Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2001-06-22
2004-04-27
Sanders, Kriellion A. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S413000, C524S431000, C523S122000, C252S182140
Reexamination Certificate
active
06727304
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a metal-containing monomer dissolved mixture, a metal-containing resin and an antifouling paint composition. More particularly, the present invention relates to a metal-containing monomer dissolved mixture which is soluble in a general organic solvent, excellent in storage stability and can be mixed with a general acrylic monomer and the like; a metal-containing resin soluble in a general organic solvent obtained by using the metal-containing monomer dissolved mixture as a raw material; and antifouling paint composition manifesting antifouling effect in sea for a long period of time.
2. Description of the Prior Art
Metal-containing monomers have been conventionally investigated to be used as an additive into an aqueous paint, aqueous ink, ultraviolet ray-curing material and the like, and usually, handled in the form of a powder or aqueous solution. In the case of a powder, it can be used as a modifier and the like for generally used resins such as an acrylic resin, epoxy resin, urethane resin, polyester resin and the like, and in the case of an aqueous solution, it can be used as a cross-linking agent and the like for a water-soluble resin and emulsion resin.
Metal-containing resins can be applied to various uses, and among them, use as a resin for an antifouling paint utilizing hydrolysis property thereof is expected.
An antifouling paint is painted, for example, on parts of ships and marine structures immersed in water for the purpose of preventing corrosion due to adhesion of marine organisms such as barnacle, teredo, algae and the like and reduction in navigating speed of a ship. Further, the same antifouling paint is painted also on a fish farming net for the purpose of preventing death of fishes due to adhesion of marine organisms.
A painted film formed of such an antifouling paint manifests an antifouling effect, for example, by elution of a rosin-based compound and antifouling component contained in the film into sea. However, when this painted film is immersed in sea for a long period of time, the proportion of an elution component decreases gradually to increase the proportion of non-eluting components, simultaneously the surface of the painted film becomes uneven, consequently, there is a tendency of significant reduction in an effect of preventing adhesion of organisms such as marine organisms and the like.
An organotin-based paint is conventionally used as an antifouling paint. This organotin-based antifouling paint is characteristic in that a painted film formed is gradually solved from the surface of the film to renew the surface, and an antifouling component is constantly exposed on the surface of the film (self polishing), consequently, an antifouling effect is manifested for a long period of time.
However, there is an afraid that an organotin-based antifouling paint exerts a reverse influence on fishes due to strong toxicity of organotin. Therefore, paints containing no organotin are on investigation. For example, an antifouling paint using an organosilicon-containing resin in which an organosilicon ester is introduced in a side chain, and antifouling paints using resins containing other metals than tin, have been suggested. Among others, antifouling paints using resins containing other metals than tin are noticed from the standpoints of an antifouling effect, cost and the like. For example, JP-A No. 63-56510 describes that a disintegrating type vinyl resin particle obtained by polymerizing a metal ester type polyfunctional polymerizable monomer can be added in an antifouling paint.
However, a painted film containing such a disintegrating type vinyl resin particle has problem that when immersed in sea for a long period, the surface of the film becomes uneven, and an antifouling ability thereof decreases significantly. For solving this problem, it is necessary that the metal-containing resin functions as a vehicle component of an antifouling paint, however, since a particle of such a metal-containing resin is scarcely soluble in a general solvent, use as a vehicle component is difficult. Namely, a metal-containing resin soluble in general solvent has been desired as a resin for an antifouling paint.
For example, JP-B No. 61-3830 suggests a metal-containing resin obtained by ion-changing a high acid value polymer or copolymer having a carboxyl group with a metal salt solution, and causing precipitation of a resin with an aqueous medium. Further, JP-A No. 5-171066 suggests an antifouling paint composition using as a vehicle component a copolymer constituted of a monomer having two or three double bonds and containing a metal. Further, JP-A Nos. 62-57464 and 62-84168 suggest self polishing type antifouling paint compositions using a copolymer having a specific divalent metal-containing group at the end of a side chain.
Most of metal-containing monomers typified by metal salts of polymerizable unsaturated organic acids are solid powders under normal temperature and normal pressure, and easily dissolved in water, however, are not easily dissolved in general organic solvents. Such metal-containing monomers are dissolved in slight amount in a large amount of alcohol-based solvent, however, when left for a certain period, manifest a tendency of deposition of a crystal, leading to poor storage stability.
When a metal-containing resin is produced by copolymerizing a metal-containing monomer with an acrylic monomer and the like in an organic solvent, copolymerizing property is low because a metal-containing monomer is not easily dissolved also with an acrylic monomer, and it is difficult to introduce a metal in sufficient amount into a polymer. Further, when a metal-containing monomer is added as a cross-linking agent to an acrylic oligomer or the like which is a ultraviolet ray-curing material, to produce a metal-containing resin, degree of cross-linking is low because the monomer is not easily solved uniformly in the oligomer, consequently, it is difficult to obtain sufficient abilities.
When a metal-containing resin obtained by introducing a metal salt into a high acid value resin described in JP-B No. 61-3830 is used as a resin for an antifouling paint, there is a tendency of decrease in water-resistance and antifouling property for a long period of a painted film. Further, this metal-containing resin has a problem that when copper oxide generally used as an antifouling agent causing duration of an excellent antifouling effect in sea for a long period of time is added, the paint is easily gelled.
Moreover, a metal-containing monomer described in JP-A No. 5-171066 has a problem that copolymerizability with acrylic monomers and the like is low, and a copolymer insoluble in a solvent is often obtained, because this metal-containing monomer is not easily dissolved with an organic solvent and acrylic monomer and the like as described above. Further, a film obtained from this antifouling paint composition tends to easily cause cracking and peeling with the lapse of time.
Furthermore, when resins having a specific divalent metal-containing group at the end of a side chain described in JP-A Nos. 62-57464 and 62-84168 are used as a resin for an antifouling resin, stability of hydrolysis of the film is low, and antifouling property of a long period is insufficient. Additionally, there is a problem that, when copper oxide is added, self polishing property decreases, and this tendency becomes remarkable particularly in a paint stored for a long period of time.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a metal-containing monomer dissolved mixture which is soluble in a general organic solvent, excellent in storage stability and can be mixed with a general acrylic monomer and the like, a metal-containing resin soluble in a general organic solvent obtained by using this monomer dissolved mixture as a raw material, and an antifouling paint composition manifesting duration of an antifouling effect in sea for a long period of time.
The present inventors have intensive
Hotta Kazuhiko
Ikegami Yukihiro
Iwase Kunio
Nagasaka Toshio
Sugihara Mitsunori
Mitsubishi Rayon Co. Ltd.
Morgan & Lewis & Bockius, LLP
Sanders Kriellion A.
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