阅读说明：本技术 防污涂料组合物 (Antifouling coating composition ) 是由 和久英典 松木崇 小林慧 冈永都 安井拓也 伊藤基道 于 2019-04-09 设计创作，主要内容包括：本发明提供一种环境安全性高的防污涂膜形成用组合物,该防污涂膜即使长时间暴露在阳光下,涂膜溶解也会持续很长时间,即使在可能附着水生生物的吃水部也能表现出良好的防污性能。根据本发明提供一种防污涂料组合物,其含有共聚物A、共聚物B、防污试剂,上述共聚物A以及B是分别通过将单体(a)和除上述单体(a)之外的聚合性不饱和单体(b)的混合物共聚而得到的,上述单体(a)由通式(1)表示,通式(1):(式中,R<Sup>1</Sup>选自氢或甲基、R<Sup>2</Sup>、R<Sup>3</Sup>、R<Sup>4</Sup>选自碳原子数3～8的支链状烷基、苯基,各自相同或不同)。上述共聚物A满足以下要求(A1)～(A2)；上述共聚物B满足以下要求(B1)～(B2):(A1)相对于上述单体(a)和上述单体(b)的总质量,上述单体(a)的含量为30～50质量％；(A2)相对于上述单体(a)和上述单体(b)的总质量,上述单体(b)中丙烯酸2-甲氧基乙酯的含量为15～30质量％；(B1)相对于上述单体(a)和上述单体(b)的总质量,上述单体(a)的含量为30～40质量％；(B2)相对于上述单体(a)和上述单体(b)的总质量,上述单体(b)中甲基丙烯酸2-甲氧基乙酯的含量为30～50质量％。<Image he="224" wi="700" file="DDA0002678234820000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides a composition for forming an antifouling coating film with high environmental safety, wherein the antifouling coating film dissolves even if exposed to sunlight for a long timeIt lasts for a long time and exhibits good antifouling performance even in the draught where aquatic organisms are likely to attach. The present invention provides an antifouling paint composition comprising a copolymer A, a copolymer B and an antifouling agent, wherein the copolymer A and the copolymer B are each obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (B) other than the monomer (a), the monomer (a) is represented by the general formula (1), the general formula (1) is (wherein R is R) 1 Selected from hydrogen or methyl, R 2 、R 3 、R 4 Selected from branched alkyl groups having 3 to 8 carbon atoms and phenyl groups, each of which may be the same or different). The copolymer A satisfies the following requirements (A1) to (A2); the copolymer B satisfies the requirements (B1) to (B2) that (A1) the content of the monomer (a) is 30 to 50 mass% based on the total mass of the monomer (a) and the monomer (B); (A2) the content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30% by mass based on the total mass of the monomer (a) and the monomer (b); (B1) the content of the monomer (a) is 30 to 40% by mass based on the total mass of the monomer (a) and the monomer (b); (B2) the content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b).)

1. An antifouling paint composition comprising a copolymer A, a copolymer B and an antifouling agent,

each of the copolymers A and B is obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (B) other than the monomer (a),

the monomer (a) is represented by the general formula (1),

general formula (1):

[ chemical formula 1 ]

In the formula, R¹Selected from hydrogen or methyl, R²、R³、R⁴Selected from branched alkyl groups having 3 to 8 carbon atoms and phenyl groups, which may be the same or different,

the copolymer A satisfies the following requirements (A1) to (A2);

the copolymer B satisfies the following requirements (B1) to (B2):

(A1) the content of the monomer (a) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b);

(A2) the content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30 mass% with respect to the total mass of the monomer (a) and the monomer (b);

(B1) the content of the monomer (a) is 30 to 40 mass% with respect to the total mass of the monomer (a) and the monomer (b);

(B2) the content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50 mass% with respect to the total mass of the monomer (a) and the monomer (b).

Technical Field

The present invention relates to antifouling coating compositions.

Background

Aquatic fouling organisms such as barnacles, serpula, common mussels, sea grass bugs, sea squirts, enteromorpha, sea lettuce, and sludge are attached to aquatic structures such as ships (particularly ship bottom parts), fishing nets, fishing net accessories, and power generation conduits, thereby causing problems such as functional damage and appearance damage of the ships.

In order to prevent such problems, a technique has been disclosed in which an antifouling coating film is formed by applying an antifouling coating composition to a ship or the like to gradually release an antifouling agent from the antifouling coating film, thereby exhibiting antifouling performance for a long period of time (patent document 1).

Prior art literature

Patent document

[ patent document 1 ] Japanese patent laid-open No. 2000-17203

Disclosure of Invention

Problems to be solved by the invention

However, even if the technique of patent document 1 is adopted, although the antifouling performance can be maintained for a long period of time in the coating film portion which is immersed in seawater, the water intake portion which is the boundary between underwater and water is repeatedly affected by various factors such as repeated wetting and drying, sunlight, and the like, and there is a problem that the antifouling performance cannot be sufficiently exhibited.

The present invention has been made in view of the above circumstances, and provides an environmentally safe composition for forming an antifouling coating film which can exhibit excellent antifouling performance even in a draught part where aquatic organisms may attach, even if the antifouling coating film is dissolved for a long time even when exposed to sunlight for a long time.

[ means for solving problems ]

The present invention provides an antifouling paint composition comprising a copolymer A, a copolymer B, and an antifouling agent, wherein each of the copolymer A and the copolymer B is obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (B) other than the monomer (a), the monomer (a) is represented by the general formula (1),

general formula (1):

[ chemical formula 1 ]

(in the formula, R¹Selected from hydrogen or methyl, R²、R³、R⁴Selected from branched alkyl groups having 3 to 8 carbon atoms and phenyl groups, which may be the same or different)

The copolymer A satisfies the following requirements (A1) to (A2);

the copolymer B satisfies the following requirements (B1) to (B2):

(A1) the content of the monomer (a) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b);

(A2) the content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30% by mass based on the total mass of the monomer (a) and the monomer (b);

(B1) the content of the monomer (a) is 30 to 40% by mass based on the total mass of the monomer (a) and the monomer (b);

(B2) the content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b).

The present inventors have studied and found that an antifouling coating film formed using a composition containing a copolymer a and a copolymer B exhibits excellent antifouling performance in a drinking water portion, and thus the present invention has been completed. Wherein the copolymer A is obtained by copolymerizing a mixture containing specific amounts of a silyl ester monomer and 2-methoxyethyl acrylate, and the copolymer B is obtained by copolymerizing a mixture containing specific amounts of a silyl ester monomer and 2-methoxyethyl methacrylate.

Means for solving the problems

The present invention is described in detail below.

1. Antifouling coating composition

The antifouling paint composition of the present invention comprises a copolymer A, a copolymer B and an antifouling agent.

1-1. copolymers A and B

The copolymers a and B are each a triorganosilyl (meth) acrylate copolymer obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (B) other than the monomer (a). That is, the copolymers a and B contain monomer units derived from the monomers (a) and (B), respectively. The compounds contained in the monomer (a) and their mixing ratio may be the same or different in the copolymers A and B. The compounds contained in the monomer (B) may be the same or different in the copolymers A and B. The compounds contained in the monomer (B) are the same in the copolymers A and B, and the mixing ratio thereof is different.

< monomer (a) >

The monomer (a) is a triorganosilyl (meth) acrylate monomer represented by the general formula (1).

General formula (1):

[ chemical formula 1 ]

(in the formula, R¹Selected from hydrogen or methyl, R²、R³、R⁴Selected from branched alkyl groups having 3 to 8 carbon atoms and phenyl groups, which may be the same or different)

Examples of the monomer (a) represented by the general formula (1) in the present invention include triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-t-butylsilyl (meth) acrylate, triisovalerylsilyl (meth) acrylate, tri (2-ethylhexyl) silyl (meth) acrylate, triphenylsilyl (meth) acrylate, diisopropylisobutylsilyl (meth) acrylate, diisopropylisopentylsilyl (meth) acrylate, diisopropyl (2-ethylhexyl) silyl (meth) acrylate, diisopropylphenylsilyl (meth) acrylate, diisopropylcyclohexylsilyl (meth) acrylate, t-butyldiisopropylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, triisobutylsilyl (, T-butyldiisobutylsilyl (meth) acrylate, t-butyldiisopentylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, and the like, triisopropylsilyl (meth) acrylate is preferable, and triisopropylsilyl (meth) acrylate is particularly preferable. These monomers may be used alone or in combination of 2 or more.

< monomer (b) >

The monomer (b) is a monomer copolymerizable with the monomer (a), and examples thereof include the following. (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate.

Zinc (meth) carbonate tert, magnesium carbonate tert (meth) acrylate, copper (meth) carbonate tert, zinc (meth) acrylate, magnesium (meth) acrylate, copper (meth) acrylate, zinc (meth) acrylate, magnesium (meth) acrylate laurate, copper (meth) acrylate laurate, zinc (meth) acrylate stearate, metal (meth) acrylates such as magnesium (meth) acrylate, copper (meth) acrylate stearate, and metal pendant (meth) acrylates such as zinc (meth) acrylate and copper (meth) acrylate

Vinyl compounds having functional groups such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyric acid, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone.

Aromatic compounds such as styrene, vinyl toluene and α -methylstyrene.

Dialkyl ester compounds of unsaturated dibasic acids such as dimethyl malate, dibutyl malate, and dimethyl fumarate.

One or more monomers, preferably (meth) acrylates, are used for each monomer (b).

< requirements (A1) to (A2) and (B1) to (B2) >

In the present invention, the copolymer A satisfies the requirements (A1) to (A2) and the copolymer B satisfies the requirements (B1) to (B2) as essential requirements.

(A1) The content of the monomer (a) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b).

(A2) The content of 2-methoxyethyl acrylate in the monomer (b) is 15 to 30% by mass based on the total mass of the monomer (a) and the monomer (b).

(B1) The content of the monomer (a) is 30 to 40% by mass based on the total mass of the monomer (a) and the monomer (b).

(B2) The content of 2-methoxyethyl methacrylate in the monomer (b) is 30 to 50% by mass based on the total mass of the monomer (a) and the monomer (b).

The points of note are as follows:

(1) the content of the monomer (a) is 30 to 50% by mass in the copolymer A and 30 to 40% by mass in the copolymer B, both of which are relatively small amounts.

(2) In the copolymer A, the monomer (B) contains 2-methoxyethyl acrylate, and in the copolymer B, the monomer (B) contains 2-methoxyethyl methacrylate.

As described above, the present invention uses 2 copolymers having a relatively small ratio of silyl ester monomer units, one of which contains 2-methoxyethyl acrylate units and the other contains 2-methoxyethyl methacrylate units. As shown in examples described later, by having such characteristics, the hydrophilicity of the coating film can be improved, the adhesion of the coating film to a highly polar surface such as glass can be improved, and the resistance in a dry-wet cycle test can be improved. This corresponds to an improvement in adhesion when the surface of the old coating film is recoated.

In the requirement (a1), the content of the monomer (a) may be, for example, 30, 35, 40, 45 or 50 mass% with respect to the total mass of the monomer (a) and the monomer (b), and may be within any 2 values among the numerical values exemplified herein.

In the requirement (a2), the content of 2-methoxyethyl acrylate based on the total mass of the monomer (a) and the monomer (b) is, for example, 15, 20, 25, 30 mass%, and may be in the range between any 2 of the numerical values exemplified herein. The monomer (B) of the copolymer A may contain 2-methoxyethyl methacrylate, but the content thereof is preferably less than the content of 2-methoxyethyl methacrylate in the monomer (B) of the copolymer B, and is preferably 1/2 or less of the content of 2-methoxyethyl methacrylate in the monomer (B) of the copolymer B. The monomer (b) of the copolymer A preferably does not contain 2-methoxyethyl methacrylate.

In the requirement (B1), the content of the monomer (a) may be, for example, 30, 35 or 40 mass% with respect to the total mass of the monomers (a) and (B), and may be any of 2 values among the numerical values exemplified herein.

In the requirement (B2), the content of 2-methoxyethyl methacrylate relative to the total mass of the monomer (a) and the monomer (B) is, for example, 30, 35, 40, 45, 50 mass%, and may be in the range between any 2 of the numerical values exemplified herein. The monomer (B) of the copolymer B may contain 2-methoxyethyl acrylate, but the content thereof is preferably less than the content of 2-methoxyethyl acrylate in the monomer (B) of the copolymer A, and is preferably 1/2 or less of the content of 2-methoxyethyl acrylate in the monomer (B) of the copolymer A. The monomer (B) of the copolymer B preferably does not contain 2-methoxyethyl acrylate.

In the copolymers a and B, the monomer (B) may contain a silyl ester other than the monomer (a). In this case, the total content of the silyl ester based on the total mass of the monomer (a) and the monomer (b) may be, for example, 30 to 60 mass%, specifically, 30, 35, 40, 45, 50, 55, 60 mass%, or may be within a range of any 2 of the numerical values exemplified herein. The content of silyl ester other than the monomer (a) is preferably less than the content of the monomer (a), and is preferably 1/2 or less, more preferably 1/5 or less of the content of the monomer (a).

The content of the copolymer A is preferably 25 to 75% by mass based on the total mass of the copolymer A and the copolymer B. At this time, the effect of the increase in the resistance in the dry-wet cycle test was significant. Specifically, the content of the copolymer a is, for example, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, and 75% by mass, and may be in a range between any 2 of the numerical values exemplified herein.

< Synthesis of copolymers A and B >

The copolymers A and B can be obtained by copolymerizing a mixture of the monomer (a) and the monomer (B). The copolymerization can be carried out, for example, in the presence of a polymerization initiator.

The weight average molecular weight of the copolymer A and B is preferably 5000 to 300000. When the molecular weight is less than 5000, the coating film of the antifouling paint becomes brittle and is liable to be peeled and cracked, and when it exceeds 300000, the viscosity of the copolymer solution increases and the handling becomes difficult. Specifically, the weight average molecular weight is, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, and may be within a range between any 2 of the numerical values exemplified herein.

Examples of the polymerization initiator include azo compounds such as Azobisisobutyronitrile (AIBN), azobisisovaleronitrile, and dimethyl azobisisobutyrate; peroxides such as benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, and 1,1,3, 3-tetramethylbutyl peroxy-2-ethylhexanoate. These polymerization initiators may be used alone or in combination of 2 or more. As the polymerization initiator, azobisisobutyronitrile and 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate are particularly preferable.

The molecular weight of the triorganosilyl ester-containing copolymer 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, and suspension polymerization. Among them, solution polymerization is particularly preferable in that the copolymer can be obtained easily and with good precision.

In the polymerization reaction, an organic solvent may be used as necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene, ethylbenzene, and toluene. And aliphatic hydrocarbon solvents such as hexane and heptane. Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate. Alcohol solvents such as isopropyl alcohol and butyl alcohol. Ether solvents such as dioxane, diethyl ether, and dibutyl ether. Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among them, an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents may be used alone or in combination of 2 or more.

The reaction temperature of the polymerization reaction is usually 70 to 120 ℃ and may be appropriately set depending on the kind of the polymerization initiator, and is preferably 70 to 100 ℃. The reaction time of the polymerization reaction may be appropriately set depending on the reaction temperature, and is usually about 4 to 8 hours.

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

1-2 antifouling agent

Examples of the antifouling agent include inorganic agents and organic agents.

Examples of the inorganic reagent include cuprous oxide, copper thiocyanate (common name: rhodamine copper), and copper powder. Among them, cuprous oxide and rhodamine copper are particularly preferable, and from the viewpoint of long-term stability during storage, cuprous oxide is more preferably surface-treated with glycerin, sucrose, stearic acid, lauric acid, lysine, mineral oil, or the like.

Examples of the organic reagent include 2-mercaptopyridine-copper N-oxide (common name: copper pyrithione), 2-mercaptopyridine-zinc N-oxide (common name: zinc pyrithione), zinc ethylenebisdithiocarbamate (common name: zineb), 4, 5-dichloro-2-N-octyl-3-isothiazolone (common name: SEA-NINE211), 3, 4-dichlorophenyl-N-dimethylurea (common name: diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (common name: Irgarol1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: ECONEA028), 4- [1- (2,3-dimethylphenyl) ethyl ] -1H-imidazole (common name: medetomidine), and the like.

These antifouling agents may be used alone or in combination of two or more.

1-3. other additives

The resin for an antifouling paint of the present invention may further contain, as required, a dissolution-adjusting agent, a plasticizer, a pigment, a dye, a defoaming agent, a dehydrating agent, a thixotropic agent, and an organic solvent as an antifouling paint.

Examples of the elution regulators include rosin, rosin derivatives, naphthenic acids, cycloalkenylcarboxylic acids, bicycloalkenylcarboxylic acids, versatic acids, trimethylisobutenylcyclohexene carboxylic acids, metal salts thereof, monocarboxylic acids and salts thereof, and alicyclic hydrocarbon resins. These may be used alone or in combination of 2 or more.

Examples of the rosin derivatives include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin. Examples of the alicyclic hydrocarbon resin include Quinton1500, 1525L, 1700 (trade name, product name of Nippon Zeon corporation) and the like as commercially available products.

Examples of the plasticizer include phosphoric acid esters, phthalic acid esters, adipic acid esters, sebacic acid esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, vaseline, polybutene, tris (2-ethylhexyl) trimellitate, silicone oil, liquid paraffin, and chlorinated paraffin. These may be used alone or in combination of 2 or more.

Examples of the dehydrating agent include synthetic zeolite adsorbents, silicates such as orthoesters, tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides and carbodiimides. These may be used alone or in combination of 2 or more.

2. Method for producing antifouling paint composition

The antifouling paint composition of the present invention can be produced by, for example, mixing and dispersing a mixed solution containing the copolymer a, the copolymer B, the antifouling agent, and other additives using a dispersing machine.

The mixed solution is preferably a solution obtained by dissolving or dispersing various materials such as a copolymer and an antifouling agent in a solvent.

As the above-mentioned disperser, for example, a disperser usable as a fine pulverizer can be preferably used. For example, a commercially available homogenizer, sand mill, bead mill, etc. can be used. The mixed solution may be mixed and dispersed by using a device in which glass beads for mixing and dispersing are added to a container equipped with a stirrer.

3. Antifouling treatment method, antifouling coating film, and coated article

The antifouling treatment method of the present invention is a method for forming an antifouling coating film on the surface of a coating film-formed article 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, whereby the adhesion of aquatic fouling organisms can be prevented.

Examples of the coating film-formed article include ships (particularly ship bottoms), fishery equipment, underwater structures, and the like.

The thickness of the antifouling coating film may be appropriately set depending on the type of the coating film-formed product, the ship's speed, the seawater temperature, and the like. For example, when the coating material is a ship bottom, the thickness of the antifouling coating film is usually 50 to 700. mu.m, preferably 100 to 600. mu.m.

[ examples ] A method for producing a compound

The following examples and the like are provided to further clarify the features of the present invention. However, the present invention is not limited to these examples.

In each of the production examples, comparative production examples, and comparative examples,% represents mass%. The viscosity is a measured value at 25 ℃ and is a value obtained by a type B viscometer. The weight average molecular weight (Mw) is a value (polystyrene equivalent) determined by GPC.

The GPC conditions were as follows.

Device … HLC-8220GPC, product of Tosoh corporation

Column … TSKgel SuperHZM-M (Tosoh Co., Ltd.) 2

Flow rate … 0.35.35 mL/min

Detector … RI

Column thermostat temperature … 40 deg.C

Eluent … THF

The heating residual component is a value measured according to JIS K5601-1-2: 1999(ISO 3251:1993) "coating composition test method-heating residual component".

The unit of the amount of each component in the table is g.

Production example 1 (production of copolymer solution SA-1) >

In a 2000ml flask equipped with a thermometer, a reflux condenser, a stirring device and a dropping funnel, 400g of xylene was charged, the temperature was raised to 83 to 87 ℃ under a nitrogen atmosphere, and a mixed solution of 150g of triisopropylsilyl methacrylate, 37g of ethyl acrylate, 238g of methyl methacrylate, 75g of 2-methoxyethyl acrylate, and 5g of 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate (PEROCTAO, manufactured by NOF corporation) was added dropwise while maintaining the temperature under stirring for 1 hour. After the dropwise addition, 0.5g of 1,1,3, 3-tetramethylbutylperoxy-2-ethylhexanoate was added dropwise three times per hour at 83 to 87 ℃ to terminate the polymerization reaction. Thereafter, 100g of xylene was added thereto and dissolved, thereby obtaining a copolymer solution SA-1. The copolymer solution SA-1 had a residual component upon heating of 49.8% and a weight-average molecular weight of 52000.

Production examples 2 to 20 and comparative production examples 1 to 4

Polymerization was carried out in the same manner as in production example 1 using the organic solvents, monomers and polymerization initiators shown in tables 1 to 3 to obtain copolymer solutions SA-2 to SA-10 of copolymer A, copolymer solutions SB-1 to SB-10 of copolymer B and copolymer solutions T-1 to T-4 of other copolymers. The residual components after heating and the weight average molecular weight of each of the obtained copolymer solutions were measured.

The results are shown in tables 1 to 3.

[ TABLE 1 ]

[ TABLE 2 ]

[ TABLE 3 ]

Production example 21 (production of rosin metal salt solution) >

240g of gum rosin (WW) produced in China and 360g of xylene were put into a flask equipped with a thermometer, a reflux condenser and a stirrer, and 120g of zinc oxide was further added to make all the resin acids in the rosin form zinc salts, followed by reflux dehydration at 70 to 80 ℃ for 3 hours under a reduced pressure atmosphere. After that, the mixture was cooled and filtered to obtain a xylene solution of zinc rosin salt (dark brown transparent liquid, solid content: 50%). The heating residual component of the resulting solution was 50.4%.

Production example 22 (production of hydrogenated rosin metal salt solution)

In a flask equipped with a thermometer, a reflux condenser and a stirrer, HYPALE CH240g and 360g of xylene were added, and further 120g of zinc oxide was added to complete the formation of zinc salts of all resin acids in the rosin, and the mixture was refluxed and dehydrated at 70 to 80 ℃ for 3 hours under a reduced pressure atmosphere. After that, the mixture was cooled and filtered to obtain a xylene solution of zinc rosin salt (dark brown transparent liquid, solid content: 50%). The heating residual component of the resulting solution was 50.3%.

< example 183 and comparative example 114>

Antifouling paint compositions were prepared using copolymer solutions SA-1 to SA-10, SB-1 to SB-10, and T-1 to T-4 in the amounts shown in tables 4 to 14.

(Dry and Wet cycle test of coating film)

A test plate was obtained by applying the antifouling paint composition to a glass plate using a 400 μm applicator.

After repeating the 40 ℃ fresh water immersion test for 12 hours and the air exposure test for 12 hours for 6 months, the physical properties of the test panels were evaluated by visual observation.

No peeling was regarded as "good", and peeling was regarded as "poor".

[ TABLE 4 ]

[ TABLE 5 ]

[ TABLE 6 ]

[ TABLE 7 ]

[ TABLE 8 ]

[ TABLE 9 ]

[ TABLE 10 ]

[ TABLE 11 ]

[ TABLE 12 ]

TABLE 12

[ TABLE 13 ]

[ TABLE 14 ]

TABLE 14

The dissolution control agent, plasticizer, stain-proofing agent, and other additives are described in detail in tables 4 to 14 below.

< dissolution controlling Agents >

Rosin Metal salt solution prepared by Using production example 21

Hydrogenated rosin metal salt solution prepared in production example 22

Gum rosin solution-a 50% xylene solution of the solid content of gum rosin (WW) produced in China

Hydrogenated gum rosin solution was a 50% xylene solid solution of HYPALE CH (available from Okawa chemical Co., Ltd.).

< plasticizer >

Chlorinated Paraffin, trade name "Paraffin Chlorinated (Cl: 40%)" (manufactured by Wako pure chemical industries, Ltd.)

E-2000H epoxidized Soybean oil, trade name "Sansosizer E-2000H" (manufactured by Nissi Sukkiso Co., Ltd.)

Tri (2-ethylhexyl) trimellitate (product name "Tri (2-ethylhexyl) trimellitate)" (manufactured by Tokyo Kasei Co., Ltd.)

Hexamoll (registered trademark) DINCH (registered trademark) manufactured by BASF, a non-phthalate plasticizer

< antifouling agent >

Cuprous oxide: trade name "NC-301" (manufactured by NISSHIN CHEMCO Co., Ltd.)

Copper pyrithione under the trade name "hopper Omadine" manufactured by Arch Chemicals Co., Ltd.)

Zinc pyrithione under the trade name "inc Omadine" manufactured by Arch Chemicals Co., Ltd.)

Zineb trade name "Zineb" (SIGMA-ALDRICH)

SeaNine (trade name "Sea Nine 211" 4, 5-dichloro-2-n-octyl-3-isothiazolone) (solid component 30% xylene solution, manufactured by Romen Haas Co., Ltd.)

medetomidine "4- (1- (2,3-Dimethylphenyl) ethyl) -1H-imidazole" (manufactured by Wako pure chemical industries, Ltd.)

Econia, trade name "Econea 028" 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)

< other additives >

Talc (CROWNTALC 3S, Sonmura industries, Co., Ltd.)

Zinc oxide (2 kinds of Zinc oxide (trade name) manufactured by Zhengshan chemical Co., Ltd.)

Iron oxide (TODACOLOREP-13D, manufactured by Toda Pigment Co., Ltd.)

Titanium oxide (made by Guhe mechanical Metal Co., Ltd., FR-41)

Tetraethoxysilane trade name "tetra Ethyl orthosilinate" (manufactured by Tokyo Kabushiki Kaisha)

Fatty acid amide thixotropic agent having the trade name "DISPARLON A603-20X" (manufactured by NAKATICHE CHEMICAL CO., LTD.)

< examination >

As is clear from table 4 and table 14, the coating films formed using the coating compositions of the present invention (example 183) had improved adhesion to the glass surface as compared with the coating films formed using the coating compositions of comparative examples 1 to 14, and no peeling of the coating films occurred even after the dry-wet cycle test (after 6 months).

On the other hand, the coating films formed using the coating compositions of comparative examples 1 to 14 had poor adhesion to the glass surface, and the peeling of the coating films occurred after the dry-wet cycle test (after 3 months).