JPH10158547A - Antifouling coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject self-polishing type composition exhibiting antifouling effect in sea over long period by using a copolymer resin containing a specific metal as a vehicle component. SOLUTION: This coating material composition contains (A) a polymerizable monomer having two double bonds and containing metal [e.g. magnesium (meth) acrylate], (B) a metal-containing monomer of the formula (R<1> is H or methyl; M is Mg, Zn or Cu; R<2> is an organic acid residue) [e.g. magnesium monochloroacetate (meth)acrylate] and (C) a copolymer obtained by polymerizing a monomer mixture comprising copolymerizable unsaturated monomers [e.g. methyl (meth)acrylate] as a vehicle. The polymerization is preferably carried out in a ratio of 90-20 pts.wt. component C to 10-80 pts.wt. total amount of the components A and B. The ratio (molar ratio) of the components A to B is preferably (70/30) to (30/70). Furthermore, the above copolymer is preferably compounded in an amount of 20-25wt.% (based on solid content) as the resin component into the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antifouling paint composition, and more particularly to an antifouling paint composition capable of preventing the adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms. .

[0002]

2. Description of the Related Art Conventionally, inundated portions of ships and marine structures have been used for the purpose of preventing corrosion due to adhesion of marine organisms such as barnacles, bark beetles, and algae, and preventing a decrease in the speed of navigation of ships. , And an antifouling paint containing rosin and organotin. In addition, anti-fouling paints containing rosin and organotin are also applied to aquaculture nets for the purpose of preventing fish and shellfish from being killed by the attachment of marine organisms.

In this antifouling paint, the rosin and the antifouling component contained in the coating film exhibit an antifouling effect by being eluted into the sea, but this coating film is immersed in the sea for a long time. In this case, the amount of elution gradually decreases, and at the same time, the surface of the coating film becomes uneven, so that the effect of preventing adhesion of marine organisms and the like is significantly reduced. Further, the self-polishing type organotin-containing paint has a strong toxicity, and thus has an adverse effect on fish and shellfish. Therefore, the demand for the development of a self-polishing antifouling paint composition having low toxicity and exhibiting an antifouling function in the sea for a long time has become extremely strong. As one of the self-polishing paints, a paint using a metal-containing copolymer has been proposed (Japanese Patent Publication No. Hei 5-
No. 45632, Tokuhei 7-64985).

[0004] However, paints using the above-mentioned metal-containing copolymers have the following problems. (1) When a metal is added to a carboxyl group-containing polymer, the carboxyl group remaining in the side chain of the polymer forms a metal complex such as a pigment or cuprous oxide, and causes gelation. (2) In the early stage when the coating film is immersed in the sea, the self-polishing property (the degree of consumption of the coating film) is observed, but the self-polishing property is not observed over time and the antifouling effect is not exhibited for a long time. (3) If the amount of metal per molecular weight is increased to maintain self-polishing properties for a long period of time, the coating film becomes hard and brittle, cracks occur in the coating film, and finally peeling occurs.

On the other hand, the present inventors have previously proposed an antifouling paint using a copolymer containing two or three double bonds and containing a metal (JP-A-05-171066). . However, although this paint shows self-polishing properties over a long period of time, the degree of wear of the coating film has not always been sufficiently satisfactory.

[0006]

DISCLOSURE OF THE INVENTION In view of the above-mentioned prior art, the present inventors have made intensive studies for the purpose of providing a self-polishing antifouling paint which exhibits an antifouling effect in the sea for a long period of time. As a result, they have found that an antifouling coating composition containing a copolymer resin containing a specific metal as a vehicle component has excellent performance, and completed the present invention.

That is, the present invention relates to (a) a polymerizable monomer having two double bonds and containing a metal, (b) a polymerizable monomer represented by the following formula (I):

[0008]

Embedded image Characterized in that it contains, as a vehicle, a copolymer obtained by polymerizing a monomer mixture consisting of a metal-containing monomer represented by the formula: and (c) a copolymerizable unsaturated monomer. In a water-soluble coating composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a metal-containing monomer used for obtaining a copolymer which is a vehicle component includes:
The polymerizable monomer (a) having two double bonds and containing a metal and the metal-containing monomer (b) represented by the above formula (I) have a self-polishing property for a long time. It is a component for maintaining and exhibiting an antifouling function.

The polymerizable monomer (a) having two double bonds and containing a metal used in the present invention (hereinafter referred to as "a")
Abbreviated as metal-containing monomer (a). ) Is, for example, magnesium acrylate [Mg (CH ₂ ＣＨCHCOO)
₂ ], magnesium methacrylate [Mg (CH ₂ ＣC
(CH ₃ ) COO) ₂ ], zinc acrylate [Zn (CH
₂ ＣＨCHCOO) ₂ ], zinc methacrylate [Zn (CH
₂ ＣC (CH ₃ ) COO) ₂ ], copper acrylate [Cu
(CH ₂ ＣＨCHCOO) ₂ ], copper methacrylate [Cu
(CH ₂ ＣC (CH ₃ ) COO) ₂ ] and the like.
These can be used alone or in combination of two or more.

The metal-containing monomer (b) used in the present invention is represented by the above formula (I). In the above formula (I), R ¹ is a hydrogen atom or a methyl group, M represents a metal of Mg, Zn or Cu, R ²
Represents an organic acid residue. Organic acid residues include monochloroacetic acid, monofluoroacetic acid, propionic acid, octylic acid,
Versatic acid, palmitic acid, cresotic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalene Examples thereof include those derived from monovalent organic acids such as carboxylic acid and purbic acid. Among these organic acid residues, a fatty acid-based paint is particularly preferred as the antifouling paint, and a paint film free from cracks and peeling can be maintained for a long time.

As a specific example of the metal-containing monomer (b) represented by the above formula (I), monochloromagnesium acetate (meth) acrylate ((meth) acrylate means acrylate or methacrylate; hereinafter the same) ,
Monochloro zinc acetate (meth) acrylate, monochloro copper acetate (meth) acrylate, magnesium monofluoro acetate (meth) acrylate, zinc monofluoro acetate (meth) acrylate, copper monofluoro acetate (meth) acrylate, magnesium propionate (meth) acrylate , Zinc propionate (meth) acrylate, copper propionate (meth) acrylate, magnesium octylate (meth) acrylate, zinc octylate (meth) acrylate, copper octylate (meth) acrylate, magnesium versatate (meth) acrylate, versatic Zinc acrylate (meth) acrylate, copper versatate (meth) acrylate, magnesium palmitate (meth) acrylate, zinc palmitate (meth) acrylate, palmitic acid (Meth) acrylate, magnesium Kuresochin acid (meth) acrylate, Kuresochin zinc (meth) acrylate, Kuresochin copper (meth) acrylate, alpha-magnesium-naphthoic acid (meth) acrylate, alpha-naphthoic acid zinc (meth) acrylate,
Copper α-naphthoate (meth) acrylate, magnesium β-naphthoate (meth) acrylate, zinc β-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 nitratophthalenecarboxylate (meth) acrylate, magnesium puruvate (meth) acrylate, zinc pluvate (meth) acrylate, copper puruvate (meth) acrylate, and the like are included. These monomers can be used alone or in combination of two or more.

Examples of the copolymerizable unsaturated monomer (c) (hereinafter abbreviated as comonomer (c)) used in the present invention include methyl (meth) acrylate and 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, isobonyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth)
(Meth) acrylate monomers such as acrylates;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Hydroxyl-containing monomers such as acrylates; 2-hydroxyethyl (meth) acrylate and ethylene oxide, propylene oxide, γ-butyrolactone or ε-caprolactone, and adducts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Dimer or trimer such as (meth) acrylate; monomer having plural hydroxyl groups such as glycerol (meth) acrylate; primary and secondary such as butylaminoethyl (meth) acrylate and (meth) acrylamide Amino group-containing vinyl monomer; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethy Tertiary amino group-containing vinyl monomers such as tylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide; heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole; styrene , Vinyl toluene, α
-Vinyl monomers such as methylstyrene, (meth) acrylonitrile, vinyl acetate and vinyl propionate. These monomers can be used alone or in combination of two or more.

In the present invention, the copolymer constituting the vehicle is a monomer mixture comprising the above-mentioned metal-containing monomer (a), metal-containing monomer (b) and copolymer monomer (c). Obtained by polymerization. At the time of polymerization, the proportion of the copolymer monomer (c) to 90 to 20 parts by weight (total 100 parts by weight) based on the total amount of the metal-containing monomers (a) and (b) of 10 to 80 parts by weight. It is preferred to polymerize with. This is because when the amount of the metal-containing monomer is less than 10 parts by weight, the dissolution rate of the coating film becomes too slow, and the intended purpose of imparting hydrolyzability cannot be achieved.
When the amount of the metal-containing monomer exceeds 80 parts by weight, the dissolution rate of the coating film becomes too high, and the original permanent antifouling property that the coating film should have cannot be maintained. It is in the range of 50 parts by weight.

The ratio of the metal-containing monomer (a) used in the polymerization and the metal-containing monomer (b) used together with the metal-containing monomer (a) is (a) / (b) (mol%). 80/2
It is preferable to set it to be 0 to 20/80. This is because if the ratio of (a) / (b) is higher than 80/20, the dissolution rate of the coating film is low, and the self-polishing property (the degree of consumption of the coating film) is sufficient.
Cannot be exhibited, while the ratio of (a) / (b) is 2
If the ratio is lower than 0/80, the self-polishing property (the degree of consumption of the coating film) is observed at the initial stage when the coating film is immersed in the sea, but the self-polishing is not observed over time.
More preferably, it is in the range of 70/30 to 30/70.

The copolymer used in the present invention is produced according to a known method. That is, the above-mentioned monomers are mixed, and this mixture is added to a mixture of 60 to 18 in the presence of a radical initiator.
The reaction is allowed to continue polymerization at a reaction temperature of 0 ° C. for 5 to 14 hours. As the polymerization method, in addition to the solution polymerization method performed in an organic solvent, an emulsion polymerization method, a suspension polymerization method, and the like can be adopted. Adopting the polymerization method is advantageous in terms of productivity and performance.

The antifouling coating composition of the present invention comprises the above copolymer as a vehicle component, and is blended with a conventionally known antifouling agent. The proportion of the copolymer 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.
It is preferable to use it in the range. This is because the more the resin component, the less the antifouling agent, and the lower the antifouling ability. This is because there is a tendency that

Examples of the antifouling agent include well-known antifouling agents conventionally used in accordance with the required performance, for example, copper-based antifouling agents such as cuprous oxide, copper thiocyanate and copper powder, as well as lead, zinc, nickel and the like. Other metal compounds, such as amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds,
A maleimide compound, a pyridine compound, or the like is used alone or in combination.

Other than antifouling agents, silicon compounds such as dimethylpolysiloxane and silicone oil, and fluorine-containing compounds such as fluorocarbon, for the purpose of imparting lubricity to the surface of the coating film and preventing the adhesion of organisms. Can also be used. Further, the antifouling paint composition of the present invention may further contain, if necessary, extenders, coloring pigments, plasticizers, various paint additives, other resins, and the like, in addition to the above-described antifouling agent.

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, port facilities, oil fences, bridges, submarine bases and the like. Brush coating, spray coating, roller coating, directly on the surface of a base material such as underwater structures, 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 thickness range is μm. The coating film is generally dried at room temperature, but may be dried by heating.

[0021]

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. The parts in the examples represent parts by weight.

Examples 1 to 9 and Comparative Examples 1 to 5
PGM (propylene glycol methyl ether) was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a stirrer.
30 parts and 40 parts of xylene are charged, and 1
The temperature was raised to 00 ° C. 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 dropping, t-butyl peroctoate 1
And 10 parts of xylene were added dropwise over 2 hours, and after stirring for 2 hours, 20 parts of xylene were added to the polymer solutions A1 to A9 and B1 to B1 for vehicle having the characteristic values shown in Table 1.
5 was obtained.

[0023]

[Table 1]

Next, antifouling paints of the present invention (Examples 1 to 9) were prepared by using the copolymer solutions A1 to A9 thus obtained in the proportions shown in Table 2. Further, using the copolymer solutions B1 to B5, antifouling paints of Comparative Examples 1 to 5 were prepared at the compounding ratios shown in Table 2.

[0025]

[Table 2]

Next, using each of the antifouling paints prepared as described above, a coating film wear test, antifouling test, and crack / peelability test were performed in the following manner.

(1) Test for Degree of Consumption of Coating Film Each antifouling paint was applied to each of 50 mm × 50 mm × 2 mm.
(Thickness) hard vinyl chloride plate, dry film thickness 240μm
After being applied by an applicator, the film was attached to a rotating drum placed in seawater, and rotated at a peripheral speed of 15 knots, and the consumed film thickness was measured every three months. Table 3 shows the results.

(2) Antifouling test Each antifouling paint 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. Was immersed in Hiroshima Bay for 36 months, and the adhesion area (%) of the adhered substance was examined every 6 months. Table 4 shows the results.

(3) Crack / peelability test A test plate similar to that used in the antifouling test was prepared, immersed in sterile filtered seawater for 24 months, and taken out of the seawater every 6 months. Is dried at room temperature of 20 ° C. for one week,
The state of cracking and peeling of the coating film was observed. Those without cracks and peeling were indicated by ○, those with only cracks were indicated by x, and those with cracks and peeling were indicated by XX. Table 5 shows the results.

[0030]

[Table 3]

[0031]

[Table 4]

[0032]

[Table 5]

As is clear from the results shown in Tables 3 to 5,
Some antifouling paint compositions using the copolymer solutions B1 to B5 (Comparative Examples 1 to 5) exhibited self-polishing properties over a long period of time, but could not obtain sufficient antifouling performance.
On the other hand, the antifouling coating compositions of the present invention using the copolymer solutions A1 to A9 (Examples 1 to 9) show a long-term self-polishing property and excellent antifouling performance, and are excellent in crack and peeling properties. Also showed good results.

[0034]

Since the antifouling coating composition of the present invention contains a copolymer containing a specific metal as a vehicle component, the coating film has few cracks and peeling, and the coating film has an appropriate speed. In addition, it is possible to exhibit an excellent antifouling effect that it can be dissolved in the sea uniformly and maintain self-polishing properties for a long period of time.

Claims (1)

[Claims] (A) a polymerizable monomer having two double bonds and containing a metal; (b) a polymerizable monomer represented by the following formula (I): Characterized in that it contains, as a vehicle, a copolymer obtained by polymerizing a monomer mixture consisting of a metal-containing monomer represented by the formula: and (c) a copolymerizable unsaturated monomer. Paint composition.