JPH05112739A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating compsn. exhibiting a long-lasting, excellent antifouling effect by combining a specific organosilicon polymer having cyclic diorganosilyl groups in its side chains with an antifouling agent. CONSTITUTION:A polymer prepd. from at least one kind of monomer of the formula [wherein X1 and X2 are each H or CH3; and Y1 and Y2 are each linear, branched, or cyclic alkyl or alkoxy, (substd.) phenyl, or (substd.) phenoxy] and/or a copolymer prepd. from the above-mentioned at least one kind of monomer and a vinyl monomer copolymerizable therewith (e.g. methyl methacrylate or dimethyl maleate) and an antifouling agent (e.g. triphenyltin chloride or copper naphthenate) are compounded as essential components to give a coating compsn., which gives a coating film which, when immersed in water, dissolves by hydrolysis uniformly at a suitable rate and exhibits a long- lasting, excellent antifouling effect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for preventing organisms from adhering to the surface of objects in water.

[0002]

2. Description of the Related Art Underwater objects such as ship bottoms, buoys, fishing nets (aquaculture nets such as hamachi and scallops, fixed nets for salmon), marine pollution prevention sheets, and various intake and drainage pipes for cooling that are immersed in water. Various obstacles occur on the surface of the plant due to fouling due to the adhesion of organisms such as barnacles, cerpra, mussels, and algae.

In order to prevent the stains from being caused by such organisms, the surface of the submerged product has an effect of preventing adhesion to organisms and is also slightly soluble in water, such as organotin copolymer and cuprous oxide. It is well known that a paint with a soiling agent is applied.

For example, as for a coating material using an organic tin compound as an antifouling agent, JP-B-40-21426, JP-B-44-9579 and JP-B-46-133.
No. 92, Japanese Patent Publication No. 49-20491, Japanese Patent Publication No. 5
It is disclosed in Japanese Patent Publication No. 1-111647 and Japanese Patent Publication No. 52-48170.

[0005]

However, all of these conventionally known coating materials have drawbacks as shown in the following (a) and (b), and improvements thereof have been strongly desired.

(B) The resin forming the coating film is not dissolved in water, and only the antifouling agent is dissolved in water, so that the type of coating material that prevents the adhesion of aquatic organisms is formed from this coating material. The initial antifouling effect of the coating film is good, but after the antifouling agent on the surface of the coating film is eluted and lost, the elution rate of the antifouling agent is slower in the deeper part of the coating film, so There was a drawback that the antifouling effect was insufficient.

(B) In the type of paint in which both the resin forming the coating film and the antifouling agent are dissolved in water, the case where only the antifouling agent is used and the case where the antifouling agent and the resin component (organic tin copolymer etc. are used) In both cases of (1) and (2), the surface of the coating film elutes, so that the active antifouling coating film surface is always maintained, and the antifouling effect is more persistent than in (a) above. However, even in this case, there is a limit to the consumption of the coating film, or conversely, the consumption is excessive, and the satisfactory effect is not obtained.

In view of the above-mentioned disadvantages (a) and (b), the present invention has an excellent antifouling property as compared with the above-mentioned coating material using the organic tin copolymer containing an antifouling agent. It is an object of the present invention to provide a novel type of coating composition in which a promising solvent-volatile type specific polymer is used and the anti-fouling agent and the specific polymer are essential components.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a specific organosilicon polymer having a diorganosilyl group in the side chain in a cyclic form is used as an antifouling agent. It was found that a coating composition capable of overcoming all of the above-mentioned conventional problems (a) and (b) and exhibiting a good antifouling effect over a long period of time can be obtained by using it in combination with It came to do.

That is, the present invention provides the following general formula (I); (In the formula, X ₁ and X ₂ are hydrogen atoms or methyl groups, Y ₁ and Y ₂ are linear alkyl groups, branched alkyl groups, cyclic alkyl groups, alkoxyl groups, phenyl groups, substituted phenyl groups, and phenoxyl groups. Group, a group selected from the group consisting of substituted phenoxyl groups, which may be the same or different from each other) one or more polymers of the monomer A, And / or a copolymer of one or more of the above-mentioned monomers A and one or more of the vinyl-based monomers B copolymerizable therewith, and an antifouling agent as essential components The present invention relates to a coating composition characterized by containing the same.

[0011]

In the coating composition of the present invention, the polymer or copolymer using the monomer A represented by the above general formula (I) has a cyclic diorganosilyl group in the side chain. Is
That is, since it has an organosilyl group in the form of a cyclic ester bond, the group having these two hydrolysis points is appropriately hydrolyzed, and the residual resin is dissolved accordingly. At the same time, the antifouling agent is gradually released into the water.
Effectively and persistently prevent biofouling on the surface of underwater objects.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the coating composition of the present invention, as one of its essential components, one or more polymers of monomer A represented by the above general formula (I) (hereinafter, Or a copolymer of one or more of the above-mentioned monomers A and one or more of the vinyl-based monomers B copolymerizable therewith (hereinafter referred to as a copolymer). Polymer AB) is used. Moreover, you may use together the said polymer A and the copolymer AB as needed.

The monomer A has a diorganosilyl group [> Si in the molecule as represented by the above general formula (I).
(Y ₁ ) (Y ₂ )] in a ring form, wherein X ₁ and X ₂ in the formula are hydrogen atoms or methyl groups, Y ₁ and Y ₂ are linear alkyl groups and branched alkyl groups, The groups selected from a cyclic alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, and a substituted phenoxyl group may be the same or different from each other.

The number of carbon atoms of each alkyl group or alkoxyl group in Y ₁ and Y ₂ is usually up to about 22, and the substituent of the substituted phenyl group or the substituted phenoxyl group is, for example, halogen or carbon. There are up to about 22 linear alkyl groups, branched alkyl groups, cyclic alkyl groups, alkoxyl groups, acyl groups and the like.

Examples of the synthesis of the monomer A include unsaturated acids such as maleic acid, α-monomethyl-substituted maleic acid and α · α′-dimethyl-substituted maleic acid, and the above-mentioned Y in the molecule. _A method of reacting a diorganosilyldiol having a ₁ , Y ₂ group to obtain by dehydration condensation,
The unsaturated acid similar to the above is reacted with the diorganodihydrosilane having the Y ₁ and Y ₂ groups in the molecule to obtain by dehydrogenative condensation, and the unsaturated acid similar to the above and the above in the molecule Of the diorganodichlorosilanes having Y ₁ and Y ₂ groups, or by a dehydrochlorination reaction in the presence of a base (eg, triethylamine, imidazole, etc.).

Examples of the vinyl-based monomer B which is a constituent of the copolymer AB include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid 2
-Methacrylic acid esters such as ethylhexyl and 2-hydroxyethyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid esters such as 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate, dimethyl maleate, diethyl maleate Maleic acid esters such as dimethyl fumarate, diethyl fumarate and other fumaric acid esters, styrenes such as styrene, vinyltoluene and α-methylstyrene, vinyl acetate, vinyl propionate, vinyl butyrate , Vinyl benzoate and other vinyl esters, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid, crotonic acid esters, itaconic acid, itaconic acid esters and the like.

The vinyl-based monomer B acts as a modifying component for imparting various performances to the antifouling coating film according to the purpose of use, and is higher than the monomer A alone. It is also a convenient component for obtaining polymers of molecular weight.

The amount of the monomer B used is set in an appropriate range in consideration of the above performance and the antifouling effect based on the monomer A. Generally, the proportion of the monomer B in the total amount of the monomer A is preferably 95% by weight or less, and particularly 90% by weight or less. That is, when the proportion of the monomer A constituting the copolymer AB is at least 5% by weight, particularly preferably at least 10% by weight, the antifouling effect based on the monomer A is sufficiently exhibited, The amount of the monomer B used may be set appropriately within the above range.

The polymer A and the copolymer AB are obtained by subjecting the above-described monomer A or the monomer B to the monomer B in the presence of a vinyl polymerization initiator according to a conventional method, such as solution polymerization, bulk polymerization and emulsification. By polymerizing by various methods such as polymerization and suspension polymerization,
Obtainable. These polymers are usually diluted with an organic solvent before use. Therefore, as a polymerization method,
It is desirable to adopt a solution polymerization method or a bulk polymerization method.

Examples of the organic solvent used for the above purpose include aromatic hydrocarbon solvents such as xylene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane,
Ester-based solvents such as ethyl acetate and butyl acetate, alcohol-based solvents such as isopropyl alcohol and butyl alcohol, ether-based solvents such as dioxane and diethyl ether, ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone. 1 type or a mixed solvent of 2 or more types.

The amount of the organic solvent used is such that the concentration of the polymer A and / or the copolymer AB in the solution is usually 5 to 90% by weight, particularly preferably 15 to 85% by weight. Good. The viscosity of the solution at this time is generally 150 poise or less / 25 ° C., which facilitates formation of a coating film.

Examples of the above-mentioned vinyl polymerization initiator include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, benzoylperoxide, di-tert-butylperoxide, manufactured by NOF Corporation. Peroxides such as per-butyl O, per-butyl I and per-butyl Z, which are trade names, can be mentioned.

The molecular weight of the polymer A and the copolymer AB obtained by such a method is 1,000 on a weight average basis.
It is desirable to be in the range of 300,000. If the molecular weight is too low, it will be difficult to form a coating that can withstand use, and if it is too high, the viscosity will be high when used as a coating agent and the resin solid content will be low, resulting in a thin coating after one coating. The problem is that only a film can be obtained, and several coats are required to obtain a dry coating film above a certain level.

In the coating composition of the present invention, conventionally known antifouling agents are widely included as another antifouling agent used as another essential component. Broadly speaking, there are organic compounds containing metal, organic compounds containing no metal, and inorganic compounds.

Examples of the organic compound containing a metal include organic tin compounds, organic copper compounds, organic nickel compounds and organic zinc compounds, and also manneb, manceb, propineb, zineb and the like.

Examples of the organic tin compounds include triphenyltin halides such as triphenyltin chloride and triphenyltin fluoride, tricyclohexyltin chloride, tricyclohexyltin halides such as tricyclohexyltin fluoride, tributyltin chloride and tributyltin fluoride. Halide, triphenyl tin hydroxide, tricyclohexyl tin hydroxide, bis (triphenyl tin) -α ・ α-dibromosuccine
Bis (tricyclohexyltin) -α ・ α-dibromosuccinate, bis (tributyltin) -α ・ α-dibromosuccinate, bis- (triphenyltin) oxide,
Bis- (tricyclohexyltin) oxide, bis- (tributyltin) oxide, triphenyltin acetate, tricyclohexyltin acetate, tributyltin acetate
, Triphenyltin monochloroacetate, triphenyltin versatate, triphenyltin dimethyldithiocarbamate, triphenyltin nicotinate and the like.

The organic copper compounds include oxine copper, copper nonylphenol sulfonate, copper bis (ethylenediamine) -bis (dodecylbenzene sulfonate),
Examples include copper acetate, copper naphthenate, and bis (pentachlorophenolic acid) copper.

Organic nickel compounds include nickel acetate and dimethyldithiocarbamate nickel, and organic zinc compounds include zinc acetate, zinc carbazate, zinc dimethyldithiocarbamate, zinc pyrithione and zinc ethylenebisdithiocarbamate.

Organic compounds containing no metal include N-trihalomethylthiophthalimide, dithiocarbamic acid, N
-Aryl maleimides, 3-substituted amino-1 .3-thiazolidine-2.4-diones, dithiocyano compounds, triazine compounds and others.

Examples of N-trihalomethylthiophthalimide include N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide, and examples of dithiocarbamic acid include bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ethylenebis (dithiocarbamine). Acid) ammonium, milneb and the like, respectively.

As N-arylmaleimide, N-
(2,4,6-trichlorophenyl) maleimide, N-
4-tolylmaleimide, N-3-chlorophenylmaleimide, N- (4-n-butylphenyl) maleimide, N
Examples thereof include-(anilinophenyl) maleimide and N- (2,3-xylyl) maleimide.

3-Substituted amino-1,3-thiazolidine-
As 2-4-dione, 3-benzylideneamino-1
3-thiazolidine-2,4-dione, 3- (4-methylbenzylideneamino) -1,3-thiazolidine-2.
4-dione, 3- (2-hydroxybenzylideneamino) -1,3-thiazolidine-2,4-dione, 3-
(4-Dimethylaminobenzylideneamino) -1,3-
Thiazoline-2,4-dione, 3- (2.4-dichlorobenzylideneamino) -1,3-thiazolidine-2,4
-There are Zeon, etc.

Examples of dithiocyano compounds include dithiocyanomethane, dithiocyanoethane, and 2.5-dithiocyanothiophene, and examples of triazine compounds include 2
-Methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine and the like, respectively.

Other organic compounds containing no metal include 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 4,5-
Dichloro-2-N-octyl-3- (2H) isothiazolone, N.N-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, 3-iodo-2- Propynyl butyl carbamate, 2- (methoxycarbonylamino)
Benzimidazole, 2,3,5,6-tetrachloro-
4- (Methylsulfonyl) pyridine, diiodomethylparatolyl sulfone, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, phenyl (bispyridine) bismuth dichloride, 2- (4-thiazolyl) benzimidazole, tetra Examples thereof include phenylboron pyridine salt.

Examples of the inorganic compound include cuprous oxide, copper powder, copper compounds such as copper thiocyanate, copper carbonate, copper chloride and copper sulfate, zinc sulfate, zinc oxide, nickel sulfate, copper-nickel alloy and the like.

In the present invention, one of the above-mentioned various antifouling agents is used alone or as a mixture of two or more thereof, and the amount thereof is the amount of the polymer A and / or the polymer. Considering the synergistic effect of the antifouling effect of the AB coating film and the chemical antifouling effect of the antifouling agent, it is set within an appropriate range. Generally, the proportion of the antifouling agent in the total amount of the polymer A and / or the polymer AB is 0.1 to 80% by weight.
Is desirable. If the antifouling agent is too small, the above synergistic effect cannot be expected, and if it is too large, defects such as cracks and peeling are likely to occur in the formed coating film, making it difficult to obtain effective antifouling properties.

If necessary, the coating composition of the present invention thus constructed may be mixed with a pigment such as red iron oxide, titanium dioxide, or a coloring agent such as a dye. Further, a usual anti-sagging agent, a color separation preventing agent, an anti-settling agent, an antifoaming agent and the like may be added.

Further, in the present invention, the following surface slip agents may be used. In addition to the polymer A and / or copolymer AB, which are essential components, and an antifouling agent, a surface lubricant is also used in combination, whereby the hydrolyzability of the coating film is appropriately controlled, and the resin and the antifouling agent are prevented. The solubility of the agent is properly maintained.

As such a surface slip agent, various substances known to impart slipperiness to the coating film surface are used. A typical example is JISK22.
Petroleum wax specified in 35, fluid paraffin specified in JIS K2231, 55,0 at 25 ° C
Silicone oil having a kinematic viscosity of not more than 00 centistokes, fatty acid having 8 or more carbon atoms and its ester having a melting point of -5 ° C or more, organic amine having an alkyl group or an alkenyl group having 12 to 20 carbon atoms, 25 ° C.
And polybutene having a kinematic viscosity of 60,000 centistokes or less.

Specific examples of the above include paraffin wax, microcrystalline wax, petrolatum and the like, and specific examples of the above include ISOVG10,
ISOVG15, ISOVG32, ISOVG68, I
Each equivalent of SOVG100 etc. is mentioned, respectively.

Specific examples of the above include trade names KF96L-0.65 and KF96L- manufactured by Shin-Etsu Chemical Co., Ltd.
2.0, KF96-30, KF96H-50,000,
KF965, KF50, KF54, KF69, etc., trade name TSF440, TSF41 manufactured by Toshiba Silicon Co., Ltd.
0, TSF4440, TSF431, TSF433, T
SF404, TFA4200, YF3860, YF38
18, YF3841, YF3953, TSF451, etc., trade names SH200, S manufactured by Toray Silicone Co., Ltd.
H510, SH3531, SH230, FS1265 and the like can be mentioned.

Of the above-mentioned silicone oils, dimethyl silicone oil is the most common, but other methylphenyl silicone oils, polyether silicone oils, cyclic polysiloxane oils, alkyl modified silicones.
Other oils such as methyl oil, methyl chlorinated phenyl silicone oil, higher fatty acid modified silicone oil, and fluorosilicone oil may be used.

Specific examples of the above include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
Stearic acid, cerotic acid, montanic acid, melissic acid,
Examples thereof include lauroleic acid, oleic acid, vaccenic acid, gadoleic acid, whale oil acid, shark oil acid, and diuniperic acid. Examples of esters of these carboxylic acids include stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, ceryl serrate, myricyl palmitate, melysyl mericate. Tomato, spermaceti wax, beeswax wax, carnauba wax, montan wax, bug wax wax, tristearin, tripalmitin, triolein, myristodilaurin, caprylolauromyristin, stearopalmitoolein, monostearin, monopalmitin, distearin , Dipalmitin, beef tallow, lard, horse fat, sheep fat, cod liver oil, coconut oil, palm oil, wood wax, capoque oil, cacao butter, Chinese fat, iritsupe fat and the like.

Specific examples of the above include dodecylamine, tetradodecylamine, hexadecylamine, octadecylamine, oleylamine, tallow alkylamine, cocoalkylamine, soybean oil alkylamine, didodecylamine, ditallow hydrogenated alkylamine, Dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine,
Octadecyl dimethylamine etc. are mentioned.

Specific examples of the above include Nippon Oil & Fats Co., Ltd.
Product name made by Nitsusan Polybutene 0N, 06N, 015
N, 3N, 5N, 10N, 30N, 200N, 0SH,
06SH, 015SH, 3SH, 5SH, 10SH, 3
Examples include 0SH and 200SH.

Further, since the polymer A and / or the polymer AB used in the present invention is hydrolyzed in the presence of water, the water contained in the antifouling agent or the pigment is used when it is made into a paint. It is also desirable to previously add a water-binding agent having a function of capturing in the system.

Examples of such water-binding agents include trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate and tributyl orthoformate, trialkyl orthoacetates such as trimethyl orthoacetate, triethyl orthoacetate and tributyl orthoacetate. Trialkyl orthoborate such as trimethyl orthoborate, triethyl orthoborate, tributyl orthoborate, tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate, tetra (2-methoxyethyl) silicate
Tetra (substituted) alkyl silicates such as tetra (2-chloroethyl) silicate, tetra (substituted) aryl silicates such as tetraphenyl silicate and tetrabenzyl silicate, and , Tetra (substituted) alkyl silicates or condensates of tetra (substituted) aryl silicates (dimer, trimer, tetramer, fuxamamer, etc.), hydrolyzable ester compounds, phenyl isocyanate And compounds having an isocyanate group, such as benzene and benzenesulphonyl isocyanate.

To form an antifouling coating film on the surface of an object to be immersed in water using the coating composition of the present invention, for example, the coating composition of the present invention as a solution is applied to the surface of the object. After application by an appropriate means, it may be dried at room temperature or under heating to remove the solvent by volatilization.

[0049]

The coating film obtained from the coating composition of the present invention exhibits hydrolyzability when dissolved in water at a suitable rate and uniformly dissolved in water. Therefore, according to the present invention, the bottom of a ship, the underwater structure such as a fish net or a cooling water pipe, which is required to prevent the aquatic biological pollution, and the marine pollution prevention sheet used for preventing the sludge diffusion in the marine civil engineering work, etc. The resulting coating film shows a remarkable antifouling effect, and can prevent biofouling fouling of submerged submerged substrates and the like over a long period of time.

[0050]

EXAMPLES Next, the present invention will be specifically described with reference to production examples, examples and comparative examples. Parts in the examples are parts by weight, viscosity is the measured value of foam viscosity at 25 ° C., and molecular weight is the weight average molecular weight by GPC. Further, the monomers A (A _{1 to} A ₇ ) used in the following production examples are the monomers represented by the above general formula (I), and are X ₁ , X ₂ , and Y _{1 in the} formula. , Y ₂ is
It is as shown in Table 1 below.

[0051]

[Table 1]

Production Examples 1 to 5 A flask equipped with a stirrer was charged with the solvent a according to the formulation shown in Table 2 below, the temperature was raised to a predetermined reaction temperature, and the monomer A, the monomer B and The mixed solution of the polymerization catalyst a was dropped into the flask over 3 hours, and after the completion of dropping, the mixture was kept at the same temperature for 30 minutes. Then, a mixture of the solvent b and the polymerization catalyst b was added dropwise over 20 minutes, and stirring was continued at the same temperature for 2 hours to complete the polymerization reaction. Finally, a diluting solvent was added to dilute the solution to obtain each polymer solution S _{1 to} S ₅ . In Table 2, "Veoba 9", which is one type of the monomer B, is a vinyl ester of a lower fatty acid under the trade name of Ciel Chemical Co., Ltd.

[0053]

[Table 2]

Production Example 6 Monomer A, monomer B and polymerization catalyst a were charged in a heat and pressure resistant container in accordance with the formulation shown in Table 3 below, completely sealed and shaken at a predetermined reaction temperature. Up to 8 at the same temperature
The reaction was completed by continuing shaking for a while. Next, a diluting solvent was added and the mixture was shaken for 1 hour to dissolve it, to obtain a polymer solution S ₆ .

Production Example 7 A flask equipped with a stirrer was charged with a solvent a, a monomer A, a monomer B and a polymerization catalyst a according to the formulation shown in Table 3 below.
The temperature was raised to a predetermined reaction temperature with stirring, the stirring was continued for 6 hours at the same temperature, and the solution was diluted with a diluting solvent to obtain a polymer solution S ₇ .

[0056]

[Table 3]

Comparative Production Example 1 As a monomer mixture, 40 parts of methyl methacrylate, 20 parts of octyl acrylate, 40 parts of tributyltin methacrylate were used.
Polymerization was carried out in the same manner as in Example 1 except that parts were used,
A polymer solution T ₈ was obtained. The molecular weight of the obtained copolymer is 9
It is a 50% by weight xylene solution at 10,000.

Examples 1 to 7 and Comparative Example 1 The polymer solutions S _{1 to} S ₇ prepared in the production examples were used as the samples of Examples 1 to 7 as they were, and the polymer solution T ₈ prepared in the comparative production example was used. The sample of Comparative Example 1 was used as it was and subjected to the following resin solubility test.

<Resin Solubility Test> Each sample was applied to one surface of a glass plate (30 mm × 50 mm × 1 mm) degreased with acetone so that the dry film thickness was 200 μm, and the mixture was placed in a desiccator at 20 ° C. Each test piece was prepared by drying under conditions of 10 mmHg or less for 16 hours. After soaking each test piece in sterilized filtered seawater for a predetermined period, soaked in distilled water for about 10 seconds,
After removing salt, it is dried. From the difference in dry weight of each test piece before and after immersion in seawater, the resin dissolution rate in seawater during the immersion period was determined. A dissolution rate in the range of 10 to 70 μg / cm ² / day was regarded as acceptable. The results are shown in Table 4 below.

[0060]

[Table 4]

Examples 8 to 14 and Comparative Example 2 100 parts of each of the polymer solutions S _{1 to} S ₇ and T ₈ (each 50 parts as a resin solid component) and 50 parts of cuprous oxide were added to 2,0.
Eight kinds of coating compositions were prepared by mixing and dispersing with a homomixer of 00 rpm.

Examples 15 to 34 and Comparative Example 3 Polymer solutions S _{1 to} S ₇ and T ₈ were used to give the following blending compositions shown in Tables 5 to 10 (numerical values in the tables are% by weight).
Twenty-three kinds of coating compositions were prepared by mixing and dispersing with a homomixer of 2,000 rpm. In addition, among the compounding ingredients, Disbaron A630-20X [trade name of Kusumoto Kasei Co., Ltd.] is an additive for preventing dripping, polybutene 06N [NOF CORPORATION]
Product name] is a surface lubricant.

[0063]

[Table 5]

[0064]

[Table 6]

[0065]

[Table 7]

[0066]

[Table 8]

[0067]

[Table 9]

[0068]

[Table 10]

The above Examples 8 to 34 and Comparative Examples 2 and 3
The following antifouling performance tests were carried out on each of the coating compositions of Example 1 to evaluate their performance. The results are shown in Table 11 below.

<Anti-fouling performance test> A tar vinyl anticorrosive paint was applied on both sides of a sandblasted steel plate (100 mm x 200 mm x 1 mm) in advance and dried, and then each coating composition was dried to give a dry film thickness. Was spray-coated on both sides so as to have a thickness of 240 μm by coating twice on one side, and dried for 1 week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% to prepare a test piece. This test piece was immersed in seawater for 18 months at Aioi Bay, Aioi City, Hyogo Prefecture, and the ratio of the area occupied by adherent organisms (adhered area) on the test coating film was measured over time.

[0071]

[Table 11]

In the results of Tables 4 and 11 above,
First, the coating film of the organotin copolymer solution T ₈ of Comparative Example 1 showed a phenomenon that the dissolution rate was slow and further slowed with the passage of time, and the coating compositions of Comparative Examples 2 and 3 using the same were observed. The coating film had an unsatisfactory long-term antifouling effect.

On the contrary, the coating films of the polymers of Examples 1 to 7 were immersed in seawater for 7 days, 30 days, 9
Stable, uniform and appropriate solubility is shown at any time after 0 days, and the coating films of the coating compositions of Examples 8 to 34 using these are completely recognized even after 18 months have passed since the attachment of organisms. Therefore, it is clear that stable antifouling performance can be maintained for a long period of time.

Claims (1)

[Claims] 1. The following general formula (I); (In the formula, X ₁ and X ₂ are hydrogen atoms or methyl groups, Y ₁ and Y ₂ are linear alkyl groups, branched alkyl groups, cyclic alkyl groups, alkoxyl groups, phenyl groups, substituted phenyl groups, and phenoxyl groups. Group, a group selected from the group consisting of substituted phenoxyl groups, which may be the same or different from each other) one or more polymers of the monomer A, And / or a copolymer of one or more of the above-mentioned monomers A and one or more of the vinyl-based monomers B copolymerizable therewith, and an antifouling agent as essential components A coating composition comprising: