KR20200089505A - Protective coating composition for ship ballast water treatment apparatus - Google Patents

Abstract

A coating composition of the present invention comprises a structural unit (1) derived from polypropylene glycol, polyisocyanate compound, hydroxyl-containing (meth)acrylate compound, and triisopropylsilyl methacrylate (i), a structural unit (2) derived from 2-methoxyethyl (meth)acrylate (ii), another monomer ethylenically unsaturated monomer silyl methacrylate-based copolymer (A) having a polymerizable double bond, and trimethylisobutenylcyclohexenecarboxylic acid (B).

Description

Protective coating composition for ship ballast water treatment apparatus

An object of the present invention is to prevent corrosion of an electrolysis tank in a highly corrosive environment inside and outside the vessel for treating ballast water.

In order to solve the above problems, the coating coating composition of the present invention is a structural unit (1) derived from polypropylene glycol, a polyisocyanate compound, a hydroxyl group-containing (meth)acrylate compound, and triisopropylsilyl methacrylate (i), Structural unit (2) derived from 2-methoxyethyl (meth)acrylate (ii), and other monomers having a polymerizable double bond Ethylene unsaturated monomer Silyl methacrylate copolymer (A) and trimethylisobutenyl It is characterized by containing cyclohexenecarboxylic acid (B).

In ships, such as tankers, when retreating to the destination after unloading crude oil, etc., sufficient resilience and proper draft are essential for safe sailing, so the ballast water must be filled in the ship before departure. .

Ballast water is basically taken from the landing port and discharged from the shipping port. Therefore, when their locations are different, plankton or microbes of microorganisms contained in ballast water move around the world. Therefore, if the ballast water is discharged from the port of loading in the landing port and other sea areas, microorganisms in other sea areas are released into the port, which may destroy the ecosystem of the sea area.

In general, ballast water is also referred to as ballast water, and refers to seawater loaded on tanks in ships to maintain the balance and provide optimum speed and efficiency during ship operation.

In addition, it is known that the ballast water of the vessel is generally filled in the vessel at the departure port and discharged from the arrival port. At this time, it is known that microorganisms or benthic organisms at the sea of departure originate into the sea at the arrival port, causing side effects that disturb the marine ecosystem.

Therefore, a water purification device for sterilizing and purifying microorganisms in ballast water is required. In the water purification method, electricity is supplied to the pipes to which ship ballast water is supplied or discharged, and an electrolysis method that kills microorganisms by electricity, and ozone is injected into the pipes. There are ozone injection method that kills organisms, UV projection system that installs ultraviolet light emitting devices in the pipe to kill organisms using ultraviolet rays, and chemical method that kills organisms by putting chemicals into the tank where the ballast water is stored. .

These water purification methods require a device for sterilizing microorganisms contained in seawater, and these devices are exposed to very high corrosive environments because they use various electrical stimulation chemicals to kill them. Electric stimulation and excessive hypochlorous acid generation Ozone, various chemicals, such as ozone, are mixed with a highly corrosive seawater environment, and are exposed to a very high corrosive environment compared to the general seawater environment, and the durability of the device tends to decrease rapidly. There are limitations in solving these problems with various heavy-duty coatings, and even in such environments, it is necessary to protect the device from corrosion and to have a highly durable protective coating.

Upon examination by the present inventors, it has been found that a coating film formed of a coating composition comprising a (co)polymer of triisopropylsilyl(meth)acrylate and a rosin compound has a problem of cracking when exposed to sunlight for a long time.

For example, a crack occurs when a block coated with an antifouling paint is exposed to sunlight for a long time in a new ship, or when the antifouling film on the surface of a ship is exposed to sunlight for a long time due to the loading amount or ballast water during operation. This should happen or should.

In the former case, repair of the antifouling film is required, which increases the shipbuilding process. In the latter case, there is a risk that the antifouling property during operation of the antifouling coating film is lowered or irregularities are generated on the bottom coating film surface due to the occurrence of cracks, thereby increasing the water frictional resistance. Since the hardness of the rosin or its metal salt is high, when the coating film containing them is exposed to sunlight, drying of the coating film progresses over time, and the hardness of the coating film is considered to ultimately cause cracking. In addition, rosin is a natural product, which is unstable in terms of quality stability and stable supply for the future.

In addition, it was found that the coating film formed of an antifouling coating composition comprising the triisopropylsilylacrylate copolymer and trimethylisobutenylcyclohexenecarboxylic acid described in Patent Document 7 has room for improvement in terms of long-term water resistance.

In addition, the anti-fouling coating film formed of the anti-fouling coating composition containing the tri-i-propylsilyl (meth)acrylate copolymer and trimethylisobutenylcyclohexene carboxylic acid disclosed in Patent Document 8 also suppresses crack generation when exposed to sunlight for a long time. There was room for improvement in that it did.

Therefore, the present invention provides long-term antifouling properties (especially static antifouling properties), long-term water resistance (specifically, adhesion to a substrate of a coating film when immersed in water for a long time, especially in seawater, crack resistance and abrasion resistance) and long-term exposure to sunlight. Providing an antifouling coating film having excellent crack resistance when it is formed (hereinafter also referred to as "long-term exposure resistance"), an antifouling coating composition for forming the antifouling coating film, an antifouling material having the antifouling coating film, and a method for manufacturing the same It is aimed at.

The present inventors studied in earnest in view of the above-mentioned problems, and included a silyl ester copolymer copolymerized with triisopropylsilyl methacrylate and 2-methoxyethyl (meth)acrylate and trimethylisobutenylcyclohexenecarboxylic acid. It has been found that the above-mentioned problems can be solved by an antifouling coating film formed of an antifouling coating composition to complete the present invention.

The antifouling coating composition of the present invention, for example, relates to the following [1] to [12].

[One]

Structural unit (1) derived from triisopropylsilyl methacrylate (i), structural unit (2) derived from 2-methoxyethyl (meth)acrylate (ii), and other monomers having a polymerizable double bond (However, triisopropyl silyl methacrylate and 2-methoxyethyl (meth) acrylate are excluded.) A silyl methacrylate-based copolymer (A) comprising a structural unit (3) derived from (iii) And an antifouling coating composition comprising trimethylisobutenylcyclohexenecarboxylic acid (B).

[2]

The antifouling coating composition according to the above [1], wherein the other monomer (iii) is an ester or a carboxylic acid.

[3]

The antifouling coating composition according to [1] or [2], wherein the proportion of the structural unit (1) in the silyl methacrylate copolymer (A) is 30 to 70% by weight.

[4]

The antifouling coating composition according to any one of [1] to [3], wherein the proportion of the structural unit (2) in the silyl methacrylate copolymer (A) is 5 to 40% by weight.

[5]

The ratio (WA/WB) of the content (WA) of the silyl methacrylate copolymer (A) and the content (WB) of the trimethylisobutenylcyclohexenecarboxylic acid (B) is 99/1 to 40 by weight. The antifouling coating composition according to any one of [1] to [4] above, which is /60.

[6]

The antifouling coating composition according to any one of [1] to [5], further comprising rosin and/or a monocarboxylic acid compound (however, trimethylisobutenylcyclohexenecarboxylic acid is excluded) (C). .

[7]

In addition, inorganic copper compounds (D), organic antifouling agents (E), coloring pigments (F), extender pigments (G), pigment dispersants (H), plasticizers (I), anti-sagging agents (J), anti-settling agents (K) , An antifouling coating composition according to any one of [1] to [6], which contains at least one component selected from the group consisting of a dehydrating agent (L) and a solvent (M).

[8]

An antifouling coating film formed from the antifouling coating composition according to any one of [1] to [7].

[9]

An antifouling material having a base material and the antifouling coating film according to [8] above provided on the surface of the base material.

[10]

The antifouling material according to [9] above, which comes into contact with sea water or fresh water.

[11]

The anti-fouling material according to the above [9] or [10], wherein the substrate is an underwater structure, a ship's outer plate or a fishing gear.

[12]

It is provided with the step of coating or impregnating the antifouling coating composition according to any one of [1] to [7] on the surface of the substrate, and the step of curing the antifouling coating applied or impregnated on the substrate by the process. Or, a method for producing an antifouling material comprising a step of forming a coating film from the antifouling coating composition and curing the coating film to form an antifouling coating film, and a step of attaching the antifouling coating film to a substrate.

The antifouling coating film of the present invention has long-term antifouling properties (especially, static antifouling properties), long-term water resistance (specifically, adhesion of a coating film when it is immersed in water for a long period of time, crack resistance and abrasion resistance) and long-term exposure resistance. This is excellent. Moreover, the antifouling coating film which exhibits such an effect can be formed by the antifouling coating composition of the present invention. In addition, according to the method for manufacturing an antifouling material of the present invention, an antifouling material exhibiting such effects can be produced.

Hereinafter, the antifouling coating composition of the present invention, an antifouling coating film, an antifouling material and a method for manufacturing the antifouling material will be described in detail.

[Antifouling paint composition]

The antifouling coating composition of the present invention (which is also simply referred to as "antifouling coating") contains a specific silyl methacrylate copolymer (A) and trimethylisobutenylcyclohexenecarboxylic acid (B), depending on the purpose. Optional components may be included.

1. Silyl methacrylate copolymer (A)

Silyl methacrylate copolymer (A) is a structural unit derived from triisopropyl silyl methacrylate (i) (hereinafter also referred to as "monomer (i)") (also referred to as "constituent unit", "repeated unit", etc.) (1), a structural unit (2) derived from 2-methoxyethyl (meth)acrylate (ii) (hereinafter also referred to as "monomer (ii)"), and another monomer having a polymerizable double bond. (However, triisopropylsilyl methacrylate (i) and 2-methoxyethyl (meth)acrylate (ii) are excluded.)) (iii) (hereinafter also referred to as "monomer (iii)") It is a silyl methacrylate-based copolymer (A) having a structural unit (3).

Also, the term “structural unit derived from X” refers to A1A

2

C=CA

3

A

4

When (C=C is a polymerizable carbon-carbon double bond.), it is a structural unit represented by the following formula, for example.

In addition, (meth)acrylate is a generic term for acrylate and methacrylate, and (meth)acrylic acid is a generic term for acrylic acid and methacrylic acid.

The monomer (ii) is preferably 2-methoxyethyl methacrylate and 2-methoxyethyl methacrylate containing at least 50% by weight of 2-methoxyethyl methacrylate from the viewpoint of producing an antifouling coating film having more stable consumption over a long period of time. It is a mixture of methoxyethyl acrylate, and more preferably 2-methoxyethyl methacrylate.

Other monomers having a polymerizable double bond (except triisopropylsilyl methacrylate (i) and 2-methoxyethyl (meth)acrylate (ii))) (iii) triisopropylsilyl methacryl Copolymerized with rate (i) and 2-methoxyethyl (meth)acrylate (ii). As said group which has the said polymerizable double bond, a vinyl group and (meth)acryloyl group are mentioned, for example.

As the monomer (iii), esters having a polymerizable double bond and carboxylic acids having a polymerizable double bond are preferable.

If the monomer (iii) is a compound of these, the monomer (iii) has good compatibility with triisopropylsilyl methacrylate (i) and 2-methoxyethyl (meth)acrylate (ii), and also triisopropyl Since it has the same degree of reactivity to silyl methacrylate (i) and 2-methoxyethyl (meth)acrylate (ii), the structural units derived from monomers (i), (ii) and (iii) are equally It can be inserted (in other words, randomly) to prepare a silyl methacrylate copolymer (A).

That is, when the polymerization reactivity between each monomer is extremely different and it is difficult for each monomer to be copolymerized, a problem arises that the resulting polymer is a homopolymer or a copolymer having a heterogeneous distribution of structural units, wherein the monomer (iii) is the compound. If this is the case, the problem can be reduced and the silyl methacrylate copolymer (A) can be stably prepared.

Examples of the esters and carboxylic acids used as the monomer (iii) include (meth)acrylic acid esters excluding the triisopropylsilyl methacrylate (i) and 2-methoxyethyl (meth)acrylate (ii), Monocarboxylic acids, dicarboxylic acids and their half esters (also referred to as monoesters) and diesters, vinyl esters, metal ester group-containing (meth)acrylates and organosiloxane group-containing (meth)acrylates Can be lifted. Moreover, styrenes are mentioned as monomers (iii) other than esters and carboxylic acids.

As specific examples of the monomer (iii), for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid lauryl ester , (Meth)acrylic acid tridecyl ester, (meth)acrylic acid stearyl ester, (meth)acrylic acid allyl ester, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid benzyl ester, (meth)acrylic acid isobornyl ester, (meth) )Acrylic acid methoxy ester, (meth)acrylic acid ethoxy ester, (meth)acrylic acid glycidyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid hydroxyethyl ester, (meth)acrylic acid hydroxypropyl (Meth)acrylic acid esters such as ester and (meth)acrylic acid hydroxybutyl ester; monocarboxylic acids such as (meth)acrylic acid; dicarboxylic acids such as itaconic acid, maleic acid and succinic acid, and half esters (mono) Esters) and diesters; styrenes such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; and the like. These may be used alone or in combination of two or more.

The silyl methacrylate-based copolymer (A) is preferably from 5 to 40% by weight, more preferably from 8 to 30% by weight, in the antifouling coating composition of the present invention from the viewpoint of improving paintability and long-term storage stability. Is included.

In addition, the silyl methacrylate-based copolymer (A) has coating workability, long-term storage stability, coating film water resistance (in other words, mechanical properties of the coating film), coating film hydrolysis property (in other words, consumable consumption of the coating film), static antifouling property of the coating film, coating appearance, etc. From being able to improve, it is preferably included in a proportion of 10 to 60% by weight, more preferably 12 to 50% by weight in 100% by weight of the solid content of the antifouling coating composition of the present invention. Here, the solid content of the antifouling coating composition is a residue obtained by maintaining 1.5 g of the antifouling coating composition in a constant temperature bath under conditions of 1 atmosphere and 108° C. for 3 hours to remove volatile components.

The weight average molecular weight of the silyl methacrylate-based copolymer (A) is preferably 5,000 to 100,000, and more preferably 10,000 to 60,000. The coating film formed of an antifouling coating composition containing a silyl methacrylate copolymer (A) having a weight average molecular weight in this range has good hydrolysis property, improved static antifouling properties, and has excellent long-term mechanical properties (specific It can exhibit the properties of the antifouling coating film of the present invention to the base material, the base coat film, and the like in the case of being immersed in water for a long period of time, and appearance characteristics such as cracks.).

In addition, the weight average molecular weight is measured by gel permeation chromatography (GPC) and is a value obtained using a standard polystyrene calibration curve. GPC conditions of molecular weight measurement are as follows.

<GPC conditions>

Apparatus: "HLC-8120GPC" (manufactured by Tosoh Corporation)

Column: "SuperH2000+H4000" (manufactured by Tosoh Corporation, 6 mm (inner diameter), each 15 cm (length))

Eluent: Tetrahydrofuran (THF)

Other conditions

Flow rate: 0.500 ml/min

Detector ：RI

Column thermostat temperature: 40℃

Standard substance: Polystyrene

Sample preparation method: A small amount of calcium chloride is added to a solution containing the copolymer (A), dehydrated, and then the filtrate obtained by filtration through a membrane filter is used as a GPC measurement sample.

In the silyl methacrylate copolymer (A), the weight (W(1)) of the structural unit (1) and the total weight of the structural unit (2) and the structural unit (3) (W(2)+(3)) The ratio of (that is, W(1)/W(2)+(3)) (hereinafter also referred to as "weight ratio (I)") is preferably 30/70 to 70/30, more preferably 40/ It is 60-65/35, More preferably, it is 45/55-65/35.

When the value of the weight ratio (I) is in the above range, an antifouling coating composition having good coating film hydrolysis property (consumable property), stationary antifouling property, and water resistance (coating property) of the coating film can be obtained.

Ratio of the weight (W(2)) of the structural unit (2) and the total weight (W(1)+(3)) of the structural unit (1) and the structural unit (3) (that is, W(2)) /W(1)+(3)) (hereinafter also referred to as "weight ratio (II)") is preferably 5/95 to 40/60, more preferably 5/95 to 30/70, more preferably 7/93 to 29/71, particularly preferably 10/90 to 28/72.

When the value of the weight ratio (II) is in the above range, the antifouling coating film formed of the antifouling coating composition exhibits long-term antifouling properties such as good static antifouling properties because it can exhibit sufficient film consumption (renewal property) when immersed in water, especially seawater. Cracks can be reduced over a long period of time.

Silylmethacrylate-based copolymers (A) are known from triisopropylsilylmethacrylate (i), 2-methoxyethyl (meth)acrylate (ii) and other monomers (iii) having polymerizable double bonds. It can be prepared by copolymerization by a polymerization method. Examples of the polymerization method include radical polymerization or ionic polymerization in solution polymerization, bulk polymerization, semi-batch polymerization, suspension polymerization, coordination polymerization, living polymerization or emulsion polymerization. Among them, toluene, xylene, methyl isobutyl ketone, n-acetic acid, considering that it is possible to prepare a copolymer (A) having a low viscosity by improving the productivity and manufacturing workability of the silyl methacrylate-based copolymer (A) It is preferable to solution polymerize the monomers (i) to (iii) using an organic solvent such as butyl.

When the viscosity of the copolymer (A) is low, the amount of the solvent added to lower the viscosity of the antifouling coating composition can be reduced, thereby reducing the amount of VOC (Volatile Organic Compounds) of the antifouling coating composition. I can do it. In addition, due to the fact that the viscosity of the antifouling coating composition can be reduced, the coating workability of the coating composition and the appearance (leveling property) of the antifouling coating film can also be improved.

As a catalyst used for radical polymerization, a known one can be widely used, and for example, 2,2'-azobis(2-methylbutyronitrile as described in Japanese Patent Laid-Open No. 2001-151830) Azo compounds such as (AMBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-isobutyronitrile, benzoyl peroxide, t-butylperoxy And peroxides such as -2-ethylhexanoate, t-butylperoxybenzoate, and t-butylperoxyoctoate.

The proportion of each content (weight) of the structural units (1) to (3) contained in the copolymer (A) is identical to the proportion of the addition amount (weight) of the monomers (i) to (iii) provided in the polymerization reaction, respectively. Tend to Therefore, the "weight ratio (I)" and "the weight ratio (II)" can be adjusted to desired values based on the weight ratio of the monomers provided in the polymerization reaction.

2. Trimethylisobutenylcyclohexenecarboxylic acid (B)

The antifouling coating composition of the present invention promotes the dissolution of the antifouling agent from the antifouling coating film formed from the viewpoint that the coating film does not generate cracks when exposed to sunlight for a long period of time and when the composition contains an antifouling agent, in particular Trimethylisobutenylcyclohexenecarboxylic acid is contained as an essential component from the viewpoint of improving the static antifouling property of this coating film.

Examples of the trimethylisobutenylcyclohexene carboxylic acid (B) include reaction products of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which are 1,2,3- Trimethyl-5-(2-methylpropa-1-en-1-yl)cyclohexa-3-ene-1-carboxylic acid and 1,4,5-trimethyl-2-(2-methylpropa-1 -En-1-yl)cyclohexa-3-ene-1-carboxylic acid is the main component (85% or more).

In addition, in the antifouling coating composition of the present invention, the ratio of the content (WA) of the copolymer (A) to the content (WB) of the trimethylisobutenylcyclohexenecarboxylic acid (that is, WA/WB) is preferably 99/by weight. 1-40/60, More preferably, it is 95/5-50/50, More preferably, it is 90/10-55/45. When the weight ratio is in this range, there is an effect of increasing the combustibility (in other words, the consumption of the coating film) in the antifouling coating film formed of the antifouling coating composition, antifouling property (especially static antifouling property), crack resistance when the coating film is exposed to sunlight for a long time. Can be improved.

3. Rosin and/or monocarboxylic acid compound (C)

The antifouling coating composition of the present invention is a rosin and/or monocarboxylic acid compound (except trimethylisobutenylcyclohexenecarboxylic acid) to further improve the antifouling property of the antifouling coating film formed of the antifouling coating composition. ). Examples of rosin include rosin derivatives such as gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, and disproportionated rosin, and examples of the monocarboxylic acid compounds include aliphatic or alicyclic monocarboxylic acids and metal salts thereof. And the like. Specific examples of the monocarboxylic acid compound include naphthenic acid, versat acid, stearic acid, salicylic acid and salts thereof.

In the antifouling coating composition of the present invention, the content of the rosin and/or monocarboxylic acid compound (C) is 100% by weight of trimethylisobutenylcyclohexene carboxylic acid (B) in terms of coating film consumption, antifouling properties, and coating film properties. It is preferably 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, and more preferably 5 to 100 parts by weight with respect to parts.

4. Inorganic copper compound (D)

The antifouling coating composition of the present invention may further contain an inorganic copper compound (D) to further improve the antifouling properties of the antifouling coating film formed of the antifouling coating composition. As a copper compound, copper oxide, copper thiocyanate, cupronickel, etc. are mentioned, for example.

Further, in the antifouling coating composition of the present invention, the content of the inorganic copper compound (D) is preferably 10 to 800 parts by weight, more preferably 100 parts by weight of the copolymer (A) from the viewpoint of improving the long-term antifouling property of the antifouling coating film. Is 100 to 750 parts by weight. The content of the inorganic copper compound (D) is usually 0.1 to 70% by weight, preferably 0.1 to 60% by weight, relative to 100% by weight of the antifouling coating composition. Moreover, it is preferable that the inorganic copper compound (D) is a copper compound which does not contain 2% or more of metal copper as an impurity based on its total weight.

5. Organic Antifouling Agent (E)

The antifouling coating composition of the present invention may further contain an organic antifouling agent (E) in order to further improve the antifouling property of the antifouling coating film formed of the antifouling coating composition, particularly to improve the antifouling effect on vegetable marine organisms. The organic antifouling agent (E) is not particularly limited as long as it is an organic compound that imparts antifouling properties to the antifouling coating film.

As the organic antifouling agent (E), for example, metal pyrithiones such as copper pyrithione and zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bro Mo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, borane-nitrogen-based base adduct (pyridine triphenylborane, 4-isopropylpyridine diphenylmethyl Borane, etc.), N,N-dimethyl-N'-(3,4-dichlorophenyl)urea, N-(2,4,6-trichlorophenyl)maleimide, 2-methylthio-4-tert-butylamino -6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalnitrile, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbame

Yttrium, chloromethyl-n-octyldisulfide, N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide, tetraalkylthiuramdisulfide, zinc dimethyldithiocarbamate, zinc Ethylenebisdithiocarbamate, 2,3-dichloro-N-(2',6'-diethylphenyl)maleimide, 2,3-dichloro-N-(2'-ethyl-6'-methylphenyl)maleimide And the like.

In the antifouling coating composition of the present invention, the content of the organic antifouling agent (E) is a copolymer (A) from the viewpoint of improving the long-term antifouling property of the antifouling coating film formed of the antifouling coating composition and maintaining the water resistance of the coating film (in other words, maintaining the mechanical properties of the coating film). ) It is preferably 0.1 to 500 parts by weight, more preferably 0.5 to 300 parts by weight with respect to 100 parts by weight. In addition, the content of the organic antifouling agent (E) is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, relative to 100% by weight of the antifouling coating composition.

The antifouling coating composition of the present invention is further colored pigment (F), extender pigment (G), pigment dispersant (H), plasticizer (I), anti-sagging agent (J), anti-settling agent (K), dehydrating agent (L), solvent It may contain one or more additives selected from the group consisting of (M). These (F) to (M) will be described in detail below.

6. Coloring Pigment (F)

The antifouling coating composition of the present invention may contain a coloring pigment (F) to adjust the color tone of the antifouling coating film formed of the antifouling coating composition or to give an arbitrary color tone.

As a coloring pigment (F), various well-known organic or inorganic coloring pigments are mentioned. Carbon black, naphthol red, phthalocyanine blue, etc. are mentioned as an organic coloring pigment. In addition, examples of the inorganic pigments include bengala, barite powder, titanium bags, and yellow iron oxide.

In addition, the antifouling coating composition of the present invention may contain a coloring agent excluding a coloring pigment (F) such as a dye together with the coloring pigment (F) or in place of the coloring pigment (F).

In the antifouling coating composition of the present invention, the content of the coloring pigment (F) is a copolymer (from the viewpoint of improving the coloring property, hiding property, exposure discoloration, antifouling property, water resistance (mechanical properties) of the antifouling coating film formed of the antifouling coating composition. A) It is preferably 0.01 to 100 parts by weight, and more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight.

Moreover, content of coloring pigment (F) is 0.1-30 weight% normally with respect to 100 weight% of antifouling paint composition, Preferably it is about 0.1-20 weight%.

7. Constitutional pigment (G)

The extender pigment (G) can improve coating film properties such as crack resistance of the antifouling coating film formed of the antifouling coating composition.

As the extender pigment (G), for example, talc, silica (diatomaceous earth, acidic clay, etc.), mica, clay, potassium feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate , Barium sulfate, zinc sulfide, and the like. Among these, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar, and zinc oxide are preferred.

In the antifouling coating composition of the present invention, the content of the extender pigment (G) is a copolymer (A) from the viewpoint of improving the water resistance (mechanical properties), antifouling property, and coating film hydrolysis (consumable property) of the antifouling coating film formed of the antifouling coating composition. It is preferably 0.1 to 500 parts by weight, more preferably 50 to 300 parts by weight with respect to 100 parts by weight. In addition, the content of the extender pigment (G) is usually 0.1 to 50% by weight, preferably 0.1 to 40% by weight, relative to 100% by weight of the antifouling coating composition.

8. Pigment Dispersant (H)

Examples of the pigment dispersant (H) include various organic and inorganic pigment dispersants. Examples of the pigment dispersant include aliphatic amines or organic acids (for example, "Duomin TDO" (manufactured by LION Corporation), "Disperbyk101" (manufactured by BYK Corporation)).

The content of the pigment dispersant (H) in the antifouling coating composition of the present invention is based on 100 parts by weight of the copolymer (A) in view of the effect of reducing the viscosity of the antifouling coating composition or improving the color separation prevention effect of the antifouling coating composition. It is preferably 0.01 to 100 parts by weight, and more preferably 0.01 to 50 parts by weight. In addition, the content of the pigment dispersant (H) is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight relative to 100% by weight of the antifouling coating composition.

9. Plasticizer (I)

It is preferable that the antifouling coating composition of the present invention contains a plasticizer (I) in order to improve the crack resistance of the resulting antifouling coating film. Examples of the plasticizer (I) include paraffin chloride (also referred to as chlorinated paraffin), petroleum resins, ketone resins, TCP (tricrediyl phosphate), polyvinylethyl ether, and dialkyl phthalates. From the viewpoint of improving the water resistance (mechanical properties) of the antifouling coating film formed from the antifouling coating composition and the hydrolysis property (consuming property) of the coating film, among them, paraffin chloride (paraffin chloride), petroleum resins, and ketone resins are preferable. . The plasticizer (I) may be used alone or in combination of two or more.

As a specific example of paraffin chloride, "Toyoparax 150", "Toyoparax A-70" (all are manufactured by Tosoh Corporation), etc. are mentioned.

Further, examples of the petroleum resins include C5, C9, styrene, dichloropentadiene, and hydrogenated products thereof.

As a specific example of petroleum resins, "Quinton 1500", "Quinton 1700" (all are manufactured by Japan Xeon Corporation), etc. are mentioned.

In the antifouling coating composition of the present invention, the content of the plasticizer (I) is a copolymer (A) 100 from the viewpoint of improving the coating film hydrolysis property (consumable property), antifouling property and water resistance (mechanical properties) of the antifouling coating film formed of the antifouling coating composition. It is preferably 0.1 to 300 parts by weight, more preferably 0.1 to 200 parts by weight, and even more preferably 0.1 to 150 parts by weight with respect to parts by weight.

In addition, the content of the plasticizer (I) is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, relative to 100% by weight of the antifouling coating composition.

10. Sagging inhibitor (J)

The antifouling coating composition of the present invention may contain an anti-sagging agent (J) (also referred to as a flow-preventing agent) from the viewpoint of reducing the occurrence of sagging due to the coating composition when coating the substrate using the anti-fouling coating composition. .

Examples of the anti-sagging agent (J) include amide wax, hydrogenated castor oil wax, mixtures thereof, and synthetic fine silica (Aerosil (registered trademark)), and the like. Among them, amide wax or synthetic fine silica is preferable. When amide wax or synthetic fine silica is used as the anti-sagging agent (J), the storage stability of the antifouling coating composition is improved, and after the antifouling coating film is formed, a coating film comprising the same antifouling coating composition or a different coating composition on the antifouling coating film (that is, When the top coat film is formed, it is possible to prevent a decrease in adhesion between the antifouling film and the top coat film (also referred to as interlayer adhesion or layering property).

In addition, as a commercial product of the anti-sagging agent (J), there may be mentioned "disparon A630-20X" (manufactured by Kusumoto Chemicals Co., Ltd.) or "ASAT-250F" (manufactured by Ito Oil Chemical Co., Ltd.).

In the antifouling coating composition of the present invention, the content of the anti-sagging agent (J) is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the copolymer (A). In addition, the content of the anti-sagging agent (J) is usually 0.1 to 20% by weight, preferably 0.1 to 10% by weight, relative to 100% by weight of the antifouling coating composition. When the content of the anti-sagging agent (J) is set in such a range, the storage stability of the antifouling coating composition is improved, and after the antifouling coating film is formed, a coating film comprising the same antifouling coating composition or a different coating composition on the antifouling coating film (top coating film) ) Is formed, it becomes possible to prevent the deterioration of adhesion (interlayer adhesion, layering property) between the antifouling coating film and the top coating film.

11. Anti-settling agent (K)

The antifouling coating composition of the present invention may contain a sedimentation-preventing agent (K) from the viewpoint of preventing generation of sediment in the coating composition during storage and also improving agitation.

Examples of the anti-settling agent (K) include stearates of Al, Ca, or Zn, polyethylene wax, and polyethylene oxide wax, and among them, polyethylene oxide wax is preferred. As a commercial item of an oxidized polyethylene wax, "disparon 4200-20X" (manufactured by Kusumoto Chemicals Co., Ltd.) is exemplified.

The content of the anti-settling agent (K) in the antifouling coating composition of the present invention is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the copolymer (A). In addition, the content of the anti-settling agent (K) is usually 0.1 to 20% by weight, preferably 0.1 to 10% by weight, relative to 100% by weight of the antifouling coating composition. When the content of the anti-settling agent (K) is set in such a range, the storage stability of the antifouling coating composition is improved, and after the antifouling coating film is formed, a coating film comprising the same antifouling coating composition or a different coating composition on the antifouling coating film (top coating film) ) Is formed, it becomes possible to prevent the deterioration of adhesion (interlayer adhesion, layering property) between the antifouling coating film and the top coating film.

12. Dehydrating agent (L)

Since the antifouling coating composition of the present invention contains a copolymer (A) having good storage stability, it has excellent storage stability, but it is possible to obtain more excellent long-term storage stability by adding a dehydrating agent (L) if necessary. Examples of the dehydrating agent (L) include inorganic dehydrating agents and organic dehydrating agents.

As the inorganic dehydrating agent, synthetic zeolite, anhydrous gypsum and semi-hydrate gypsum are preferable. Examples of the organic dehydrating agent include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane and trimethylethoxysilane, and polyalkoxysilane condensates thereof And alkyl orthoformates such as methyl orthoformate and ethyl orthoformate.

The dehydrating agent (L) is preferably included in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the copolymer (A).

13. Solvent (M)

The antifouling coating composition of the present invention may contain a solvent (M) such as water or an organic solvent, if necessary, in order to improve the dispersibility of the copolymer (A) or the like and to adjust the viscosity of the composition. The solvent (M) may be a solvent used when preparing the copolymer (A), or a solvent added separately when mixing the copolymer (A) and other components as necessary.

Examples of the organic solvent include aromatic organic solvents such as xylene, toluene, and ethylbenzene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatics such as ethanol, isopropyl alcohol, n-butanol, and isobutanol (carbon number 1 ~10, preferably about 2 to 5) monohydric alcohols; ester solvents such as ethyl acetate and butyl acetate; and the like.

When the content of the solvent (M) in the antifouling coating composition of the present invention is 100% by weight, the antifouling coating composition is usually 20 to 80% by weight, preferably 30 to 70% by weight.

(Method of manufacturing antifouling coating composition)

The antifouling coating composition of the present invention can be produced by appropriately using a known method. For example, the copolymer (A), trimethylisobutenylcyclohexene carboxylic acid (B) and other components, if necessary, are added to the stirring vessel at once or in any order, and prepared by mixing with known stirring and mixing means. Can.

In addition, after mixing each component, a sagging inhibitor (J) (amide wax (e.g., disparon A630-20X, etc.)) is added and dispersed (e.g., the mixture is stirred for about 10 to 20 minutes). It is preferable to prepare an antifouling coating composition). This is because the occurrence of sagging can be reduced when the obtained antifouling coating composition is applied to a substrate.

As the stirring and mixing means, high speed dispersers, sand grind mills, basket mills, ball mills, three roll mills, los mixers, planetary mixers, all-purpose Shinagawa stirrers, etc. may be mentioned.

[Antifouling film and antifouling material]

The antifouling coating film of the present invention is composed of the solid content of the antifouling coating composition of the present invention. The antifouling coating film of the present invention is

It is formed of an antifouling coating composition, for example, if the antifouling coating composition contains a solvent (M), the antifouling coating composition of the present invention applied on a substrate, for example, using a drying means such as natural drying or heater It can be formed by curing (that is, by removing the solvent (M)).

In addition, the antifouling material of the present invention is composed of a substrate and the antifouling coating film of the present invention formed on the surface of the substrate, and the antifouling coating composition of the present invention is described as a substrate (the substrate is also an antifouling object or an object to be coated). Applying or impregnating with a coating means such as air spray, airless spray, brush, roller, etc., or impregnating the coating composition impregnated with the substrate, such as natural drying (i.e., drying at a temperature around room temperature) or heater It can be produced by drying and curing using a drying means to form an antifouling coating on the substrate.

Alternatively, the antifouling material of the present invention can also be produced by forming an antifouling coating film on the surface of the temporary substrate from the antifouling coating composition of the present invention, removing the antifouling coating film from the temporary substrate, and attaching the antifouling coating film to the substrate for antifouling. At this time, an antifouling coating film may be applied to the substrate through the adhesive layer.

The substrate is not particularly limited, but is preferably a substrate that comes into contact with seawater or freshwater, specifically, water supply or drainage of various power plants (thermal power, nuclear power) or Manan Road, submarine tunnels, port facilities, or various oceans such as canals or waterways. Or underwater structures such as sludge diffusion prevention membranes used in river civil works, ship outer plates (especially the seabed part from the ship's draft), and fishery materials (fishing gear such as ropes, fishing nets, floats or buoys).

Examples of materials for these substrates include steel, aluminum, wood, and FRP in the case of shipboards, natural or synthetic fibers in the case of fishing nets, and synthetic resins in the case of floats and buoys. The material is not particularly limited as long as it is a substrate that is required to have antifouling properties or the like in water.

Antifouling paint composition of the present invention once or multiple times in the same manner as described above on the surface of the primer-treated substrate after primers such as anti-corrosive paints are usually applied to the surface of steel substrates, especially when the substrates are on the surface of these substrates. (Anti-fouling paint) is applied, and coating or impregnation (impregnation is performed especially when the base material is a fishing net, etc.) is cured to form an anti-fouling coating composition to form an antifouling coating film, stalagmites, barnacles, greens, sherpula, oysters, large bundles. It has excellent properties (antifouling properties, particularly static antifouling properties) that prevents aquatic organisms such as moss from adhering over a long period of time, and is particularly antifouling components in antifouling coating films (for example, the inorganic copper compound (D), the organic antifouling agent (E)) ) Is included, the antifouling component may be sustained over a long period of time.

Usually, the surface of the base material may have a primer treatment or may have a layer formed of various binder paints. When the substrate is an outer shell of a ship (particularly its bottom), aquatic structures, etc., the antifouling coating composition is applied multiple times on the surface of the substrate (also referred to as thick film. The dry film thickness of the formed coating film is about 100 to 600 μm). The anti-fouling material obtained by .) exhibits good anti-fouling properties and adequate flexibility and excellent crack resistance.

In manufacturing the antifouling material, when the substrate is a steel plate or a fishing net with a deteriorated antifouling coating film, the antifouling coating composition of the present invention may be directly applied to the surface, or when the substrate is a fishing net or the like, the present invention The antifouling coating composition may be impregnated, and when the base material is a steel sheet, after forming a base layer by applying a base material such as a rust inhibitor or primer to the base surface in advance, the present invention is applied to the surface of the base layer. You may apply the antifouling coating composition of. In addition, the antifouling coating film of the present invention may be further formed on the surface of a substrate on which the antifouling coating film of the present invention or a conventional antifouling coating film is formed for a plurality of purposes.

In addition, the thickness of the antifouling coating film of the present invention formed by a single coating operation is not particularly limited, but when the substrate is a ship or an underwater structure, it is, for example, about 30 to 250 μm.

The underwater structure having the antifouling coating film of the present invention can maintain the function of the underwater structure for a long time due to being able to prevent aquatic organisms from being attached over a long period of time. In addition, the fishing net having the anti-fouling coating film of the present invention can prevent clogging of the network due to the fact that it is possible to prevent adhesion of aquatic organisms as well as less concern about environmental pollution.

Example

The present invention will be described in more detail based on examples below, but the present invention is not limited by these examples.

[Assessment Methods]

Evaluation of the copolymer, coating composition, coating film, etc. which will be described later was performed as follows.

(1) Content of solid content in polymer solution

1.5 g (X1 (g)) of the polymer solution was maintained in a constant temperature bath at 1 atm and 108° C. for 3 hours to remove volatiles to obtain solids (nonvolatiles). Subsequently, the amount (X2(g)) of the remaining solid content (non-volatile content) was measured, and the content (%) of the solid content contained in the polymer solution was calculated based on the following formula.

Content of solid content (%) = X2 / X1 x 100

(2) Average molecular weight of the copolymer

The weight average molecular weight (Mw) of the copolymer was measured using GPC (gel permeation chromatography) under the following conditions.

GPC conditions

Apparatus ："HLC-8120GPC" (manufactured by Tosoh Corporation)

Column: "SuperH2000+H4000" (manufactured by Tosoh Corporation, 6 mm (inner diameter), each 15 cm (length))

Eluent: Tetrahydrofuran (THF)

Flow rate: 0.500 ml/min

Detector ：RI

Column thermostat temperature: 40℃

Standard substance: Polystyrene

Sample preparation method: A small amount of calcium chloride was added to the polymer solution prepared in each production example, dehydrated, and the filtrate obtained by filtration through a membrane filter was used as a GPC measurement sample.

(3) Viscosity of polymer solution

The viscosity (unit: mPa·s) of the polymer solution at a liquid temperature of 25° C. was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).

(4) Coating film deterioration test (evaluation of coating film appearance and adhesion)

Using an applicator on a sandblast plate (150 mm×70 mm×1.6 mm), use an applicator to make the epoxy film (epoxy AC paint, trade name "Banno 500", manufactured by Chugoku Paint Co., Ltd.) to 150 µm in dry film thickness. Applying and curing to form a cured coating film, and then using an applicator on the cured coating film, a vinyl binder paint (trade name "Silvax SQ-K", manufactured by Chugoku Paint Co., Ltd.) to a dry film thickness of 40 mu m. It was coated to produce a test plate.

Subsequently, on the test plate (i.e., on the surface of the dry coating film formed of a vinyl binder coating), each coating composition of Examples and Comparative Examples was coated with a dry film thickness of 150 µm using an applicator and dried at 23° C. for 1 day to prevent stain coating. Was formed, and further coated on the surface of the antifouling film with a dry film thickness of 150 μm, dried at 23° C. for 7 days to form an antifouling film to prepare a test plate with an antifouling film.

The test plate with antifouling coating film was immersed in artificial seawater at 50°C, and the appearance and adhesion of the coating film were examined based on the following evaluation criteria at intervals of one month from the start of immersion.

Appearance evaluation

The degree of crack was visually observed on the surface of the antifouling film of the test plate with the antifouling film, and the amount of crack was graded as shown in the table below in accordance with JIS K5600-8-4.

Adhesion evaluation

Nine squares were produced by drawing four cutting lines each in the horizontal and vertical directions at 4 mm intervals on the surface of the anti-fouling coating of the test plate with anti-fouling coating using an NT cutter, and cello tape (registered trademark) was applied to the surface of the square coating on which the square was produced. After pressing, the cello tape was quickly peeled off and the squares were observed. Subsequently, the area of nine squares was 100%, and the area of the coating film remaining in the squares after the peeling operation (hereinafter referred to as "remaining area of the coating") was calculated (%), and the following evaluation criteria were calculated. The adhesion was evaluated on the basis.

[Evaluation criteria of adhesion]

0: The remaining area of the coating film is 95% or more.

1: The remaining area of the coating film is less than 75 to 95%.

2: The remaining area of the coating film is less than 50 to 75%.

3: The remaining area of the coating film is less than 50%.

(5) Exposure test (evaluation of coating film appearance)

Using an applicator on a sandblast plate (150 mm×70 mm×1.6 mm), use an applicator to make the epoxy film (epoxy AC paint, trade name "Banno 500", manufactured by Chugoku Paint Co., Ltd.) to be 150 mu m in dry film thickness. Applying and curing to form a cured coating film, and then using an applicator on the cured coating film, a vinyl binder paint (trade name "Silvax SQ-K", manufactured by Chugoku Paint Co., Ltd.) to a dry film thickness of 40 mu m. It was coated and dried at room temperature for 1 day to prepare a test plate.

Subsequently, the next day, on the test plate (ie, on the surface of the cured coating film formed of a vinyl binder coating), each coating composition of Examples and Comparative Examples was coated to a dry film thickness of 150 μm using an applicator and dried at 23° C. for 1 day. An antifouling coating film was formed, and the coating composition was applied to the surface of the antifouling coating film to have a dry film thickness of 150 μm, dried at 23° C. for 7 days to form an antifouling coating film, thereby preparing a test plate with an antifouling coating film.

This test board with antifouling film was exposed by placing the antifouling film side up on an outdoor exposure stand installed in the site of Chugoku Paints Co., Ltd. in Otake City, Hiroshima, and inclining at an angle of 45° to the south facing the surface. The state of the coating film 1, 3, and 6 months after the start of exposure was observed.

(6) Political antifouling test

Using an applicator on a sand blast plate (300 mm×100 mm×3.2 mm), make the epoxy film (epoxy AC paint, trade name "Banno 500", manufactured by Chugoku Paint Co., Ltd.) to 150 µm in dry film thickness. After coating and curing, a cured coating film was formed, and then a vinyl binder paint (trade name "Silbags SQ-K", manufactured by Chugoku Paint Co., Ltd.) was applied on the cured coating film to a dry film thickness of 40 µm to be applied indoors. It was dried for 1 day to prepare a test plate.

Subsequently, on the next day on the test plate (i.e., on the surface of the dry coating film formed of a vinyl binder coating), each coating composition of Examples and Comparative Examples was coated to a dry film thickness of 150 μm using an applicator and dried at 23° C. for 1 day to prevent contamination. A coating film was formed, and further, the coating composition was applied to the surface of the antifouling film so as to have a dry film thickness of 150 μm, dried at 23° C. for 7 days to form an antifouling film to prepare a test plate with an antifouling film.

The area of the area where the aquatic organisms on the antifouling coating film is attached when the test plate with the antifouling coating film is immersed in Nagasaki Bay and the total area of the antifouling coating film of the test plate is set to 100% at intervals of one month from the start of immersion. It is also referred to as "adhesive area.") (%) was measured, and the political antifouling property was evaluated based on the following evaluation criteria.

[Evaluation standard]

0: The adhesion area is 0%.

0.5: The adhesion area is less than 0-10%.

1: The adhesion area is less than 10-20%.

2: The adhesion area is less than 20-30%.

3: The adhesion area is less than 30-40%.

4: The adhesion area is less than 40-50%.

5: The adhesion area is 50 to 100%.

(7) Coating film consumption test

Each coating composition obtained in Examples and Comparative Examples was coated on a hard vinyl chloride plate (50 mm×50 mm×1.5 mm) with an applicator with a dry film thickness of 150 μm and dried to prepare a test plate. The obtained test plate was mounted on a rotating drum, and the rotating drum was immersed in seawater and rotated at a speed of 15 knots under the condition of seawater temperature of 25°C, measuring the film thickness consumed for 12 months at intervals of 1 month from the start of immersion to determine the monthly average film consumption I got it.

[Production Example A1]

Add 53 parts by weight of xylene to a reaction vessel equipped with a stirrer, reflux cooler, thermometer, nitrogen introduction tube and dropping funnel, and heat it until the temperature of xylene in the reaction vessel reaches 85° C. under normal pressure while stirring xylene with a stirrer under a nitrogen atmosphere. Did. While maintaining the temperature of xylene in the reaction vessel at 85°C, 60 parts by weight of TIPSMA (triisopropylsilyl methacrylate), 10 parts by weight of MEMA (2-methoxyethyl methacrylate) and 20 parts of MMA (methyl methacrylate) Part, a monomer mixture consisting of 10 parts by weight of BA (butyl acrylate) and 1 part by weight of AMBN (2,2'-azobis (2-methylbutyronitrile)) was added into the reaction vessel over 2 hours using a dropping funnel. Did.

Subsequently, 0.5 part by weight of t-butylperoxyoctoate was further added to the reaction vessel, and stirring of the liquid in the reaction vessel was continued for 2 hours with a stirrer while maintaining the liquid temperature in the reaction vessel at 85°C under normal pressure. Further, the liquid temperature in the reaction vessel was raised from 85°C to 110°C, and stirring was performed for 1 hour. Then, 14 parts by weight of xylene was added to the reaction vessel, and the temperature of the liquid in the reaction vessel was lowered to stop stirring when the temperature reached 40°C. A polymer solution A1 containing a methacrylate copolymer was obtained.

Various properties of the polymer solution A1 were measured. Table 2 shows the results.

Table 2

[Production Examples A2 to A9 and Production Examples B1 to B2]

A polymer solution containing a silyl (meth)acrylate copolymer was prepared in the same manner as in Production Example A1, except that a monomer mixture having a composition shown in Table 2 or 3 was used instead of the monomer mixture used in Production Example A1. Prepared, various physical properties were measured. The results are shown in Tables 2 and 3. In Tables 2 and 3, polymer solutions A2 to A9 and polymer solutions B1 to B2 represent solutions containing the copolymers obtained in Production Examples A2 to A9 and Production Examples B1 to B2, respectively. In addition, MEA and EA represent 2-methoxyethylacrylate and ethylacrylate, respectively.

Table 3

[Example 1]

<Preparation of antifouling coating composition>

In a plastic container (capacity: 1,000 ml), 17.8 parts by weight of xylene as a solvent, trimethylisobutenylcyclohexenecarboxylic acid (1,2,3-trimethyl-5-(2-methylpropa-1-en-1-yl) Cyclohexa-3-ene-1-carboxylic acid and 1,4,5-trimethyl-2-(2-methylpropa-1-en-1-yl)cyclohexa-3-ene-1-carboxylic acid 6.4 parts by weight of the reaction product (50% xylene solution) of 2,6-dimethylocta-2,4,6-triene and methacrylic acid as a main component (85% or more) and 16 parts by weight of polymer solution A1 The mixture was then mixed using a paint shaker until each component was uniformly dispersed or dissolved. Subsequently, an additive (1) (3 parts by weight of talc FC-1, 4 parts by weight of zinc oxide (zinc oxide 3), 45 parts by weight of copper oxide NC301, 0.3 parts by weight of Novopalm F5RK, titanium bag R in an additional plastic container 2 parts by weight of -5N, 1 part by weight of copper-o-madin (copper pyrithione) and 2 parts by weight of disparon 4200-20X) were added and stirred using a paint shaker for 1 hour to disperse these components.

After dispersion, 2.5 parts by weight of Disparon A630-20X was further added, stirred using a paint shaker for 20 minutes, and then the mixture was filtered through a filter screen (mesh diameter: 80 mesh) to remove residue and filtrate (paint composition A1). Got Table 4 shows the sources of the various additives.

Various properties of the obtained coating composition A1 were evaluated. Table 7 shows the results.

[Examples 2 to 19 and Comparative Examples 1 to 4]

A coating composition was prepared in the same manner as in Example 1, except that the types and amounts of the blending components were changed as shown in Tables 5 to 6, and various physical properties were measured. The results are shown in Tables 7-8.

In addition, the coating compositions A2 to A19 and the coating compositions B1 to B4 shown in Tables 5 to 8 represent the coating compositions obtained in Examples 2 to 19 and Comparative Examples 1 to 4, respectively.

Table 4

Claims (1)

Claim 1
From structural units (1) and 2-methoxyethyl (meth)acrylates (ii) derived from polypropylene glycol, polyisocyanate compounds, hydroxyl-containing (meth)acrylate compounds and triisopropylsilyl methacrylate (i) Structure derived from structural unit (2) derived, and other monomers having a polymerizable double bond (except triisopropylsilyl methacrylate and 2-methoxyethyl (meth)acrylate)) (iii) A coating composition for a ballast water treatment apparatus comprising a silyl methacrylate copolymer (A) containing a unit (3) and a trimethylisobutenylcyclohexenecarboxylic acid (B).
Claim 2
According to claim 1,
The other monomer (iii) is a paint composition for a ballast water treatment device of the esters or carboxylic acids.
Claim 3
According to claim 1,
Coating composition for a ballast water treatment apparatus having a ratio of 30 to 70% by weight of the structural unit (1) in the silyl methacrylate copolymer (A).
Claim 4
According to claim 1,
Coating composition for ballast water treatment device in which the proportion of the structural unit (2) in the silyl methacrylate copolymer (A) is 5 to 40% by weight
Claim 5
According to claim 1,
The ratio (WA/WB) of the content (WA) of the silyl methacrylate copolymer (A) and the content (WB) of the trimethylisobutenylcyclohexenecarboxylic acid (B) is 99/1 to 40 by weight. Coating composition for ballast water treatment equipment for /60 people.

.