JP2022129226A - Anti-fouling coating composition - Google Patents

Abstract

To provide an anti-fouling coating composition capable of retaining an excellent coated film surface state and excellent anti-fouling performance over an extended period.SOLUTION: An anti-fouling coating composition contains a copolymer A and fiber B. The copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a). The monomer (a) is represented by the general formula (1).SELECTED DRAWING: None

Description

The present invention relates to an antifouling coating composition.

Aquatic fouling organisms such as barnacles, serpra, mussels, mussels, sea squirts, green laver, sea lettuce, and slimes may be found on ships (especially on the bottom of ships), fishing nets, fishing tools such as fishing net accessories, and underwater structures such as power plant water pipes. There are problems such as the deterioration of the functions of the ships and the like and the deterioration of the appearance due to the adhesion.

In order to prevent such problems, an antifouling coating composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is slowly released from the antifouling coating film, thereby providing long-term antifouling. Techniques for exhibiting performance are known (Patent Documents 1 to 4).

However, the antifouling coating film composed of a polymer containing a (meth)acrylic acid alkoxycarbonylmethyl ester group described in Patent Documents 1 to 4 has remarkably low coating film solubility, and therefore exhibits antifouling properties over a long period of time. It was difficult to demonstrate.
In order to solve these problems, a technique has been proposed in which the coating film dissolves over a long period of time to exhibit antifouling performance (Patent Document 5).

Japanese Patent Publication No. 63-61989 Japanese Patent Application Laid-Open No. 2003-119420 Japanese Patent Application Laid-Open No. 2003-119419 Japanese Patent No. 2002-3776 WO2020/045211

The antifouling coating film made of the antifouling coating composition described in Patent Document 5 has improved coating film solubility, but tends to show poor uniformity in coating film solubility at the beginning of immersion and after a long period of time. There is also room for improvement in terms of coating film physical properties such as cracks and peeling, and an antifouling paint composition that can maintain excellent coating film surface conditions and antifouling performance over a long period of time is desired. was rare.

The present invention has been made in view of such circumstances, and provides an antifouling coating composition capable of maintaining excellent coating film surface conditions and antifouling performance over a long period of time.

According to the present invention, an antifouling coating composition containing a copolymer A and a fiber B, wherein the copolymer A comprises a monomer (a) and ethylene other than the monomer (a) It is a copolymer with a polyunsaturated monomer (b), and the monomer (a) is represented by the general formula (1).

Means for Solving the Problems As a result of intensive studies aimed at solving the above problems, the present inventors have found that the above antifouling coating composition can solve the above problems, and have completed the present invention.

The present invention will be described in detail below.

1. Antifouling Paint Composition The antifouling paint composition of the present invention contains the copolymer A and the fiber B.

1-1. Copolymer A
1-1-1. Composition of Copolymer A Copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a). Copolymer A contains monomer units derived from monomers (a) and (b). The content of the monomer (a) with respect to the sum of the monomers (a) and (b) is preferably 10-90% by mass, more preferably 20-70% by mass. Specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, and the numerical values exemplified here It may be in the range between any two. In this case, the coating film solubility is particularly good.

<Monomer (a)>
Monomer (a) is represented by general formula (1).

In the formula, R ¹ represents hydrogen or a methyl group, R ² represents hydrogen, a methyl group, or a phenyl group, and R ³ represents a carbon atom optionally substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group. It is an alkyl group of numbers 1-8 or represents a phenyl group, and n represents an integer of 2-10.

R ² is preferably hydrogen or a methyl group.

The number of carbon atoms in the alkoxy group or alkyl group of R ³ is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and within the range between any two of the numerical values exemplified here good too. R ³ is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, benzyl group, phenyl group, 2-methoxyethyl group, 4-methoxybutyl group, vinyl group or allyl group, preferably methyl group, ethyl group, isopropyl group or n-butyl group.

n represents an integer of 2 to 10, preferably 2 to 6 from the viewpoint of long-term antifouling properties. n is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, and may be in the range between any two of the numerical values exemplified here.

Examples of the monomer (a) include methyl (meth) acrylate poly(oxycarbonylmethyl), ethyl (meth) acrylate poly(oxycarbonylmethyl), isopropyl (meth) acrylate poly(oxycarbonylmethyl), (meth) ) n-propyl poly (oxycarbonylmethyl) acrylate, n-butyl poly (oxycarbonylmethyl) (meth) acrylate, t-butyl poly (oxycarbonylmethyl) (meth) acrylate, 2-ethylhexyl poly (meth) acrylate (oxycarbonylmethyl), cyclohexyl(meth)acrylate poly(oxycarbonylmethyl), benzyl(meth)acrylate polyoxycarbonylmethyl), phenyl(meth)acrylate poly(oxycarbonylmethyl), (meth)acrylic acid 2 - methoxyethyl poly(oxycarbonylmethyl), 4-methoxybutyl poly(oxycarbonylmethyl) (meth)acrylate, allyl (meth)acrylate poly(oxycarbonylmethyl), vinyl (meth)acrylate poly(oxycarbonylmethyl), (Meth)methyl acrylate poly[1-(oxypolycarbonyl)ethyl], ethyl(meth)acrylate poly[1-(oxypolycarbonyl)ethyl], (meth)acrylic acid n-propylpoly[1-(oxypolycarbonyl) ) ethyl], (meth) isopropyl acrylate poly [1-(oxypolycarbonyl) ethyl], (meth) n-butyl acrylate poly [1-(oxypolycarbonyl) ethyl], (meth) t-butyl acrylate poly [ 1-(oxypolycarbonyl)ethyl], methyl(meth)acrylate poly[α-(oxycarbonyl)benzyl], and ethyl(meth)acrylate poly[α-(oxycarbonyl)benzyl]. Preferably, methyl (meth) acrylate poly (oxycarbonylmethyl), ethyl (meth) acrylate poly (oxycarbonylmethyl), isopropyl (meth) acrylate poly (oxycarbonylmethyl), (meth) acrylate n-propyl poly ( oxycarbonylmethyl), (meth)acrylic acid n-butylpoly(oxycarbonylmethyl), (meth)methylacrylate poly[1-(oxypolycarbonylethyl)], (meth)acrylate poly[1-(oxypolycarbonylethyl) )] and the like. These monomers (a) can be used individually or in combination of 2 or more types.

As the monomer (a), it is preferable to include those in which n is 2 in the general formula (1) and those in which n is 3 to 10. In terms of solid content, the mass ratio (n (2) /n (2 to 10)) is preferably 0.4 to 0.8, more preferably 0.5 to 0.7. In this case, it is preferable from the viewpoint of coating film solubility and coating film physical properties. Specifically, this value is, for example, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, where It may be in a range between any two of the numerical values given.

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

Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, (meth) ) 2-ethylhexyl acrylate, lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, benzyl (meth)acrylate , phenyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, propylene glycol monomethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate Glycidyl acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-[2-(2-hydroxyethoxy) methacrylate Ethoxy]ethoxy]ethyl, mono(2-(meth)acryloyloxyethyl) succinate, N-(3-dimethylaminopropyl)(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2 - [2-(2-methoxyethoxy) ethoxy] ethyl, acrylic acid esters such as N,N'-dimethyl (meth) acrylamide; methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, ( meth)isopropoxycarbonylmethyl acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, t-butoxycarbonylmethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate oxycarbonylmethyl, cyclohexyloxycarbonylmethyl (meth)acrylate, benzyloxycarbonylmethyl (meth)acrylate, phenoxycarbonylmethyl (meth)acrylate, 2-methoxyethoxycarbonylmethyl (meth)acrylate, (meth)acrylic acid 4-Methoxybutoxycarbonylmethyl, (meth)aryloxycarbonylmethyl acrylate, vinyloxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)ethyl (meth)acrylate, 1-(ethoxycarbonyl(meth)acrylate) ) Ethyl, 1-(n-propoxycarbonyl) ethyl (meth)acrylate, ( 1-(isopropoxycarbonyl)ethyl meth)acrylate, 1-(n-butoxycarbonyl)ethyl (meth)acrylate, 1-(t-butoxycarbonyl)ethyl (meth)acrylate, α-(meth)acrylate (Meth)acrylate alkoxycarbonylmethyl esters such as (methoxycarbonyl)benzyl and α-(ethoxycarbonyl)benzyl (meth)acrylate;
(meth) triisopropylsilyl acrylate, triisobutylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, triisopentylsilyl (meth) acrylate, triphenylsilyl meth (meth) acrylate, (meth) ) diisopropylphenylsilyl acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropyl s-butylsilyl (meth)acrylate, diisopropylisopentylsilyl (meth)acrylate, isopropyldiisobutylsilyl (meth)acrylate, (meth)acrylic acid Isopropyldi-s-butylsilyl, t-butyldiisoptylsilyl (meth)acrylate, t-butyldiisopentylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, diisopropyl(meth)acrylate Silsilyl, diisopropylcyclohexylsilyl (meth)acrylate, tricyclohexylsilyl (meth)acrylate, tri-1,1-dimethylpentylsilyl (meth)acrylate, tri-2,2-dimethylpropylsilyl (meth)acrylate, ( (Meth)acrylic acid silyl esters such as tricyclohexylmethylsilyl methacrylate, diisopropylcyclohexylmethylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate and tri-2-propylpentylsilyl (meth)acrylate and the like.

Examples of vinyl compounds include vinyl compounds having functional groups 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 aromatic compounds include styrene, vinyltoluene, α-methylstyrene and the like.

Dialkyl ester compounds of dibasic acids include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.

In the present invention, these monomers (b) can be used alone or in combination of two or more. In particular, the monomer (b) is preferably a (meth)acrylic acid ester from the viewpoint of coating film solubility and coating film physical properties, and particularly from the viewpoint of crack resistance, methyl (meth)acrylate, (meth) Butyl acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, ( 2-Hydroxyethyl meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and the like are more preferred, and from the viewpoint of coating film solubility, (meth)acrylic More preferred are triisopropylsilyl acid, t-butyldiphenylsilyl (meth)acrylate, and tri-2-ethylhexylsilyl (meth)acrylate.

1-1-2. Physical Properties and Production Method of Copolymer A The weight average molecular weight (Mw) of Copolymer A is preferably 5,000 to 300,000. If the molecular weight is less than 5,000, the coating film of the antifouling paint becomes brittle and easily peels off or cracks. Specifically, this Mw is, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000. may be within the range.

Examples of methods for measuring Mw include gel permeation chromatography (GPC method).

Copolymer A is a random copolymer, alternating copolymer, periodic copolymer, or block copolymer of monomer (a) and monomer (b). may

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

Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile ), dimethyl-2,2′-azobisisobutyrate, dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (N-butyl-2-methylpropionamide and other azo compounds; benzoylper oxide, di-tert-butylperoxide, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , di-t-hexyl peroxide, t-butyl peroxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, t- Peroxides such as amyl peroxyneodecanoate, t-hexyl peroxypivalate, t-amyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, etc. These polymerization initiators can be used alone or in combination of two or more. -methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate is preferred, and 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, and non-aqueous dispersion polymerization. Among these, solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that the copolymer A can be obtained easily and accurately.

In the polymerization reaction, an organic solvent may be used as necessary. The organic solvent is not particularly limited, but for example, aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents; ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, propylene glycol 1-monomethyl ether. ester solvents such as 2-acetate; alcohol solvents such as isopropyl alcohol, butyl alcohol and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. mentioned.
Among them, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene and xylene are preferred. 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 inert gas atmosphere such as nitrogen gas or argon gas.

1-2. Fiber B
Fiber B of the present invention comprises any fiber in the group of natural inorganic fibers, synthetic inorganic fibers, natural organic fibers, synthetic organic fibers and metallic fibers or mixtures thereof and has one long dimension and two short dimensions. characterized by

For example, mineral fiber such as mineral glass fiber, wollastonite fiber, montmorillonite fiber, tobermonite fiber, attapulgite fiber, calcined bauxite fiber, volcanic rock fiber, bauxite fiber, rock wool fiber, mineral fiber processed from mineral wool, polyethylene fiber, polypropylene fiber , cotton fibers, cellulose fibers, polyacrylonitrile fibers, pre-oxidized polyacrylonitrile fibers and polyester fibers.

The surface of fiber B may or may not have been modified (surface treated) by chemical or physical methods. Examples of fiber modification methods include carbonization; silylation; surface oxidation; etching, such as treatment with alkali metal hydroxides, treatment with hydrofluoric acid; adsorption method; hydrogen bonding method; cation bonding method; esterification;

Among these, particularly preferred are mineral glass fiber, wollastonite fiber, montmorillonite fiber, tobermorite fiber, attapulgite fiber, calcined bauxite fiber, volcanic rock fiber, bauxite fiber, rock wool fiber, and mineral fiber processed from mineral wool. mineral fiber.

Examples of commercially available fiber B include volcanic rock fiber MS600 (untreated, average fiber length 125 μm, average fiber thickness 5 μm), volcanic rock fiber MS603 (untreated, average fiber length 125 μm, average fiber thickness 5 μm) (Lapinus Fibers BV), rock wool F 554/1 SR (average fiber length 500 μm, average fiber thickness 5 μm), ceramic F 580/1 S (average fiber length 500 μm, average fiber thickness 2.8 μm), polyacrylonitrile F PAC 238/ 040 (average fiber length 500 μm), polyester/polyamide F PES 231/040 (average fiber length 500 μm, average fiber thickness 10-20 μm), preoxidised polyacrylonitrile F PAC O 245/040 (average fiber length 500 μm, average fiber thickness 10-12 μm), polypropylene fiber F PP 261/040 (average fiber length 500 μm, average fiber thickness 21 μm), polyacrylonitrile fiber F PAC 235/040 (average fiber length 500 μm) (manufactured by Schwarzwalder Textil-Werke) , Glass fiber PF E-001 (untreated), PF E-301 (silane-based treatment), Glass fiber SS 05C-404 (Silane-based treatment, average cut length 0.1 mm), Glass fiber SS 10-420 (Silane-based Treatment, average cut length 0.3 mm) (manufactured by Nitto Boseki Co., Ltd.), glass fiber EPH 80M-10A (silane treatment, average cut length 80 μm), glass fiber EPH 80M-80A (silane treatment, average cut length 80 μm) (manufactured by Nippon Electric Glass Co., Ltd.) and the like, which are preferable in terms of improving their mechanical properties.

The content of the fiber B in the composition of the present invention is not particularly limited, but is usually 0.1 to 20% by mass, preferably 1 to 15% by mass, particularly preferably 4 to 10%, in terms of solid content. % by mass. Specifically, the content of the fiber B is, for example, 0.1, 1, 2, 4, 5, 6, 7, 8, 9, 10, 15, 20% by mass, and any of the numerical values exemplified here It may be in a range between the two.

1-3. Antifouling Agents Antifouling agents include, for example, inorganic agents and organic agents.
Examples of inorganic chemicals include cuprous oxide, copper thiocyanate (common name: rhodan copper), and copper powder. Among these, cuprous oxide and rhodan copper are particularly preferable, and cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, lycithin, mineral oil, etc. is preferred for long-term storage stability. is more preferable.
Examples of organic agents include copper 2-mercaptopyridine-N-oxide (generic name: copper pyrithione), zinc 2-mercaptopyridine-N-oxide (generic name: zinc pyrithione), zinc ethylene bisdithiocarbamate (generic name: Zineb ), 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name: Seanine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 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 (common name: medetomidine) and the like.
Among these antifouling agents, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) is particularly useful from the viewpoint of antifouling performance in the immersion test after the weather resistance test. ) is preferred. These antifouling agents can be used singly or in combination of two or more.

The content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60% by mass, preferably 1 to 50% by mass, in terms of solid content. Specifically, the content of the antifouling agent is, for example, 0.1, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass. It may be in a range between any two of the numerical values given.

1-4. Other Additives Further, the antifouling paint resin of the present invention may optionally contain resin components other than copolymer A, elution modifiers, plasticizers, pigments, dyes, antifoaming agents, dehydrating agents, thixotropic An antifouling paint can be prepared by adding an agent, an organic solvent, or the like.

Examples of other resin components include polymer P and the like.
Polymer P is a polymer obtained by polymerizing the monomer (b). Monomer (b) is any ethylenically unsaturated monomer other than monomer (a). The monomer (b) used for the polymerization of the polymer P may have the same composition as the monomer (b) used for the polymerization of the copolymer A, or may have a different composition.
In the present invention, the monomer (b) can be used alone or in combination of two or more. In particular, from the viewpoint of compatibility with the copolymer A, methyl (meth)acrylate and ethyl (meth)acrylate , Butyl (meth)acrylate, Isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-(meth)acrylate Ethoxyethyl, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, triisopropylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, (meth)acrylic Tri-2-ethylhexylsilyl acid and the like are preferred.
The polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, and the like can be applied to the method described above for copolymer A.
The content of the polymer P in the composition of the present invention is not particularly limited, but the content ratio with the copolymer A, in terms of solid content, the mass ratio (polymer P / copolymer A) is usually 0 .1 to 0.5, preferably 0.1 to 0.3.

Dissolution modifiers include, for example, monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof. salts or the above alicyclic hydrocarbon resins. These can be used singly or in combination of two or more.
Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
Examples of the alicyclic hydrocarbon resin include commercially available products such as Quinton 1500, 1525L, and 1700 (trade names, manufactured by Nippon Zeon Co., Ltd.).
Among these, rosin, rosin derivatives, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferred.

Examples of the plasticizer include phosphates, phthalates, adipates, sebacates, polyesters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonylpentasulfide. , vaseline, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, and the like. These can be used singly or in combination of two or more.

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

2. Method for producing antifouling coating composition The antifouling coating composition of the present invention can be prepared, for example, by mixing and dispersing a mixed liquid containing copolymer A, fiber B, other additives, etc. using a disperser. can be manufactured. Alternatively, the fiber B may be added after mixing and dispersing a mixed liquid containing the copolymer A, the antifouling agent, other additives, etc. using a disperser.

The mixed liquid is preferably prepared by dissolving or dispersing various materials such as the copolymer A and the fiber B in a solvent. As the solvent, the same organic solvent as described above can be used.

As the disperser, for example, one that can be used as a fine pulverizer can be suitably used. For example, commercially available homomixers, sand mills, bead mills, dispersers, paint shakers and the like can be used. Alternatively, the mixed liquid may be mixed and dispersed using a container equipped with a stirrer to which glass beads or the like for mixing and dispersing are added.

3. Antifouling Treatment Method, Antifouling Coating Film, and Coated Object In the antifouling treatment method of the present invention, the antifouling coating composition is used to form an antifouling coating film on the surface of a coating film-forming object. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing adhesion of aquatic fouling organisms.
Examples of the object to be coated include ships (particularly ship bottoms), fishing tools, underwater structures, and the like.
The thickness of the antifouling coating film may be set as appropriate according to the type of object to be coated, sailing speed of the ship, seawater temperature, and the like. For example, when the object to be coated is the bottom of a ship, the thickness of the antifouling coating is usually 50-700 μm, preferably 100-600 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 indicates % by mass. The weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC. The conditions for GPC are as follows.
Apparatus: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSKgel SuperHZM-M 2 Flow rate: 0.35 mL/min
Detector... RI
Column constant temperature bath temperature: 40°C
Eluent... THF
The heating residue is a value measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Coating component test method-heating residue".

<Production Example 1 (Production of Monomer a1)>
(First reaction)
A four-necked flask equipped with a thermometer, a condenser, and a stirrer was charged with 215 g (1.85 mol) of sodium monochloroacetate, 201 g (1.85 mol) of methyl chloroacetate, and 300 g of N-methyl-2-pyrrolidone. , and stirred at 70-80° C. for 6 hours. After completion of the reaction, 500 ml of toluene was added to the reaction solution, and the organic layer was washed in this order with city water, hydrochloric acid, and sodium bicarbonate.

(Second reaction)
Then, 200 g (1.20 mol) of methoxycarbonylmethyl chloroacetate, which is the product of the first reaction, and 87 g (1.20 mol) of acrylic acid were added to a four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel. 20 mol), 4-methoxyphenol: 0.1 g, and ethyl acetate: 500 g were charged, and triethylamine: 122 g (1.20 mol) was added dropwise while stirring while maintaining the temperature at 40°C or lower. After the dropwise addition was completed, the mixture was stirred at 70 to 80°C for 6 hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water and sodium bicarbonate water in that order, and the solvent was distilled off by vacuum concentration to obtain 230.6 g of monomer a1.

<Production Examples 2 to 20 (production of monomers a2 to a20)>
Monomers a2 to a20 were obtained by carrying out reactions in the same manner as in Production Example 1 using the raw materials shown in Table 1. Table 1 shows the reaction conditions and yields of Production Examples 2 to 20.

The details of the raw materials in Table 1 are as follows.
CANa: sodium monochloroacetate CAMe: methyl chloroacetate CAEt: ethyl chloroacetate NMP: N-methyl-2-pyrrolidone AA: acrylic acid MAA: methacrylic acid TEA: triethylamine MEHQ: 4-methoxyphenol

<Production Example 21 (Production of copolymer solution A-1)>
A four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel was charged with 50 g of xylene and 50 g of propylene glycol monomethyl ether as solvents, nitrogen gas was introduced, and the temperature was maintained at 88°C while stirring. did. There, the monomers (a) and (b) shown in Table 2 and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator: 2.0 g (initial addition) was added dropwise over 3 hours while maintaining the mixture at 88°C. Then, after stirring at 88 ° C. for 1 hour, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate: 0.1 g was added 3 times every hour, and the temperature was the same. After stirring for 2 hours at , the mixture was cooled to room temperature to obtain a copolymer solution A-1. Table 2 shows the heating residue and Mw of A-1.

<Production Examples 22 to 27 (production of copolymer solutions A-2 to A-5, polymer solutions P-1 and P-2)>
Copolymer solutions A-2 to A-5, polymer solutions P-1 and P- got 2. Table 2 shows the heating residue and Mw of each. Numerical values for compounding amounts in the table are % by mass.

<Production Example 28 (Production of gum rosin zinc salt solution)>
In a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene are added to the flask, and 120 g of zinc oxide is added so that all the resin acids in the rosin form zinc salts. was added, and dehydration was carried out under reduced pressure at 70 to 80° C. for 3 hours. Thereafter, the mixture was cooled and filtered to obtain a xylene solution of rosin zinc salt (dark brown transparent liquid, solid content 50%). The heating residue of the resulting solution was 50.2%.

2. Examples and Comparative Examples (Production of coating composition)
A coating composition was produced by blending the components shown in Tables 3 to 5 in the proportions (% by mass) shown in the tables, and mixing and dispersing the mixture with glass beads having a diameter of 1.5 to 2.5 mm.

Details of each component in Tables 3 to 5 are as follows.
<Fiber B>
PF E-001: Untreated cut glass fiber, trade name “PF E-001” (manufactured by Nitto Boseki Co., Ltd.)
PF E-301: Silane-based cut glass fiber, trade name "PF E-301" (manufactured by Nitto Boseki Co., Ltd.)
SS 05C-404: Silane-based cut glass fiber, trade name "SS 05C-404", average cut length 0.1 mm (manufactured by Nitto Boseki Co., Ltd.)
MS600: Rock wool, trade name “MS600”, average cut length 125 μm (manufactured by Lapinus)
F PAC O 245/040: polyacrylonitrile, pre-oxidized polyacrylonitrile, trade name "F PAC O 245/040", average cut length 0.5 mm (manufactured by Schwarzwalder Textil-Werke)

<Elution modifier>
Gum rosin zinc salt solution: Use the one produced in Production Example 28 Gum rosin solution: Chinese gum rosin (WW) solid content 50% xylene solution

<Anti-fouling agent>
Cuprous oxide: trade name “NC-301” (manufactured by Nisshin Chemco Co., Ltd.)
Copper pyrithione: trade name “Copper Omagin” (manufactured by LONZA Co., Ltd.)
Zinc pyrithione: trade name “Zinc Omazine” (manufactured by LONZA Co., Ltd.)
SEANINE 211N: 4,5-dichloro-2-n-octyl-3-isothiazolone (manufactured by R&H, active ingredient 30% xylene solution)
ECONEA 028: 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
SELEKTOPE: Product name “Selektope” (manufactured by ITEC)

<Other additives>
Bengara: Product name "Bengara goldfish" (manufactured by Morishita Bengara Kogyo Co., Ltd.)
Talc: Product name “Talc MS” (manufactured by Nippon Talc Co., Ltd.)
Zinc oxide: Product name “Type 2 zinc oxide” (manufactured by Seido Chemical Industry Co., Ltd.)
Titanium oxide: trade name “FR-41” (manufactured by Furukawa Co., Ltd.)
Disparlon A603-20X: fatty acid amide-based thixotropic agent, trade name "Disparlon A603-20X" (manufactured by Kusumoto Kasei Co., Ltd.)
Tetraethoxysilane: trade name “Ethyl Silicate 28” (manufactured by Colcoat Co., Ltd.)
Tricresyl phosphate: (manufactured by Daihachi Chemical Industry Co., Ltd.)

3. Evaluation The following tests were performed on the coating compositions of Examples and Comparative Examples. The test results are shown in Tables 3-5. As shown in Tables 3 to 5, in all examples, the state of the coating film after 24 months was better than in the comparative example, and the uniformity of the amount of dissolved coating film was high. Such an effect was exhibited by the combination of the copolymer A and the fiber B. Comparative Examples 1 to 4 containing the copolymer A but not the fiber B, and Comparative Examples 5 and 6 containing polymer P and fiber B did not exhibit the above effects. Also, the results of Comparative Examples 7 and 8 containing the polymer P but not containing the fiber B were comparable to those of Comparative Examples 5 and 6. This indicates that the effect of improving the state of the coating film and uniforming the dissolution amount of the coating film by adding the fiber B is unique to the copolymer A.

<Test example (rotary test)>
A rotating drum with a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank, and it was made to rotate by a motor. In addition, a cooling device for keeping the seawater temperature constant and a pH automatic controller for keeping the seawater pH constant were installed.

A test plate was prepared according to the following method.
First, on a titanium plate (71×100×0.5 mm), an antirust paint (epoxy vinyl A/C) is applied so that the thickness after drying is about 100 μm, and dried to form an antirust coating film. did. After that, the coating compositions obtained in Examples and Comparative Examples were applied so that the dry film thickness was about 300 μm, and dried at 40° C. for 3 days to prepare a test panel.

The prepared test plate was fixed to the rotating drum of the rotating device of the apparatus so as to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During this period, the temperature of the seawater was kept at 25°C and the pH at 8.0-8.2, and the seawater was replaced every two weeks.

After 12 months and 24 months from the rotary test on each test plate, the surface of each coating film was observed with the naked eye and a microscope to evaluate the surface condition of the coating film.

The coating film surface condition was evaluated according to the following criteria.
◎: When there is no abnormality ○: Less than 10% of the total surface area of the coating film, hair cracks can be seen △: Hair cracks can be seen in 10 to 30% of the total surface area of the coating film ×: Coating surface Those with hair cracks in more than 30% of the total area

In addition, the remaining film thickness of each test plate at the initial stage and every 12 months after the start of the test was measured with a shape measurement laser microscope VK-X100 manufactured by Keyence Corporation, and the dissolved coating film thickness was calculated from the difference. An average coating film dissolution amount per month (μm/month) was obtained. Calculate the average coating film dissolution amount T1 for 0 to 12 months from the start of the test and the average coating film dissolution amount T2 for 12 to 24 months from the start of the test, and calculate the ratio (T1/T2) that indicates the uniformity of the coating film dissolution amount. Calculated.

Claims (1)

An antifouling paint composition containing a copolymer A and a fiber B,
The copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a),
The antifouling paint composition, wherein the monomer (a) is represented by the general formula (1).

(In the formula, R ¹ represents hydrogen or a methyl group, R ² represents hydrogen, a methyl group, or a phenyl group, and R ³ may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group. It is an alkyl group having 1 to 8 carbon atoms or represents a phenyl group, and n represents an integer of 2 to 10.)