Process for producing metal-containing resin and composition...

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...

Reexamination Certificate

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C526S091000, C526S095000, C526S240000, C526S317100, C526S318200, C526S319000, C526S329600, C524S779000, C524S780000, C524S783000, C524S784000, C524S785000

Reexamination Certificate

active

06555640

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a process for producing a metal-containing resin and an antifouling coating composition containing this metal-containing resin as an active constituent.
BACKGROUND OF THE INVENTION
Heretofore, a resin containing a carboxylate of tin has been widely used as an antifouling coating binder. However, due to its toxicity, it has been strongly desired to switch from it to other resins. In recent years, a resin containing a carboxylate of copper or zinc has been mainly studied. In order to exhibit a long-term antifouling property, it was required to control the abrasion speed of a coating film. The assignee of the present application proposed a process which comprises reacting a resin having a carboxyl group and a polyalkylene glycol structure with an oxide or hydroxide of copper or zinc, as a process for producing a resin containing a carboxylate of copper or zinc which is capable of controlling the abrasion speed of a coating film and exhibiting a long-term antifouling property, as disclosed in Japanese Laid-Open Patent Publication No. 11-080255/1999.
SUMMARY OF THE INVENTION
However, since this process comprised the production of a carboxyl-group containing resin and the subsequent formation of a carboxylate of a metal such as copper or zinc by reacting the carboxyl group contained in the resin with an oxide or hydroxide of copper or zinc, a long total reaction time, such as 24 hours, was required for the synthesis of the carboxyl-group containing resin and the formation of the carboxylate, which is a problem of this process.
Further, when a resin having a metal carboxylate structure in the molecule was to be produced by a process of copolymerizing polymerizable unsaturated monomers having a metal carboxylate structure, there occurs the problem that gelation occurring at the time of copolymerization makes the synthesis difficult.
It is the object of the present invention to provide a process that is capable of synthesizing a metal-containing resin having a good antifouling property in a short period of time without having such problems associated with the synthesis as gelation.
The present inventors found that the metal-containing resin having a good antifouling property can be synthesized in a short period of time without having such problems associated with the synthesis as gelation by conducting the polymerization of a monomer mixture containing a carboxyl group-containing polymerizable unsaturated monomer in a specific organic solvent in the presence of water and an oxide or hydroxide of a metal and the formation of a carboxylate of a metal simultaneously. The present invention was completed by this finding.
Thus, according to the present invention, there is provided a process for producing a metal-containing resin by conducting a copolymerization reaction of a monomer mixture (A) comprising 1 to 50% by weight of a carboxyl group-containing polymerizable unsaturated monomer (a) and 50 to 99% by weight of other polymerizable unsaturated monomer (b) in an organic solvent in the presence of water and an oxide or hydroxide of a metal having a valency of at least 2, in which the amount of water is 1 to 30 parts by weight based on 100 parts by weight of the monomer mixture (A), and the formation of a metal carboxylate bond occurs together with the copolymerization of the monomer mixture (A).
Further, according to the present invention, there is also provided an antifouling coating composition containing, as an active constituent, a metal-containing resin produced by the above production process.
PREFERRED EMBODIMENT OF THE INVENTION
The present invention will be described in detail hereinafter.
First, description will be given to the process of the present invention for producing a metal-containing resin.
In the process of the present invention for producing a metal-containing resin, the monomer mixture (A) to be subjected to the copolymerization reaction comprises (a) a carboxyl group-containing polymerizable unsaturated monomer and (b) other polymerizable unsaturated monomer. Illustrative examples of the above carboxyl group-containing polymerizable unsaturated monomer (a) include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.
Illustrative examples of the above other polymerizable unsaturated monomer (b) include a polymerizable unsaturated monomer having a polyoxyalkylene structure represented by the following general formula (1):
—(C
m
H
2m
O)
n
—R
1
  (1)
(wherein R
1
is hydrogen or a linear, branched or cyclic alkyl or aralkyl group having 1 to 20 carbon atoms, m is an integer of 1 to 4, and n is an integer of 2 to 100); vinyl aromatic compounds such as styrene, &agr;-methyl styrene, vinyltoluene and &agr;-chlorostyrene; alkyl esters or cycloalkyl esters having 1 to 24 carbon atoms of acrylic acid or methacrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (n-, i-, t-)butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate and isobornyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, perfluoroalkyl (meth)acrylates such as perfluorobutylethyl (meth)acrylate, perfluoroisononylethyl (meth)acrylate and perfluorooctylethyl (meth)acrylate; fluoroolefins represented by the general formula CX
2
═CX
2
(wherein the four Xs may be the same or may be different, and can be H, Cl, Br, F, an alkyl group or a haloalkyl group, provided that at least one F is included in the formula) such as CF
2
═CF
2
, CHF═CF
2
, CH
2
═CF
2
and CClF═CF
2
; and polymers which comprise at least one of the above monomers and have a copolymerizable double bond at one end, e.g., macromonomers.
In the polymerizable unsaturated monomer having a polyoxyalkylene structure represented by the above general formula (1), the polyoxyalkylene structure has the effect of improving wearing properties without impairing the physical properties of a coating film. In the formula (1), it is appropriate that m is an integer of 1 to 4, preferably 2 or 3 and that the number of alkylene glycol repeating units, n, is an integer of 2 to 100, preferably 2 to 20. When m is larger than 4 or n is larger than 100, there cannot be seen the effect of improving the wearing properties of the antifouling coating film.
Illustrative examples of the polymerizable unsaturated monomer having the polyoxyalkylene structure include (meth)acrylic ester having the polyoxyalkylene structure represented by the above formula (1) in the side chain, as specifically exemplified by methoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate and methoxypolypropylene glycol (meth)acrylate.
Illustrative examples of the organic solvent used in the copolymerization reaction in the present invention include alcohol solvents such as methanol, ethanol, n-propanol, i-propanol and (n-, i-, t-)butanol; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methoxy butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl cellosolve acetate, cellosolve acetate, diethylene glycol monomethyl ether acetate and carbitol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as dioxane, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and ethylene glycol monopropyl ether; aromatic hydrocarbon solvents such as toluene, xylene, and high-boiling petroleum solvents such as SWASOL 1000 and SWASOL 1500 (products of Cosmo Oil Co., Ltd.) and SOLVESSO 100 and SOLVESSO 150 (products of Esso Oil Co., Ltd.); and mineral spirits. In the process of the present invention, it is suitable from the viewpoint of dispersibility of an oxide or hydroxide of a metal (hereinafter referred to as “metal compound”) in the or

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