TW200911935A - Antifouling paint composition, antifouling coating film, and vessels and underwater structures - Google Patents

Abstract

An antifouling paint composition comprising both a binder resin (A) and an antifouling agent (B) wherein the antifouling agent (B) contains a metal pyrithione (B1), a salt (B2) of triphenylborane with amine, and a sulfamide compound (B3) represented by the general formula (1) [wherein R is hydrogen or straight-chain or branched alkyl having 1 to 10 carbon atoms]; antifouling films made from the paint composition; and vessels and underwater structures, which have the antifouling films. The paint composition can give antifouling coating films which keep antifouling effect for a long period and are excellent in crack resistance.

Description

200911935 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to an antifouling coating composition, and more particularly to an antifouling coating film which can form a high long-term antifouling property and is excellent in crack resistance. Antifouling coating composition. Further, the present invention relates to an antifouling coating film formed from the antifouling coating composition, and a ship and an underwater structure having the antifouling coating film. [Prior Art] Water structures such as various fish nets, harbor facilities, oil dykes, distribution materials, bridges, buoys, industrial water systems, and submarine bases, which are mainly used for ships and cultures, are often exposed to the water inhabited by organisms. In the meantime, when the time passes, the microorganisms such as bacteria adhere to each other, and the animals and plants such as barnacles, mussels, sarcophagus, and diatoms are attached to the food. When the surface of a ship or underwater structure is covered by such microorganisms and animals and plants, the part of the rot may occur. The ship's oil is increased due to the increased resistance of the ship to seawater friction: the efficiency is lowered, and the mesh of the fishing net is plugged. Living and causing a large number of violent marine products, floating only due to reduced buoyancy and settlement, and reduced operational efficiency. In addition, industrial water systems such as cooling water such as natural water such as river water or lake water, and circulating cooling devices for water in the middle of use, may cause deterioration of water quality due to the growth of bacteria, curtains, cyanobacteria, etc. The cooling efficiency is lowered due to the adhesion of the wall, and the barrier of the water pipe and the flow rate are reduced. As a method of preventing the adhesion of such pests, there has been a method of applying an antifouling paint in the past.

2075-9848-PF 5 200911935 The compound acts as an antifouling agent. In recent years, the use of such antifouling agents has been banned from the point of view of the safety of ecosystems. For example, Japanese Laid-Open Patent Publication No. H-29-725 (Patent Document No.), Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin (Patent Document 4 \ & Ge Bu) 驮 4), which can be used as an antifouling agent for replacing an organotin compound, such as 'copper oxide, copper rhodanate, ethylene double bis Manganese thiocarbamate, dimethyldichlorophenylurea, 4,5-di-2-non-octyl-3-(2H)-isothiazoline, 2-pyridinyl mercaptan-1-oxo Zinc salt (pyridinone), N,N,-didecyl N, benzophenone (N-fluoro-methylmethylthio)sulfonamide, pyridine-triphenylboron, and the like. In addition, the above antifouling agents have also been used in combination. For example, Japanese Patent Publication No. 2 001 329228 (Patent Document 5) and Japanese Patent Laid-Open No. 9-A (Patent Document 6) disclose the use of a mixture of pyridine triphenyl boron and 2 pyridine thiol-hydrazine-oxy zinc. Salt (pyridinone), 2_pyridinethiol_ι_oxygen copper (comparison to thione), cuprous oxide, thiocyanate (3) rhodamine, 4 r a # '-chlorine Any one or more antifouling coating compositions of n-octyl-3-(2H)-isoindole. Japanese Patent Publication No. Hei 9-3366 (Patent Document 7) discloses a type 2 including. It is effective as the first antifouling property to form free ethylene bisdithiocarbamic acid phthalic acid, ethylene bis-thioamine phthalic acid zinc, diethyl dithioamine. Base bismuth bisdithiocarbamate zinc phthalate, cuprous oxide, cuprous thiocyanate, bis(2-pyridinethio-oxo) copper or N,(fluorodichloromethylthio) _o-phthalimide (II)

2075-9848-PF 6 200911935 Chloropurine methylthio)_N,,N,_dimethyl-N-phenylthioguanamine, 4,5-dichloro-2-n-octyl-isothiazoline-3 Any one of ketone, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine and 3-iodo-2-propargylbutyl carboxylic acid is the second antifouling active ingredient. Japanese Patent Publication No. Hei No. 0-298455 (Patent Document 8) discloses an antifouling coating composition comprising cuprous oxide, bis(2-pyridinethiol-1, copper salt, and selected from 2, 4 , 5, 6 - tetrahydrogen nitrile, N, N-dimethyl-dichlorophenyl urea, zinc monomethyldithiocarbamate, any one of the compounds. 曰本特开2GG 342432号 ( Patent Document 9), which discloses a combination of cuprous and 4'5-dichloro-2-n-octyl-3(2H)jD plug (4) with a combination of 2 - thiol thiol + oxy zinc salt; and oxidation Cuprous, mouth ratio σ疋 thiol-1 - oxygen recording sleep A % ^ 辛 · ^ and ethylene bisdithiocarbamic acid zinc group, etc., but the above antifouling coating composition 'both In the anti-fouling period, there is room for change in the anti-fouling period. In addition, there is room for a large amount of anti-fouling agent to be fully protected against pollution. The agent and the countermeasures against pollution have also been improved in the seawater-soil-coated film ship#, which will repeatedly immerse the circulation of the U-man's upper jaw. Therefore, for the anti-fouling coating film, it is necessary to be flexible and stain-resistant. Coating film does not: In the case of the antifouling coating composition, there is a case where the coating film is cracked. , Li Li Document 1. 曰本特开平11-29725号 Libli Literature 2. 曰本特开平11-172159号3. 曰本特开20 02-26 5849号

Japanese Patent Publication No. 2001-32922 No. JP-A No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The object of the present invention is to improve the antifouling coating composition, which is excellent in antifouling property and excellent in crack resistance even if it is blended with the prior antifouling agent in the It A u period. Another object of the present invention is to provide an antifouling coating film formed of the antifouling coating composition, even if a cycle of seawater immersion to landing is repeated, and cracking is not likely to occur; And a ship and an underwater structure having the antifouling coating film. [Means for Solving the Problem] The inventors of the present invention have studied the antifouling agent in order to solve the problem of the upper armor β and the class. 'Discover by using a specific The antifouling of the stain, ', U' can have a long-term antifouling property even if it is blended with a small amount of antifouling agent, and it can be provided with an antifouling coating film which imparts excellent crack resistance. The present invention is as follows. The present invention is an antifouling coating composition '., which comprises an antifouling coating composition of gluing tree t (A) and antifouling agent (B). Cut the anti-suppressant (β), containing:

2075-9848-PF 8 200911935 Metal ° ratio thione (B1), triphenylboramine salt (B2) thiolamine compound (B 3 ): 0R ~ and the following formula (])

FC^CS - N \ S02N(CH3)2 In the above formula (1), R is a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 Å. The above-mentioned base amine salt (B2) contains hydrazine. It is better to fix the triphenyl shed. In addition, it is preferable that the ruthenium compound (β3) contains one or more compounds selected from the group consisting of the following formula (2) and the following formula (3):

2)

FCl2CS"TM*N 0 (3) FDI2CS-N.

It is preferable that so2n_2 /CHS S〇2N(CH3)2 has at least one lower and the above-mentioned binder resin (A)' is contained in the resin of the group represented by the side chain (4):

—oX丫— (4)

It is a hydrocarbon, ruthenium is a divalent metal, A represents a group, and k is 0 or 1 is an organic acid residue of a monobasic acid.

2075-9848-PF 9 200911935 Further, the above-mentioned binder resin (A) is a resin of the formula (5) which is preferably 0II | —〇. —_—— R2 is contained in the side chain and has at least one of the following 5) In the general formula (5), 'R!, R2 and R3 represent the same or different hydrocarbon residues having 1 to 20 carbon atoms. Further, the above-mentioned binder resin (A) is in the side chain to the group represented by the formula (4), and the resin represented by the following formula (/, the following is preferably: kg) is 0 (4) Ο R1 c Ο Si Si Si R R R R Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si Si In the above formula (5), R1, }^2, and 1 to 2 0 of a hydrocarbon residue. a divalent metal, the same or different, the carbon number of the above monobasic acid, a monobasic cyclic organic acid as a preferred acid, selected from the group consisting of rosin, hydrogenated rosin, sputum rosin, and the above-mentioned unary, Naphthenic acid,

2075-9848-PF 10 200911935 at least one of the group consisting of rosin acid, dehydroabietic acid, and aerated rosin acid; and, in the antifouling coating composition of the present invention, a binder resin (a), and the above The hydrolyzable resin may be added to or substituted for the hydrolyzable resin, and may be a binder resin other than the hydrolyzable resin. Other gluing resins can be used well in gasified paraffin, rosin, and hydrogenated rosin. Further, the present invention provides an antifouling coating film which is formed by using any of the antifouling coating compositions described above, and a ship or underwater structure having the antifouling coating film. [Effect of the Invention] According to the antifouling coating composition of the present invention, even if a small amount of the antifouling agent is blended, the antifouling property can be maintained for a long period of time, and an anti-cracking property can be formed which is excellent in crack resistance. The antifouling paint of the present invention can be suitably used for antifouling of various structures such as various fishing nets, harbor facilities, oil dikes, piping materials, bridges, buoys, industrial water facilities, seabed bases, etc., which are led by ships and cultures. Antifouling paint. [Embodiment] The antifouling coating composition of the present invention is an antifouling coating composition comprising a binder resin (A) and an antifouling agent (B), the antifouling agent (β) comprising: metal pyrithione ( Β1), triphenylboramine salt (Β2), and thiourethane compound (B3) d By such a configuration, an antifouling coating film having extremely high antifouling property and excellent crack resistance can be formed. Hereinafter, each component contained in the antifouling coating composition of the present invention will be described in detail. <Glue resin (A)&gt;

2075-9848-PF 200911935 A binder resin used in the antifouling coating composition of the present invention can be used as a prior art, and a hydrolyzable resin is preferred. By using a hydrolyzable resin as the binder resin, the high antifouling property by the antifouling agent can be maintained for a long period of time. As the hydrolyzable resin, a resin previously used for an antifouling paint can be used, but an acrylic resin can be preferably used, and the acrylic resin can be an acrylic resin having a base represented by the following formula (4); u) an acrylic resin having a group represented by the following formula (5); (iii) an acrylic resin having a group represented by the following formula (4) and a group represented by the following formula (5) Acrylic resin, etc. These may be used alone or in combination of two or more. Further, in the specification +, "acrylic resin" means that at least one part of the resin is (meth)acrylic acid or a derivative thereof, or a resin composed of a constituent unit of (meth)acrylic acid vinegar. The derivative of methyl acrylic acid also contains a metal salt of (meth)acrylic acid: "(4) In the above formula (4), the X system represents a 丄~ group k 〇 or a y system Carbide, hydrazine is a divalent metal, A is an organic acid residue of a -acid acid; II | Ib. One 'one 2 (s) R3 The above formula (5) φ pi n 2 ^ 3 R, R, R series means the same or different, carbon number 1~2 0

2075-9848-PF 12 200911935 Hydrogen chloride residue. The above-mentioned (preferable specific example of the acrylic resin) is an acrylic resin (hereinafter also referred to as "acrylic resin (A1)) having at least one group represented by the above formula (4) in the side chain. Since the obtained coating film can be long: a polishing rate of three, a more excellent long-term property can be exhibited. In the above formula (4), the oxime is a divalent metal', for example, 3 Α to 7 Α, 8 in the periodic table. In the above formula (4), the organic acid residue of the monobasic acid is preferred. The preferred monobasic acid may, for example, be a monocyclic organic acid or the like. The cyclic organic acid is not particularly limited, and examples thereof include a cyclic acid having a naphthenic acid, a resin acid such as tricyclic glycolic acid, and the like. The tricyclic resin is not particularly limited. For example, a compound having a skeleton of a bismuth-based hydrocarbon skeleton, for example, a compound having a skeleton of a rosin yard, a stone rosin, an exotic pine or a garden, may be mentioned. , remnantic acid, neo-abietic acid, dehydrogenated di-: hydrogenated rosin acid, yang strinic acid, sea pine acid, different sea夂 = pimaric acid, dextran pimaric acid, sandalwood pimaric acid, and these lipid salts are better than rosin acid, hydrogenated scented hydrazine, and these fatty salts. Good one yuan ring has

Machine, can be raised at a price of 220 K〇H

SftUIl/g or less. By using an acid &lt;below alpha-like organic knockdown of 22 〇mg_/g or less, the viscosity of the resulting glue resin can be lowered, and the mixture can be reduced by I. The viscosity of the gluing resin is relatively large in accordance with the interaction of the formula (4). Use a gel with a secret of 220mgKOff/g or less.

2075-9848-PF 13 200911935

Jix nt. ( li \ two-dimensional: the steric obstacle of the organic acid of the element r has a tendency to become larger, and the body disorder hinders the interaction of the functional groups represented by the general formula (4), and as a result, the glue resin can be lowered (human) The viscosity of the two-membered cyclic organic acid is not required to be highly purified, and for example, a resinous resin such as pine can be used. Examples thereof include rosin, aroma, disproportionated rosin, and the like. The rosin, the gum rosin, the tar rosin, etc. The rosin, hydrogenated rosin is cheap and suitable for Dan, one person blows the rosin, easy to start 'operability is excellent, can play a long-term anti-fouling point and two ... yuan The cyclic organic acid may be used singly or in combination of two or more. It may be used in one of the materials of the present invention. 7 and the cyclic organic acid may, for example, be acetic acid, propionic acid 'butyric acid, lauric acid, Stearic acid, human ricinoleic acid, oleic acid, gaseous acetic acid, fluorocalic acid, valeric acid, etc. Carbonic acid 2, etc. These monobasic acids may be used singly or in combination of two or more. 乍 is the above formula (4) The γ is not particularly limited as long as it is a hydrocarbon, and for example, 'polymerization' The residue of the dibasic acid such as phthalic acid, succinic acid or maleic acid is added to the unsaturated organic monomer. The method for producing the acrylic acid resin (9) is not particularly limited, and for example, (a) a method of reacting a polymerizable unsaturated organic acid with another copolymerizable unsaturated monomer, and a method of reacting a monobasic acid with a metal compound; (b) reacting the polymerizable unsaturated organic acid with a metal compound, or A method in which a polymerizable unsaturated organic acid is reacted with a metal salt of a monobasic acid to polymerize the obtained metal-containing unsaturated monomer 'with other copolymerizable unsaturated monomers.

2075-9848-PF 14 200911935 The polymerizable unsaturated organic acid of the above (A) and (B) is not particularly limited. More than one polymerized unsaturated organic acid of the lysine. More specifically, it may, for example, be an unsaturated monobasic acid such as (meth)acrylic acid; an unsaturated dibasic acid such as maleic acid and its monoalkyl, itaconic acid or its monoalkyl vinegar; Alkyl ester; maleic acid adduct of 2-hydroxyethyl (meth)acrylate, phthalic acid adduct of 2-hydroxyethyl (meth)acrylate, 2-hydroxyl (meth)acrylate An ester succinic acid adduct or the like. These polymerizable unsaturated organic acids may be used singly or in combination of two or more. Further, in the method (ii), as the metal-containing unsaturated monomer, a part or all of it may be replaced by a divalent (meth)acrylic acid divalent metal salt. When a divalent metal salt of bis(indenyl)acrylic acid is used, the resin is bridged via the group represented by the formula (4), and such a resin can also be used. The above other copolymerizable unsaturated monomers are not particularly limited, for example, 'as (meth) acrylates, there are (mercapto) decyl acrylate, (meth) acrylate, _, (meth) acrylate Isopropyl ester '(mercapto)acrylic acid n-butyl vinegar, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, ethyl hexanoic acid (meth) acrylate, lauric acid (mercapto) acrylate The carbon number of the brewing part such as ester, (mercapto) styrene stearin is the alkyl (meth) acrylate of (20), (2-) propyl propyl acrylate, 2-hydroxyl (meth) acrylate a (meth)acrylic acid alkyl ester having a hydroxyl group of 1 to 20 in an ester portion such as ethyl ester; a (fluorenyl)acrylic acid cyclic hydrocarbon such as (meth)acrylic acid or cyclohexyl acrylate (meth) acrylate (meth) acrylate, polyalkylene glycol (meth) acrylate such as polyethylene glycol mono (meth) acrylate having a polymerization degree of 2 to 10; carbon number 1~ In addition to the oxy (indenyl) acrylate of 3, etc., (meth) acrylamide; stupid B

2075-9848-PF 15 200911935 a vinyl compound such as methyl styrene, vinyl acetate, ethylene propionate, ethylene benzoate, vinyl toluene, acrylonitrile, etc.; crotonate; maleic acid bis(tetra), Clothing "two vinegars and other unsaturated. The second acid of the acid. The ester moiety of the above (meth) acrylate is preferably an alkyl group having a carbon number of 8 and preferably an alkyl group having 1 to 6 carbon atoms. Preferred are methyl methacrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl methacrylate. These may be used singly or in combination of two. The metal compound is not particularly limited, and examples thereof include metal oxides, hydroxides, IU compounds, sulfides, alkali carbonates, and metal acetate salts. X 'the above-mentioned mono-acid' is not particularly limited, and examples thereof include those described above. The number average molecular weight (Gpc, polystyrene-exchanged acid) of the acrylic resin (Α1) is not particularly limited, and is preferably 2,000 or more and 1 Torr or less, more preferably (10) or more and 40% or less. When it is less than 2 inches, the film-forming property of the coating film is lowered. If it exceeds 1,000 00, not only the storage stability of the obtained coating material is deteriorated, but it is not suitable for practical use, and it is common to use a large amount of diluent solvent during coating. The point of health and economy is not good. Further, the acrylic resin (A1) needs to contain at least one group represented by the formula (4), and the dissolution rate of the coating film against water I can be adjusted by adjusting the content of the group represented by the formula (4). Controlled to the desired rate of dissolution. The acrylic resin preferably has an acid value of 100 to 25 〇 mgKOH/g. When the amount is less than 1〇〇mgK〇H/g, the amount of metal salt in the side chain of the key is less, and the antifouling property is poor. When the temperature is 250 mgKOH/g, the dissolution rate is too fast, and it is difficult to obtain long-term antifouling. Sexual orientation.

2075-9848-PF 16 200911935 A preferred specific example of the acrylic resin of the above (u) is exemplified by at least a side chain! An acrylic resin (hereinafter also referred to as an acrylic resin (A2)) represented by the above formula (5). As a result, the obtained coating film can maintain a stable polishing rate for a long period of time, and can exhibit a more excellent antifouling property. x is the above formula (5), and RH R3 represents the same or different carbon number residue of carbon number 20, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, or the like. #butyl, t-butyl, tert-butyl, pentane: hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl a linear or branched alkyl group having a carbon number of 2 G ^; a cyclic alkyl group such as a cyclohexyl group or a substituted cyclohexyl group; an aryl group, and the like. The substituted aryl group may, for example, be an aryl group substituted with an alkyl group having a carbon number of 18 or a substituted base such as a terracotta base, a schlossyl group or an amine group. Among them, the obtained coating film can obtain a stable polishing rate (10) shehrngRate), and the viewpoint of maintaining stable antifouling performance for a long period of time is preferably isopropyl or the like. The acrylic resin (A2) is, for example, a method in which a polymerizable unsaturated monomer is copolymerized with a triorganoyl group as a monomer component, and the following formula (6) is used. Shown; Z 0 6) H2CS^C——.0 〇g--r5

Re (mercapto) acrylic acid triorganic money _ and other copolymerizable unsaturated monomer copolymerization are preferred. The above other copolymerizable unsaturated monomer is not particularly limited, as described above with respect to the above acrylic resin (4)), or

2075-9848-PF 17 200911935 Unsaturated organic acid. The polymerizable unsaturated organic acid described in the above-mentioned acrylic acid resin (A1) may be used alone or in combination, or two or more kinds may be used in combination. Mouth" (7) 7F (meth)acrylic acid triorgano 7 vinegar, z: table j chlorine! Sub or methyl. The above mv is a hydrocarbon residue of the same or a phase, and is not a slave, and examples thereof include the same hydrocarbon residues of R1, R2 and R3. The specific example of the triorganosylalkyl (meth)acrylate represented by the above formula (6) is not particularly limited, and examples thereof include trimethyl sulfonate (meth) acrylate and (meth) acrylate three. Ethyl sulphuric acid vinegar, tri-n-butyl sulfonium (meth) acrylate, triisopropyl decyl (meth) acrylate, di-n-butyl decyl (meth) acrylate, ethyl (meth) acrylate Dimethyl decyl ester, tri-second decyl (meth) acrylate, tri-n-pentyl decyl (meth) acrylate, tri-n-hexyl decyl (meth) acrylate, tri-n-octyl (meth) acrylate矽alkyl ester, tri-n-decyl decyl (meth) acrylate, triphenyl decyl (meth) acrylate, tri-p-methylphenyl decyl (meth) acrylate, trisyl decyl (meth) acrylate , ethyl dimethyl methacrylate (meth) acrylate, n-butyl dimethyl methacrylate (meth) acrylate, diisopropyl n-butyl ketone (meth) acrylate, (meth) acrylic acid N-octyl di-n-butyl sulphuric acid ester, (meth)acrylic acid monoisopropyl a lipid sulphur ester, a dicyclohexyl phenyl decyl (meth) acrylate, a t-butyl diphenyl decyl (meth) acrylate, a lauryl diphenyl decyl (meth) acrylate, ( Methyl)acrylic acid tert-butyl-nitrophenylmethyl oxalate and the like. Among them, the point of the polishing rate which can maintain stability for a long period of time is preferably triisopropyl methacrylate (2075-9848-PF 18 200911935). These trialkyl decyl (meth) acrylates may be used singly or in combination of two or more. The number average molecular weight of the acrylic resin (A2) is not particularly limited, and is preferably 2,000 or more and 100,000 or less, more preferably 3 Å or more and 4 Å or less. When the film is less than 2,000, the film forming property of the coating film is lowered. When the film thickness exceeds 1 Torr, not only the storage stability of the obtained coating material is deteriorated, but it is not suitable for practical use, and a large amount of a diluent solvent is used for coating. The point of public health and economy is not good. The preferred example of the above-mentioned acrylic resin is an acrylic resin having at least one group represented by the above formula (4) and having at least one group represented by the above formula (5) (hereinafter, Also known as the acrylic resin (10).) By adjusting the content of the group represented by the formula (5), the polishing rate (Pc3linShingRate) can be changed to a desired speed, so that more excellent long-term antifouling properties can be exhibited. The method for producing the acrylic resin (A3) is not particularly limited, and examples thereof include (I) dispersing polymerization by polymerization and organic acid and (meth) of the above formula (6). A method for reacting a resin with a monobasic acid and a compound of the genus of a triorgano-based yttrium-doped yttrium-bis-beta and other copolymerizable unsaturated precursors; (II) a poly-delta-saturated organic compound The acid reacts with the metallized human « ^ σ substance and the monobasic acid, or reacts the unsaturated unsaturated organic acid with the monobasic acid and the ruthenium metal salt to obtain the metal-containing unsaturated soap body, and ^ ^ ^ ^, formula (6) The (meth)acrylic acid triorganism stone is shown on the next day, Other methods for the polymerization of unsaturated monomers, etc. The acryl resin (A3) has at least one side chain of the above formula (5), for example, at least , from the above-mentioned Tong Niang Gonggong, the side chain of the (meth)acrylic acid triorganosilyl ester), and the above-mentioned side chain shown by the general flying (4).

2075-9848-PF 19 200911935 The total content of the groups represented by the formula (4) and the formula (5) is such that the polishing rate (PoUnshing Rate) of the obtained coating film is changed to a desired speed. Further, in the present invention, as the binder resin (a), a binder resin other than the above-described hydrolyzable resin may be used. Excellent antifouling properties and crack resistance can be obtained by using other glue resin libraries. Other gluing resins can be exemplified by chlorinated paraffin hydrocarbons, polyvinyl ether, polyacrylic acid polyacrylate, partially hydrogenated such as benzene polyacetate, poly(methyl)acrylic acid vinegar, polyether polyol , alkyd resin, polyester resin, polyvinyl chloride, eucalyptus oil, moon rat, petrolatum, mobile stone soot, rosin, hydrogenated rosin, ring burning acid, fatty acid and these divalent metal salts. Among them, gasified fossil hydrocarbons, rosin, and relaxing fragrance are preferred. The other glue resin' may be used alone or in combination of two or more. Here, the binder resin (A)' may contain only the above-mentioned hydrolyzable resin, or may contain only the above other binder resin'. "Also, a hydrolyzable resin and other binder resin may be used together." The hydrolyzable resin is combined with other glues. The resin is contained in a ratio of 100: 〇~5 〇 : [resolvable tree], [other knee resin] according to the mass ratio of the resin solid content, and particularly excellent long-term antifouling properties can be obtained. X, together with the hydrolyzed resin, and the other binder resin described above can be used to more easily adjust the physical properties of the coating film or the consumption rate of the coating film. - In the antifouling coating composition of the present invention, the content of the binder resin (A), 3 is preferably 30% by mass, more preferably 40 65 mil %, in the solid content of the anti-3 coating composition. When the amount is less than 3% by mass, there is a tendency that the coating film has defects such as cracks and detachment. Moreover, when it exceeds 7〇 mass%, it is difficult to obtain

2075-9848-PF 20 200911935 The tendency of the desired antifouling effect. Furthermore, the solid content means the product contained in the anti-chick coating composition. The combination of the components other than the solvent of the anti-mite composition <Antifouling agent (B)&gt; The antifouling coating composition of the present invention has a ratio of a metal (β j ) to a metal. A thioketone) a base (tetra) salt (β2), and a sulfur-coated amine (8). According to the combination of the antifouling agents, the anti-fouling agent, the anti-pollution agent, the Β Β Β 仰 仰 仰 仰 § § § § § 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别The antifouling property of the agent 'above the blending degree of the antifouling agent can exert an unexpected effect equivalent to the previous water. As a result, in the past, in order to obtain the antifouling property of the coating film, the blending amount of the antifouling agent to be blended was increased, and the film was used for the long-term use of the crack resistance of the crack: the problem was solved. An antifouling coating film excellent in antifouling property and resistant to cracking can be obtained. The gold "material (10), 'sodium, magnesium, calcium, barium, aluminum, copper, zinc, woven, iron, and strontium sulfonthione) of the antifouling coating composition of the present invention may be mentioned. It is preferably 2-pyridinium zinc (zinc pyrithione), alcohol + copper oxide (copper bite thione), etc. These may be used alone or in combination. Inclusion ratio: thioketone (10) content (To the total amount when using the complex number), 5~15 quality denier = solid content of the material composition, preferably 3 to 20% by mass. 'Stain effect: Pour: When less than 3 mass%, it is difficult to obtain The tendency to prevent it. In addition, when it exceeds 20% by mass, cracking occurs in the coating film.

2075-9848-PF 21 200911935 The tendency to strip defects. The triphenylboramine salt (B2) contained in the antifouling coating composition of the present invention is a complex formed by triphenylbenzene and an amine. The amine is not limited, and examples thereof include n-propylamine, n-butylamine, n-hexylamine, n-ylamine, n-decylamine, n-dodecylamine, and n-trisole-Cg' Amine, n-hexadecylamine, n-octadecylamine, aniline, primary amine of toluene; di-n-butylamine, di-n-hexylamine, di-n-octylamine, dinonylamine, di-n-dodecane Amine, di-n-tridecylamine, di-n-tetradecylamine, di-n-hexadecylamine, di-n-octadecylamine, diphenylamine-like amine; tri-n-butylamine, tri-n-hexylamine , tri-n-octylamine, tri-n-decene: amine,: n-dodecylamine, tri-n-tridecylamine, three-nine four-yard base: tri-n-hexadecane, tri-n-octyl Amine, triphenylamine, etc., Μ: "基心定," base bite, 4-methyl bite, 2_ gas', pyridine or 4-chloropyridine, etc. , Wait. These triphenylboramine salts, on the class. One type may be used, or two types may be used in combination. Among them, pyridine using pyridine as an amine has excellent performance and can be suitably used. - the content of the base boron, antifouling triphenylboramine salt (B2) (in the case of a plurality of solids contained in the solid content of the antifouling coating composition, 3 to 3. 质二里)' to 5~ 25% by mass is better. When it is less than 3 mass%, For better, the tendency of antifouling effect. Also, more than 3. When the mass is %, the tendency to be a defect such as cracking or peeling is desired. ', film-forming turtle, sulfur-burning amine compound contained in the antifouling coating composition of the present invention

2075-9848-PF 22 200911935

(10) is a compound represented by the following formula (1): R 0 1) S02NCCH3) 2 In the above formula (1), R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. From the viewpoint of the antifouling effect, it is preferred that the R of the above formula (1) is a t-atom or a thiolamine compound of the formula (2) or (3). (2) S〇2N (CHab, ch3 ft (3) S02N(CH3)2 Further, the compound of the above formula (2) is called N_(dichlorofluoromethylthio)-N ' Ν' - two a compound of methyl-N-phenylthioguanamine or l-dichloro-N-[(dimethylamino) hydrazine]-fluoro-N-phenylmethane sulfoximine, also known as N, N 'Dimethyl-N,_phenyl-(N-fluorodimethylsulfonylthio)thioguanamine or N~(N~di-fluoromethylthio)-Ν', N'-dimethyl- In the case of N-phenylthioguanamine, the compound of the above formula (3) is referred to as N-(dichloro-methylthio)-Ν', N,-dimethyl-N-(4-mercaptobenzene) a compound of thioguanamine, dichloro N [(-methylamino) feldspar]- fluoro-n-(4-methylphenyl) thioindole. The above formula (2) and formula ( 3) The compound ' can be used alone or in combination with 2075-9848-PF 23 200911935. The content of the β-thioguanamine compound (8)) (the amount in the plural) is the solid content contained in the antifouling coating composition. In, to 3, quality, better, to 5 seven quality «good. When it is less than 3% by mass, it is difficult to obtain a desired antifouling effect. In addition, when it exceeds 2 mass%, there is a tendency that cracks such as cracks and peeling occur in the coating film. And _ again, the total content of the above metal 0 to 0 ketone (10), triphenyl urethane salt (10)) and sulphuric amine compound (B3) is contained in the solid content of the antifouling coating composition, illusion~ 50% by mass is preferred, and 15% by mass is more preferred. When it is less than 1% by mass, it is difficult to obtain an antifouling effect. X, more than 5 enamels, there is a tendency to cause defects such as cracks and peeling on the coating film. , the content of triphenylboronamine salt (B2) (the amount of potted leaves when using a complex number), = the content of the 吼 phase (10) (the total amount when the plural is used) ratio (mass ratio less than 5/0; 5: ~1〇/1 is better to be better than 5/1. When the quality is not: 5/1, the resistance to animal antifouling is reduced. When it is super (10), the antifouling property is reduced. The tendency of the amine compound (8)) (when the complex number is used, the total sulfur content is determined, and the content of (10) (the amount when the plural is used). 2: not:) when the curry is 0/ι: 〇·5/1 The antifouling property tends to decrease. In addition, the anti-fouling resistance to algae tends to decrease. The soil-removable coating composition is an antifouling agent other than the above (B1) to (B3). Other antifouling agents are not particularly limited to those which use L, and may, for example, be inorganic compounds or contain metals.

2075-9848-PF 24 200911935 Organic compounds and organic compounds containing no metals. Specific examples of the other antifouling agent are not particularly limited, and examples thereof include cuprous oxide sethyl bisdithiocarbamic acid I, dimethyl zinc, and 2-methylthio-4-tetrabutyl. Amino + cyclopropylamino _s: acid 2 base 4: = m-benzene: carbonitrile dimethyl dichlorophenyl urea: zinc bisdithiocarbamate, cuprous thiosulfate Rh〇d_te), 4,5, digas + n-octyl-3(10)-isoindole, 7 'one gas methylthio) o-zinc imine, tetramethylthiuram disulfide, disordered phenyl Maleidin, 2, 3, 5, 6-tetrachloro+ (methylsulfonate, 3-iodo-2-propylbutylcarbamic acid, diiodomethyl-triyl (bipyridyl) 2 gasification bismuth, 2_(4_thiazolyl)-benzimidazole, etc. The anti-fouling agent can be used alone or in combination of two or more. When other anti-agents are used, the total amount of all anti-fouling agents is The ratio of the other antifouling agent is preferably 55 mass% J^, more preferably 5 mass% or less. When the content of the other antifouling agent exceeds 55 mass%, the above is not sufficiently obtained by k. ) (B3), the result is that the long-term antifouling property and crack resistance cannot be fully coexisted. <Other additives> The antifouling coating composition of the present invention may further contain an additive such as a plasticizer, a pigment, a preparation, etc. The plasticizer may, for example, be dioctyl phthalate or a neighbor. An phthalic acid-based plasticizer such as dimethyl phthalate or dicyclohexyl phthalate; a fat-free one of isobutyl adipate or dibutyl sebacate; Plasticizer; diethylene glycol diphenyl phthalate, isopentanol shuang · S 曰 and other diol brewing plasticizer; phenyl phosphate, trichloroethyl phosphate, etc.

2075-9848-PF 25 200911935 Phosphate-based plasticizer; epoxy-based plasticizer; ring-type plasticizer such as di-zinc-oxystearic acid octyl vinegar, etc., trioctyl benzoic acid, tributyl vinegar, etc. The organotin may be used singly or in combination of two or more. ,. The special plasticizer, Miao Shiyan: "For example, sedimentation lock, talc, clay, white stack, white stone, white oxide, turbid soil, etc.; oxidized white alkaline sulfuric acid, oxygen彳 彳 、 、 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 钛 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Examples of the solvent include hydrocarbons such as 'toluene, xylene octane, heptane, cyclohexanide, oxime, pentane, and quinone essential oil; dioxane, tetrahydrofur. South, ethylene glycol monomethyl Ether, decanediol dibutyl hydrazine, - B, B, B, B, D, D, B, B, B, B, B, B, B, B, B, B, B, B, B Acetate, acetic acid, acetic acid, ethylene glycol monomethyl ether acetate, _ class: 6 ^ acetate and other esters; ethyl isobutyl ketone, methyl isobutyl ketone, etc. The solvent may be used alone or in combination of two or more. In addition to the above, it is also possible to add, for example, 'monobutyl phthalate monobutyl ester, succinic acid monooctyl ester, and the like. Single, ^ 'sucking, castor oil; water binding agent, anti-drip 4 square color separating agent; anti-settling agent; blistering agent, etc. The antifouling coating composition of the present invention, for example, in the above hydrolyzable tree Knife Q resin (Α) 'Add the above antifouling agent (Β1) to (8)), and other conventional additives such as antifouling agents, plasticizers, coating film consumption adjusters, pigments, solvents, etc., in a ball mill , stone grinding machine, roller grinding machine,

Buckle 75-9848-PF 26 200911935 A mixer such as a sand mill is mixed and prepared. The antifouling coating film can be formed by subjecting the obtained antifouling coating composition to a surface of the object to be coated, and then removing the solvent at a normal temperature or under heating. There are no special duties for the objects to be coated, such as ships, or fish nets, harbor facilities, oil dams, piping materials, bridges, buoys, water structures for facilities such as seabeds, and the like. The antifouling coating film formed by using the anti-π coating composition of the present invention has long antifouling property and excellent crack resistance, and is excellent in long-term anti-reading and turtle resistance. The crack-resistant antifouling film is achieved by the peculiar composition of the coating composition of the present invention. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, which are not limited thereto. Manufacture (manufacturing example 1) acrylic resin varnish 调 调 扑 扑 扑 、 、 冷却 冷却 冷却 冷却 冷却 冷却 冷却 冷却 冷却 冷却 冷却 冷却 : : : : “ “ “ 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶 瓶In the formulation (mass part) of Table 1, the monomer hour, etc. (4) The mixture of the 2 mass parts is 3 2, and the temperature is kept for 3 minutes. After that, the second part: the amount of f, the mass of n-butanol, and the mass of ... hexyl hexanoate dibutyl ester 0, 2 詈 詈 纠 纠 纠 丄 入 入 入 ^ 所 所 所 所 b b b b b b b b b b b b b b 混合 b 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合 混合The solid knives in the lacquer ί,, the resin varnish X ^ ^ 4 49· 8 ft % - | έ ^ ^ 4.43⁄4 ° 〆田树月曰&gt; The acid value of the resin in the moon paint and the resin clear... The solid form is arranged in the heart of the heart;

The abbreviation of the monomer described in 2075-9848-PF 27 200911935 is the following compound. (1) EA: Acetic acid ethyl acetate (2) CHMA: cyclohexyl methacrylate (3) CHA: cyclohexyl acrylate (4) M-90G: methoxypolyethylene glycol methacrylate (NK ESTER M-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.) (5) MMA: Methyl methacrylate (6) AA: Acrylic acid (ΌΜΑΑ: mercaptoacrylic acid\ (8) TIPSI: propyl acrylate triisopropyl sulphate followed by 4质量质量,2。 In the same reaction vessel, the resin varnish I 1 〇〇 mass part, acetic acid rheme 25. 4 mass parts, naphthenic acid (NA-165, acid price 165, manufactured by Daiwa Oil & Fats Co., Ltd.) 32. 4 quality, two The styrene resin varnish was prepared by the removal of the acetic acid to obtain a solid content of 41.5% by mass of the acrylic resin varnish 1. The viscosity was 12.3 poise. (Production Example 2) Acrylic resin varnish 2 was prepared in the same reaction vessel as in the above Production Example 1, and 64 parts by mass of xylene was added, and the mass portion of n-butanol U was kept at U5t. The monomer and peroxy-2- which were formulated according to the formula (mass part) according to the formula A mixed liquid composed of 3 parts by mass of the third butyl hexanoate was dropped into the solution at a constant rate for 3 hours, and the mixture was incubated for 30 minutes after the completion of the dropwise addition. It will be divided into three parts: the mass fraction of xylene, the n-butyl portion and the third portion of peroxy-2-ethylhexanoate 〇·2, and the 3G is divided into medium-speed drops. After the end of the drip, the heat is passed to the end. Resin varnish Π. The solid form in the obtained resin varnish II is divided into 49.

20波泊。 2075-9848-PF 28 200911935 %, viscosity of 9. 5 poise. Further, the resin in the resin varnish 11 has a number average molecular weight (GPC' polystyrene equivalent) of 6,500 and an acid value of 16 Å. The acid value of the obtained resin and the solid content in the resin varnish 11 were summarized in Table 1. Then, a reaction was carried out in the same manner as in the above Production Example 1 except that a resin varnish II 1 mass portion, a copper acetate 29.6 mass portion, and a tridecyl acetic acid 12.6 mass portion were added to the same reaction vessel to obtain a solid fraction of 4 5 . 2% by mass of acrylic resin varnish 2. (Production Example 3) The acrylic resin varnish 3 was prepared in the same reaction container as in the above Production Example 1, and the mass fraction of xylene was added to 90 ° C. The mixture of the monomer according to the formulation (mass section) of Table 1 and the mass fraction of the third butyl peroxy-2-ethylhexanoate i was dropped into the solution at a constant rate for 3 hours, and after the completion of the dropwise addition. Keep warm for 3 minutes. After that, a mixture of 7 mass parts of xylene and a mass part of terp-butyl peroxy-2-ethylhexanoate 〇·2 was dropped at a constant rate of 30 minutes, and the temperature was lowered by the end of the dropwise addition. · 5 hours. Thereafter, it was cooled to 6 〇t: Acrylic resin varnish 3 was obtained by adding bismuth benzene to 1 〇 mass 邛. The solid knives in the obtained acrylic resin varnish 3 were 60% by mass and had a viscosity of 7.5 poise. Further, the number average molecular weight (Gpc, polystyrene conversion) of the resin in the acrylic resin varnish 3 was 80 Å. The solid content in the acrylic resin varnish 3 and the Gardner viscosity (251) of the acrylic resin varnish 3 are summarized in Table 1. (Production Example 4) Preparation of Acrylic Resin Varnish 4 In the same reaction vessel as in the above Production Example 1, 16 mass portions of P-n-butanol in the mass of diphenylbenzene were added and maintained at 11 5 °C. The mass of the monomer according to Table 1 (3⁄4 parts) and the third part of peroxy-2-ethylhexanoate 2

2075-9848-PF 29 200911935 The mixed liquid was dropped into the solution at a constant rate for 3 hours, and the mixture was allowed to stand for 30 minutes. Thereafter, it is composed of 16 mass parts of xylene, n-butanol = quantity part, and peroxy-2-ethylhexanoic acid tributylate. · 2 mass parts of the 4 quality liquid 30 minutes of medium-speed drop, after the end of the drop, by the insulation [ 浥 • J λ], 3 ^ to the resin varnish ih obtained in the resin varnish IV is divided into % The viscosity is 6 poise. Further, the number of resins in the resin varnish 丨v, the average molecular weight (in terms of GPC' polystyrene) was 6000, and the acid value was 27 〇mgKOH/g. The acid value of the obtained resin and the resin varnish 丨v: The solid content of hydrazine was summarized in Table 1. Next, 'in the same reaction vessel', a resin varnish IV 100 mass part, a copper acetate 37.06 mass part, a naphthenic acid (ΝΑ-165, an acid value 165, manufactured by Daiwa Oil & Fats Co., Ltd.) 60. 6 mass parts, The reaction was carried out in the same manner as in the above-mentioned Production Example J to obtain a dilute acid resin varnish 4 having a solid content of 50.6 % by mass. [Table 1 ]

Manufacturing Example 26.02 15.00 10. 00 8. 98 40. 00 49

IV 70 2075-9848-PF 30 200911935 <Examples 1 to 35 and Comparative Examples ^~^> The above-mentioned Production Examples 1 to 4 #4 acrylic resin varnishes 1 to 4 and other components shown in the table were used, and sorghum was used.八# id b 逯 政 政 政 , , 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制Furthermore, the details of the components contained in Tables 2 to 5 are as follows. (1) Cuprous oxide 1 TECH (shares) system "Nc-3 〇 1" (2) Zinc Hua. 堺Chemical Industry Co., Ltd. "2 kinds of acidified lead" (3) Titanic. Toda Industrial Co., Ltd. TODACOLLOR KN-R" (4) Anti-fouling agent 1. ZPT (zinc ratio. ketone) (r Zinc Omadine manufactured by ARCH CHEMICAL) (5) Anti-drug 2 · CupT (copper pyridone) (made by ARCH CHEMical) "Copper Omadine j (6) Antifouling agent 3: Pyridinium triphenyl boron ("PK" manufactured by Kituching Chemical Industry Co., Ltd.) (7) Antifouling agent 4. Triphenylboron n-octadecylamine (Benny-Toyama system γυν_18_2〇)) (8) Anti-π agent 5: 1, Bu 2 gas _ Ν _ [(didecylamino) sulfonyl kebu fluoro- Ν - stupid methane sulfin Indoleamine ("prewntoi A4S" manufactured by LANXESS) (9) Anti-π agent 6 : 1, dichloro-N_[(dimethylamino)sulfonyl]-fluoro-N-(4-methylbenzene Methane sulfoximine (r Preventol A5S j by LANXESS) (10) Antifouling agent 7. 4, 5-Dichloro-2-n-octyl-4-isothiazolin-3-one (4,5 -diqi-2-n-octyl_3(2H)isothiazolinone) (R〇hm and肫"

2075-9848-PF 31 200911935 "Sea-Nine 211" (11) chlorinated paraffin: "T0Y0PARAX A50" manufactured by T0S0 (shares) (12) Wood rosin: "WW Rosin" manufactured by Arakawa Chemical Industry Co., Ltd. (13) Anti-drip agent: "DISPERON A600-20X" manufactured by Nanben Chemical Co., Ltd. [Table 2]

Unit: Mass Section Example 1 2 3 4 5 6 7 8 9 10 11 12 13 Acrylic resin varnish 1 38 38 44 58 38 38 37 39 45 43 7 17 Acrylic resin varnish 2 Acrylic resin varnish 3 Acrylic resin varnish 4 Cuprous oxide Zinc Hua 29 29 ?,9 29 29 29 23 13 31 31 31 31 Iron Dan 6 6 — ~ 3 6 6 6 6 6 6 6 6 6 Antifouling Agent 1 2 2 2 2 2 4 3 0.5 2 2 2 Antifouling Agent 2 3 Antifouling agent 3 6 6 fi 12 7 6 8 12 2 7 7 7 Antifouling agent 4 6 Antifouling agent 5 2 Antifouling agent 6 2 2 3 3 2 2 3 3 0.5 2 2 2 Antifouling agent 7 Gasification Paraffin hydrocarbon 1 1 ] 1 1 1 1 1 1 4 2 2 Wood rosin 3 15 12 6 Anti-drip agent 2 2 ?, 2 2 2 2 2 2 2 2 2 2 butyl cellosolve 2 2 ?, 2 2 2 2 2 2 2 2 2 2 xylene 12 ~ ΪΓ 20 9 12 10 12 13 12 29 27 23 Total 100 100 inn 100 100 100 100 100 100 100 100 100 100 Long-term antifouling for 3 months 0 o' 0 0 0 0 0 0 0 0 0 0 0 6 months 0 0 ~ _ 0 n 0 0 0 0 0 0 0 0 0 0 12 months 0 0 0 0 0 0 0 0 5 10 5 0 18 months 0 0 n 0 0 0 0 0 0 10 20 10 0 24 Month 0 0 Π 0 0 0 0 0 0 20 30 20 0 film state A A A A A A A A A A A A A crack resistance A A A A A A A A A A 17 A A 2075-984S-PF 32 200911935 [Table 3]

Unit: Quality Department Example 14 15 16 17 18 19 20 21 22 Acrylic resin varnish 1 Acrylic resin varnish 2 40 8 18 Acrylic resin varnish 3 41 7 17 Acrylic resin varnish 4 44 8 19 Cuprous oxide 20 20 20 20 20 20 20 20 20 Ironing 7 7 7 7 7 7 7 7 7 Antifouling agent 1 Antifouling agent 2 3 3 3 3 3 3 3 3 3 Antifouling agent 3 10 10 10 9 9 9 9 9 9 Antifouling agent 4 Staining agent 5 Antifouling agent 6 3 3 3 3 3 3 3 3 3 Antifouling agent 7 Chlorinated paraffin hydrocarbon 2 2 2 3 3 2 3 3 2 Wood rosin 12 6 2 12 6 2 12 6 Anti-drip agent 2 2 2 2 2 2 2 2 2 butyl cellosolve 2 2 2 1 1 1 1 1 1 xylene 11 31 27 9 33 30 6 32 28 total 100 100 100 100 100 100 100 100 100 long-term antifouling for 3 months 0 0 0 0 0 0 0 0 0 6 months 0 0 0 0 0 0 0 0 0 12 months 0 5 0 0 0 0 0 0 18 months 0 10 0 0 5 0 0 5 0 24 months 0 20 0 0 10 0 0 10 0 Film state AAAAAAAAA Crack resistance AAAAAAAAA 33

2075-9848-PF 200911935 [Table 4]

Unit: Mass Section Example 23 24 25 26 27 28 29 30 31 32 33 34 35 Acrylic resin varnish 1 46 8 18 Acrylic resin varnish 2 45 8 18 Acrylic resin varnish 3 43 7 17 Acrylic resin varnish 4 44 8 19 Cuprous oxide 10 10 10 10 10 10 10 10 10 10 10 10 10 Zinc Hua 10 10 10 10 10 10 10 10 10 10 10 10 10 Iron Dan 8 8 8 8 8 8 8 8 8 8 8 8 8 Antifouling Agent 1 Antifouling Agent 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Antifouling agent 3 7 7 7 7 7 7 7 6 6 6 6 6 6 Antifouling agent 4 Antifouling agent 5 Antifouling agent 6 2 2 2 2 2 2 2 2 2 2 2 2 2 Antifouling agent 7 Gasified paraffin hydrocarbon 4 1 2 2 1 2 2 1 3 2 1 3 2 Wood rosin 16 12 6 12 6 2 12 6 2 12 6 Anti-drip agent 2 2 2 2 2 2 2 2 2 2 2 2 2 butyl cellosolve 1 1 1 1 1 1 1 1 1 1 1 1 1 xylene 38 11 36 32 12 36 32 13 37 34 12 36 32 Total 100 100 100 100 100 100 100 100 100 100 100 100 100 Long-term anti-fouling property for 3 months 0 0 0 0 0 0 0 0 0 0 0 0 0 6 months 0 0 0 0 0 0 0 0 0 0 0 0 12 months 5 0 5 0 0 5 0 0 0 0 0 0 0 18 months 15 0 10 0 0 10 0 0 5 0 0 5 0 24 months 25 0 20 0 0 20 0 0 10 0 0 10 0 Film state AAAAAAAAAAAAA Crack resistance 15 AAAAAAAAAAAA 2075-9848-PF 34 200911935 [Table 5] Unit: Quality Department Comparative Example 1 2 3 4 5 6 7 8 9 10 11 Acrylic resin varnish 1 43 43 43 38 37 Acrylic resin varnish 2 36 38 Acrylic resin varnish 3 35 Acrylic resin varnish 4 37 Cuprous oxide 35 35 35 35 35 35 Zinc华6 6 6 29 18 铁丹 7 7 7 6 6 4 5 4 2 2 2 Antifouling agent 1 10 13 2 10 15 6 10 Antifouling agent 2 15 15 15 Antifouling agent 3 16 16 6 Antifouling agent 4 Antifouling Agent 5 10 13 13 4 Antifouling agent 6 Antifouling agent 7 2 Chlorinated paraffin hydrocarbon 1 1 1 1 4 3 4 1 1 2 4 Wood rosin 15 3 4 15 Anti-drip agent 2 2 2 2 2 2 2 2 2 2 2 Butyl cellosolve 2 2 2 2 2 1 1 1 1 1 1 xylene 13 13 13 12 30 4 5 5 4 4 31 Total 100 100 100 100 100 100 100 100 100 100 100 Long-term antifouling for 3 months 0 0 0 0 20 0 0 0 0 0 0 6 months 30 30 40 50 70 40 50 40 0 30 30 12 months 50 60 70 80 100 60 80 60 10 50 60 18 months 70 80 90 100 100 80 100 80 40 70 100 24 months 100 100 100 100 100 100 100 100 60 90 100 Film state AAAABBBBBBB Crack resistance AAAA 7 10 15 12 13 14 5 2075-9848-PF 35 200911935 (Evaluation) (1) Long-term antifouling property The antifouling coating compositions of Examples 1 to 35 and Comparative Examples 1 to 11 were applied to a rustproof coating in advance. The shot blasting sheet of the coating was dried to a film thickness of 300 #m, and was dried by a room for 2 days and night to obtain a test plate having an antifouling coating film. The test plate will be obtained in Okinawa, Okayama, Japan.

The Nippon Paint Marin Coatings company set up a laboratory for the bioadhesion test to assess the antifouling properties. The results are shown in Tables 2 to 5. The number of months in Tables 2 to 5 indicates the period of impregnation of the crucible. In addition, the numerical value indicates the ratio (%) of the area of the coating area of the bio-adhesive area (visual judgment), and is 15% or less. During the period of the anti-fouling test of the edition, the state of the test for 6 months during the impregnation period was evaluated by visual observation and friction observation. The results are shown in 2 to 5. For those who have not confirmed the crack, a is confirmed, and it is confirmed that the crack is β ^, and the table (3) is resistant to cracking test (dry and wet alternating test) - by using a shot blasting sheet to make the dry film thickness a coating film The test plate, which was placed in a f 4 instrument, was dried to obtain an anti-fouling plate, and the obtained test plate was immersed in 4 Torr. After entering the seawater for κ, indoors for 1 week, • Ding is dried for 1 week, which is the maximum implementation of i cycles to ^ ‘father test, &quot; to 20 cycles. On the way, when the film is cracked, the body is 4 μ — ± turtle table, and the turtle is produced.

Even if you enter the ho ju ring, there is no blame for ^(4) in Tables 2~5. 2075-9848-PF 36 200911935 As shown in Tables 2 to 5, it is known that the &lt;- 丨乃里膜 obtained from the antifouling coating composition of the example can be excellent as 4 & . Especially,? Excellent anti-fouling property 'About cracking resistance #一疋 and using acrylic resin varnish 1~4 of hydrolyzable resin _ and / or rosin to 1 〇〇: 〇~5〇: 5〇 ratio, then It can provide excellent antifouling properties for a long time. The modes and examples of the embodiments are merely illustrative and not considered to be limiting. The scope of the present invention is not described above, and the description of "Shenyue &amp; ® Table τ ' includes all the meanings and ranges within the scope of the request. [Simple description of the diagram] Benefits $ *»\ Main component symbol description

2075-9848-PF 37

Claims (1)

200911935 (B) Patent application scope: 1. An antifouling coating, the antifouling agent (B) containing the gelatin resin (A), the antifouling salt (B2), and the lower FCIgCS-N 0 The metal pyrithione (B1) of the formula (1) and the thiosamine compound (B3): S〇2N(CH3)2 c 1 in the above formula (1), κ κ A ruthenium atom or a linear or branched alkyl group having 1 to 10 carbon atoms. 2. The antifouling coating composition of claim 2, wherein the triphenylboramine salt (Β2) comprises „pyridyltriphenylboron. 3. The invention as recited in claim 1 In the antifouling coating composition, the sulfonamide compound (63) contains one or more compounds selected from the group consisting of the compounds represented by the following formula (2) and the following formula (3): FC ^QS ^ (2) X) S防2N(CH3)2 CH, 0, so2n (ch3) 2 (3) 4: The antifouling coating composition of claim i, wherein the above-mentioned binder resin (A) is contained in a side chain, at least A resin based on the following ', denoted: J, J 2075-9848-PF 38 200911935 ο fX) (u, -C', μ~~~a (4) In the above formula (4), X system 0 π II : &quot;〇~Cγ—. 2 valent metal, A is a coating composition * Its base formula (5) represents a base 'k system 〇 or 1, γ series hydrocarbon, M is a monobasic acid 5. The organic acid residue as described in claim 1, wherein the above-mentioned binder resin (A) comprises a resin having at least a group represented by a side chain: R1 &lt; S) C-〇一- 31··R3 above In the formula (5), the hydrocarbon residues of the R1, R2, and V systems are - or different, and the carbon number is 20. 6. For the antifouling coating composition of the first aspect of the invention. The above-mentioned binder resin (A) has a side group, and |, ', 斛矣-·&gt; 廿v has one group represented by the following formula (4), and the following formula (5) Resin based on: 0 * A (4) 〇 - M - 〇 R1 II | (6) 0 - Ο - Si - R2 R3 In the above formula (4), X is 2075-9848-PF 39 200911935 -0 —C—V— is a tantalum carbide, M is a divalent metal, A is a base, k is 〇 or 1, an organic acid residue of a monobasic acid, and in the above formula (5), r1, r The system is the same or different, and the carbon number is 7. The anti-fouling coating combination described in the above-mentioned monobasic acid is as described in claim 4, and the patent range is: oxime: organic acid. The antifouling coating of the unitary crucible, the above-mentioned item, the combination of rosin, deciduous rosin, and -acid acid is selected from the group consisting of rosin, hydrogen hydrogenated abietic acid, abietic acid, rosin acid, dehydrogenation Rosin acid , Q - at least one of the group. 9. The above-mentioned adhesive resin (1) as claimed in the patent application. The antifouling coating composition according to the invention, which is at least one type of hydrogen rosin. 匕3 is selected from the group consisting of chlorinated paraffin Hydrocarbons, rosins, and 10%-type antifouling smear coatings. The antifouling coating: the underwater structure described in the first paragraph of the patent application scope has the patent application scope 1() 2075-9848-PF 40 200911935 VII. Designated representative map: (1) Designation of the case The representative picture is: None (2) The symbol of the symbol of this representative figure is simple: No. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: FC[2CS_N, S02N{CH3}2 2075-9848-PF 4