Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints

Definitions

• the present invention relates to a metal-containing polymerizable monomer used for producing a copolymer that is a constituent of a coating composition having antifouling properties, and a method for producing the monomer.
• the coating film formed from the antifouling paint exhibits an antifouling effect when the antifouling agent contained therein elutes into the sea.
• a coating film formed from a disintegrating antifouling paint using a rosin compound is immersed in the sea for a long period of time, the eluted components gradually decrease and the non-eluting components increase. The film surface becomes uneven, and as a result, the effect of preventing the adhesion of organisms such as marine organisms is significantly reduced.
• the coating film formed from the hydrolyzable antifouling paint gradually dissolves and renews the surface of the coating (self-polishing), and the antifouling component is always exposed on the coating film surface. Long-term antifouling effect is demonstrated.
• Patent Document 1 a resin having at least one group containing zinc, copper, or tellurium atoms at the end of at least one side chain, and the resin is soluble.
• a hydrolyzable antifouling paint composition comprising a metal-containing resin composition comprising an organic solvent is disclosed.
• Patent Document 2 proposes a hydrolyzable antifouling paint composition containing a copolymer containing a polymerizable monomer unit containing a metal atom as a constituent and an antifouling agent.
• the antifouling paint using the metal atom-containing copolymer described in Patent Document 1 and Patent Document 2 has a decrease in antifouling property in a stationary state due to a decrease in hydrolyzability or generation of cracks. There is a problem that it is difficult to obtain an antifouling effect in a stationary state for a long time.
• the object of the present invention is to solve these problems, maintain an excellent antifouling performance even in a stationary state for a long period of time, and is useful for the preparation of an antifouling coating composition that does not cause coating film defects.
• An object of the present invention is to provide a metal-containing copolymer, and to provide a metal-containing polymerizable monomer as a raw material for the metal-containing copolymer.
• the first invention is a metal-containing polymerizable monomer (a1) represented by the following general formula (1).
• M represents a divalent metal
• R 8 and R 9 each independently represent H or CH 3
• R 1 and R 6 each independently represent a hydrocarbon having 2 or 3 carbon atoms.
• n is an integer from 1 to 20
• p is an integer from 0 to 20.
• the second invention is a metal-containing polymerizable monomer (a2) represented by the following general formula (2).
• M is a divalent metal
• R 8 and R 9 are each independently H or CH 3
• R 1 is a hydrocarbon having 2 or 3 carbon atoms
• R 4 and R 5 are carbonized. Indicates hydrogen.
• n is an integer from 1 to 20.
• the third invention is a metal-containing polymerizable monomer (a3) represented by the following general formula (3).
• M represents a divalent metal
• R 8 and R 9 each independently represent H or CH 3
• R 2 , R 3 , R 4 and R 5 represent hydrocarbons.
• m is 0 or 1.
• the fourth invention is a metal-containing polymerizable monomer (a4) represented by the following general formula (4).
• M represents a divalent metal
• R 8 represents H or CH 3
• R 1 represents a hydrocarbon having 2 or 3 carbon atoms
• R 7 represents an organic acid residue.
• n is an integer from 1 to 20.
• the fifth invention is a metal-containing polymerizable monomer (a5) represented by the following general formula (5).
• M represents a divalent metal
• R 8 represents H or CH 3
• R 2 and R 3 represent hydrocarbons
• R 7 represents an organic acid residue.
• the sixth invention is the process for producing a metal-containing polymerizable monomer according to any one of [1] to [5], wherein an inorganic metal compound and a carboxyl group-containing polymerizable monomer are reacted.
• the metal-containing copolymer obtained by using the metal-containing polymerizable monomer of the present invention has no coating film defects such as cracks, and is capable of maintaining excellent performance over a long period even in a stationary state. It is useful as a component of the composition for dirty paint.
• (meth) acryl means acryl or methacryl.
• Metal-containing polymerization monomer (a1) Specific examples of the metal-containing polymerizable monomer (a1) represented by the general formula (1) include the following. Di (3-acryloyloxypropionic acid) zinc, di (3-acryloyloxypropionic acid) copper, di (3-acryloyloxypropionic acid) magnesium, di (3-methacryloyloxy-2-methylpropionic acid) zinc, di (3 -Methacryloyloxy 2-methylpropionic acid) copper, di (3-methacryloyloxy-2-methylpropionic acid) magnesium, (meth) acrylic acid 3-acryloyloxypropionic acid zinc, (meth) acrylic acid 3-acryloyloxypropionic acid copper (Meth) acrylic acid 3-acryloyloxypropionate magnesium, (meth) acrylic acid 3-methacryloyloxy 2-methylpropionate zinc, (meth) acrylic acid 3-methacryloyloxy-2-methylpropionate copper, and (meth) )acrylic 3-methacryloyloxy
• Metal-containing polymerizable monomer (a2) Specific examples of the metal-containing polymerizable monomer (a2) represented by the general formula (2) include the following. 2- (meth) acryloyloxyethyl succinic acid, zinc 3-acryloyloxypropionate, 2- (meth) acryloyloxyethyl 3-succinic acid, copper acryloyloxypropionate, 2- (meth) acryloyloxyethyl 3-acryloyloxy succinate Magnesium propionate, succinic acid 2- (meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate zinc, succinic acid 2- (meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate copper, succinic acid 2- (Meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate magnesium, 2- (meth) acryloyloxyethyl 3-acryl
• metal-containing polymerizable monomer (a3) Specific examples of the metal-containing polymerizable monomer (a3) represented by the general formula (3) include the following. Di (succinic acid 2- (meth) acryloyloxyethyl) zinc, di (2- (meth) acryloyloxyethyl) succinic acid copper, di (2- (meth) acryloyloxyethyl) succinic acid magnesium, di (phthalic acid 2 -(Meth) acryloyloxyethyl) zinc, di (2- (meth) acryloyloxyethyl) phthalate, di (2- (meth) acryloyloxyethyl) magnesium phthalate, di (hexahydrophthalic acid 2- (meth) ) Acryloyloxyethyl) zinc, di (hexahydrophthalic acid 2- (meth) acryloyloxyethyl) copper, di (hexahydrophthalic acid 2- (meth)
• Metal-containing polymerizable monomer (a4) Specific examples of the metal-containing polymerizable monomer (a4) represented by the general formula (4) include the following. 3- (meth) acryloyloxypropionic acid (versaic acid) zinc, 3- (meth) acryloyloxypropionic acid (octylic acid) zinc, 3- (meth) acryloyloxypropionic acid (stearic acid) zinc, 3- (meth) Zinc acryloyloxypropionate (abithienoic acid), 3- (meth) acryloyloxypropionic acid (versaic acid) copper, 3- (meth) acryloyloxypropionic acid (octylic acid) copper, 3- (meth) acryloyloxypropionic acid ( Stearic acid) copper, 3- (meth) acryloyloxypropionic acid (abitienoic acid) copper, 3- (meth) acryloyloxypropionic acid (versaic acid) magnesium,
• Metal-containing polymerizable monomer (a5) Specific examples of the metal-containing polymerizable monomer (a5) represented by the general formula (5) include the following. 2- (meth) acryloyloxyethyl (versaic acid) zinc succinate, 2- (meth) acryloyloxyethyl (octylate) zinc succinate, 2- (meth) acryloyloxyethyl (stearic acid) zinc succinate, succinic acid 2- (meth) acryloyloxyethyl (abithienic acid) zinc, succinic acid 2- (meth) acryloyloxyethyl (versaic acid) copper, succinic acid 2- (meth) acryloyloxyethyl (octylic acid) copper, succinic acid 2- (Meth) acryloyloxyethyl (stearic acid) copper, succinic acid 2- (meth) acryloyloxyethyl (abithienic acid)
• Metal-containing polymerizable monomers (a1), (a2), (a3), (a4) and (a5) represented by the general formulas (1) to (5) (hereinafter referred to as “bivalent metal-containing polymerizable monomers”).
• the monomer (a) “may be collectively referred to as”) can be produced by the following method.
• the metal-containing polymerizable monomers (a1), (a2), and (a3) can be produced, for example, by a method of reacting an inorganic metal compound and a carboxyl group-containing polymerizable monomer.
• the metal-containing polymerizable monomers (a4) and (a5) include, for example, an inorganic metal compound, a carboxyl group-containing polymerizable monomer and a carboxyl group-containing non-polymerizable compound (hereinafter referred to as “carboxyl” It may be referred to as a “group-containing compound”).
• carboxyl group-containing polymerizable monomer means a compound having a polymerizable unsaturated double bond
• non-polymerizable compound means a compound having no polymerizable unsaturated double bond.
• the reaction temperature may be a temperature at which the carboxyl group-containing polymerizable monomer is not polymerized, and is preferably 120 ° C. or lower.
• a reaction method a method in which an inorganic metal compound and a carboxyl group-containing compound are reacted in an organic solvent containing an alcohol compound is preferable. By this method, the compatibility between the divalent metal-containing polymerizable monomer (a) of the present invention and the divalent metal-free polymerizable monomer (b) described later is improved, and the metal-containing copolymer is obtained. Polymerization for obtaining is facilitated.
• Examples of alcohol compounds contained in the organic solvent include ethanol, isopropanol, butanol, and propylene glycol monomethyl ether.
• inorganic metal compounds include metal oxides such as magnesium oxide, copper oxide, and zinc oxide; metal hydroxides such as magnesium hydroxide, copper hydroxide, and zinc hydroxide; metal chlorides such as magnesium chloride, copper chloride, and zinc chloride. Thing etc. are mentioned.
• the carboxyl group-containing polymerizable monomer includes a group of divalent metal-containing polymerizable monomers (a) represented by the general formulas (1), (2), (3), (4) and (5). What is necessary is just to select so that the 1 or more types of polymerizable monomer selected from may be produced
• 2-Carboxyethyl acrylate, 2-carboxypropyl methacrylate, and ⁇ -CEA are preferable from the viewpoint of good antifouling properties of the resulting coating film.
• Examples of the carboxyl group-containing non-polymerizable compound include the following. 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, Stearol acid, ricinoleic acid, ricinoelaidic acid, brassic acid, erucic acid, ⁇ -naphthoic acid, ⁇ -naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline Carboxylic acid, nitrobenzoic acid, nitronaphthalene carboxylic acid, purbinic acid, naphthenic acid, abietic acid,
• the ratio of the metal atom in the inorganic metal compound to the carboxyl group-containing polymerizable monomer is such that the metal atom is 0.3 mol or more and 2.5 mol or less with respect to 1 mol of the carboxyl group-containing polymerizable monomer. Preferably there is. If the metal atom is 0.3 mol or more, the amount of the metal and unreacted carboxyl groups is reduced, and the water resistance of the coating film tends to be good. If the metal atom is 2.5 mol or less, the amount of the polymerizable monomer in the raw material mixture for the reaction is increased, so that the amount of the metal-containing polymerizable monomer generated is increased. It becomes easy for the coating film to be continuously dissolved over a long period of time.
• the ratio of the metal atom in the inorganic metal compound to the carboxyl group-containing compound is preferably such that the metal atom is 0.6 mol or less with respect to 1 mol of the carboxyl group-containing compound.
• the metal atom is 0.6 mol or less, the carboxyl group and the unreacted metal atom are reduced, and the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b)
• the transparency of the mixture tends to be good.
• the metal-containing polymerizable monomers (a1) to (a5) since the antifouling property and crack resistance of the coating film over a long period of time are good, the metal-containing polymerizable monomers (a1), (a2) ) And (a4) are particularly preferred.
• the monomers other than the metal-containing polymerizable monomers (a1) to (a5) contained in the reaction product mixture include zinc (meth) acrylate, copper (meth) acrylate, and (meth) acrylic. Examples include magnesium acid.
• the content of the divalent metal-containing polymerizable monomer (a) in the total amount of the reaction product is preferably 5% by mass or more, particularly preferably 10% by mass or more.
• the obtained coating film has good hydrolyzability, and further has good crack resistance, and an excellent antifouling effect can be exhibited over a long period of time.
• the divalent metal-containing copolymer includes at least one monomer selected from the group consisting of metal-containing polymerizable monomers (a1) to (a5) containing a divalent metal of the present invention, and a divalent metal non-divalent metal. It can manufacture by polymerizing the containing polymerizable monomer (b).
• the divalent metal-free polymerizable monomer (b) is a polymerizable monomer that does not contain a divalent metal, and is particularly a monomer having a polymerizable unsaturated double bond. It is not limited, For example, the following are mentioned.
• Acid ester monomer water such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Group-containing (meth) acrylic acid ester monomers; hydroxyl-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene oxide, propylene oxide, Adducts with ⁇ -butyrolactone or ⁇ -caprolactone; carboxyl group-containing monomers such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, sorbic acid; carboxylic acids such as itaconic anhydride and maleic anhydride Anhydride group-containing monomers; dicarboxylic acid monoesters such as monoalkyl itaconate and monoalkyl maleate; hydroxyl group-containing (meth) acrylic such as 2-
• a polymerization method can be used as a method for polymerizing at least one of the metal-containing polymerizable monomers (a1) to (a5) containing a divalent metal and the divalent metal-free polymerizable monomer (b).
• the chain transfer agent is preferably a chain transfer agent other than mercaptan, and preferably styrene dimer.
• the solvent known organic solvents can be used, and examples thereof include the following. Xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, n-butanol and the like. The solvent may be used alone or in combination of two or more.
• the polymerization temperature is not particularly limited and is, for example, about 60 to 180 ° C.
• the polymerization time is not particularly limited and is, for example, about 2 to 14 hours.
• the ratio of the charged amounts of the divalent metal-containing monomer (a) and the divalent metal-free polymerizable monomer (b) as the polymerization raw material is not particularly limited, and is 5:95 to 70: It is about 30 (mass%).
• the divalent metal can be appropriately selected as necessary, but is selected from the group consisting of zinc, copper, magnesium and calcium from the viewpoint of solubility of the resulting divalent metal-containing copolymer in water. From the viewpoint of the water resistance of the coating film, zinc and copper are particularly preferable.
• the antifouling coating composition containing a divalent metal-containing copolymer obtained by using the divalent metal-containing polymerizable monomer (a) of the present invention as a constituent component contains a divalent metal-containing copolymer.
• This antifouling paint composition can further improve antifouling performance by blending an antifouling agent.
• the antifouling paint contains an antifouling agent or a pigment component together with the antifouling paint composition
• the proportion of the divalent metal-containing copolymer in the antifouling paint is usually 15% by mass (as a resin component Solid content conversion) or more is preferable.
• the blending amount is 15% by mass or more, the solubility of the divalent metal-containing copolymer in the antifouling paint is good, and the antifouling property and crack resistance of the coating film are good.
• the antifouling agent can be appropriately selected and used according to the required performance, and examples thereof include the following. Copper antifouling agents such as cuprous oxide, thiocyanic copper and copper powder; metal compounds such as lead, zinc and nickel; amine derivatives such as diphenylamine; nitrile compounds, benzothiazole compounds, maleimide compounds and pyridine compounds. These can be used alone or in combination.
• Antifouling paints may contain silicone compounds such as dimethylpolysiloxane and silicone oil, fluorine-containing compounds such as fluorocarbons, etc. for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms. it can. Furthermore, extender pigments, color pigments, plasticizers, various paint additives, other resins, and the like can be blended in the antifouling paint as necessary.
• Examples of the solvent for dilution used in the antifouling paint include organic solvents such as xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, and n-butanol.
• the organic solvent may be used alone or in combination of two or more.
• Examples of articles having antifouling paint coatings include ships, various fishing nets, powerhouse conduits, oil fences, bridges, buoys, and submarines.
• Formation of the coating film using the antifouling paint is performed, for example, by the following method (1) or (2).
• An antifouling paint is directly applied to the surface of a substrate such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base.
• a primer such as wash primer, chlorinated rubber, epoxy, etc. to the base material, an intermediate coating, etc., and apply a brush, spray, roller, or submerged coating on the resulting coating. Apply antifouling paint by any means.
• the amount applied is generally an amount that results in a dry coating thickness of 50 to 400 ⁇ m.
• the coating film is generally dried at room temperature, but may be dried by heating.
• a coating with a thickness of about 300 ⁇ m was formed on a sandblasted steel plate that had been coated with a rust-preventive paint in advance, and the resulting specimen was immersed in Hiroshima Bay for 12 months. After 6 months, And the adhesion area (%) of the attached organism after 12 months was examined. The determination was made according to the following criteria.
• C The adhesion area of the attached organism after 12 months is 40% or more and less than 80%.
• D The adhesion area of attached organisms after 12 months is 80% or more and 100% or less.
• a coating film having a thickness of about 300 ⁇ m is formed on a sandblasted steel plate to which a rust preventive paint has been applied in advance, and the obtained test piece is sterilized and filtered at 20 ° C. for 6 months and 12 months. After soaking, it was dried at 20 ° C. for 1 week. And the coating-film surface was observed. Evaluation was performed according to the following criteria. A: Cracks and peeling are not observed at all. B: Slight cracks are observed. C: Cracks and peeling are partially observed. D: Cracks and peeling are observed on the entire surface.
• Example 1 In a four-necked flask equipped with a condenser, thermometer, dropping funnel and stirrer, 142 parts of PGM (propylene glycol methyl ether) as an initial solvent and 41 parts of zinc oxide were charged, and the temperature of the liquid in the flask was stirred. The temperature was raised to 75 ° C. On the other hand, a mixture (reaction raw material) consisting of 144 parts of 2-carboxyethyl acrylate and 5 parts of water was placed in the dropping funnel. This mixture was dropped into the flask over 3 hours with a constant addition amount per unit time. Further, after stirring the liquid in the flask for 2 hours, 10 parts of PGM was added to obtain a transparent divalent metal-containing polymerizable monomer (a) mixture M1. The solid content of the mixture M1 was 51.4% by mass.
• PGM polypropylene glycol methyl ether
• Examples 2 to 16 and Comparative Examples 1 to 4 Contains divalent metal in the same manner as in Example 1 except that the amount of the initial solvent in the four-necked flask and the type and amount of the reaction raw material in the dropping funnel were changed to the conditions shown in Table 2 or Table 3. Mixtures M2 to M20 of sexual monomers were produced. The solid contents of the mixtures M2 to M20 are shown in Table 2 or Table 3.
• the obtained antifouling paint was applied onto a predetermined substrate so that the dry film thickness was about 300 ⁇ m, and dried at room temperature for 1 week.
• the obtained coating film was subjected to a wear degree test, an antifouling test, and a crack resistance test. The evaluation results are shown in Table 6.
• the obtained antifouling paint was applied onto a substrate in the same manner as in Reference Example 27 to obtain a coating film.
• the evaluation results are shown in Table 6.

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• 2012
  • 2012-06-01 KR KR1020137032792A patent/KR101668909B1/ko active IP Right Grant
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