JP2022069873A - Antifouling coating composition - Google Patents

Abstract

To provide an antifouling coating composition that can exhibit antifouling effect even on a low-speed ship while keeping a stable coating dissolution rate for a long time, which has been difficult in the conventional art, the antifouling coating composition having high long-term time storage stability.SOLUTION: An antifouling coating composition contains a polymer A and a component B, the polymer A being a copolymer of a monomer (a) and an ethylenic unsaturated monomer (b), different from the monomer (a), the monomer (a) represented by the general formula (1), and the component B being a calcium salt of rosin or a rosin derivative.SELECTED DRAWING: None

Description

The present invention relates to an antifouling coating composition.

Conventionally, a triorganosilyl group-containing copolymer having low toxicity and low environmental load has been developed and used as an antifouling paint.

When a copolymer obtained by copolymerizing a silyl ester-containing monomer in which an alkyl group is linear, such as a tri-n-butyl silyl ester-containing copolymer, is used as the triorganosilyl group-containing copolymer. Since the hydrolysis rate of the coating film is very fast and the water resistance is poor, it is difficult to control the dissolution rate of the coating film. Therefore, it has been studied to use a copolymer obtained by copolymerizing a triorganosilyl ester-containing monomer in which an alkyl group such as an isopropyl group or a t-butyl group is branched (Patent Documents 1 to 7). However, when the coating composition containing the copolymer is used, it dissolves in seawater at a constant rate in the initial stage, but when the dissolution rate of the coating film gradually increases and a long period of time elapses, the coating film becomes The dissolution rate becomes too high, making paint design difficult.

Therefore, attempts have been made to adjust the dissolution rate of the coating film by using the triorganosilyl ester-containing copolymer in combination with a resin acid such as rosin (Patent Documents 8 to 12). However, in recent years, the ship speed has decreased remarkably, and a more highly soluble antifouling paint has been desired. Therefore, attempts have been made to increase the hydrophilicity of the coating film and increase the dissolution of the coating film. On the other hand, if a large amount of hydrophilic monomer is added, the physical characteristics of the coating film tend to deteriorate. Specifically, as the water permeability to the coating film increases, problems such as cracks, blister, and peeling are likely to occur over time.

Further, a coating composition using the triorganosilyl ester-containing copolymer in combination with a metal salt of rosin has also been proposed. However, with zinc salts and copper salts that are generally used, the dissolution of the coating film is not stable, and proper drug release cannot be achieved. Further, when immersed in seawater for a long period of time, there is a problem that coating film abnormalities such as hair cracks (fine cracks) occur, and as a result, the antifouling performance is deteriorated.

Japanese Unexamined Patent Publication No. 7-102193 Japanese Unexamined Patent Publication No. 8-269389 Japanese Unexamined Patent Publication No. 2001-26621 Japanese Unexamined Patent Publication No. 2001-26729 Japanese Unexamined Patent Publication No. 2001-226440 JP-A-2005-35881 Japanese Patent Application Laid-Open No. 2005-082725 Japanese Unexamined Patent Publication No. 10-30071 Japanese Unexamined Patent Publication No. 11-116857 JP-A-2002-53796 JP-A-2002-53797 Japanese Patent Application Laid-Open No. 2003-261816

However, even if the technique of the above-mentioned patent document is adopted, it is difficult to maintain a stable coating film dissolution rate for a long period of time and to exhibit antifouling performance for a ship navigating at a low speed. Further, depending on the coating composition, when it is stored at a high temperature for a long period of time, it causes gelation or solidification, and there is a problem in stability.

The present invention has been made in view of such circumstances, and even on a low-speed ship, which has been difficult until now, a stable coating film dissolution rate can be maintained for a long period of time, and antifouling performance can be exhibited for a long period of time. It provides an antifouling coating composition having high storage stability.

According to the present invention, the antifouling coating composition containing the polymer A and the component B, wherein the polymer A is ethylenically non-monomer other than the monomer (a) and the monomer (a). It is a copolymer with the saturated monomer (b), the monomer (a) is represented by the general formula (1), and the component B is a calcium salt of rosin or a rosin derivative, which is an antifouling agent. A coating composition is provided.

As a result of diligent research to solve the above problems, the present inventor has found that the composition containing the polymer A and the component B can solve the above problems, and has completed the present invention.

Hereinafter, the present invention will be described in detail.
1. 1. Antifouling paint composition The antifouling paint composition of the present invention contains polymer A and component B.

1-1. Polymer A
The polymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a). Polymer A contains monomeric units derived from the monomers (a) and (b).

（式中、Ｒ^１はメチル基、Ｒ^２～Ｒ^４はそれぞれ同一又は異なって炭素数３～８の分岐アルキル基又はフェニル基を示す） <Monomer (a)>
The monomer (a) is a triorganosilyl methacrylate monomer and is represented by the general formula (1).

(In the formula, R ¹ indicates a methyl group, and R ² to R ⁴ indicate the same or different branched alkyl group or phenyl group having 3 to 8 carbon atoms, respectively).

Examples of the branched alkyl group having 3 to 8 carbon atoms of ^R2 to ^R4 include isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group and 1-methyl. Pentyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methyl Examples thereof include a heptyl group, a 2-methylbutyl group, a 2-ethylbutyl group, a 2,2-dimethylpropyl group, a cyclohexylmethyl group, a 2-ethylhexyl group, a 2-propylpentyl group and a 3-methylpentyl group. Preferred as ^R2 to ^R4 are an isopropyl group, an s-butyl group, a t-butyl group, a phenyl group, and a 2-ethylhexyl group. Particularly preferred are an isopropyl group and a 2-ethylhexyl group.

Examples of the monomer (a) include triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tris-butylsilyl methacrylate, triisopentylsilyl methacrylate, triphenylsilyl methacrylate, diisopropylphenylsilyl methacrylate, and methacrylic acid. Diisopropylisobutylsilylate acid, diisopropyls-butylsilylmethacrylate, diisopropylisopentylsilyl methacrylate, isopropyldiisobutylsilylacrylate silyl, isopropyldiisopropylmethacrylate s-butylsilyl, t-butyldiisoputylsilyl methacrylate, t-butyldiisomethacrylate Pentylsilyl, t-butyldiphenylsilyl methacrylate, diisopropyltexylsilylmethacrylate, diisopropylcyclohexylsilylmethacrylate, tricyclohexylsilylmethacrylate, tri-1,1-dimethylpentylsilyl silylate, tri2,2-dimethylpropyl methacrylate Examples thereof include silyl, tricyclohexylmethylsilyl methacrylate, diisopropylcyclohexylmethylsilyl methacrylate, tri2-ethylhexylsilyl methacrylate, tri2-propylpentylsilyl methacrylate and the like. Preferred examples thereof include triisopropylsilyl methacrylate, tris-butylsilyl methacrylate, t-butyldiphenylsilyl methacrylate, tri2-ethylhexylsilyl methacrylate and the like. These monomers (a) can be used alone or in combination of two or more.

<Monomer (b)>
The monomer (b) is an ethylenically unsaturated monomer other than the monomer (a), and is, for example, a (meth) acrylic acid ester, a vinyl compound, an aromatic compound, a dialkyl ester compound of a dibasic acid, or the like. Can be mentioned. In addition, in this specification, (meth) acrylic acid ester means acrylic acid ester, or methacrylic acid ester.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and (meth). ) Acrylic acid 21 ethylhexyl, (meth) acrylate lauryl, (meth) acrylate 2-methoxyethyl, (meth) acrylate 2-methoxypropyl, (meth) acrylate 4-methoxybutyl, (meth) acrylate benzyl , (Meta) phenyl acrylate, (meth) 2-ethoxyethyl acrylate, (meth) propylene glycol monomethyl acrylate, (meth) 2-hydroxyethyl acrylate, (meth) 2-hydroxypropyl acrylate, (meth) Glycidyl acrylate, (meth) flufuryl acrylate, (meth) tetrahydroflufuryl acrylate, (meth) dimethylaminoethyl acrylate, (meth) diethylaminoethyl acrylate,
2- [2- (2-Hydroxyethoxy) ethoxy] ethoxy] ethyl methacrylate, mono (2- (meth) acryloyloxyethyl), N- (3-dimethylaminopropyl) (meth) acrylamide, (meth) 2- [2- (2-Methoxyethoxy) ethoxy] ethyl acrylic acid, N, N'-dimethyl (meth) acrylamide, 2- (2-methoxyethoxy) ethyl (meth) acrylic acid, (meth) acrylic acid, acrylic Hydropyl acrylate, 2- (acetoacetyloxy) ethyl methacrylate, 2- (2-hydroxyethoxy) ethyl methacrylate, N-vinyl-2-pyrrolidone, 2- [2- (2-ethoxyethoxy) ethoxy] acrylate ethyl,
4-Hydroxybutyl acrylate glycidyl ether, N-isopolopylacrylamide, 2- (dimethylamino) ethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, Acrylic acid esters such as 3-chloro-2-hydroxypropyl acrylate, 2- [2- (2-ethoxyethoxy) ethoxy] ethyl methacrylate, N, N'-diethylacrylamide, 3-methoxybutyl acrylate, etc.
And so on.

Examples of the vinyl compound include vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone. Be done.

Examples of the aromatic compound include styrene, vinyltoluene, α-methylstyrene and the like.

Examples of the dialkyl ester compound of dibasic acid include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.

In the present invention, these monomers (b) can be used alone or in two or more kinds. In particular, as the monomer (b), (meth) acrylic acid ester is preferable from the viewpoint of the physical properties of the coating film, and methyl methacrylate, butyl (meth) acrylate, and (meth) acrylic acid are particularly preferable from the viewpoint of crack resistance. Isobutyl acrylate, t-butyl (meth) acrylate, 21-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , (Meta) glycidyl acrylate, (meth) flufuryl acrylate, tetrahydrofurfuryl (meth) acrylate and the like are more preferred.

The ratio of the monomer (a) to the total of the monomers (a) and the monomer (b) is preferably 5 to 75% by mass, more preferably 30 to 60% by mass. Specifically, the content of the monomer (a) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75% by mass. , It may be within the range between any two of the numerical values exemplified here.

When the polymer A within the above range is used as the coating composition of the present invention, the solubility of the coating film is particularly good.

The weight average molecular weight (Mw) of the polymer A is preferably 5000 to 300,000. This is because if the molecular weight is less than 5,000, the coating film of the antifouling paint becomes fragile and easily peels or cracks, and if it exceeds 300,000, the viscosity of the polymer solution increases and handling becomes difficult. Specifically, this Mw is, for example, 5000, 10000, 20000, 30000, 40,000, 50000, 60000, 70000, 80000, 90000, 100000, 200,000, 300,000, and is between any two of the numerical values exemplified here. It may be within the range.

Examples of the method for measuring Mw include gel permeation chromatography (GPC method). When Mw is measured by GPC, Mw is displayed as a value (polystyrene conversion value) obtained by creating and measuring a calibration curve using polystyrene as a standard substance.

The glass transition temperature (Tg) of the polymer A is preferably about 30 to 80 ° C, more preferably about 35 to 70 ° C. When the Tg is about 30 to 80 ° C., the hardness of the coating film is hardly affected by the water temperature and the air temperature, and the appropriate hardness and toughness can be maintained for a long period of time, so that cold flow, cracks, peeling, etc. The coating film abnormality is unlikely to occur.

The polymer A is a copolymer of a random copolymer of the monomer (a) and the monomer (b), an alternating copolymer, a periodic copolymer, or a block copolymer. May be good.

The polymer A can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.

Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethylvaleronitrile). ), Dimethyl-2,2'-azobisisobutyrate, dimethyl2,2'-azobisisobutyrate, 2,2'-azobis (N-butyl-2-methylpropionamide and other azo compounds; benzoylper Oxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , Di-t-hexyl peroxide, t-butylperoxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t- Amilperoxyneodecanoate, t-hexylperoxypivalate, t-amylperoxypivalate, peroxides such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, etc. These polymerization initiators can be used alone or in combination of two or more. The polymerization initiators include, in particular, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2). -Methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate is preferable. The molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.

Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, non-aqueous dispersion polymerization and the like. Of these, solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that the polymer A can be obtained easily and accurately.

In the polymerization reaction, an organic solvent may be used if necessary. The organic solvent is not particularly limited, but for example, an aromatic hydrocarbon solvent such as xylene and toluene; an aliphatic hydrocarbon solvent; an ester solvent such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl. Alcohol-based solvents such as alcohol, butyl alcohol and propylene glycol monomethyl ether; ether-based solvents such as dioxane, diethyl ether and dibutyl ether; ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned.

Among them, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene and xylene are preferable. These solvents can be used alone or in combination of two or more.

The reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually 50 to 160 ° C, preferably 60 to 150 ° C.

The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

1-2. Ingredient B
Component B is a calcium salt of rosin or a rosin derivative. Examples of the rosin include tall rosin, gum rosin, and wood rosin, and examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin obtained by reacting rosin with maleic anhydride, formylated rosin, and polymerized rosin.

The calcium salt of the rosin or the rosin derivative can be prepared by a known method. For example, a method of reacting the rosin or a rosin derivative with a calcium compound while heating in a solvent (for example, at about 70 to 80 ° C.) can be mentioned.

Examples of the calcium compound include calcium hydroxide and calcium oxide. These can be used alone or in combination of two or more.

The amount of the calcium compound used is not particularly limited, and all of the resin acids may be set so as to form a calcium salt.

The solvent is not particularly limited as long as it does not inhibit the reaction. For example, xylene, methanol and the like can be mentioned. These can be used alone or as a mixed solvent of two or more kinds.

It is preferable that the calcium salt of the rosin or the rosin derivative is substantially free of the rosin having a free carboxyl group and the rosin derivative. For example, it is preferably about 1% by mass or less in the component B. Since rosins and rosin derivatives having a free carboxyl group are highly hydrophilic, they tend to reduce the water resistance of the coating film, which may cause abnormalities such as blister and cracks in the coating film.

The content of the component B in the composition of the present invention is not particularly limited, but the ratio of the solid content of the component B to the total solid content of the polymer A and the component B is preferably 1 to 99% by mass, preferably 5 to 95% by mass. % Is more preferable. When used within the above range, advantageous effects such as improvement of the adhesion prevention effect during the fitting period, improvement of the coating film forming ability, and improvement of the coating film physical characteristics become remarkable. This ratio is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99% by mass. Yes, it may be within the range between any two of the numerical values exemplified here.

1-3. Antifouling agent C
Examples of the antifouling agent include inorganic agents and organic agents.
Examples of the inorganic agent include cuprous oxide, copper thiocyanate (generic name: copper rodane), copper powder and the like. Of these, cuprous oxide and copper rodane are particularly preferable, and copper sulfite surface-treated with glycerin, sucrose, stearic acid, lauric acid, rishitin, mineral oil, etc. is the point of long-term stability during storage. Is more preferable.

Examples of the organic drug include 2-mercaptopyridin-N-copperoxide (generic name: copperpyrcyone), 2-mercaptopyridin-N-zinc oxide (generic name: zincpyrythion), and zincethylenebisdithiocarbamate (generic name: zineb). ), 4,5-Dichloro-2-n-octyl-3-isothiazolone (generic name: cinine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diurone), 2-methylthio-4- t-Butylamino-6-cyclopropylamino-s-triazine (generic name: irgalol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) , 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (generic name: medetomidin) and the like.
Among these antifouling agents, 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) is particularly effective from the viewpoint of antifouling performance in the immersion test after the weather resistance test. ) Is preferable.
These antifouling agents can be used alone or in combination of two or more.

The content of the antifouling agent C in the composition of the present invention is not particularly limited, but is usually 0.1 to 60.0% by mass in terms of solid content. The content of the antifouling agent C is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40. , 45, 50, 55, 60% by mass, and may be within the range between any two of the numerical values exemplified here.

1-4. Other Additives Further, the resin for antifouling paint of the present invention includes resin components other than polymer A, elution adjusters, plasticizers, pigments, dyes, defoamers, dehydrating agents, and rocking agents, if necessary. , An organic solvent or the like can be added to obtain an antifouling paint.

Examples of the polymer and resin component other than the polymer A include (meth) acrylic resin, polyester resin, vinyl resin, petroleum resin, metal-containing resin, bipolar ion compound-containing resin, silicone resin, and fat. Cyclic hydrocarbon resin, etc. may be mentioned.

Examples of the elution adjuster include rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts other than calcium thereof, and the like. Examples thereof include an acid and a salt thereof, or the alicyclic hydrocarbon resin. These can be used alone or in two or more types.

Examples of the plasticizer include phosphoric acid esthetics, phthalates, adipates, sebacic acid esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, and vaseline. Examples thereof include polybutene, tristrimellitic acid (2-ethylhexyl), silicone oil, chlorinated paraffin and the like. These can be used alone or in two or more types.

Examples of the dehydrating agent include calcium sulfate, synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These can be used alone or in combination of two or more.

2. 2. Method for Producing Antifouling Paint Composition The antifouling paint composition of the present invention is obtained by, for example, mixing and dispersing a mixed solution containing the polymer A, component B, other additives and the like using a disperser. Can be manufactured. Further, a mixed solution containing the polymer A, an antifouling agent, other additives and the like can be mixed and dispersed using a disperser, and then the component B can be added to produce the mixture.

The mixed solution is preferably one in which various materials such as the polymer A and the component B are dissolved or dispersed in a solvent.

As the disperser, for example, one that can be used as a fine pulverizer can be preferably used. For example, a commercially available homomixer, sand mill, bead mill, disper or the like can be used. Further, the mixed liquid may be mixed and dispersed by using a container equipped with a stirrer to which glass beads or the like for mixing and dispersing are added.

3. 3. Antifouling treatment method, antifouling coating film, and coated material In the antifouling treatment method of the present invention, an antifouling coating film is formed on the surface of the coating film to be formed by using the above antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film is gradually dissolved from the surface and the surface of the coating film is constantly renewed, so that adhesion of aquatic polluted organisms can be prevented.
Examples of the coating film-forming product include ships (particularly the bottom of ships), fishing gear, underwater structures, and the like.
The thickness of the antifouling coating film may be appropriately set according to the type of the coating film to be formed, the navigation speed of the ship, the seawater temperature, and the like. For example, when the coating film to be formed is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 700 μm, preferably 100 to 600 μm.

Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to the examples and the like.
% In each production example, example and comparative example shows mass%. The weight average molecular weight (Mw) is a value (polystyrene conversion value) obtained by GPC. The conditions of GPC are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column ・ ・ ・ TSKgel SuperHZM-M 2 flow rate ・ ・ ・ 0.35mL / min
Detector ・ ・ ・ RI
Column constant temperature bath temperature ・ ・ ・ 40 ℃
Eluent ・ ・ ・ THF
The heating residue is a value measured in accordance with JIS K 5601-1-2: 1999 (ISO 3251: 1993) "Paint component test method-heating residue".

1. 1. Production Example <Production Example 1 (Production of Polymer Solution A-1)>
260 g of xylene was placed in a flask equipped with a thermometer, a reflux cooler, a stirrer and a dropping funnel, and while stirring at 85 ± 5 ° C. under a nitrogen atmosphere, 255 g of triisopropylsilyl methacrylate, 155 g of methyl methacrylate, and 2 acrylic acid were added. A mixed solution of 90 g of methoxyethyl and 3 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator was added dropwise over 2 hours. Then, after stirring at the same temperature for 1 hour, 0.5 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added 5 times every hour to complete the polymerization reaction. Then, 240 g of xylene was added and dissolved to obtain a polymer solution A-1. The viscosity of the obtained polymer solution was 450 mPa · s (25 ° C.), the heating residue was 50.8%, and Mw was 46,000.

<Production Examples 2 to 11, (Production of Polymer Solutions A-2 to A-8, P-1 to P-3)>
Using the monomer mixture shown in Table 1, the polymerization reaction was carried out in the same manner as in Production Example 1 to obtain polymer solutions A-2 to A-8 and P-1 to P-3. .. Table 1 shows the viscosities, heating residues, and Mw of each polymer solution obtained.

<Production Example B-1 (Production of Xylene Solution B-1 of Calcium Rosin Salt)>
200 g of Chinese gum rosin (WW) and 200 g of xylene were placed in a 1000 ml flask equipped with a thermometer and a stirrer and dissolved. 40 g of calcium oxide was added so that all the resin acids in the rosin formed a calcium salt, and 100 g of methanol was further added and mixed uniformly. Then, an appropriate amount (about 400 ml) of glass beads (diameter 2.5 to 3.5 mm) was added, and the mixture was stirred at 70 to 80 ° C. for 8 hours and then kept warm at 50 ° C. for 2 days. Then, the obtained mixed solution was cooled to room temperature (25 ° C.), filtered, and then concentrated under reduced pressure to distill off the methanol component. Then, by adding xylene to the obtained concentrate, a xylene solution (brown transparent solution, solid content of about 50%) B-1 of the calcium rosin salt was obtained. The heating residue of the obtained xylene solution was 50.5%.

<Production Example B-2 (Production of Xylene Solution B-2 of Calcium Hydrogenated Rosin Salt)>
200 g of hydrogenated rosin and 200 g of xylene were placed in a 1000 ml flask equipped with a thermometer and a stirrer and dissolved. 50 g of calcium hydroxide was added so that all the resin acids in the hydrogenated rosin formed a calcium salt, and 100 g of methanol was further added and mixed uniformly. Then, an appropriate amount (about 400 ml) of glass beads (diameter 2.5 to 3.5 mm) was added, and the mixture was stirred at 70 to 80 ° C. for 8 hours and then kept warm at 50 ° C. for 2 days. Then, the obtained mixed solution was cooled to room temperature (25 ° C.), filtered, and then concentrated under reduced pressure to distill off the methanol component. Then, by adding xylene to the obtained concentrate, a xylene solution (brown transparent solution, solid content of about 50%) B-2 of the calcium hydrogenated rosin salt was obtained. The heating residue of the obtained xylene solution was 50.1%.

<Production Example C-1 (Production of xylene solution C-1 of zinc rosin salt)>
200 g of Chinese gum rosin (WW) and 200 g of xylene were placed in a 1000 ml flask equipped with a thermometer and a stirrer and dissolved. 50 g of zinc oxide was added so that all the resin acids in the rosin formed a zinc salt, and 100 g of methanol was further added and mixed uniformly. Then, an appropriate amount (about 400 ml) of glass beads (diameter 2.5 to 3.5 mm) was added, and the mixture was stirred at 70 to 80 ° C. for 8 hours and then kept warm at 50 ° C. for 2 days. Then, the obtained mixed solution was cooled to room temperature (25 ° C.), filtered, and then concentrated under reduced pressure to distill off the methanol content. Then, by adding xylene to the obtained concentrate, a xylene solution (brown transparent solution, solid content of about 50%) C-1 of the zinc rosin salt was obtained. The heating residue of the obtained xylene solution was 50.7%.

<Production Example C-2 (Production of xylene solution C-2 of rosin copper salt)>
200 g of Chinese gum rosin (WW) and 200 g of xylene were placed in a 1000 ml flask equipped with a thermometer and a stirrer and dissolved. 60 g of copper hydroxide was added so that all the resin acids in the rosin formed a copper salt, and 100 g of methanol was further added and mixed uniformly. Then, an appropriate amount (about 400 ml) of glass beads (diameter 2.5 to 3.5 mm) was added, and the mixture was stirred at 70 to 80 ° C. for 8 hours and then kept warm at 50 ° C. for 2 days. Then, the obtained mixed solution was cooled to room temperature (25 ° C.), filtered, and then concentrated under reduced pressure to distill off the methanol component. Then, by adding xylene to the obtained concentrate, a xylene solution of the zinc rosin salt (dark green transparent solution, solid content of about 50%) C-2 was obtained. The heating residue of the obtained xylene solution was 50.1%.

2. 2. Examples 1 to 14 and Comparative Examples 1 to 5 (manufacturing of a coating composition)
The components shown in Tables 2 to 4 were blended in the proportions (% by mass) shown in the same table, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to produce a coating composition.

The details of each component in the table are as follows.
<Plasticizer>
Chlorinated paraffin: Product name "Paraffin Chlorinated (Cl: 40%)" (manufactured by Wako Pure Chemical Industries, Ltd.)
E-2000H: Epoxidized soybean oil: Product name "Sun Sizar E-2000H" (manufactured by Shin Nihon Rika Co., Ltd.)
DINCH: 1,2-Cyclohexanedicarboxylic acid diisononyl: Trade name "HEXAMOLL (R) DINCH (R)" (manufactured by BASF)

<Anti-fouling agent>
Copper oxide: Product name "NC-301" (manufactured by Nissin Chemco Co., Ltd.)
Copper Pyrithione: Product name "Copper Omagin" (manufactured by Arch Chemical Co., Ltd.)
Sea Nine: Product name "Sea Nine 211" 4,5-dichloro-2-n-octyl-3 (2H) isothiazolin (solid content 30% xylene solution, manufactured by Rohm and Haas)
Econia: Product name "Econea 028" 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
Medetomidine: Product name "4- (1- (2,3-Dimethylphenyl) ethyl) -1H-imidazole" (manufactured by Wako Pure Chemical Industries, Ltd.)

<Other additives>
Talc: Product name "Crown Talc 3S" (manufactured by Matsumura Sangyo Co., Ltd.)
Zinc oxide: Product name "Zinc oxide 2" (manufactured by Shodo Kagaku Co., Ltd.)
Bengala: Product name "TODA COLOR EP-13D" (manufactured by Toda Pigment Co., Ltd.)
Titanium oxide: Product name "FR-41" (manufactured by Furukawa Co., Ltd.)
Tetraethoxysilane: Product name "Tetraethyl Orthosilicate" (manufactured by Tokyo Kasei Co., Ltd.)
Aliphatic amide-based shaker: Product name "Disparon A603-20X" (manufactured by Kusumoto Kasei Co., Ltd.)

3. 3. Evaluation 3-1. Paint Stability Test The paint compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 5 were placed in a 100 ml wide-mouth tin can, sealed, and stored in an incubator at 45 ° C. for 3 months, and then the paint composition was obtained. The viscosity of the object was measured with a B-type viscometer.
The evaluation was performed according to the following criteria based on the change in the viscosity of the paint at 25 ° C.
⊚: Change in paint viscosity is less than 500 mPa · s ○: Change in paint viscosity is 500 mPa · s or more and less than 5000 mPa · s Δ: Change in paint viscosity is 5000 mPa · s or more and less than 100,000 mPa · s ×: Change in paint viscosity Table 5 shows the results that are 100,000 mPa · s or more or the viscosity cannot be measured.

From Table 5, it can be seen that the paints formed by using the paint compositions of the present invention (Examples 1 to 14) have good storage stability.

3-2. Adhesion test of coating film
Adhesion test of the coating film was performed according to the regulations of JIS K-5600-5-6. Specifically, the coating compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 5 are placed on a blast-finished tin plate (75 x 150 x 2 mm) to have a thickness of about 100 μm as a dry coating film. After applying so as to be, and drying at 40 ° C. for 1 day, an adhesion test was carried out.
The evaluation was performed by the following method.
With a cutter, 11 scratches in each of the vertical and horizontal directions reaching the base (tin plate) were put into the coating film after drying in the shape of a grid to prepare 100 squares of 2 mm square. Attach cellophane tape (tape width 24 mm manufactured by Nichiban Co., Ltd.) to the 100 squares so that air bubbles do not enter, hold one end of this tape in your hand and quickly peel it off, and visually check the adhesion state of the coating film. Examined.
⊚: When the number of non-peeled goats is 70 to 100 ○: When the number of unpeeled goats is 40 to 69 △: The number of unpeeled goats is 20 ~ In the case of 39 pieces ×: When the number of unpeeled rice grains is 0 to 19

The results are shown in Table 5.
From Table 5, it can be seen that the coating film formed by using the coating composition of the present invention (Examples 1 to 14) firmly adheres to the tin plate.

3-3. Flexibility test of coating film The coating composition obtained in Examples 1 to 14 and Comparative Examples 1 to 5 was applied to a tin plate (75 × 150 × 2 mm) having a blast finish, and the thickness as a dry coating film was about 100 μm. After the coating film was applied at 40 ° C. and dried at 40 ° C., the coating film was bent at 90 ° C. and the state of the coating film was confirmed by visual observation.
The evaluation was performed by the following method.
⊚: Almost no cracks occurred ○: Fine cracks occurred Δ: Large cracks occurred ×: Part of the coating film was easily peeled off

The results are shown in Table 5.
From Table 5, it can be seen that the coating films formed by using the coating compositions of the present invention (Examples 1 to 14) have excellent bending resistance.

3-4. A rotary drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the rotary test water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of seawater constant and an automatic pH controller for keeping the pH of seawater constant were installed.

Two test plates were prepared according to the following method.
First, a rust-preventive coating film (vinyl-based A / C) was applied onto a hard vinyl chloride plate (75 × 150 × 1 mm) so that the thickness after drying was about 50 μm, and dried to form a rust-preventive coating film. Then, the coating compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 5 were applied onto the rust-preventive coating film so that the thickness after drying was about 300 μm. The obtained coating film was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 300 μm.

One of the prepared test plates was fixed to the rotating drum of the rotating device of the above device so as to be in contact with seawater, and the rotating drum was rotated at a speed of 8 knots. During that time, the temperature of the seawater was kept at 25 ° C. and the pH was maintained at 8.0 to 8.2, and the seawater was replaced every week.

The residual film thickness of each test plate at the initial stage and every 3 months after the start of the test is measured with a laser focus displacement meter, and the dissolved coating film thickness is calculated from the difference to determine the dissolved coating film amount per month (μm / month). ) Was obtained. The measurement was carried out for 24 months, and the amount of the coating film dissolved was calculated every 12 months.

Further, after the test plate after the completion of the rotary test (24 months later) was dried, the surface of each coating film was visually observed to evaluate the state of the coating film.

The evaluation was performed by the following method.
◎: When there is no abnormality ○: Slight hair cracks can be seen △: Hair cracks can be seen on the entire surface of the coating film ×: Large cracks, blister or peeling can be seen on the coating film

The results are shown in Table 6.

From Table 6, the coating film formed by using the coating composition of the present invention (Examples 1 to 14) has a dissolution amount of about 1 to 6 μm per month even in a testing machine having a speed of 8 knots (years). (Average), and it can be seen that a sufficient amount of dissolution can be obtained even at low speeds. Further, it can be seen that the coating film formed by using the coating composition of the present invention is stably dissolved for a long period of time. Moreover, the coating film formed by using the coating composition of the present invention has excellent water resistance and does not cause coating film abnormalities such as cracks and hair cracks, so that the antifouling performance can be maintained for a long period of time.

On the other hand, since the coating film formed by using the coating film composition of Comparative Example 1 has low water resistance, rapid dissolution of the coating film occurs in the latter half of the test, and an abnormality of the coating film of hair cracks occurs. The coating film formed by using the coating film of Comparative Example 2 has good water resistance, but the amount of the coating film dissolved is low from the initial stage, and hair cracks occur after a long period of time. Further, the coating film formed by using the coating films of Comparative Examples 3 and 4 has high water permeability and shows appropriate dissolution of the coating film at the initial stage, but hardly dissolves in the latter half of the test, and a residual layer is formed. As a result, coating film abnormalities such as cracks occur. Further, the coating film formed by using the coating film composition of Comparative Example 5 causes rapid dissolution of the coating film in the latter half of the test, causes cracks and peeling, and cannot exhibit antifouling performance for a long period of time.

3-5. Antifouling property test The coating compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 5 were applied to both sides of a hard vinyl chloride plate (100 x 200 x 2 mm) so that the thickness of the dry coating film was about 300 μm. bottom. The obtained coating film was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 300 μm. This test plate was immersed 1.5 m below the sea surface in Owase City, Mie Prefecture, and stains on the test plate due to deposits were observed 12 months and 24 months later.

The evaluation was performed by visually observing the state of the coating film surface, and judged according to the following criteria.
◎: No attachment of polluted organisms such as shellfish and algae, and almost no slime.
◯: A level at which there is no attachment of polluted organisms such as shellfish and algae, and slime is thinly attached (to the extent that the coating film surface can be seen), but it can be lightly wiped off with a brush.
Δ: There is no adhesion of polluted organisms such as shellfish and algae, but the slime is so thick that the coating film surface cannot be seen, and it cannot be removed even if it is wiped strongly with a brush.
×: Level at which polluted organisms such as shellfish and algae cover an area of less than 50% of the test plate.
XX: A level at which polluted organisms such as shellfish and algae cover an area of 50% or more of the test version.

The results are shown in Table 6.

From Table 6, in the coating film formed by using the coating composition of the present invention (Examples 1 to 14), the antifouling agent is effectively released with the appropriate dissolution of the coating film, and the antifouling agent is effectively released for a long period of 24 months. It can be seen that there are no attached organisms and that it exhibits good antifouling performance. On the other hand, in the coating film formed by using the coating film composition of Comparative Example 1, the coating film abnormality such as hair cracks occurs due to the rapid dissolution of the coating film in the latter half, and biofouling caused by the abnormality is observed. In Comparative Example 2, the coating film was dissolved very slowly from the initial stage, the necessary antifouling agent was not released, and biofouling was observed at an early stage. In Comparative Examples 3 and 4, the antifouling agent escaped at an early stage in the initial stage, and the residual layer of the resin was formed on the surface of the coating film, resulting in immediate adhesion of organisms. Comparative Example 5 is a coating film composed of a coating film using an acrylic acid triorganosilyl ester polymer. However, due to the rapid dissolution of the coating film in the latter half, the balance with the release of the drug is lost and no biofouling is observed. Thick slime is attached.

Claims (1)

An antifouling coating composition containing the polymer A and the component B.
The polymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a).
The monomer (a) is represented by the general formula (1).
The component B is an antifouling coating composition which is a calcium salt of rosin or a rosin derivative.

(In the formula, R ¹ indicates a methyl group, and R ² to R ⁴ indicate the same or different branched alkyl group or phenyl group having 3 to 8 carbon atoms, respectively).