGMAC); Alcohol solvents such as isopropyl alcohol Is mentioned.

Production method and use of antifouling paint composition The antifouling paint composition of the present invention can be produced by the same means as a general paint. For example, a copolymer containing a metal salt bond (A), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B), and 2-pyridinethiol-1-oxide zinc (C) In addition, titanium oxide (D) and other components as necessary may be added to the solvent at once or sequentially, and stirred and mixed. The composition ratio of the antifouling paint composition is determined by various factors such as the viscosity of the paint (workability), the type of base material to be applied, the coating method, the environment in which the coating operation is performed, and the film thickness and hardness of the antifouling coating film. Depending on conditions, it can be designed as appropriate, preferably within the predetermined range as described above.

  The antifouling paint composition of the present invention produced as described above can be used by being applied to a substrate such as a ship, and the surface of the substrate is formed from the antifouling paint composition. By covering with a coating film, fouling by aquatic organisms can be prevented. The antifouling paint composition of the present invention can be applied to the surfaces of the above-mentioned various substrates by the same means as general paints.

  The object to which the antifouling coating composition is applied is not particularly limited, and is a substrate whose surface is constantly or intermittently in contact with seawater or fresh water, for example, underwater such as water supply / drainage ports of ships, thermal power / nuclear power plants. Examples include structures, coastal roads, submarine tunnels, harbor facilities, sludge diffusion prevention films for various civil engineering works such as canals and waterways, and fishing materials (eg ropes, fishing nets, fishing gear, floats, buoys).

  The antifouling coating composition of the present invention can be applied directly regardless of whether the material of the substrate such as a ship (outer plate) is FRP, steel, wood, aluminum alloy or the like. In addition, a primer, an anticorrosive paint, or the like may be preliminarily applied to the base material (after further applying a tie coat if necessary), and then applied over these coating films. The antifouling paint composition of the present invention is particularly excellent in adhesion to an epoxy resin anticorrosive paint.

  Thus, the antifouling coating film formed from the antifouling paint composition of the present invention is capable of continuously preventing adhesion of aquatic organisms such as Aosa, Barnacles, Aonori, Serpura, Oyster, Fusakomushi, etc. for a long period of time. It is useful for maintaining the operation efficiency of the ship and the function of the underwater structure (for example, preventing the mesh of the fishing net from being blocked).

The following products were used as components of the antifouling coating composition in the following Examples and the like.
(B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one: “Sea Nine 211” manufactured by Rohm and Haas. Solid content 30%.
・ (C) 2-Pyridinethiol-1-oxide zinc ... “Zinc Omarine” manufactured by Nippon Olin
-(D) Titanium oxide: "Titone R-5N" manufactured by Sakai Chemical Co., Ltd. Rutile type. Surface treatment with Al compound. Average primary particle size 0.25 μm.
-(D) Titanium oxide: "Ti-Pure R-960" rutile type manufactured by Dupon. Surface treatment with Al compound and Si compound. Average primary particle size 0.21 μm.
・ (E) Zinc oxide: “Zinc Hana 3” manufactured by Kyushu Hakusui Chemical Co., Ltd.
・ (F) Triphenylboronpyridine: “PK Boron” manufactured by Hokuko Chemical Co., Ltd.
(F) 4-Isopropylpyridine-diphenylmethylborane: “KM-2” manufactured by Keisei Kasei Co., Ltd.
-(G) Inorganic dehydrating agent "Yakigypsum FT-2" manufactured by Noritake Company Limited. Hemihydrate gypsum (CaSO ₄ · 1 / 2H ₂ O), average particle size 15 μm.
(G) Inorganic dehydrating agent "Soluble anhydrous gypsum D-1" manufactured by Noritake Company Limited. CaSO ₄ , white powder, average particle size 15 μm.
・ (H) Plasticizer: “Cereclor S-52” manufactured by Ineos Chlor. Chlorinated paraffin.
-(H) Plasticizer: "Terpene phenol YP90L" manufactured by Yasuhara Chemical Co., Ltd. Flaked phenol-modified terpene resin.
・ External pigment (talc): “NKK-F” manufactured by Fuji Talc
・ Coloring pigment (red): “Bengara Moonlight BB” manufactured by Toda Kogyo Co., Ltd.
-Color pigment (red): "Fuji First Red 2305W" manufactured by Sanyo Dye
・ Taking agent (polyamide wax): “Disparlon A630-20X” manufactured by Enomoto Kasei Co., Ltd. Xylene paste, 20% solids.
・ Other resins: Chinese “WW Rosin”. Xylene solution, 50% solids.
-Other resin: "Laroflex MP-25" manufactured by BASF. Vinyl chloride / isobutyl vinyl ether copolymer resin.

Moreover, the measuring method of various physical properties in the following examples etc. is as follows.
・ Solid content ratio of reaction solution: The reaction solution weight is the weight of the reaction solution (total weight of raw materials used) excluding the weight of volatile solvents contained in those raw materials. The proportion of the solid content in the solution was calculated. In addition, in the reaction solution at the time of manufacturing a metal salt bond-containing copolymer, almost all the weight of the solid content was regarded as the weight of the metal salt bond-containing copolymer, and was used for calculation of the ratio of the blend composition.
-Number average molecular weight (Mn) and weight average molecular weight (Mw) of the metal salt bond-containing copolymer: Polystyrene conversion value by GPC. Measured with Tosoh HLC-8120. Use two TSK-gel α-type separation columns (α-M) and eluent of dimethylformamide with 20 mM LiBr added.
-Gardner viscosity of the copolymer containing a metal salt bond: a measured value at 25 ° C at a resin concentration of 35% by weight according to 4.3 of JIS K7233.

[Preparation Example 1]
Preparation of metal-containing monomer (a1-1) In a four-necked flask equipped with a condenser, thermometer, dropping funnel and stirrer, 85.4 parts of propylene glycol monomethyl ether (PGM) and 40.7 parts of zinc oxide were added. The temperature was raised to 75 ° C. while charging and stirring. Subsequently, a mixture consisting of 43.1 parts of methyl methacrylate (MMA), 36.1 parts of acrylic acid (AA), and 5 parts of water was dropped at a constant rate over 3 hours from the dropping funnel. After completion of the dropwise addition, the reaction solution became transparent from the milky white state. After further stirring for 2 hours, 36 parts of PGM was added to obtain a reaction solution containing the metal-containing monomer (a1-1). Table 1 shows the raw materials used and the solid content ratio of the obtained reaction liquid.

[Preparation Example 2]
Preparation of metal-containing monomer (a1-2) In the method described in Preparation Example 1 above, except that butanol and xylene were used instead of propylene glycol monomethyl ether (PGM), a metal-containing monomer ( a1-2) was prepared (see Table 1).

[Adjustment Example 3]
Preparation of metal salt bond-containing copolymer (A-1) A four-necked flask equipped with a condenser, thermometer, dropping funnel and stirrer was charged with 30 parts of propylene glycol monomethyl ether (PGM) and 40 parts of xylene and stirred. The temperature was raised to 100 ° C. Subsequently, 52 parts of the reaction solution of the metal-containing monomer (a1-1) obtained in Preparation Example 1, 1 part of methyl methacrylate (MMA), and 66 of ethyl acrylate (EA).
2 parts, 5.4 parts 2-methoxyethyl acrylate (2-MEA), “NOFMER MSD” (
Nippon Oil & Fats Co., Ltd.) 1 part, azobisisobutyronitrile (AIBN) 2.5 parts, azobismethylbutyronitrile (AMBN) 7 parts and xylene 10 parts transparent mixture from the dropping funnel over 3 hours Was dropped at a constant speed. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate (TBPO) and 10 parts of xylene were added dropwise over 2 hours, and the mixture was further stirred for 2 hours. A reaction solution containing the coalescence (A-1) was obtained. Table 2 shows the raw materials used and the solid content ratio of the obtained reaction liquid.

[Adjustment Example 4]
Preparation of metal salt bond-containing copolymer (A-2) In the method described in Production Example 1 above, except that the metal-containing monomer and other copolymerization monomers used were changed, the metal salt bond-containing copolymer was used. A copolymer (A-2) was produced (see Table 2).

[Examples 1 to 11]
An antifouling paint composition was produced according to a conventional method using the composition shown in Table 3 (unit: parts by weight).

[Comparative Examples 1-5]
An antifouling paint composition was produced according to a conventional method with the composition shown in Table 4 (unit: parts by weight).

[Test Example 1]
Coating Film Consumability Test The antifouling paint compositions according to Examples 1 to 11 and Comparative Examples 1 to 5 were directly dried on a hard vinyl chloride resin plate (50 mm × 50 mm × 1.5 mm) that had not been primed. It was applied with an applicator so that the thickness was 150 μm. The obtained test plate with antifouling coating was attached to a rotating drum installed in seawater in Nagasaki Bay, Nagasaki Prefecture, rotated at a peripheral speed of 15 knots, and the degree of coating consumption (cumulative consumption film thickness immediately after installation of coating) ) Was measured every 2 months for 6 months. The results are as shown in Tables 3 and 4.

[Test Example 2]
Static antifouling test Sand blasted steel plate (length 300 mm x width 100 mm x thickness 3.2 mm) is pre-coated with an epoxy-based anticorrosive paint (epoxy AC paint, trade name “Banno 500”, manufactured by China Paint Co., Ltd.) It was applied so that the dry film thickness was 150 μm, and then an epoxy binder paint (trade name “Banno 500N”, manufactured by China Paint Co., Ltd.) was applied so that the dry film thickness was 100 μm. Thereafter, the antifouling paint composition according to Examples 1 to 11 and Comparative Examples 1 to 5 was applied once to the test plate with the above-mentioned undercoating so that the dry film thickness was 150 μm, and it was 7 days at room temperature. It dried and created the test board with an antifouling coating film. In addition, all the above-mentioned three times of coating were 1 day / 1coat. Then, the prepared test plate was immersed in Nagasaki Bay, Nagasaki Prefecture for 6 months, and during that period, the adhesion area (%) of aquatic organisms was measured and converted to the degree of adhesion according to the following evaluation criteria. The results are as shown in Tables 3 and 4.

Evaluation criteria for the degree of attachment of aquatic organisms;
0 points: no aquatic organisms attached 0.5 points: aquatic organisms attached area of about 10% 1 point: aquatic organisms attached area of about 20% 2 points: aquatic organisms attached area of about 30% 3 points …… Aquatic organisms attachment area of about 40% 4 points …… Aquatic organisms attachment area of about 50% 5 points …… Aquatic organisms attachment area of about 100%

Claims (11)

A metal salt bond-containing copolymer (A) having a structure represented by the following formula (I), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B), and 2- An antifouling coating composition comprising pyridinethiol-1-oxide zinc (C) and titanium oxide (D);

[In formula (I), M represents a zinc atom or a copper atom, and R ¹ independently represents a hydrogen atom or a methyl group. ]   The antifouling paint composition according to claim 1, wherein 5 to 40 parts by weight of titanium oxide (D) is contained in 100 parts by weight of the total solid content of the antifouling paint composition. In 100 parts by weight of the total solid content of the antifouling coating composition, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B) and 2-pyridinethiol-1-oxide zinc (C) The antifouling paint composition according to claim 1, comprising 0.1 to 15 parts by weight in total.   Furthermore, 10-30 weight part of zinc oxide is contained in 100 weight part of total solid of an antifouling paint composition, The antifouling paint composition in any one of Claims 1-3 characterized by the above-mentioned. Further, 0.1% of boron organic antifouling agent is added to 100 parts by weight of the total solid content in the antifouling coating composition.
The antifouling paint composition according to any one of claims 1 to 4, comprising 10 to 10 parts by weight. Further, an inorganic dehydrating agent is added in an amount of 0.02 to 1 in 100 parts by weight of the total solid content in the antifouling coating composition.
The antifouling paint composition according to any one of claims 1 to 5, which is contained in a proportion of 0 part by weight. The plasticizer is further contained in a proportion of 0.1 to 5 parts by weight in 100 parts by weight of the total solid content in the antifouling paint composition, according to any one of claims 1 to 6. Antifouling paint composition.   The antifouling paint composition according to any one of claims 1 to 7, which contains substantially no cuprous oxide. The acrylic resin type metal salt bond-containing copolymer (A) comprises a metal-containing monomer (a1) capable of deriving the structure represented by the formula (I), and a copolymer containing these metal-containing monomers. It was obtained by copolymerization with a polymerizable metal-free monomer (a2),
The blending amount of the metal-containing monomer (a1) is 2 to 50% by weight and the blending amount of the metal-free monomer (a2) is 50 to 98% by weight based on the whole of these monomers. The antifouling paint composition according to any one of claims 1 to 8, wherein The metal-containing monomer (a1) is composed of at least one selected from the group consisting of zinc di (meth) acrylate and copper di (meth) acrylate, and the metal-free monomer The body (a1) is composed of at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate, The antifouling paint composition according to any one of claims 1 to 9.   Furthermore, at least 1 sort (s) of a vinyl resin, an acrylic resin, a terpene phenol resin, a ketone resin, a coumarone resin, a petroleum resin, a rosin, a pine tar, or a versatic acid is contained, The claim 1 characterized by the above-mentioned. The antifouling paint composition as described.