JP3483524B2 - Metal-containing resin composition and antifouling paint composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal-containing resin composition, and more particularly to a metal-containing resin composition soluble in a general organic solvent. This metal-containing resin composition is not particularly limited in use, but preferably an underwater structure, a fishing net, an antifouling paint capable of forming a coating film that prevents the adhesion of marine organisms and seaweed to the bottom of the ship. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, as a metal-containing resin obtained by polymerizing a metal-containing monomer, there is a collapsible vinyl resin particle described in JP-A-63-56510. These are particles obtained by polymerizing a metal ester-type polyfunctional polymerizable monomer in a solvent that does not dissolve the produced polymer. It is obtained by adding a monomer, an acrylic polymerizable monomer and a polymerization initiator.

The metal-containing resin thus obtained is
It is insoluble in general organic solvents and slightly swells depending on the composition. Further, the metal ester-type polyfunctional polymerizable monomer itself is a powder, and it is difficult to mix it with a general acrylic monomer, and it has been difficult to copolymerize with an acrylic monomer in a general organic solvent.

Metal-containing resins are expected to be used in various applications, especially antifouling paints for the purpose of imparting hydrolyzability have been proposed, and metal-containing resins soluble in general organic solvents are desired. ing.

The antifouling paint is applied to the submerged portions of ships and marine structures for the purpose of preventing corrosion due to the adhesion of marine organisms such as barnacles, beetles, algae, and preventing the navigation speed of ships from decreasing. Further, the same net antifouling paint is applied to the nets for aquaculture for the purpose of preventing the death of fish and shellfish due to the adhesion of marine organisms.

A coating film formed from such an antifouling paint exhibits an antifouling effect by elution of rosin compounds and antifouling components contained therein into the sea.
However, when such a coating film is immersed in the sea for a long time, the elution amount gradually decreases and the non-elution amount increases, and the coating film surface becomes uneven at the same time. The effect of preventing adhesion of living organisms tends to be significantly reduced. Further, a coating film formed from a coating material containing organotin gradually dissolves and renews the surface of the coating film, and the antifouling component is always exposed on the coating film surface (self-polishing).
Although it has a long-term antifouling effect, it is feared that the strong toxicity of organotin may adversely affect fish and shellfish, and paints containing no organotin are being investigated.

For example, an antifouling paint using an organosilicon-containing copolymer having an organosilicon ester introduced into the side chain and an antifouling paint using a copolymer containing a metal other than tin have been proposed. Among them, those using a copolymer containing a metal other than tin have been attracting attention because of their high antifouling effect and relatively low cost.

Further, for example, Japanese Patent Laid-Open No. 63-1830 proposes a metal-containing resin. In producing this resin, a polymer or copolymer having a carboxyl group is ion-exchanged with a metal salt solution. , A metal-containing resin containing a metal salt is precipitated in an aqueous medium. Such a resin precipitates when it becomes insoluble in water by ion exchange, so that a carboxyl group which is not a metal salt remains in the side chain. When such a resin is used as an antifouling paint, there are problems that the water resistance of the coating film decreases, the paint gels when using cuprous oxide, and the long-term antifouling property decreases.

In Japanese Patent Laid-Open No. 63-56510, an average particle having a cross-linking point containing a metal ester bond, which is obtained by polymerizing a produced polymer in a solvent that does not dissolve, is 0.01-2.
50 μm collapsible vinyl resin particles have been proposed. This resin itself is insoluble in a general organic solvent, and since it is a particle by itself, it does not have a film forming ability and cannot be used as a vehicle for antifouling paint.

JP-A-62-57464 and JP-A-6-57464
JP-A 2-84168 proposes an antifouling coating composition using a resin having a metal salt of a specific monovalent organic acid at the end of the side chain. However, it contains an organic acid as the counterion of the metal salt, and when the metal decomposes in seawater,
Since the organic acid is released, the hydrolysis efficiency is poor, and there are problems in the hydrolysis stability of the antifouling coating film and the long-term antifouling property.

[0011]

Regarding the metal-containing resin, a polymer obtained by polymerizing a reaction product of an inorganic metal compound and a carboxyl group-containing radically polymerizable monomer is insoluble in a general organic solvent, In addition, there is a problem that it cannot be used as a vehicle for antifouling paint because it has no film forming ability. Various paints using a resin containing a metal as an antifouling paint have been proposed, but a method of introducing a metal salt into a high acid value resin as disclosed in JP-A-61-3830 and JP-A-8-209005 is not known. The paint containing cuprous oxide has poor storage stability and long-term stain resistance. In addition, JP-A-62
Antifouling coating films using a resin having a metal salt of a specific monovalent organic acid at the end of the side chain as disclosed in JP-A-57464 and JP-A-62-84168 have hydrolyzable stability. Poor, the long-term antifouling property was insufficient.

The object of the present invention is to obtain a polymer obtained by polymerizing a reaction product of an inorganic metal compound and a carboxyl group-containing radically polymerizable monomer, which is soluble in a general organic solvent. An antifouling paint using the above is to provide a self-polishing antifouling paint composition that maintains a long-term hydrolyzability and exhibits an excellent antifouling effect in the sea for a long time.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a reaction between a specific inorganic metal compound and a carboxyl group-containing radically polymerizable monomer
Obtained metal-containing polymerizable monomer having two unsaturated groups
-Containing resin composition obtained by polymerization using a metal-containing monomer mixture containing a body-containing reaction product, a specific organic solvent, and a specific amount of water as constituent components, and this metal-containing resin composition A coating film formed from an antifouling paint containing a vehicle component has been found to solve the above problems,
The present invention has been completed.

That is, the present invention includes a divalent inorganic metal.
Gold having two unsaturated groups obtained by the reaction of free inorganic metal compound and a carboxyl group-containing radical-polymerizable monomer
A metal-containing monomer mixture (A) consisting of a reaction product containing a genus-containing polymerizable monomer , an organic solvent containing at least an alcoholic solvent, and water, and having a water content of 0.01 to 30% by mass. A composition obtained by copolymerizing the above-mentioned reaction product with another radically polymerizable unsaturated monomer (B), wherein the copolymer obtained by the copolymerization is dissolved in the organic solvent. It is a metal-containing resin composition.

Further, the present invention is an antifouling coating composition characterized by using this metal-containing resin composition. The use of the metal-containing resin composition here typically means a case where it is contained as a vehicle of an antifouling paint.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the metal-containing monomer mixture (A) is used as a constituent component of the metal-containing resin composition, and by using this, it is soluble in a general organic solvent. A metal-containing polymer composition can be obtained. For example, when used as a vehicle for antifouling paint, it is a component that imparts high self-polishing property to the resulting coating film for a long period of time and exerts an excellent antifouling effect.

The method for producing the metal-containing monomer mixture (A) is as follows:
It is not particularly limited, for example, at the decomposition temperature of the metal salt or less, by heating and stirring an inorganic metal compound, a carboxyl group-containing radically polymerizable monomer, an organic solvent containing at least an alcohol compound, and water. can get.

In the metal-containing monomer mixture (A),
The inorganic metal compound is used as a constituent component of the organic solvent-soluble metal-containing monomer mixture and reacts with the carboxyl group-containing radically polymerizable monomer to form a metal salt. As the inorganic metal compound, for example,
Examples thereof include metal oxides, hydroxides and chlorides. However, it is not limited to these, and any one that reacts with a carboxyl group to form a metal salt can be used.

Examples of metal oxides include zinc oxide, aluminum oxide, calcium oxide, cupric oxide, magnesium oxide and manganese oxide, and examples of metal hydroxides include zinc hydroxide, aluminum hydroxide and calcium hydroxide. , Chlorides of metals such as cupric hydroxide and magnesium hydroxide, zinc chloride, aluminum chloride, calcium chloride,
Examples thereof include cupric chloride, magnesium chloride, manganese chloride and the like.

The metal of the inorganic metal compound is I in the periodic table.
b, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, V
It is selected from the group consisting of b, VIb, VIIb, and VIII metals, and if necessary, two or more kinds may be used in combination. When Cu is used, it is preferable to use Zn in combination for the purpose of improving the copolymerizability with the acrylic monomer. From the viewpoint of excellent transparency of the resin, Zn,
Mg, Ca and Al are preferred. Especially divalent Zn and Mg
Is preferable because it can suppress an increase in viscosity during resin production. When used as an antifouling paint, Z
When n or Mg is used, the transparency of the obtained metal-containing resin tends to be high and the color tone of the applied coating tends to be beautiful, and the solubility in commonly used organic solvents is high, resulting in workability. Tends to be good. In particular, when Zn is used, the water resistance of the resin becomes good, which is more preferable.

In the metal-containing monomer mixture (A),
Examples of the carboxyl group-containing radically polymerizable monomer include methacrylic acid, acrylic acid, itaconic acid, maleic acid (anhydrous), monoalkyl itaconate (eg, methyl, ethyl, butyl, 2-ethylhexyl, etc.), maleic acid. Monoalkyl (eg, methyl, ethyl, butyl, 2-ethylhexyl, etc.) and the like can be mentioned.
One kind or a combination of two or more kinds can be used.

In the metal-containing monomer mixture (A),
The organic solvent contains at least an alcohol compound. From the viewpoint of solubility of the metal salt compound, alcohol-based solvents such as ethanol, isopropanol, butanol, propylene glycol monomethyl ether are particularly preferable. When the alcohol-based solvent is not included, the solution loses fluidity and solidifies during the production of the metal-containing monomer mixture (A), and therefore, it cannot be mixed and polymerized with a general acrylic monomer.

As the organic solvent, if necessary, an aliphatic hydrocarbon solvent such as pentane, hexane or heptane,
Aromatic hydrocarbon solvents such as benzene, toluene, xylene, ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are mixed with alcohol solvents. be able to. When mixed and used, the alcohol solvent in the organic solvent is preferably 5% by mass or more. When the amount is 5% by mass or more, the solubility of the reaction product in the solvent is improved, no crystal substance is generated, and storage stability is exhibited. More preferably,
It is 25 mass% or more.

The content of the metal contained in the metal-containing monomer mixture (A) varies depending on the kind of the metal, but is 0.
1-60 mass% is preferable. When the content is 60% by mass or less, the compound becomes soluble in an organic solvent and can be mixed with an acrylic monomer and polymerized. Also, 0.1 mass%
By the above, workability in polymerizing the metal-containing resin composition is improved. More preferably 3 to 25% by mass
Is.

The ratio of the inorganic metal compound and the carboxyl group-containing radically polymerizable monomer in the metal-containing monomer mixture (A) is not particularly limited, but the ratio of the inorganic metal compound to 1 mole of the carboxyl group-containing polymerizable monomer is The compound ratio (the number of moles) is preferably 0.6 mol or less. When the amount is less than 0.6 mol, the transparency of the mixture is not particularly problematic, but when the amount is more than 0.6 mol, unreacted inorganic metal compound tends to remain in the mixture and the transparency of the monomer is deteriorated. Therefore, the varnish polymerized by using it becomes slightly cloudy.

When the resin composition of the present invention is used as a vehicle for antifouling paint, the metal-containing monomer mixture (A) is used.
The ratio of the inorganic metal compound and the carboxyl group-containing radically polymerizable monomer therein is optimally about 0.5 mol: 1 mol. When the ratio (mol number) of the inorganic metal compound to the carboxyl group-containing polymerizable monomer is large, there is no particular problem with the coating film performance. On the other hand, when the amount is small, the water resistance of the coating film is lowered and the storage stability of the coating is lowered when cuprous oxide is added.

The amount of water contained in the metal-containing monomer mixture (A) excludes water produced by the reaction of the inorganic metal compound and the carboxyl group-containing radically polymerizable monomer (in the present invention, "water"). "Quantity" means this)
And is in the range of 0.01 to 30% by mass. All of the water may be added during the reaction, or may be added again during the reaction and after the completion of the reaction.

If water is not added during the reaction, the solution tends to lose fluidity and solidify during or immediately after the reaction of the inorganic metal compound and the carboxyl group-containing radical-polymerizable monomer, and therefore the solution is mixed with an acrylic monomer. It becomes difficult to polymerize. Once solidified, a large amount of water and a solvent are required to dissolve it again, which is not preferable because the workability is lowered due to the separation from the acrylic monomer and the decrease in solid content. By adding water during the reaction, a reaction solution can be obtained in a state of being dissolved in an organic solvent without losing fluidity, and can be mixed and copolymerized with an acrylic monomer.

The amount of water added during the reaction is 0.0
By adding 1 mass% or more, a solution can be obtained in a solution state without losing fluidity during the reaction, and it becomes possible to polymerize by mixing with an acrylic monomer or a general organic solvent.
More preferably, it is 0.2 mass% or more.

By setting the amount of water in the metal-containing monomer mixture (A) to 30% by mass or less, the solubility with general acrylic monomers and organic solvents becomes good and copolymerization with various acrylic monomers is possible. preferable. More preferably, it is 15 mass% or less.

When the amount of the organic solvent used is increased for the purpose of reducing the content of water in the metal-containing monomer mixture (A), the solid content is lowered and the workability during polymerization is deteriorated, which is not preferable. In order to improve workability at the time of polymerization by making the metal-containing monomer into a high solid, it is preferable to contain water in an amount of 0.01 to 5 times the mole of the inorganic metal compound used. The solid content of the mixture (A) is 2
It is preferably in the range of 5 to 70%. Especially 0.0
It is preferable to contain water in the range of 5 to 3 times mol, and the solid content of the mixture (A) is preferably in the range of 45 to 60%.

When the metal-containing resin composition of the present invention is used as an antifouling paint, it is not particularly limited, but when the water content in the metal-containing monomer mixture (A) is in the range of 20% by mass or less, the The amount of water contained in
When it is made into a paint, it is possible to suppress an increase in viscosity and a decrease in hydrolyzability of the coating film. More preferably, 15 mass%
The range is as follows.

The metal-containing resin composition of the present invention has been described above.
Metal-containing monomer mixture (A)Inorganic metal compounds
Reaction product of carboxylic group-containing radically polymerizable monomer
And other radically polymerizable unsaturation that can be copolymerized with it
It is obtained by copolymerizing the monomer (B).

When the metal-containing resin composition of the present invention is used as an antifouling paint, the amount of the other radically polymerizable unsaturated monomer (B) used is 1 in total of the component (A) and the component (B).
It is preferably 16 to 97 parts by mass based on 00 parts by mass. By adjusting the amount to 16 parts by mass or more, the various properties of the obtained antifouling paint tend to be balanced, and by adjusting the amount to 97 parts by mass or less, good hydrolysis of the formed coating film for a long period of time can be achieved. Is given
The coating film tends to have a good balance with crack resistance and hydrolysis resistance. It is more preferably 40 to 90 parts by mass, and particularly preferably 60 to 85 parts by mass.

Examples of the radically polymerizable unsaturated monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate and phenoxy. Ethyl (meth) acrylate, 2- (2-ethylhexaoxy) ethyl (meth) acrylate, 1-methyl-2-methoxyethyl (meth) acrylate, 3-
Methoxybutyl (meth) acrylate, 3-methyl-3
-Methoxybutyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate, o-methoxyphenylethyl (meth) acrylate, m-methoxyphenylethyl (meth) acrylate, p-methoxyphenyl 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, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, gly (Meth) acrylic acid ester monomers such as di (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth ) Hydroxyl group-containing monomers such as acrylate and 4-hydroxybutyl (meth) acrylate; 2-hydroxyethyl (meth)
Addition product of acrylate with ethylene oxide, propylene oxide, γ-butyrolactone or ε-caprolactone; dimer or trimer of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; glycerol ( Monomers having a plurality of hydroxyl groups such as (meth) acrylate; butylaminoethyl (meth) acrylate, vinyl monomers containing primary and secondary amino groups such as (meth) acrylamide; dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth)
Acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide,
Tertiary amino group-containing vinyl monomers such as dimethylaminopropyl (meth) acrylamide; heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole; styrene, vinyltoluene, α-methylstyrene And vinyl monomers such as (meth) acrylonitrile, vinyl acetate and vinyl propionate. In the present invention, “(meth) acrylic” means
Means "acrylic and / or methacrylic".

When the metal-containing resin composition of the present invention is used as an antifouling paint, the metal content in the resin is 0.5 to 25.
It is preferably in the range of mass%. When the amount is 0.5% by mass or more, the self-polishing property of the coating film formed tends to be exhibited, and when the amount is 25% by mass or less, the effect of improving the balance between crack resistance and hydrolysis resistance. Becomes remarkable, the self-polishing property is maintained for a long time, and the antifouling effect tends to be improved. More preferably, it is 1 to 10 mass%.

When the metal-containing resin composition of the present invention is used as an antifouling paint, the weight average molecular weight of the resin is 1,000 to
20000 is preferable. When the amount of metal exhibiting hydrolyzability is incorporated into the resin, the viscosity of the resin solution can be lowered by setting the molecular weight to 20000 or less, the metal cross-linking between the polymers can be reduced, and the gelation of the resin can be suppressed. By the above, there is a tendency that crack resistance can be exhibited. More preferably 300
It is 0 to 10000.

The method for producing the copolymer used as the vehicle component of the present invention is not particularly limited,
For example, the above-mentioned monomers are mixed, and this mixture is added in the presence of a radical initiator at a reaction temperature of 60 to 180 ° C. for 5 to 1
It can be produced by reacting for 4 hours.
Further, in the case of increasing the metal content in the copolymer, a chain transfer agent can be used for high solidification and improvement of productivity, particularly for suppressing the formation of cullet during polymerization. From the viewpoint of compatibility with the metal-containing polymerizable monomer, chain transfer agents other than mercaptan are preferable, and styrene dimer and the like are preferable. As the polymerization method, in addition to the solution polymerization method performed in an organic solvent, an emulsion polymerization method, a suspension polymerization method or the like can be adopted, but toluene, xylene, methyl isobutyl ketone, acetic acid n-
Adopting a solution polymerization method using a general organic solvent such as butyl is advantageous in terms of productivity and coating performance.

The proportion of the copolymer as a vehicle in the antifouling coating composition is not particularly limited, but it is usually used in the range of 20 to 25% by mass (solid content) as a resin component in the antifouling coating composition. Is preferred. This is because by appropriately containing the resin component, the coating film performance such as crack resistance becomes good, and by not containing it excessively,
This is because it tends to be easy to incorporate an antifouling agent in an amount sufficient to maintain a good antifouling ability into the antifouling coating composition.

The antifouling coating composition of the present invention can retain the antifouling property in the coating film formed by containing the above metal-containing copolymer as a vehicle component. By adding a soiling agent, the antifouling performance can be further improved.

The antifouling agent can be appropriately selected and used according to the required performance. For example, cuprous oxide, copper thiocyanate, including copper-based antifouling agents such as copper powder, lead, zinc, nickel and other metal compounds, amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds, maleimide compounds, Examples include pyridine compounds. These can be used alone or in combination. In particular, those selected by the Japan Shipbuilding Industry Association and the like as targets for research and study are preferable.
For example, Manganese ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N , N-Dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate, copper rhodan, 4,5-dichloro-2-n octyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N'- Dimethyl-N'-phenyl-
(N-fluorodichloromethylthio) sulfamide, 2
-Pyridine thiol-1-oxide zinc salt, tetramethyl thiuram disulfide, Cu-10% Ni solid solution alloy, 2,4,6-trichlorophenylmaleimide 2,3,3
5,6-Tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatrisulfone, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, phenyl (bispyridyl) bismuth Mention may be made of dichloride, 2- (4-thiazolyl) -benzimidazole, pyridine-triphenylborane.

In addition to the antifouling coating composition of the present invention,
Silicone compounds such as dimethylpolysiloxane and silicone oil, and fluorine-containing compounds such as fluorocarbon can be added for the purpose of imparting lubricity to the surface of the coating film and preventing the adhesion of organisms. Further, extender pigments, coloring pigments, plasticizers, additives for various paints, other resins and the like can be blended as necessary.

In order to form a coating film using the antifouling coating composition of the present invention, the antifouling coating composition as described above is applied to ships, various fishing nets, port facilities, oil fences, bridges, submarine bases, etc. Brush directly on the surface of the base material such as underwater structure, or on the coating film with wash primer, chlorinated rubber type, epoxy type primer, intermediate coating etc. applied to the base material,
It is applied by means such as spray coating, roller coating, and dip coating. The coating amount is generally 50 to 40 as a dry coating film.
The amount is such that the thickness is 0 μm. The coating film is generally dried at room temperature, but it may be dried by heating.

[0044]

EXAMPLES 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 addition, the part in an example represents a mass part.

[Production Example M1] PGM (propylene glycol methyl ether) 85.4 parts and zinc oxide 40.7 parts were charged into a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, and stirred. The temperature was raised to 75 ° C. Then, from the dropping funnel, methacrylic acid 43.1
Part, 36.1 parts of acrylic acid, and 5 parts of water were added to 3 parts of the mixture.
It was added dropwise at a constant rate over time. After completion of the dropping, the reaction solution became transparent from a milky white state. After stirring for another 2 hours, add 3 parts of PGM.
6 parts were added to obtain a transparent metal-containing monomer mixture M1. The solid content was 44.8%.

[Production Example M2] nBuOH was placed in a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer.
(N-Butanol) 24.3 parts, xylene 61.1 parts and zinc oxide 40.7 parts were charged, and the mixture was stirred at 75 ° C.
The temperature was raised to. Then, methacrylic acid 4 from the dropping funnel
A mixture of 3.1 parts, 36.1 parts of acrylic acid, and 5 parts of water was added dropwise at a constant rate over 3 hours. After completion of the dropping, the reaction solution became transparent from a milky white state. After stirring for another 2 hours, 36 parts of xylene was added to obtain a transparent metal-containing monomer mixture M.
Got 2. The solid content was 44.9%.

[Production Example M3] PGM (propylene glycol methyl ether) 85.4 parts and zinc oxide 46.8 parts were charged into a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, and stirred. The temperature was raised to 75 ° C. Then, methacrylic acid 46.1 from the dropping funnel
Part, 36.1 parts of acrylic acid, and 5 parts of water were added to 3 parts of the mixture.
It was added dropwise at a constant rate over time. After completion of the dropping, the reaction solution became translucent from a milky white state. After further stirring for 4 hours, 43.5 parts of PGM was added to obtain a slightly turbid metal-containing monomer mixture M3. The solid content was 44.9%.

[Production Example M4] 70 parts of PGM (propylene glycol methyl ether) and 15.4 water in a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer.
Parts and 40.7 parts of zinc oxide were charged, and the mixture was stirred for 7
The temperature was raised to 5 ° C. Subsequently, a mixture of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 20.6 parts of water was added dropwise from the dropping funnel at a constant rate over 3 hours. After completion of the dropping, the reaction solution became transparent from a milky white state. After further stirring for 2 hours, 20.4 parts of PGM was added to obtain a transparent metal-containing monomer mixture M4. The solid content was 44.2%.

[Production Example M5] PGM (propylene glycol methyl ether) 85.4 parts and acid value magnesium 20.2 parts were charged into a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, and stirred. While 75
The temperature was raised to ° C. Then, methacrylic acid 4 from the dropping funnel
A mixture of 3.1 parts, 36.1 parts of acrylic acid, and 5 parts of water was added dropwise at a constant rate over 3 hours. After completion of the dropping, the reaction solution became transparent from a milky white state. After stirring for another 2 hours, PG
A transparent metal-containing monomer mixture M5 by adding 11 parts of M
Got The solid content was 44.6%.

[Production Example M6] PGM (propylene glycol methyl ether) 85.4 parts, acid value zinc 40.5 parts, cupric oxide were placed in a four-necked flask equipped with a condenser, thermometer, dropping funnel and stirrer. 0.2 part was charged and the temperature was raised to 75 ° C. with stirring. Subsequently, a mixture of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 5 parts of water was added dropwise at a constant rate from a dropping funnel over 3 hours. After the dropping was completed, the reaction solution became green. After stirring for another 2 hours, PGM
Was added to obtain a transparent metal-containing monomer mixture M6. The solid content was 44.9%.

Example 1 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Then, from the dropping funnel, 1 part of methyl methacrylate and 66.2 of ethyl acrylate.
Parts, 5.4 parts of 2-methoxyethyl acrylate, 52 parts of the metal-containing monomer mixture described in Preparation Example M1, xylene 1
0 parts, chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION) 1
Part, AIBN 2.5 parts, AMBN 7 parts was added dropwise at a constant rate in 6 hours. T after dropping
-Butyl peroctoate 0.5 parts and xylene 7 parts 3 parts
It was added dropwise at 0 minutes, and after stirring for 1 hour and 30 minutes, 4.4 parts of xylene was added to give a heating residue of 45.6% and a light yellow transparent metal-containing resin having an insoluble matter and having a Gardner viscosity -Y. A composition P1 was obtained.

Example 2 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 60 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Then, from the dropping funnel, 10 parts of methyl methacrylate and 62.
6 parts, 5.4 parts of 2-methoxyethyl acrylate, 40 parts of the metal-containing monomer mixture described in Production Example M1, 10 parts of xylene, chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION) 1
Part, AIBN 2.5 parts, AMBN 5.5 parts was added dropwise at a constant rate in 6 hours. After the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes, and after stirring for 1 hour and 30 minutes, 8 parts of xylene was added, and the heating residue was 46.1% and Gardner viscosity. A light yellow transparent metal-containing resin composition P2 having no insoluble matter having + V was obtained.

Example 3 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Then, 14.6 parts of methyl methacrylate and 5 parts of ethyl acrylate from the dropping funnel.
2.6 parts, n-butyl acrylate 7.5 parts, Production Example M
47.4 parts of the metal-containing monomer mixture described in 1 above, 10 parts of xylene, a chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION) 1
Part, AIBN 2.5 parts, AMBN 8.5 parts was added dropwise at a constant rate in 6 hours. After the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes, and after stirring for 1 hour and 30 minutes, 6.9 parts of xylene was added, and the heating residue was 45.8%. A light yellow transparent metal-containing resin composition P3 having a Gardner viscosity of -Z2 and having no insoluble matter was obtained.

Example 4 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 61 parts of xylene and 4 parts of ethyl acrylate and stirred. The temperature was raised to 100 ° C. Then, from the dropping funnel, 18 parts of methyl methacrylate and 61 parts of ethyl acrylate.
Part, 37.8 metal-containing monomer mixture described in Preparation Example M1.
Parts, 10 parts of xylene, 1 part of a chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION), 2.5 parts of AIBN, and 7 parts of AMBN were added at a constant rate over 6 hours. After the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes, and after stirring for 1 hour and 30 minutes, 8.2 parts of xylene was added, and the heating residue was 46.0.
%, And a light yellow transparent metal-containing resin composition P4 having a Gardner viscosity of + T and no insoluble matter was obtained.

Example 5 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate and stirred. The temperature was raised to 100 ° C. Subsequently, 5 parts of methyl methacrylate and 64.9 of ethyl acrylate were added from the dropping funnel.
Parts, 5.4 parts of 2-methoxyethyl acrylate, 40 parts of the metal-containing monomer mixture described in Preparation Example M1, Preparation Example M5
6 parts of the metal-containing monomer mixture described, 10 parts of xylene,
Chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION) 1 part, AI
A transparent mixture consisting of 2.5 parts of BN and 6 parts of AMBN was added dropwise at a constant rate in 6 hours. After the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then xylene was added at 7.7.
Part, and heating residue 46.2%, Gardner viscosity + U
A light yellow transparent metal-containing resin composition P5 having no insoluble matter was obtained.

Example 6 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate and stirred. The temperature was raised to 100 ° C. Then, from the dropping funnel, 1 part of methyl methacrylate and 66.2 of ethyl acrylate.
Parts, 5.4 parts of 2-methoxyethyl acrylate, 52 parts of the metal-containing monomer mixture described in Production Example M6, xylene 1
0 parts, chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION) 1
Part, AIBN 2.5 parts, and AMBN 7 parts were added dropwise at a constant rate in 6 hours. T after dropping
-Butyl peroctoate 0.5 parts and xylene 7 parts 3 parts
The mixture was added dropwise at 0 minutes, and after stirring for 1 hour and 30 minutes, 4.4 parts of xylene was added to give a heating residue of 45.2% and a green metal-containing resin composition P6 having a Gardner viscosity of + V and no insoluble matter. Got

Example 7 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether) and 61 parts of xylene and heated to 100 ° C. with stirring. did. Then, from the dropping funnel, methylmethacrylate 49.55
Parts, 50 parts of ethyl acrylate, 1 part of the metal-containing monomer mixture described in Production Example M1, 2.5 parts of AIBN, AMBN
A transparent mixture consisting of 2 parts was added dropwise at a constant rate in 4 hours. After completion of dropping, t-butyl peroctoate 0.5
Parts and 7 parts of xylene were added dropwise in 30 minutes, and further 1 hour and 30 minutes
After stirring for 3 minutes, 38.45 parts of xylene was added to obtain a transparent metal-containing resin composition P7 having a heating residue of 44.7% and a Gardner viscosity + B and having no insoluble matter.

Example 8 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 61 parts of xylene and 4 parts of ethyl acrylate, and stirred. The temperature was raised to 100 ° C. Then, from the dropping funnel, 18 parts of methyl methacrylate and 61 parts of ethyl acrylate.
Part, 37.8 metal-containing monomer mixture described in Preparation Example M2.
Parts, 10 parts of xylene, 1 part of a chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION), 2.5 parts of AIBN, and 7 parts of AMBN were added at a constant rate over 6 hours. After the dropwise addition, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes, and after stirring for 1 hour and 30 minutes, 8.2 parts of xylene was added, and the heating residue was 46.2.
%, A light yellow transparent metal-containing resin composition P8 having a Gardner viscosity + Y and no insoluble matter was obtained.

Example 9 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 57 parts of xylene and 4 parts of ethyl acrylate and stirred. The temperature was raised to 100 ° C. Subsequently, 1 part of methyl methacrylate and 64.9 of ethyl acrylate were added from the dropping funnel.
Parts, 5.4 parts of 2-methoxyethyl acrylate, 55 parts of the metal-containing monomer mixture described in Preparation Example M3, xylene 1
0 parts, chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION) 1
Part, AIBN 2.5 parts, AMBN 7.5 parts was added dropwise at a constant rate in 6 hours. After the dropping was completed, 0.5 part of t-butyl peroctoate and 7 parts of xylene were added dropwise over 30 minutes, 3.1 parts of xylene was added after stirring for 1 hour and 30 minutes, and the heating residue was 46.3%. A slightly cloudy pale yellow metal-containing resin composition P9 having a Gardner viscosity + W was obtained.

Example 10 A four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged with 46.8 parts of PGM (propylene glycol methyl ether), 25.2 parts of xylene and 4 parts of ethyl acrylate. The temperature was raised to 90 ° C. with stirring. Then, from the dropping funnel, 1 part of methyl methacrylate, 66.2 parts of ethyl acrylate and 5.4 parts of 2-methoxyethyl acrylate.
Parts, 52 parts of the metal-containing monomer mixture described in Preparation Example M4,
PGM 10 parts, chain transfer agent (NOFMER MS manufactured by NOF CORPORATION)
D) A transparent mixture consisting of 1 part, 2.5 parts of AIBN and 8 parts of AMBN was added dropwise at a constant rate in 6 hours. After the dropping was completed, 0.5 part of t-butyl peroctoate and xylene 7 were added.
Part was added dropwise in 30 minutes, the temperature was raised to 100 ° C., the mixture was stirred for 1 hour, and 4.4 parts of xylene was added, and the heating residue was 4
A slightly cloudy pale yellow metal-containing resin composition P10 having a Gardner viscosity + V of 5.9% was obtained.

[Production Example C1] PGM (propylene glycol methyl ether) (15 parts), xylene (61 parts) and ethyl acrylate (4 parts) were placed in a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, and stirred. The temperature was raised to 100 ° C. Then, from the dropping funnel, 18 parts of methyl methacrylate and 61 parts of ethyl acrylate.
Parts, powder zinc diacrylate salt (manufactured by Asada Chemical Co., Ltd.) 7.75 parts, powder zinc dimethacrylate salt (manufactured by Asada Chemical Co., Ltd.) 9.25 parts, PGM 18.79 parts, water 2.2 parts , Xylene 10 parts, chain transfer agent (NOFMER MSD manufactured by NOF CORPORATION), AIBN 2.5 parts, AMBN6
The solution which became opaque because the di (meth) acrylate salt of zinc consisting of 1 part was not added was added dropwise at a constant rate in 6 hours. After the dropping was completed, 0.5 part of t-butyl peroctoate and 7 parts of xylene were dropped in 30 minutes, and further 2
After stirring for an hour, 7.46 parts of xylene was added to obtain a white solution C1 in which an insoluble matter having a heating residue of 44.2% and a Gardner viscosity A or less was mixed.

[Production Example C2] Xylene was added to a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer.
Charge 0 parts and 30 parts of n-butanol and stir 1
The temperature was raised to 10 ° C. Then, from the dropping funnel, 60 parts of ethyl acrylate, 25 parts of 2-ethylhexyl acrylate,
A mixture of 15 parts of acrylic acid and 2 parts of azobisisobutyronitrile was added dropwise at a constant rate over 3 hours. 2 after completion of dropping
Stir for hours, heating residue 39.7%, Gardner viscosity +
A varnish having a characteristic value of J was obtained.

Next, the obtained varnish 10 was placed in a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer.
Add 0 parts, 20 parts naphthenic acid, 7 parts copper hydroxide,
The temperature was raised to ℃ and the mixture was stirred for 2 hours, and the water (2.6
After dehydration of g), heating residue 51.9%, Gardner viscosity +
A metal-containing resin C2 having a characteristic value of H was obtained.

Table 1 shows the charged amount (molar ratio) of the metal-containing monomer mixture of Production Examples M1 to M6, the amount of solvent in the metal-containing monomer mixture and the water content (mass%), and the solid content of the metal-containing monomer mixture. Described.

In Table 2, the charged amount (mass ratio) of the metal-containing resin composition of Examples P1 to P10, the viscosity (Gardner) of the obtained resin composition, the solid content (%) and the molecular weight (MW) of the resin are shown. Described.

[0066]

[Table 1]

[0067]

[Table 2]

As for the molecular weight, the molecular weight of the metal-containing resin measured by HLC-8120GPC is calculated by TSK-gel α type (α
-M) DM with 2 additions of 20 mM LiBr
Measured with F eluent. The weight average molecular weight was calculated in terms of polystyrene.

Then, using the copolymer solutions P1 to P6 and P8 to P10 thus obtained, the antifouling coating composition of the present invention (Examples 11 to 19) was prepared according to the compounding ratio shown in Table 3.
Was prepared. Further, using the copolymer solutions C1 and C2,
The antifouling paints of Comparative Examples 1 and 2 were prepared with the compounding ratios shown in Table 3.

[0070]

[Table 3]

Then, using each of the antifouling paints prepared as described above, a storage stability test, a coating film consumption test, and
An antifouling test and a crack / peeling resistance test were performed.

(1) Storage stability test Table 4 shows the measurement results of the paint viscosity of each antifouling paint immediately after preparation and after storage in a constant temperature water tank at 40 ° C. for 1 month.

[0073]

[Table 4]

(2) Test of degree of wear of coating film Each antifouling paint was applied to each of 50 × 50 × 2 mm (thickness).
Was coated on a hard vinyl chloride plate of No. 2 with an applicator so as to have a dry film thickness of 240 μm, mounted on a rotary drum installed in seawater, and rotated at a peripheral speed of 15 knots to measure the consumed film thickness every 3 months. The results are shown in Table 5.

[0075]

[Table 5]

(3) Antifouling test Each antifouling paint was applied to a sandblasted steel plate to which a rust preventive paint had been applied in advance so that the dry film thickness was 240 μm to prepare a test plate. It was left to stand still for 36 months in Hiroshima Bay, and the adhered area (%) of the adherent substance was examined every 6 months. The results are shown in Table 6.

[0077]

[Table 6]

(4) Crack / Peelability Test Example 1 was performed on each of the following substrates (1) and (2).
1 to 19 and the antifouling coating compositions of Comparative Examples 1 and 2 were applied so that the dry film thickness would be 240 μm to prepare a test plate. The test plate was coated with the same antifouling paint applied when the substrate (2) was prepared. Base (1): A base made of sandblasted steel plate to which anti-rust paint has been applied beforehand. Substrate (2): A film having a film thickness of 240 μm formed by the antifouling coating composition of Examples 11 to 19 and Comparative Examples 1 and 2 was formed on the substrate (1), respectively, and 3 times in sterile filtered seawater. A substrate obtained by soaking for one month and then drying at room temperature for one week.

The above test plate was immersed in sterilized filtered sea water for 24 months, and the test plate taken out from the sea water every 6 months was dried at room temperature of 20 ° C. for 1 week to crack and peel the coating film. I observed the situation. A sample having no cracks and peeling was indicated by ◯, a sample having slight cracks was indicated by Δ, and a sample having cracks on the entire surface or peeling was indicated by x. The results are shown in Table 7.

[0080]

[Table 7]

The antifouling coating compositions (Comparative Examples 1 and 2) exhibited self-polishing properties and antifouling properties at the initial stage.
It was not seen over a long period of time, and the antifouling property was poor. Further, in Comparative Example 2 in which the metal salt was added to the high acid value polymer, the viscosity of the coating was increased and the storage stability was insufficient, and in Comparative Example 1 in which the metal salt powder was polymerized,
The resistance to cracking and separation was poor, and the recoatability was poor.

On the other hand, copolymers P1 to P6 and P8 to P10
The antifouling coating composition of the present invention (Examples 11 to 1)
No. 9) showed long-term self-polishing property and excellent antifouling performance, and further had excellent crack resistance and peeling resistance, and had good recoatability.

[0083]

As described above, according to the present invention,
It is possible to provide a metal-containing resin composition in which a polymer obtained by polymerizing a reaction product of an inorganic metal compound and a carboxyl group-containing radically polymerizable monomer is soluble in a general organic solvent. Antifouling paints using the polymer obtained here, when used as a vehicle for antifouling paints, can be dissolved in the sea evenly at an appropriate rate and maintain self-polishing properties for a long period of time. In addition to exhibiting an excellent antifouling effect that can be done, it has features that are excellent in crack resistance and peelability,
It is very useful industrially.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09D 7/12 C09D 7/12 143/00 143/00 157/10 157/10 (72) Inventor Kazuhiko Hotta Higashi Ward, Nagoya City, Aichi Prefecture Sunadabashi 4th Town No. 1-60 Mitsubishi Rayon Co., Ltd. Product Development Laboratory (72) Inventor Toshio Nagasaka 1st 60 Sunadabashi 4th Town Mitsubishi Rayon Co., Ltd. (72) Invention Kunio Iwase 1-60, 4th-cho, Sunadabashi, Higashi-ku, Nagoya, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Research Laboratory (56) Reference JP-A-9-286933 (JP, A) JP-A-63-56510 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 220/10-220/40 C08F 230/04 C08L 33/04-33/16 C08L 43/00 C08L 57/10 C09D 5/16 C09D 133/04-133/16 C09D 143/00 C09D 157/10

Claims (6)

(57) [Claims] 1. A reaction between an inorganic metal compound containing a divalent inorganic metal and a carboxyl group-containing radically polymerizable monomer.
Obtained metal-containing polymerizable monomer having two unsaturated groups
And reactions containing an organic solvent containing at least an alcohol-based solvent, and water, wherein 0.01 is the content of water
A composition obtained by copolymerizing the reaction product in the metal-containing monomer mixture (A), which is 30% by mass, with another radically polymerizable unsaturated monomer (B), and by the copolymerization A metal-containing resin composition in which a copolymer is dissolved in the organic solvent. 2. The metal-containing resin composition according to claim 1, wherein the metal-containing monomer mixture (A) contains water in an amount of 0.01 to 5 times the mole of the inorganic metal compound used . 3. The metal-containing resin composition according to claim 1, wherein the organic solvent in the metal-containing monomer mixture (A) contains an alcohol solvent in an amount of 5 to 100% by mass. 4. The metal-containing monomer mixture (A) comprises
Metal oxides made of lead, copper or magnesium, water
Oxide or chlorideWhen((Meth) acrylic acidReactant
And an organic solvent containing at least an alcohol solvent, and water
And gold consisting of zinc, copper or magnesium
Genus oxides, hydroxides or chloridesuseTo the number of moles
And containing 0.05 to 3 times the molar amount of water.
The metal-containing resin composition according to any one of claims. 5. An antifouling coating composition using the metal-containing resin composition according to any one of claims 1 to 4. 6. The weight average molecular weight of the resin component is from 1000 to 1,000.
The antifouling coating composition according to claim 5, which is in the range of 20,000.