JPH1088038A - Antifouling coating composition comprising trialkyl germyl ester copolymer and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent, antifouling coating compsn. which does not contain tin and possesses excellent transparency, water resistance, cracking resistance, peeling resistance and other properties and, at the same time, antifouling property and self-grindability (consumability), and to provide a transparent antifouling coating using the transparent antifouling coating composition and a method for preventing a submerged, transparent structure from being fouled. SOLUTION: This transparent antifouling coating compsn. comprises a trialkyl germyl (meth)acrylate copolymer. In this case, the trialkyl germyl (meth)acrylate copolymer comprises 15 to 45mol% constituent units, represented by the formula, derived from a trialkyl germyl (meth)acrylate. In the formula, R<1> to R<3> , which may be the same or different, represent a 3C or higher alkyl group; and R<4> represents a hydrogen atom or a methyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling paint containing a trialkylgermyl copolymer and its use. The present invention relates to a soil paint composition, a coating film formed from the antifouling paint composition, an antifouling method using the antifouling paint composition, and a hull or an underwater structure covered with the coating film.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Underwater structures, ship bottoms, fishing nets, etc.
By being exposed to water for a long period of time,
Animals such as barnacles, algae such as laver (seaweed), and various aquatic organisms such as bacteria may adhere and propagate, and their appearance may be impaired and their functions may be impaired.

Conventionally, to prevent such contamination,
The above structure is coated with an antifouling paint containing, for example, a copolymer (tin polymer) of tributyltin methacrylate and methyl methacrylate and the like and cuprous oxide (Cu ₂ O). Was.

The copolymer in this antifouling coating film is hydrolyzed in sea water to form bistributyltin oxide (tributyltin ether, Bu ₃ Sn—O—SnBu ₃ : Bu is a butyl group) or tributyltin halogen. (Bu ₃ Sn)
X: X is a halogen atom) and releases an organic tin compound to exert an antifouling effect, and the hydrolyzed copolymer itself becomes water-soluble and dissolves in seawater. Since it is a "sweeping paint", the surface of the coating film can always maintain an active surface without leaving any resin residue.

However, such organotin compounds are highly toxic, and are susceptible to marine pollution, generation of malformed fish, adverse effects on ecosystems due to the food chain, and the like. There is a need for the development of antifouling coating compositions using coalescence.

When an antifouling paint is applied to a structure requiring transparency, such as an underwater window of an underwater observatory or an underwater sensor of a submarine, copper oxide (Cu) is contained in the antifouling paint composition.
_{If an} antifouling agent such as ₂ O) is contained, the coating film becomes colored or the coating itself becomes opaque. Therefore, a transparent antifouling paint that can exhibit antifouling properties without containing an antifouling agent. There is also a need for the development of compositions. As such a transparent antifouling coating composition, tin polymer is a promising compound because the polymer itself has antifouling properties, but as described above, its use is not preferred in view of environmental problems.

As such an antifouling coating film containing no tin, for example, Japanese Patent Publication No. 7-64985 discloses zinc,
Metal-containing resin compositions comprising copper or tellurium atoms are disclosed. However, the antifouling property of the composition itself is insufficient, and the composition is colored depending on the type of metal, which is not preferable for applications requiring colorless transparency.

Japanese Patent Application Laid-Open No. 7-102193 discloses that
There is disclosed an antifouling paint composition containing a copolymer comprising an unsaturated monomer having a triorganosilyl group and an antifouling agent as essential components. However, such an antifouling coating composition containing silicon atoms contains an antifouling agent, so that the coating film is opaque or colored, so that antifouling coating compositions requiring transparency are required. It cannot be used for membranes. In addition, the copolymer comprising an unsaturated monomer having a triorganosilyl group has a disadvantage in that it has low physiological activity per se and is significantly inferior in antifouling properties as compared with a tin-containing coating film.

JP-A-3-278059 discloses polymers and copolymers of triethylgermyl (meth) acrylate. However, antifouling coating films using such polymers and copolymers are inferior in water resistance and hydrolysis resistance. There were problems such as collapse and disappearance in a short period of time.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. The object of the present invention is to contain no tin, and to improve transparency, water resistance, crack resistance, peel resistance and the like. Transparent antifouling paint composition excellent in physical properties, antifouling property and self-cleaning property (consumable), and antifouling of transparent antifouling coating film and submerged transparent structure using this transparent antifouling paint composition It is intended to provide a way.

Further, the present invention provides an antifouling paint composition which is excellent in antifouling properties, self-cleaning properties (consumable properties), and is capable of forming an antifouling coating film having excellent properties such as crack resistance and peeling resistance. A coating film formed from such an antifouling coating composition, an antifouling method using such an antifouling coating composition, and an object of providing a hull or an underwater structure coated with the coating film. I have.

[0012]

SUMMARY OF THE INVENTION The transparent antifouling coating composition according to the present invention is characterized by comprising a trialkylgermyl (meth) acrylate copolymer.

The above trialkylgermyl (meth) acrylate copolymer is characterized by containing a structural unit derived from a trialkylgermyl (meth) acrylate represented by the following general formula (I). .

[0014]

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(Wherein R ^{1 to} R ³ may be the same or different and each represents an alkyl group having 3 or more carbon atoms;
⁴ represents a hydrogen atom or a methyl group. The component unit derived from the trialkylgermyl (meth) acrylate in the copolymer is preferably 15 to 45 mol%.

The transparent antifouling coating film according to the present invention is formed from the above transparent antifouling coating composition. The method for antifouling a submerged transparent structure according to the present invention is characterized in that the transparent antifouling coating composition is applied to the surface of the submerged transparent structure to form a transparent antifouling coating film.

In this antifouling method, the submerged transparent structure is preferably an underwater window, an aquarium, or an underwater light cover. The antifouling method for an underwater sensor, underwater marking or marine propeller according to the present invention is characterized in that the transparent antifouling paint composition is formed on the surface of an underwater sensor, underwater marking or a marine propeller.

The antifouling coating composition according to the present invention comprises an antifouling agent and a trialkylgermyl (meth) acrylate copolymer. It is preferable that the trialkylgermyl (meth) acrylate copolymer contains a structural unit derived from a trialkylgermyl (meth) acrylate represented by the following general formula (I).

[0019]

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(Wherein, R ^{1 to} R ³ may be the same or different and each represents an alkyl group having 3 or more carbon atoms;
⁴ represents a hydrogen atom or a methyl group. The component unit derived from the trialkylgermyl (meth) acrylate in the copolymer is preferably 15 to 45 mol%.

The antifouling coating film according to the present invention is formed from the above antifouling coating composition. The antifouling method for a hull or underwater structure according to the present invention is characterized in that the antifouling coating composition is applied to the surface of a hull or an underwater structure to form an antifouling coating film.

The hull or the underwater structure according to the present invention is characterized in that the surface of the hull or the underwater structure is coated with a coating film comprising the antifouling coating composition.

[0023]

DETAILED DESCRIPTION OF THE INVENTION The antifouling coating composition according to the present invention will be specifically described below. [ Transparent antifouling coating composition ] The transparent antifouling coating composition according to the present invention comprises a trialkylgermyl (meth) acrylate copolymer.

Such a copolymer is represented by the following general formula (I)
And a structural unit derived from a trialkylgermyl (meth) acrylate represented by the formula:

[0025]

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In the formula, R ^{1 to} R ³ may be the same or different and each is an alkyl group having 3 or more carbon atoms, preferably an alkyl group having 3 or more carbon atoms in which R ^{1 to} R ³ are all the same. is there. R ⁴ is a hydrogen atom or a methyl group.

Such a trialkylgermyl (meth)
Specific examples of the acrylate include tri-n-propylgermyl (meth) acrylate, tri-i-propylgermyl (meth) acrylate, tri-n-butylgermyl (meth) acrylate, tri-i-butylgermyl (meth) acrylate, tri-s- Butylgermyl (meth) acrylate, and the like. Of these, tri-i-butylgermyl (meth) acrylate is preferably used.

As the monomer (comonomer) to be copolymerized with the above trialkylgermyl (meth) acrylate, any polymerizable unsaturated compound (ethylenically unsaturated monomer) can be used. Specific examples of such a polymerizable unsaturated compound include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, ( Alkyl (meth) acrylates such as cyclohexyl (meth) acrylate and 2-methoxyethyl (meth) acrylate; styrenes such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; -Vinylpyrrolidone and the like. These comonomers can be used arbitrarily according to required film forming properties, hardness, consumability and the like.

As a comonomer of tri-n-butylgermyl (meth) acrylate and tri-i-butylgermyl (meth) acrylate, methyl methacrylate (MM)
A), lower alcohol esters of methacrylic acid such as methacrylic acid ethyl ester (EMA) and methacrylic acid butyl ester (BMA) are preferred.
MA or BMA is preferably used in a comonomer (ethylenically unsaturated monomer) in an amount of usually 30% by weight, preferably 50% by weight or more.

Such a copolymer contains 15 to 45 mol%, preferably 20 to 45 mol% of a component unit derived from a trialkylgermyl (meth) acrylate in the trialkylgermyl (meth) acrylate copolymer. Mol%, more preferably in the range of 20 to 40 mol%.
Within such a range, a transparent antifouling paint composition having excellent long-term antifouling properties can be obtained.

Such a copolymer is a random copolymer of a component unit derived from a methacrylate and a component unit derived from a trialkylgermyl ester,
It is a block copolymer. In particular, a random copolymer is excellent in ease of synthesis, film forming property of a coating film, and long-term antifouling property.

The copolymer has a number average molecular weight (Mn) measured by GPC of 1,000 to 100,000, preferably 1,000 to 80,000, more preferably 100 to 100,000.
0-40000, and weight average molecular weight (Mw)
Is from 1000 to 250,000, preferably from 1000 to 1
50,000, and the molecular weight distribution (M
w / Mn) is usually 1.0 to 10.0, preferably 1.0.
And the glass transition temperature (Tg) of the copolymer is usually -10 to 100 ° C, preferably 0 to 80 ° C. For example, 30% by weight (a mixed solvent of toluene and n-butyl acetate, a weight ratio of toluene: n-butyl acetate = 1: 1)
1) The viscosity (25 ° C.) of the solution is usually 10,000 cp
s or less, preferably 5000 cps or less, and more preferably 3000 cps or less.

The number average molecular weight of this copolymer is in the above range 1
When it is in the range of 000 to 40,000, the coating workability, the coating film antifouling performance for a long period of time, and the coating state and storage stability of the obtained coating composition become excellent.

Such a trialkylgermyl (meta)
As the acrylate copolymer, specifically, a copolymer composed of 41 to 66% by weight of tri-n-propylgermyl methacrylate or tri-i-propylgermyl methacrylate and 59 to 34% by weight of methyl methacrylate;
Any one or more of butylgermyl (meth) acrylate, tri-i-butylgermyl (meth) acrylate and tris-butylgermyl (meth) acrylate
And a copolymer comprising 55% by weight of methyl methacrylate and 55 to 31% by weight of methyl methacrylate.

With respect to the comonomer methyl methacrylate, it is possible to replace part or all of the comonomer with ethyl methacrylate, propyl methacrylate or butyl methacrylate, and to substitute other monomers up to half of the methyl methacrylate. .
By performing the replacement in this manner, it is possible to set an arbitrary coating film hardness and wearability.

For example, a monomer having a low glass transition temperature, such as butyl acrylate and 2-ethylhexyl acrylate, is used when flexibility is required for the coating film, and 2-methoxyethyl acrylate, vinyl pyrrolidone is used when more wear is required. When more water resistance is required, a hydrophilic monomer such as t-butyl methacrylate and cyclohexyl methacrylate may be appropriately used.

The number average molecular weight of these copolymers (M
n) is from 1000 to 100,000, preferably from 1000 to 100,000
45,000 and a weight average molecular weight (Mw) of 1000
２５０250,000, preferably 1,000 to 150,000, and a molecular weight distribution (Mw / Mn) of 1.0 to 10.0, preferably 1.0 to 6.0, and a glass transition temperature (Tg).
Is -10 to 100C, preferably 0 to 80C,
For example, the viscosity (25 ° C.) of a solution of these copolymers in a 30% by weight (a mixed solvent of toluene and n-butyl acetate, weight ratio of toluene: n-butyl acetate = 1: 1) solution is 3000.
Those which are not more than cps are preferred.

Such a trialkylgermyl (meth)
To prepare the acrylate copolymer, for example, usually under an inert atmosphere such as in a nitrogen stream, toluene, xylene,
In an organic solvent such as butyl acetate and methyl isobutyl ketone, a trialkylgermyl ester such as tributylgermyl (meth) acrylate and methyl methacrylate in an amount of 50% by weight or more (eg, 80% by weight) in the comonomer. With the contained polymerizable unsaturated compound, a polymerization initiator such as azo or peroxide such as 2,2'-azobisisobutyronitrile, and a polymerization regulator such as n-octyl mercaptan if necessary. The reaction may be performed by a method such as radical polymerization at a temperature of about 50 to 120 ° C. for about 2 to 12 hours in the presence of the above. The polymerization initiator is used in an amount of 0.1 to the total amount of the trialkylgermyl ester and the comonomer.
The polymerization regulator may be contained in an amount of 0 to 10% by weight based on the total amount of the trialkylgermyl ester and the comonomer.

The trialkylgermyl (meth) acrylate copolymer thus obtained contains each component unit in an amount corresponding to the amount of each monomer used.
The polymerization method is not limited to the above-mentioned simple radical solution polymerization method, and conventionally known methods such as emulsion polymerization, suspension polymerization and bulk polymerization can be employed.

The solvent can be arbitrarily selected from the above-mentioned aromatic, ester, and ketone solvents, as well as various solvents commonly used for paints, such as aliphatic, ether, and alcohol solvents.

The transparent antifouling coating composition according to the present invention contains, in addition to the above trialkylgermyl (meth) acrylate, other conventionally known solvents, resins, dissolution aids, as long as the transparency is not lost. It may contain soiling agents, plasticizers and additives.

Solvents include aromatic compounds such as toluene and xylene, ester compounds such as ethyl acetate and butyl acetate, ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone, aliphatic compounds such as hexane and heptane, dioxane, propylene glycol monomethyl. Examples include ether solvents such as ether, and alcohol solvents such as isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol. Such a solvent is based on 100 parts by weight of the trialkylgermyl (meth) acrylate copolymer.
It may be contained in an amount of 10 to 1000 parts by weight, preferably 15 to 100 parts by weight.

Examples of the resin include an alkyd resin, a chlorinated rubber resin, an acrylic resin, a styrene resin, a vinyl ether resin, an epoxy resin, and a petroleum resin. Such a resin may be contained in an amount of 0 to 300 parts by weight, preferably 0 to 100 parts by weight, based on 100 parts by weight of the trialkylgermyl (meth) acrylate copolymer.

Examples of the dissolution aid include rosin, rosin metal salts, naphthenic acid, and naphthenic acid metal salts.
Such an elution aid is used in an amount of 0 to 100 parts by weight of the trialkylgermyl (meth) acrylate copolymer.
500 parts by weight, preferably 0 to 100 parts by weight may be contained.

As the antifouling agent, an organic antifouling agent such as 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and soluble in a solvent is preferred in terms of transparency. Preferably, such an antifouling agent is contained in an amount of 0 to 50 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the above trialkylgermyl (meth) acrylate copolymer.

Examples of the plasticizer include known plasticizers such as phthalate esters such as chlorinated paraffin, dibutyl phthalate and dioctyl phthalate, and phosphate esters such as tricresyl phosphate. Such a plasticizer may be contained in an amount of 0 to 100 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of the trialkylgermyl (meth) acrylate copolymer.

Examples of the additives include conventionally known thickeners, defoaming agents, leveling agents, and stabilizers such as dehydrating agents. Such an additive is added to 100 parts by weight of the trialkylgermyl (meth) acrylate copolymer.
It may be contained in an amount of 0 to 20 parts by weight, preferably 0 to 10 parts by weight.

The transparent antifouling coating film according to the present invention is formed from the above transparent antifouling coating composition. The method of forming the coating film can be arbitrarily selected as long as it is a conventionally known coating method. For example, dipping, brushing,
Examples include roller coating, air spray coating, airless spray coating, and aerosol spraying. The thickness of the coating film thus formed is 1 μm to 10 mm, preferably 5 μm to 1 mm.

When the above transparent antifouling coating composition is applied to the surface of the submerged transparent structure to form a transparent antifouling coating,
The adhesion of aquatic organisms such as shellfish can be prevented without impairing the transparency of the submerged transparent structure.

In particular, it is preferable to form a transparent antifouling coating film on the surface of an underwater window, a water tank, an underwater light cover or the like without impairing the transparency and aesthetic appearance. Further, when the transparent antifouling coating film as described above is formed on the surface of an underwater sensor such as a submarine, it is possible to prevent aquatic organisms from adhering to the sensor unit and to maintain the function of the sensor for a long time.

Further, when this transparent antifouling coating film is formed on the test piece or the marking portion of the underwater structure in a submerged environment, it is possible to prevent the adhesion of shellfish and the like to the marking portion and to prevent the adhesion of the marking portion. Since it has visibility, it is easy to confirm the mark in water or after lifting.

Furthermore, when a transparent antifouling coating film made of such a transparent antifouling paint composition is formed on the surface of a marine propeller, the antifouling agent (such as cuprous oxide) is not contained. It is possible to prevent such an adverse effect that the surface is corroded by a potential difference between the propeller base material (such as copper alloy) and the propeller base material (such as a copper alloy). In addition, since it is a transparent coating film, cracks and corrosion state of the propeller base material can be visually confirmed.

[Antifouling paint composition] The antifouling paint composition according to the present invention comprises an antifouling agent and a trialkylgermyl (meth) acrylate copolymer.

The trialkylgermyl (meth) acrylate copolymer contains a structural unit derived from a trialkylgermyl (meth) acrylate represented by the following general formula (I).

[0055]

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[0056] In the formula, R ¹ to R ³ may be the same or different from each other, it indicates an alkyl group having 3 or more carbon, R ⁴
Represents a hydrogen atom or a methyl group. The component unit derived from the trialkylgermyl (meth) acrylate in the copolymer is 15 to 45 mol%, preferably 20 to 4 mol%.
It is 5 mol%, more preferably 20 to 40 mol%.

Such a trialkylgermyl (meth)
Examples of the acrylate copolymer include the above-described trialkylgermyl (meth) acrylate copolymer. The presence of a carboxylic acid residue in such a copolymer may reduce the storage stability of the obtained antifouling coating composition. Desirably, no residue is present. When synthesizing the copolymer, it is preferable to use a high-purity monomer having no carboxylic acid residue.

As a solvent to be used at the time of or after the synthesis, a solvent having a particularly low water content is preferable. When such a low-water solvent is used, the above-mentioned reaction and the subsequent hydrolysis reaction can be avoided. Therefore, it is preferable.

In the coating composition of the present invention, conventionally known antifouling agents, which are other essential components, can be used. Specific examples of antifouling agents include copper powder, cuprous oxide,
Copper compounds such as rodan copper (CuSCN), copper-nickel alloy, copper 8-oxyquinoline, copper naphthenate, copper salt of 2-pyridinethiol-1-oxide, zinc salt of 2-pyridinethiol-1-oxide, zinc dimethyldithio Carbamate, zinc ethylenebisdithiocarbamate, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, zinc compounds such as zinc oxide, isothiazolone derivatives such as 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, 2 Trimethyl compounds such as -methyl-4-t-butylamino-6-cyclopropylamino-s-triazine, maleimide derivatives such as N- (2,4,6-trichlorophenyl) maleimide,
N, N-dimethyl-dichlorophenylurea, 2,4,5,6-tetrachloroisophthalonitrile, pyridine-triphenylboron, tetramethylthiuram disulfide, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl
-N'-phenyl- (N'-fluorodichloromethylthio) sulfamide, 3-iodo-2-propynylbutylcarbamate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, diiodomethylparatolyl Sulfone and the like.

Such antifouling agents can be used alone or in combination of two or more. Such antifouling agents are
Types of antifouling agents and trialkylgermyl (meth) acrylate copolymers used in preparing the antifouling paint composition, or types of ships and the like to which such an antifouling paint composition is applied (for ships, (For sailing-coastal use, for various seawater areas, wooden-for steel ships, etc.)
The antifouling agent is used in an amount of usually 0.1 to 1500 parts by weight, preferably 1 to 1200 parts by weight, based on 100 parts by weight of the film-forming copolymer.

For example, when the cuprous oxide is used as an antifouling agent, the cuprous oxide is usually used in an amount of about 80 to 1200 parts by weight based on 100 parts by weight of the trialkylgermyl (meth) acrylate copolymer. It may be contained in the antifouling coating composition in an amount.

The antifouling coating composition according to the present invention contains an antifouling agent and a trialkylgermyl (meth) acrylate copolymer. It may contain auxiliaries, plasticizers and additives, and may contain various pigments and dehydrating agents.

As the pigment, known coloring pigments and extender pigments can be used. Further, in the antifouling paint composition containing a dehydrating agent, the storage stability can be improved.
O ₄ ), synthetic zeolite-based adsorbents (trade name: molecular sieve, etc.), orthoesters such as methyl orthoformate, methyl orthoacetate, etc., orthoborate esters, silicates and isocyanates (trade name: Additive TI)
Etc.).

[ Production of antifouling paint composition ] Such an antifouling paint composition can be produced by appropriately utilizing a conventionally known method. For example, the above trialkylgermyl (meth) acrylate A copolymer, and an antifouling agent (for example, 80 to 1200 parts by weight of cuprous oxide) in an amount of 0.1 to 1500 parts by weight based on 100 parts by weight of the trialkylgermyl (meth) acrylate copolymer. 5-400
Zinc white, which is used as required in parts by weight, and an optional amount of dehydrating agent (eg, anhydrous gypsum, molecular sieve), plasticizer, anti-sagging / anti-settling agent, pigment, solvent, etc., all at once or in any order And stirring, mixing and dispersion.

The antifouling coating composition as described above is applied to the surface of an underwater structure (eg, a water supply / drain opening of a nuclear power plant) or
On the surface of sludge diffusion prevention membranes for the construction of various types of marine civil engineering equipment such as gulf roads, submarine tunnels, harbor facilities, canals and waterways, or on various molded objects such as ships and fishing gear (eg ropes, fishing nets) If the antifouling coating film is formed by coating the surface once or a plurality of times according to a conventional method, an antifouling coating film-coated hull or underwater structure having excellent antifouling properties can be obtained. The antifouling paint composition according to the present invention may be applied directly to the surface of the above-mentioned hull or underwater structure, or a hull or underwater structure to which a base material such as a rust preventive or a primer has been applied in advance. It may be applied to the surface of an object or the like. Furthermore, the surface of a hull, underwater structure, or the like, which has already been coated with a conventional antifouling paint or has been coated with the antifouling paint composition of the present invention, is used as a repair for the antifouling of the present invention. The coating composition may be overcoated. The thickness of the antifouling coating film formed on the surface of the hull, underwater structure or the like in this manner is not particularly limited, but is, for example, about 30 to 150 μm / time.

[0066]

The transparent antifouling coating composition according to the present invention has excellent physical properties such as water resistance, hydrolysis resistance, crack resistance and peeling resistance, and contains a tin polymer. Like the composition, a transparent antifouling coating film having excellent antifouling properties and self-cleaning properties (consumable properties) can be formed.

Therefore, it is suitable for antifouling of submerged underwater structures, such as underwater windows and underwater light covers, which require transparency of the coating film, underwater sensors, underwater marking, and marine propellers.

The antifouling paint composition according to the present invention has excellent physical properties such as water resistance, hydrolysis resistance, crack resistance, and peeling resistance, and is similar to the antifouling paint composition containing a tin polymer. In addition, an antifouling coating film having excellent antifouling properties and self-cleaning properties (consumable properties) can be formed.

[0069]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, “parts” means “parts by weight”. In addition, the amounts of each component in the table are indicated by “parts by weight” unless otherwise specified.

[Evaluation Method] The properties of the antifouling coating composition according to the present invention were measured as follows. The copolymer solution is applied to one side of a 76 × 26 × 1 mm slide glass using an applicator so that a dry film thickness is about 60 μm, and dried in a room for 7 days. To form a coating film.

The slide glass on which the coating film is formed is immersed in a beaker containing ion-exchanged water for 48 hours, the state of the coating film after immersion is observed, and the change in IR spectrum before and after immersion is measured.

Antifouling test (transparent antifouling paint) A copolymer solution is applied on both sides of a 200 × 100 × 5 mm glass plate by brush coating so that the dry film thickness becomes 200 μm.

A test specimen was hung from a test raft installed in Nagasaki Bay to a point at a depth of 1 m, and the antifouling property after 6 months was evaluated according to the following evaluation criteria. Evaluation criteria 5: Almost no deposits were observed and the transparent state was maintained. 4: Thin slime layer was observed and translucent. 3: Adhesion of slime and macro organisms was observed, but partially semi-transparent state. Recognize the site.

2: Adhesion of slime and macro organisms was observed, and poor visibility was observed. 1: Adhesion of slime and macro organisms was observed, and no visibility was observed. Consumable (transparent antifouling paint) In antifouling test The marking part of the used test piece is rubbed with a finger, and the wearability of the coating film is evaluated according to the following evaluation criteria according to the state of the finger touching the step.

[0075] Antifouling properties (antifouling paint) 100 x 300 x 2 mm sandblasted steel plate with epoxy zinc rich primer (80% by weight zinc content in dry coating), epoxy anticorrosive paint, vinyl binder coat, each dry film 20μm, 150μ thick
m and 75 μm every day, and then the test antifouling paint composition was applied to a dry film thickness of 100 μm to obtain a test plate. This test plate was hung from a test raft installed in Hiroshima Bay to a point at a depth of 1 m, and the adhesion area of various aquatic organisms to the test plate after 12 months was measured to evaluate the antifouling property. .

Consumability (Anti-fouling paint) A 70 × 200 × 3 mm sand blast plate was prepared which was bent so that it could be attached to the side of a rotating drum installed in the sea of Hiroshima Bay. On this sandblast board,
Epoxy zinc rich primer (80% by weight zinc dust content in dry coating), epoxy anticorrosion paint, vinyl binder coat each having a dry film thickness of 20 μm,
After successively coating 50 μm and 50 μm, the test antifouling paint composition was dried to a thickness of 200 μm.
m to obtain a test plate.

The test plate was attached to a rotating drum, and the operation of the ship was simulated at a peripheral speed of 15 knots for 6 months. Thereafter, the decrease in film thickness was measured to evaluate the wearability.

[0078]

Example 1 [ Transparent antifouling coating composition] Production of copolymer G-1 60 parts of toluene, acetic acid-n in a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, heating / cooling jacket.
60 parts of -butyl was charged and heated and stirred under a nitrogen stream at a temperature of 85 ° C.

While maintaining the same temperature, triisobutylgermyl methacrylate was introduced into the reactor from the dropping device.
A mixture of 4 parts, 30.6 parts of methyl methacrylate and 0.5 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was added dropwise over 4 hours.

After stirring for 4 hours at the same temperature, 0.1 part of 2,2'-azobisisobutyronitrile was added to the reactor, and stirring was continued for 4 hours at the same temperature to obtain colorless and transparent. Was obtained as a copolymer solution G-1.

[0081] The resulting copolymer solution G-1 a heating residue after heating for 3 hours at 105 ° C. is 39.9 wt%, ¹
The composition of the copolymer determined by H-NMR was equal to the charged monomer composition, and it is considered that the copolymer was a copolymer in which each monomer component was randomly arranged.

The glass transition temperature (Tg) of the copolymer in the copolymer solution G-1 measured by DSC was 58 ° C., and the viscosity of the copolymer solution G-1 at 25 ° C. was 15 ° C.
20 cps, and the number average molecular weight (M
n) is 16100 and the weight average molecular weight (Mw) is 3
8,600. Table 1 shows the properties of such a copolymer solution G-1.

Using this copolymer solution G-1, a transparent antifouling coating film was prepared, and the water resistance, antifouling property and wear resistance of the coating film were evaluated as described above. Table 2 shows the results.

[0084]

Examples 2 and 3 Production of Copolymer G-2,3 In the production of the above-mentioned copolymer G-1, the components to be dropped were as shown in Table 1.
The copolymer G-2,3 was obtained in the same manner as described above, except that the copolymer was changed as shown in the above, and a transparent antifouling coating film using these copolymers (solutions) was obtained in the same manner as in Example 1. Water resistance, antifouling property, and consumability were evaluated. Table 2 shows the results.

[0085]

Reference Examples 1 and 2 Production of Copolymer H-1,2 In the production of the above copolymer G-1, the components added dropwise were as shown in Table 1.
Except that the copolymer was changed as shown in the above, a copolymer H-1,2 was obtained in the same manner as described above, and a transparent antifouling coating film was formed using these copolymers (solutions) in the same manner as in Example 1. .

[0086]

[Table 1]

[0087]

Comparative Example 1 The same procedure as in Example 1 was carried out except that the following polymer was used as the copolymer H-3 copolymer. evaluated. Table 2 shows the results.

H-3: tin polymer solution Monomer composition: tributyltin methacrylate / methyl methacrylate = 65/35 (weight ratio) Heating residue: 40% by weight Solvent: xylene Mw: 50,000

[0089]

Comparative Example 2 The same procedure as in Example 1 was carried out except that the following polymer was used as the copolymer H-4 copolymer to obtain a transparent antifouling coating film having water resistance, antifouling property, and wear resistance. evaluated. Table 2 shows the results.

H-4: Non-functional acrylic polymer solution Monomer composition: butyl methacrylate / methyl methacrylate = 60/40 (weight ratio) Heating residue: 40% by weight Solvent: xylene Mw: 50,000

[0091]

[Table 2]

As shown in Table 2, Examples 1 to 3 have the same water resistance, hydrolysis resistance, antifouling property, and wear resistance as Comparative Example 1 (the tin polymer coating film). When the surface of the coating film after immersion in seawater of Example 1 and Example 2 and the IR spectrum of the inner surface obtained by cutting the surface with a knife were measured by a Fourier transform infrared-microscopic analysis system, the surface layer showed some hydrolysis. Other than that observed, the surface and internal IR spectra are very similar.In the coating film, hydrolysis and elution occur only at the contact surface with weakly alkaline seawater while having hydrolysis resistance. It was shown that. FIG. 6 shows the IR spectra of the coating film surface and the inside of the coating film of Example 2.
Shown in The IR spectrum of Comparative Example 1 (the tin polymer coating film) also showed the same tendency as in Examples 1 and 2 (FIG. 7).

[0093]

Examples 4 to 8 and Comparative Examples 3 and 4 Production Examples of Antifouling Paint Compositions Each antifouling paint composition having the composition shown in Table 3 was produced (the amount of each component is indicated in parts by weight).

In preparing an antifouling paint composition having the composition shown in Table 3, these ingredients were shaken together for 2 hours in a paint shaker containing glass beads, and then aged at room temperature for 12 hours. Was done. Next, the mixture was filtered through a 100-mesh filter to obtain a desired antifouling paint composition.

The antifouling paint composition was evaluated for the antifouling property and consumable property described above.

[0096]

[Table 3]

The names of the components in the table are as follows. "Toyo Parax 150" Chlorinated paraffin manufactured by Tosoh Corporation, average carbon number: 1
4.5, chlorine content (amount) 50%, viscosity: 12 poise /
25 ° C, specific gravity: 1.25 / 25 ° C. "Molecular sieve 4A" Dehydrating agent, manufactured by Union Showa Co., Ltd., synthetic zeolite powder. "Dispalon 305" A hydrogenated castor oil-based sagging agent manufactured by Kusumoto Kasei Co., Ltd. "Dispalon 4200-20" A polyethylene oxide anti-settling agent manufactured by Kusumoto Kasei Co., Ltd.
0% xylene paste.

[0098]

[Table 4]

[Brief description of the drawings]

FIG. 1 is a change in IR spectrum of a coating film formed from the transparent antifouling coating composition of Example 1 before and after immersion in ion-exchanged water.

FIG. 2 shows a change in IR spectrum of a coating film formed from the transparent antifouling coating composition of Example 3 before and after immersion in ion-exchanged water.

FIG. 3 shows a change in IR spectrum of a coating film formed from the transparent antifouling coating composition of Comparative Example 1 before and after immersion in ion-exchanged water.

FIG. 4 shows changes in the IR spectrum of the coating film surface and the inside of the coating film after immersion of the coating film of Example 2 in seawater.

FIG. 5 shows changes in IR spectra of the coating film surface and the inside of the coating film of Comparative Example 1 after immersion in seawater.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuhito Hijichi 1 in 1 Meiji Shinkai, Otake City, Hiroshima Prefecture Inside China Paint Co., Ltd. (72) Inventor Naoya Nakamura 1 in Meiji Shinkai, Otake City, Hiroshima Prefecture 7 Inside China Paint Co., Ltd. (72) Inventor Makoto Tsuboi Inside 7 China Paint Co., Ltd. at 1 Meiji Shinkai, Otake City, Hiroshima Prefecture

Claims (13)

[Claims] 1. A transparent antifouling coating composition comprising a trialkylgermyl (meth) acrylate copolymer. 2. The trialkylgermyl (meth) acrylate copolymer comprises a structural unit derived from a trialkylgermyl (meth) acrylate represented by the following general formula (I). The transparent antifouling paint composition according to claim 1. Embedded image (In the formula, R ^{1 to} R ³ may be the same or different and each represents an alkyl group having 3 or more carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.) 3. The copolymer according to claim 1, wherein the component unit derived from trialkylgermyl (meth) acrylate is 15 units.
The transparent antifouling coating composition according to claim 1, wherein the composition is in an amount of from about 45 mol% to about 45 mol%. 4. A transparent antifouling coating film formed from the transparent antifouling coating composition according to claim 1. 5. The transparent antifouling coating composition according to claim 1, which is applied to the surface of the submerged transparent structure to form a transparent antifouling coating film. Antifouling method for structures. 6. The antifouling method according to claim 5, wherein the submerged transparent structure is an underwater window, a water tank, or an underwater light cover. 7. A transparent antifouling coating composition according to any one of claims 1 to 3, wherein the composition is applied to an underwater sensor, underwater marking or a marine propeller surface to form a transparent antifouling coating film. Then the underwater sensor, underwater marking or marine propeller antifouling method. 8. An antifouling coating composition comprising an antifouling agent and a trialkylgermyl (meth) acrylate copolymer. 9. The trialkylgermyl (meth) acrylate copolymer contains a structural unit derived from a trialkylgermyl (meth) acrylate represented by the following general formula (I). The antifouling paint composition according to claim 8, wherein Embedded image (In the formula, R ^{1 to} R ³ may be the same or different and each represents an alkyl group having 3 or more carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.) 10. The copolymer according to claim 10, wherein the component unit derived from trialkylgermyl (meth) acrylate is 15 units.
The antifouling paint composition according to claim 8, wherein the content is -45 mol%. 11. An antifouling coating film formed from the antifouling coating composition according to claim 8. 12. An antifouling coating composition according to claim 8, which is applied to the surface of an underwater structure to form an antifouling coating film. Dirty method. 13. A hull or underwater structure, wherein the surface of the hull or underwater structure is coated with a coating film comprising the antifouling coating composition according to any one of claims 8 to 10.