TW200837159A - Stain-proof coating composition, method for production of the composition, stain-proof coating film formed by using the composition, coated article having the coating film on the surface, and stain-proof treatment method for forming the coating - Google Patents

Abstract

This invention is to provide a composition for forming a stain-proof coating film that can exert a stain-proofing property in sea water for a long term and is highly safe on the environment. Specifically disclosed is a stain-proof coating composition comprising: (1) a polymeric plasticizer comprising an ethylenically unsaturated carboxylic acid ester polymer having a glass transition temperature of -20 DEG C or lower and a number average molecular weight of 500 to 20000; (2) a triorganosilyl (meth)acrylate copolymer, which is a copolymer of a triorganosilyl (meth)acrylate monomer A represented by the general formula (I): (I) [wherein R1 represents a hydrogen atom or a methyl group; R2 to R4 independently represent a branched alkyl group having 3 to 8 carbon atoms or a phenyl group] and an ethylenically unsaturated monomer B that is different from the monomer A, and which has a glass transition temperature of 0 degree centigrade or higher and a number average molecular weight of 5000 to 100000; (3) at least one salt selected from rosin zinc, rosin-derivative zinc, rosin copper, and rosin-derivative copper; and (4) a stain-proofing agent.

Description

200837159 IX. Description of the invention: The invention relates to an antifouling coating composition, a method for producing the composition 5, an antifouling coating film formed using the composition, and having the surface a coating of a coating film and an antifouling treatment method for forming the coating film.

L Prior Art; J Background Art Aquatic fouling organisms such as barnacles, dragon worms, siberian scallops, bryozoa, sea squirts, green seaweed, 10 sarcophagus and slime molds are attached to ships (especially the bottom part of the ship) and fishing nets and fishing nets. In the case of underwater structures such as fishery appliances such as accessories and water pipes for power generation, problems such as damage to the functions and appearance of the ship, etc. 0. The antifouling coating containing the tin-copolymer is applied to the ship. The surface of the fishery utensils and the underwater structure is intended to prevent the adhesion of the fouling organism, for example, coating a coating film containing an antifouling coating containing a polymer of a dibutyltin group, and the coating composition is slowly dissolved. The surface of the coating film is frequently renewed in the seawater, thereby preventing the aquatic organism from adhering to the coating film. Further, after the dissolution, the coating film can be further applied to continuously exhibit the antifouling performance. However, the use of such antifouling coatings has been suspended due to marine pollution problems. In recent years, in order to replace the organotin-containing complex, a copolymer containing triterpene has been developed and used. '= Read has a lower organic toxicity than the organic group, and is less organic and less organic.矽基(Patent Literature! “Cost of the burden”) However, a coating film containing a copolymer containing triorgano 5 200837159 decyl ester will dissolve at a certain rate in seawater, but if it passes for a long period of time, the coating film dissolution rate will be Gradually increasing, and having the problem that the coating is not difficult. Therefore, the copolymer containing triorganomite vinegar is used in combination with rosin, rosin derivative or the metal salt (Patent Document (8) ~ called. 5 10 15 20 When rosin and rosin derivatives are used, a part of the free carboxylic acid of the rosin or rosin derivative will react with the metal compound contained in the antifouling coating composition during the production of the paint and during the preservation of the coating, and at the same time as the production of the metal salt Therefore, when the antifouling paint is stored for a long period of time, the triorganosyl ester is contained, and the material is gradually hydrolyzed by the generated water to form a metal and a salt contained in the composition. The materials crosslink with each other through the metal to increase the viscosity of the soil. Even if the coating is diluted by a diluent for easy coating, the coating formed by the coating still has poor coating properties and antifouling effects. Therefore, proposals have been made to use inorganic dehydrating agents in addition to rosins and rosin derivatives (Patent Documents 6 to 9 and 12). However, when inorganic dehydrating agents are used, if the content of rosin is small, Dehydration to a certain extent, it is still impossible to avoid the above difficulties in coating design. If the amount of rosin is too large, it will not be fully dehydrated and will not prevent the viscosity of the coating from rising. In addition, the Japanese, rosin derivatives or such metal salts are based on these. The side (depending on the metal type, etc.) differs in the solubility of seawater. Moreover, depending on the manufacturing conditions and storage conditions of the paint, the types of rosin and the like and the types of metal salts also change. The above reasons seem to be difficult. The coating film 6 is not too difficult to use. When using rosin, rosin derivatives or these metal salts, the coating film 6 200837159 will become brittle and prone to cracking. A plasticizer is used, and a plasticizer which is conventionally used may, for example, be a phosphate ester (such as tricresyl phosphate) or a phthalic acid ester (dioctyl phthalate). Adipate (dioctyl adipate, etc.), polybutene, epoxidized fats and oils (epoxidized soybean oil, etc.), burnt 5 vinyl ester polymer (Lutnard A25: BASF products Name, ethyl vinyl ester polymer, etc.), chlorinated paraffin, etc. However, when using a dish of acid trimethylbenzene, a plasticizer such as monooctyl phthalate or monooctyl adipate In addition, although the physical properties of the coating film at the initial stage of coating film formation are improved, it is difficult to maintain the coating property and the solubility in the seawater for a long period of time. In other words, since the plasticizer is gradually dissolved from the coating film, the coating film becomes weak. Cracks and peeling occurred on the coating film. As a result, the coating films still had no antifouling effect. Further, when cracks and peeling occur in the coating film, it becomes difficult to directly apply the antifouling paint (poor recoatability). Therefore, it is necessary to maintain the antifouling property of μ, and it is necessary to completely remove the coating film and then re-form the coating film and other complicated and costly operations. Further, when a plasticizer such as polybutylene epoxidized soybean oil or Heldena A25 is used, the water solubility is lowered, and there is a problem that bubbles and peeling easily occur in a long-term use. 2〇, outside, chlorinated stone is an organic gas compound, which has doubts about its environmental safety due to its toxicity. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9-48947 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei 9-48947 (Patent Document 3) [Patent Document 7] [Patent Document 8] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] [Problem to be Solved by the Invention] The object of the present invention is to provide a subject of the present invention. A composition for forming an antifouling coating film which can effectively exert antifouling properties for a long period of time in seawater and which has high environmental safety. MEANS TO SOLVE THE PROBLEM The present inventors have intensively studied to solve the above problems, and as a result, have found that a composition containing a specific plasticizer can solve the above problems, and the present invention has been completed. 20, the present invention relates to an antifouling coating composition, a method for producing the composition, an antifouling coating film formed using the composition, a coating having the coating film on a surface thereof, and a method for forming the same Antifouling treatment method of coating film. An antifouling coating composition comprising: (1) a polymer plasticizer, an ethylenically unsaturated carboxylic acid ester polymer having a glass transition temperature of -20 ° C or less and a number of 8 200837159 having an average molecular weight of 500 to 20,000 (2) a triorganooxime (meth)acrylate copolymer having a number average molecular weight of from 5,000 to 100,000, which is a triorganooxime (meth)acrylate 5 monomer A represented by the formula (I) a copolymer with an ethylenically unsaturated monomer B other than the monomer A; R1 R2 H2C=C——C——0—Si—R3 (I)

II I 〇R4 (wherein R1 is a hydrogen atom or a methyl group; R2 to R4 are each the same or different and represent a branched alkyl group having a carbon number of 3 to 8 or a phenyl group) 10 (3) is selected from the group consisting of rosin zinc salts And at least one salt of a salt of a rosin derivative, a copper salt of rosin and a copper salt of a rosin derivative; and (4) an antifouling agent. 2. The antifouling coating composition according to Item 1, wherein the ethylenically unsaturated carboxylic acid ester polymer is an acrylate polymerization having a glass transition temperature of -40 ° C or less and a number average of 15 parts of 1000 to 10,000. Things. 3. The antifouling coating composition of item 1, wherein the monomer A is triisopropyl decyl (meth) acrylate. 4. The antifouling coating composition according to Item 1, which comprises 20 to 200 parts by weight of the (meth) propylene triorganooxime copolymer 20, and contains 10 to 70 parts by weight based on 100 parts by weight of the salt. Part of the ethylenically unsaturated carboxylic acid ester polymer. 5. The antifouling coating composition of item 1, which comprises a dehydrating agent and/or a water binding agent. 9 200837159 6. The antifouling treatment method is an antifouling coating film formed on the surface of a coating film formation using the antifouling coating composition of the first item. 7. An antifouling coating film formed by using the antifouling coating composition of the first item. 5 8. A type of paint, which is the antifouling film of item 7 on the surface. 9. A method for producing an antifouling coating composition, which comprises mixing a dispersion containing the following components, namely: (1) a polymer plasticizer, which has a glass transition temperature of -20 ° C or less and a number average The composition of the ethylenically unsaturated carboxylic acid ester polymer having a molecular weight of 500 to 20,000, (2) the (meth)acrylic acid oxime copolymer having a number average molecular weight of 5,000 to 100,000, which is a formula (I) a copolymer of triorganooxime (meth) acrylate monomer A and ethylenically unsaturated monomer B other than monomer A; [Chemical 2] 15 h2c= R1 Ic-c-〇

(I) (wherein R1 is a hydrogen atom or a methyl group; R2 to R4 are each the same or different and each represents a branched alkyl group having a carbon number of 3 to 8 or a phenyl group) (3) is selected from the group consisting of rosin zinc salt and rosin At least one salt of a derivative salt, a rosin copper salt, and a copper salt of a rosin derivative; and 20 (4) an antifouling agent. The antifouling coating composition of the present invention comprises: (1) a polymer plasticizer, which is an ethylenically unsaturated carboxylic acid polymer having a glass transition temperature of -20 ° C or less and a number of 10 200837159 and an average molecular weight of 500 to 20,000. (2) a (trimethyl) acrylate (trimethyl phthalate) copolymer having a number average molecular enthalpy of 5000 to 1 〇 qq (10), which is a triorganomenyl ester of (meth) acrylate represented by the formula (1) a copolymer of fluorene and an ethylenically unsaturated monomer oxime other than the monomer oxime; R1 R2 • R3 (1) H2C=C-C-Ο-δΐ- Ο R4 (wherein R1 is a hydrogen atom or Methyl; R2 to R4 are each the same or different, and represent a branched or agglomerated group of 3 to 8 (10) selected from the group consisting of rosin zinc salt, rosin derivative salt, rosin copper salt and rosin At least one salt of a copper salt of a derivative; and (4) an antifouling agent. (1) Polymer plasticizer> The antifouling paint composition of the present invention contains an ethyl squash unsaturated carboxylic acid condensate 15 σ物斤 constitutes the heart plasticizer, the glass transition temperature (Tg) of the ethylene unsaturated vinegar polymer is less than the money, preferably the following and the number average The amount is 〜20_, and the aging is _~1〇〇〇〇. When the film is high, it is not possible that the composition of the present invention is sufficiently plastic 2', and the coating film formed is fragile, and the coating film is prone to cracks and 20 peeling. The adhesiveness to the coating film formation is insufficient. The composition of the present invention can be more reliably imparted to plasticity. When a polymer having a number average molecular weight (Mn) of less than 5 (9) is used, the polymerization is carried out in seawater 11 200837159. The coating will be preferentially detached from the coating film, so that the coating film is in a certain direction. Further, the polymer having Mn exceeding 20,000 cannot impart the coating film formed by the present invention, and the coating film is weak, and the coating is cracked and peeled off. The adhesion to the coating film formation is inferior to that of 涂 ^ ^ ^ , ^ ^ can increase the amount of the polymer to effectively avoid the above problem. As 阜 V. Έ — - the addition of a substance When the hydrolysis speed of the coating film is extremely low, the antifouling effect cannot be effectively exerted. The Μη is 1000 to 10000 to impart more plasticity to the composition of the present invention. Further, the addition amount of X can be further suppressed to form The coating film effectively exerts antifouling effect In the case of the plasticizer, for example, an acrylate polymer, a methacrylate: a mouth, a maleic acid g-polymer, and a fumaric acid-g-polymer may be mentioned. These plasticizers may be used alone. Or two or more kinds may be used in combination. The above plasticizer is particularly preferably an acrylate polymer. The monomer of the plasticizer is preferably methacrylate, butyl acrylate 9 butyl acrylate, 2-ethylhexyl acrylate. , lauryl acrylate, propylene I octadecyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, propylene fluorene 2-ethoxyethoxy ethane, benzoic acid 2-benzene Acrylates such as oxyethyl vinegar, 2-methoxypropyl acrylate, 4-methoxybutyl acrylate, butyl butyl acrylate acrylate, and phenyl acrylate. The uranium plasticizer may be a polymer obtained by polymerizing a single type of monomer, or may be a copolymer obtained by polymerizing two or more kinds of monomers. When the plasticizer is a copolymer, it may be any of an alternating copolymer, a periodic copolymer or a block copolymer. For example, the foregoing monomer can be polymerized in the presence of a polymerization initiator to obtain the aforementioned plasticizer. The polymerization initiator used in the above polymerization reaction may, for example, be 2,2,-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyrate and a 2'- An azo compound such as azobisisobutyl ester; benzoquinone peroxide, peroxygen = a 5th third butyl group, a third butyl peroxybenzoate, a third butadiene, and a _J roll of isopropyl peroxide A peroxide such as a carbonate or a third butyl peroctoate. These polymeric creping agents may be used singly or in combination of two or more. The polymerization initiator is particularly preferably tributyl peroctoate. The molecular weight of the ethylenic non-saturated carboxylate polymer can be adjusted by appropriately setting the amount of the polymerization initiator to be used. From the viewpoint of easily and accurately producing the aforementioned plasticizer, the polymerization method is preferably a solution polymerization or a local temperature block polymerization. When the solution is concentrated, a polymerization regulator such as an α-mercaptoethylene dimer may be added as needed. In the polymerization of the solution, the reaction temperature in the polymerization reaction can be appropriately set depending on the type of the polymerization initiator, etc., and is usually 70 to 140 ° C, and preferably 80 to 120 ° C. The reaction time may be appropriately set according to the reaction temperature or the like, and is usually about 4 to 8 hours. The polymerization in the solution polymerization is preferably carried out under an inert gas atmosphere such as nitrogen or argon. When high temperature bulk polymerization is employed, the reaction temperature is preferably 200 to 300 ° C. The reaction time may be appropriately set in accordance with the reaction temperature and the like. <(2) Triorganodecyl (meth)acrylate copolymer> Triorganodecyl (meth)acrylate copolymer (hereinafter, simply referred to as copolymer (2)) is a general formula (I) The triorganosilyl (meth)acrylate monomer A (hereinafter sometimes referred to simply as "monomer A") and the ethylenically unsaturated monomer B other than the monomer a 200837159 (hereinafter, The copolymer is only abbreviated as "monomer B". The triorganooxime (meth) acrylate copolymer means a triorgano oxime acrylate copolymer or a triorgano oxime methacrylate copolymer. (Meth)propylene Triorganosilate monomer A means triorganomoperyl acrylate monomer A or triorganosilyl methacrylate monomer A. In the formula (I), R2 to R4 are each the same or different and each represents a branched alkyl group having a carbon number of 3 to 8 or a phenyl group. The branched alkyl group having a carbon number of 3 to 8 may, for example, be an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, a 2-methylbutyl group, a 2-ethylbutyl group 10 group or a 3-methyl group. Kepentyl and the like. R2 to R4 are preferably an isopropyl group, a second butyl group, a third butyl group and a phenyl group. Among them, isopropyl is preferred. Examples of the monomer A include triisopropyl decyl (meth) acrylate, triisobutyl decyl (meth) acrylate, tributyl decyl methacrylate, and triiso(meth) acrylate. Amyl decyl ester, triphenyl decyl (meth) acrylate, diisopropyl isobutyl decyl (meth) acrylate, diisopropyl butyl methacrylate (meth) acrylate, Diisopropylisoamyl decyl (meth)acrylate, diisopropylphenyl decyl (meth) acrylate, isopropyl diisobutyl decyl (meth) acrylate, (meth) acrylate Propyl di-tert-butyl decyl ester, tert-butyl diisobutyl decyl (meth) acrylate, tert-butyl diisoamyl decyl (meth) acrylate and (methyl 20 - meth) acrylate Butyl diphenyl decyl ester and the like. Preferred are triisopropyl methacrylate (meth)acrylate, tri-tert-butyl decyl (meth)acrylate, and tert-butyldiphenyl decyl (meth)acrylate. These monomers A may be used singly or in combination of two or more. From the viewpoints of manufacturing procedures, manufacturing costs, ease of obtaining raw materials, and environmental safety, it is considered that 'monomer A is particularly preferably R2 to R4, all of which are isopropyl (meth) acrylic acid triisopropyl rock eve. S purpose. The monomer B is an ethylenically unsaturated monomer other than the monomer A, and examples thereof include a (meth) acrylate, a vinyl compound, an aromatic compound, and a dialkyl ester compound of a dibasic acid. Further, in the specification of the present invention, (meth) acrylate means propyl acrylate or methacrylic acid. Examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and (meth)acrylic acid. 2-methoxyethyl ester, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (methyl 10-)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate Wait. Examples of the vinyl compound include vinyl chloride, ethyl dichloroethylene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and A vinyl compound having a functional group such as vinylpyrrolidone 15. Examples of the aromatic compound include styrene, vinyl toluene, and cardiomethylstyrene. Examples of the dibasic acid dialkyl ester compound include dimethyl maleate, dibutyl maleic acid S, and dimethyl maleic acid. In the present invention, the monomers B may be used singly or in combination of two or more. In particular, the monomer B is preferably a (meth) acrylate, and more preferably decyl decyl acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate or the like. A preferred aspect of the copolymer (2) contained in the composition of the present invention is selected from the group consisting of: 15 200837159 (decyl) triisopropyl decyl acrylate, (diyl) acrylic acid tri-tert-butyl decyl ester and At least one monomer A of decyl)butyl butyl diphenyl decyl acrylate and one selected from the group consisting of methyl methacrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (methyl) a copolymer of at least one of monomers B of 2-methoxypropyl acrylate and 2-methoxyethyl 5 (meth)acrylate. The copolymer (2) is preferably obtained by copolymerizing a monomer A of 30 to 65 wt% with a monomer B35 to 70 wt%. When the monomer A accounts for 30% by weight to 65% by weight, the ruthenium can effectively exert the desired antifouling effect. Further, the town can appropriately suppress the hydrolysis rate of the coating film and can exhibit the antifouling effect for a long period of time. 0 The average molecular weight (Μη) of the copolymer (2) is 5000~looooo, and it is preferably 10000~50000. When Μη is less than 5〇〇〇, the film is easy to become brittle. When the number average molecular weight exceeds 100,000, the coating film is hardly dissolved in seawater, and the desired antifouling effect cannot be effectively exerted. The method of measuring Μη can be exemplified by gel permeation chromatography (Gpc). The copolymer (2) may be a random copolymer of a monomer a and a monomer oxime, an interactive copolymer, a periodic copolymer or a strand-wire of a block copolymer. / The burdock is obtained by polymerizing a monomer ruthenium with a monomer ruthenium in the presence of a polymerization initiator to obtain a copolymer (2). The polymerization initiator used in the reaction may be used singly or in combination of two or more of the above-mentioned examples. The above polymerization initiation _ shot is AIBN and a third butyl peroctoate. Dilute acid,, and field. Further, the amount of the polymerization initiator used is adjusted to adjust the molecular weight of the (meth) propylene triorganoester copolymer. The soil may be exemplified by solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization of 200837159. From this point of view, the copolymer (2) is produced in a simple and precise manner and is solution polymerization. In the above polymerization reaction, the solvent may, for example, be xylene or an organic solvent may be used as needed. An aromatic hydrocarbon solvent such as organic or toluene; an ester solvent such as hexane or heptane; an ester solvent such as acetic acid B, acetic acid butyl, isobutyl acetate or methoxyacetate; An alcohol such as isopropyl alcohol or butyl alcohol is a solvent such as oxalate, diethyl acetonide or dibutyl ether; a ketone solvent such as methyl ketone or methyl isobutyl ketone. Among them, in particular, aromatic: a compound/mixture is preferred, and xylene is more preferable. These solvents may be used singly or in combination of two or more. 10 The reaction temperature of the polymerization reaction can be appropriately set according to the type of the polymerization initiator, etc., and is usually 7 〇 to i4 〇 ° C, and preferably a 80 to 12 (rc. The reaction time of the polymerization reaction only needs to be determined. The reaction temperature and the like may be appropriately set, and it is usually about 4 to 8. The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. Gas 3) Salt of rosin salt and rosin derivative > In the present invention, rosin Salts of salt and rosin derivatives use zinc salts and/or sodium salts. The salt of the rosin salt and the rosin derivative is highly compatible with the above-mentioned polymer plasticizer buckle, and can be stably present in the coating film. Therefore, the composition of the present invention has excellent long-term storage properties. The copper salt is less soluble in water than the zinc salt described above, and is less soluble in water than in the present invention. The amount of the salt of the coating salt and the copper salt can be appropriately adjusted to adjust the hydrolysis rate of the coating film, thereby designing a moderate degree of display. And a soluble coating film. For example, when the composition of the present invention is used as a ship bottom $ 17 200837159, the content of the zinc salt to the copper salt in the composition is preferably 100:0 to 20:80 °. Listed as rosin gum (or such as salt, wood rosin, rosin (or copper), Yanfeng, 5% (or copper) salt, etc.. These cockroaches use one or two (also (i steel) salt , pine oil rosin zinc (5 or more. The zinc (or copper) salt of the rosin derivative can be exemplified by maleic acid rosin (or copper) salt, formazanized rosin zinc (or copper) salt, polymerized rosin (or a copper salt, a nitrogen-added rosin (or copper) salt, a heterogeneous rosin zinc (or copper) salt, etc. These may be used alone or in combination of two or more. 10 In particular, the composition of the present invention preferably contains a compound selected from the group consisting of Rosin gum (or copper) salt, wood rosin zinc (or copper) salt, pine oil rosin zinc (or copper) salt, hydrogenated rosin zinc (or steel) At least one of salt and non-uniform rosin zinc (or copper) salt, and more preferably rosin zinc (or copper) salt, hydrogenated rosin (or copper) salt and uneven rosin (or copper) At least one of the salts. 15 The salt of the rosin salt and the rosin derivative can be used as a commercially available product. Further, it can be obtained by a conventional method. For example, a zinc salt of rosin (or a rosin derivative) can be borrowed. It is synthesized by reacting rosin (or rosin derivative) having a free carboxyl group (COO-group) with zinc oxide while heating in a solution. Gas 4) Antifouling agent >>0, _ Anti-π agent It is not particularly limited as long as it has a killing or repellent effect on marine fouling organisms, and examples thereof include inorganic chemicals and organic chemicals. /, m Inorganic agents may, for example, be cuprous oxide or copper thiocyanate. (general name: Luodan steel), copper nickel and copper powder, etc. Female, ', t /, dry especially copper and copper thiocyanate are 18 200837159. Organic agents can be listed as: 2- Wei Organic copper compound such as 唆-N-copper oxide (general name: u-pyridylthione copper); mercaptopyridine-N-oxygen Zinc (general name: pyridine sulfur_zinc), ethylene bisdithiocarbamate (general name: zinc 5 Napo), bis(dimethyldithiocarbamic acid) (general name: thiram zinc) (Ziram)), an organic compound such as bis(dimethyldithiocarbamate) ethylene bis(dithiocarbamate) dizinc (general name: polyurethane); Pyridine triphenylborane, 4-isopropylpyridyldiphenylmethylborane, 4-phenylpyridyl-diphenylborane, triphenylboron-n-octadecylamine, triphenyl [3 -(2-Ethyl 10 hexyloxy)propylamine] boron or other organoboron compound; 2, 4, 6-trichloromale fluorene, N-(2,6-ethylphenyl) 2, 3--male quinone imine and other maleic imine compounds; others, such as 4,5-dichloro-2-n-octyl-3-isothiazolone (general name: Sinai 211), 3, 4 -Dichlorophenyl-NN·dimethylurea (general name: Diuron), 2-mercaptothio- 4_t-butylamino group _6_cyclopropylamino group + 15 three Nitrogen (general name: IrSaro1 1〇51), 2, 4, 5, 6·tetrachloroisoindolyl (general name: tetrachloroisophthalonitrile), N_dichlorofluoromethylthio-N ,N,-Dimethyl-N-p-tolyl sulphate (general name: Tolyfluanide), N-dimethylmethylthio-N,, 1^'-dimethyl-N-phenylsulfonamide (general name) ··Dichi〇fluanid), 2-(4-thiazolyl)benzimidazole (general name thiabendazole), 3-(benzene 20 and [b]thiophen-2-yl)- 5,6_Dihydro-1,4,2-oxathiat-4-oxide (general name · Betoxazine), 2-(p-phenyl)_3_cyanobromo-5-trifluoromethyl吼 slightly (general name: Econea28) and so on. Among them, especially pyrithione, copper pyrithione, pyridine triphenylborane, 4-isopropylpyridyldiphenylmethylborane, Betoxazine, zinc naproxil, Sinai 211 and irgar〇l 1〇 51 is preferred, and pyridine 19 200837159 is better than copper thioketone, acridinium thione, pyridine triphenyl borane and Betoxazine. These antifouling agents may be used alone or in combination of two or more. <Antifouling Coating Composition> The antifouling coating composition of the present invention contains the above polymer plasticizer, the copolymer of the above 5 (2), the aforementioned rosin salt and/or the salt of the aforementioned rosin derivative, and the aforementioned antifouling agent . A preferred embodiment of the antifouling composition of the present invention is a composition comprising the following components: (1) a polymer plasticizer having a glass transition temperature of _4 (rc or less and a number 10 average molecular weight of 1000 to 10,000) A composition of an ethylenically unsaturated carboxylic acid ester polymer, (2) a triorganosilyl (meth)acrylate copolymer having a Μη of 10,000 to 50,000, which is a copolymer of a monomer oxime and a monomer ruthenium, and is 3〇~65wt% of monomer A is obtained by copolymerizing 35~70% by weight of monomer B, which is selected from 15% triisopropyl methacrylate (methyl) At least one of tributyl decyl acrylate and tributyl phenyl phenyl methacrylate, and the monomer B is selected from methyl methacrylate, (methyl) At least one of ethyl acrylate, butyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and 2-methoxypropyl (meth)acrylate; 20 (3) is selected from rosin gum ( Or a copper salt, a hydrogenated rosin zinc (or copper) salt, and at least one salt of a heterogeneous rosin (or copper) salt; and (4) an antifouling agent selected from the group consisting of Pyridone, copper thiocyanate, zinc pyrithione, copper thioketone, bismuth triphenylboron, 4-isopropylpyridinyldiphenylmercaptoborane, Betoxazine, At least one of Shino Na, Sinai 2u & Irgar 〇 1 20 200837159 1051. A more preferable aspect is a composition containing the following components. (1) A polymer plasticizer having a glass transition temperature of -50 ° C The following is a composition of an ethylenically unsaturated carboxylic acid styrene polymer having an average molecular weight of from 2000 to 4,000; (2) a triorgano oxime (meth) acrylate copolymer having a Mn of from 16,000 to 20,000, which is a monomer A Copolymerization with monomer B, which is obtained by copolymerizing 30 to 65 wt% of monomer A with 35 to 70 wt% of monomer B, which is triisopropyl (meth)acrylate a quinone ester, wherein the monomer B is at least one selected from the group consisting of methyl 10, butyl (meth) acrylate and 2-methoxyethyl (meth) acrylate; (3) selected from At least one salt of rosin gum zinc salt, hydrogenated rosin salt and uneven rosin zinc salt; and (4) antifouling agent selected from the group consisting of oxymethylene oxide and copper thiocyanate. The pyridine 5 is at least one of sulphur-copper, 0-pyridyltriphenyl rot and Betoxazine. In the antifouling coating composition of the present invention, the content of the copolymer (2) is not particularly strict. The igh is 20 to 200 parts by weight, and more preferably 50 to 150 parts by weight, based on 100 parts by weight of gg of the aforementioned rosin salt and/or the aforementioned rosin derivative. 2〇 〇 copolymer (2) When the content is less than 2 parts by weight, the coating formed by the composition of the present invention is weak and the adhesion to the coating film formation (base) is deteriorated and is used. When the difference between η and 认 is 2 (10)% by weight or more, the initial film solubility is too high, and the antifouling effect cannot be exhibited. In the composition of the antifouling paint of the present invention, the polymer plasticizer contained in the above-mentioned polymer plasticizer 21 is not particularly limited to: but is less than 100% of the salt of the above (4) salt and/or the rosin derivative, preferably 10 ~ 70 parts by weight, and more preferably 2 〇 ~ 6 〇 weight injury. When the content of the plasticizer is 1 part by weight or more based on 100 parts by weight of the salt of the rosin salt and/or the rosin derivative, it is possible to prevent cracking and peeling due to brittleness of the coating film. When the content of the plasticizer is less than 70% by weight, the coating film can maintain an appropriate hardness, and no coating film abnormality such as cold flow occurs during navigation of the ship. The antifouling agent content in the antifouling paint composition of the present invention is not particularly limited, but it is preferably in the antifouling paint composition, and preferably accounts for 5 to 7 〇 10% by weight. When the content of the antifouling agent is less than 1% by weight, the antifouling effect cannot be sufficiently exhibited. When the content of the antifouling agent exceeds 80% by weight, the coating film becomes weak and cannot withstand actual use. The antifouling coating composition of the present invention preferably contains a chemical for removing the water of the composition (hereinafter sometimes referred to as "water removing agent"). Specifically, the water removing agent preferably contains a dehydrating agent and/or a water binding agent. The dehydrating agent is a compound having the property of ingesting water into crystal water, thereby removing water in the coating composition. The water binding agent is a compound having the property of removing water from the coating composition by reacting with water. Examples of the dehydrating agent include anhydrous gypsum, molecular sieve (Molecular sieve), magnesium sulfate and sodium sulfate, and water-binding agents include alkyl myristate such as methyl formic acid and ethyl formate; tetraethoxy Decane, tetrabutoxy oxime, tetraphenoxydecane, fluorene (2-ethoxybutoxy)decane, methyltriethoxy 22 200837159 decane, dimethyldiethoxy decane, trimethyl An alkoxy decane such as ethoxy decane or diphenyldiethoxy decane; an acid anhydride such as maleic anhydride or phthalic anhydride. Among them, anhydrous gypsum and tetraethoxysilane are particularly preferred. These dehydrating agents and water-binding agents may be used alone or in combination of two or more. The content of the water repellent in the above composition is not particularly limited, but it is preferably 0.1 to 20% by weight, and more preferably 0.2 to 5% by weight, based on the antifouling coating composition. When the content of the degreaser is less than 11% by weight, the storage stability of the coating is still insufficient in practical use. If the content of the water scavenger exceeds 20% by weight, the coating film becomes weak and cannot withstand actual use. The antifouling coating composition of the present invention may further contain a conventional pigment, a conventional plasticizer other than the above plasticizer, and an anti-sagging agent. Examples of the pigment include oxidized words, Bengara, talc, titanium oxide, cerium oxide, calcium carbonate, barium sulfate, and calcium oxide. These pigments may be used alone or in combination of two or more. 15 Conventional plasticizers include phosphates such as tricresyl phosphate, trioctyl phosphate, and triphenyl phosphate; dibutyl phthalate, dioctyl phthalate Phthalates such as phthalates; adipates such as dibutyl adipate and dioctyl adipate; and adipic acid such as dibutyl sebacate and dioctyl alginate Esters; 20 epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil; alkyl vinyl ether ice polymers such as methyl vinyl ether polymer and ethyl vinyl ether polymer; polyethylene glycol, Polyalkylene glycols such as polypropylene glycol; third sulfhydryl pentasulfide, petrolatum, polybutene, trimellitic acid ginseng (2-ethylhexyl), anthrone oil, mobile paraffin, and gasified paraffin. These may be used alone or in combination of two or more. 23 200837159 The aforementioned anti-sagging agent may, for example, be Bentonite, oxidized polyethylene and various guanamine compounds. These anti-sagging agents may be used in the form of two or more species. The anti-sagging agent can be used after being dispersed in an organic solvent such as xylene. Others may contain a dye, an antifoaming agent, etc. as needed. 5 The composition of the present invention is usually dissolved or dispersed in an organic solvent in advance. This can be used as a coating material. The organic solvent may, for example, be dimethylbenzene, toluene, mineral spirit, MIBK or butyl acetate. Among these, xylene or MIBK is preferred. These organic solvents may be used singly or in combination of two or more kinds. 10 The antifouling coating composition of the present invention has excellent stability and hardly adheres, gels or solidifies even after long-term storage. <Manufacturing Method of Antifouling Coating Composition> The method for producing the antifouling coating composition of the present invention is a mixture of the following components, that is, 15 (1) a polymer plasticizer, a glass transition temperature of -20 ° C or less and a number average molecular weight of 500 to 20000 of ethylenic unsaturated carboxylic acid ester polymer; (2) number average molecular weight of 5000 ~ 1 〇〇〇〇〇 (methyl An organic oxime copolymer of acrylic acid, which is a copolymer of triorganoester (meth) acrylate mono 20 A represented by the formula (1) and an ethylenically unsaturated monomer B other than the monomer A; 】 R1 R2 —C—C—〇—Si—R3

II IO R4 24 (I) 200837159 (wherein r1 is a hydrogen atom or a methyl group; R2 to r4 are each the same or different, and represent a carbon number of 3 to P branched or phenyl) (3) selected from rosin zinc At least one salt of a salt of a salt, a rosin derivative, a copper salt of a rosin, and a copper salt of a rosin derivative; and 5 (4) an antifouling agent. That is, according to the production method of the present invention, a mixture containing the polymer plasticizer, the copolymer (2), the rosin salt and/or the salt of the rosin derivative, and the antifouling agent may be mixed and dispersed. The aforementioned antifouling coating composition. 10 The above-mentioned polymer plasticizer, copolymer (2), the aforementioned rosin salt and/or the salt of the aforementioned rosin derivative and the content of the aforementioned anti-caries agent are not particularly limited, and only need to be appropriately adjusted to the above antifouling paint. The polymer plasticizer, the copolymer (2), the salt of the rosin salt and/or the rosin derivative, and the antifouling agent may be contained in the composition. 15 The aforementioned mixture may contain a pigment or the like as needed. In the production method of the present invention, it is preferred that the above-mentioned full compound is mixed by a disperer or the like, and then mixed and dispersed by a mill (ball mill, sand mill, granulator, pulverizer, etc.). . For example, the polymer plasticizer, the copolymer (2), the salt of the rosin salt and/or the rosin derivative, the antifouling agent of the above 20, the water scavenger, the pigment, and other additives are each dissolved or dispersed in a solvent. In this state, mixing is carried out, and mixing and dispersion are carried out using a mill. The solvent to be used may, for example, be xylene, toluene, mineral spirits, MmK or butyl acetate. Among them, xylene is preferred. These solvents may be used alone or in combination of two or more. 25 200837159 <Antifouling treatment method, antifouling coating film, and coating material> The antifouling treatment method of the present invention uses the above-mentioned antifouling coating film formation table (4) to form an antifouling agent. (4) The present invention is controlled by the antifouling coating film. The antifouling coating film is gradually dissolved from the surface, and the new antifouling coating film prevents the adhesion of aquatic organisms. Further, the composition can be directly applied and the antifouling effect can be continuously exerted. The composition of the coating film can be, for example, a ship (especially a ship bottom) or a structure for fishery. For fishing equipment, for example, buoys and ropes used in fishing nets for fishing or fixed use can be cited. For example, water pipes, bridges and harbor equipment for power generation can be cited. The medium structure & object can be coated with the coating composition on the coating film or the portion to form the anti-m. The surface of the product (the method of the full coating may be, for example, a brushing method, a reading method, or a spin coating method. These methods may be carried out singly or in combination of two or more kinds. The coating method may be followed by drying, and the drying temperature may be room temperature. The thickness of the coating film, etc. (4) is appropriate. The antifouling coating film of the present invention formed by (1) the anti-money k-form is formed, and 1) even if it is in contact with seawater for a long period of time, marks, separation, etc.; Raw clothing marks and peeling 3) Adhesive to the film formation: not easy & raw "is abnormal coating film; speed suppression is appropriate, can, =) has excellent water solubility; and 5) long-term maintenance of antifouling performance due to hydrolysis. When the thickness of the sewage coating film and the seawater temperature are appropriate, the temperature is the same as that of the ship, and when the ship is sailing at the bottom of the ship, the antifouling can be used. For example, the coating is soil, and the thickness is usually 50. 〜50〇μιη, preferably 26 200837159 100~400μηι. The anti-, ++ love film of the present invention has an appropriate hardness. That is, the anti-soil of the present invention has an abnormal coating film such as a cold flow and a cold flow. The degree of hardness.

The Dn ^ clothing has the aforementioned antifouling coating film on the surface. The coating of the present invention may have the aforementioned antifouling coating film on the whole or a part of the time-saving clothing surface. The coating material of the present invention is provided with an antifouling coating film having the advantages of the above 1) to 5), and can be used as an IT description ship (specially suitable for use, which is a ship bottom), a fishing tool, and an underwater structure. 10 15 20 For example, when the antifouling coating film is formed on the surface of the bottom of the ship 4 μ, ° °, the surface of the coating film is spleened by the spleen of the antifouling coating film. Often this is the case: the water-stopping organisms are attached. Λ,, ^W The hydrolysis rate of the antifouling film is preferably suppressed. Therefore, the ship can maintain the prevention and death of the long-term π , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , s after the complete removal of the coating film, the weight is formed to suitably form the antifouling. The coating material can be directly coated with the antifouling coating film. The antifouling private (four) can be used in a simple and low-cost invention. The antifouling hydrolysis rate of the invention. In Bubbi, materials, and products can be used to suppress the coating film. The composition of the coating film can maintain long-term and prevent the reading of the moon. Further, the composition of the present invention has excellent long-term retention σ, and the composition of the present invention hardly cuts or gels and solidifies even after long-term storage. Furthermore, the composition of the antifouling paint of the present invention is very versatile, and even if it is dissolved in sea water, there is almost no problem of pollution of the sea. m υ υ 〉 m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m Abnormal; 3) coating: high adhesion; 4) excellent (four) water-based; and 5) anti-fouling performance can be maintained for a long time due to the suppression of the rotation speed. π本明明The coating is provided with the aforementioned 1 ) 5) Advantages of the antifouling coating film: 乍 is suitable for use in the above-mentioned ships (especially the bottom of the ship), fishing equipment and underwater structures, etc. γ | ^ 么 , , 1 σ, formed on the ship's bottom surface of the ship When the antifouling coating film is formed, the film will be slowly dissolved from the surface to make the surface of the coating film renewed frequently, and the surface of the coating film can be stopped. The antifouling coating film has a moderate solubility. Therefore, the boat y Long-term, anti-fouling performance, for example, even in the stagnation of the mooring and equipment rigging period, there is almost no attachment or storage of aquatic fouling organisms π A σ long anti-fouling effect. Therefore, it is expected that fuel will be saved during navigation due to the reduced resistance of the ship. “In addition, even after a long period of time, the antifouling coating on the surface is basically not damaged. Therefore, the above-mentioned coating material can be directly applied to the anti-fouling coating film by directly coating the p, _, and thus the coating film composition. Continuous antifouling performance can be maintained easily and at low cost. 28 200837159 C ^=δτ Examples However, each of the production examples, comparative production examples, examples, and comparisons = amount %. The viscosity is the measured value obtained under the pit and is B-type viscosity = the desired value. The number average molecular weight _ is the value obtained by Gpc (polystyrene conversion value). The conditions of GPC are as follows. Clothing Set · · · HTC-8220GPC pipe column made by Dongsuo Co., Ltd. · · · TSKgel SuperHZM-M 2 pieces Flow 3: · · · 0.35 mL/min

Detector · · · RJ column temperature bath temperature · · · 40°C

Free liquid · · · THF The heating residue is obtained by heating at ll ° ° C for 3 hours. Further, the unit of the amount of each component in Table 1 is g, and the ratio of the weight in the brackets to the total amount of the monomer A and the monomer B is in parentheses. In the 20 iOOOml flask equipped with a thermometer, a reflux condenser, a stirrer, and a titration funnel, 350 g of xylene was placed in a reconstituted U copolymer, and the temperature was raised to 85 to 90 ° C while stirring under a nitrogen atmosphere. While maintaining 85 to 90 ° C for 1 hour, titrate 225 g of triisopropyl acrylate, 200 g of methyl methacrylate, 25 g of n-butyl acrylate, 50 g of 2-dimethoxyethyl acrylate and AIBN 4 g in the flask. (Polymerization initiator: first addition) mixture. After the titration, the polymerization reaction was carried out at 2 hours 29 10 200837159 at 85 to 90 ° C, whereby the reaction liquid 1 was obtained. Next, AIBN 2 g (polymerization initiator: second addition) was added to the obtained reaction liquid 1, and polymerization reaction was further carried out at 85 to 90 ° C for 2 hours to obtain a reaction liquid 2. Thereafter, 150 g of xylene was added to the reaction liquid 2 and dissolved, whereby the copolymer solution (2)-1 was obtained. (2) _1 has a viscosity of 350 mPa · s/25 ° C, a heating residue of 50.5%, and a Μη of 17,000 (Table 1). Production Examples 2 to 9 and Comparative Manufacturing (丨) Polymer Solution (2)_2~(2)-9 and Η? In accordance with the amounts shown in Table 1, the solvents, monomers, and polymerization initiators shown in Table 1 were used. The same operation as in Production Example 1 was carried out, whereby a copolymer solution (2)_2~(2)-9 and hydrazine were obtained. Further, when the polymerization initiator was a third butylperoctanoate, it was 95. The polymerization reaction was carried out at ~10 ° C. The viscosity, heating residue and number average molecular weight (Μη) of each of the obtained copolymer solutions are shown in Table 1 Table 1 The initial part of the classification component name _: f solvent in the container; ΜΗ 5Κ Imm t ~3&〇" 225 C4S) 3SD 230 (SO)

3SQ css) 350 350

Mm A initial base * enoic acid 'M inside « 夕 额 K K K K K K — 苯 苯 苯 苯 ΐ & & & & 酸 酸 酸 酸 酸 酸 酸 s s s s s s s s s s s 酷 酷 酷 酷 酷 酷 酷 酷 酷:m Έ^^μ^2μ " Along the decanoic acid 2-φ gas box?: 觭(4) citric acid 2 φ followed by 2. 0(10) JS(5)_ 200 (A0) 23(5) ---- --~__ 2〇〇UG) m 50(10) 5氓10) 250 (50) i$b) 250(10) 3ίΧϊ (6D) 75(15) 50(10: 100 (.20 75 C155 5000: 150(30 50 (10) 10(1;(10) δ〇(1〇> 100 {?0) 50 ί10) 300 (6〇> 150 (30) SD (10) Move (10) _ 125(25) hn 11C) bD (10Ϊ ^03(20} 50 U) 00000 笫2 add the first

ABX No.: Ding Guanyue AIBN " : System two φ benzene mm & ex) a total of m brewing (mh * s /? 5eC)................... d Μπ , itrr, 3kS)

130 95-100 95-100 390 m- 500 * 50 2 ίβ.ΟΟΟ I π,οαο (2)-7 m 150 5-100 {2)-^ 350 4§9 KC£i)0 ~ <2b9

30 200837159 Production Example 10 (Manufacture of plasticizer (1)-1) In a 1000 ml flask equipped with a thermometer, a reflux condenser, a stirrer, and a titration funnel, 5 〇〇g of diphenylbenzene was placed, and the mixture was stirred under a nitrogen atmosphere. While raising the temperature to 125 to 130 ° C, holding 125 to 130 ° C and taking 1 hour, titrating 2-methoxyethyl acrylate 350 g, n-butyl acrylate 150 g and t-butyl peroxide in the 5 bottles A mixture of octanoic acid i5g and a-methylstyrene dimer (product name "Rhofuma MSD" manufactured by Nippon Oil & Fats Co., Ltd.). After the titration, the obtained reaction liquid was kept at 125 to 130 ° C, and the third butyl peroctoate lg was added three times per hour, and the mixture was further stirred for 2 hours to obtain an acrylic resin plasticizer solution 10 (1)-1. . The viscosity of (1)-1 was 45 mPa·s/25 °C, the heating residue was 52.6%, the Μη was 3500, and the Tg was -51 °C. Production Example 11 (Production of Co., Ltd. (1)-2) 500 g of diphenylbenzene was placed in a 1000 ml flask equipped with a thermometer, a reflux condenser, a stirrer, and a titration funnel, and then heated while stirring under a nitrogen atmosphere. To 125 to 130 t: while maintaining 125 to 130 ° C, a mixture of 500 g of n-butyl acrylate and 20 g of a third butyl peroctoate was titrated in the flask. After the titration, the obtained reaction liquid was kept at 125 to 130 ° C, and the third butyl peroctoate lg was added three times per hour, and the mixture was further stirred for 2 hours to obtain an acrylic resin plasticizer solution (1)-2. The viscosity of (1)-2 was 22 mPa·s/25QC, the addition of 20 heat residues was 52.2%, the Μη was 2900, and the Tg was -54 °C.

Production Example 12 (Firmant ΠV3 0刍诰A) 500 g of diphenylbenzene was placed in a 1000 ml flask equipped with a thermometer, a reflux condenser, a stirrer, and a titration funnel, and then heated to 125 to 130 while stirring under a nitrogen atmosphere. While maintaining a temperature of 125 to 130 ° C, a mixture of 5 〇〇g of 2-ethylhexyl acrylate and 20 g of a third butyl peroctoate was added to the flask at the same time. After the titration, the reaction was allowed to proceed. The liquid was kept at 125 to 130 ° C, and the third butyl peroctoate lg was added three times per hour, and the mixture was further stirred for 2 hours to obtain an acrylic resin plasticizer solution 0)-3. The viscosity of (1)-3 was 12 mPa·s/25 °C, and the heating residue was 51·〇% ′ Μη was 2300, and Tg was -85 °C.多多f produced 2 (Tg2 wei. C acryl resin solution), in a 1000ml flask equipped with a thermometer, reflux cooler, mixer and titration funnel, filled with 500g of xylene, under nitrogen atmosphere While stirring, the temperature was raised from 1125 to 130 C, and the temperature was maintained at 125 to 130 ° C, and a mixture of 500 g of n-butyl methacrylate and 2 g of n-butyl peroctoate 2 〇 g C7) was added to the flask. After the titration, the obtained reaction liquid was kept at 125 to 130 ° C, and the third butyl peroctoate lg was added three times per hour, and the mixture was further stirred for 2 hours to obtain an acrylic resin > gluten solution. The viscosity was 200 mPa · s / 25 ° C, the heating residue was 51.0%, the Μη was 2300, and the Tg was 20 °C. 15 刍 13 13 ( ( ( 13 13 13 13 13 13 13 13 13 13 13 13 松 松 松 松 松 松 松 松 松 松 松 松 松 松 松 松 松 松 松 13 13 13 松 13 13 13 13 13 13 13 13 13 13 13 13 13 〇1〇〇g and xylene 5(^, under reduced pressure at 7〇~8(). (: reflux for 3 hours. After that,

About 50% of the ingredients). The heating residue of the obtained rosin gum salt solution was 50.5%. Production Example 14 (hydrogenated rosin word gj

Adding hydrogenated rosin II

, ZnO, reflux cooler and mixer 1000ml flask toluene solution (solid content 5〇%)

400g, ZnO 32 200837159 _ and dimethyl methoxide, under reduced pressure (four) expensive reflux dehydration. Further, the hydrogenated rosin zinc salt was prepared to obtain a heating residue of 50% by weight of the dimethyl sulfoxide solution of the hydrogenated rosin zinc salt. 5 Production Example 15 (. Five in a flask equipped with a thermometer, a reflux cooler, and a mixer), adding a heterogeneous rosin xylene solution (solid content 5 〇%) _, fine 〇〇g and two 5〇g of toluene, dehydrated under reduced pressure at 70~801, 3 shoud, but then to the temperature (25〇c) and then transitioned to produce one of the 10% salt of toluene and gluten. Brown transparent solution, solid content of about 5%). The heating residue of the resulting heterogeneous rosin salt xylene solution is 50%. 衣k例16 (Manufacture of rosin gum copper salt, equipped with thermometer, reflux cooling In a 1000ml flask of the mixer and the blender, add rosin gum xylene solution (solid content 50%) 400g, Cu2〇15 2008, methanol 1〇〇§ and glass beads (diameter 2.5~3.5111111), 7〇~80° (: stirring for 8 hours. After stirring, the resulting mixture was allowed to react at 5 Torr: 2 days, and then cooled to room temperature (25 ° C). The residue was concentrated under reduced pressure to distill off the methanol portion. Xylene is added to the concentrate to prepare a xylene solution of rosin gum copper salt (a concentrated cyan transparent solution, about 50% solid content). The resulting rosin gum The heating residue of the copper 20 salt xylene solution is 50.8%. 1^〇7 (hydrogenated rosin copper salt 刍诰1 is added to the hydrogenated rosin II in a 1000 ml flask equipped with a thermometer, a reflux cooler and a stirrer. Benzene solution (solid content 50%) 400g, Cu2〇20〇g, methanol l〇〇g and glass beads (diameter 2.5~3.5 Na), give 33200837159 at 70~80°c for 8 hours. After stirring, make The resulting mixture was incubated at 5 (rc for 2 days, and then cooled to room temperature (25. After filtration), the residue was concentrated under reduced pressure to distill off the methanol portion, and then diphenylbenzene was added to the desired material. A hydrogenated rosin copper salt solution was prepared (concentrated cyan transparent solution, solid content of about 50 〇 / 〇). The heating residue of the obtained hydrogenated pine scented copper salt xylene solution was 50.3%. 18 (uneven rosin 锢鹱 f f) In a 1000 ml flask equipped with a thermometer, a reflux cooler and a stirrer, add a heterogeneous rosin xylene solution (solid content 5 〇%) 4 〇〇 g, Cu 2 〇 2〇〇g, methanol l〇〇g and glass beads (diameter 2.5~3.5mm), mix with 70~8 (TC stir for 10 hours for 8 hours. After mixing, make the mixture The liquid was kept at 50 ° C for 2 days, and then cooled to room temperature (25 ° C) and filtered. The residue was concentrated under reduced pressure to distill off the methanol portion, and then xylene was added to the obtained concentrate to obtain unevenness. Xylene solution of rosin copper salt (concentrated cyan transparent solution, about 50% solid content). The heating residue of the resulting heterogeneous rosin copper salt xylene solution is 50.2%. 15 Complex bases 1 to 12 and comparative example 1 ～5 (Production of Coating Composition) The copolymer (2) was obtained by using the copolymer solutions (2)-1 to (2)-9 obtained in Production Examples 1 to 9 and the copolymer solution obtained in Comparative Production Example 1. The zinc salt of the rosin zinc salt or the rosin derivative is a xylene solution (about 50% of a solid component) of the salt, copper salt and rosin gum prepared in Preparation Examples 13 to 18, and a hydrogenated rosin dimethyl 20 benzene solution. (a solid content of about 50%) and a non-homogenous rosin-containing bismuth benzene solution (about 50% of a solid content), and the plasticizer is produced by using the plasticizers UM~(1)·3 obtained in Production Examples 10 to 12, and comparatively manufactured. Acrylic resin solution of Tg 20 ° C obtained in Example 2, acrylic resin (product name "ARUFONUP-1080" manufactured by Toagosei Co., Ltd., 100% solid content) Tg: -61 ° C, Μη : 2400), phosphorus 34 200837159 tricresyl acid ester, ethyl vinyl ether copolymer (product name "Lutner Α-25" BASF company), epoxidized soybean oil (product) The name "Sansocizer Ε-2000Η" is a new physicochemical system), chlorinated paraffin (chlorine content is about 4%), and other antifouling agents, pigments, additives and solvents listed in Table 2 are shown in Table 2. The ratio (% by weight) was blended, and a coating composition was prepared by using a small table sand mill for experiments (using a glass bead having a diameter of 1.5 to 2.5 πιη) as a mixed dispersion. Table 2 Ingredient name ie a) « m 'i _ η Song Na cargo phase A magical dream and r soldiers shallow ingredients 妗 笨 两 两 > Song Nen mw, run two · 〆拗 济 济 ) ) 遝.筲 筲 赞 赞 ί ί ί 筲 ί ί ί 戍 戍 戍 戍 戍 戍 戍 戍 戍 戍 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 3⁄43⁄4 points? ??<»;? Old benzene inspection: jfm JU ^ ^ . <et ζ* >Λ*ψλ^Τ *# ** >**21 TL * -X- «•; taste a*赞三净琢?r about m lie Α ΰ ΰ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

:Think pyt-ihitHKi t4"Fang - "fSSi?, Unlttaar-'ft + two na 1_

Test Example 1 (Coating the stability of the coating composition to determine the stability of the coating composition', and measuring the viscosity change of the coating composition after the long period of storage, 35 200837159. Specifically, the measurement was carried out according to the following method. The viscosity of the coating composition obtained in Examples 丨 to 12 and Comparative Example 5 was measured by a Brookfield viscometer. Then, the above coating composition was placed in a 200 ml wide mouth tinplate can and sealed. After the 〇5 C thermostat was stored for 1 month, the viscosity of the coating composition was measured again with a B-type viscometer. The viscosity change of the coating was less than 5 〇〇 lnPa · s / 25 ° c (the paint state was almost unchanged) ◎, the viscosity change of the paint is 5〇〇~5〇〇〇111?3·s/25 C (slightly thickened) is 〇, the viscosity of the coating changes to 10 5G()G~W(8)(8)mPa · s The temperature at /25 °C (larger viscosity increase) is Δ, and the viscosity of the paint changes to be undetectable (becoming gelatinous or solidified) as the parent. The results are shown in Table 3. From Table 3, it can be seen that Tri-n-methacrylate-containing methacrylate with monomer n of n-butyl group The composition of the thiol ester (Comparative Example 2) and the composition containing the rosin or rosin derivative which is not the salt of the 15 salt and the copper salt (Comparative Examples 3 to 5) lacked long-term stability. The antifouling coating compositions obtained in Examples 1 to 12 and Comparative Example 5 were coated on a transparent glass plate (75 x 150 x lmrn), and dried at 4 ° C for 1 day to make the thickness of the dry 2 〇 uncoated film About 10 is called melon. The coating film hardness of the obtained dried coating film was measured at 25 ° C using a pendulum type hardness tester (pendulum hardness meter). The results (return numbers) are shown in Table 3. The number of returns 20 to 50 is better in practical use. As is apparent from Table 3, the coating film formed using the coating film composition of the present invention (Examples 丨 to 12) had an appropriate hardness. 36 200837159 Test Example 3 (Adhesion test of coating film) <Test method> The adhesion test of the coating film was carried out in accordance with JIS K-5600-5-6. Specifically, it is tested according to the following method. First, the coating compositions obtained in Examples 1 to 12 and 5 Comparative Examples 1 to 5 were applied to a fiber-reinforced plastic sheet (FRP sheet) (75 x 150 x 2 mm) and a tinplate (75 x 150 x 2 mm) to which sandblasting had been applied, and dried. The thickness of the coating film was about 100 μm. Next, the obtained coating material was brought to 40. (: Drying for 1 day, thereby producing a dried coating film having a thickness of about ΐ〇〇μπ!, and performing an adhesion test (2 mm x 2 mm, net 10 mesh number = 100) with respect to the dried coating film. 70 to 100 are ◎, the number of unpeeled meshes is 40 to 69, the number of unpeeled meshes is 2 to 39, and the number of unpeeled mesh is 0 to 19 is X. It is not shown in Table 3. 15 As can be seen from Table 3, the coating film formed using the coating film composition of the present invention (Examples 1 to 12) can be firmly adhered to either the FRP plate or the tinplate. Test Example 4 (Y-Flexibility Test of Coating Film) The coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 were applied to a 20-sand-iron-coated tinplate (75 x 150 mm) to make the thickness of the dried coating film Then, the obtained coating material was dried for 4 days, and a dry coating film having a thickness of about ΙΟΟμηη was produced. The tinplate sheet having the dried coating film was bent at 90 degrees, and the coating film was visually observed to confirm the coating film. State. The person who has almost no cracks is ◎, and the person who produces fine cracks is 〇, producing 37 20 0837159 A very large crack is △, and a part of the coating film is easily peeled off as X. The results are shown in Table 3. From Table 3, it was found that the coating film composition of the present invention (Examples 1 to 12) was used. The coating is not fragile and is a strong coating. 5毽例5 (Change 彳^彳水遂蓝) Apply anti-rust coating (B-A) to the wool glass board (75x150xlmm) After drying, the thickness was about 5 μm, and dried to form a rust-preventive coating film. Thereafter, the antifouling coating compositions obtained in the examples and the comparative examples 1 to 5 were applied onto the rust-preventive coating film to make The film thickness of the dried coating film was about 10 100 Pm. The obtained coating material was dried at 4 rc to prepare a test piece having a dried coating film having a thickness of about 1 μm. The test piece was immersed at 35 ° C. After 3 months in the natural seawater, the state of the coating film was visually confirmed. • If the coating film was not changed, it was ◎, and if it was slightly discolored, it was 〇, and if some microbubbles were generated, Δ was cracked, swollen, peeled, and the like. 15 The results are shown in Table 3. From Table 3, it can be seen that 'the coating film formed by using the coating film composition of the present invention (Example 丨~12) Excellent water resistance. 38 200837159 Table 3 安 安 stability 40 Ϊ ' imiH after coating hard 褎 test _ sexual test · test phase ϊϊ ί hours FRP plate tinplate 3S \: ' 3 he u two heart 1 @ 40 ◎ @ 2 @ 45 ◎ © © 3 ◎ 3β L ® © © 4 © 3β © © @ 5 30 © @ @ β @ 33 @ © @ 7 @ 33 © ◎ @ 8 ◎ 32 © @ ® i— 9 ύ 30 © ◎ © 10 © 42 ◎ @ © ^ © 11 © @ @ 12 ◎ 38 @ @ @ % 1 51 XXX 2 X 18 © © X - Comparative Example 3 A as © @ @ 4 △ 23 ◎ © X 5 1/ ◎ Γ ◎ ❹ ;^- Test Example 6 (Coating film name: 2 Taret test (旌 试 test)) A rotating drum of 515 mm in diameter and 440 mm in height was attached to the center of the water tank, so that it could be rotated by the horse. In addition, is the wire used to keep the temperature of the sea water constant? 11 keep it fixed? 11 automatic controller. A rust-preventive coating (vinyl type A/C) was applied to a hard vinyl chloride plate (75 x 150 x 1 mm) to a thickness of about 5 Å μm after drying, and dried to form a rust-proof coating film. Thereafter, the antifouling paint compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 5 were applied onto the above rust-preventive coating film to have a thickness of about 3 μM after drying. The obtained coating material was dried at 4 (TC for 3 days to prepare a test plate having a dry coating film having a thickness and a force of 300 μm. The prepared test plate was fixed on a rotating drum of a spinner rotating device to be in contact with seawater. The rotating drum was rotated at a speed of 20 浬 39 200837159. During the period, the seawater was kept at a temperature of 25 ° C and the pH was 8.0 to 8.2, and the seawater was replaced every other week. The initial stage of each test plate was measured by a laser focus variator. The film thickness and the residual film thickness after every 6 months were calculated from the difference, and the dissolved film thickness was calculated to determine the amount of coating film dissolved. 5 The film dissolution amount was the amount of film dissolved per month ( The results are shown in Table 4. From Table 4, it is understood that the amount of the coating film formed by using the coating film composition of the present invention (Examples 1 to 12) in seawater is 3 to 8 μm per month. That is, the coating film formed by using the coating film composition of the present invention (Examples 1 to 12) was dissolved to a certain extent by the hydrolysis rate of 10 degrees, and was dissolved stably for a long period of time. Further, the coating of the present invention was used. Film formed by the film composition (Examples 1 to 12) even after 24 No cracks or peeling occurred after a month. Therefore, the antifouling film composition can be directly coated and the antifouling coating film can be appropriately formed to maintain the antifouling performance. As can be seen from Table 4, t丨15 is used. It is not easily dissolved in seawater, and the coating film formed using the coating film composition of Comparative Example 1 formed by the coating composition of 2 to 5 cannot effectively exhibit the antifouling effect. The crack and peeling of the comparative example are used. Low in nature, occurs midway 40 200837159 Table 4 During the test period, after coating for 12 months, after 12 months, after 18 months, after 24 months, remarks 1 30 56 82 113 2 26 48 75 98 3 26 55 80 106 4 42 90 135 170 5 40 84 121 156 Example 6 32 60 88 118 7 20 37 58 81 8 24 45 64 87 9 23 42 65 92 10 27 50 75 101 11 25 43 72 97 12 30 58 90 119 1 12 20 29 42 2 105 220 No coating film Comparative Example 3 72 126 Coating film peeling 6 months from cracking of the film 4 88 154 Film peeling 6 months from coating cracks 5 92 164 Film peeling 6 months from coating m Crack test Example 7 (Antifouling test) The results obtained in Examples 1 to 12 and Comparative Examples 1 to 5 On both surfaces of dirt or paint composition coated on the cloth 5 B rigid gas Hay plate (100x200x2mm) so that the thickness of the dry coating film became about 200μιη. The obtained coating material was dried at room temperature (25 ° C) for 3 days to prepare a test plate having a dried coating film having a thickness of about 200 μm. The test panel was immersed under the sea surface of Owase City, Mie Prefecture, Japan for 1.5 m, and the test plate caused by the adhering matter was stained for 24 months. 10 The results are shown in Table 5. In addition, the numbers in the table indicate the adhesion area (%) of the fouling organism. 41 200837159 It can be seen from Table 5 that the coating film formed by using the coating film composition of the present invention (Examples 1 to 12) is almost the same as the coating film formed by using the coating film compositions of Comparative Examples 1 to 5. Aquatic fouling organisms are not attached. This is because the hydrolysis rate of the coating film formed by using the coating film composition of the present invention (Examples 1 to 12) is suppressed to some extent by a certain degree, and can be stably dissolved at a constant rate for a long period of time. Table 5: 4 months after the test, after 12 months, after 12 months, after 18 months, after 24 months, the attachment notes 1 0 0 0 0 no 2 0 0 0 0 no 3 0 0 0 0 no 4 0 0 0 0 no 5 0 0 0 0 No embodiment 6 0 0 0 0 No 7 0 0 0 0 No 8 0 0 0 0 No 9 0 0 0 0 No 10 0 0 0 0 No 11 0 0 0 0 No 12 0 0 0 0 No 1 0 30 80 100 Dragon worm barnacle 2 0 0 0 30 Long worm barnacle 24 months after no part of the film comparison example 3 0 10 50 100 Dragon worm barnacle 12 months after the film crack 4 0 10 40 100 Barnacle 12 months after licking crack 5 α 10 40 100 Long worm barnacle 12 months after coating cracks L pattern simple description 3 (none) 10 [Main component symbol description] (none) 42

Claims (1)

200837159 X. Patent application scope: 1. An antifouling coating composition comprising: (1) a polymer plasticizer, which is composed of a glass transition temperature of -20 ° C or less and a number average molecular weight of 500 to 20,000. a compound composed of a saturated carboxylic acid ester poly-m 5 compound; (2) a triorganooxime (meth)acrylate copolymer having a number average molecular weight of 5,000 to 100,000, which is represented by the formula (I) a copolymer of triorganoyl acrylate monomer A and an ethylenically unsaturated monomer B other than monomer A; 10 [Chemical Formula 1] R1 R2 H2C=C——C—0—Si—R3 (I) II I o R4 (wherein R1 is a hydrogen atom or a methyl group; R2 to R4 are each the same or different and represent a branched alkyl group having a carbon number of 3 to 8 or a phenyl group) (3) selected from the group consisting of rosin zinc salt and rosin-derived At least one salt of a zinc salt, a rosin copper salt, and a copper salt of a '15 rosin derivative; and (4) an antifouling agent. 2. The antifouling coating composition according to claim 1, wherein the ethylenically unsaturated carboxylic acid ester polymer is an acrylate having a glass transition temperature of -40 ° C or lower and a number average molecular weight of 1000 to 10,000. polymer. The antifouling coating composition of claim 1, wherein the monomer A is triisopropyl decyl (meth)acrylate. 4. The antifouling coating composition of claim 1, which comprises 20 to 200 parts by weight of the (meth) propylene triorgano oxime ester copolymer in an amount of from 10, 2008,37,159 to 100 parts by weight of the salt, and contains 10 ～70 parts by weight of the ethylenically unsaturated carboxylic acid ester polymer. 5. The antifouling coating composition of claim 1 which contains a dehydrating agent 5 and/or a water binding agent. 6. An antifouling treatment method which comprises forming an antifouling coating film on the surface of a coating film formation using the antifouling coating composition of claim 1 of the patent application. 7. An antifouling coating film formed by using the antifouling coating composition of claim 1 of the patent application. 10 8. A type of coating is applied to the antifouling film on the surface of claim 7 of the patent application. 9. A method for producing an antifouling paint composition, which comprises mixing a liquid containing a mixture of the following components, namely: (1) a polymer plasticizer, wherein the glass transition temperature is -20 ° C or less and 15 A composition of an ethylenically unsaturated carboxylic acid ester polymer having an average molecular weight of 500 to 20,000; (2) an organic oxime ester copolymer of (meth)acrylic acid having a number average molecular weight of 5,000 to 100,000, which is a formula (I) A total of 20 copolymers of the triorganomoperyl acrylate monomer A and the ethylenically unsaturated monomer B other than the monomer A; R 2 R 2 H 2 C = C - C - 〇 - Si—R 3 (I) II IO R4 44 200837159 (wherein R 1 is a hydrogen atom or a methyl group; and R 2 to R 4 are each the same or different, and represent a branched alkyl group having a carbon number of 3 to 8 or a phenyl group) (3) And at least one salt selected from the group consisting of rosin salt, rosin derivative salt salt, rosin copper salt and rosin derivative copper salt; and 5 (4) antifouling agent. 45 200837159 VII. Designated representative map: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: