JPH10101969A - Antifouling coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a self-grinding coating material which exhibits an antifouling effect in the sea for a long term by using a copolymer obtained by polymerizing a monomer mixture comprising an Mg-containing monomer, a Zn-containing monomer and a copolymerizable unsaturated monomer as the vehicle. SOLUTION: The structure of the Mg-containing monomer is represented by formula I (wherein R<1> is H or methyl; and R<2> is a residue of an organic acid), and the structure of the Zn-containing monomer is represented by formula II (wherein R<3> is H or methyl; and R<4> is a residue of an organic acid). An example of the compound represented by formula I is magnesium (meth)acrylate monochloroacetate, and an example of the compound represented by formula II is zinc (meth)acrylate monochloroacetate. An example of the copolymerizable unsaturated monomer is methyl (meth)acrylate. The mixing ratio among the starting materials for the copolymer is such that 10-95 pts.wt., in total, metal- containing monomers are used per 90-5 pts.wt. (100 pts.wt. in total) unsaturated monomer.

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.

[0003] 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 period of 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 prevention of 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, less toxic,
Demands for the development of a self-polishing antifouling paint composition which exhibits an antifouling function in the sea for a long time have become extremely strong. One of the self-polishing paints is zinc,
Periodic table IIa, IIb, IIIa, IV excluding copper and tellurium
A paint using a metal-containing copolymer selected from metals a, VIa, VIb, VIIb, and VIII has been proposed (Japanese Patent Publication No. 05-45632).

[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. Further, when polymerizing a metal-containing monomer, the metal-containing monomer is difficult to dissolve in a normal organic solvent, so that it is difficult to copolymerize in a normal solution polymerization. (2) Although the self-polishing property (the degree of wear of the coating film) is observed in the early stage when the coating film is immersed in the sea, 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 in order 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, a self-polishing antifouling paint using a metal-containing copolymer selected from zinc, copper and tellurium has been proposed (Japanese Patent Publication No. 07-64985).
Long-term self-polishing properties are not always satisfactory.

[0006]

DISCLOSURE OF THE INVENTION In view of the above-mentioned prior art, the present inventors have enthusiastically aimed at providing a self-polishing antifouling paint composition which exhibits an antifouling effect in the sea for a long time. As a result of study, the present inventors 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) the following formula (I)

[0008]

Embedded image (B) a metal-containing monomer represented by the following formula (II):

[0009]

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.

[0010]

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:
A metal-containing monomer (a) represented by the above formula (I) and a metal-containing monomer (b) represented by the above formula (II); A component that always exposes a fresh coating film in seawater, maintains self-polishing properties over a long period of time, and exerts an antifouling function.

In the above formulas (I) and (II), R ¹ and R ³ are a hydrogen atom or a methyl group;
² , R ⁴ 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,
Examples thereof include those derived from monovalent organic acids such as 4,5-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 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 (a) represented by the above formula (I), monochloromagnesium acetate (meth) acrylate ((meth) acrylate means acrylate or methacrylate; hereinafter the same) ,
Magnesium monofluoroacetate (meth) acrylate,
Magnesium propionate (meth) allylate, magnesium octylate (meth) acrylate, magnesium versatate (meth) acrylate, magnesium palmitate (meth) acrylate, magnesium cresotinate (meth) acrylate, magnesium α-nephthoate (meth) acrylate, β-naphthomagnesium (meth) acrylate, magnesium benzoate (meth) acrylate, 2,4,5-trichlorophenoxy acetate magnesium (meth) acrylate, 2,4-dichlorophenoxy acetate magnesium (meth) acrylate, magnesium quinolinecarboxylate (Meth) acrylate, magnesium nitrobenzoate (meth) acrylate, magnesium nitronaphthalenecarboxylate (meth)
Acrylate and magnesium (meth) acrylate.

Further, specific examples of the metal-containing monomer (b) represented by the above formula (II) include zinc monochloroacetate (meth) acrylate and zinc monofluoroacetate (meth).
Acrylate, zinc propionate (meth) acrylate, zinc octylate (meth) acrylate, zinc versatate (meth) acrylate, zinc palmitate (meth) acrylate, zinc cresate (meth) acrylate, zinc α-naphthoate (meth) Acrylate, β-
Zinc naphthoate (meth) acrylate, zinc benzoate (meth) acrylate, zinc 2,4,5-trichlorophenoxyacetate (meth) acrylate, zinc 2,4-dichlorophenoxyacetate (meth) acrylate, zinc quinolinecarboxylate (meth) A) acrylate, zinc nitrobenzoate (meth) acrylate, zinc nitronaphthalenecarboxylate (meth) acrylate, zinc puruvate (meth) acrylate, and the like.

In the metal-containing monomer used in the present invention, the metal contained is a metal other than magnesium and zinc, for example, barium, cadmium, mercury, aluminum, lead,
Selenium, chromium, molybdenum, manganese, iron, cobalt, nickel and the like are not preferred because they tend to be difficult to dissolve in ordinary organic solvents. In addition, copper other than magnesium and zinc can be cited as a metal which is easily dissolved in an ordinary organic solvent, but it is difficult to achieve the object of the present invention by using this copper-containing monomer.

That is, in the present invention, the monomer (a) represented by the above formula (I) containing magnesium as a metal-containing monomer is added to the monomer (a) represented by the above formula (II) containing zinc. By using the body (b) in combination, an antifouling paint composition capable of maintaining self-polishing properties for a long period of time, which is the object of the present invention, can be obtained.

The unsaturated copolymerizable monomer (c) used in the present invention includes, 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,
(Meth) acrylates such as lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobonyl (meth) acrylate, cyclohexyl (meth) acrylate, and glycidyl (meth) acrylate Monomer; 2-hydroxyethyl (meth) acrylate;
Hydroxyl-containing monomers such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; 2-hydroxyethyl (meth) Acrylate and ethylene oxide, propylene oxide γ-butyrolactone or ε
An adduct with caprolactone or the like; a dimer or trimer such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; a monomer having a plurality of hydroxyl groups such as glycerol (meth) acrylate; Primary and secondary amino group-containing vinyl monomers such as butylaminoethyl (meth) acrylate and (meth) acrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Tertiary amino group-containing vinyl monomers such as dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide Isomers; heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine, vinylcarbazole, etc .; vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate, vinyl propionate, etc. Body. These monomers may be used alone or
Used in combination of more than one species.

In the present invention, the copolymer constituting the vehicle is a monomer comprising the above-mentioned metal-containing monomer (a), metal-containing monomer (b) and copolymerizable unsaturated monomer (c). It is obtained by polymerizing a monomer mixture. Upon polymerization, the total amount of the metal-containing monomers (a) and (b) is 1
The copolymerizable monomer (c) is 9 to 0 to 95 parts by weight.
The polymerization is preferably performed at a ratio of 0 to 5 parts by weight (total 100 parts by weight). This is because the amount of metal-containing monomer is 10
If the amount is less than 10 parts by weight, the dissolution rate of the coating film is too slow to achieve the intended purpose of imparting hydrolyzability, while if the metal-containing monomer exceeds 95 parts by weight, This is because the dissolution rate of the coating film becomes too high, and the original permanent antifouling property of the coating film cannot be maintained. It is more preferably in the range of 25 to 65 parts by weight, and still more preferably in the range of 35 to 55 parts by weight.

The ratio of the metal-containing monomer (a) used in the polymerization and the metal-containing monomer (b) used in combination with the metal-containing monomer (a) is 95: magnesium / zinc (mol%).
/ 5 to 20/80. This is because if the ratio of magnesium to zinc is too high, the hydrolysis rate of the coating film is very fast, and the antifouling agent on the coating film surface is rapidly eluted and lost in the early stage when the coating film is immersed in the sea. On the other hand, when the ratio of magnesium is too low, the coating film is not easily hydrolyzed, and it is difficult to maintain self-polishing properties for a long period of time. More preferably 85/1
5/30/70, more preferably 80 / 20-50 /
The range is 50.

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 according to 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 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 thickness range is μm. The coating film is generally dried at room temperature, but may be dried by heating.

[0024]

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 the examples, parts and%
Represents parts by weight and% by weight, respectively.

[Examples 1 to 8, Comparative Examples 1 to 4]
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
Parts and 10 parts of xylene were added dropwise over 2 hours, and the mixture was further stirred for 2 hours. After that, 20 parts of xylene were added, and polymerization solutions A1 to A8 and B1 to B4 for vehicles having the characteristic values shown in Table 1
I got

[0026]

[Table 1]

Next, antifouling paints of the present invention (Examples 1 to 8) were prepared by using the copolymer solutions A1 to A8 thus obtained in the proportions shown in Table 2. Further, using the copolymer solutions B1 to B4, the antifouling paints of Comparative Examples 1 to 4 were prepared at the compounding ratios shown in Table 2.

[0028]

[Table 2]

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

(1) Test for Degree of Consumption of Coating Film Each antifouling paint was applied to a 50 mm × 50 mm × 2 mm film.
(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.
It was shown to.

(2) Antifouling test Each of the antifouling paints was applied to a sandblasted steel plate to which a rust preventive paint had been applied in advance so that the dry film thickness became 240 μm to prepare a test plate. 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.

(4) Storage stability Each of the antifouling paints was prepared to have an initial viscosity of 6 to 8 ps, placed in a 200 ml mayonnaise bottle, stored in a constant temperature water bath at 40 ° C. for 3 months, and tested for viscosity. The changes were examined. Table 5 shows the results.

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

As is clear from the results shown in Tables 3 to 5,
The antifouling paint compositions using the copolymer solutions B1 to B4 (Comparative Examples 1 to 4) did not exhibit self-polishing properties over a long period of time and could not obtain sufficient antifouling performance. On the other hand, the antifouling paint compositions of the present invention using the copolymer solutions A1 to A8 (Examples 1 to 8) show a long-term self-polishing property and excellent antifouling performance, It can be seen that good results are also exhibited in storage stability.

[0038]

The antifouling coating composition of the present invention contains a copolymer containing a specific metal as a vehicle component, so that the stability of the coating during storage is good, and There is no cracking or peeling, the coating film dissolves in the sea at an appropriate speed and uniformly, and an excellent antifouling effect that self-polishing properties can be maintained for a long time can be exhibited.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 220/10 C08F 220/10 230/04 230/04

Claims (1)

[Claims] (A) The following formula (I): (B) a metal-containing monomer represented by the following formula (II): 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.