JP2000273366A - Antifouling coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifouling coating composition which does not exhibit the degradation in properties even after a long storage after its production by incorporating an Mg, Zn or Cu salt of an organic acid and a copolymer of a monomer mixture containing a metal-containing polymerizable monomer into the same. SOLUTION: This composition contains a compound represented by the formula: R1-M-R2 and a copolymer of a monomer mixture which contains a metal- containing polymerizable monomer preferably having two unsaturated groups (e.g. magnesium acrylate) and/or a metal-containing polymerizable monomer of formula I and preferably further contains a polymerizable monomer of formula II. In the formulas, M is Mg, Zn or Cu; R1, R2 and R4 are each an organic acid residue; R3 and R5 are each H or CH3; and R6 and R7 are each a 1-10C alkyl, cycloalkyl or the like. Preferably, the copolymer comprises 1-50 wt.% units derived from the metal-containing polymerizable monomer having two unsaturated groups, 1-60 wt.% units derived from the monomer of formula I, and 1-90 wt.% units derived from the monomer of formula II. Preferably, the composition contains 20-25 wt.% copolymer and 0.01-15 wt.% compound of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling paint composition, and more particularly, to forming a coating film for preventing the adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms. The present invention relates to an antifouling paint composition which can be used as a paint.

[0002]

2. Description of the Related Art Conventionally, rosin-based compounds and organic tin have been used in the inundated parts of ships and marine structures for the purpose of preventing corrosion due to adhesion of marine organisms such as barnacles, bark beetles, and algae, and preventing the speed of navigation of ships. The antifouling paint contained is painted. A similar antifouling paint is also applied to aquaculture nets for the purpose of preventing lethality of fish and shellfish due to adhesion of marine organisms.

[0003] A coating film formed from such an antifouling paint exhibits an antifouling effect by eluting a rosin compound or an antifouling component contained therein into the sea. When the membrane has been immersed in the sea for a long time, the amount of eluted gradually decreases and the amount of unelutable increases,
At the same time, the surface of the coating film becomes uneven, so that the effect of preventing adhesion of organisms such as marine organisms tends to be significantly reduced. In addition, a coating film formed from a coating material containing an organotin has a long-term anti-fouling property by gradually dissolving and renewing the surface of the coating film and by constantly exposing the antifouling component to the coating film surface (self-polishing). Although it has a fouling effect, there is a concern that the strong toxicity of organotin has an adverse effect on fish and shellfish. For this reason, the demand for the development of a paint that forms a coating film having low toxicity and exhibiting an antifouling function for a long time in the sea has become extremely strong.

[0004] Various studies have been made on self-polishing paints that do not use organotin. For example, JP-A-62-57464 and JP-A-62-84168 disclose a metal in the end of a side chain. An antifouling paint composition using a copolymer having a containing group has been proposed. JP-A-5-171066 discloses an antifouling coating composition comprising a copolymer having two or three double bonds and a monomer-containing monomer as a vehicle component. Has been proposed.

[0005]

However, Japanese Patent Application Laid-Open No. Sho 62-62
The antifouling paint using a metal-containing copolymer as described in JP-A-57464, JP-A-62-84168, and JP-A-5-171066 has deteriorated in performance when stored for a long time. There was a problem that it was easy. For example, when 6 months or more have passed after the production, the self-polishing property of the coating film formed is significantly reduced as compared with that immediately after the production, so that a sufficient antifouling effect tends to be not obtained.

[0006] An object of the present invention is to provide an antifouling paint composition capable of maintaining excellent performance for a long period of time without reducing the antifouling effect of a formed coating film even after a long time has passed after production. It is to provide things.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on the above problems, and as a result, have found that a specific metal-containing copolymer,
In addition, the present inventors have found that an antifouling coating composition containing a specific metal-containing compound as a component solves the above-mentioned problems, and have completed the present invention.

That is, the present invention comprises a copolymer (A) of a monomer mixture containing a metal-containing polymerizable monomer (a) and a compound (B) represented by the following general formula (I). The present invention relates to an antifouling paint composition characterized by the above.

[Formula 4]

Wherein M is Mg, Zn or Cu, R ¹ , R ²
Represents an organic acid residue. )

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION A metal-containing polymerizable monomer (a) used as a component of a copolymer which is a vehicle component
Is a component for imparting a high self-polishing property to the obtained coating film for a long period of time and exhibiting an excellent antifouling effect. Preferably, a metal-containing polymerizable monomer having two unsaturated groups ( a
₁ ) or a metal-containing polymerizable monomer (a ₂ ) represented by the following general formula (II).

[Formula 5]

(Wherein, R ³ represents a hydrogen atom or a methyl group, M represents Mg, Zn or Cu, and R ⁴ represents an organic acid residue)

The metal-containing polymerizable monomer (a ₁ ) having two unsaturated groups can maintain the self-polishing property of the formed coating film for a long time by using the same. is there.

As the component (a ₁ ), for example, magnesium acrylate [(CH ₂ ＣＨCHCOO) ₂ Mg], magnesium methacrylate [(CH ₂ ＣC (CH ₃ ) COO) ₂ M]
g], zinc acrylate [(CH ₂ ＣＨCHCOO) ₂ Z
n], zinc methacrylate [(CH ₂ ＣC (CH ₃ ) CO
O) ₂ Zn], copper acrylate [(CH ₂ ＣＨCHCOO) ₂
Cu], copper methacrylate [(CH ₂ ＣC (CH ₃ ) CO
O) ₂ Cu]. One or more of these components (a ₂ ) can be appropriately selected and used as needed. Among them, when zinc (meth) acrylate is used, the resulting polymerization product has high transparency. Therefore, the color tone of the painted film tends to be beautiful,
Further, since the solubility in a generally used organic solvent is high, the workability tends to be good, which is preferable. (Note that
(Meth) acryl means acryl or methacryl. same as below).

The unit of the component (a ₁ ) in the copolymer is
Although not particularly limited, it is preferably in the range of 1 to 50% by weight. When the content is 1% by weight or more, the self-polishing property of the formed coating film tends to be maintained for a long time, and when the content is 50% by weight or less, the change in hardness of the coating film after immersion in seawater is reduced. This is because the effect of improving the balance between crack resistance and adhesion is remarkable, while maintaining long-term self-polishing properties and improving the properties of the coating film. More preferably, 5
-30% by weight.

The metal-containing polymerizable monomer (a ₂ ) represented by the general formula (II) can improve the antifouling effect of a coating film formed by using the same. is there. In the general formula (II), R ³ represents a hydrogen atom or a methyl group, M represents a metal of Mg, Zn or Cu, and R ⁴ represents an organic acid residue. As the organic acid residue, acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, caproic acid, caprylic acid, 2-ethylhexylic acid,
Capric acid, versatic acid, isostearic acid, palmitic acid, cresotic acid, oleic acid, elaidic acid,
Linoleic acid, linolenic acid, stearolic acid, ricinoleic acid, ricinoleic acid, brassic acid, erucic acid, α
-Naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5
Examples thereof include those derived from monovalent organic acids such as trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, and purbic acid. Among these organic acid residues, a fatty acid-based paint is particularly preferred as an antifouling paint, and there is a tendency that a paint film free from cracks and peeling can be maintained for a long time.

Specific examples of the compound represented by the above general formula (II) include, for example, magnesium acetate (meth) acrylate, zinc acetate (meth) acrylate, copper acetate (meth)
Acrylate, monochloromagnesium acetate (meth) acrylate, monochloro zinc acetate (meth) acrylate, monochloro copper acetate (meth) acrylate, magnesium monofluoroacetate (meth) acrylate, zinc monofluoroacetate (meth) acrylate, copper monofluoroacetate (meta) ) Acrylate, magnesium propionate (meth) acrylate, zinc propionate (meth) acrylate, copper propionate (meth) acrylate, magnesium caproate (meth) acrylate, zinc caproate (meth) acrylate, copper caproate (meth) acrylate , Magnesium caprylate (meth) acrylate, zinc caprylate (meth) acrylate, copper caprylate (meth) acrylate, magnesium 2-ethylhexylate (meth) acrylate , Zinc 2-ethylhexylate (meth) acrylate, copper 2-ethylhexylate (meth) acrylate, magnesium caprate (meth) acrylate, zinc caprate (meth) acrylate, copper caprate (meth) acrylate, magnesium versatate (Meth) acrylate, zinc versatate (meth) acrylate, copper versatate (meth) acrylate, magnesium isostearate (meth) acrylate, zinc isostearate (meth) acrylate, copper isostearate (meth) acrylate, magnesium palmitate (meta) ) Acrylate, zinc palmitate (meth) acrylate, copper palmitate (meth)
Acrylate, magnesium cresate (meth) acrylate, zinc (meth) acrylate, copper (meth) acrylate, magnesium oleate (meth) acrylate, zinc oleate (meth)
Acrylate, copper oleate (meth) acrylate, magnesium elaidate (meth) acrylate, zinc elaidate (meth) acrylate, copper elaidate (meth) acrylate, magnesium linoleate (meth) acrylate, zinc linoleate (meth) acrylate, Copper linoleate (meth) acrylate, magnesium linolenate (meth) acrylate, zinc linolenate (meth) acrylate, copper linolenate (meth) acrylate, stearol magnesium (meth) acrylate, zinc stearate (meth) acrylate, stear Copper roll (meth) acrylate, magnesium ricinoleate (meth) acrylate, zinc ricinoleate (meth) acrylate, copper ricinoleate (meth) acrylate, magnesium ricinoleate Beam (meth) acrylate, ricinelaidic zinc (meth) acrylate, ricinelaidic copper (meth) acrylate, brassidic acid magnesium (meth) acrylate, brassidic zinc (meth)
Acrylate, copper brassic acid (meth) acrylate,
Magnesium erucate (meth) acrylate, zinc erucate (meth) acrylate, copper erucate (meth) acrylate, magnesium α-naphthoate (meth) acrylate, zinc α-naphthoate (meth) acrylate, α-
Copper naphthoate (meth) acrylate, β-magnesium naphthoate (meth) acrylate, β-zinc naphthoate (meth) acrylate, copper β-naphthoate (meth) acrylate, magnesium benzoate (meth) acrylate, zinc benzoate ( (Meth) acrylate, copper benzoate (meth) acrylate, magnesium 2,4,5-trichlorophenoxyacetate (meth) acrylate, 2,4
5-trichlorophenoxyacetate zinc (meth) acrylate, 2,4,5-trichlorophenoxyacetate copper (meth)
Acrylate, magnesium 2,4-dichlorophenoxyacetate (meth) acrylate, zinc 2,4-dichlorophenoxyacetate (meth) acrylate, copper 2,4-dichlorophenoxyacetate (meth) acrylate, magnesium quinolinecarboxylate (meth) acrylate, Zinc quinolinecarboxylate (meth) acrylate, copper quinolinecarboxylate (meth) acrylate, magnesium nitrobenzoate (meth) acrylate, zinc nitrobenzoate (meth)
Acrylate, copper nitrobenzoate (meth) acrylate, magnesium nitronaphthalenecarboxylate (meth)
Acrylates, zinc nitronaphthalenecarboxylate (meth) acrylate, copper nitrate naphthalenecarboxylate (meth) acrylate, magnesium puruvate (meth) acrylate, zinc pluvate (meth) acrylate, copper pluvate (meth) acrylate, and the like are included. One or more of these metal-containing polymerizable monomers (a ₂ ) can be appropriately selected and used as needed, and among them, a zinc-containing polymerizable monomer is preferable. In particular,
When zinc (meth) acrylate is used in combination with zinc oleate (meth) acrylate or versatic acid (meth) acrylate, the balance between sufficient hydrolysis properties and crack resistance / peelability tends to be good, which is more preferable.

The unit of the component (a ₂ ) in the copolymer is
Although not particularly limited, it is preferably in the range of 1 to 60% by weight. When the content is 1% by weight or more, the coating tends to have excellent crack resistance and peelability, and when the content is 60% by weight or less, the coating tends to have excellent self-polishing property and antifouling effect. Because there is. More preferably, it is in the range of 5 to 40% by weight.

When the component (a ₁ ) and the component (a ₂ ) are used in combination as the constituent components of the copolymer, the component (a ₂ ) units in the copolymer / the component (a) in the copolymer ( It is preferred that the ratio (mol%) of the a ₁ ) units be in the range of 20/80 to 80/20. This is because, by setting the ratio to 80/20 or less, a change in the hardness of the coating film after immersion in seawater is small, and there is a tendency that coating physical properties excellent in crack resistance and adhesion are obtained. This is because the self-polishing property of the coating film to be formed tends to be maintained for a long period of time when the ratio is 80 or more. More preferably 30 / 70-
It is in the range of 70/30.

Further, when a polymerizable monomer (b) represented by the following general formula (III) is used as a component of the copolymer, excellent crack resistance and peeling resistance of the formed coating film are obtained. It tends to be able to achieve both good polishing properties and high self-polishing properties, which is preferable.

[0020]

[Formula 6]

(Wherein, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, and a phenyl group, R ⁷ is an alkyl group having 1 to 10 carbon atoms, cycloalkyl Group and phenyl group)

When the component (b) is used in combination with the component (a ₁ ) and the component (a ₂ ), a change in the hardness of the coating film after immersion in seawater is small, and the coating film has excellent crack resistance and excellent adhesion. , And furthermore, a sufficient self-polishing property can be exhibited for a long period of time, which is particularly preferable.

As the component (b), for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (2-ethylhexaoxy) ethyl (meth)
Acrylate, 1-methyl-2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (Meth) acrylate, o-
Methoxyphenylethyl (meth) acrylate, m-methoxyphenylethyl (meth) acrylate, p-methoxyphenylethyl (meth) acrylate and the like can be mentioned. One or more of these can be appropriately selected and used, and among them, 2-methoxyethyl acrylate and 3-methoxybutyl acrylate are preferable.

The unit of the component (b) in the copolymer is not particularly limited, but is preferably in the range of 1 to 90% by weight. When the content is 1% by weight or more, the self-polishing property and the crack resistance
This is because the releasability tends to be good, and when the content is 90% by weight or less, the balance between the crack resistance and the releasability of the formed coating film and the self-polishing property tends to be good. More preferably, it is in the range of 5 to 60% by weight,
More preferably, it is in the range of 10 to 50% by weight.

The constituents of the copolymer may be, if necessary, an unsaturated monomer (c) copolymerizable with the above-mentioned components (a ₁ ), (a ₂ ) and (b). Can be used. As such a component (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i- Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) (Meth) acrylate monomers such as acrylate, cyclohexyl (meth) acrylate, and glycidyl (meth) acrylate; 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-
Hydroxyl-containing monomers such as hydroxybutyl (meth) acrylate; adducts of 2-hydroxyethyl (meth) acrylate with ethylene oxide, propylene oxide, γ-butyrolactone or ε-caprolactone;
Dimers or trimers such as hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; monomers having a plurality of hydroxyl groups such as glycerol (meth) acrylate; butylaminoethyl (meth) acrylate; ) Primary and secondary amino group-containing vinyl monomers such as acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, Tertiary amino group-containing vinyl monomers such as dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide; vinylpyrrolidone, vinylpyridine, vinylcarbazole and the like The heterocyclic system basic monomers, and the like; styrene, vinyl toluene, alpha-methyl styrene, and (meth) acrylonitrile, vinyl acetate, vinyl monomer such as vinyl propionate. One or more of these monomers can be appropriately selected and used.

The unit of the component (c) in the copolymer which is the vehicle component of the present invention is not particularly limited, but is preferably in the range of 0 to 89% by weight. When the content is 89% by weight or less, a good hydrolytic property is imparted to the coating film formed over a long period of time, the hardness of the coating film after immersion in sea water is small, and the crack resistance and adhesion of the coating film are small. This is because there is a tendency for the balance between the two to be good. More preferably, it is in the range of 7 to 75% by weight, and even more preferably, it is in the range of 10 to 70%.

[0027] The method for producing the copolymer used as the vehicle component of the present invention is not particularly limited. For example, the above-mentioned monomers are mixed, and this mixture is added in the presence of a radical initiator. It can be produced by reacting at a reaction temperature of 60 to 180 ° C for 5 to 14 hours. As the polymerization method, in addition to a solution polymerization method performed in an organic solvent, an emulsion polymerization method, a suspension polymerization method, or the like can be adopted, but a general organic solvent such as toluene, xylene, methyl isobutyl ketone, or n-butyl acetate is used. Adopting the solution polymerization method is advantageous in terms of productivity and performance.

The proportion of the copolymer (A) as a vehicle in the antifouling coating composition is usually 20 to 25% by weight (solid content) as a resin component in the antifouling coating composition. Is preferred. This is because by appropriately containing the resin component, the coating performance such as crack resistance becomes good,
This is because by not including the antifouling agent in an excessive amount, it becomes easy to include an antifouling agent in an antifouling coating composition in an amount sufficient to maintain good antifouling ability.

The compound (B) used in the present invention is represented by the above-mentioned general formula (I). It is a component to prevent a drop.

In the above general formula (I), M is Mg, Z
represents a metal of n or Cu; ¹, R^TwoIndicates an organic acid residue
You. R¹And R^TwoMay be the same organic acid residue. Organic
Acetic acid, monochloroacetic acid, monofluoro acid
Acetic acid, propionic acid, caproic acid, caprylic acid, 2-d
Tylhexyl acid, capric acid, versatic acid, isos
Tearic acid, palmitic acid, cresotic acid, olein
Acid, elaidic acid, linoleic acid, linolenic acid, stearo
Luic acid, ricinoleic acid, ricinoleic acid, brassic
Acid, erucic acid, α-naphthoic acid, β-naphthoic acid,
Benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,
4-dichlorophenoxyacetic acid, quinolinecarboxylic acid,
Torobenzoic acid, nitronaphthalene carboxylic acid, purvin
Those derived from monovalent organic acids such as acids are exemplified.

One or more of these compounds (B) can be appropriately selected and used as necessary. Among them, acetic acid or propionic acid having a low molecular weight and exhibiting a sufficient effect in a small amount can be used. The compounds used are preferred.

The method for producing the compound (B) is not particularly limited, but it can be produced, for example, by reacting an organic acid with a metal oxide, a metal hydroxide, a metal halide or the like.

The proportion of the compound (B) in the antifouling coating composition is preferably in the range of 0.01 to 15% by weight. This is because when the content is 0.01% by weight or more, even after a long time has passed since the production of the coating material, the coating film to be formed is excellent in the effect of preventing a large decrease in self-polishing property and a reduction in the antifouling effect. When the content is 15% by weight or less, the balance with the properties of the coating film such as crack resistance tends to be good. More preferably, 0.
It is in the range of 1 to 7% by weight.

The antifouling coating composition of the present invention can further improve the antifouling performance by further blending an antifouling agent.

The antifouling agent used in the antifouling coating composition of the present invention can be appropriately selected and used according to the required performance. For example, cuprous oxide, copper thiocyanate, copper antifouling agents such as copper powder, lead, zinc, other metal compounds such as nickel, amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds, maleimide compounds, Pyridine compounds and the like can be mentioned. These can be used alone or in combination. In particular, those selected and selected by the Japan Shipbuilding Manufacturers Association for the purpose of research and investigation are preferable. For example, manganese ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6 -Cyclopropylamino-s-triazine, 2,4,5,6,
Tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, rodan copper, 4,5-dichloro-2-noctyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) Phthalimide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt, tetramethylthiuram disulfide, Cu
-10% Ni solid solution alloy, 2,4,6-trichlorophenylmaleimide 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, Examples thereof include diiodomethyl paratrisulfone, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, 2- (4-thiazolyl) -benzimidazole, and pyridine-triphenylborane.

The antifouling coating composition of the present invention may further comprise a silicone compound such as dimethylpolysiloxane or silicone oil, fluorocarbon, etc. for the purpose of imparting lubricity to the surface of the coating film and preventing the adhesion of organisms. Can be also blended. Further, the antifouling paint composition of the present invention may contain an extender pigment, a color pigment, a plasticizer, various paint additives, other resins, and the like, if necessary.

In order to form a coating film using the antifouling paint composition of the present invention, the above antifouling paint composition is applied to ships, various fishing nets, harbor facilities, oil fences, bridges, submarine bases and the like. Brush coating, spray coating, roller coating, directly on the surface of a substrate such as an underwater structure, or on a wash primer, chlorinated rubber-based, epoxy-based primer, intermediate coating, etc. It is applied by means such as immersion coating. The coating amount is generally 50 to 400 as a dry coating film.
The amount is such that the thickness is μm. The coating film is generally dried at room temperature, but may be dried by heating.

[0038]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, the part in an example represents a weight part.

[Production Examples A1 and A5] In a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 30 parts of PGM (propylene glycol methyl ether) and 40 parts of xylene were charged and heated to 100 ° C. while stirring. The temperature rose. Subsequently, a mixture composed of the monomers and the polymerization initiator shown in Table 1 was dropped at a constant rate over 3 hours from the dropping funnel. After the addition, 1 part of t-butyl peroctoate and 1 part of xylene
0 parts were added dropwise over 2 hours, and after stirring for 2 hours, 20 parts of xylene were added to obtain copolymer solutions A1 and A5 for vehicles having the characteristic values shown in Table 1.

[Production Examples A2, A3, A4, A6, A7] A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 20 parts of PGM (propylene glycol methyl ether) and 40 parts of xylene. The temperature was raised to 100 ° C. while stirring. Next, PGM was dropped from the dropping funnel.
A mixture of 10 parts, 10 parts of xylene, a monomer shown in Table 1, and a polymerization initiator was dropped at a constant speed in 4 hours.
After completion of the dropwise addition, 1 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 1 hour, and after stirring for 2 hours, 10 parts of xylene was added. The copolymer solution for a vehicle having the characteristic values shown in Table 1 was added. A2, A3, A4, A6, and A7 were obtained.

[Production Example B1] In a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 52 parts of PGM (propylene glycol methyl ether) and 52 parts of water were placed.
81.4 parts of zinc oxide were charged and the temperature was raised to 90 ° C. while stirring. Subsequently, 120.1 parts of acetic acid was added from the dropping funnel to 1 part.
After dropping at a constant speed over a period of time, the mixture was stirred for 2 hours to obtain a pale yellow reaction product solution. The active ingredient was 60%, excluding PGM as a solvent, water and generated water.

Production Example B2 51 parts of PGM (propylene glycol methyl ether) and 51 parts of water were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer.
79.6 parts of cupric oxide was charged, and the temperature was raised to 90 ° C. while stirring. Subsequently, 120.1 parts of acetic acid was dropped from the dropping funnel at a constant speed in 1 hour, and then stirred for 2 hours to obtain a green reaction product solution. The active ingredient was 60%, excluding PGM as a solvent, water and generated water.

[Production Example B3] 62 parts of PGM (propylene glycol methyl ether) and 62 parts of water were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer.
81.4 parts of zinc oxide were charged and the temperature was raised to 90 ° C. while stirring. Subsequently, propionic acid was added from the dropping funnel.
After 2 parts were dropped at a constant speed in 1 hour, the mixture was stirred for 2 hours to obtain a pale yellow reaction product solution. The active ingredient was 60%, excluding PGM as a solvent, water and generated water.

[Production Example B4] A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 60 parts of PGM (propylene glycol methyl ether) and 60 parts of water.
79.6 parts of cupric oxide was charged, and the temperature was raised to 90 ° C. while stirring. Then, from the dropping funnel, add 148.
After 2 parts were dropped at a constant speed in 1 hour, the mixture was stirred for 2 hours to obtain a green reaction product solution. The active ingredient was 60%, excluding PGM as a solvent, water and generated water.

Production Example B5 55 parts of PGM (propylene glycol methyl ether) and 55 parts of water were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer.
79.6 parts of cupric oxide was charged, and the temperature was raised to 90 ° C. while stirring. Subsequently, 60.1 parts of acetic acid and 74.1 parts of fluoric acid were dropped at a constant speed over 1 hour from the dropping funnel, followed by stirring for 2 hours to obtain a green reaction solution. The active ingredient is a component excluding PGM which is a solvent, water and generated water,
60%.

[Production Example B6] 254 parts of PGM (propylene glycol methyl ether) and 81.4 parts of zinc oxide were charged into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and stirred at 80 ° C. The temperature rose.
Subsequently, 344 parts of versatic acid was dropped at a constant speed from the dropping funnel in 1 hour, and then stirred for 2 hours to obtain a pale yellow transparent reaction product solution. The active ingredient was 60%, excluding PGM as a solvent and water produced.

[Production Example B7] 252 parts of PGM (propylene glycol methyl ether) and oxidized second acid were placed in a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer.
79.6 parts of copper were charged, and the temperature was raised to 80 ° C. while stirring. Subsequently, 344 parts of versatic acid was dropped from the dropping funnel at a constant speed for 1 hour, followed by stirring for 2 hours to obtain a green reaction product solution. The active ingredient was 60%, excluding PGM as a solvent and water produced.

[Production Example B8] 389 parts of PGM (propylene glycol methyl ether) and 81.4 parts of zinc oxide were charged into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and stirred at 80 ° C. The temperature rose.
Subsequently, 565 parts of oleic acid were added dropwise from the dropping funnel at a constant speed for 1 hour, followed by stirring for 2 hours to obtain a pale yellow transparent reaction product solution. The active ingredient was 60%, excluding PGM as a solvent and water produced.

[Production Example B9] In a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 388 parts of PGM (propylene glycol methyl ether) and oxidized
79.6 parts of copper were charged, and the temperature was raised to 80 ° C. while stirring. Subsequently, 565 parts of oleic acid were dropped from the dropping funnel at a constant speed in 1 hour, and then stirred for 2 hours to obtain a green reaction solution. The active ingredient was 60%, excluding PGM as a solvent and water produced.

[Production Example B10] 326 parts of PGM (propylene glycol methyl ether) and 79.6 parts of cupric oxide were charged into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and stirred. The temperature was raised to 80 ° C. Subsequently, 282 parts of oleic acid and 172 parts of versatic acid were dropped at a constant speed over 1 hour from the dropping funnel, followed by stirring for 2 hours to obtain a green reaction solution. The active ingredient is a component excluding PGM which is a solvent and water generated, and 60%
%.

[0051]

【table 1】

Next, using the copolymer solutions A1 to A7 thus obtained and the compounds B1 to B10 shown in Table 2, antifouling paints were prepared at the compounding ratios shown in Table 3 (Examples). 1 to 10, Comparative Examples 1 to 3).

[0053]

[Table 2]

[0054]

[Table 3]

(Note) Diesperon 4200 (Kusumoto Kasei Co., Ltd., anti-sagging agent)

Next, using each of the antifouling paints prepared as described above, a wear degree test of the coating film, an antifouling test,
A peel test was performed.

(1) Test for Degree of Consumption of Coating Film Each antifouling paint was applied to 50 × 50 × 2 mm (thickness).
Was applied with an applicator so as to have a dry film thickness of 240 μm, attached to a rotating drum placed in seawater, and rotated at a peripheral speed of 15 knots, and the consumable film thickness was measured every three months. Table 4 shows the results of the test after painting two weeks after the preparation of the paint. In addition, Table 5 shows the results of coating and testing 6 months after the preparation of the paint.

[0058]

[Table 4]

Note: For Example 6, 21 months later, Example 7
About 12 months, about 9 months after 21 months, and about 10 months after 21 months.
All coatings of 40 μm were consumed.

[0060]

[Table 5]

Note: For Example 6, 21 months later, Example 7
About 12 months, Example 9 after 24 months, and Example 10 after 21 months.
All coatings of 40 μm were consumed.

(2) Antifouling test Each of the antifouling paints was applied to a sandblasted steel plate to which a rustproof paint had been applied in advance so that the dry film thickness was 240 μm, and a test plate was prepared. The sample was immersed in Hiroshima Bay for 36 months, and the area (%) of the adhered substance was examined every 6 months. Table 6 shows the results of the test after painting two weeks after the preparation of the paint. In addition, Table 7 shows the results of a test conducted after painting six months after the preparation of the paint.

[0063]

[Table 6]

[0064]

[Table 7]

(3) Crack / peelability test Example 1 was placed on the following base (1) and base (2), respectively.
10 and Comparative Examples 1 to 3 were applied so that the dry film thickness became 240 μm, and test plates (A) and (B)
It was created. The test plate (B) was coated with the same antifouling paint applied when the substrate (2) was prepared. Base (1): A base made of a sandblasted steel plate to which a rust-preventive paint has been applied in advance Base (2): A 240 μm-thick coating film of the antifouling paint composition of Examples 1 to 10 and Comparative Examples 1 to 3 A substrate obtained by immersing the substrate on the substrate (1) in sterile filtered seawater for three months and then drying at room temperature for one week.

The test plates (A) and (B) were immersed in sterile filtered seawater for 24 months, and the test plates taken out of the seawater every 6 months were dried at a room temperature of 20 ° C. for 1 week, The state of cracking and peeling of the coating film was observed.も の indicates that there was no crack and no peeling, ○ indicates that there was only part of the crack, △ indicates that there was some peeling, and x indicates that the crack occurred and peeling occurred on the entire surface. Table 8 shows the results of the test after painting two weeks after the preparation of the paint. In addition, Table 9 shows the results of a test conducted after painting six months after the preparation of the paint.

[0067]

[Table 8]

[0068]

[Table 9]

For the antifouling paint composition (Comparative Examples 1 to 3), the result of painting after 6 months was compared with the result of painting after 2 weeks from the preparation of the paint. Of the antifouling effect over a long period of time.

On the other hand, the antifouling paint compositions (Examples 1 to 10) were applied two weeks after the paint was prepared,
As a result of coating and testing after a month, the self-polishing properties were almost the same, and no long-term decrease in the antifouling effect and no decrease in crack resistance and peeling resistance were observed.

[0071]

The antifouling coating composition of the present invention can be used without significantly reducing the self-polishing property of the formed coating film or the antifouling effect even after a long time has passed since the production. It can maintain excellent performance for a long time,
It is very useful industrially.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C09D 133/02 C09D 133/02 133/14 133/14 143/00 143/00 (72) Inventor Toshio Nagasaka Mitsubishi Rayon Co., Ltd., Product Development Laboratory (72) 4-72 Sunadabashi, Higashi-ku, Aichi Prefecture, Japan (72) Inventor Kunio Iwase 4-160 Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture, Mitsubishi Rayon Co., Ltd. Product Development Laboratory F-term ( 4H011 AD01 BA07 BB06 BB07 BB09 BB13 BB14 BB16 BB18 BC19 DA12 DD01 DF04 DH19 DH20 4J038 CL001 JA46 JA47 NA05

Claims (3)

[Claims] Claims 1. A composition comprising a copolymer (A) of a monomer mixture containing a metal-containing polymerizable monomer (a) and a compound (B) represented by the following general formula (I). Antifouling paint composition. [Formula 1] (In the formula, M represents Mg, Zn or Cu, and R ¹ and R ² represent organic acid residues.) The component (a) includes a metal-containing polymerizable monomer (a ₁ ) having two unsaturated groups and / or a metal-containing polymerizable monomer represented by the general formula (II) ( _{2. The} antifouling coating composition according to claim 1, wherein a2) is used. [Formula 2] (Wherein, R ³ is a hydrogen atom or a methyl group, M is Mg, Z
n or Cu, R ⁴ represents an organic acid residue) 3. A copolymer (A) of a monomer mixture containing a polymerizable monomer (b) represented by the following general formula (III):
The antifouling coating composition according to any one of claims 1 to 2, further comprising: Embedded image (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is
An alkyl group, a cycloalkyl group and a phenyl group of 10 to 10, and R ⁷ represents an alkyl group, a cycloalkyl group and a phenyl group having 1 to 10 carbon atoms)