JPH08269390A - Coating composition - Google Patents

Abstract

PURPOSE: To obtain a coating composition capable of giving a coating film which is free from cracks or debonding, soluble undersea at an appropriate rate, and has sustainable undersea antifouling performance, comprising an antifouling agent and polymers made from a triorganosilyl group-bearing monomer and an oxyethylene group-bearing monomer. CONSTITUTION: This coating composition having the above advantages essentially comprises a polymer made from a triorganosilyl group-bearing unsaturated monomer of formula I (R<1> -R<3> are each an alkyl or aryl; X is aryloyloxy, methacryloyloxy, maleinoyloxy, fumaroyloxy or itaconoyloxy) (e.g. trimethylsilyl methacrylate), another polymer made from an alkoxy or aryloxypolyethylene glycol group-bearing unsaturated monomer of formula II (R<4> is an alkyl or aryl; Y is the same kind as X; (n) is an integer of 1-25) (e.g. methoxyethyl acrylate), and an antifouling agent (e.g. cuprous oxide).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a coating composition for preventing organisms from adhering to the surface of objects in the sea.

[0002]

2. Description of the Related Art Barnacles are on the surface of underwater objects such as ship bottoms, buoys, fishing nets (aquaculture nets, fixed nets, etc.) submerged in seawater, the base of offshore structures, and various intake and drain pipes for cooling. Various obstacles occur due to the attachment of marine organisms such as, cerpra, mussel, and algae. It is well known that paints are applied to the surface of underwater objects to prevent the organisms from adhering to them in order to prevent their contamination.

The following paints have been used as paints for preventing such stains, that is, antifouling paints. One is that the resin that forms the basic skeleton that forms the antifouling coating does not dissolve in seawater, but rosin, which is one component of the resin component, dissolves, and at the same time, the antifouling agent is extracted from the coating and enters the seawater. It is a type of paint that prevents the adhesion of marine organisms by dissolving. This type of paint generally has a good initial antifouling effect, but since the resin component of the basic skeleton remains on the surface of the coating film for a long time, it becomes difficult to extract the antifouling agent and the antifouling effect is insufficient. There was a drawback that caused it.

As an improved type, there is a hydrolyzable self-polishing antifouling paint. This type of paint uses a resin having a basic skeleton that forms a coating film, which is hydrolyzed by seawater. As a result, it has been known that this type of paint elutes the coating film surface itself together with the antifouling agent, so that the active antifouling coating film surface is always maintained and a stable antifouling effect can be obtained for a long period of time. Organic tin polymers have been widely used as such hydrolyzable self-polishing antifouling paints. However, in recent years, marine pollution due to organotin compounds released as an antifouling agent after hydrolysis has been pointed out,
Its use has been restricted because it has become a major social problem.

Therefore, as a hydrolyzable self-polishing antifouling paint for preventing such a problem of marine pollution, antifouling paints using polymers in which various hydrolyzable groups are introduced have been proposed. However, none of them has been put to practical use.
Among them, for example, in Japanese Patent Publication No. 60-500452, various examples of various hydrolyzable groups are disclosed. Among them, organosilicon (having an alkoxysilyl group or organosilyl group) (meth) acryle An antifouling paint using an organosilyl group-containing polymer, which utilizes the hydrolyzability of the polymer, has been proposed.

[0006]

However, in the above-mentioned Japanese Patent Publication No. Sho 60-500452, the embodiment is described as follows.
Tris (4-methyl-2-) as an organosilicon group-containing monomer
Only a pentoxy) silyl acrylate monomer is shown, the polymer composition is not particularly described, and the test results as an antifouling paint are not specified. Further, regarding the organosilyl group, although SiR ₃ is described in the claims, there is no description in the examples, and it is not mentioned at all which composition shows suitability as an antifouling paint. Not not.

The present inventors have examined acrylic acid ester resins, methacrylic acid ester resins, maleic acid ester resins, fumaric acid ester resins and itaconic acid ester resins having an organosilyl group in the side chain, and as a result,
Only by having an alkylsilyl group in the side chain, solubility in the most important rotary test (hydrolysis rate of the coating film applied to a cylindrical drum with a constant film thickness) is the most important as a hydrolysis type resin. Not showing, not showing good antifouling property in the antifouling immersion test, and not showing good adhesion to the substrate and undercoating due to cracking, so the coating film falls off when immersed in seawater, It was found that it did not show suitability as a dirty paint.

In view of the above-mentioned circumstances, the present invention shows no cracking or peeling of the coating film, exhibits hydrolyzability capable of being uniformly dissolved in the sea at an appropriate rate, and exhibits excellent antifouling performance for a long period of time. It is intended to provide a coating composition.

[0009]

Means for Solving the Problems As a result of intensive studies on the above objects, the present inventors have found that a specific polymer having a triorganosilyl group introduced into the molecular side chain and an alkoxy or aryloxy group in the molecular side chain. When a specific polymer with a polyethylene glycol group introduced is used in combination with an antifouling agent, the coating does not crack or peel, and the coating dissolves in the sea at an appropriate speed and uniformly. The inventors have found that a coating composition that exhibits hydrolyzability and exhibits excellent antifouling performance for a long period of time can be obtained, and has completed the present invention.

That is, the present invention provides the following general formula (1); (In the formula, each of R ^{1 to} R ³ is a group selected from an alkyl group and an aryl group, and may be the same or different from each other. X is acryloyloxy. Group, methacryloyloxy group, maleinoyloxy group,
It is a fumaroyloxy group or an itaconoyloxy group. ) And polymer using a monomer A represented by the general formula of the following _{(2); Y- (CH 2} CH 2 O) n-R 4 ... (2) ( wherein, R ⁴ is an alkyl group Or an aryl group, Y.
Is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group. n is an integer of 1 to 25. )
The present invention relates to a coating composition characterized by containing a polymer using the monomer B represented by the above and an antifouling agent as essential components.

[0011]

In the coating composition of the present invention,
As one of the essential components, a polymer using the monomer A represented by the general formula (1) (hereinafter referred to as polymer A), that is, a homopolymer consisting of only one kind of the monomer A, Two or more copolymers of the above monomer A, or the above monomer A
Or a copolymer of one or more of the above and one or more of other monomers copolymerizable therewith.

The monomer A is, as represented by the general formula (1), an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group [mainly mono] as an unsaturated group (X) in the molecule. Alkyl (C1-6) ester maleinoyloxy group], Fumaroyloxy group [mainly monoalkyl (C1-6) ester fumaroyloxy group]
Alternatively, it has an itaconoyloxy group [mainly a monoalkyl (carbon number 1 to 6) ester itaconoyloxy group] and a triorganosilyl group.

In the triorganosilyl group, the three alkyl groups or aryl groups (R ^{1 to} R ³ ) may be the same or different. Specifically, a linear alkyl group having 20 or less carbon atoms such as methyl, ethyl, propyl, and butyl, or an isopropyl group, isobutyl group, s-butyl group, t-butyl group, or the like having 20 or less carbon atoms. Branched alkyl groups, cyclic alkyl groups such as cyclohexyl and substituted cyclohexyl, aryl groups and substituted aryl groups
And the like. Examples of the substituted aryl group include halogen, an alkyl group having up to about 18 carbon atoms, an aryl group substituted with an acyl group, a nitro group, an amino group and the like.

Examples of the monomer A having a (meth) acryloyloxy group in the molecule include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate and tri-n-propylsilyl. (Meth) acrylate, triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate
Tri-s-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n
-Hexylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p- Methylphenylsilyl (meth) acrylate, tribenzylsilyl (meth)
Examples include acrylate.

Other examples having a (meth) acryloyloxy group in the molecule include ethyldimethylsilyl (meth) acrylate and n-butyldimethylsilyl (meth).
Acrylate, diisopropyl-n-butylsilyl (meth) acrylate, diisopropylstearylsilyl (meth) acrylate, dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, Examples thereof include lauryl diphenylsilyl (meth) acrylate.

Further, as those having a maleinoyloxy group or a fumaroyloxy group in the molecule, triisopropylsilylmethyl maleate, triisopropylsilylamyl maleate, tri-n-butylsilyl-n-butyl maleate, t- Butyldiphenylsilylmethyl male
, T-butyldiphenylsilyl-n-butylmale
, Triisopropylsilylmethyl fumarate, triisopropylsilyl amyl fumarate, tri-n-butylsilyl-n-butyl fumarate, t-butyldiphenylsilylmethyl fumarate, t-butyldiphenylsilyl -N-butyl fumarate and the like can be mentioned.

Further, as those having an itaconoyloxy group in the molecule, triisopropylsilylmethylitaconate, triisopropylsilylamylitaconate,
Tri-n-butylsilyl-n-butyl itaconate, t
-Butyldiphenylsilylmethyl itaconate, t-butyldiphenylsilyl-n-butyl itaconate and the like can be mentioned.

Other monomers copolymerizable with the monomer A include acrylic acid ester, methacrylic acid ester,
Vinyl esters such as styrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyltoluene, α-methylstyrene, crotonic acid esters,
Various vinyl-based monomers such as itaconic acid esters can be used. The amount of these other copolymerizable monomers in the total amount with the monomer A is usually 99% by weight or less, preferably 95% by weight or less.

In the coating composition of the present invention, the monomer B represented by the general formula (2) is used as another essential component.
Polymer using (hereinafter, referred to as polymer B), that is,
A homopolymer consisting of only one kind of the above-mentioned monomer B, a copolymer of two or more kinds of the above-mentioned monomer B, or one of the above-mentioned monomer B
1 or 2 or more and one of the other monomers copolymerizable therewith
Either one or a copolymer of two or more kinds is used.

The monomer B, as represented by the general formula (2), has an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group [mainly a monomonomer] as an unsaturated group (Y) in the molecule. Alkyl (C1-6) ester maleinoyloxy group], Fumaroyloxy group [mainly monoalkyl (C1-6) ester fumaroyloxy group]
Alternatively, it has an itaconoyloxy group [mainly a monoalkyl (carbon number 1 to 6) ester itaconoyloxy group] and also has an alkoxy or aryloxypolyethylene glycol group.

In the alkoxy or aryloxy polyethylene glycol group, the degree of polymerization (n) of polyethylene glycol is 1 to 25, and the alkyl group or aryl group (R ⁴ ) is methyl or ethyl. Linear alkyl groups having 12 or less carbon atoms, such as propyl, butyl, isopropyl group, isobutyl group, s-butyl group, t
Examples thereof include branched alkyl groups having 12 or less carbon atoms such as -butyl group, cyclic alkyl groups such as cyclohexyl and substituted cyclohexyl, aryl groups and substituted aryl groups. Examples of the substituted aryl group include halogen, an alkyl group having up to about 18 carbon atoms, an aryl group substituted with an acyl group, a nitro group, an amino group and the like.

Examples of the monomer B having a (meth) acryloyloxy group in the molecule include, for example, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and propioxyethyl. (Meth) acrylate, butoxyethyl (meth) acrylate, hexaoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytri Examples thereof include ethylene glycol (meth) acrylate.

Further, as a compound having a maleinoyloxy group or a fumaroyloxy group in the molecule, for example,
Methoxyethyl-n-butyl maleate, ethoxydiethylene glycol methyl maleate, ethoxytriethylene glycol methyl maleate, propoxydiethylene glycol methyl maleate, butoxyethyl methyl maleate
Hexaoxyethylmethyl maleate, methoxyethyl-n-butyl fumarate, ethoxydiethylene glycol methyl fumarate, ethoxytriethyleneglycol
Lumethyl fumarate, propoxydiethylene glycol
Lumethyl fumarate, butoxyethyl methyl fumarate
And hexaoxyethyl methyl fumarate.

Further, those having an itaconoyloxy group in the molecule include, for example, methoxyethyl-n-butyl itaconate, ethoxydiethylene glycol methyl itaconate, ethoxytriethylene glycol methyl itaconate and propyne. Oxydiethylene glycol methyl itaconate, butoxyethyl methyl itacone
And hexaoxyethyl methyl itaconate.

Other monomers copolymerizable with the monomer B include acrylic acid ester, methacrylic acid ester,
Vinyl esters such as styrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyltoluene, α-methylstyrene, crotonic acid esters,
Various vinyl-based monomers such as itaconic acid esters can be used. The content of these other copolymerizable monomers in the total amount with the monomer B is usually 99% by weight or less, preferably 95% by weight or less.

In the present invention, the polymer A is obtained by polymerizing the monomer A or other monomer copolymerizable therewith in the presence of a vinyl polymerization initiator according to a conventional method such as solution polymerization, bulk polymerization, It can be obtained by polymerizing by various methods such as emulsion polymerization and suspension polymerization. Further, the polymer B can be obtained by polymerizing the monomer B or another monomer copolymerizable therewith in the same manner as above. When these polymers A and B are used for paints, it is convenient to dilute them with an organic solvent to obtain a polymer solution having an appropriate viscosity. For that purpose, a solution polymerization method or a bulk polymerization method is adopted. It is desirable to do.

Examples of the above vinyl polymerization initiator include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, benzoyl peroxide and di-t.
Examples thereof include peroxides such as -butyl peroxide, t-butyl peroxybenzoate, and t-butyl peroxyisopropyl carbonate.

As the above-mentioned organic solvent, aromatic hydrocarbon solvents such as xylene and toluene, hexane,
Aliphatic hydrocarbon solvents such as heptane, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dioxane and diethyl ether, methyl ethyl ketone,
A ketone solvent such as methyl isobutyl ketone may be used, and one or more of these solvents may be used.

Polymers A and B obtained by such a method
Is 1,000 to 300,000 in weight average.
It is desirable to be in the range of. If the molecular weight is too low, it is difficult to form a normal coating film, and if the molecular weight is too high, a thin coating film can be obtained by one coating, which requires a larger number of coatings. Further, the polymer A and the polymer B
The viscosity of the polymer solution containing and is conveniently not more than 150 poise at 25 ° C., for which the solids content of the polymer solution is between 5 and 90% by weight, preferably between 15 and 85% by weight. It is better to set the range.

In the coating composition of the present invention, the polymer A,
As the antifouling agent used as an essential component other than the resin component consisting of B, conventionally known ones are widely included. Broadly classified, there are inorganic compounds, organic compounds containing metals, and organic compounds containing no metals.

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. To be

Examples of the organic compound containing a metal include organic copper compounds, organic nickel compounds and organic zinc compounds, and other compounds such as maneb, manceb,
Propineb can also be used. Organic copper compounds include oxine copper, copper nonylphenol sulfonate, copper bis (ethylenediamine) -bis (dodecylbenzene sulfonate), copper acetate, copper naphthenate, and bis (pentachlorophenolic acid) copper. The organic nickel compounds include nickel acetate and dimethyldithiocarbamate nickel, and the organic zinc compounds include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, and bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarba. -Bamate, zinc ethylenebisdithiocarbamate and the like can be mentioned respectively.

Examples of the metal-free organic compound include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compound, There are 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.

The N-arylmaleimide includes 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-
(2,4-dichlorobenzylideneamino) -1,3-thiazolidine-2,4-dione and the like.

Examples of dithiocyano compounds include dithiocyanoethane and 2,5-dithiocyanothiophene.
Further, as the triazine-based compound, 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 and 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-
Examples thereof include 4- (methylsulfonyl) pyridine, diodomethylparatolylsulfone, 2- (4-thiazolyl) benzimidazole and triphenylboronpyridine.

In the present invention, one kind or two or more kinds are selected and used from the various antifouling agents as described above, and the amount of the antifouling agent is usually 0 in the coating solid content. .1
˜80 wt%, preferably 1-60 wt%. If the amount of the antifouling agent is too small, the antifouling effect cannot be expected. If the amount of the antifouling agent 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 having the above-described structure further comprises coloring agents such as pigments and dyes such as stalks, titanium dioxide and talc, water binders and dioctyl phthalate. (DOP), tricresyl phosphite (TCP), plasticizers such as chlorinated paraffin, acrylic resins, chlorinated rubber, resins such as rosin, water binders, anti-sagging agents commonly used in paints, color components An anti-skid agent, an anti-settling agent, an antifoaming agent and the like can be appropriately added.

In order to form an antifouling coating film on the surface of an object to be immersed in seawater using the coating composition of the present invention, it is applied to the surface of the object by an appropriate means and then at room temperature or under heating. It suffices to volatilize and remove the solvent below, and a dry coating film can be easily formed on the surface of the object by this method.

[0042]

INDUSTRIAL APPLICABILITY The coating composition of the present invention can be used for ship bottoms that require prevention of biological pollution in the sea, underwater structures such as fish nets and cooling water pipes, and for preventing sludge diffusion in marine civil engineering work. , Its coating film is free from cracking and peeling, and shows hydrolyzability that dissolves uniformly in the sea at an appropriate rate, and has excellent antifouling performance for a long period of time against the above-mentioned biofouling fouling. Can last.

[0043]

EXAMPLES Next, the present invention will be specifically described with reference to polymer production examples, examples and comparative examples. In addition, the part in an example is a weight part and molecular weight is polystyrene conversion weight average molecular weight by GPC.

Further, the monomers A (A _{1 to} A used in the production examples
₈ ) is a monomer represented by the general formula (1), and R ^{1 to} R ³ and X in the general formula (1) are as shown in Table 1 below. Further, the monomer B (B _{1 to} B ₈ ) used in Production Examples is a monomer represented by the general formula (2), and is Y, n and R ^{4 in the} general formula (2). Is
It is as shown in Table 2 below.

[0045]

[Table 1]

[0046]

[Table 2]

Production Examples 1 to 8 Solvent a was charged in a flask equipped with a stirrer according to the formulations shown in Tables 3 and 4 below, and the temperature was raised to 80 ° C. with stirring while introducing nitrogen gas. While stirring, mix the monomer A, the other monomer, and the polymerization catalyst a into a flask.
After the dropping, the temperature was maintained for 30 minutes at the same temperature.
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 and obtain each polymer solution S _{1 to} S ₈ . The solid content concentration of each solution and the molecular weight of the polymer are shown in Tables 3 and 4.

[0048]

[Table 3]

[0049]

[Table 4]

Production Examples 9 to 16 A flask equipped with a stirrer was charged with the solvent a in accordance with the formulations shown in Tables 5 and 6 below, and the temperature was raised to 80 ° C. with stirring while introducing nitrogen gas. While stirring, the mixed solution of the monomer B, the other monomer and the polymerization catalyst a was put into a flask.
After the dropping, the temperature was maintained for 30 minutes at the same temperature.
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 and obtain polymer solutions S _{9 to} S ₁₆ . The solid content concentration of each solution and the molecular weight of the polymer are shown in Tables 5 and 6.

[0051]

[Table 5]

[0052]

[Table 6]

Comparative Production Example 1 Polymerization solution T ₁₇ was obtained by polymerizing in the same manner as in Production Example 1 except that 100 parts of tri-n-butylsilyl methacrylate was used as the monomer. . The polymer obtained has a molecular weight of 42,000 and is a 50 wt% xylene solution.

Comparative Production Example 2 Polymerization was carried out in the same manner as in Production Example 1 except that 50 parts of tri-n-butylsilyl methacrylate and 50 parts of methyl methacrylate were used as the monomer mixture. A polymer solution T ₁₈ was obtained. The molecular weight of the obtained polymer is 40,000.
And is a 50 wt% xylene solution.

Comparative Production Example 3 Ethoxyethyl acrylate 50 was used as a monomer mixture.
Parts and 50 parts of methyl methacrylate were used,
Polymerization was carried out in the same manner as in Production Example 1 to obtain a polymer solution T ₁₉ . The polymer obtained has a molecular weight of 41,000 and is a 50 wt% xylene solution.

Examples 1 to 20 Using polymer solutions S _{1 to} S ₈ and polymer solutions S _{9 to} S ₁₆ ,
The respective components were mixed in the compounding compositions shown in the following Tables 7 to 11 (the numerical values in the tables are% by weight), and mixed with a paint shaker to give 2
Zero coating compositions were prepared. In each table, "Days Baron A630-20X" [trade name of Kusumoto Kasei Co., Ltd.] is
It is an additive for preventing dripping.

[0057]

[Table 7]

[0058]

[Table 8]

[0059]

[Table 9]

[0060]

[Table 10]

[0061]

[Table 11]

Comparative Examples 1 to 3 Using the polymer solutions T _{17 to} T ₁₉ , the respective components were mixed according to the blending composition shown in the following Table 12 (numerical values in the table are% by weight).
Three paint compositions were prepared with a paint shaker. In the table, "Disbaron A630-20X" is the same as in the case of Tables 7 to 11 above.

[0063]

[Table 12]

The above Examples 1 to 20 and Comparative Examples 1 to 3
Each of the coating compositions was subjected to an antifouling performance test, a coating consumption test, an adhesion test and a crack resistance test in the following manner. These results were as shown in Tables 13 to 16 below.

<Anti-fouling performance test> Each coating composition was coated on a sandblasted steel sheet with a tar vinyl anticorrosive coating in advance (100 mm x 200 mm x 1 mm) on both sides, and the dry film thickness was on one side. Spray coating was applied twice to a thickness of 120 μm, followed by drying for 1 week in a constant temperature and constant 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 in Aioi Bay, Aioi City, Hyogo Prefecture, which is a sea area where biological adherence is severe, and the ratio of the area occupied by adherent organisms (adhered area) on the test coating film was measured over time. did.

<Coating Film Depletion Test> Each coating composition was spray-coated on the surface of a steel plate (100 mm × 100 mm × 1 mm) with a rust-proof coating on the back surface so that the dry film thickness was 200 μm, and the temperature was 20 ° C. A test piece was prepared by drying in a room at ℃ for 1 week. After fixing the above test piece to the outer surface of a cylindrical drum with a diameter of 50 cm, 1 below the sea surface in Yura Bay, Sumoto City, Hyogo Prefecture
The drum was immersed in m and rotated with a motor so that the peripheral speed of the drum was 16 knots, and the consumed coating film thickness was measured every 3 months for 18 months. Also, the average speed of film thickness consumption (μm / month)
Was calculated. In addition, if the average speed of coating film thickness consumption is 3 μm / month or more, it is correlated with good antifouling performance.

<Adhesion test> A blast steel sheet was spray-coated twice with a tar-epoxy rust-preventive coating so that a dry film thickness of 125 μm was obtained, and then a tar vinyl-based sealant was applied. -Coating was performed so that the dry film thickness was 70 μm. On top of this, apply each coating composition to a dry film thickness of 10
Spray twice to achieve 0 μm,
A test piece was prepared by drying for 1 week in a constant temperature and humidity room at a temperature of 20 ° C. and a humidity of 75%. This test piece was dipped in artificial seawater, and pulled up after 3 months, 6 months, 9 months, 12 months and 18 months, and a goggles test was conducted at 2 mm intervals. The number of peeled pieces by this test is 0
The case of 25 pieces / piece was ◯ (pass), and the case where the number of peeled pieces was 1 or more / 25 pieces was x (fail).

<Crack resistance test> In the adhesion test, when the test piece was pulled up from the artificial seawater, the coating film was visually observed to check for the occurrence of cracks. Those without cracks were marked with O (pass), and those with cracks were marked (fail).

[0069]

[Table 13]

[0070]

[Table 14]

[0071]

[Table 15]

[0072]

[Table 16]

As is clear from the results of Tables 13 to 16 above, in each of the coating compositions of Comparative Examples 1 to 3 using the polymer solutions T _{17 to} T ₁₉ , both the coating film dissolution rate and the antifouling performance were The results were unsatisfactory, and there were defects in adhesion and crack resistance, but the polymer solutions S _{1 to} S ₈ and the polymer solutions S ₉ to
The coating compositions of Examples 1 to 20 using S ₁₆ show satisfactory results in all tests, and the coating compositions of the present invention also have excellent performances from these test results. It is understood that it is one.

Claims (1)

[Claims] 1. The following general formula (1); (In the formula, each of R ^{1 to} R ³ is a group selected from an alkyl group and an aryl group, and may be the same or different from each other. X is acryloyloxy. Group, methacryloyloxy group, maleinoyloxy group,
It is a fumaroyloxy group or an itaconoyloxy group. ) And polymer using a monomer A represented by the general formula of the following _{(2); Y- (CH 2} CH 2 O) n-R 4 ... (2) ( wherein, R ⁴ is an alkyl group Or an aryl group, Y.
Is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group. n is an integer of 1 to 25. )
A coating composition comprising a polymer using the monomer B represented by and an antifouling agent as essential components.