TW200932852A - Antifouling coating composition, process for producing the composition, antifouling coating film formed from the composition, coated object having the coating film on surface, and method of antifouling treatment by forming the coating film - Google Patents

Abstract

An antifouling coating composition is provided which can form in seawater a coating film which stably dissolves away from the beginning to show a satisfactory antifouling effect, has excellent water resistance, and can effectively produce the antifouling effect over long. The composition is reduced in the content of volatile organic compounds (VOCs) vaporizing off into the air and is highly safe environmentally. The antifouling coating composition comprises (A) a polymer which is obtained by polymerizing a polymerizable unsaturated triorganosilyl carboxylate and has a number-average molecular weight of 1,000-20,000 and (B) at least one zinc salt selected among zinc salts of rosins and zinc salts of rosin derivatives. In the composition, (1) the weight ratio of the content of the polymer (A) to the content of the zinc salt (B), (A)/(B), is from 45/55 to 10/90, (2) the composition has a nonvolatile content of 75 wt.% or higher, and (3) the composition substantially contains neither a rosin nor a rosin derivative each having a free carboxyl group.

Description

200932852 VI. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to an antifouling coating composition, a method for producing the composition, an antifouling coating film formed using the composition, and a surface having the coating a coating of a film, and an antifouling treatment method for forming the coating film. C. Prior Art 3 Background of the Invention 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 the surface, and a formation The antifouling treatment method of the coating film. Aquatic fouling organisms such as Haishengjie, snake silkworm, purple fetus, bryozoan, sea worm, cyanobacteria, stone, slime, etc., attached to ships (especially the bottom part of the ship) or fishing nets, fishing nets In the case of underwater structures such as fishery appliances or water pipes, 15 pipes, etc., the performance of these ships and the like may be impaired and unsightly. G In the past, antifouling coatings containing organic tin copolymers were applied to the surface of ships, fishing equipment and underwater structures to prevent the adhesion of aquatic organisms. For example, a coating film formed by coating an antifouling coating material 20 containing a copolymer of tributyltin group, the copolymer is slowly dissolved in water, and the surface of the coating film is constantly renewed, thereby preventing the waterborne fouling material from being applied to the coating film. Attached. Further, after the dissolution, the coating film is applied to the surface to stably exhibit the antifouling performance. However, the use of this antifouling coating has been forced to be based on the problem of marine pollution. 200932852 In recent years, instead of containing organic tin copolymer as a hydrolyzable copolymer, we have developed a lower toxicity than organic tin base and less environmental load. A triorganooxime copolymer having a diorganofluorenyl group is used.仁疋, 3 has the coating film containing the two organic vinegar copolymer, if it is a copolymer obtained by copolymerization of an alkyl group containing tri-n-butyl decyl ester, which is a linear triorganocyanate monomer, The hydrolysis rate of the film is fast, so when the dissolution rate of the coating film is gradually increased and after a long period of time, the dissolution rate of the coating film becomes too large, and the water resistance is also deteriorated, and expansion or cracking occurs, so that it is difficult to use for a long time. . 10 Therefore, we have begun to study all triorganodecyl ester copolymers of branched alkyl groups having an organic group (Patent Documents 6 to 12). However, the triorganomide-containing copolymer having only a branched alkyl group can improve the water resistance, but the hydrolysis rate of the coating film is very slow, and it takes too much time before the coating film starts to dissolve, so the initial anti-3 effect is not Preferably, there is a problem that aquatic organisms will adhere at an early stage in a sea area where the biological activity is deficient or the sea temperature is low. In order to solve these problems, attempts have been made to combine a triorganocylidene-containing copolymer with pine mash (or a rosin derivative) to adjust the dissolution rate of the coating film (Patent Documents 2 to 10). In the case where turpentine (or a rosin derivative) is used, a part thereof may react with a metal compound contained in the coating composition to become a metal salt at the time of production of the coating, and the reactivity is insufficient, thereby causing A rosin (or rosin derivative) having a free carboxylic acid remains in the coating composition. In particular, in the case where rosin is used in a large amount, it is found that the proportion of the rosin (or rosin derivative) remaining in the coating composition becomes high. The rosin (or rosin derivative) 200932852 has high hydrophilicity, so that the water resistance of the coating film is lowered, and as a result, the coating film is likely to cause abnormalities such as foaming or cracking. Then, a method of premixing an excess metal compound with turpentine has been proposed (Patent Documents 9 and 10). However, in this method, although the metal compound is excessively used, the metal compound and the rosin are still insufficiently reacted, so that it is difficult to completely eliminate the rosin (or rosin derivative) having a free carboxylic acid. In addition, based on environmental problems in recent years, solvent-based coatings volatilize a large amount of organic solvents in air enthalpy, so they are subject to worldwide restrictions. We also strive to reduce the content of organic solvents (Patent Documents 11, 12). In these methods, it is difficult to obtain an antifouling coating which can simultaneously have good film properties and antifouling properties. Also, in the construction of a new ship, in order to make effective use of the shipyard, the ship's hull is sometimes built in the dock, and after the bottom of the ship is painted, the hull 15 is floated on the sea outside the dock. The interior of the hull was completed and then re-introduced into the canal for completion. However, it takes three months for the hull to float on the sea for internal loading, during which time there may be organisms attached to the painted surface, or even if the organism is adhered, the mucus may adhere. This organism or mucus can not be removed sufficiently with water. Once the coating is completed in the state 20 where the organism or mucus adheres, the coating film may be cracked, peeled, etc. during navigation, causing problems. [Patent Document 1] Japanese Patent Laid-Open No. Hei 11-116857 (Patent Document 3) Japanese Laid-Open Patent Publication No. Hei 11-116858 (Patent Document 3) [Patent Document 4] [Patent Document 5] [Patent Document 5] [Patent Document 7] [Patent Document 7] [Patent Document 8] [Patent Document 9] [Patent Document No. 2000] [JP-A-2000] [J] JP-A-2000-265107, JP-A-2000-265107, JP-A-2002-53796, JP-A-2002-53796 [Patent Document 10] JP-A-2003-261816 (Patent Document 11) WO 2005/005516 A1 10

[Patent Document 12] JP-A-2005-082725 SUMMARY OF INVENTION Technical Problem The object of the present invention is to provide an antifouling coating composition which can form a coating film, which is a coating film. In the early stage of seawater, the membrane can exhibit stable solubility and good antifouling effect, excellent water resistance, and can effectively exert antifouling effect for a long time. Moreover, the antifouling coating composition is a volatile organic compound that scatters into the atmosphere. The compound (VOC) is small and the environmental safety is high. Means for Solving the Problems As a result of intensive research on the above-mentioned problems, the present inventors have found that a specific composition can solve the above problems and complete the present invention. That is, 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 a surface coating of 5 liters, and a coating film formed thereon. Antifouling treatment method. An antifouling coating composition comprising: 200932852 (A) a polymer having a number average molecular weight of from 1,000 to 20,000 by polymerizing a polymerizable unsaturated carboxylic acid triorgano oxime ester; and (B) being selected from rosin a zinc salt of at least one zinc salt of a zinc salt and a rosin derivative; 5 ❹ 10 15 20 Further, the antifouling coating composition is: (1) the content of the polymer (A) and the zinc salt (B) The weight ratio of the two ((A) / (B)) is 45 / 55 ~ 10 / 90; (2) the content of non-volatile components is above 75 wt%; and (3) substantially free of free carboxyl groups Rosin and turpentine derivatives. 2. The antifouling coating composition according to Item 1, wherein the polymer (A) has a number average molecular weight of from 2,000 to 15,000 and a molecular weight dispersion of less than 2.5. 3. The antifouling coating composition according to Item 1 or 2, wherein the glass transition temperature of the polymer (Α) is 2〇~7 (TC. 4. The antifouling coating composition according to item 1, wherein The polymer (A) is a triisopropyl decyl (meth) acrylate copolymer. The antifouling coating composition according to item 3, wherein the aforementioned (meth)acrylic acid diisopropyl ruthenium vinegar copolymer system (4) 30 to 60% by weight of triisopropyl methacrylate, (b) 1 to 50% by weight of methyl methacrylate, and (c) other than (a) and (b) above ( 6. The composition of the antifouling coating according to Item 1, wherein the rosin zinc salt is selected from the group consisting of rosin gum salt, wood rosin zinc salt, pine. At least one zinc salt of the group consisting of a rosin ester zinc salt; the salt of the rosin derivative is at least one selected from the group consisting of hydrogenated 7 200932852 rosin zinc salt and disproportionated rosin zinc salt. The antifouling coating composition according to Item 1, wherein the content of the non-volatile component is 80% by weight or more, and The viscosity at 25 ° C measured by a viscometer is 80 to 100 KU. The antifouling coating composition of item 1, wherein the volatile organic compound content is less than 400 g/L. The antifouling coating composition further contains 10 to 100 parts by weight of the total amount of the polymer (A) and the zinc salt (B), and contains 10 to 100 parts by weight of the oxidation term. The antifouling coating composition further contains 100 to 400 parts by weight of cuprous oxide with respect to 1 part by weight of the total of the polymer (A) and the zinc salt (B). The antifouling coating composition 'the foregoing cuprous oxide is cuprous oxide having an average particle diameter of 8 to 20 μm. 15 12. The antifouling coating composition of item 1, which is more related to the aforementioned polymer (Α) and the foregoing The total amount of the salt (Β) is 100 parts by weight, and the organic antifouling agent is contained in an amount of 1 to 100 parts by weight. 13. The antifouling coating composition according to item 1, which is further related to the above polymer (Α) and the foregoing The total amount of the zinc salt (Β) is 1 part by weight, and contains 20 to 50 parts by weight of the plasticizer. 14. The antifouling coating composition of item 13, wherein The plasticizer is an epoxidized oil or fat. The antifouling coating composition according to Item 1, which further contains 100 parts by weight of the total amount of the polymer (Α) and the zinc salt (Β), and contains water removal. The antifouling coating composition according to Item 15, wherein the water repellent agent is at least one selected from the group consisting of alkoxy decanes and alkyl orthoformate. 17. The antifouling coating composition according to Item 1, which further comprises 1 part by weight of the total of 5 ❹ 10 15 ❹ 20 (A) and the above-mentioned salt (B), and contains a fatty acid guanamine The dispersing agent is 1 to 50 parts by weight. 18. An antifouling treatment method comprising forming an antifouling coating film on a surface of a coating film formation product by using the antifouling coating composition according to the above item 17. An antifouling coating film formed by using the antifouling coating composition recorded in the above-mentioned item No. 20. A coated article comprising the antifouling coating film according to item 19 above. 21. A method for producing an antifouling coating composition, comprising: (A) polymer having a number average molecular weight of from 1,000 to 20,000 by polymerizing a polymerizable unsaturated carboxylic acid triorgano oxime ester; and (B) The zinc salt of at least one of the salt of the rosin zinc salt and the rosin derivative is mixed, and (1) the weight ratio of the content of the polymer (A) to the content of the zinc salt (B) (( A)/(B)) is 45/55 to 10/90; (2) the nonvolatile content is above 75 wt%; and (3) substantially free of rosin and rosin derivatives having free carboxyl groups. 22. The method for producing an antifouling coating composition according to Item 21, which, in addition to the polymer (A) and the zinc salt (B), is further mixed with cuprous oxide having an average particle diameter of 3 to ΙΟμΓη. The resulting mixture was mixed and dispersed by a disperser 9 200932852. 23. The method for producing an antifouling coating composition according to item 21, which is obtained by mixing and dispersing a mixture obtained by mixing the polymer (A) with the zinc salt (B) by a disperser. The oxidized 5 cuprous copper having a particle size of 1 〇 2 〇 μ η is mixed. Antifouling Coating Composition The antifouling coating composition of the present invention comprises: (Α) a polymer having a number average molecular weight of 1000 to 20000 obtained by polymerizing a polymerizable unsaturated carboxylic acid triorgano oxime ester (polymer (a ()) an antifouling coating composition selected from the group consisting of rosin salt and rosin derivatives, and at least (1) the polymer (Α) The weight ratio of the content of the zinc salt (Β) to ((Α) / (Β)) is 45/55~10/90, 15 (2) the content of non-volatile components is above 75 wt%, (3) substantially Contains no rosin and rosin derivatives with free carboxyl groups. <Polymer The antifouling coating composition of the present invention contains a polymer obtained by polymerizing a polymerizable unsaturated carboxylic acid triorgano oxime ester (containing a polymerizable unsaturated carboxylic acid tri- 20 oxime ester unit polymer), The number average molecular weight (?n) of the polymer is from 1,000 to 20,000, and more preferably from 2 to 15,000. By containing the above polymer (Α), it is possible to form a coating film which effectively exhibits antifouling performance and can appropriately prevent adhesion of aquatic organisms. When the 聚合物η of the polymer (Α) is in the range of 1000 to 20000, the coating film formed in 200932852 is excellent in the physical properties of the coating film (hardness and toughness of the coating film), so that it is less likely to be cracked or peeled off, and as a result, it can be prevented for a long period of time. Pollution effect. When Μη is less than 1000, the amount of dissolution of the coating film becomes large, but the coating film becomes brittle and is liable to cause cracks. When Μη exceeds 20,000, the antifouling effect by the coating film cannot be maintained for a long period of time. Specifically, when the Μη exceeds 20,000, the coating film becomes tough, but the solubility of the coating film is deteriorated, and there is a fear that the antifouling effect is gradually lowered. When the Μη exceeds 20,000, the viscosity of the polymer (Α) becomes high, so that the viscosity of the coating composition containing the polymer (a) itself is too high. If this coating composition is used as a 10 coating, a large amount of organic solvent (diluent) must be used, which is environmentally problematic and has low economic efficiency. The method of measuring Μη is, for example, a gel chromatography instrument (GpC). When Μη is measured by Gpc, Μη is expressed by measuring the enthalpy (polystyrene-converted 値) obtained by measuring the polystyrene as a standard material. The dispersion of the molecular weight of the aforementioned polymer (Α) is preferably less than 3.0. When the molecular weight dispersion is less than 3.0, the adhesion of the coating composition can be appropriately lowered, and the amount of solvent used as a coating material can be effectively reduced. Further, the coating film has good physical properties, and an antifouling coating which can effectively exert an antifouling effect for a long period of time can be obtained. 20 In particular, as the polymer (Α), a polymer having a Μη of 2000 to 15000 and a molecular weight dispersion of less than 2.5 is preferable, and a Μη of 5000 to 10000, and a molecular weight dispersion of 2 〇1 to 1 〇 The polymer is better. The glass transition temperature (Tg) of the aforementioned polymer (Α) is preferably 20 to 7 (TC is preferably 30 to 60 ° C. Tg is 20 to 7 (in the case of TC, it is less susceptible to water temperature 11 200932852 or The effect of temperature can maintain moderate hardness and toughness for a long time. If the temperature is less than 20 ° C, a weak coating film will be obtained. Therefore, when the water temperature or temperature becomes high, the coating film will become When it is more than 60 ° C, the coating film becomes too hard, and it is likely to cause cracks or peeling on the coating film 5. The polymer (A) is at least The triorganosenyl group-containing monomer represented by the following formula (1) is obtained by (co)polymerization.

〇 R2

II I R1 —C-〇-Si-R3 (1)

I R4 ίο In the formula (1), R1 is not particularly limited as long as it is a hydrocarbon group having a polymerizable unsaturated double bond. However, it is preferred that the formula is as follows: (Chemical 2) ch2=c (ch3) . , ch2=ch—, ch2=ch—ch2—ch2_,

〇 R6 〇 ii I ii R5—〇—C_CH=CH—, and — R7—Si—〇—c—CH=CH_

I R8 is preferably CH2=C(CH3)-, or, ch2=ch-. 15 R5 may, for example, be a straight bond or a branched bond group having a carbon number of 1 to 8, a cycloalkyl group, an unsaturated alkyl group or an aralkyl group. a linear or branched alkyl group having 1 to 8 carbon atoms, and examples thereof include an anthracenyl group, an ethyl group, a n-propyl group, an isopropyl group, an isobutyl group, a second butyl group, a third butyl group, and a 2- 12 group. 200932852 Methyl butyl, 2-ethyl butyl, pentyl, 3 曱 pentyl, hexyl, heptyl, octyl and the like. The cycloalkyl group may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. 5 Φ 10 15 Φ 20 The unsaturated alkyl group may, for example, be a 2-propenyl group, a 2·butenyl group, a 3-butenyl group, a 2-pentenyl group, a 3-pentenyl group or a 4-pentenyl group. The aralkyl group may, for example, be a benzyl group, a phenethyl group or a phenylpropyl group. Further, the above-mentioned alkyl group, cycloalkyl group, unsaturated alkyl group, aralkyl group or the like may have a substituent. The substituent may, for example, be an alkoxy group, a decyl group or the like. The number of substituents, the position of substitution, and the like are not particularly limited as long as they do not impair the effects of the present invention. R6 to R8 represent a branched alkyl group or a phenyl group which are the same or different and have a carbon number of 3 to 8. The branched alkyl group having 3 to 8 carbon atoms may, for example, be isopropyl, isobutyl, second butyl, second butyl, 2-methylbutyl, isopentyl, 2-ethylbutyl, 3 _Methylpentyl and the like. In particular, R6 to R8 are preferably an isopropyl group, a second butyl group, a tert-butyl group or a phenyl group, and an isopropyl group is more preferred. In the formula (I), R2 to R4 are preferably a branched alkyl group or a phenyl group which are the same or different and have a carbon number of 3 to 8. The branched alkyl group having 3 to 8 carbon atoms is the same as the alkyl group exemplified in R6 to R8. In particular, R2 to R4 are preferably an isopropyl group, a second butyl group, a tert-butyl group or a phenyl group, and an isopropyl group is more preferred. The triorganofluorenyl group-containing monomer represented by the formula (I) may, for example, contain a triisopropyl sulphate monomer, a triisobutyl benzyl group-containing monomer, and a tri-butyl butyl group. a triisocyanoyl group containing a triphenyl group, a diisopropyl isobutyl silk monomer, a diisopropyl second butyl 7 group monomer, and a diisopropyl group Isoamyl fragment monomer, diisopropylphenyl oxalate monomer containing 13 200932852 isopropyl diisobutyl fluorenyl monomer, isopropyl dibutyl fluorenyl monomer, containing A tributyl diisobutyl fluorenyl monomer, a third butyl diisoamyl fluorenyl group-containing monomer, a third butyl diphenyl fluorenyl group-containing monomer, or the like. These triorganofluorene-containing monomers may be used singly or in combination of two or more. Wherein, 5 is particularly preferably a triisopropyl fluorenyl group-containing monomer, a third butyl fluorenyl group-containing monomer, and a third butyldiphenyl fluorenyl group-containing monomer, and a triisopropyl fluorenyl group-containing monomer. Better. Particularly, in view of manufacturing engineering, manufacturing cost, availability of raw materials, and environmental safety, the triorganofluorenyl group-containing monomer is preferably a triisopropylsulfonium group-containing monomer in which R2 to R4 are all isopropyl groups. © ίο The triisopropyl sulfhydryl monomer may specifically be triisopropyl decyl (meth) acrylate, triisopropyl decyl 4-pentenoate or bis (triisopropyl) maleate Ester ester), methyl triisopropyl decyl maleate, ethyl triisopropyl decyl maleate, n-butyl triisopropyl decyl maleate, butene Isobutyl triisopropyl phthalate, tert-butyl triisopropyl sulfonate maleate, n-pentyl triisopropyl decyl maleate, maleic acid Butyl triisopropyl decyl ester, 2-ethylhexyl triisopropyl decyl maleate, cyclohexyl triisopropyl decyl maleate, bis (triisopropyl) Base oxime), bismuthyl fumarate, ethyl triisopropyl decyl fumarate, n-butyl triisopropyl decyl methacrylate, anti Butyric acid 20 isobutyl triisopropyl decyl ester, n-pentyl triisopropyl decyl fumarate, isoamyl triisopropyl decyl fumarate, fumaric acid 2-ethylhexyltriisopropyl decyl ester, cyclohexyl triisopropyl decyl fumarate . These may be used alone or in combination of two or more. In particular, the triisopropyl fluorenyl group contains a mono-system of triisopropyl hydrazide (mercapto) acrylate. 14 200932852 Further, the term "triisopropylsulfonyl (meth) acrylate" means triisopropyl sulfenyl acrylate or triisopropyl fluorenyl hydrazide. 5 10 15 ❹ 20 The above polymer (A) is preferably a triisopropyl decyl (meth) acrylate copolymer (copolymer (A)). In particular, it is preferable that the above-mentioned copolymer (A) is copolymerized by the following (a), (b), and (c) in the following weight percentages, that is, (a) (indenyl) diisopropyl fluorenyl 30 to 60 The weight percentage is preferably from 30 to 50% by weight of (b) methacrylate methacrylate 10 to 50% by weight, preferably 10 to 40% by weight; and (c) (a) and (8) (曱) The acrylate is preferably 0 to 60% by weight, preferably 0 to 50% by weight. Further, the "weight percentage" is a ratio of the use ratio of each monomer in the case where the total amount of the monomers to be copolymerized is 100% by weight. When the use ratio of the monomer (a) is from 30 to 60% by weight, the formed coating film can effectively exhibit a desired antifouling effect. Further, the hydrolysis rate of the coating film can be appropriately suppressed, and the antifouling effect can be exhibited for a long period of time. Moreover, the water resistance and the strongness of the coating film can be improved. When the ratio of use of the monomer (a) is less than 30% by weight, the solubility of the coating film may be poor, so that it is difficult for the coating film to exert a long-term antifouling effect. When the use ratio of the monomer (a) exceeds 60% by weight, the solubility of the coating film may become too large, and the coating film design may become difficult. Further, it is impossible to impart sufficient water resistance and toughness to the coating film. When the use ratio of the above monomer (b) is from 1 50 to 50% by weight, the obtained coating film can maintain moderate hardness and toughness for a long period of time. When the use ratio of the monomer (b) is less than 1% by weight, the coating film becomes weak, and an abnormal state such as cold flow is likely to occur. On the other hand, when the ratio of the use of the monomer (b) is more than 50% by weight, the toughness of the coating film is increased, but it becomes too hard, and cracks or peeling may occur. The "other (meth) acrylate" of the monomer (c) means an acrylate or a mercapto acrylate other than decyl decyl acrylate. For example, it may be 5 decyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (methyl) An alkyl (meth)acrylate such as 2-ethylhexyl acrylate or lauryl (meth)acrylate; 2-methoxyethyl (meth) acrylate or 2-methoxy (meth) acrylate Alkoxyalkyl (meth)acrylates such as propyl ester, 4-methoxybutyl (meth)acrylate, 2-ethoxyethyl 10(meth)acrylate; (meth)acrylic acid ethanol a (meth)acrylic acid alkylene glycol monomethyl ester such as an oxime ester or a (meth)acrylic acid propylene glycol monomethyl ester; (meth)acrylic acid 2·hydroxyethyl ester or (meth)acrylic acid 2-hydroxypropyl ester; (Mercapto) hydroxyalkyl acrylates; (meth)acrylic acid dimethylamine ethyl ester, (methyl) acrylic acid monoethylamine ethoxylate 15 categories; tri-n-butyl decyl (meth) acrylate, triisobutyl methacrylate (meth) acrylate, three (meth) acrylate a triorganophosphonium (meth)acrylate other than the above monomer (a), such as a fluorenyl ester, a triphenyl decyl (meth) acrylate or a tert-butyl diphenyl decyl methacrylate Base esters and the like. Other examples include benzyl (meth)acrylate and phenyl (meth)acrylate. The monomer (c) exemplified above may be used alone or in combination of two or more kinds as the monomer component of the above copolymer (1). The monomer (c) is especially ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, More preferably, 2-methoxypropyl (meth)acrylate. When the copolymer (A) is synthesized, particularly if it does not affect the water resistance 16 200932852 or the solubility of the coating film, it is also possible to use a combination other than the above monomers (a), (b) and (c). body. The monomer which can be used in combination may, for example, be an ethylene compound having a functional group, an aromatic compound, acrylic acid or methacrylic acid. The vinyl compound having a functional group may, for example, be vaporized ethylene, vaporized vinylene, (meth)acrylonitrile, vinyl phthalate, butyl vinyl ether, lauryl vinyl ether or N-vinylpyrrolidone. The aromatic compound may, for example, be styrene, vinyl benzene or α-methyl styrene. In particular, the aforementioned copolymer (Α) is preferably triisopropyl sulfonium (meth) acrylate (monomer (a)), methyl methacrylate (monomer (b)), and selected from Ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and (mercapto)acrylic acid 2_ a copolymer of at least one monomer (monomer (c)) of the group consisting of methoxypropyl ester. The aforementioned copolymer (A) may be any copolymer of a random copolymer, an interactive copolymer, a periodic copolymer (periodic coP〇1ymer), or a bulk copolymer. The polymer (A) is obtained by polymerizing the monomer (a), the monomer (b) and the monomer (c), for example, in the presence of a polymerization initiator. The polymerization initiator used in the above polymerization reaction may, for example, be 2,2'-2〇 azobisisobutyronitrile (AIBN), 2,2'-azobis 2-f-butyronitrile, or dimethyl group. Azo compounds such as -2,2'-azobisisobutyric acid; benzhydryl peroxide, bis(3-methylbenzylidene) peroxide, benzamidine (3- Dimethyl peroxide compounds such as methotrexate) peroxides and dilauric acid peroxides; di-tert-butyl peroxide, t-butyl peroxybenzoate, 17 200932852 Tert-butyl peroxide compound such as tributylperoxyisopropyl carbonate or t-butyl peroxyoctanoate; third amyl peroxy-2-ethylhexanoate, Tripentyl peroxyacetate, third amyl peroxyisophthalic acid vinegar, third amyl peroxybenzoic acid vinegar, third amyl peroxyacetic acid vinegar, third amyl peroxyoctanoic acid vinegar, 5 two ( a third pentyl peroxide compound such as a third pentyl peroxide), a 1,1-di(tripentylperoxy)cyclohexyl or the like; a third hexylperoxy-2-ethylhexanoate , third hexyl peroxybenzoate, third hexyl peroxy-isopropyl Carbonates, tertiary-hexyl peroxy trimethyl acetate, hexyl third peroctoate, tertiary-hexyl peroxyneodecanoate like third hexyl peroxide compounds © 10 and the like. These polymerization initiators may be used singly or in combination of two or more. The polymerization initiator is preferably a dimercapto peroxide compound, a third butyl peroxide compound, a third amyl peroxide compound, and a third hexyl peroxide compound, more preferably a third pentane. Base peroxide compounds and third hexyl peroxide compounds. By using the third amyl peroxide compound and the third hexyl peroxide compound as the polymerization initiator, a copolymer having a narrow molecular weight distribution and a low viscosity can be obtained more than other polymerization initiators. 0 The molecular weight of the above polymer (A) can be adjusted by appropriately setting the amount of the polymerization initiator used. The polymerization method may, for example, be solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like. Among them, in the case where the polymer (A) can be synthesized simply and accurately, it is particularly preferred to carry out solution polymerization. In the foregoing polymerization reaction, an organic solvent may be used as needed. The organic solvent may, for example, be an aromatic flue-based solvent such as xylene or toluene; an aliphatic flue-based solvent such as calcined or gamma 18 200932852; _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ (4) solvent; alcohol solvent such as isopropyl alcohol or butanol; ether solvent of di(Ji(Di〇xane), diethyl _==j蜮4; methyl ethyl ketone, methyl isobutyl ketone, etc. A ketone solvent or the like. Among them, especially aromatic (four), soluble (four) good, dimethyl stupid is better. These solvents can be used alone or in combination of two or more. ❿ 10 15

20 The reaction temperature at the time of the polymerization reaction may be appropriately set depending on the type of the polymerization initiator, etc., and is usually 7 G to 14 (rc, 峨 to 12 generations are preferred. The reaction time at the time of polymerization is only required to correspond to the reaction temperature, etc.) It can be appropriately set, usually 4 to 8 hours. The W ° polymerization reaction is preferably carried out under an inert (inert) atmosphere such as nitrogen or argon. <Zinc salt (B)> Antifouling of the present invention The coating composition contains at least one zinc salt (zinc salt (B)) selected from the group consisting of a zinc salt of a pine salt and a rosin derivative, and the zinc salt has high compatibility with the polymer (A). The composition of the present invention is excellent in long-term storage property. As a metal salt of rosin (or rosin derivative), sodium salt, calcium salt, and magnesium salt other than the above-mentioned salt are used. In the case of the same, although the degree is not such as rosin (or rosin derivative) having a free carboxyl group, the sodium salt or the like is too hydrophilic, so that the water resistance of the coating film may be inferior. For example, the rosin zinc salt may be mentioned. Gum r〇sin zinc salt, wood pine Zinc salt, tall oil talc zinc salt, etc. These may be used alone or in combination. The zinc salt of the rosin derivative may, for example, be maleic acid rosin zinc salt, 19 200932852 formazan rosin zinc salt, polymerization. The rosin zinc salt, the hydrogenated rosin zinc salt, the disproportionated rosin zinc salt, etc. These may be used alone or in combination. In the present invention, the rosin zinc salt is preferably selected from the group consisting of rosin gum rosin zinc salt, wood rosin zinc salt and pine. The zinc salt of the rosin derivative is preferably at least one zinc salt selected from the group consisting of hydrogenated rosin salt and disproportionated rosin zinc salt. The salt and the rosin derivative salt can be used commercially, and the rosin salt and the rosin derivative salt can be produced by a known method. For example, a zinc salt of rosin (or a rosin derivative) can be used. It is synthesized by reacting 10 rosin (or rosin derivative) having a free carboxyl group (coo_ group) in a solution while heating it with zinc oxide. The composition of the present invention is characterized in that it is comparatively comparatively high. The amount of the zinc salt (B). The weight ratio of the content of the polymer (A) to the content of the above-mentioned salt (B) ((A) / (B)) is 45/55 to 10/90. Preferably, it is preferably 15 40/60 to 20/80. When the weight ratio is 45/55 to 1 〇/9 〇, the hardness and the strongness of the coating film are good, so that the dissolution of the coating film can be appropriately suppressed. The coating film can exert the antifouling effect for a long time. The zinc salt of the rosin zinc salt and the rosin derivative has a lower viscosity than other metal salts such as copper salt or the polymer (A). It is possible to reduce the viscosity of the product by using more than 20 parts of the zinc salt of the rosin zinc salt and the rosin derivative to reduce the viscosity of the product. In this case, the obtained coating composition has a low viscosity, so the composition is When the material is used as a coating, the use of the solvent can be suppressed, and as a result, an antifouling coating having a low content of a nonvolatile component, that is, a volatile organic compound (V〇C) content (low 200932852 VOC antifouling coating) can be appropriately obtained. 5 ❹ 10 15 Ο 20 The composition of the present invention does not substantially contain rosin and rosin derivatives having a free carboxyl group. Specifically, the content of the aforementioned rosin and rosin derivatives in the composition of the present invention is preferably 1% by weight or less, more preferably 〇~0.1% by weight. The rosin and rosin derivatives with free rebel are hydrophilic. Therefore, when the coating film contains the rosin and rosin derivatives, the coating film may have poor water resistance, so that the coating film may have abnormalities such as bubbles or cracks. < Cuprous oxide> The antifouling coating composition of the present invention preferably contains cuprous oxide. The aforementioned cuprous oxide can function as an antifouling agent. The coating film formed by containing cuprous oxide can effectively exhibit an antifouling effect. The shape of the cuprous oxide is not particularly limited as long as it does not impair the effects of the present invention. For example, particulate cuprous oxide can be used. The average particle diameter of the particulate cuprous oxide is preferably 3 to 2 Å μηη, more preferably 8 to 20 μίη. When the average particle diameter of cuprous oxide is 3 to 2 (wherein 111), the dissolution rate of the coating film can be appropriately suppressed, and as a result, the antifouling effect can be exhibited for a long period of time. Further, the average particle diameter of cuprous oxide is 8 to 20 μm. Further, the viscosity of the coating composition of the present invention can be further reduced, and as a result, a low VqC antifouling coating can be obtained. The foregoing cuprous oxide is preferably coated with a coating agent, for example, in the form of particles (four). In the case of the above-mentioned oxidized sub- _, it is preferred to coat the surface of each particle by a coating agent. By coating with a coating agent, it is possible to prevent the oxidation of the cuprous oxide as appropriate 21 200932852. The coating agent may, for example, be stearic acid or laurel. The above-mentioned coating agent may be used singly or in combination of two or more kinds. The composition of the present invention is preferably used with respect to the above polymer (A) and the aforementioned zinc salt ( The total weight fraction of B) is preferably from 200 to 300 parts by weight, based on 1 to 4 parts by weight of the cuprous oxide, and more preferably the content of the former vaporized cuprous copper relative to the aforementioned polymer ( A) and the aforementioned zinc salt 1〇〇 parts by weight if the total amount of 100~400 parts by weight, the antifouling coating film can be appropriately played *

fruit. U The cuprous oxide in the above composition is preferably coated with the polymer (VIII), the zinc salt (8), an organic solvent described later, or the like. When the oxidized oxidized granule is not sufficiently coated with the polymer (4) or the like, the cuprous oxide may not be sufficiently dispersed in the above composition, and conversely, there may be agglomeration. Once the cuprous oxide is agglomerated, the formed coating film will easily be cracked or peeled off. The composition of the present invention may contain an inorganic antifouling agent other than the cuprous oxide as long as it does not impair the antifouling effect. The inorganic antifouling agent may, for example, be copper thiocyanate (general name: Rodin bronze), steel nickel or copper powder. These can be used alone or in combination of two or more. <Pigment> The antifouling paint composition of the present invention may contain various pigments. By containing a pigment, the strength, weather resistance and water resistance of the coating film, and the solubility of the coating film can be improved. 22 200932852 “In particular, the composition of the present invention is preferably further contained in an oxidized word. Hunting from 3 with zinc oxide can promote the dissolution of the coating film of Qingcheng. It is effective in anti-fouling county. The shape of zinc oxide is not For example, a particulate matter may be used as the zinc oxide. When the particulate zinc oxide is used, the particle diameter thereof is not limited as long as it does not impair the effects of the present invention. Zinc content relative to the aforementioned polymerization

10 15

The total weight fraction of the compound (A) and the zinc salt (8) is preferably 0.000 parts by weight, more preferably (10) to 50 parts by weight. When the content of the zinc oxide is 10 to 100 parts by weight based on the total amount by weight of the polymer (A) and the zinc salt (8), the dissolution rate of the coating film can be appropriately adjusted. The content of the above-mentioned oxidized word is less than 1 G by weight (four) with respect to the amount of the polymer (4) and the zinc salt (8), and no material is added to promote dissolution of the coating film to seawater. When the content of the zinc oxide is more than 1 part by weight based on the total amount of the polymer (A) and the zinc salt (8), the coating film solubility is too large, and the dissolution rate of the coating film is difficult. . Negative, in addition to the aforementioned oxidation, a well-known water-soluble pigment and a water-insoluble pigment may be added as a pigment. The water-soluble pigment may, for example, be cuprous oxide, copper oxide, copper thiosulfate, zinc carbonate, zinc sulfide, food secret, Gu 35, Qing 33, iron carbonate, iron, hydrogen and carbon, and carbon. This is preferably a single (four)-type or a combination of two or more, so that it is preferable to use at least one water-soluble pigment selected from the group consisting of oxidized steel and copper thiocyanate. 23 200932852 10 15 20 The cuprous oxide of 水溶性 as a water-soluble pigment can be the same as or different from the cuprous oxide of the above-mentioned &lt;copper oxide&gt; item. Examples of water-insoluble bismuth oxides include titanium oxide, iron oxide, talc, calcium carbonate, emulsified stone, and ridge. _ M pearl stone, mica, barium sulfate, graphite, carbon black, etc. Or use two or more combinations. The non-aqueous pigment is preferably selected from at least a water-insoluble pigment selected from the group consisting of titanium oxide, iron oxide, talc, calcium carbonate, cerium oxide, lanthanum-A-alumina and barium sulfate. 1 In the water-soluble pigment, there is an effect that the coating mold can be dissolved in seawater. The oxidized particles ^ in the water-insoluble two-dimensional axis / 4 have an inhibitory coating film on the sea. Therefore, the solubility of the coating film can be adjusted by appropriately adjusting the kind of the water-soluble decomposable effect pigment, the amount of the pigment, and the amount of the water-insoluble compound. Adjusting the coating material The pigment content in the composition of the present invention is preferably adjusted to the coating film formed in the film, and is preferably from 20 to 50%, preferably from 25 to 45%. , 枓 枓 volume concentration (PVC) PVC less than 2〇% _, its soft coating film, its blue and easy to crack. 4 feet. (4) Exceeding, PVC can be calculated by the following formula. PVC (%) = pigment (including untransformed green _ total metering - total solid volume (four) total amount x l00 〃) volume _ in the above formula 'so-called "full solid volume two of the aforementioned polymer (A), the above-mentioned salt (B) and the like, the composition of the pigment, and the phase product. The composition of the present invention ❹ 24 200932852 The cuprous oxide described in the item containing the above &lt;copper oxide, the organic antifouling agent described later, In the case of a plasticizer, a water scavenger, a dispersant, etc., the volume is also included in the aforementioned "full solid volume". The aforementioned city towel is the same as the above-mentioned cuprous oxide, and preferably coated with a polymer (A) or the like. When the pigment is sufficiently coated with the polymer (a) or the like, it is possible to effectively prevent smearing or peeling of the formed coating film. &lt;Organic antifouling agent&gt; The antifouling coating composition of the present invention may further contain an organic antifouling agent. The organic antifouling agent is not particularly limited as long as it has a killing or taboo action on marine fouling organisms. For example, an organic copper compound such as 2-pyridylpyridine-N-copper oxide (general name: copper thiolate); 2-mercaptopyridine-N-zinc oxide (general name: zinc thiolate), ethylene 15 double Zinc dithiocarbamate (general name: Zineb), bis(dimethyldithiocarbamate) zinc (general name: JI), bis(dimethyldithiocarbamate) ethylene bis (disulfide) An amino acid such as diammonium hydride (general name: polysulfide [substituted] urethane); "bipyridyl triphenylboron, 4-isopropyl n-butyl-diphenyl" Methyl butterfly, 4-phenyl β-biti-diphenyl benzene, triphenyl-n-octadecylamine, triphenyl 20-[3-(2-ethylhexyloxy)propylamine] An organic boron compound such as boron; 2,4,6-tri-s-butylene succinimide, fluorene-(2,6-diethylphenyl) 2,3-di-s-butylene diimide, etc. a maleimide compound; the other is 4,5-dichloro-2-n-octyl-3-isohydrothiazolone (general name: CNINE211), 3,4-dichlorophenyl-fluorene -Ν-dimethylurea (general name: Diuron), 2·methylthio group 25 200932852 -4-second butylamino-6-cyclopropylamino- One two η Qin (a generic name: Irgarol 1051), 2,4,5,6-tetra-iso-p-terephthalonitrile (general name: Chlorothalonil), N-dichlorofluoromethane -N',n'-dimethyl-NP-tolyl decylamine (general name: fluanid), N-dioxylthio-anthracene, Ν'-5-mercapto- Ν-Benji sylvestre (general name · dichlofluanid), 2_(4_嗟0 sitting base) and ° ° ° sitting (general name thiabendazole), 3- (benzo [b] porphin-2-yl)-5,6-diylidene-1,4,2ϋ嗓_4_oxide (general name: bethoxazine), 2-(ρ-gas phenyl)-3-cyanide 4--4-bromo-5-trifluorodecylpyrrole (general name: ECONIA028) and the like. Among them, especially thiol pyridinium 10 zinc, copper thiolate pyridinium, pyridine, triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, bethoxazine, nectar, CNINE211 and Irgarol 1051 is preferred, and mercaptan beta is better than copper biting and mercaptan than zinc bite, bismuth triphenylboron and bethoxazine. These organic antifouling agents may be used singly or in combination of two or more. The content of the organic antifouling agent in the composition of the present invention is preferably 1 part by weight based on the total amount of the polymer (A) and the zinc salt (B). More preferably, the amount of the organic antifouling agent is less than 1 part by weight based on 1 part by weight of the total of the polymer (A) and the zinc salt (9). The antifouling effect by the organic antifouling agent cannot be sufficiently exhibited. The content of the organic antifouling agent is 1 〇〇 based on the total amount of the polymer (A) and the zinc salt (B). In the case of more than 50 parts by weight, the p-staining effect is not increased by the aforementioned organic antifouling agent. The improvement causes a wasteful economic waste. &lt;Plasticizer&gt; 26 200932852 The anti-caries coating composition of the present invention may further contain a plasticizer. The plasticity of the composition can be improved by making it contain a plasticizer. A tough coating film can be formed as appropriate. Further, the adhesion of the coating film to the coating film formation can be improved. 5 e 10 15 e 20 The aforementioned plasticizer can, for example, be trimethyl phenol phosphate or trioctyl phosphate. Phosphates such as triphenyl phosphate; phthalates such as dibutyl phthalate and dioctyl phthalate; dibutyl adipate, dioctyl hexane An adipate such as an acid ester; a sebacate such as dibutyl sebacate or dioctyl sebacate; an epoxidized fat or oil such as an epoxidized soybean oil or an epoxidized linseed oil; a hospital-based ethylene ether copolymer such as a mercapto vinyl ether copolymer or an ethyl vinyl ether copolymer; a polyglycol glycol such as polyethanol or polypropylene glycol; and a third nonenyl pentasulfide, petrolatum, Polybutene, bismuth meptanate (2-ethylhexyl), oxime resin oil, stream Paraffin wax, gasified paraffin wax, ethylenically unsaturated carboxylic acid ester copolymer having a Tg of -20 ° C or lower, etc. These may be used alone or in combination of two or more. In the present invention, as the plasticizer, it is preferably selected from the group consisting of It is at least a kind of group consisting of a dish of acid and vinegar, an epoxidized oil and fat, and an ethylidene unsaturated Wei vinegar polymer having a Tg of _2 m, and an epoxy group is more preferable. The content of the plasticizer in the compound, the content of the plasticizer of the rosin salt and/or the rosin derivative salt in the system is preferably in the range of 5 to 3 parts by weight. ^ When the amount of the total amount of 27 200932852 is less than 1 part by weight, the improvement effect of physical properties (toughness, adhesion, etc.) is not sufficiently exhibited. When the content of the plasticizer exceeds 50 parts by weight based on 100 parts by weight of the total of the polymer (A) and the salt (B), the formed coating film is weak and not practical. problem. &lt;Water remover&gt; The antifouling paint composition of the present invention may further contain a water removal dance j. The above water scavenger is an agent for removing water in the above composition. The water remover can be a water binder and a dehydrating agent. For the water-binding agent and the dehydrating agent, it can be used alone or in combination. The above water binding agent means a compound having a property of removing water in a coating composition by reacting with water. For example, a raw carboxylic acid such as formic acid methyl vinegar or orthoformic acid ethane vinegar may be used; tetraethoxy cerium, tetrabutoxy decane, tetraphenoxy decane, tetrakis (2-ethoxybutoxy) Alkoxy groups such as decane, decyltrimethylhexyloxydecane, methyltriethoxydecane, dimethyldiethoxydecane, trimethylethoxydecane, diphenyldiethoxydecane A fatty acid such as decane, cis-butyl succinic anhydride or phthalic acid gf.前述 The aforementioned dehydrating agent means a compound having a property of removing water from the above composition by drawing water as water of crystallization. For example, anhydrite, 20 molecular sieves, sulfuric acid, sodium sulfate, and the like. Preferably, the water-removing agent is preferably a water-binding agent, and more preferably a water-binding agent selected from the group consisting of alkaloids and orthoformic acid-based vinegar, and the tetraethoxy decane is the most good. The content of the above-mentioned water scavenger in the composition of the present invention is not particularly limited to 28 200932852, but is 1 to 50 by weight based on the total amount of the polymer (A) and the zinc salt (b) (7) by weight. Preferably, it is preferably 2 to 3 parts by weight. When the content of the water-repellent agent is less than 1 part by weight based on the total amount of the polymer (Α) and the zinc salt (Β), it may be impossible to obtain sufficient storage property. When the content of the water-removing agent is more than 5 parts by weight based on the total amount of the polymer (Α) and the zinc (Β), the coating amount may become brittle. In particular, water binders tend to volatilize in air. Therefore, based on environmental protection issues and the like, in the case of using a water-binding agent as a water-removing agent, it is preferably used in an amount of 1 part by weight relative to the person 10 of the aforementioned polymer (Α) and the aforementioned zinc salt (Β). It is 30 parts by weight or less. 〇 &lt;Dispersant&gt; The composition of the present invention may further contain a dispersant (precipitation preventing agent). By containing a dispersing agent, the composition of the present invention can effectively prevent precipitation of components (for example, pigment, cuprous oxide, zinc oxide, titanium oxide, 15 iron oxide red, talc, etc.) into hard hydrazine during storage. Slag (hard cake; stubborn sink). Further, when the composition of the present invention forms a coating film on the surface of the film-formed product, the problem of dripping of the above-mentioned composition (paint) can be effectively solved. Examples of the dispersing agent include an oxidized polyethylene-based dispersing agent, a fatty acid amide-based dispersing agent, a fatty acid S-based dispersing agent, a hydrogenated kumquat oil-based dispersing agent, a 20-plant polymer oil-based dispersing agent, and a poly- and vinegar-type interfacial activity. Agent, sulfuric acid pear anion surfactant, polycarboxylate amine dispersant, polyacid dispersant, south molecular polyether dispersant, propylene polymer dispersant, special lanthanide dispersant, talc A dispersing agent, a bentonite dispersing agent, a kaolmite dispersing agent, a ceria colloidal dispersing agent, and the like. These points 29 200932852 Powders may be used alone or in combination of two or more. The composition of the present invention preferably contains a fatty acid-containing amine-based dispersant as the dispersant. The composition of the present invention is produced, for example, by preparing a mixed solution containing the above copolymer (A) and the like, and then mixing and dispersing the mixed solution. In the case where the above-mentioned mixed solution contains the fatty acid-derived amine-based dispersing agent described above, the storage stability of the mixed liquid can be improved, and the composition of the present invention can be obtained more easily and surely. Commercially available materials can be used as the above dispersing agent. For example, a fatty acid amide-based dispersing agent can be used, for example, Desparon A603-10X (or 20X), Disparron 690〇-1〇χ (or 2〇χ), Desparon 681〇_1〇χ (or 2) (Taiwan Chemical Co., Ltd., which is made up of 0 10), Talian 7500-20, and Frono-1000 (all of which are manufactured by Kyoeisha Chemical Co., Ltd.). The dispersant may be used by being dispersed in an organic solvent such as xylene. The content of the dispersing agent in the composition of the present invention is not particularly limited, but it is preferably 1 to 50 parts by weight, and preferably 1 to 50 parts by weight, based on the total amount of the polymer (Α) and the zinc salt. More preferably, it is 2 to 30 parts by weight. When the content of the dispersant is less than 1 part by weight based on 100 parts by weight of the total of the polymer (Α) and the zinc salt (Β), the effect of using the dispersant (ie, suppressing 粕) I may not be able to fully play the effect of slag formation. That is to say, the storage stability of the composition of the present invention may be insufficient. When the content of the dispersant exceeds 5 parts by weight based on 100 parts by weight of the total of the polymer (Α) and the zinc salt (Β), the viscosity of the composition may become too high, and there is fear Difficulty in painting, and the increase in the content of the above-mentioned sub-governing agent does not increase the resulting t-fruit, but it causes economic waste. 30 200932852 &lt;Other additives and the like> The composition of the present invention may further contain a dye, a color separation preventing agent, an antifoaming agent, and the like. The composition 'is of the present invention' is usually dissolved or dispersed in the organic solvent 5. Thereby, it can be suitably used as a coating material. The organic solvent may, for example, be diphenyl, acenaphine, mineral spirits, MIBK, butyl acetate or the like. Among them, xylene or MIBK is preferred. These organic solvents may be used singly or in combination of two or more. In the case of using the composition of the present invention, the use of the above-mentioned solvent can be suppressed. This is because the viscosity of the composition of the present invention is low. Coatings using such compositions are known in the industry as "high solids coatings". That is, the μ product of the present invention can be utilized as a low v〇c antifouling paint composition. The coating material using the composition of the present invention has a volatile organic compound which scatters little to the atmosphere, thereby reducing the load on the environment. 15 The composition of the present invention has a v〇c content of preferably less than 400 g/L, more preferably 300 to 350 g/L. The composition of the present invention has a nonvolatile content of 75 wt% or more, preferably 80 wt% or more, more preferably 85 wt% or more. 20 The composition of the present invention preferably has a viscosity of from 70 to 100 KU at a 25 r measured by a Stomap viscometer, and more preferably 8 〇 to 1 〇〇 κ 。. When the viscosity at 25 hours measured by the Stoma's viscometer is 70 to 100 KU, the coating composition of the present invention can be easily formed into a thick coating film even if the amount of the solvent used is small. Further, it can be preserved for a long period of time while effectively preventing precipitation of 31 200932852 (e.g., pigment, cuprous oxide, zinc oxide, oxidized iron, red iron oxide, talc, etc.) in the composition of the present invention. The aforementioned viscosity can be measured in accordance with JIS_5400 (or astm D562-〇i). The Stoma viscosity meter can be used only by the market seller. 5 The composition of the present invention is excellent in storage stability and hardly gels and solidifies even after storage for a long period of time. Method for Producing Antifouling Coating Composition The method for producing the antifouling (IV) composition of the present invention is to mix the following (8) and (B): Ο 10 (A) Polymerization of a polymerizable unsaturated carboxylic acid triorgano oxime ester a polymer (polymer (A)) having a number average molecular weight of 1000 to 20,000; and (B) at least one zinc salt selected from the group consisting of rosin salt and a zinc salt of a rosin derivative (say salt (B)) . Further, in the method for producing the antifouling paint composition, the weight ratio ((A)/(B)) of the content of the polymer (A) to the content of the zinc salt (B) is 45/ 55 to 10/90; a nonvolatile content of 75 wt% or more; and ◎ substantially free of rosin and rosin derivatives having a free carboxyl group. According to the production method of the present invention, the above-mentioned 20 antifouling paint composition of the present invention can be suitably produced. When the polymer (A) and the zinc salt (B)' are used, the polymer (A) and the salt described in the items of the above-mentioned &lt;polymer (A)&gt; and <zinc salt (B)&gt; can. Further, it is also possible to add a mixture of the above-mentioned pigment, the above-mentioned cuprous oxide, the above-mentioned organic antifouling agent, the above-mentioned water scavenger, and the above dispersing agent, etc., in accordance with the demand. The amount of the polymer (Α), the above-mentioned salt (Β), etc., can be appropriately condensed into the aforementioned polymer in the antifouling coating composition (Α^ 言言盐(Β) 5 鹌1〇^ When mixing, it is preferred to disperse or disperse various materials such as the above polymer (Α) in a solvent. For example, the above polymer (Α) and the aforementioned zinc The dragon () can be mixed with other materials (the above-mentioned smudges, etc.) in a state where it is dissolved or dispersed in a solvent, respectively, and the above-mentioned corrections can be, for example, toluene, toluene, mineral spirits, hydrazine, acetic acid. Butyl ester, etc. Among them, xylene is preferred. These solvents may be used singly or in combination of two or more. In the case of using the cuprous oxide in the production of the antifouling coating composition of the present invention, oxidation is required. The average particle size of the cuprous copper is preferably the following production method and the production method 2. 15 Specifically, the cuprous oxide is made of an average particle diameter of 3 to 1 〇μηη, and Q is 3 to 8 μm 2 of cuprous oxide. Preferably, in this case, the following manufacturing method 1 is preferably employed. 1&gt; 2 In addition to the above-mentioned polymer (Α) and the aforementioned zinc salt (Β), after further mixing a cuprous oxide having an average particle diameter of 3 to 10 qing, preferably 3 to _, using a dispersing machine The obtained present compound is mixed and dispersed. The cuprous oxide having an average particle diameter of 3 to 1 Å is very capable of secondary coagulation. Therefore, if only the materials containing cuprous oxide are mixed, the obtained composition is obtained. As a result, a clot is generated, and as a result, the formed coating film is cracked, etc. 33 200932852 虞. According to the above-mentioned manufacturing method, a mixture containing a cuprous oxide having an average particle diameter of 3 to 2 is mixed by a disperser to obtain a compound. The dispersion of cuprous oxide or the like can thereby destroy the cuprous oxide which has been secondaryly agglomerated, and at the same time, obtain an antifouling coating composition which has been suitably dispersed in the foregoing cuprous oxide. 5 Material manufacturing method 1, by using a dispersing machine The antifouling coating composition can be produced by mixing and dispersing a mixture containing the above-mentioned polymer (Α) 'the above-mentioned zinc salt (Β) and the above-mentioned average particle diameter of 3 qing  1 〇 氧化 氧化 氧化 氧化 。. Can also be used as needed The pigment, the organic antifouling agent, the water scavenger, and the dispersing agent are added in various amounts, and the content of the polymer (4), the salt (Β), and the cuprous oxide in the mixture is The content of the polymer (Α), the salt (8), and the cuprous oxide in the antifouling paint composition may be appropriately adjusted. 15 The mixture is preferably dissolved in various materials such as the polymer (4). And even if it is prepared by dispersing in a solvent, for example, in the state in which the above-mentioned polymer (Α) and the aforementioned zinc salt (9) are dissolved or dispersed in a bulking agent, respectively, and other materials (the aforementioned organic The antifouling agent or the like is simultaneously mixed. The solvent may be the same as the solvent described above. 2 〇 (4) The dispersing machine ' can be used as a fine pulverizer, for example, as appropriate. For example, a grinder or a dissolver can be used. The aforementioned mill may, for example, be a ball mill, a sand mill, a bead mill, a pearl mill, a Dyn〇 mill, a c_s _, a basket mill, a grinder, a melter, etc. For the mixing and dispersion of paints = 34 200932852 mill. The dissolver is provided with a rotary vane grinder, and the mixture can be mixed and dispersed by rotating the grinder. When the dissolver is used as the aforementioned dispersing machine, it is preferable to rotate the grinder 5 of the aforementioned dissolver at a high speed. By rotating the aforementioned grinding machine at a high speed, it is possible to appropriately destroy the cuprous oxide which has been secondarily accumulated. Further, the aforementioned dissolver is also called dispar. ❹ 10 15 ❹ 20 When a cuprous oxide having an average particle diameter ΐυ~ζυμπι, more preferably ~3 to 20 μm is used, the following production method 2 can be employed. &lt;Production Method 2&gt; By mixing the mixture of the above polymer (Α) and the aforementioned zinc salt (Β), the mixture is mixed and dispersed by a disperser, and then the average particle diameter is 10 to 2 〇 μηη, more preferably It is 13 to 20 μm of cuprous oxide and mixed. Cuprous oxide having an average particle diameter of 10 to 20 μm is less likely to cause secondary aggregation than that of cuprous oxide having an average particle diameter of 10 to 20 μm. Therefore, 'using the dispersing machine will contain the aforementioned polymer (4) and the pre-material _) _ silk age reading, in the mixed mixture of the township: before the addition of Weihua Lai, as far as possible to make cuprous oxide = r ... Further, ==::_ is sufficiently coated with the cuprous oxide polymer (A) or the like in the above-mentioned composition. T好TT description 35 200932852 When the surface area of the cuprous oxide is too small, the aforementioned polymer (A), the above-mentioned salt (B), organic solvent, etc. required for coating the surface of cuprous oxide can be reduced. The amount of use, the result can be properly obtained low voc antifouling paint. Further, in the antifouling coating film, when the surface area of the cuprous oxide is too small, 5 even when the seawater temperature is high, specifically, when the seawater temperature is 3 (rc or more, the coating film can be effectively suppressed. Further, according to the above-described production method 2, the processing time by the dispersing machine can be shortened, and the manufacturing cost of the composition of the present invention can be controlled. The above mixture, except for the above-mentioned cuprous oxide, The mixture of the above-mentioned production method 1 is the same. The amount of the cuprous oxide to be added may be appropriately adjusted to the content of cuprous oxide in the composition of the antifouling paint. The disperser may be used in the above-mentioned production method. The mixing device is not particularly limited, and a well-known mixing device can be used. For example, the above dissolving device can also be used. When the dissolving device is used, it is preferable to rotate the grinding machine at a medium speed or a low speed. The medium-speed or low-speed rotation can effectively prevent the pulverization of the cuprous oxide. The antifouling treatment method, the antifouling coating film, and The antifouling treatment method of the present invention is characterized in that the antifouling coating film is formed on the surface of the film to be coated by the antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film is The surface gradually dissolves, and the surface of the coating film can be renewed for a long period of time, thereby preventing the adhesion of the aquatic organisms. Further, after the coating film is dissolved, the surface of the composition can be surface-coated, and can be continuously used. 5 10 15 Lu 20 As a coating film formation, for example, a ship (especially a ship bottom), a fishery tool, an underwater structure, etc., for example, a fishing or fixed net, the fishing net can be used. A fishing net attachment such as a buoy or a cable, etc. The underwater structure may be, for example, a water conduit, a bridge, a harbor facility, etc. of the power generation. The antifouling coating film of the present invention may be formed on the surface of the film to be coated (in whole or in part). The coating method is applied by applying the antifouling coating composition. Examples of the coating method include a brush coating method, a spray method, a dipping method, a shower coating method, a spin coating method, and the like. It is carried out by using one type or two types. After coating, it is dried. The drying temperature can be room temperature. The drying time can be appropriately set depending on the thickness of the coating film, etc. The thickness of the above antifouling coating film can be determined according to The type of the coating film formation, such as the speed of the ship, the sea water temperature, etc., may be appropriately set. For example, in the case where the coating film formation is the bottom of the ship, the thickness of the antifouling film is usually 50~5〇〇μηι, preferably 1〇〇~400μηι. The antifouling coating film of the invention has the following advantages: · The coating is stable in the seawater for a long time, and the surface of the coating film can be frequently updated. Therefore, the antifouling effect is good, and even if it is in the sea for a long time, there is no attachment of marine organisms on the surface of the coating film. 2) The water resistance of the coating film is good, and even if the coating film is in the sea for a long time, there is no abnormality in the coating film such as bubbles, swelling, cracks, etc. on the surface of the coating. 3) Since the coating film has an appropriate hardness, coating film abnormalities such as cold flow do not occur, and 4) its adhesion to the coating film formation is high, and the construction is easy to sound. 37 200932852 The coated article of the present invention has the aforementioned antifouling coating film on its surface. The coated article of the present invention may have the above-mentioned antifouling coating film as a whole or may have only the antifouling coating film partially. Since the coated article of the present invention has the antifouling coating 5 film having the advantages of the above 1) to 4), it can be suitably used as the above-mentioned ship (especially a ship bottom), a fishing implement, a structure in water, or the like. For example, when the antifouling coating film is formed on the surface of the bottom of the ship, the antifouling coating film is gradually dissolved from the surface to constantly update the surface, so that adhesion of the aquatic fouling organism can be prevented. 10 15 Moreover, the rate of hydrolysis of the antifouling medium in seawater is appropriately suppressed. Therefore, the ship can maintain the antifouling performance for a long period of time. For example, even in a stationary state such as a shutdown or a period of squeaking, there is almost no adhesion or accumulation of aquatic organisms, and the antifouling effect can be exhibited for a long period of time. Further, even after a long period of time, the antifouling coating film on the surface did not substantially cause cracking. Therefore, it is not necessary to perform an operation such as completely removing the coating film and then re-forming the coating film. Thus, by the aforementioned antifouling coating

The film composition is directly surface coated to form a suitable antifouling coating medium. In this way, q is simple and uses money to maintain continuous anti-fouling performance. Advantageous Effects of Invention According to the antifouling coating composition of the present invention, since the content of the organic compound (organic or the like) is suppressed, it is necessary to smash the thick antifouling coating film in the middle, and it is necessary to fly into the air. The load on the environment is reduced. The compound of the present invention is excellent in long-term storage stability. Also printed, the composition of the present invention 38 200932852 hardly thickens, gels, and solidifies even after long-term storage. Further, the antifouling coating composition of the present invention has high environmental safety, and there is almost no problem of marine pollution even if it is dissolved in seawater. The antifouling coating film formed by the antifouling coating composition of the present invention has the following advantages: 丨) The coating film can be stably dissolved in seawater for a long period of time, and the surface of the coating film can be constantly renewed, so that the antifouling effect is good. Even if it is in the sea for a long time, there is no attachment of marine organisms on the surface of the coating. 2) The coating film has a good water-repellent property, and even if the coating film is in seawater for a long period of time, the coating film surface does not have an abnormal state of the coating film such as bubbles, swelling, and cracks. 3) Since the coating film has a moderate hardness, it is difficult to cause an abnormal coating film such as cold flow. Further, 4) its adhesion to the film-formed product is high and construction is easy. Since the coated article of the present invention has the antifouling coating film having the above-described advantages, it can be suitably used as the above-mentioned ship (especially a ship bottom), a fishery tool, a structure in water, or the like. For example, when the antifouling coating film is formed on the bottom surface of the ship's bottom surface, the antifouling coating film is gradually dissolved from the surface to constantly update the surface, thereby preventing the adhesion of the aquatic fouling organism. Further, the above antifouling coating film has moderate solubility. Therefore, even if the ship is in a medium static state during berthing and assembly of the rigging, there is almost no adhesion or accumulation of aquatic fouling organisms, and the antifouling effect can be exerted for a long time. Thereby, the frictional resistance of the ship is reduced, and the fuel saving at the time of sailing can be expected. Further, in the antifouling coating film on the surface, even after a long period of time, substantially no coating film defects occurred. Therefore, after the coating material is used for a predetermined period of time, the antifouling coating film can be suitably formed by directly coating the antifouling coating film composition on the surface. Thereby, the continuous antifouling performance can be maintained simply and at a low cost. I: Embodiments: j [Embodiment] 5 The following shows the embodiments and the like, and further clarifies the features of the present invention. However, the invention is not limited to the embodiments. The percentages in the respective production examples, comparative production examples, examples, and comparative examples indicate weight percentages. The viscosity of the copolymer (A) solution is the value measured at 25 ° C, based on the value obtained by the b-shaped © 10 viscometer. The residual portion to be heated is a value obtained by heating at 125 ° C for 1 hour in accordance with JIS K-5601-1-2 (or IS03251). The number average molecular weight (??) is a value measured by GPC (polystyrene conversion value). The conditions of 15 GPC are as follows. Device: HLC-8220GPC (Dongsuo Co., Ltd.) (East ^ one type of meeting system) ❹

Column: TSKgel SuperHZM-M Two Flows: 0.35 mL/min 20 Detector: RI

Column temperature bath temperature: 40 ° C Free solution: THF The molecular weight dispersion is the value obtained by dividing the weight average molecular weight (Mw) obtained by the above GPC by Μη. 40 200932852 The glass transition temperature (Tg) of the copolymer is a value measured by a differential scanning pyrolyzer of Seiko Instruments SSC/5200 in accordance with the provisions of JIS K 7121. 5 Lu 10 15 ❹ The viscosity of the coating composition is the value measured at 25 ° C using a Stowe viscometer in accordance with JIS K 5400. The measurement conditions are as follows.

Stoma viscosity meter: Coating test industry (:?1 in 4 &gt; 只 只 工业 - industry) Stoma viscosity meter N0.453 Measurement temperature: 25 ± 0.5 ° C Sample size: 500ml (added to 500ml sample The mark line of the can) The code: 75~10〇〇g Measurement method: The time until the rotation of the rotary wing is measured 100 times. Change the code to perform the measurement. The time from the rotation of 10 turns is 27 to 33 seconds, and the value closest to 30 seconds is selected. The number of seconds from the time of rotation up to 100 times and the weight of the weight used. Use the KU conversion table to obtain the ruler 1; value. Further, the unit of mixing amount of each component in Table 1 is g. Production Example 1 (Production of Copolymer (A) Solution) In a 1000 ml flask equipped with a thermometer, a reflux condenser, a stirrer, and a titration funnel, 330 g of xylene was added, and then stirred at 115 to 120 ° C under a nitrogen atmosphere. On the other hand, in the flask, l50 g of triisopropyl decyl acrylate, 15 parts of methacrylate, 15 g of n-butyl acrylate, and 2 methoxyethyl methacrylate 15 〇g were added for 3 hours. And a mixture of tert-butyl peroctyl ester 5g. After the dropwise addition, the polymerization reaction was carried out for 5 hours at U5 to 12 (rc), and then, in the obtained reaction liquid, (additional addition of 2 g of butyl perchlorin 2 g' at 115 to 12 (TC was further carried out for 2 hours). Reaction, obtaining copolymer (4) 20 200932852 Solution S-1. Viscosity, heating residual, number average molecular weight (Μη), molecular weight dispersion (Mw/Mn), glass transition temperature (Tg) of S-1 are shown in Table 1. Production Examples 2 to 6 (Production of Copolymer (A) Solution) Using the solvent, monomer, and polymerization initiator shown in Table 1, polymerization was carried out in accordance with the operation of Production Example 51, whereby a copolymer (A) was obtained. The solutions S-2 to S-6. The viscosity, heating residual, number average molecular weight (??), molecular weight dispersion (Mw/Mn), and glass transition temperature (Tg) of each of the obtained copolymer solutions are shown in Table 1. Production Example 1 (Production of Copolymer Solution H-1) ❹ 10 Using the organic solvent, monomer, polymerization initiator, and reaction temperature shown in Table 1, polymerization was carried out in accordance with the same operation as in Production Example 1, thereby obtaining a copolymer. Solution H-1. Viscosity, heating residual, amount of the obtained copolymer solution The average molecular weight (Μη), the molecular weight dispersion (Mw/Mn), and the glass transition temperature (Tg) are shown in Table 1. 15 Comparative Production Example 2 (Production of Copolymer Solution H-2) A thermometer and a reflow cooler were provided. After adding 330 g of xylene to a 1000 ml flask of a stirrer and a dropping funnel, the mixture was stirred under a nitrogen atmosphere at 90 to 10 ° C, and the triisopropyl methacrylate was dropped in the flask for 2 hours. 150 g of fluorenyl ester, 150 g of methyl methacrylate, 50 g of n-butyl acrylate, 100 g of n-butyl methacrylate, 50 g of 2-methoxyethyl methacrylate, and t-butyl peroctyl ester After the dropwise addition, the polymerization reaction was carried out for 2 hours at 90 to 100 ° C. Next, 2 g of t-butyl peroctyl ester was added (additionally) to the obtained reaction liquid at 90 to 100 ° C further 2 hours of polymerization to obtain a copolymer solution H-2. H-2 viscosity, heating residue 42 200932852 remainder, number average molecular weight (Μη), molecular weight dispersion (Mw / Mn), glass transition temperature (Tg) is shown in Table 1. [Table 1-1]

Ingredient classification ingredient name Production example 1 2 3 4 5 6 Phase-injection solvent Diphenylbenzene 330 330 330 330 330 330 Monomer (a) Triisopropyl sulfonate 150 200 225 250 Triisopropyl methacrylate Eugenyl ester 150 250 monomer (b) methyl methacrylate 150 175 200 200 150 125 monomer (6) ethyl acrylate 25 n-butyl acrylate 50 50 50 25 50 25 n-butyl methacrylate 25 2-methoxy acrylate Ethyl ethyl ester 50 25 2-methoxyethyl methacrylate 150 25 150 75 Polymerization initiator Initially added tert-butyl peroxyoctanoate 5 5 Third amyl peroxyoctanoate 5 5 5 Third hexyl Peroxyoctanoate 5 Addition of t-butyl peroxyoctanoate 2 2 Third amyl peroxyoctanoate 2 2 2 Third hexyl peroxyoctanoate 2 Additional solvent xylene reaction temperature (°c) 115 ~120 115 ~ 120 115 ~ 120 115 ~ 120 115 ~ 120 115 ~ 120 Copolymer &amp; Physical Properties Viscosity (mPa · S / 25 ° C) 710 680 980 970 1050 880 Heating Residue (%, 125 ° C, 1 hrs) 60.0 59.8 60.2 60 .5 60.3 60.6 Number average molecular weight (Μη) 8,3〇〇7,900 7,500 7,800 8,1〇〇7,700 Molecular weight distribution (Mw/Mn) 2.7 2.7 2.3 2.4 2.4 2.2 Glass transition temperature (Tg, °c) 33 29 39 51 45 57 Copolymer name S-1 S-2 S-3 S-4 S-5 S-6 43 200932852 [Table 1-2] Component classification component name comparison Manufacturing example 1 2 Initially placed solvent xylene 330 330 monomer (8) Triisopropyldecyl acrylate 100 isopropyl isopropyl acrylate 150 monomer (b) methyl methacrylate 200 150 monomer (c) ethyl acrylate n-butyl acrylate 50 50 methacrylic acid n-Butyl ester 50 100 2-methoxyethyl methacrylate 2-methoxyethyl ester 50 50 Polymerization initiator Initially added tert-butyl peroxyoctanoate 3 1 Third amyl peroxyoctanoate Third hexyl peroxyoctanoate added t-butyl peroxyoctanoate 2 2 third amyl peroxyoctanoate di-hexyl peroxyoctanoate additional solvent diterpene 170 reaction temperature (°C) 115 ~120 90~100 Copolymer Properties Viscosity (mPa · S/25°C) 1150 228 0 Heating residue (%, 125 ° C, 1 hrs) 60.7 49.6 Quantity average molecular weight (Μη) 12,300 22,300 Molecular weight distribution (Mw/Mn) 3.2 3.7 Glass transition temperature (Tg,. 〇 77 46 Copolymer name H-1 Η—2

44 200932852 Examples 1 to 2 and Comparative Examples 1 to 5 (Production of Coating Composition) The copolymers (A) obtained in Preparation Examples 1 to 6 were S-1 to S 6 (solid content of about 80%), or Comparing the copolymer solutions H-1 to H-2 (solid content of about 60%) obtained in Production Example 2 to 2 as a copolymer, 5 in a xylene solution of rosin gum (solid content of about 60%), or hydrogenation A bismuth benzene solution of rosin zinc salt (solid content of about 6〇%) as a rosin zinc salt, a xylene solution of rosin gum (solid content of about 6〇%), or a xylene solution of hydrogenated rosin (solid form about 60%) As turpentine, φ is a cuprous oxide having an average particle diameter of Mm or 6 μm, and 10 is an organic antifouling agent, a pigment, an additive, and a solvent described in Table 2, and is expressed in the ratio shown in Table 2 (weight). The percentages were mixed and mixed by using an experimental small table sander (using glass beads having a diameter of 1 to 5 mm to 2.5 mm) to prepare a coating composition. The non-volatile content, VOC content, PVC and coating viscosity of the obtained coating composition are shown in Table 2. 15 Examples 3 to 8 (Production of Coating Composition) The copolymer (1) solution s_3 to s_6 obtained in Production Examples 3 to 6 was used as a copolymerized φ substance, and a bismuth benzene solution of rosin gum zinc salt was formed. 60%), or a xylene solution of a hydrogenated rosin salt (about 60% solid content) as a rosin zinc salt, and an organic antifouling agent, a pigment, an additive, and a solvent described in Table 2, The ratio (weight percentage) was mixed and mixed by the experiment using a small table sand mixer (using a glass bead having a diameter of 1.5 to 2.5 mm) to obtain a mixture and take it out. Next, cuprous oxide having an average particle diameter of 13 μm or 19 μm was added to the above mixture and slowly mixed with a stirring blade to prepare a coating composition. The non-volatile content, V〇C 25 content, PVC and coating viscosity of the obtained coating composition are shown in Table 2. 45 200932852 [Table 2-1] Ingredient name Example 1 2 3 4 5 6 7 8 Copolymer S-1 7.5 5 S-2 7.5 5 S-3 7.5 S-4 5 S-5 5 S-6 5 H- 1 H-2 rosin rosin gum zinc salt solution (solid component about 60% xylene solution) 17.5 17.5 17.5 20 hydrogenated rosin zinc salt solution (solid component about 60% xylene solution) 20 20 20 20 rosin gum solution (solid component About 60% xylene solution) Hydrogenated rosin solution (solid form about 60% diterpene solution) Plasticizer tricresyl phosphate 1 ARUFON UP-1080 3 3 3 3 3 3 2 Lutonal A25 three speed SANSOCIZER E-2000 1 ] 1 1 1 1 1 1 Vaporized wax oxide cuprous oxide NC-301 (made by Rijin Chemical Co., Ltd., average particle size 3 μιη) 45 RED COP 97Ν PREMIUM (Amerika Kami special, average Particle size 6 μπι) 45 PURPLECOPP (Amerikan Camelot, average particle size 13μπι) 45 45 45 LOLO-TINT97 (Amerikan Camelot, average particle size 19μτη) 45 45 45 Organic k agent thiol pyridinium copper 3 3 2 3 3 3 3 3 yifaling (dichlofluanid) 1 fluanid 1 Irgarol 1051 1 Zineb 1 pigment iron oxide red (Bengala) 3.5 3.5 3.5 2.5 2.5 3 3 3 talc 2 2 2 2 2 2 2 zinc oxide 5 5 5 5 5 5 5 titanium oxide 1 1 1 1 1 Fuji red 1 1 1 1 1 1 Other additives anhydrite (dehydrating agent) tetraethoxy oxime ( Water binder) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Disparron Α603-20χ (aliphatic carboxylic acid, nanbencheng, dispersant) 2 2 2 2 2 2 Talian 7500-20 (fatty acid guanamine, co-prosper Du fat, dispersant) 2 2 Change with #38 (expanded soil) 1 Solvent xylene 8 8 8 8 8 7.5 7.5 7.5 Total 100 100 100 100 100 100 100 100 Nonvolatile content (% by weight) 80 80 80 80 80 80 80 80 Volatile content (g/L) 378 376 376 376 376 367 367 367 PVC (pigment volume %) 41 41 39 42 42 40 42 42 Coating viscosity (KU value / 25 ° c) 95 93 89 85 86 86 84 85 46 200932852 [Table 2-2]

Ingredient name comparison example 1 2 3 4 5 Community S-1 17.5 S-2 17.5 S-3 17.5 S-4 S-5 S-6 H-1 20 H-2 17.5 Rosin rosin gum zinc salt solution (solid component About 60% xylene solution) 7.5 5 7.5 7.5 Hydrogenated rosin zinc salt solution (solid component about 60% xylene solution) 6 rosin gum solution (solid component about 60% xylene solution) 2.5 Hydrogenated rosin solution (solid composition about 60%) Xylene solution) 1.5 Plasticizer Tricresol-based acid ester ARUFON UP-1080 Lutonal A25 3 3 3 3 2 Three-speed Saize (SANSOC1ZER) E-2000 Chlorinated paraffin 1 Cuprous oxide NC-301 (Nikkei Chemical Co., Ltd., average particle size 3 μπι) 45 45 45 45 45 RED COP 97Ν PREMIUM (Amerikan Camelot, average particle size 6 μπι) PURPLECOPP (Amerikak Camelot, average particle size 13 μπι) LOLO -TINT97 (Amerikan Camelot, average particle size 19μΐϋ) Organic anti-I agent thiol acridine copper 3 3 3 2 2 Yifiling (dichlofluanid) Flophilic (fhianid) Irgarol 1051 Zinc Zineb 1 Pigment Iron Oxide Red (Bengala) 2 2 2 2 2 Talc 2 2 2 2 2 Oxidation 5 5 5 5 5 Oxidation 1 1 1 1 1 Fuji Red 1 1 1 1 1 Other Additives Anhydrite ( Dehydrating agent) 0.5 0.5 0.5 Tetraethoxy decane (water binder) 0.5 0.5 Disparron A603-20x (aliphatic carboxylic acid, lycopene, dispersant) 2 2 2 2 2 Talian 7500-20 (fatty acid)醯amine, Gongrongshe grease, dispersant) Change Tong #38 (expanded soil) Solvent xylene 10.5 10.5 10.5 9 10.5 Total 100 100 100 100 100 Nonvolatile content (% by weight) 78 78 78 78 77 Volatile content (g/L) 413 413 409 413 423 PVC (pigment volume %) 42 42 42 39 41 Coating viscosity (KU value / 25 ° C) 116 110 112 115 125 47 200932852 Test example 1 (spray coating) The coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were spray-coated on a tinplate (75 x 150 nm) which had been subjected to grit blasting, and the thickness of the dried coating film was about ΙΟΟμηι. The case where the spray coating was possible was evaluated as 5 ◎, and the evaluation that the spray coating could not be performed was X. Test Example 2 (Stability test of paint) The paint compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were placed in a 100 ml wide-mouth tin can and sealed, and stored in a thermostat at 40 ° C. After the month, the viscosity of the coating group 10 was measured by a B-type viscometer. The viscosity change of the coating is less than 500mPa · s / 25 ° C (the shape of the paint is almost unchanged) is evaluated as ◎, the viscosity of the coating changes from 500 to 5000 mPa • s / 25 ° C (some increase in viscosity) is evaluated as 〇 The viscosity change of the coating is estimated to be △ at 5000~lOOOOmPa · s/25 °C (large viscosity increase), and the viscosity change of the coating has reached the unmeasured (contained or cured) X° The results are shown in Table 3. As is apparent from Table 3, the composition of the rosin (or rosin derivative) having a free carboxyl group (Comparative Examples 2 and 3) was lacking in long-term stability. 20 Test Example 3 (Coating film hardness) The antifouling coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied onto a transparent glass plate (75 x 150 x 1 mm) so that the thickness of the dried coating film was about ΙΟΟμηι ' Allow it to dry at 40 ° C. The film hardness of the obtained dried coating film was measured at 25 ° C using a pendulum hardness tester (pendulum hardness tester) 200932852. The results (measured numbers) are shown in Table 3. The measured number is from 2〇 to 50 for practicality. As can be seen from Table 3, the coating composition of the present invention (the coating film formed by the embodiment of the invention has moderate hardness. Test Example 4 (Adhesion test of coating film) 5 ❹ 10 15 ❹ 20 Follow JIS K -5600-5-6, the adhesion test of the coating film was carried out. Specifically, the test was carried out according to the following method. First, the coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied to A fiber-reinforced plastic sheet (FRP sheet) (75xl5〇x2mm) and a tinplate (75x 150x2mm) that have been sandblasted to make the thickness of the dried coating film about ι〇〇μηη. Then, dry it at 4 °τ for one day, borrow Thus, a dry coating film having a thickness of about 10 (^111) was prepared. The adhesion test was performed on the s dry coating film (2 mm x 2 mm, the number of squares = 1 )). The number of unpeeled chessboards was 70 to 100. The situation was evaluated as ◎, the number of unpeeled chessboards was evaluated as 〇 in the case of 40 to 69, the number of unpeeled chessboards was evaluated as △ in the case of 20 to 39, and the number of unpeeled chessboards was evaluated in 〇~19 It is X. The results are shown in Table 3. It can be seen from Table 3 that the composition of the coating of the present invention is utilized. (Examples 88) The formed coating film can be firmly adhered to either the FRP sheet or the tinplate. Test Example 5 (Flexibility Test of Coating Film) Examples 1 to 8 and Comparison The coating composition obtained in Examples 1 to 5 was applied onto a sandblasted tinplate (75 x 150 mm) so that the thickness of the dried coating film was about ιμηη. Then, the obtained coating material was dried at 4 ° C. 49 200932852 One day, a dry coating film having a thickness of about ΙΟΟμηι was produced, and a tinplate formed with a dried coating film was bent at 90 degrees, and the state of the coating film was confirmed by visual observation. The evaluation of almost no crack generation was ◎, The evaluation 5 which caused some cracks was 〇, the evaluation of the occurrence of large cracks was Δ, and the evaluation of the partial peeling of the coating film was X. The results are not shown in Table 3. From Table 3, it is known that the composition of the coating film of the present invention is utilized. (Examples 1 to 8) The coating film formed was a non-fragile and strong coating film. 1) Test Example 6 (Water resistance test of paint) A rustproof paint was applied on a frosted glass plate (75 x 150 x 1 mm) Vinyl A/C) 'dry After that, the thickness was about 5 μm, and it was dried to form a rust-preventive coating film. Then, the coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied onto the rust-preventive coating film to dry-coat. The film thickness of the film was about 丨(9), and the coating obtained in 15 was dried at 40 Torr for one day, thereby preparing a test piece having a dry 骐 thickness of ΙΟΟμηι. The test piece was immersed in 35t: natural seawater. After the month, the state of the coating film was confirmed by visual observation. The film was evaluated as ◎, and some people who were discolored were evaluated as 〇, and the evaluation of bubble generation was △, and it was confirmed that there was cracking and peeling. The disparity anomaly is evaluated as X. The results are shown in Table 3. As can be seen from Table 3, the coating film formed by the coating film composition of the present invention (Example) has excellent water resistance. 200932852 [Table 3] Example 1^ Comparison #) Spray coating paint Stability adhesion test Flexibility test water resistance test 40 ° c 1 month after FRB plate tinplate 35. "After 3 months 1 ◎ ◎ ◎ ◎ ◎ ◎ 2 ◎ ◎ ◎ ◎ ◎ ◎ 3 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 1 X ◎ Δ ◎ 〇 Δ ratio 2 XX ◎ ◎ ◎ X Comparative Example 3 X Δ ◎ ◎ ◎ X 4 X ◎ Δ ◎ Δ Δ 5 X ◎ 〇 ◎ ◎ Δ

Test Example 7 (Solubility test of coating film (rotation test)) A roller having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank, and 5 was rotated by a motor. Further, a cooling device for keeping the temperature of the seawater fixed and a pH automatic controller for keeping the pH of the seawater fixed are installed. Two test panels were prepared according to the method described below. First, a rust-proof 10 coating (ethylene-based A/C) was applied to a rigid polyvinyl chloride plate (75 x 150 x 1 mm) to a thickness of about 50 μm after drying, and dried to form a rust-preventive coating film. Thereafter, the antifouling 51 200932852 coating composition obtained in Examples 1 to 8 and Comparative Examples 1 to 5 was applied onto the rust-preventive coating film so that the film thickness of the dried coating film was about 3 μm. The obtained coating material was dried at 40 ° C for three days to prepare a test piece having a dry coating film having a thickness of 300 μm. One of the produced test pieces was fixed to the drum of the rotating device of the above apparatus to contact the seawater, and the drum was rotated at a speed of 20 knots. During this period, the seawater temperature is maintained at 25 ° C, ρ Η 8.0 to 8.2, and the seawater is replaced every other week. The initial film thickness of each test plate, the residual film thickness after one month, three months, and six months were measured by a laser lock focus shift meter, and the thickness of the film dissolved by 10 was calculated based on the difference. The amount of film dissolution in the initial six months was determined. The amount of dissolution is expressed by the total amount of coating film dissolved (μιη) during this period. The results are shown in Table 4. As is clear from Table 4, the coating film formed by the coating composition of the present invention (Examples 1 to 8) had a large amount of dissolution from the initial stage, and the initial antifouling effect was excellent. Further, it was found that the coating film formed by the coating compositions of Comparative Examples 1 to 5 was not easily dissolved in seawater at first, and the antifouling effect could not be effectively exhibited. Further, the coating film formed by the coating compositions of Comparative Examples 2 and 3 was cracked and peeled off in the middle due to poor water resistance. 20 52 200932852 ❹ [Table 4] The name of the coating dissolved in the coating (μπι) 1 month after 2 months 3 months later 6 months after 1 8 15 20 36 2 7 13 18 31 3 6 11 16 28 Real 4 7 12 17 30 Example 5 5 10 14 26 6 6 12 17 29 7 5 11 16 31 8 6 10 15 30 1 2 4 5 11 Comparison 2 3 5 8 15 3 2 4 7 13 Example 4 1 2 3 7 5 0 1 2 5

Test Example 8 (mucus adhesion test) The coating compositions obtained in Examples 5 to 8 and Comparative Examples 1 to 5 were applied to both sides of a rigid polystyrene sheet (100 x 200 x 2 mm) so that the thickness after drying was about ΙΟΟμηη. The obtained coating material was dried at room temperature (25 ° C) for three days, thereby producing a test plate having a dry coating film having a thickness of ΙΟΟμηι. The test plate was immersed in the sea surface of the city of Sakamoto, Wakayama Prefecture, Japan, and was visually observed to confirm the attachment of the mucus to the test plate one month later, two months later, and three months after the immersion. . The results are shown in Table 5. 53 200932852 The figures in the table also indicate the degree of adhesion of mucus. It is almost impossible to identify the liquid. Some people have a liquid attachment of 1, a thick mucus attached to the whole surface and a bristles. (4) The removal is 2, and the entire surface has a thick mucus attached and it is difficult to remove the bristles by 3. As can be seen from Table 5, the coating film formed by the coating film compositions of Comparative Examples 1 to 5 was coated with the coating composition of the present invention (Example (4). The coating film 4 had no mucus adhesion. This is because the paint and the composition of the present invention are used (the coating film formed in Example 1 to ride is necessary and sufficient to dissolve the coating film from the beginning. 0 10 Test Example 9 (surface coating test) Test Example 8 has been carried out The test plate of the mucus test was washed with ion-exchanged water at room temperature (25 〇 and dried for one day. Thereafter, the coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were respectively It is applied to one side of the test plate so that the thickness of the dried coating film is about 丨(8). The coating is dried at room temperature (25. The resulting coating of 15 is dried for three days), and the surface is coated on the old coating film. A test plate of a new coating film having a thickness of about ΙΟΟμπι. These are in accordance with JIS κ_56〇〇5 6

The test panel was subjected to adhesion test of the coating film (2 mm x 2 mm, number of squares = 1 〇〇 Q). The number of unpeeled chessboards was evaluated as ◎ in the case of 70 to 1 inch, the number of chessboards not peeled off 2 inches was evaluated as 〇 in the case of 40 to 69, and the number of unstriped chessboards was in the range of 20 to 39. It is estimated that △, the number of unpeeled chessboards is evaluated as X in the case of 〇~μ. The results are shown in Table 5. As can be seen from Table 5, the coating film formed by the coating composition of the present invention (Examples 1 to 8) was used as compared with the coating film formed by the coating film composition 54 200932852 of Comparative Examples 1 to 5, The coating film can be sufficiently adhered to the old coating film. This is because the coating film formed by the coating film compositions of Comparative Examples 1 to 5 has poor solubility in the initial coating film, so that the mucus adheres in a short time, and the coating formed by the coating composition of the present invention is used. The film has a sufficient coating film dissolution from the beginning, so that the surface of the coating film is renewed, and the mucus hardly adheres.

[Table 5] Coating mucus adhesion test surface coating test 1 month after 2 months and 3 months later Example 1 0 0 0 ◎ 2 0 0 0 ◎ • 3 0 0 0 ◎ 4 0 0 0 ◎ 5 0 0 0 ◎ 6 0 0 0 ◎ 7 0 0 0 ◎ 8 0 0 0 ◎ Comparative Example 1 0 1 2 X 2 0 1 2 X 3 0 1 2 X 4 1 2 3 X 5 2 3 3 X 55 200932852 Test Example (Prevention Staining test) The coating compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were applied to both sides of a rigid polyvinyl chloride plate (100 x 200 x 2 mm) so that the thickness after drying was about 2 μm. The obtained coating material was dried at room temperature (25 ° C. for three days, thereby producing 5 a test plate having a dry coating film having a thickness of about 20 μm. The test plate was immersed in 15 m below the sea surface of Owase City, Mie Prefecture, Miemoto. The flowers were stained by the attachments for 24 months. The results are shown in Table 6_. The numbers in the table indicate the area (%) of the fouling organisms. 0 10 The coating film formed by the coating composition of the present invention (Example 8) was hardly adhered to the coating film formed by the coating film compositions of Comparative Examples 1 to 5, and there was almost no adhesion to the soil. This is because the coating film formed by the coating composition of the present invention is inhibited to some extent by a coating film, and is stably dissolved at a fixed rate for a long period of time. 15 56 200932852 [Table 6]

Attached organisms during the coating test 6 months after 12 months and 18 months after 24 months after the example 1 0 0 0 0 No (stick back small) 2 0 0 0 0 No (sticky small) 3 0 0 0 0 None (sticky small) 4 0 0 0 5 No (sticky small) 5 0 0 0 0 No (sticky small) 6 0 0 0 0 No (sticky small) 7 0 0 0 0 No (sticky small) 8 0 0 0 0 No (sticky small) Comparative example 1 0 0 0 0 No (stick: 3⁄4 large) 2 0 0 0 0 No (viscosity is large) 3 0 0 0 0 Benefit (sticky i) 4 0 0 20 50 Haishengjie snake silkworm 5 0 10 50 100 Haishengjie snake silkworm [Simple diagram 3 (none) [Main component symbol description] (none) 57

Claims (1)

200932852 VII. Patent application scope: L A kind of antifouling coating composition, including (4) silk compound fresh „San Youcai (4) combined number 5; the average molecular weight of 1000~20000 polymer; and 5 (8) At least i zinc salts from the zinc salt of turpentine (tetra) and rosin derivatives; and 'the antifouling coating composition: Θ(1) The weight ratio of the content of the above polymer (A) to the content of the aforementioned zinc salt (9) ((A)/(B)) is 45/55-10/90; 10 (2) The content of the nonvolatile matter is 75 wt% Above; and (3) substantially free of rosin and rosin derivatives having a free carboxyl group. 2. The antifouling coating composition according to claim 1, wherein the polymer (A) has a number average molecular weight of from 2 〇〇 0 to 15,000 and a molecular weight dispersion of less than 2.5. The antifouling coating composition according to claim 1 or 2, wherein the glass transition temperature of the polymer (A) is 20 to 70 °C. 4. The antifouling coating composition of claim 1, wherein the polymer (A) is a triisopropyl decyl (meth)acrylate copolymer. 5. The antifouling coating composition of claim 3, wherein the aforementioned (曱20-based) triisopropyl decyl acrylate copolymer is: (a) triisopropyl decyl (meth) acrylate 30 -60% by weight, (b) 10 to 50% by weight of methyl mercaptomethyl ester, and (c) (meth)acrylates other than (a) and (b) copolymerized to 60% by weight By. 58 200932852 6. The antifouling coating composition according to claim 1, wherein the rosin salt is at least selected from the group consisting of rosin gum zinc salt, wood rosin zinc salt, and pine oil rosin zinc salt. The zinc salt of the rosin derivative is at least one zinc salt selected from the group consisting of hydrogenated rosin zinc salt and disproportionated rosin salt. 7. The antifouling coating composition according to claim 1, wherein the non-volatile content is 80% by weight or more, and the viscosity at 25° C. measured by a Stomap viscometer is 8〇~1 〇 〇κυ. 8. The antifouling coating composition of claim 1, wherein the volatile organic compound is less than g. 9. The antifouling coating composition of claim 1, further comprising 10 to 100 parts by weight of zinc oxide with respect to the total amount of the polymer (A) and the zinc salt (B) . 10. The antifouling coating composition of claim 1 which further comprises 100 to 400 parts by weight of cuprous oxide in an amount of 1 part by weight based on the total amount of the polymer (A) and the zinc salt (B). Share. 11. The antifouling coating composition of claim 10, wherein the cuprous oxide is cuprous oxide having an average particle diameter of 8 to 2 Å μm. 12. The antifouling coating composition according to claim 1, wherein the organic antifouling agent 1 is contained in an amount of 1 part by weight relative to the total amount of the polymer (Α) and the zinc salt (Β). ~1〇〇 parts by weight. 13. The antifouling coating composition of claim 1, further comprising 1 to 50 parts by weight of a plasticizer, based on 1 part by weight of the total of the polymer (Α) and the zinc salt (β). . 59 200932852 14. The antifouling coating composition of claim 13, wherein the plasticizer is an epoxidized fat or oil. 15. The antifouling coating composition of claim 1 which is further contained in an amount of 1 to 50 parts by weight with respect to the total amount of the polymer (A) and the zinc salt, and 5 parts by weight of the water removing agent. . 16. The antifouling coating composition of claim 15, wherein the water repellent is a water binding agent selected from the group consisting of alkoxy decanes and alkyl orthoformate. 17. The antifouling coating composition according to claim 1, further comprising a fatty acid guanamine dispersant in an amount of 1 part by weight based on 10 parts by weight of the total of the polymer (A) and the zinc salt (B). 1 to 5 parts by weight. 18. An antifouling treatment method comprising forming an antifouling coating film on a surface of a film-formed product by using the antifouling paint composition of the above-mentioned item 丨~^. 19. - Antifouling (4) 'The antifouling coating composition of Article 17 of the Lectures. 20· - A coating material having the antifouling coating film of the above item 19 on the surface. 21. A method for producing an antifouling coating composition, comprising: (A) a polymer having a number average molecular weight of from 1,000 to 20,000 polymerized by a polymerizable unsaturated ship; and (b) selected from the group consisting of: Mixing at least one zinc salt of Yusong 20 fat zinc salt and zinc salt of rosin derivative, and (1) weight ratio of the content of the polymer (A) to the content of the zinc salt (9) ((A)/ (B)) is 45/55 to 10/90; (2) the nonvolatile content is above 75 weight percent; and 200932852 (3) the antifouling coating composition is substantially free of rosin and rosin derivatives having free carboxyl groups . 22. The method for producing an antifouling coating composition according to claim 21, which comprises, in addition to the polymer (A) and the zinc salt (B), a mixed average particle size of 3 to ΙΟμιη After cuprous oxide, the obtained mixture was mixed and dispersed by a disperser. 23. The method for producing an antifouling coating composition according to claim 21, wherein the mixture obtained by mixing the polymer (Α) with the yttrium zinc salt (yttrium) is mixed and dispersed by a disperser. Thereafter, a cuprous oxide having an average particle size of 10 to 20 μm is added and mixed. 61 200932852 IV. Designated representative map: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: