WO2019221047A1 - Antifouling coating material composition - Google Patents

Abstract

Provided is an antifouling coating material composition which makes it possible to form a coating film which exhibits improved cracking resistance, adhesion properties and flexibility. The present invention provides an antifouling coating material composition which contains a polymer A, a component B, and an antifouling agent, wherein: the polymer A is a copolymer of a monomer (a) and an ethyleny unsaturated monomer (b) which is not the monomer (a); the monomer (a) is represented by general formula (1); and the component B is a paraffin-based mineral oil which contains an aromatic hydrocarbon.

Description

Antifouling paint composition

The present invention relates to an antifouling paint composition.

Aquatic fouling organisms such as barnacles, cell plastics, blue mussels, scallops, sea squirts, blue sea breams, blue sea breams, slime, etc., become submarine structures such as ships (especially ship bottoms), fishing nets, fishing net accessories, etc. Adhering causes problems such as damage to the functions of the ship and the like, and the appearance.

In order to prevent such problems, an antifouling coating composition is applied to a ship or the like to form an antifouling coating, and the antifouling agent is gradually released from the antifouling coating, thereby preventing the antifouling over a long period A technique for demonstrating performance is known (Patent Document 1).

JP 2000-17203 A

The effect of the antifouling paint greatly depends on the thickness of the coating film. The bow, stern, drafting section, etc. may be painted thickly during the navigation of the ship, especially because water pressure is often applied. Therefore, the coating film is likely to be cracked, cracked or peeled off.

The present invention has been made in view of such circumstances, and provides an antifouling paint composition capable of forming a coating film having improved crack resistance, adhesion, and flexibility.

According to the present invention, there is provided an antifouling paint composition comprising a polymer A, a component B, and an antifouling agent, wherein the polymer A comprises a monomer (a) and the monomer (a). Other than the ethylenically unsaturated monomer (b), the monomer (a) is represented by the general formula (1), and the component B is a paraffin containing an aromatic hydrocarbon. An antifouling paint composition that is a mineral oil is provided.

As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing the polymer A, the component B, and the antifouling agent can solve the above problems, and completed the present invention. It was.

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

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). The polymer A includes monomer units derived from the monomers (a) and (b).

<Monomer (a)>
Monomer (a) is a triorganosilyl (meth) acrylate monomer and is represented by general formula (1).

(Wherein R ¹ is hydrogen or a methyl group, and R ² to R ⁴ are the same or different and each represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group)

Examples of the branched alkyl group having 3 to 8 carbon atoms of R ² to R ⁴ include isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 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 include heptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2,2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpentyl group, and 3-methylpentyl group. Preferred as R2 to R4 are isopropyl group, s-butyl group, t-butyl group, phenyl group, and 2-ethylhexyl group. Particularly preferred are isopropyl group and 2-ethylhexyl group.

Examples of the monomer (a) include triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, triisopentylsilyl (meth) acrylate, meta (Meth) acrylic acid triphenylsilyl, (meth) acrylic acid diisopropylphenylsilyl, (meth) acrylic acid diisopropylisobutylsilyl, (meth) acrylic acid diisopropyl s-butylsilyl, (meth) acrylic acid diisopropylisopentylsilyl, (meth) Isopropyl diisobutylsilyl acrylate, isopropyl dis-butylsilyl (meth) acrylate, t-butyldiisoptylsilyl (meth) acrylate, t-butyldiisopentylsilyl (meth) acrylate, t- (meth) acrylate Butyldi Phenylsilyl, (meth) acrylate diisopropyl texylsilyl, (meth) acrylate diisopropylcyclohexylsilyl, (meth) acrylate tricyclohexylsilyl, (meth) acrylate tri-1,1-dimethylpentylsilyl, (meth) acrylate tri 2,2-dimethylpropylsilyl, (meth) acrylate tricyclohexylmethylsilyl, (meth) acrylate diisopropylcyclohexylmethylsilyl, (meth) acrylate tri-2-ethylhexylsilyl, (meth) acrylate tri-2-propylpentylsilyl Etc. Preferred examples include triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, tri-2-ethylhexylsilyl (meth) acrylate, and the like. These monomers (a) can be used alone or in combination of two or more.

<Monomer (b)>
Monomer (b) is an ethylenically unsaturated monomer other than monomer (a), such as (meth) acrylic acid ester, vinyl compound, aromatic compound, dibasic acid dialkyl ester compound, etc. 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) Glycidyl acrylate, furfuryl (meth) acrylate, (meth) acrylic Tetrahydrofurfuryl, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- [2- (2-hydroxyethoxy) ethoxy] ethoxy] ethyl methacrylate, mono (2- (meth) acryloyl succinate) Oxyethyl), N- (3-dimethylaminopropyl) (meth) acrylamide, 2- [2- (2-methoxyethoxy) ethoxy] ethyl (meth) acrylate, N, N′-dimethyl (meth) acrylamide, ( 2- (2-methoxyethoxy) ethyl (meth) acrylate, (meth) acrylic acid, hydroxypropyl acrylate, 2- (acetoacetyloxy) ethyl methacrylate, 2- (2-hydroxyethoxy) ethyl methacrylate, N- Vinyl-2-pyrrolidone, acrylic acid 2- [2- (2-ethoxy ) Ethoxy] ethyl,
4-hydroxybutyl acrylate glycidyl ether, N-isopropyl acrylamide, 2- (dimethylamino) ethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, Acrylic esters such as 3-chloro-2-hydroxypropyl acrylate, 2- [2- (2-ethoxyethoxy) ethoxy] ethyl methacrylate, N, N′-diethylacrylamide, 3-methoxybutyl acrylate,
Etc.

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-vinyl pyrrolidone. It is done.

Examples of the aromatic compound include styrene, vinyl toluene, α-methyl styrene and the like.

Examples of dibasic acid dialkyl ester compounds include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

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 properties, and particularly from the viewpoint of crack resistance, methyl methacrylate, butyl (meth) acrylate, (meth) acrylic. Isobutyl acid, 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 preferable.

The monomer (a) in the polymer A 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 a 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 coating film solubility is particularly good.

The weight average molecular weight (Mw) of the polymer A is desirably 5000 to 300,000. If the molecular weight is less than 5,000, the antifouling coating film becomes brittle and easily peels and cracks. 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, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, and between any two of the numerical values exemplified here. It may be within the range.

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

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

Polymer 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 the like; 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-amylperoxyneodecanoate, t-hexylperoxypivalate, t-amylperoxypi Examples thereof include peroxides such as barate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, etc. These polymerization initiators can be used alone or in combination of two or more thereof. As polymerization initiators, in particular, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) Dimethyl 2,2′-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are preferred. By appropriately setting, it is possible to adjust the molecular weight of the copolymer A.

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 preferable in that the polymer A can be obtained easily and accurately.

In the polymerization reaction, an organic solvent may be used as necessary. Examples of the organic solvent include, but are not limited to, aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; isopropyl Examples include alcohol solvents such as 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.
Of these, 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 kind of the polymerization initiator and the like, and is usually 50 to 160 ° C., preferably 60 to 150 ° C.

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

1-2. Component B
Component B is a paraffinic mineral oil containing aromatic hydrocarbons.
Mineral oil is refined petroleum fraction and is composed of paraffin, naphthene, aromatic hydrocarbons and the like. Ring analysis (NDM method) by ASTM D3238 is composed of paraffin carbon number (% CP), naphthene carbon number (% CN), aromatic carbon number (% CA), and% Cp is 50% or more Mineral oil is called paraffinic mineral oil. % Cp is, for example, 50 to 95%, specifically, for example, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95%, and any one of the numerical values exemplified here is 2 It may be within a range between the two.

This component B is a paraffinic mineral oil containing aromatic hydrocarbons, and the content of the aromatic hydrocarbons is, for example, 0.1%% CA by ring analysis (ndM method) according to ASTM D3238. -20%, preferably 0.1-15%, more preferably 0.3-12%, still more preferably 8-12%. Specifically,% CA is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, between any two of the numerical values illustrated here It may be within the range.

The aniline point of Component B is preferably from 80 to 123 ° C., more preferably from 80 to 120 ° C., and even more preferably from 80 to 110 ° C., from the viewpoint of preventing coating film abnormality. Specifically, this value is, for example, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123 ° C It may be within a range between any two of the numerical values exemplified here. The aniline point is a value measured in accordance with JIS K2256.

As component B, for example, Cosmo Pure Safety 10M, Cosmo Pure Safety 22, Cosmo Pure Safety 32, Cosmo Pure Safety 46, Cosmo Pure Safety 68, Cosmo Pure Safety 100, Cosmo Pure Safety Tea 150, Cosmo Neutral 100, Cosmo Neutral 150, Cosmo Neutral 350, Cosmo Neutral 500, Cosmo Neutral 700, Cosmo SP10, Cosmo SP15, Cosmo SP83 (trade name, manufactured by Cosmo Oil Lubricants Co., Ltd.).

1-3. Antifouling agent Examples of the antifouling agent include inorganic agents and organic agents.
Examples of the inorganic agent include cuprous oxide, copper thiocyanate (generic name: rhodan copper), copper powder, and the like. Of these, cuprous oxide and rhodan copper are particularly preferred, and cuprous oxide is surface-treated with glycerin, sucrose, stearic acid, lauric acid, lysine, mineral oil, etc., for long-term stability during storage. And more preferable.
Examples of organic agents include 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylene bisdithiocarbamate (generic name: Genev). ), 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name: cineine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4- t-Butylamino-6-cyclopropylamino-s-triazine (generic name: Irgarol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea 28) , 4- [1- (2,3-Dimethylphenyl) ethyl] -1H-imidazole Generic name: medetomidine), and the like.
These antifouling agents can be used alone or in combination of two or more.

1-4. Other additives Furthermore, the resin for antifouling paints of the present invention includes, if necessary, resin components other than the polymer A, elution regulator, plasticizer, pigment, dye, antifoaming agent, dehydrating agent, thixotropic agent. An organic solvent or the like can be added to make an antifouling paint.

Examples of other resin components include polymer P.
The polymer P is a polymer obtained by polymerizing the monomer (b). The monomer (b) is any ethylenically unsaturated monomer other than the monomer (a). The monomer (b) used for polymerizing the polymer P may have the same composition as the monomer (b) used for polymerizing the polymer A or a different composition.
In the present invention, the monomer (b) can be used alone or in combination of two or more, and in particular, from the viewpoint of compatibility with the polymer A, methyl (meth) acrylate, ethyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxy (meth) acrylate Ethyl, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and benzyl (meth) acrylate are preferred.
For the polymerization method, the initiator, the solvent, the temperature, other conditions, the Mw measurement method, and the like, the method described above for the polymer A can be applied.
The content of the polymer P in the composition of the present invention is not particularly limited, but the content ratio with the polymer A is usually 0.1, and the mass ratio (polymer P / polymer A) is 0.1. Is 9.0, preferably 0.1 to 4.0.

Examples of the elution regulator include monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof, and the like. Examples thereof include a salt or the alicyclic hydrocarbon resin. These can be used alone 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 Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like as commercially available products.
Among these, rosin, rosin derivatives, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferable.

Examples of the plasticizer include phosphate esters, phthalates, adipic esters, sebacic esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, petrolatum, Examples include polybutene, trimellitic acid tris (2-ethylhexyl), silicone oil, chlorinated paraffin, and the like. These can be used alone or in combination of two or more.

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

2. Process for producing antifouling paint composition The antifouling paint composition of the present invention is prepared by, for example, mixing a mixed solution containing the polymer A, component B, an antifouling agent, and other additives using a disperser. It can be manufactured by dispersing.
The mixed solution is preferably prepared by dissolving or dispersing various materials such as polymer A, component B and antifouling agent in a solvent.
As the disperser, for example, one that can be used as a fine pulverizer can be suitably used. For example, a commercially available homomixer, sand mill, bead mill, disper, etc. can be used. Alternatively, the mixed solution may be mixed and dispersed using a container provided with a stirrer to which glass beads for mixing and dispersing are added.

3. Antifouling treatment method, antifouling coating film, and coated article The antifouling treatment method of the present invention forms an antifouling coating film on the surface of a film-forming article using the antifouling coating composition. 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 the adhesion of chickenpox fouling organisms.
Examples of the coating film formation include ships (particularly ship bottoms), fishing equipment, underwater structures, and the like.
What is necessary is just to set the thickness of an antifouling coating film suitably according to the kind of coating-film formation thing, the navigation speed of a ship, seawater temperature, etc. For example, when the coating film forming object 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 will be described below to further clarify the features of the present invention. However, the present invention is not limited to the examples.
% In each production example, example and comparative example represents mass%. The weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC. The conditions of GPC are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column ... TSKgel SuperHZM-M 2 flow rate ... 0.35 mL / min
Detector ... RI
Column bath temperature ... 40 ° C
Eluent: THF
The heating residue is a value measured according to JIS K 5601-1-2: 1999 (ISO 3251: 1993) “Paint component test method—heating residue”.

<Production Example 1 (Production of Polymer A Solution_A-1)>
Into a four-necked flask equipped with a thermometer, a cooler, a stirring device, and a dropping funnel, 40 g of xylene (initial solvent) was charged, nitrogen gas was introduced, and the temperature was maintained at 88 ° C. while stirring. Thereto, monomers (a) and (b) shown in Table 1 and 0.8 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator (initial addition) ) Was added dropwise over 3 hours while maintaining at 88 ° C. Then, after stirring for 1 hour at 88 ° C., 0.2 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (post-addition) was added three times every hour, After further stirring for 2 hours at the same temperature, 60 g of xylene (diluting solvent) was added and cooled to room temperature to obtain a polymer A solution A-1. Table 1 shows the heating residue and Mw of A-1.

<Production Examples 2 to 10 (Production of Polymer A Solution_A-2 to A-7, Polymer Solution_P-1 to P-3)>
Polymer A solutions A-2 to A-7 were prepared by carrying out the polymerization reaction in the same manner as in Production Example 1 under the respective reaction temperature conditions using the monomers, polymerization initiators and solvents shown in Table 1. Polymer solutions P-1 to P-3 were obtained. Table 1 shows the heating residues and Mw of A-2 to A-7 and P-1 to P-3. The numerical values in the table are mass%.

<Production Example 11 (Production of 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 placed in the flask, and 120 g of zinc oxide is formed so that all resin acids in the rosin form a zinc salt. And refluxed and dehydrated under reduced pressure at 70-80 ° 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 obtained solution was 50.2%.

<Production Example 12 (Production of hydrogenated rosin zinc salt solution)>
In a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of High Pale CH (hydrogenated gum rosin) and 360 g of xylene are placed in the flask, and zinc oxide is formed so that all resin acids in the rosin form a zinc salt. 120 g was added and reflux dehydrated under reduced pressure at 70-80 ° C. for 3 hours. Thereafter, the solution was concentrated, cooled, and filtered to obtain a hydrogenated rosin zinc salt xylene solution (dark brown liquid, solid content 65%). The heating residue of the obtained solution was 65.1%.

<Examples 1 to 27 and Comparative Examples 1 to 12 (Production of Coating Composition)>
The components shown in Tables 2 to 7 were blended in the proportions (mass%) shown in these tables, and were mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to produce coating compositions.

Details of component B, antifouling chemicals, and other additives in the table are as follows.
<Component B>
Cosmo SP83:% CP67.2,% CN32.5,% CA0.3, aniline point 119.0 ° C
Cosmo SP15:% CP67.1,% CN31.6,% CA1.3, aniline point 102.0 ° C.
Cosmo Neutral 700:% CP66.8,% CN25.3,% CA7.9, aniline point 110.1 ° C
Cosmo neutral 150:% CP68.3,% CN27.7,% CA4.0, aniline point 104.9 ° C
Cosmo Pure Safety 68:% CP63.1,% CN27.7,% CA9.2, aniline point 99.5 ° C
Cosmo Pure Safety 32:% CP64.0,% CN25.7,% CA10.3, aniline point 93.4 ° C
Cosmo Pure Safety 22:% CP62.1,% CN28.3,% CA9.6, aniline point 88.8 ° C
Cosmo Pure Safety 10:% CP59.0,% CN30.3,% CA10.7, aniline point 81.6 ° C
Moresco White P-350P:% CP70,% CN30,% CA0, aniline point 122 ° C
Moresco White P-260:% CP70,% CN30,% CA0, aniline point 118.0 ° C
Moresco White P-100:% CP70,% CN30,% CA0, aniline point 108.2 ° C

<Anti-fouling agent>
Cuprous oxide: Trade name “NC-301” (manufactured by Nisshin Chemco)
Copper pyrithione: trade name "Copper Omagine" (manufactured by LONZA Corporation)
Zinc pyrithione: Trade name “Zinc Omagine” (manufactured by LONZA Corporation)
Copper thiocyanate (I): trade name "copper thiocyanate (I)" (Wako Pure Chemical Industries, Ltd.)
Zineb: Trade name "Gineb" (manufactured by SIGMA-ALDRICH)
DCOIT: 4,5-dichloro-2-n-octyl-3-isothiazolone (manufactured by Tokyo Chemical Industry Co., Ltd.)
Econea: Trade name “Econea 028” 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
Medetomidine: (±) -4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (manufactured by Wako Pure Chemical Industries, Ltd.)

<Other additives>
Toyoparax A40S: Chlorinated paraffin, chlorine content 40.5% (manufactured by Tosoh Corporation)
Sansosizer E-2000H: Epoxidized soybean oil (manufactured by Shin Nippon Rika Co., Ltd.)
Rosin zinc salt solution: Use the one produced in Production Example 11. Gum rosin solution: Chinese gum rosin (WW) solid content 50% xylene solution Hydrogenated rosin solution: Product name “Hyper CH” (manufactured by Arakawa Chemical Industries, Ltd.) 50% solids xylene solution.
Hydrogenated rosin zinc salt solution: Use the one produced in Production Example 12. Bengala: Trade name “Bengarakinkyokoku” (Morishita Valve Industrial Co., Ltd.)
Talc: Trade name "Talc MS" (Nippon Talc Co., Ltd.)
Zinc oxide: Trade name "Zinc oxide 2 types" (manufactured by Shodo Chemical Co., Ltd.)
Titanium oxide: Trade name “FR-41” (Furukawa Machine Metal Co., Ltd.)
Ethyl silicate 28: Trade name “Ethyl silicate 28” (manufactured by Colcoat Co., Ltd.)
Hemihydrate gypsum: “NP3D” (manufactured by Noritake Company Limited)
Disparon A603-20X: Amide thixotropic agent: Trade name “Disparon A603-20X” (manufactured by Enomoto Kasei Co., Ltd.)
Disparon 4200-20: Polyethylene oxide thixotropic agent: Trade name “Disparon 4200-20” (manufactured by Enomoto Kasei Co., Ltd.)

The following tests were conducted on the coating compositions of Examples and Comparative Examples.
<Test Example 1 (Film physical property test)>
A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were attached.
A test plate was prepared according to the following method.
First, on a titanium plate (71 x 100 x 0.5 mm), a rust preventive paint (epoxy vinyl A / C) is applied so that the thickness after drying is about 100 μm and dried to form a rust preventive coating. did. Then, the coating composition obtained by the Example and the comparative example was apply | coated so that a dry film thickness might be set to about 100 micrometers and about 200 micrometers, and the test board was prepared by making it dry at 40 degreeC for 3 days. Four test plates were prepared for each coating composition.
One of the produced test plates was fixed to the rotating drum of the rotating device of the apparatus so as to contact seawater, and the rotating drum was rotated at a speed of 20 knots. Meanwhile, the temperature of the seawater was kept at 25 ° C. and the pH was kept at 8.0 to 8.2, and the seawater was changed every two weeks.
After drying the test plates having a dry film thickness of about 100 μm and about 200 μm after 3 months and 6 months of the rotary test, the surface of each coating film was visually observed to evaluate the state of the coating film. Evaluation was performed by the following method.
◎: When there is no abnormality ○: Less than 10% of the total surface area of the coating film, and hair cracks are observed △: Hair cracking is observed in 10 to 30% of the total surface area of the coating film ×: Surface of the coating film Hair cracks can be seen in more than 30% of the total area. XX: Large cracks, blisters or peelings (only the surface of the coating film or part of the edge is peeled off), peeling (the whole coating film is peeled off, test coating) Abnormality is seen in the paint film such as no film remaining)

<Test Example 2 (Paint Adhesion Test)>
A coating adhesion test was performed in accordance with JIS K-5600-5-6. Specifically, after drying a test plate having a dry film thickness of about 100 μm and about 200 μm after 3 months and 6 months of the rotary test, 6 scratches reaching the base are placed in a grid pattern to obtain a 3 mm square. Twenty-five lattice patterns were formed. A 24 mm wide tape made by Nichiban Co., Ltd. is affixed to this lattice pattern so that no air bubbles enter, and the tape is firmly rubbed with a fingertip. One end of the tape was held and peeled off at a stretch, and the state of adhesion of the coating film was examined visually.
◎: 22 to 25 lattices that were not peeled ◯: 16 to 21 lattices that were not peeled △: 11 to 15 lattices that were not peeled ×: 0 to 10 lattices that were not peeled

<Test Example 3 (Coating Flexibility Test)>
After drying a test plate having a dry film thickness of about 100 μm and about 200 μm after 3 months and 6 months of the rotary test,
The film was bent at 90 degrees and the state of the coating film was visually confirmed.
◎: Almost no cracking or peeling is observed. ○: Small cracking or peeling is observed. △: Medium cracking or peeling is observed. X: Large cracking or peeling is recognized.

<Test results>
From the results of Test Examples 1 to 3, it was confirmed that the crack resistance of the coating film was improved, the adhesion of the coating film was improved, and the flexibility of the coating film was improved.

Claims (1)

1. An antifouling paint composition comprising a polymer A, component B, and an antifouling agent,
   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 paint composition, which is a paraffinic mineral oil containing an aromatic hydrocarbon.
   

   

   (Wherein R ¹ is hydrogen or a methyl group, and R ² to R ⁴ are the same or different and each represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group)