JP2003119420A - Antifouling coating material composition and coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifouling coating material composition capable of forming a coated film having excellent long-term antifouling activities in a highly polluted sea area, and free from tin. SOLUTION: The antifouling composition contains (A) a vinylic polymer containing (a-1) a repeating unit represented by formula (I) (wherein, R<1> and R<2> are each independently hydrogen atom or methyl group; R<3> is hydrogen atom, a phenyl group or a 1-12C alkyl group; R<4> is a monovalent organic group), (a-2) a repeating unit derived from a vinylic monomer containing an N- substituted carboxylic acid amide group, and/or (a-3) a repeating unit derived from an N-vinylcarboxylic acid amide as essential repeating unit, and (B) an antifouling agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel antifouling coating composition containing a vinyl polymer containing a specific repeating unit and an antifouling agent, and an antifouling formed from the composition. Regarding the coated object covered with a coating film, for details,
TECHNICAL FIELD The present invention relates to a coated article that effectively prevents biofouling by applying it to structures, ships, fishing nets, etc. used in seawater, and an antifouling coating composition that can form this.

[0002]

2. Description of the Related Art Ship bottoms, underwater structures, fishing nets, etc. are soaked in water for a long period of time during use, so that the surface of oysters, mussels, barnacles, etc. and plants such as laver, or bacteria A variety of aquatic organisms such as species attach to them, and their appearance impairs due to their breeding.
There was a problem that its function was impaired. In particular, if such aquatic organisms adhere to the bottom of the ship and propagate, the surface roughness increases, resulting in a decrease in ship speed and a decrease in fuel efficiency. In addition, a great deal of labor is required to remove such aquatic organisms from the bottom of the ship.

Conventionally, as an antifouling paint for forming a coating film excellent in antifouling property on the bottom of a ship, for example, tributyltin methacrylate (hereinafter abbreviated as TBTMA) has been used in order to prevent damage due to adhesion of aquatic organisms. A paint containing a polymer and cuprous oxide was used. A coating film obtained from such an antifouling coating material exhibits an antifouling effect by releasing the organotin compound such as tributyltin hydroxide or tributyltin halide by the copolymer being hydrolyzed in seawater, It functions as a so-called "hydrolyzable self-polishing coating film".

[0004]

However, in the above-mentioned paint, since the organotin compound produced by the hydrolysis of the copolymer of TBTMA is highly toxic, it pollutes the ocean and adversely affects the ecosystem. Is a concern. In addition, as an antifouling paint that does not contain tin, Japanese Patent Publication Sho 63
No. 61989 discloses a copolymer of (meth) acrylic acid alkoxycarbonylalkyl ester homopolymer or (meth) acrylic acid alkoxyoxycarbonylalkyl ester with a carboxyl group-free or hydroxyl group-free monomer. It is disclosed that a polymer is used as a binder resin component, and when the binder resin is dissolved in the sea, cuprous oxide, which is an antifouling agent, is released to exhibit antifouling properties. However, this special public Sho 63-6198
The coating film obtained from the antifouling paint described in JP-A No. 9-90 is insufficient in solubility of the binder resin in seawater,
The long-term antifouling property in the highly polluted sea area was insufficient.

The present invention has been made to solve the above problems, and is capable of forming a coating film excellent in long-term antifouling property in a highly polluted sea area, and further, an antifouling coating composition containing no tin, and It is intended to provide a coated article obtained by applying a coating composition.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a repeating unit derived from a specific vinyl monomer containing an alkoxycarbonylmethyl ester group and a specific repeating unit. An antifouling coating composition comprising a vinyl polymer (A) containing a repeating unit derived from a monomer containing a carboxylic acid amide group as an essential repeating unit, and an antifouling agent (B). The inventors have found that a coating film excellent in long-term antifouling property is formed in a highly polluted sea area, and have completed the present invention.

That is, the antifouling coating composition of the present invention comprises a vinyl monomer containing a repeating unit (a-1) represented by the following general formula (I) and an N-substituted carboxylic acid amide group. Derived repeating unit (a-2) and / or N-vinylcarboxylic acid amide-derived repeating unit (a-3)
It is characterized by containing a vinyl polymer (A) containing as an essential repeating unit and an antifouling agent (B).

[Chemical 2] (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ⁴ is a monovalent organic group. Shall represent a group.)

The coated article of the present invention is characterized in that it is coated with an antifouling coating film formed from the above antifouling coating composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
It The vinyl polymer (A) used in the present invention is
A repeating unit (a-1) represented by the general formula (I), N
A vinyl-based monomer containing a substituted carboxamide group
Derived repeating unit (a-2) and / or N-vinyl
A repeating unit (a-3) derived from a carboxylic acid amide;
Is contained as an essential repeating unit. Scarecrow
Of the repeating units represented by the general formula (I)
R contained in the unit (a-1)³ Is a hydrogen atom,
Represents a nyl group or an alkyl group having 1 to 12 carbon atoms.
You And such R³ Of which the number of carbon atoms is 1
A typical example of the 12 alkyl groups is a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl
Group, isobutyl group, tert-butyl group, n-hexyl group
Group, 2-ethylhexyl group, n-decyl group, n-dode
Examples thereof include a sil group. R ³ Especially preferred among
Examples of the hydrogen atom include a hydrogen atom and a methyl group.

Representative examples of the monovalent organic group R ⁴ contained in the repeating unit (a-1) include an alkyl group, a substituted alkyl group, a cycloalkyl group, an aryl group,
Examples thereof include substituted aryl groups and the like. Among such monovalent organic groups, typical examples of the alkyl group include various groups described above as typical examples of the alkyl group having 1 to 12 carbon atoms in R ^3. In addition, n-tridecyl group, n-hexadecyl group, n-octadecyl group, etc. are mentioned.

A typical example of the substituted alkyl group is:
2-methoxyethyl group, 2-ethoxyethyl group, 2-
(N-Propoxy) ethyl group, 2- (n-butoxy) ethyl group, 2- (n-hexyloxy) ethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 4- (n-
Propoxy) butyl group, 6-ethoxyhexyl group, 6-
Alkoxy group-substituted alkyl group such as (n-hexyloxy) hexyl group; 2-phenoxyethyl group, 2- (4
An alkyl group substituted with an aryloxy group such as -methylphenoxy) ethyl group; an alkyl group substituted with an aralkyloxy group such as a 2-benzyloxyethyl group and a 2- (2-phenylethoxy) ethyl group; a benzyl group
Such as 1-phenylethyl group and 2-phenylethyl group,
Examples thereof include an alkyl group substituted with an aryl group.

Typical examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group and a cyclooctyl group. A typical aryl group is a phenyl group,
Examples thereof include a 1-naphthyl group and a 2-naphthyl group. Typical examples of the substituted aryl group include a 2-methylphenyl group, a 4-methylphenyl group, a 4-chlorophenyl group, a 4-nitrophenyl group and a 4-methyl-1-naphthyl group. Among these, preferred as R ⁴ is an alkoxy group-substituted alkyl group having 3 to 8 carbon atoms, which includes an alkyl group having 1 to 8 carbon atoms or an alkoxy group, and a particularly preferred one is It is an alkyl group having 1 to 4 carbon atoms.

In order to introduce the above-mentioned repeating unit (a-1) having various R ³ and R ⁴ into the vinyl polymer (A), for example, the following method is preferably adopted. A method of copolymerizing a vinyl-based monomer represented by the following general formula (II).

[0014]

[Chemical 3] (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ⁴ is a monovalent organic group. Shall represent a group.)

A vinyl polymer having a carboxyl group, which is obtained by copolymerizing a monomer having a carboxyl group represented by the following general formula (III), in the presence of a basic compound is used. A method of reacting with the compound represented by (IV).

[0016]

[Chemical 4] (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group.)

[0017]

[Chemical 5] (In the formula, R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, R ⁴ represents a monovalent organic group, and X represents a halogen atom such as a chlorine atom or a bromine atom. It shall be.)

In the above method, the repeating unit (a
-1) A typical vinyl-based monomer used for introducing [1] (hereinafter, abbreviated as monomer (m-1)] is methoxycarbonylmethyl (meth) acrylate or ethoxycarbonylmethyl. (Meth) acrylate,
n-propoxycarbonylmethyl (meth) acrylate, n-butoxycarbonylmethyl (meth) acrylate, 2-ethylhexyloxycarbonylmethyl (meth) acrylate, cyclohexyloxycarbonylmethyl (meth) acrylate, benzyloxycarbonylmethyl (meth) acrylate, phenoxy Carbonylmethyl (meth) acrylate, 2-methoxyethoxycarbonylmethyl (meth) acrylate, 4-methoxybutoxycarbonylmethyl (meth) acrylate, 1- (methoxycarbonyl) ethyl (meth) acrylate, 1-
(Ethoxycarbonyl) ethyl (meth) acrylate,
1- (n-propoxycarbonyl) ethyl (meth) acrylate, 1- (n-butoxycarbonyl) ethyl (meth) acrylate, α-methoxycarbonylbenzyl (meth) acrylate, α-ethoxycarbonylbenzyl (meth) acrylate, (Meth) acrylic acid esters; methoxycarbonylmethyl crotonate, ethoxycarbonylmethyl crotonate, cyclohexyloxycarbonylmethyl crotonate, benzyloxycarbonylmethyl crotonate, 2-methoxyethoxycarbonylmethyl crotonate, 1- (methoxycarbonyl) ethyl Examples include crotonic acid esters such as crotonate, 1- (ethoxycarbonyl) ethyl crotonate, and α-methoxycarbonylbenzyl crotonate.

Then, such a vinyl monomer (m-
Preferred among 1) are the alkyl groups having 1 to 8 carbon atoms as R ⁴ , wherein in the general formula (II), R ¹ is a hydrogen atom, R ³ has a hydrogen atom or a methyl group. Or, the number of carbon atoms including the alkoxy group is 3 to 8
Is a (meth) acrylic acid ester having an alkoxy group-substituted alkyl group. Of these, a particularly preferred one is a (meth) acrylic acid ester having a hydrogen atom or a methyl group as R ³ , and an alkyl group having 1 to 4 carbon atoms as R ⁴ .

A repeating unit (a-2) derived from a vinyl monomer containing an N-substituted carboxylic acid amide group, which is an essential repeating unit constituting the vinyl polymer (A).
In order to introduce the repeating unit (a-3) derived from N-vinylcarboxylic acid amide and / or N-vinylcarboxylic acid amide into the vinyl polymer (A), various known and conventional methods can be applied, but N-substituted A vinyl monomer containing a carboxylic acid amide group [hereinafter, abbreviated as a monomer (m-2)] and / or a monomer containing an N-vinyl carboxylic acid amide group [hereinafter, a monomer ( abbreviated as m-3)] is simple and preferable.

The N-substituted carboxylic acid amide group contained in the monomer (m-2) is a secondary carboxylic acid amide group having one substituent on the nitrogen atom, or 2 on the nitrogen atom.
It refers to a tertiary carboxylic acid amide group having 4 substituents. Typical examples of such a substituent on the nitrogen atom include a lower alkyl group having about 1 to 4 carbon atoms, a substituted alkyl group, and a divalent divalent group that is bonded to the amide nitrogen atom to form a ring. An organic group etc. are mentioned. Typical examples of the lower alkyl group having about 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group and the like. Specific examples of the substituted alkyl group include methoxymethyl group, ethoxymethyl group, n
-Alkoxymethyl group having a lower alkoxy group such as propoxymethyl group, n-butoxymethyl group, isopropoxymethyl group; hydroxymethyl group, chloromethyl group, 2-chloroethyl group, 1,1-dimethyl-3-oxobutyl group Etc. Specific examples of the divalent organic group which is bonded to the amide nitrogen atom to form a ring include a tetramethylene group, a pentamethylene group, a 3-oxapentylene group and a 3-methylazapentylene group. .

Typical examples of the monomer (m-2) containing such a substituent on the nitrogen atom are N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn. -Butyl (meth) acrylamide, N-
N-mono-substituted (meth) such as hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide diacetone (meth) acrylamide Acrylamides; N,
N, N-disubstituted (meth) acrylamides such as N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide; N- (meth) acryloyl Pyrrolidine,
N- (meth) acryloylpiperidine, N- (meth) acryloylmorpholine, N-methyl-N '-(meth) acryloylpiperazine, an amide-based monomer having a cyclic structure; N-methylcrotonic acid amide, N- Ethyl crotonic acid amide, N-n-butyl crotonic acid amide, N
N-monosubstituted crotonic acid amides such as -hydroxymethyl crotonic acid amide, N-methoxymethyl crotonic acid amide, N-ethoxymethyl crotonic acid amide, N-n-butoxymethyl crotonic acid amide; N, N-dimethyl crotonic acid N, such as amides, N, N-diethyl crotonic acid amide, N, N-di-n-butyl crotonic acid amide,
Examples thereof include N-di-substituted crotonic acid amides.

Typical examples of the monomer (m-3) containing an N-vinylcarboxylic acid amide group are aliphatic compounds such as N-vinylformamide, N-vinylacetamide and N-vinylpropionic acid amide. Carboxamide N
-Vinyl derivatives.

The vinyl polymer (A) may be composed only of the repeating unit (a-1) and the repeating unit (a-2) and / or the repeating unit (a-3). Further, it may further contain a repeating unit derived from a vinyl-based monomer other than these [hereinafter abbreviated as repeating unit (a-4)]. When the repeating unit (a-4) is introduced, the monomer (m-1),
Various monomers copolymerizable with (m-2) and / or (m-3) may be copolymerized.

Typical examples of such various copolymerizable monomers [hereinafter abbreviated as monomers (m-4)] include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-
Butyl (meth) acrylate, iso-butyl (meth)
Alkyl (meth) acrylates such as acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate.

Cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; benzyl ( Aralkyl (meth) acrylates such as (meth) acrylate or 2-phenylethyl (meth) acrylate; styrene, p-tert-butylstyrene, α
-Aromatic vinyl monomers such as methylstyrene and vinyltoluene; vinyl esters of carboxylic acids such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and vinyl benzoate; methyl crotonic acid , Crotonic acid alkyl esters such as n-butyl crotonic acid, 2-ethylhexyl crotonic acid.

Unsaturated dibasic acid dialkyl esters such as dimethyl maleate, di-n-butyl maleate, dimethyl fumarate, di-n-butyl fumarate, dimethyl itaconate, di-n-butyl itaconate; Alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether and n-hexyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether and 4-methylcyclohexyl vinyl ether;

Further, various cyano group-containing vinyl monomers such as (meth) acrylonitrile and crotononitrile; vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene. Various fluoroolefins such as;
Chlorinated olefins such as vinyl chloride and vinylidene chloride; α-olefins such as ethylene and propylene; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyether diol having both oxyethylene unit and oxypropylene unit Mono (meth) acrylates of polyoxyalkylene glycols; monomethoxylated polyethylene glycol, monoethoxylated polyethylene glycol, mono-n-butoxylated polyethylene glycol, monomethoxylated polypropylene glycol, monomethoxylated polytetramethylene glycol, oxyethylene Of various monoalkoxylated polyoxyalkylene glucos, such as a monomethoxy compound of a polyether diol having both units and oxypropylene units. Esters of Le and (meth) acrylic acid, and the like.

Further, carboxyl group-containing monomers such as acrylic acid, methacrylic acid and crotonic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, A hydroxyl group-containing monomer such as 2-hydroxyethyl vinyl ether can also be used within a range that does not impair the stability of the coating composition of the present invention or the antifouling performance of the coating film obtained from the composition.

There are no particular restrictions on the polymerization method for preparing the above vinyl polymer (A), and various known and conventional polymerization methods can be applied. Among them, the solution radical polymerization method particularly in an organic solvent is simple and preferable.

When this solution radical polymerization method is applied,
As the polymerization initiator, various known and commonly used compounds can be used. Typical examples are 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbutyronitrile), 2,2'-azobis (2-methylbutyronitrile). ) Azo compounds; tert-butylperoxypivalate, tert.
-Butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-
Examples thereof include peroxides such as butyl peroxide, cumene hydroperoxide and diisopropyl peroxycarbonate.

As the organic solvent used in the solution radical polymerization method, various known and commonly used compounds can be used. Typical compounds used as the solvent include n-hexane, n-heptane and n-hexane.
Aliphatic or alicyclic hydrocarbons such as octane, cyclohexane and cyclopentane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; methanol, ethanol, n-butanol, ethylene glycol monomethyl ether, propylene Alcohols such as glycol monomethyl ether; ethyl acetate, acetic acid n
-Esters such as butyl, n-amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, cyclohexanone.

Also, such as diethylene glycol dimethyl ether and diethylene glycol dibutyl ether,
Polyalkylene glycol dialkyl ethers; 1,
Ethers such as 2-dimethoxyethane, tetrahydrofuran and dioxane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate and the like can be mentioned. And these compounds may be used alone or in combination of two or more kinds.

As described above, the vinyl polymer (A)
The repeating unit (a-1), the repeating unit (a-2) and / or the repeating unit (a-3), and further the repeating unit (a-4) are introduced into the polymer. The amount of these repeating units introduced is 100 for the vinyl polymer (A).
The repeating unit (a-1) is 20 to 99 parts by weight, the repeating unit (a-2) and / or (a-2) is 1 to 20 parts by weight, and the repeating unit (a-4) is 0 to 100 parts by weight. It is preferable to set it in the range of 79 parts by weight, the repeating unit (a-1) is 30 to 97 parts by weight, and the repeating unit (a-
2) and / or (a-3) is preferably 3 to 15 parts by weight, and the repeating unit (a-4) is preferably 0 to 67 parts by weight.

The weight average molecular weight of the vinyl polymer (A) is set in the range of 2,000 to 200,000, but it is set in the range of 4,000 to 100,000. Is preferred.

As the antifouling agent (B) in the antifouling coating composition of the present invention, various known and commonly used inorganic antifouling agents and organic antifouling agents can be used. Representative examples of the inorganic antifouling agent include various inorganic compounds containing copper and metal atoms. Among these, a compound containing Cu (I) is preferable from the viewpoint of excellent antifouling effect, and examples thereof include cuprous oxide, cuprous thiocyanate, basic cuprous sulfate, and cuprous chloride. Among these, cuprous oxide and cuprous thiocyanate are particularly preferable. On the other hand, as an organic antifouling agent, for example, cuprous acetate, oxine copper, copper nonylphenol sulfonate, copper bis (ethylenediamine) -bis (dodecylbenzene sulfonate), copper naphthenate, copper rosin, bis (pentachlorophenolic acid)
Copper, metal pyrithione, tetramethylthiuram disulfide, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, pyridine-triphenylboron, 4,5-dichloro-2-n-octyl -4-isothiazolin-3-one, 2,4,6-
Trichlorophenylmaleimide, 2-methylthio-4-
tert-butylamino-6-cyclopropylamino-
Carbamate compounds such as s-triazine, zinc dimethyldithiocarbamate, and manganised ethylene bisdithiocarbamate may be used.

Among such organic antifouling agents, metal pyrithione, N, N-dimethyldichlorophenylurea, pyridine-triphenylboron, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-
Butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile are especially protected. It is preferable in terms of excellent stain resistance. Further, as the metal pyrithione, copper pyrithione and zinc pyrithione are particularly preferable. The various antifouling agents described above may be used alone,
Moreover, you may use together 2 or more types.

Regarding the compounding amount of the antifouling agent (B), for example, the antifouling agent (B) is 1 to 70% by weight in the antifouling coating composition, but the effect of the present invention is remarkable. Is preferable, and particularly preferably 2 to 65% by weight. It is also preferable to use a copper compound and a metal pyrithione together as the antifouling agent (B), since the antifouling effect becomes remarkable.
When the copper compound and the metal pyrithione are used in combination, the content of the copper compound is 2 to 65% by weight in the antifouling coating composition, and the content of the metal pyrithione is 0.5 to 40% by weight in the composition. It is preferable to use it within the range.

By incorporating zinc oxide into the antifouling coating composition of the present invention, the strength of the coating film can be improved and the rate of consumption of the coating film can be effectively controlled. When zinc oxide is contained, it is preferably contained in the antifouling coating composition in an amount of 0.5 to 35% by weight, from the viewpoints of consumption rate adjustment and coating film hardness adjustment.
It is more preferable to contain 5% by weight.

Further, in the antifouling coating composition of the present invention, by containing an elution accelerator, the elution of the resulting coating film is enhanced to accelerate the consumption rate of the coating film and to make the antifouling effect remarkable. be able to. Such elution accelerators include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, low melting point disproportionated rosin, hydrogenated rosin, polymerized rosin, maleated rosin, aldehyde-modified rosin, and polyoxyalkylene ester of rosin. , Rosin alcohol, metal salts of rosin (copper salt of rosin, zinc salt of rosin, magnesium salt of rosin, etc.), rosin such as rosin amine;
Monocarboxylic acids such as fatty acids having 5 to 30 carbon atoms, synthetic fatty acids, naphthenic acid; aliphatic carboxylic acid salts such as Cu salts, Zn salts, Mg salts, Ca salts of the above-mentioned carboxylic acids. To be Among the dissolution enhancers,
Rosin is particularly preferable because it has an excellent elution promoting effect.
When such an elution accelerator is added, the elution accelerator contains 0.1 to 30% by weight, particularly 0.1% by weight, in the antifouling coating composition from the viewpoints of the antifouling performance of the coating film, the consumption rate and the water resistance. 5
It is preferably contained in the range of ˜15% by weight.

Further, in the antifouling coating composition of the present invention, by containing a vinyl ether polymer, the crack resistance and adhesion of the resulting coating film are improved and the consumption rate stability is improved. be able to. Examples of such vinyl ether-based polymers include polymethyl vinyl ether, polyethyl vinyl ether, polyisopropyl vinyl ether, polyisobutyl vinyl ether and the like. When blending this vinyl ether polymer,
From the viewpoint that the crack resistance, adhesion, and consumption rate stabilization effect of the resulting coating film are effectively exhibited, the vinyl ether polymer is contained in the antifouling coating composition in an amount of 0.1 to 10% by weight, particularly 0%. It is preferable to contain in the range of 0.2 to 5% by weight.

In the antifouling coating composition of the present invention, a hydrophilic group-containing polymer other than the vinyl ether polymer may be used in combination. Typical examples of the hydrophilic group-containing polymer include various (alkoxy) polyalkylene glycol mono (meth) acrylate (co) polymers such as (methoxy) polyethylene glycol mono (meth) acrylate (co) polymer. Can be mentioned.

Further, the antifouling coating composition of the present invention may contain various plasticizers generally used for coatings, and by adding the plasticizer, the crack resistance of the resulting coating film may be improved. Can be improved. Examples of the plasticizer include orthophosphate, chlorinated paraffin,
Phthalates, adipates, and the like,
Especially preferred are chlorinated paraffins and orthophosphates. When such a plasticizer is blended, the antifouling coating composition contains the plasticizer in an amount of 0.05 to 20% by weight, particularly 0.1 to 1%.
It is preferably contained in the range of 5% by weight.

In the antifouling coating composition of the present invention, the storage stability can be improved by adding a dehydrating agent. Examples of the dehydrating agent include inorganic dehydrating agents such as anhydrous gypsum (CaSO ₄ ) and synthetic zeolite, orthocarboxylic acid esters such as methyl orthoformate and methyl orthoacetate, orthoboric acid esters, silicate compounds, p-toluenesulfonyl isocyanate and the like. Examples include organic dehydrating agents such as isocyanate compounds. When such a dehydrating agent is blended, 0.01 to 2 of the dehydrating agent is added to the antifouling coating composition.
It is preferably contained in an amount of 0% by weight, particularly 0.1 to 8% by weight.

Further, in the antifouling coating composition of the present invention, various pigments such as coloring pigments and extender pigments, dyes, resins other than the above vinyl ether-based polymers, anti-sagging agents, anti-settling agents, antifoaming agents, It may contain various additives such as a color separation preventing agent and a leveling agent. As the anti-sagging agent or the anti-settling agent, salts of polyvalent metals such as Al, Cu and Zn and acids such as stearic acid, lecithin and alkylsulfonic acid, polyethylene wax, hydrogenated castor oil type wax, polyamide type wax, Examples thereof include waxes such as oxidized polyethylene wax, and synthetic fine powder silica.

As the pigment, known and commonly used organic pigments and inorganic pigments can be used. Examples of inorganic pigments include titanium oxide, iron oxide, talc, mica, and aluminum flakes. Examples of organic pigments include carbon black, phthalocyanine blue, phthalocyanine green, and quinacridone red. Further, the antifouling coating composition of the present invention may further contain a polymer of triorganosilyl ester of maleic acid or fumaric acid.

Here, in the antifouling coating composition of the present invention, when a liquid plasticizer or a liquid dehydrating agent is contained, the coating composition is used without containing a solvent. be able to. On the other hand, when a liquid plasticizer or a liquid dehydrating agent is not contained, it is necessary to use a solvent. Further, even when a liquid plasticizer or a liquid dehydrating agent is contained, it is preferably used in a state of containing a solvent. Specific examples of the solvent to be used include the above-mentioned various organic solvents that can be used when preparing the vinyl polymer (A) used in the present invention. When the solvent is contained, the content thereof is preferably 5 to 95% by weight, particularly preferably 10 to 80% by weight in the antifouling coating composition. In order to prepare the antifouling coating composition of the present invention using each of the above-mentioned components, various known and conventional methods can be applied. For example, a predetermined amount of each of the above-mentioned components can be applied at once or at any time. It may be added in order, and stirring, mixing, dispersion and the like may be performed.

The antifouling coating composition of the present invention provides a coating film which is one-pack type and has excellent storage stability, crack resistance, adhesion and long-term antifouling property. Therefore, according to the antifouling coating composition of the present invention, the antifouling coating composition can be used as a marine structure such as a water supply port or a drainage port of a nuclear power plant, a sludge diffusion prevention film for various marine civil engineering works, a fishing gear such as a ship, a rope or a fishing net. A hull coated with an antifouling coating film excellent in crack resistance, adhesiveness, and antifouling property by coating the surface of various molded products (base materials) such as It is possible to form coated objects such as marine structures and fishing gear, that is, the coated objects of the present invention.

Although the antifouling coating composition of the present invention can be directly applied to the above-mentioned substrate, it may be applied to a substrate previously coated with a base treatment agent such as a rust preventive agent and a primer. Good. Furthermore, the surface of a hull, a marine structure, etc., which has already been coated with the conventional antifouling coating composition or has been coated with the antifouling coating composition of the present invention, has the anti-fouling property of the present invention for repair. The stain paint composition may be overcoated.

The thickness of the antifouling coating film thus formed on the surface of the hull, marine structure, etc. is not particularly limited, but 30 to 500 μm indicates that the long-term antifouling property of the coating film is good. It is preferable because In order to form a coating film having such a thickness, for example, a coating treatment for forming a coating film having a thickness of 30 to 150 μm at one time may be performed once or several times. In this way, crack resistance, excellent adhesion,
In addition, the consumption rate is well controlled, and an antifouling coating film having excellent antifouling properties, particularly long-term antifouling properties in a highly polluted sea area can be obtained. Further, a coated article obtained by coating with such an excellent antifouling coating film can be obtained.

[0051]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but it goes without saying that the present invention is not limited to these examples. In the following, all parts and% are based on weight unless otherwise specified.

[Reference Example 1] [Preparation of vinyl polymer (A)] 500 parts of xylene (Xy) and n-acetic acid were added to a reactor equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen gas inlet. Butyl (BAc) (295 parts) was charged, and the temperature was raised to 80 ° C. with stirring under a nitrogen gas stream. Next, at the same temperature, methoxycarbonylmethylmethacrylate (MCMM
A) 350 parts, methyl methacrylate (MMA) 600
Part, N-methoxymethylacrylamide 50 parts, ter
t-Butylperoxy-2-ethylhexanoate (T
A mixture of 30 parts of BPEH) and 200 parts of BAc was added dropwise over 4 hours. Then continue the reaction at the same temperature,
Two hours after the end of the dropping, a mixture of 5 parts of BAc and 5 parts of TBPEH was added. Then, the mixture was heated and stirred at the same temperature for 13 hours. Then, it is diluted with a mixed solvent of Xy / BAc = 50/50 (weight ratio) so that the nonvolatile content becomes 50.0%, and alkoxycarbonylmethyl having a Gardner viscosity of Z4 to Z5 and a weight average molecular weight of 45,300. A solution of a vinyl polymer having an ester group and an N-substituted carboxylic acid amide group was obtained. Hereinafter, this polymer solution is abbreviated as vinyl polymer (A-1).

Reference Example 2 [Preparation of Vinyl Polymer (A)] 300 parts of propylene glycol monomethyl ether (PGME) and BAc495 were added to the same reactor as in Reference Example 1.
A portion was charged and the temperature was raised to 80 ° C. with stirring under a nitrogen gas stream. Next, at the same temperature, 460 parts of MCMMA and MMA
440 parts, N-methoxymethyl acrylamide 100
Part, 200 parts of BAc, and 40 parts of TBPEH were added dropwise over 4 hours. Then, the reaction was continued at the same temperature, and 2 hours after the dropping was completed, 5 parts of BAc and TBPEH were added.
A mixture of 5 parts was added. Then, at the same temperature,
Heating and stirring were performed for a period of time. Then, the nonvolatile content is 50.
It is diluted with a mixed solvent of PGME / BAc = 30/70 (weight ratio) so that it becomes 0%, and the Gardner viscosity is Z2 to Z.
A solution of a vinyl polymer having an alkoxycarbonylmethyl ester group and an N-substituted carboxylic acid amide group having a weight average molecular weight of 59,800 was obtained. Hereinafter, this polymer solution is abbreviated as a vinyl polymer (A-2).

[Reference Example 3] [Preparation of vinyl-based polymer (A)] As vinyl-based monomer, 460 parts of MCMMA and MMA3
Polymerization was performed in the same manner as in Reference Example 1 except that 90 parts and 150 parts of N, N-dimethylacrylamide were used. Next, Xy / BAc is adjusted so that the nonvolatile content becomes 50.0%.
= 50/50 (weight ratio), diluted with a mixed solvent, Gardner viscosity is Z3 to Z4, and weight average molecular weight is 42,500.
To obtain a solution of a vinyl polymer having an alkoxycarbonylmethyl ester group and an N-substituted carboxylic acid amide group. Hereinafter, this polymer solution was added to the vinyl polymer (A-
3) is abbreviated.

[Reference Example 4] [Preparation of vinyl polymer (A)] As a vinyl monomer, 580 parts of MCMMA and MMA
Polymerization was carried out in the same manner as in Reference Example 2 except that 370 parts and N-vinylformamide 50 parts were used. Then, PGME / BAc = 3 so that the nonvolatile content becomes 50.0%.
Contains a repeating unit derived from an alkoxycarbonylmethyl ester group and an N-vinylcarboxylic acid amide having a Gardner viscosity of Z2 to Z3 and a weight average molecular weight of 37,300 when diluted with a mixed solvent of 0/70 (weight ratio). A vinyl polymer solution was obtained. Hereinafter, this polymer solution is abbreviated as a vinyl polymer (A-4).

[Reference Example 5] [Preparation of vinyl-based polymer having alkoxycarbonylmethyl ester group for comparative experiment but not containing N-substituted carboxylic acid amide group] As a vinyl-based monomer, MCM
Polymerization was carried out in the same manner as in Reference Example 1 except that 350 parts of MA and 650 parts of MMA were used. Next, the nonvolatile content is 5
Dilute with a mixed solvent of Xy / BAc = 50/50 (weight ratio) so that the concentration becomes 0.0%, and the Gardner viscosity is from Z2 to Z.
3. A solution of a vinyl-based polymer having an alkoxycarbonylmethyl ester group having a weight average molecular weight of 30,500 but having no carboxylic acid amide group was obtained. Hereinafter, this polymer solution is abbreviated as a vinyl polymer (RP-1).

"Example 1" (Preparation of antifouling coating composition and evaluation of performance of antifouling coating film) An antifouling coating material having a composition shown in Table 1 was prepared by a conventional method. That is, 37 parts of a vinyl-based polymer (A-1) which is a solution of the copolymer prepared in Reference Example 1, 41 parts of cuprous oxide, 6 parts of titanium oxide, and "Disparlon A as a sagging preventive agent.
603-20X ”(fatty acid amide wax manufactured by Kusumoto Kasei Co., Ltd.) A mixture of 2 parts and 14 parts of xylene was dispersed for 2 hours with a paint conditioner using glass beads as a dispersant, and then 100 mesh. After filtering with a filter of No. 1, an antifouling coating composition was obtained.

"Examples 2 to 10" Each antifouling coating composition was prepared in the same manner as in Example 1 except that the components were used in the ratios shown in Tables 1 to 4.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

"Comparative Example 1" An example except that the vinyl polymer (RP-1) synthesized in Reference Example 5 was used as the vehicle component and various other components shown in Table 4 were used. An antifouling coating composition was prepared in the same manner as in 1.

Examples 1 to 10 thus obtained,
Each antifouling coating composition of Comparative Example 1 was used to prepare a coated panel (test plate) for a test described later. Then, as described below, "fouling resistance", "coating wear rate", and "coating state" such as the presence or absence of blister, peeling and cracking were evaluated. The evaluation results are shown in Tables 5, 6, and 7.

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[Table 5]

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[Table 6]

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[Table 7]

The contents of each component shown in Tables 1 to 4 are as follows. (1) Inorganic copper compound cuprous oxide: "NC303" manufactured by Nisshin Chemro Co., Ltd. (2) Organic antifouling agent B-1: copper pyrithione B-2: pyridine-triphenylboron B-3: 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one B-4: zinc pyrithione B-5: 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (3) zinc oxide JIS Class 3 was used. (4) Elution promoting component rosin solution: A 50% xylene solution of WW rosin was used. Copper naphthenate solution: A xylene solution of copper naphthenate having a copper content of 8% was used. (5) Vinyl ether-based polymer "Ruttonal A-25": Polyethyl vinyl ether manufactured by BASF, Germany. (Viscosity: 2.5-6.0 Pa · s
[23 ° C., specific gravity; 0.96 [20 ° C.]) (6) Plasticizer “Toyo Parax 150”: chlorinated paraffin manufactured by Tosoh Corporation. (Average carbon atom number 14.5, chlorine content 50
% By weight, viscosity 12 poise [25 ° C.], specific gravity 1.25 [2
5 ° C]). TCP: Abbreviation for tricresyl phosphate. (7) Dehydrating agent "soluble anhydrous gypsum D-1": manufactured by Noritake Co., Ltd. (8) Pigment titanium oxide: "Titanium White R-5" manufactured by Sakai Chemical Industry Co., Ltd.
N "was used. Red iron oxide: a ferric oxide content of 80% by weight or more was used. (9) As an additive anti-sagging agent, "Disparlon A603-20X [fatty acid amide wax manufactured by Kusumoto Kasei Co., Ltd. concentration 20%
Xylene paste] was used. (10) Solvent PGME: Abbreviation for propylene glycol monomethyl ether.

[Evaluation of Antifouling Property] A 70 × 200 × 3 mm sandblasted steel plate was prepared. This steel plate was bent in advance so that it could be attached to the side surface of a rotary drum installed in seawater in Hiroshima Bay in advance. Next, an epoxy-based zinc rich primer, an epoxy-based anticorrosive paint, and a vinyl-based binder coat were sequentially coated on this steel sheet every day so that the respective dry film thicknesses were 20 μm, 150 μm, and 50 μm. It was dried at room temperature for 7 days. Next, the antifouling coating composition was applied onto the obtained multilayer coating film so that the dry film thickness was 200 μm, and then dried at room temperature for 7 days to prepare a test plate. The test plate thus obtained was attached to the rotary drum, and the peripheral speed was 15 knots and 50% operating conditions (at night 12
Alternating operation of hourly operation and 12 hour daytime stop) 3, 6,
Tests were carried out under high pollution environment conditions for 12 and 18 months to evaluate the antifouling property.

The antifouling property was evaluated visually and the following criteria were used. (Evaluation Criteria) 5: No adhered matter is observed on the surface of the coating film. 4: Adhesion of thin slime is recognized on the coating film surface. 3: Adhesion of thick slime is recognized on the surface of the coating film. 2: Adhesion of slime and partial adhesion of plants such as Shio Midoro are recognized on the surface of the coating film. 1: The entire surface of the coating film is covered with plants such as Shio midoro (Aonori).

"Evaluation of consumption rate and state of coating film" A disk-shaped sandblasted steel plate having a diameter of 300 mm and a thickness of 3 mm was prepared. Next, an epoxy zinc rich primer, an epoxy anticorrosive paint, and a vinyl binder coat were applied to this steel sheet, each having a dry film thickness of 20 μm,
The coating was successively applied every day so as to have a thickness of 150 μm and 50 μm, and then dried in a room for 7 days. Then, the antifouling coating composition was applied radially on the obtained multilayer coating film using an applicator having a gap of 500 μm from the center to the outer peripheral direction, and then dried at room temperature for 7 days to give a test plate. It was made. The test plate thus obtained was mounted on a motor in a constant temperature bath containing seawater at 25 ° C. Then, the film was rotated at a peripheral speed of 15 knots for 2 months, and further, 1 month later, 3 months later, and 6 months later, the film thickness reduction in the vicinity of the circumference was measured to evaluate the coating film consumption rate. It was Further, the state of the coating film around the circumference after being rotated for 24 months under the same conditions was visually observed and evaluated.

As is clear from Table 5, Table 6 and Table 7, the coating film obtained from the antifouling coating composition of the present invention has a moderate coating film consumption rate and exhibits excellent antifouling property over a long period of time. Shows sex. Further, even when immersed in seawater for 24 months, blister, crack, peeling, etc. did not occur, and an excellent coating film state was maintained. On the other hand, the coating film obtained from the antifouling coating composition of Comparative Example 1 was inferior in antifouling property, and cracks occurred after immersion in seawater, and a good coating film state was not maintained.

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As described above, the antifouling coating composition of the present invention contains a repeating unit derived from a specific vinyl monomer containing an alkoxycarbonylmethyl ester group and a specific carboxylic acid amide group. A vinyl polymer (A) containing a repeating unit derived from a vinyl monomer as an essential repeating unit, and an antifouling agent (B), which does not contain tin, It is possible to form an excellent antifouling coating film that is excellent in long-term antifouling property in a highly polluted sea area and that does not cause cracking or decrease in adhesion even after being immersed in seawater for a long time. Further, the coated article of the present invention obtained by applying such a coating composition is excellent in long-term antifouling property in a highly polluted sea area, and even if it is immersed in seawater for a long period of time, It is less likely that cracks will occur in the dirty coating film or the adhesiveness will decrease.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Tanabe             7 Chinese paint at 1st Meiji Shinkai, Otake City, Hiroshima Prefecture             Co., Ltd. (72) Inventor Makoto Tsuboi             7 Chinese paint at 1st Meiji Shinkai, Otake City, Hiroshima Prefecture             Co., Ltd. (72) Inventor Masataka Ooka             6-11-4 Tomigaoka, Nara City, Nara Prefecture (72) Inventor Hiroshi Matsuzawa             2-3-6 Chiyoda, Takaishi-shi, Osaka F-term (reference) 4J038 CC061 CD101 CD111 CD121                       CD131 CE051 CE052 CF071                       CF091 CG021 CG141 CG142                       CG151 CG161 CG171 CG201                       CH031 CH041 CH071 CH081                       CH121 CH142 CH161 CR071                       HA126 HA216 KA01 KA10                       LA02 MA14 NA05 NA11 NA12                       NA27 PB02 PB05 PB07

Claims (8)

[Claims] 1. A repeating unit (a-1) represented by the following general formula (I) and a repeating unit (a-2) derived from a vinyl-based monomer having an N-substituted carboxylic acid amide group, and / Or an antifouling agent containing a vinyl polymer (A) containing the repeating unit (a-3) derived from N-vinylcarboxylic acid amide as an essential repeating unit, and an antifouling agent (B) Coating composition. [Chemical 1] (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 12 carbon atoms, and R ⁴ is a monovalent organic group. Shall represent a group.) 2. The vinyl polymer (A) comprises the repeating unit (a-1) in an amount of 20 to 99% by weight and the repeating unit (a).
-2) and / or 1 to 20 weight% of repeating units (a-3) are contained, The antifouling coating material composition of Claim 1. 3. The weight average molecular weight of the vinyl polymer (A) is 4,000 to 100,000.
Or the antifouling coating composition according to item 2. 4. The antifouling coating composition according to claim 1, which contains the antifouling agent (B) in a range of 1 to 70% by weight. 5. The antifouling coating composition according to any one of claims 1 to 4, which contains 0.1 to 30% by weight of the dissolution accelerator (C). 6. The antifouling coating composition according to claim 1, which contains 0.5 to 35% by weight of zinc oxide. 7. A vinyl ether polymer is used in an amount of 0.1 to 1
The composition according to claim 1, which contains 0% by weight. 8. A coated article coated with an antifouling coating film formed from the antifouling coating composition according to any one of claims 1 to 7.