JP2001342421A - Antifouling coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling coating material capable of providing a coated film having crack resistance and long-term antifouling properties. SOLUTION: This antifouling coating material is characterized in that the coating material contains a resin composition of an acrylic resin having at least one group represented by formula (1) [wherein, X is a group represented by formula (2); n is 0 or 1; Y is a hydrocarbon; M is a divalent metal; and A is an organic acid residue of a monobasic acid], on a side chain of the resin, and 5-100 mol% of the organic acid residue possessed by the side chain is a cyclic organic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling paint using a novel metal-containing resin composition, and more particularly to a metal-containing resin comprising a hydrolyzable resin having a specific group at a side chain terminal. The present invention relates to an antifouling paint containing the composition as a vehicle.

[0002]

2. Description of the Related Art Ships, fishing nets and other underwater structures include:
Marine organisms such as barnacles, mussels, and algae are easily attached,
As a result, efficient operation is hindered in ships and the like, resulting in waste of fuel, and in fishing nets and the like, clogging occurs and the service life is shortened. In order to prevent organisms from adhering to these underwater structures, an antifouling paint is usually applied to the surface thereof. Typical antifouling paints conventionally used include matrix type antifouling paints in which rosin is blended with a vinyl resin or alkyd resin insoluble in seawater. However, since this paint elutes the antifouling agent together with rosin in seawater, stable antifouling properties cannot be expected for a long time, and since the insoluble resin portion remaining in the coating film forms a skeleton structure, When applied to a ship, it has the drawback that the resistance between seawater and the coated surface increases, leading to a reduction in speed and the like.

[0003] In recent years, among antifouling paints, hydrolytic antifouling paints have been widely used because of their excellent advantages such as being able to exhibit antifouling properties over a long period of time, and one of them includes a metal-containing resin composition. Paints have been developed. JP-A-62-101653 and JP-A-63-1280 of the present applicant
No. 08, JP-A-63-128084 and JP-A-08-73536 disclose a metal-containing resin in which a pendant acid group forms a salt with a metal atom together with a monobasic organic acid, and a method for producing the same. It has been disclosed. When this resin is used as an antifouling paint, the resin is gradually hydrolyzed in seawater, releasing antifouling metal ions, and at the same time, the resin itself becomes water soluble and gradually dissolves, exhibiting a self-polishing effect. . However, even these antifouling paints have some difficulty in longer-term antifouling properties.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antifouling paint having a coating having crack resistance and long-term antifouling properties.

[0005]

According to the present invention, there is provided a resin having a side chain having the formula

[0006]

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(Where X is

[0008]

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Wherein n is 0 or 1, Y is a hydrocarbon, M is a divalent metal, and A is an organic acid residue of a monobasic acid. ) Is an acrylic resin having at least one group represented by the formula (1), wherein 5 to 100 mol% of the organic acid residues include a resin derived from a cyclic organic acid. The acid value of the organic acid is 120 to 190.
It is preferred that Further, the cyclic organic acid used is preferably a monobasic acid having a diterpene-based hydrocarbon skeleton or a salt thereof, more preferably abietic acid,
It is selected from the group consisting of hydrogenated abietic acid and salts thereof, or is selected from the group consisting of rosins, hydrogenated rosins and disproportionated rosins. in addition,
Preferably, the divalent metal is copper or zinc. Further, it is preferable that the acrylic resin is contained in the entire vehicle component in an amount of 30 to 100% by weight in terms of solid content.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The acrylic resin used in the novel antifouling paint of the present invention is an acrylic resin having at least one group represented by the above formula in the resin side chain, and can be easily produced by, for example, any of the following methods. That is, (1) a resin obtained by copolymerizing a polymerizable unsaturated organic monomer with another polymerizable unsaturated monomer is reacted with at least an equivalent amount of a metal compound and a monobasic organic acid, Or a method of transesterification using a metal ester of a monobasic organic acid, or (2) reacting an unsaturated organic acid monomer with a metal compound and a monobasic organic acid to synthesize a metal-containing polymerizable unsaturated monomer. And then copolymerizing it with another polymerizable unsaturated monomer. In the above (1), the resin obtained by copolymerizing a polymerizable unsaturated organic acid monomer with another polymerizable unsaturated monomer has an acid value of 100 to 25.
It is preferably 0 mgKOH / g. If it is less than 100, the amount of the metal ester bonded to the side chain will be small, and the antifouling property may be poor. If it exceeds 250, the dissolution rate is too fast, and a long-term antifouling effect cannot be expected.

The polymerizable unsaturated monomers used in the above method include, for example, (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and i- (meth) acrylate. Propyl, n-butyl (meth) acrylate, i-butyl (meth) acrylate,
T-butyl (meth) acrylate, 2 (meth) acrylate
An ester moiety such as ethylhexyl, lauryl (meth) acrylate, and stearyl (meth) acrylate having 1 carbon atom;
(20) alkyl esters of (meth) acrylate; 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc., wherein the ester moiety has 1 to 20 carbon atoms and a hydroxyl group-containing alkyl (meth) acrylate. Esters: (meth) acrylic acid cyclic hydrocarbon esters such as phenyl (meth) acrylate and cyclohexyl (meth) acrylate; (poly) ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) having a polymerization degree of 2 to 10 (Meth) acrylic acid polyalkylene glycol esters such as acrylates; and, in addition to alkoxyalkyl (meth) acrylates having 1 to 3 carbon atoms,
(Meth) acrylamide; vinyl compounds such as styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl toluene and acrylonitrile; and crotonic esters; maleic diesters and itaconic diesters Diesters of unsaturated dibasic acids can be mentioned. The ester portion of the acrylic acid esters is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Preferred are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate. These monomers may be used alone or in combination of two or more.

The unsaturated organic acid monomer used in the above method includes one having one or more carboxyl groups, such as (meth)
Unsaturated monobasic acid such as acrylic acid; unsaturated dibasic acid such as maleic acid and its monoalkyl ester, itaconic acid and monoalkyl ester and its monoalkyl ester; maleic acid of 2-hydroxyethyl (meth) acrylate Adducts, dibasic acid adducts of unsaturated monobasic hydroxyalkyl esters such as phthalic acid adducts of 2-hydroxyethyl (meth) acrylate and succinic acid adducts of 2-hydroxyethyl (meth) acrylate are mentioned. Can be

The resin obtained by copolymerization in the above (1) has a number average molecular weight of 2,000 to 100,000, particularly 300
It is preferably in the range of 0 to 40,000. This is necessary to maintain a balance between film forming properties, workability and dissolution rate.

The metal forming the metal ester with the acrylic resin is a metal element, that is, 3A to 7A in the long-term periodic table,
It can be selected from 8,1B to 7B group elements. Among them,
Copper and zinc are preferred. The metal is preferably contained in the acrylic resin solid content in an amount of 0.3 to 20% by weight. If it is less than 0.3% by weight, the elution in the resin is extremely slow even if the metal ester portion is hydrolyzed, and if it exceeds 20% by weight, the elution rate is too fast, and both are not preferred. More preferably, it is 0.5 to 15% by weight. The metal compound is not particularly limited, and examples thereof include metal oxides, hydroxides, chlorides, sulfides, and basic carbonates. These can be used alone or in combination of two or more.

The organic acid residue of the monobasic acid introduced into the side chain of the acrylic resin of the present invention is 5 to 100 mol%.
Is a cyclic organic acid. Preferably it is 15-100 mol%, More preferably, it is 25-100 mol%. If it is less than 5 mol%, it is not possible to achieve both long-term antifouling properties and crack resistance of the coating film.

The acid value of the monobasic cyclic organic acid used to introduce the above monobasic cyclic organic acid residue is from 120 to 190.
It is preferred that When it is within this range, hydrolysis of the acrylic resin in the present invention is performed appropriately,
The antifouling effect can be maintained for a long time. More preferably,
140-185.

The monobasic cyclic organic acid is not particularly limited, and examples thereof include those having a cycloalkyl group such as naphthenic acid, resin acids such as tricyclic resin acids, and salts thereof. The tricyclic resin acid is not particularly limited and includes, for example, monobasic acids having a diterpene-based hydrocarbon skeleton, and such examples include, for example, abietane, pimaran, isopimaran,
There are compounds having each labdan skeleton, for example, abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, parastolic acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid and the like. Can be. Of these, abietic acid, hydrogenated abietic acid, and salts thereof are preferable because the hydrolysis is performed moderately, so that it has excellent long-term antifouling properties, and also has excellent crack resistance and easy availability of the coating film. The monobasic cyclic organic acid does not need to be highly purified, and may be, for example, rosin, pine resin acid, and the like. Additional rosins, disproportionated rosins, and the like can be given. The rosins here include gum rosin, wood rosin, tall oil rosin and the like. Rosins, hydrogenated rosins, and disproportionated rosins are preferable in that they are inexpensive, easily available, have excellent handling properties, and exhibit long-term antifouling properties. The monobasic cyclic organic acids may be used alone or in combination of two or more.

Among the monobasic organic acids that can be used in the present invention,
Other than the above monobasic cyclic organic acids, for example, acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, oleic acid, chloroacetic acid, fluoroacetic acid, valeric acid, etc. Can be mentioned. The above reaction can be carried out by a conventionally known method, but it is desirable that heating, stirring and the like be carried out at a temperature not higher than the decomposition temperature of the metal ester.

The Y in the above formula is not particularly limited as long as it is a hydrocarbon. For example, the residue in the case where a dibasic acid such as phthalic acid, succinic acid or maleic acid is added to an unsaturated organic acid monomer. Can be mentioned. The above Y can be introduced by adding a dibasic acid to the unsaturated monobasic acid hydroxyalkyl ester as described above and copolymerizing the dibasic acid to obtain a resin, or After the production, the dibasic acid may be introduced in the presence of the above-mentioned dibasic acid. In this case, n = 1.

The hydrolyzable metal-containing acrylic resin thus obtained can be prepared into an antifouling paint by adding conventional additives including an antifouling agent. This antifouling paint is a self-polishing antifouling paint.

In the antifouling paint of the present invention, the above acrylic resin is contained in all vehicle components in the antifouling paint in an amount of 30 to 30 in terms of solid content.
It is preferred to contain 100% by weight. If the content is less than 30% by weight, it is not preferable because excellent long-term antifouling property and crack resistance of the coating film cannot be maintained at the same time.

In the above antifouling paint, in addition to the above acrylic resin,
For example, conventional additives such as an antifouling agent, a plasticizer, a coating film wear regulator, a pigment, and a solvent can be added. As the antifouling agent, known compounds can be used.For example, inorganic compounds, organic compounds containing metals, organic compounds containing no metals can be used, for example, cuprous oxide, manganese ethylenebis Dithiocarbamate, zinc dimethylcarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine,
2,4,6-tetrachloroisophthalonitrile, N, N
-Dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, copper rhodan, 4,5, -dichloro-2-n-octyl-3 (2H) isothiazolone, N-
(Fluorodichloromethylthio) phthalimide, N, N
'-Dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, 2-pyridinethiol-
1-oxide zinc salt and copper salt, tetramethylthiuram disulfide, 2,4,6-trichlorophenylmaleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2- Propyl butyl carbamate, diiodomethyl paratrisulfone,
Phenyl (bispyridyl) bismuth dichloride, 2-
(4-Thiazolyl) -benzimidazole and triphenylboronpyridine salt can be exemplified. The above antifouling agents may be used alone or in combination of two or more.

The amount of the antifouling agent to be used is as follows:
0.1-80% by weight is preferred. If the amount is less than 0.1% by weight, the antifouling effect cannot be expected. If the amount exceeds 80% by weight, defects such as cracks and peeling may occur in the coating film.
Preferably it is 1 to 60% by weight.

Examples of the plasticizer include phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate and dicyclohexyl phthalate; aliphatic dibasic ester plasticizers such as isobutyl adipate and dibutyl sebacate; diethylene glycol dibenzoate; Glycol ester plasticizers such as pentaerythritol alkyl ester; phosphate ester plasticizers such as tricleandiphosphoric acid and trichloroethyl phosphoric acid; epoxy soybean oil;
Epoxy plasticizer such as octyl epoxy stearate;
Organic tin-based plasticizers such as dioctyltin laurylate and dibutyltin laurylate; trioctyl trimellitate, triacetylene, and the like;

Examples of the coating film consumption adjusting agent include paraffin chloride, polyvinyl ether, polypropylene sebacate, partially hydrogenated terphenyl, polyvinyl acetate, poly (meth) acrylic acid alkyl ester, polyether polyol, alkyd resin, Examples include polyester resin, polyvinyl chloride, silicone oil, wax, petrolatum, liquid paraffin, rosin, naphthenic acid, fatty acid, and divalent metal salts thereof.

Examples of the above pigments include extenders such as precipitated barium, talc, clay, chalk, silica white, alumina white, bentonite, etc .; titanium oxide, zircon oxide, basic lead sulfate, tin oxide, carbon black, graphite , Chromium yellow, phthalocyanine green, phthalocyanine blue, quinacridone and the like.

As the solvent, for example, toluene,
Hydrocarbons such as xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane and white spirit; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, Ethers such as diethylene glycol monoethyl ether; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; ketones such as ethyl isobutyl ketone and methyl isobutyl ketone; n-butanol And alcohols such as propyl alcohol.

In addition to the above, other additives are not particularly limited. For example, monobasic organic acids such as monobutyl phthalate and monooctyl succinate, camphor, castor oil, etc .; water binders, anti-sagging agents; Inhibitors; anti-settling agents; defoamers and the like.

The antifouling paint of the present invention is obtained, for example, by adding a conventional additive such as an antifouling agent, a plasticizer, a coating consumption control agent, a pigment, a solvent, etc. to the acrylic resin composition of the present invention. It can be prepared by mixing using a mixer such as a ball mill, a pebble mill, a roll mill, and a sand grind mill. The antifouling paint can be applied to the surface of the article to be coated according to a conventional method, and then a solvent can be volatilized and removed at room temperature or under heating to form a dry coating film.

[0030]

The present invention will be described in more detail with reference to the following examples.
As will be described, the present invention is limited to only these examples.
is not. Parts represent parts by weight.Varnish production example 1  Stirrer, cooler, temperature controller, nitrogen inlet tube, dropping row
Xylol, n-
16 parts of butanol was added and kept at 100 ° C. In this solution
7.3 parts of ethyl acrylate, 2-ethyl methacrylate
Hexyl 22.1 parts, cyclohexyl methacrylate 15
Part, methoxypolyethylene glycol methacrylate
Ter (NK ester M-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30
Parts, acrylic acid 25.6 parts, t-butyl peroxy-2
A mixture of 2 parts ethylhexanoate in 3 hours
The solution was dropped at a constant speed. After the completion of the dropwise addition, the temperature was maintained for 30 minutes. So
After that, 16 parts of xylol, 4 parts of n-butanol, t-butyl
0.2 parts of tilperoxy-2-ethylhexanoate
Is dropped at a constant speed over 30 minutes
Thereafter, the temperature was kept for 1 hour and 30 minutes. Solid content in the obtained resin solution
Is 50.5%, viscosity is 20 poise, number average molecular weight is 7000
Of varnish A was obtained. The obtained resin has an acid value (solid content.
Same below. ) Was 200.

[0031]Varnish production example 2  Xylol 50 was placed in the same reaction vessel as in Varnish Production Example 1.
And 50 parts of n-butanol. This
58.3 parts of ethyl acrylate and acrylic acid
Clohexyl 25 parts, acrylic acid 16.7 parts, t-butyl
Consists of 3 parts of luperoxy-2-ethylhexanoate
The mixed solution was dropped at a constant speed over 3 hours, and 2 hours after the dropping was completed.
Insulated. The solid content in the obtained resin solution is 51.0%,
Varnish B having a viscosity of 3.2 poise and a number average molecular weight of 4000
Obtained. The obtained resin had an acid value of 130.

[0032]Varnish production example 3  Xylol 40 was placed in the same reaction vessel as in Varnish Production Example 1.
And 40 parts of n-butanol. This
Ethyl acrylate in a solution of 48.2 parts, methacrylic acid
15 parts of 2-ethylhexyl, NK ester M-90G
17.5 parts, acrylic acid 19.3 parts, t-butyl peroxid
A mixture of xy-2-ethylhexanoate (2 parts) was added for 3 hours.
At a constant speed for 30 min.
Warmed. Then, xylol 10 parts, n-butanol 1
0 parts, t-butylperoxy-2-ethylhexanoe
0.2 part of the mixture was dropped at a constant speed over 30 minutes,
After the completion of the dropping, the temperature was maintained for 1 hour and 30 minutes. In the obtained resin solution
Solid content of 50.0%, viscosity 12 poise, number average molecular weight
7000 Varnish C was obtained. The resulting resin has an acid value of 1
It was 50.

[0033]Varnish production example 4  Xylol 64 was placed in the same reaction vessel as in Varnish Production Example 1.
And 16 parts of n-butanol. this
Ethyl acrylate 21.9 parts, methacrylic acid i
Sobutyl 30 parts, NK ester M-90G 22.5
Parts, acrylic acid 25.6 parts, azobisisobutyronitrile
The mixture of 2 parts was dropped at a constant speed over 3 hours, and the dropping was completed.
After that, it was kept warm for 30 minutes. Thereafter, 16 parts of xylol, n-
Butanol 4 parts, azobisisobutyronitrile 0.2 parts
Is dropped at a constant speed over 30 minutes.
Incubated for hours. The solid content in the obtained resin solution is 49.8.
%, Viscosity 7.5 poise, number average molecular weight 8000 varnish
D was obtained. The obtained resin had an acid value of 200.

[0034]Varnish production example 5  Xylol 64 was placed in the same reaction vessel as in Varnish Production Example 1.
And 16 parts of n-butanol. This
20 parts of methyl methacrylate and ethyl acrylate
28.3 parts of chill, 2-ethylhexyl methacrylate 25
Part, NK ester M-90G 10 parts, acrylic acid 1
6.7 parts, t-butylperoxy-2-ethylhexano
A mixture of 3 parts of Eat is dropped at a constant speed over 3 hours
After the completion, the temperature was kept for 30 minutes. Then, 16 parts of xylol,
4 parts of n-butanol, t-butylperoxy-2-ethyl
Luxanoate 0.2 part mixture over 30 minutes
The solution was dropped at a constant speed, and the temperature was kept for 1 hour and 30 minutes after the completion of the dropping. Obtained
51.5% solids in the resin solution, viscosity 6.7 poi
And a varnish E having a number average molecular weight of 5,000. Got
The resin had an acid value of 130.

[0035]Varnish production example 6  Xylol 64 was placed in the same reaction vessel as in Varnish Production Example 1.
And 16 parts of n-butanol, and the mixture was kept at 100 ° C. This
80.7 parts of ethyl acrylate, acrylic acid
A liquid mixture of 19.3 parts and 2 parts of azobisisobutyronitrile
At a constant rate over 4 hours and keep warm for 30 minutes after dropping
did. Then, xylol 16 parts, n-butanol 4
Part of a mixture of 0.2 parts of azobisisobutyronitrile and 3 parts of
Drop at a constant speed over 0 minutes and keep it warm for 2 hours after dropping
Was. The solid content in the obtained resin solution is 50.2%, the viscosity is
Varnish F having 4.5 poises and a number average molecular weight of 6000 was obtained.
Was. The obtained resin had an acid value of 150.

[0036]Varnish production example 7  Stirrer, nitrogen inlet tube, reflux condenser, decanter, temperature control
100 parts of varnish A in a four-necked flask equipped with a control device,
Copper acetate 37.1 parts, WW rosin (acid value 160) 62.5
Parts and 140 parts of xylol to reflux temperature
Raise the temperature and remove the mixed solution of acetic acid, water and solvent
The reaction was continued for 14 hours while replenishing the same amount of xylene.
Was. The end point of the reaction is determined by quantifying acetic acid in the effluent solvent.
Was. After cooling, butanol and xylene were added and the solid content was 3
6.5% of Varnish 1 was obtained.

[0037]Varnish production example 8  Varnish B100 was placed in a reaction vessel similar to that of Varnish Production Example 7.
Parts, zinc acetate 25.4 parts, hydrogenated rosin (acid value 160) 4
Same as varnish production example 7 except that 0.6 part is used
The varnish 2 having a solid content of 50.4% was obtained.

[0038]Varnish production example 9  Varnish C100 was placed in a reaction vessel similar to that of Varnish Production Example 7.
Parts, 27.8 parts of copper acetate, disproportionated rosin (acid value 160) 4
Same as varnish production example 7 except that 6.9 parts were used
To give Varnish 3 having a solid content of 36.8%.

[0039]Varnish production example 10  Varnish D100 was placed in the same reaction vessel as in Varnish Production Example 7.
Parts, zinc acetate 39.1 parts, abietic acid (acid value 160)
Same as varnish production example 7, except that 53.5 parts were used.
In the same manner to obtain Varnish 4 having a solid content of 37.7%.
Was.

[0040]Varnish production example 11  Varnish E100 was placed in the same reaction vessel as in Varnish Production Example 7.
Parts, copper acetate 24.1 parts, disproportionated rosin (acid value 160) 4
Same as varnish production example 7 except that 0.6 part is used
The varnish 5 having a solid content of 44.4% was obtained.

[0041]Varnish production example 12  In a similar reaction vessel as in Varnish Production Example 7, Varnish F100
Parts, 27.8 parts of copper acetate, hydrogenated rosin (acid value 160) 4
Same as varnish production example 7 except that 6.9 parts were used
The varnish 6 having a solid content of 52.6% was obtained.

[0042]Varnish production example 13  Varnish A100 was placed in the same reaction vessel as in Varnish Production Example 7.
Parts, 37.1 parts of copper acetate, hydrogenated rosin (acid value 160) 6
Same as varnish production example 7 except that 2.5 parts are used
The varnish 7 having a solid content of 40.2% was obtained.

[0043]Varnish production example 14  Varnish C100 was placed in a reaction vessel similar to that of Varnish Production Example 7.
Parts, 27.8 parts of copper acetate, naphthenic acid (NA-165, acid
Using 45.5 parts of 165, manufactured by Daiwa Yushi Kogyo KK
The reaction was carried out in the same manner as in Varnish Production Example 7, except that
35.0% of varnish 8 was obtained.

[0044]Varnish production example 15  Varnish A100 was placed in the same reaction vessel as in Varnish Production Example 7.
Parts, 37.1 parts of copper acetate and 30.3 parts of versatic acid
The reaction was carried out in the same manner as in Varnish Production Example 7, except that
A varnish 9 having a solid content of 34.7% was obtained.

[0045]Varnish production example 16  Varnish B100 was placed in a reaction vessel similar to that of Varnish Production Example 7.
Parts, zinc acetate 25.4 parts, naphthenic acid (NA-200,
(Acid value 200, manufactured by Daiwa Yushi Kogyo Co., Ltd.)
And the reaction was carried out in the same manner as in Varnish Production Example 7,
A varnish 10 having a fraction of 42.1% was obtained.

[0046]Varnish production example 17  Varnish D100 was placed in the same reaction vessel as in Varnish Production Example 7.
Parts, 39.1 parts of zinc acetate and 50.3 parts of oleic acid
Other than that, the reaction was performed in the same manner as in Varnish Production Example 7,
Varnish 11 having a solid content of 39.0% was obtained.

[0047]Varnish production example 18  Varnish E100 was placed in the same reaction vessel as in Varnish Production Example 7.
Parts, 24.1 parts of copper acetate and 19.7 parts of versatic acid.
The reaction was carried out in the same manner as in Varnish Production Example 7, except that
A varnish 12 having a solid content of 39.8% was obtained.

[0048]Examples 1 to 18, Comparative Examples 1 to 4  Varnishes 1 to 12 obtained in varnish production examples 7 to 18 and
Using the other components shown in Table 1 for high-speed dispers
To prepare a coating composition, and the following evaluation method
The long-term antifouling property and the state of the coating film were evaluated according to the above. Evaluation
The results are shown in Table 2. The antifouling agents listed in Table 1 are as follows.
The compound described above. Antifouling agent 1: Zinc dimethyl dithiocarbamate Antifouling agent 2: Manganese ethylene bisdithiocarbamate
Antifouling agent 3: 2-methylthio-4-t-butylamino-6
-Cyclopropylamino-s-triazine antifouling agent 4: 2,4,5,6 tetrachloroisophthalonite
Lil antifouling agent 5: N, N-dimethyldichlorophenylurea antifouling agent 6: 4,5-dichloro-2-noctyl-3 (2
H) Isothiazolone antifouling agent 7: N- (fluorodichloromethylthio) phthal
Imide antifouling agent 8: N, N {dimethyl-N'-phenyl- (N-
Fluorodichloromethylthio) sulfamide antifouling agent 9: 2,4,6-trichlorophenylmaleimide antifouling agent 10: 2,3,5,6-tetrachloro-4- (meth
Tylsulfonyl) pyridine antifouling agent 11: 3-iodo-2-propenylbutylcarba
Mate antifouling agent 12: diiodomethyl paratolyl sulfone antifouling agent 13: dimethyldithiocarbamoyl zinc
Anti-fouling agent 14: phenyl (bispyridine) bismuth dichloro
Ride antifouling material 15: 2- (4-thiazoyl) benzimidazo
Le antifouling agent 16: pyridine triphenylborane antifouling agent 17: zinc ethylenebisdithiocarbamate antifouling agent 18: stearylamine-triphenylboron antifouling agent 19: laurylamine-triphenylboron

[0049]

[Table 1]

(Evaluation)Coating condition  Brass coated with the rust-preventive paint beforehand
To a dry thickness of 300 μm on a plate
It was left in a room and dried to obtain a test plate. Hold the test plate directly
Attached to the cylindrical side of 750mm in diameter and 1200mm in length,
It was rotated continuously in seawater at a peripheral speed of 15 knots for 6 months. 6
Visual observation of the coating condition of the test plate after a lapse of months
Was evaluated. Table 2 shows the results.

[0051]Long-term antifouling properties  After observing the state of the coating film as described above, the test plate was placed in Tamano, Okayama Prefecture.
Live on a laboratory raft set up by Nippon Paint Co., Ltd.
A substance adhesion test was performed to evaluate the antifouling property. The results are shown in Table 2.
You. The number of months in Table 2 indicates the raft immersion period, and the number is
Shows the ratio to the coating film area.

[0052]

[Table 2]

The paints of Examples 1 to 14 exhibited long-term antifouling properties and excellent coating conditions. The paints of Comparative Examples 1 to 4 could not achieve both the state of the coating film and the long-term antifouling property.

[0054]

According to the present invention, it has excellent long-term antifouling properties,
In addition, an antifouling coating composition capable of maintaining an excellent coating state despite long-term immersion in seawater can be obtained.

Continued on the front page (72) Inventor Kiyoaki Higo 1-26 Komagabayashi Minamicho, Nagata-ku, Kobe Japan Paint Marine Co., Ltd. (72) Inventor Masayuki Matsuda 1-26 Komagabayashi-Minamicho, Nagata-ku, Kobe Japan F-term (for reference) in Paint Marine Co., Ltd. 4J038 CG091 CG141 GA06 NA05

Claims (7)

[Claims] (1) a resin having a formula: (Wherein X is N represents 0 or 1, Y represents a hydrocarbon, M represents a divalent metal, and A represents a monobasic acid organic acid residue. An acrylic resin having at least one group represented by the formula (1), wherein 5 to 100 mol% of the organic acid residues are derived from a cyclic organic acid. 2. The antifouling paint according to claim 1, wherein the acid value of the cyclic organic acid is from 120 to 190. 3. The antifouling paint according to claim 1, wherein the cyclic organic acid is a monobasic acid having a diterpene hydrocarbon skeleton or a salt thereof. 4. The antifouling paint according to claim 1, wherein the cyclic organic acid is selected from the group consisting of abietic acid, hydrogenated abietic acid and salts thereof. 5. The antifouling paint according to claim 1, wherein the cyclic organic acid is selected from the group consisting of rosins, hydrogenated rosins, and disproportionated rosins. 6. The antifouling paint according to claim 1, wherein said divalent metal is copper or zinc. 7. The antifouling paint according to claim 1, wherein said acrylic resin is contained in an amount of 30 to 100% by weight in terms of solid content in all vehicle components.