TWI333947B - Novel cycloalkenylcarboxylic acid, novel dicycloalkeylcarboxylic acid and derivatives thereof, uses thereof, formulating agent for antifouling coating made from said carboxylic acid and derivatives thereof, antifouling composition, antifouling coating f - Google Patents

Description

1333947 VII. Designated representative map: (1) The representative representative of the case is: (1). (2) The symbolic representation of the symbol of the representative figure is as follows: (The representative figure has no component symbol and the meaning it represents) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:

..[V] [VI] 4 316720 1333947 IX. Description of the invention: [Technical field of invention] Novel dicycloolefin carboxylic acid, compounding agent, antifouling coating ship, water structure The present invention relates to a novel cyclic olefin carboxylate An acid, a derivative thereof, a composition for an antifouling coating formed by the above, an antifouling coating film, a coating method for the antifouling coating film, a fishing gear or a fishing net, and a method for preventing the same. More specifically, the present invention relates to a novel cycloolefin _ • - lysine, and a glamour thereof, and the coating film formed by the antifouling coating prepared by the above is a small environmental load. After a long period of time, the film is still coated; the speed of the pre-twisting is uniform and the excellent anti-fouling performance can be maintained for a long time, and the anti-fouling property is excellent in the high-contamination sea area or the static environment, and the balance of these characteristics is excellent. The antifouling coating for the antifouling coating film is excellent in storage stability, the antifouling coating film, the ship, the underwater structure coated with the antifouling coating film, the fishing gear or the fishing net and the antifouling method thereof. [Prior Art] Due to prolonged exposure to water, Lu is attached to the surface of the ship's bottom, underwater structures, fishing nets, etc., when breeding animals such as snails, shell vegetables, barnacles, plants such as seaweed, or various aquatic organisms such as bacteria. , it may damage its function and function. In particular, if the aquatic organisms are attached and propagated at the bottom of the ship, the overall volume of the vessel = surface roughness increases, which may result in a decrease in the speed of the ship and an increase in fuel costs. In addition, when bacteria, mucus (colloidal sludge) or large-scale attached organisms adhere to and propagate on the surface of underwater structures such as iron-steel structures, the structure is spoiled and damages the structure in the coated water. For the anti-corrosion coating, the strength, function and life of the 316720 ^ ° meta-salt structure are significantly reduced. Further, the removal of the aquatic organisms from the structure of the medium requires a lot of labor and working time. In order to prevent damage such as 5 hai, it has been conventionally applied to ships, water structures, and the like, and a method of applying an antifouling paint has been carried out. The anti-fouling 2 of the current anti-fouling coating can be roughly divided into the extraction type (diffusion type) in which the anti-fouling agent is extracted by the coating film, and the surface of the coating film is renewed and the new anti-fouling agent is in contact with seawater. The type has the disadvantage that the surface roughness increases with time and is resistant. Therefore, it is preferable to use a self-polishing type antifouling paint for a base of a ship, an underwater structure or the like which requires long-term antifouling properties. The auto-grinding type anti-Z coating can maintain the smoothness of the coating film and the surface because the surface of the prepared coating film is slowly dissolved, and can adjust the dissolution rate of the coating film to have a long-term controllable antifouling agent. The dissolution rate maintains excellent resistance during long periods of time. • Eight-material self-grinding antifouling coating, known antifouling coating composition package 3 Synthetic resin made from natural pine rosin and reinforced rosin coating film strength. The rosin is mainly composed of abietic acid and its isomers. The sigma is known to be slightly soluble in seawater, and is widely used as a coating resin.巧 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The polymer of vinegar is coated with 316720 33947 anti-fouling as an essential component in the long-term two: the product. Moreover, the composition of the coating is more stupid than the formation of the surface of the coating film. Defects, after a long time, can still exert the attachment of marine organisms::: Sex (TM (4) with anti-ocean two = compound during the period, because of the natural matter and stable t ^ brother instability 'the future also has resources The risk of depletion. Furthermore, because of the origin, the type of trees, and the purification strip: the problem of the coating composition. It is easy to make a good fixed quality, and it can be used for the second generation. And the second; the new anti-fouling paint with long-term anti-fouling problem. And the development of the agricultural 杬 涂料 coating composition must consider the following questions::::=::==r: Construction 2 is caused by the long-term mooring of the sea area where the search/sense is proliferating, thus An anti-fouling coating composition that can be used for a long time to exhibit a high performance in a high-contamination environment, which is more expensive than the conventional ones, tax > paintable, after being sold in the market, may also be used in such occasions It is also required that no deterioration or deterioration of the coating material occurs. s, τ臧' The inventor's goal is to develop a coating group 3, 6720 1333947 which satisfies all of the requirements, and conducts research to find the addition of a diene compound. The reaction, the open c-unsaturated tarenic acid and the ruthenium salt are novel compounds; at the same time, the two specific cyclic tick-acids and their metal genus salts, and the metal-type slow-acid derivatives of the metal and its anti-fouling coating film The hydrolysis regulator or the anti-(4) upper (1) acts as a compounding agent for the anti-fouling coating; contains an auxiliary agent, etc., and is suitable for the body-grinding antifouling coating for copolymerization and anti-fouling coating composition, long-term storage =:: Dream vinegar co-polymer) ^ film formed by hardening and hardening; ;; and coating the group under the dynamic environment, the anti-fouling property is in the long-term static ring, and successfully completed this Invention. L Hai et al # balance of the balance of excellent [invention content 】 (Problems to be solved by the invention) 4 = The purpose is to solve the problems associated with the above-mentioned conventional techniques, and to stabilize the supply, and the quality is more uniform - and it is suitable for the new Lai ring roasting acid, new two The present invention provides a reductive coating for the antifouling coatings having the above properties derived from the novel cyclophosphonic acid, the novel gamma acid, and the like. The environment of the anti-fouling coating formed is small: after a long period of time, the film is still consumed at a predetermined speed (uniform consumption of the film), and can maintain excellent antifouling performance for a long time (long-term 8 316720) 1333947 Performance), especially in high-contamination sea areas or static setbacks, and its balance of characteristics, clever anti-fouling composition, this characteristic: anti-fouling:: coated ship, underwater structure, A fishing gear, a fishing net, and the like (a means for solving the problem) The novel cycloolefin carboxylic acid of the present invention is represented by the following formula [V]. The novel dicycloolefin carboxylic acid of the present invention is represented by the following formula [VI].

(C〇〇)mR7 {in the formula [V], R fluorenyl I butene 41, 3-methyl-2-butenyl (also known as 2' methyl); base) or 2 to methyl + Propyl fluorenyl (2_methyl | propyl hydrazine | 戊 \ \ table ^ hydrogen atom, R 2 represents 4-? -3 - pentyl (2 'methyl 1 terminal)) 'R3, R4 represents a hydrogen atom , dT: base | butadiene (2-methyl-2-indolyl-4') when 'but 1 fluorenyl, R3, R4 represent a hydrogen atom, R2 is not 2-mercapto-1 -propenyl ( 2-mercapto-2-propenyl-3-yl) R--atom atom, representing methyl; ^ 316720 9 1333947 R5, R6 respectively represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; m and η represent 0, respectively. Or 1 (except that m and η are different at 0); R7 and R8 respectively represent a hydrogen atom or a hydrocarbon group; when m is 0, R7 is a hydrogen atom, and when m is 1, R7 is a hydrogen atom or a hydrocarbon group, When η is 0, R8 is a hydrogen atom, and when η is 1, R8 is a hydrogen atom or a hydrocarbon group (except that R7 and R8 are not hydrocarbon groups at the same time)};

Novel dicycloolefin carboxylic acid "VII

In the formula [VI], any of Rn or R16 represents an isopropyl group, and when <A> is an isopropyl group, R12 and R13 represent a hydrogen atom, R14 represents a fluorenyl group, and f5 and 1^6 respectively represent hydrogen. An atom or an alkyl group having 1 to 10 carbon atoms, m and η respectively represent a number of 0 or 1 (except that m and η are not 0 at the same time), and either one is 0 and the other is preferably 1.

Rn, R]8 represent a hydrogen atom or a hydrocarbon group, respectively, and k and 1 are 0.

]〇 316720 A 丄 / \ ' R2. Representing a hydrogen atom, the above R ^ represents a hydrogen atom or a carbon group having a carbon number of 1 to 1 G, when 〇 is, R" is a hydrogen atom, and a: 1 is 'a hydrogen atom, a nicotinic group or a metal atom, When η is 〇, 'R】8 is a hydrogen atom, a hydrocarbon group; when 1 is 'R, 8 is a nitrogen atom or a hydrocarbon group (only, ~, and also <B> R, 6 is an isopropyl group, R 'F represents A hydrogen atom,

Rl3 represents a methyl group, RM represents a hydrogen atom, ^ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m and η respectively represent hydrazine, and R and Rl8 represent a hydrogen atom, either of which is 0 and the other is 1 preferably means 〇 or! The number (only, k, 盍ί), and - ". 丨 J Ye Ma 0), and R2 ° means that the hydrogen atom or the hydrocarbon group respectively represents a hydrogen atom or a carbon number U 〇 炫 且 and the aforementioned k is 0 When it is a hydrogen atom, when k is 】, R19 is a hydrogen atom or a hydrocarbon group. When I is 0, R20 is a hydrogen atom, and when the hydrocarbon group is 1, R2° is a hydrogen atom or a hydrocarbon group (mR2. In a preferred embodiment, the above formula m represents a cycloalkenonic acid which is preferably lower than η 316720 1333947 by the following formulas [Va], [Vb], [Vc], [Vd], [Ve], [Vf], %] Or [Vn] represents 'and the dicycloolefin carboxylic acid represented by the formula [VI] is preferably the following formula [▽13], [\^11)], [\^(:] or [¥1(1] The expression (except that in the equation |^3] to [¥卜], and [Via] to [VId], when the atom or the group bonded to a carbon atom is a hydrogen atom (H), the expression is omitted. The text is the same).

12 316720 i 1333947

.COOH Ι<ΫΛ [Vb] V1

316720 1333947

COOH V^COOMe [Vg] 4 Φ

V

Nf [Vhh

(Me: methyl)

The novel method for producing a novel cyclic olefinic carboxylic acid or a novel dicycloolefin carboxylic acid of the present invention, characterized in that: [•1] is made from allo-ocimene (311〇-〇(3丨11^1^), basil ocimene (ocimene) At least one type of beta tereene compound is selected from the group consisting of: myrcene, a-terpiene, and α-phel landrene. a dilute compound), and 14 3] 6720 1333947 [K] at least one selected from the group consisting of α,β-unsaturated monocarboxylic acids & α,β-unsaturated diterpenic acid The saturated acid is subjected to an addition reaction. The novel cyclic olefinic carboxylic acid metal salt of the present invention and the novel dicycloolefin carboxylic acid gold j salt are reacted with a metal compound represented by the formula [V] or [VI]. The monocarboxylic acid metal salt of the clothing is generally represented by the general formula "(RC00)XM" indicating that the metal atom 'X represents the valence of the metal atom". • Other details of its construction and method are described below. The compounding agent (A) for an antifouling coating of the present invention is a cyclic carboxylic acid, a cyclic carboxylic acid derivative (except a metal salt) formed by an addition reaction of an unsaturated carboxylic acid and a conjugated diene compound, and a ring type. Any of a carboxylic acid metal salt and a cyclic carboxylic acid derivative metal salt. Preferred embodiments of the compounding agent for antifouling coatings of the present invention are the above-mentioned cyclic acid, cyclic carboxylic acid derivative (excluding metal salt), cyclic carboxylic acid metal salt and metal salt of cyclic carboxylic acid derivative Preferably, it is a ring-shaped slow acid or a bicyclic acid or a salt thereof as shown in the above formula [V] 4 [VI]. The antifouling coating composition of the present invention is characterized by comprising the above-mentioned antifouling coating compounding agent (A) and a self-polishing antifouling coating copolymer (B). The antifouling coating composition of the present invention preferably contains an antifouling agent (c), and the antifouling agent (C) preferably contains copper or a copper compound (c1). In the present invention, the above antifouling agent (C) may also contain an organic antifouling agent (C2) (except for copper or copper compound (C1)). In the present & month, the above-mentioned self-polymerizing antifouling coating copolymer (b) is a polymerizable unsaturated carboxylic acid hydroxymetalate-based copolymer. 316720 15 1333947 The above-mentioned self-grinding antifouling coating copolymer (8) is preferably in the form of a knife: R]_c〇〇_M_aH___________[ I ] H:〇C : 二 / is CHCC(CH3) —, d, H00C-CH=CH_, can be brought into full = corpse) - indicates an organic group containing an unsaturated bond, _C00H is also a salt or SI'M represents a polymerizable unsaturated salt The component unit to be derived, preferably a component derived from propylene propylene, is preferably a copolymer of a component unit derived from a wide range of L, L or steel salts. Preferably, the above-mentioned self-polymerized antifouling coating copolymer (8) ····3 has a component unit derived from an acid metal compound which does not contain a hydroxyl group bonded to a metal atom, and is equivalent to: :: a component unit derived from a metal compound of a hydrophilic unsaturated carboxylic acid, bonded to a gold metal hydride group, particularly preferably a bond or a carboxyl group The (meth)acrylic acid zinc salt or the steel salt is derived from the polymerized unsaturated (tetra) metal compound-based copolymer. Formula: R丨-COO-M-Ln-------- [ jjj {where [(1) ' R1 is CH2=C(CH3)-, CCH-, _C__CH, H〇〇C-CH=C( CH3)- represents an organic group containing an unsaturated bond, and is also a genus (: Γ 'Μ represents a metal atom, and L represents an organic acid residue, a coffee" (R represents an alkyl group, a cycloalkyl group, may have a substituent) Earth or square base), η represents the number of valences of metal ruthenium, and in the invention of the second invention, 'the above-mentioned self-grinding type anti-fouling coating copolymer (8) bauxite is an unsatisfactory unsaturated acid-lowering metal salt Coating film coating formed by the polymer composition 'the polymerizable unsaturated 3' 6720 coating composition. Antifouling method for fishing gear and fishing nets The surface of the fishing gear and the fishing net is coated with the coating film. The ship and underwater structure of the present invention The object is characterized in that the ship or the underwater structure is formed by any of the above-mentioned antifouling coating compositions (effect of the invention). The present invention provides the same as turpentine, and can be used as an anti-drug and anti-fouling agent (four). Compared with rosin, it can be used as a novel terpene carboxylic acid, a novel dicycloolefin carboxylic acid, etc., which are suitable as a compounding agent for antifouling coatings, etc. Salt, etc., * The present invention also provides the same as the rosin formed by the above novel cycloolefinic acid, novel bicyclic dilute carboxylic acid, and the like, and can be used as an antifouling coating modifier and an antifouling agent. A auxiliaries, etc., which are safer than rosin, and which are more uniform in quality - are suitable for antifouling coatings for antifouling coatings. Further, the present invention provides the antifouling coating system formed. The environmental load is small, f is evenly consumed at a predetermined rate after a long period of time (the film is uniform), and can maintain excellent antifouling performance for a long time (long-term anti-fouling performance), especially Anti-fouling coating film with excellent anti-fouling performance in high-contamination sea area or in a static environment, and excellent anti-fouling coating film with excellent balance of properties, anti-fouling coating film, anti-fouling a coating-coated ship, an underwater structure, a fishing gear or a fishing net, and the like, and an anti-fouling method thereof. [Embodiment] The following is a novel cycloolefinic acid, a novel bicyclic dicarboxylic acid: a derivative thereof, such as a compounding agent for antifouling coatings, and antifouling a material composition, an antifouling coating film, a ship coated with the antifouling coating film, a structure of 18 316720 water, a fishing gear or a fishing net, etc. a dicycloolefin carboxylic acid, a hydrazine thereof, and a compounding agent ( A) κ novel (2) ring derivative teaching ^ ^ The novel cycloolefin carboxylic acid, novel dicycloolefin carboxylic acid of the present invention (cycloolefin carboxylic acid and dicycloolefin carboxylic acid are also collectively referred to as "(di) ring Alkene carboxylic acid"), and the like, and a mixture of a fine compound and an unsaturated drum acid are added to form a cyclic carboxylic acid by a Diels_Alder reaction. a cyclic carboxylic acid derivative (excluding a metal salt), a cyclic carboxylic acid metal salt, or a metal salt of a cyclic carboxylic acid derivative. Among the compounds, the novel cycloolefin carboxylic acid [v] or a salt thereof (of the present invention) Hereinafter, the cycloolefin carboxylic acid compound [v]) is represented by the following formula [v], and the novel dicycloolefin carboxylic acid I; V丨] of the present invention or a salt thereof (hereinafter also referred to as dicycloolefin) The carboxylic acid compound [VI]) is represented by the following formula [VI]. The novel compounds [v], [vi], as described hereinafter, are diene components in natural terpene oils, which are [j]: from allo-eci (nelo-oci) , 〇cimene (myrcene), α-terpinene α_water axene (a_pheUandrene) are grouped, and at least one of them Dilute compound), and .

[K] an addition reaction of at least one unsaturated carboxylic acid selected from the group consisting of an α,β-unsaturated monocarboxylic acid and an α,β-unsaturated dicarboxylic acid or a monoester thereof (Diels-Al Degas into a reaction). Further, the novel (di)cycloalkenylcarboxylic acid compound [ν] '[VI] can also be exemplified by 19 316720 1333947. Forming salt, etc. from these novel (di) ring rare

(C〇〇)roR: (C00)nR8 ·· [V] propyl ketone (2-methyl-2-propanyl- 3- 隹[m ' r1 represents hydrogen shoulder, 3_methyl_2 one Dingfuji-2-buten-4-yl) or 2-methyl-byl), R residual atom, methyl or 4_methyl_3_戍 dilute (2-methyl- 2_ 戍-5-yl), R3, R4 represent a hydrogen atom or a fluorenyl group, and pentene is a dihydrogen group, and 'R2 represents a 4-mercapto-3-pentenyl group (2-methyl-2-decene-5) -Base), R3, R4 represent a hydrogen atom, palpitary: group | butyl group (2-methyl group; butyl group + base), a dialkyl group, R3, R4 represents a hydrogen atom, and R represents a 2-fluorenyl group. A propylene group (2_methyl-2~ represents a ruthenium atom, R3, R4 represents a fluorenyl group; and R and R respectively represent a hydrogen atom or a carbon number 丨 to 丨〇 [V], m and n respectively Indicates 〇 or i of several soils, when 〇); , m ' n different R, R8 respectively represent a hydrogen atom or a hydrocarbon group; and 316720 20 1333947 When m is 0, r7 is a hydrogen atom, and when m is 1, 'R7 is When a hydrogen atom or a hydrocarbon group is 0, R8 is a hydrogen atom; when η is 1, R8 is a hydrogen atom or a hydrocarbon group (except that R7 and R8 are not hydrocarbon groups at the same time). As detailed below, R1 in the formula [V] represents a hydrogen atom, a 3-indolyl-2-butenyl group (2-indolyl-2-buten-4-yl) or a 2-indenyl-indole-propene group. Base (2_mercapto-2-propene _3-base). Here, when R1 represents a hydrogen atom, it is represented by the following formula [Ve] (5a) 4 [Vf] (5b), and R 2 represents 4-mercapto-3-pentenyl (2_fluorenyl-2- pentyl) Alkene-5-yl), R3, R4 represent a hydrogen atom; R represents a 3-mercapto-2-butenyl group (2-methyl-2-phenylene-4-yl), such as the following formula [Vc] ( 4a) or [Vd] (4b), R2 represents a fluorenyl group, r3, r4 represents a hydrogen atom, and R1 represents a 2-methyl-1-propenyl group (2-indolyl-2-propenyl_3_yl group) It is as shown in the following formula [Va] (3a) or [Vb] (3b), R2 represents a hydrogen atom, and R3 and R4 represent a fluorenyl group. R3 and R6 each represent a hydrogen atom or a carbon group having a carbon number of i to 1 Å, preferably a carbon number of from j to 5, particularly preferably a carbon number of from 1 to 3. The alkyl group may be a ring (C6 or higher) having a branch or a chain or may have a substituent of the above alkyl group, wherein the chain is easy to manufacture, inexpensive, and contained in the antifouling film. It is preferable to appropriately adjust the hydrolysis rate and the dissolution rate of the antifouling agent. Specific examples thereof include mercapto, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl '316720 21 丄:):>:)y4/ It is better to meet the above requirements. η is different. m and n respectively represent the number of 〇 or 1 (but 0 as described later). In the case of m, η = 0, "_(C00)m", "-(C00)n" means any _: early key one", m, n = 1 "-(coo)B", "-(co〇)n" table =) 壬. One is a carbonyloxy group "-C00". (In the case of k and 1 described later, R and R8 respectively represent a hydrogen atom or a hydrocarbon group. R7 and R8 represent a hydrogen atom or a hydrocarbon group (for example, carbon number 1 to 1 bauxite, and car father's carbon number 1) When the 兀〇 is 'mt, the m of the "_(c〇〇)mR7" part of the above formula [v] is such as stone 1, not milk atom (H); when m is 1, R7 represents a hydrogen atom or a nicotine group (for example, an alkyl group having a carbon number of from 1 to 10, preferably an alkyl group having a carbon number of i to 5.), that is, "-(coo)m R7" in the formula m is m= 0, R7 (Η), * +H • 々土"' m υ κ 马虱 atoms borrowed "表不_Η", or when m = 1, f is a hydrogen atom (Η), indicating, two ~ C_J; or when R7 is a hydrocarbon group, the table * "Κ" is as described above, and in the present invention, "when the m and n are different in the formula [V], it is 〇. When the two are simultaneously 0 ((4) "- (called R7", "_((10))nR8": all become "-H", compound [" does not become a slow acid or its derivatives (example, salt temple), and these are not included in this In the compound of the invention (7), "-(C00)nR8" in the formula π is the same as the above-mentioned "-(C is called r" = that is, when the above n is 0, 'R8" represents a hydrogen source (H); Record a hydrogen atom (·Η) or the same hydrocarbon group as above. 316720 22 1333947 Therefore, ''-(COO)n R') means that H is in the case of n = 〇d8, 1 7 〇, and R8 is a hydrogen atom (H). When η is a wind atom (h), it means that a few bases are "one (c) and (4), and when the ruler is a smoke base, it means "K(4). In the present invention, when i4R and R8 are different, the φ is also The acid compound [V] is a small acid or a derivative thereof, and may be exemplified by a monolonge represented by the formula (3a) to (5b) or a monocarboxylic acid as represented by the formulae (8a) to (8b) ( The monocarboxylic acid of the dicarboxylic acid) The above-mentioned carboxylic acid derivative may, for example, be a metal salt of such a carboxylic acid.

In a preferred aspect of the present invention, the novel ring-reducing acid [V] represented by the above formula [V] is specifically 5' and may be exemplified by the following formula: [Va]{l,5,6-three Base - 3-(2-mercapto-1-propanyl) 4-cyclohexyl-1 -yl-rebel acid, [Vb]丨1' 4, 5-trimethyl-2-(2-A -1-propylidene)_3_cyclohexyl-1_yl-rebel acid, [Vc] U,4~dimercapto-3_(3-mercapto-2-butenyl)_3-cyclohexene -1-yl-carboxylic acid}, [Vd] {1, didecyl-2-(3-methyl-2-butenyl)_3_cyclohexen-1-yl-carboxylic acid}, [Ve] U-Mercapto-4-(4-methyl-3-pentenyl)-4__cyclohexene-diyl-carboxylic acid}, [Vf] U-mercapto-3-(4-indolyl-3 -pentenyl)-3-cyclohexene-buyl-carboxylic acid}, [Vg] {2-oximeoxycarbonyl-3-(2-mercapto-1-propenyl)_5,6-didecyl-4- Cyclohexene-buyl-carboxylic acid}, and 316720 23 1333947 [丨2 carboxy-3-(2-methyl+propyl propyl)> Cyclohexyl-1-yl-carboxylic acid methyl ester oxime. One T group 4 For the production of the new Lai lion compound m 2: two low-cost and uniform quality, it can be used as an anti-fouling agent, etc., and used as an anti-fouling coating agent in antifouling coatings. The compound (7) In the antifouling coating film may be suitably adjusted since the rate of hydrolysis of the points ^, antifoulant dissolution rate, and enhance good stain resistance and the like.

Further, in the above-mentioned respective compounds of the present invention, it is very difficult to separate the mixture of isomers during the formation reaction. When f is used as a compounding agent for antifouling coatings in the mixture, it can suppress the crystallization of the coating material and the coating (4), and obtain excellent adhesion to the target material. The advantage of coating film. The rosin which has been widely used in the past is also the same as the above-mentioned novel cyclic carbene carbazine compound [v] (the compounding agent for antifouling coatings) of the present invention, and the substance composed of a plurality of isomers has the above advantageous features. The above cyclic olefinic acid compound [V] of the present invention is also similar thereto.

24 316720 1333947

/COOH r<S[C [Va] i (3a)

25 316720 /\5 (8)1333947

\^®\^COOMe xy COOH [Vh] (8b) The novel dicycloolefincarboxylic acid [VI] (dicycloolefincarboxylic acid compound _ [VI]) of the present invention is represented by the following formula [VI]. Riken carboxylic acid-based compound "νη:

{However, in the formula [VI], R 丨丨 R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R Respectively > _ , R16矣- , no wind atom or carbon number 1 to 10 when R is not isopropyl. The alkyl group of the double 1 main oxime (particularly C1 〜1 〇, more preferably R = another hydrogen atom or a hydrocarbon group (preferably the same _). 5' is particularly a county of Π~3. When 与 316720 26 1^33947 10, η, k or 1 is 〇, respectively, corresponding to R", r] 8 ' r19 p20 * % K represents no hydrogen atom. 2〇m, n, k or 1 When it is 1, it corresponds to Rn, R, 8, R, 9 or represents a hydrogen atom or a via group (preferably the same as above), and meets the following conditions (i) and (ii). 〃 _ ( 1) When Rl1 is isopropyl, R12 and R13 represent a hydrogen atom (H), R]4 represents a fluorenyl group, k = 1 = 0, R, 9 and R2° represent a hydrogen atom (H); p (_ii) When R16 is isopropyl, 'Rn, 尺12 and Rl4 represent a hydrogen atom (H), a fluorenyl group, m=n=〇 (except, in any aspect, r]7 and a different sulfhydryl group rb And R2. It is not a smoke base at the same time, and the claws are different from ^ and 1 as 〇). "R and R22 respectively represent a hydrogen atom or an alkyl group having 1 to 1 carbon number}. In the sample, the above formula [Chuanzhong, ... or any of them = isopropyl group] and R" in the formula [VI] to r22 (r"except) ι, η, 3 car father The following relationship is satisfied. Hereinafter, a preferred embodiment of the case where the disk R]6 % field sentence /, Γ ', and propyl group in the formula [VI] is isopropyl, the formula [VI] In the case of isopropyl group, <a>>22 η, k, 1 minute k represents a hydrogen atom, that is, R12 RU in the formula [VI] The methyl group, the subunit 2Γ is the same as R5"6 in the above training, and represents the alkyl group of chloroproton to 10, respectively, preferably K5 and R6 are the same, and 316720 27 丄 mn represents the number of 〇 or 1 (only Preferably, any of them is 0, and the other represents i, m η is not 〇), and R, R18 and the above formula [V] neutron or hydrocarbon group (preferably with the above-mentioned phase group). R8 is the same as R8, and represents hydrogen as the same as the above. (However, RnA R18 is not a hydrocarbon at the same time. In the above formula [VI], k and 1 represent 〇, 广, and r2. It means a chlorine atom. ^ That is, the above formula is called (c〇〇)kRl9u[_((10))iR2〇] table

Do not]. Therefore, considering the above [m, η is not the same as 〇], Rn is a propyl group, and the above formula [¥1] is a number of carbonyloxy groups (c〇〇) or carboxyl groups (C(8)Η). For 1 to 2 'not including 3 to 4 existing patterns. Therefore, when R" is an isopropyl group, the dicycloolefin carboxylic acid compound [VI] is the same as the above-mentioned cycloalkenic carboxylic acid compound [V], and is a monocarboxylic acid or a metal ruthenium or the like. 1 C again, when m = η = 〇, [一(c〇〇)bR]7] and [一(c〇〇)nRl8] are both [-H] 'At this point, consider the above [_( C〇〇)kRl9] and [―(c〇〇)]r2. The compound [VI] is not a carboxylic acid, and the substances are not included in the compound [VI]) of the present invention. R and R are the same as R5 and R6 in the above formula [V], and each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. However, in the present invention, when m of the moiety [_(C00)ffiR] in the above formula [VI] is 0, Rn is a hydrogen atom, and when m is oxime, V7 is a hydrogen atom or a hydrocarbon group (preferably and The above are the same). Therefore, only [-(COO)»Rn] is the same as [-((200)1«1^] in the above formula [V], 111 = 〇, |^< is 1^(hydrogen) "Atom" means "_only"; 28 316720 1333947 and m = 1, when R" is Η (hydrogen atom), 'represents carboxyl group _c〇〇Hj; when m = 1, when R is a radical, The ester group "_c〇〇γ". In the present invention, when n in the above formula [VI] (C00) nR] 8] is 0, 'R18 is a hydrogen atom, and n is ', when R»8 is a hydrogen atom or a hydrocarbon group (preferably the same as above). Therefore 'only for [-(_,], the same as [-(_'] (or -(COO)nR7) in the above formula [v]' Indicates "_h", listens to "__ or "-COO R8" (ester group). - (only 'R18 is not a hydrocarbon group at the same time." Thus, R21 is an isopropyl group <A>, in the above formula [νι] a part of the carbonyloxy group (C00) [-(C00)mRl7] " 丨- and [-((10)), R, of the four parts, [一(C〇〇)lR2.]" Η", thus the bicyclic dilute _ [VI] can be a monocarboxylic acid or a derivative thereof (salt), and does not form a di-di-tetracarboxylic acid, etc. ', three ~, this again, as in the above formula In [VI] R" and Rl8 are not at the same time - the ring-back (four) system compound is called § when it is a single two soil. Because of the acid single vinegar, etc. 'excluding the second s| (except the ring two cool) ^ day, two slow iB> R16 is isopropion: When η R16 is isopropyl, r12 to r22 in the formula [VI] (rk, l respectively represent the following. ” 01′, that is, P′R in the formula ΠΠ] 〖2 indicates a hydrogen atom,

Rl3 represents a fluorenyl group, R14 represents a hydrogen atom, and 316720 29 1333947 R is the same as the above, and represents a hydrogen atom or an alkyl group having a carbon number of 丨 to 1 再. Further, in the above formula [VI], m and n represent o, ! ^7, ^表 不气原二再再, k, 1 are 0 or 1 respectively (only, k, 1 is not 〇), 幸乂佳 means that one of them is 0, the other is 1. That is, [-((:00), 7] and [_((:00)|8] in the above formula [VI]] [4]. Therefore, consider [the following [k, i are different) 0], in the case where R11 is an isopropyl group, and R.6 is an isopropyl group, the oxy group ((10)) or a slow group (C_, etc.) in the above formula [VI] has a number of 2 to 2 2, 3 to 4 are present. 3 Therefore, when R16 is an isopropyl group, a dicycloolefin acid-lowering compound [the same as the above compound, a monocarboxylic acid or a metal salt thereof, etc. R, R, Rn, which is the same as R1 in the case where R11 is an isopropyl group, or R7 or R«), respectively, represents a hydrogen atom or the same substituent group as above. R2H and R" are isopropyl groups, R, 5, RU (or the same as in the above formula m) respectively represents a hydrogen atom or a carbon number no. The portion of the group (CO〇) kR19] is a hydrogen atom or the above. However, in the present invention, the above formula [VI] When k is 0, R19 is a hydrogen atom; when k is 丨, the same hydrocarbon group as r19."; and k, R19

Therefore, 7 is only [-(C00)kR, when [-(COOW] is the same as '-(COOW), when k = 〇, and R19 is Η, it means "-H and ~1' R is H When the carboxyl group "-COOIi i ·" and 316720 30 1333947 are sulfhydryl groups, it means that the aryl group "_C〇〇. (4) 'in the above formula m', in the servant (10) part, when the 虱 atom '1 is 1' R is a hydrogen atom or a hydrocarbon similar to the above: 'On the basis of [-((10)W, when it is an isopropyl group, the H group or the ester group "-COO R8"." When the above R16 is an isopropyl group, R19 and R20 in the formula [VI] are not a hydrocarbon group at the same time. In the case where f is an isopropyl group, <B>, when the above RII is an isopropyl group (10) ^[-(c〇〇)km and [一(C00)lR2.] in the four parts of the compound having a carbonoxy group ((10)) in ^π], which means "one η" as described above, and thus: The compound is called a mono-sweet acid or a derivative thereof (metal orphan) and does not become a _, a _, and, in addition, the above formula [Chuanzhong, by the above t can be ^m, n, k^, m one n, at least one of them is the 1st temple, k and 1 are both 〇, and k'! at least:: 1 day Both m and n are 〇. Therefore, the formula [VI] contains a monoterpic acid, or a salt thereof, and does not contain a di- or more of a di-, tri- or tetra-acid. Also, it does not include these three-fourth, acid vinegar, salt, and then the above-mentioned formula [¥1] represented by the bicyclic olefinic acid compound [Chuan is a carboxylic acid of dicarboxylic acid, which means In a preferred embodiment of the present invention, the novel physico-acid compound [VI] represented by the above formula [VI] is specifically the following formula, or the above The novel bicyclic dilute acid represented by the formula [VI] can be exemplified by the following formula [VIa] (I)-isopropyl-4-indenyl-bicyclo[2,2,2]2_xin-baked_5_ Base_slow acid), (7) is called 316720 31 1333947 propyl-4-mercapto-bicyclo[2, 2, 2]2-octene-6-yl-carboxylic acid), [vIc] (6-iso Propyl-3-methyl-bicyclo[2,2,2]2-octene-8-yl-carboxylic acid), or [VId](6-isopropyl-3-indolyl-bicyclo[2 , 2, 2] 2-octene-yl·carboxylic acid). The novel bicyclonecarboxylate compound [VI] represented by the formulas [Via] to [VId] has the advantages of easy manufacture, low cost, and certain quality, and is suitable as a compounding agent for antifouling coatings, and the like. In the antifouling paint, as a modifier for the dissolution rate of the antifouling agent, when the compound [¥1] is contained in the antifouling coating film, the hydrolysis rate, the dissolution rate of the antifouling agent, and the like can be appropriately adjusted.

iSJ deficient coating agent α 1 The compounding agent (A) for antifouling coating of the present invention contains an addition reaction of an unsaturated carboxy hydrazine with a conjugated diene compound (Dilles-Alder addition reaction) 316720 32 ^33947 Any one or more of a cyclic carboxylic acid or a cyclic carboxylic acid derivative (for example, a metal salt or the like) formed by a cyclic carboxylic acid. The preferred aspect of the compounding agent for the antifouling coating is the above ring; the 夂酉夂, * type of tickic acid derivative (for example: the ring-shaped acid or the new Lai bicycline, or The second novel is ^Λ^ΜΛΜΜΛΜ.

The invention comprises the above-mentioned novel lysine carboxylic acid 'new bisbicyclo(tetra) acid (two, inductively referred to as ring (tetra)) or a method for producing the same, the cyclic acid of the invention, an ester thereof or a salt thereof The manufacturing method is ·· χ "[J] by allocene (all〇-ocimene), basilene (〇cim such as geranene (myrcene), α-terpinene α_phelene (α-phel landrene At least one terpenoid diene compound (conjugated diene compound) is selected from the group, and [K] is composed of α,β-unsaturated monocarboxylic acid & alpha, ρ-unsaturated dicarboxylic acid or The at least one unsaturated carboxylic acid, the ester thereof or the salt thereof (unsaturated carboxylic acid compound) selected from the group t of the monoesters is subjected to an addition reaction. Further, in the present invention, the terpene-based diene compound is first [ 】] reacting with an unsaturated acid in the above unsaturated traconic acid compound [K ], followed by esterification, salt formation, etc. The novel cyclic carboxylic acid or salt thereof obtained by the method described above is The cyclic carboxylic acid, the ester thereof or the salt thereof obtained by the above-mentioned production method is suitable for use as the above antifouling paint for the above reasons 33 316720 1333947 In the present invention, even if the above-mentioned cyclic carboxylic acid, ester or salt thereof is suitable as a compounding agent for an antifouling coating or the like, the unsaturated carboxylic acid and the conjugated diene compound are also used. The addition reaction (Dilles-Alder addition reaction) or the like is formed. The above novel compound [V] & [VI] is used, and the above conjugated diene compound used in the synthesis of the above cyclic carboxylic acid can be used. For example, butadiene, isoprene, 1,3-pentadiene, allocene (all〇_〇cimene), ocimene (ocimene), geranene (myrcene) and other chain compounds; furan, a cyclic compound such as cyclopentamethylene, 1,3-cyclohexadiene or α-terpinene α-phellandrene. In the present invention, among the above conjugated dilute compounds, preferably Diene, % pentadiene, allo-e-cimene, geranene, α-terpiene. The above-mentioned light-dilute compound has a molecular weight of 54 to 600. The olefin is excellent in the antifouling property and the appropriate consumability of the obtained coating film. The novel compound [V] and [VI] of the present invention are included in the synthesis. In the case of a cyclic carboxylic acid, an unsaturated compound (dienophile) to be added to a conjugated diene may, for example, be an unsaturated carboxylic acid or a compound of an unsaturated carboxylic acid. Examples of the carboxylic acid include (meth)acrylic acid, linoleic acid, linolenic acid, 〇ieic acid, and propi〇iic acid (HOCCOOH). ), such as monounsaturated acid; monomethyl maleate, monoethyl maleate, monopropyl maleate, horse 34 3] 6720 1333947 acid monobutyl vinegar, maleic acid monophenyl vinegar, rich Monobasin vinegar, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, monoamyl fumarate, itaconic acid monoterpene, itaconic acid monoethyl ester, clothing Monoethyl propylate, monobutyl itaconate, monoamyl itaconate, monoterpene ester of citrac〇nic acid, monoethyl citrate, monobutyl citrate, etc. a monomorphic ester of a diacidic half ester (alkyl group of 1 to 20); a monoaryl group of a half ester of an unsaturated dicarboxylic acid such as monophenyl maleate or fumaric acid Ester and the like.

Among the above unsaturated carboxylic acids, (meth)acrylic acid is preferred. Examples of other diolefins include p-benzopyrene and the like. Further, the diene affibody used in the present invention may have (four) adjacent to the unsaturated bond in addition to the unsaturated carboxylic acid (having a combination of the groups, corresponding to p-benzone, etc.) An active group such as a nitrile group, a sulfonyl group, a hexyl group, an ethoxy group, a phenyl group, a sulfonium group, a sulfonium group, an amine group or the like. The cyclic tasting acid formed by the addition reaction of the above-mentioned compound diene compound with the unsaturated state of the genus (Diels-Alder addition reaction) can be exemplified by: a single f-coating [2,2'1]2-heptene-6-yl-carboxylic acid [compound 1] quinone (CPD) and acrylic acid (AA) 1 molar mass: 138); addition (2) is not the addition of pentadiene (CPD) and methacrylic acid (maa) by the addition reaction of 忐 R R field β ' 酸酸 [化~" --bicyclo[2,2,1]2-heptene Iyl- 竣[lower (10) and other monocyclic acid; (3) shown by allo-e (le) and methyl propylene 316720 35 1333947 1,5,6-trimethyl-3(2-methyl-1-propenyl)4-cyclohexene-buyl-carboxylic acid formed by the addition reaction of enoic acid (MAA) [Compound a-3a ](MW : 222), 1,4,5-trimethyl-2(2-methyl_1-propenyl) 3 -cyclohexene - bromo - acid (compound A-3b) (MW : 222) a monocyclic carboxylic acid; a dimethyl group formed by the addition reaction of ocimene and acrylic acid (AA) represented by the following formula (4) (3-fluorenyl-2-butenyl group) 4_cyclohexene-buki''carboxylic acid [Compound A-4a] (MW: 222), 1, 3 a monocyclic carboxylic acid such as dimethyl 2(3methyl-2-butenyl) 3 -cyclohexene-diyl-carboxylic acid [Compound A_4b] (MW: 222); 1-methyl-4(4-methyl-3-pentenyl) 4-monohexene-1-yl group formed by the addition reaction of myrcene with methacrylic acid (MAA) Carboxylic acid [Compound A-5a] (MW: 222), ;-Methyl 3 (4-methyl 3-pentenyl) 3 -cyclohexyl-1 -yl-carboxylic acid [Compound A_5b] (MW: 222 a monocyclic carboxylic acid; an isopropyl-4-yl group formed by the addition reaction of α-terpiene and acrylic acid (AA) represented by the following formula (6) Bicyclo[2'2'2]2-octenyl-carboxylic acid [Compound A-6a] (MW: 208), Iso-indenyl-[2,2,2]2-octene-6-yl- It is formed by the addition reaction of a 2-ring carboxylic acid such as acid [Compound A-6b] (MW: 208); a-phel landrene disk represented by propylene 6-isogas (?) 6-Isopropyl-3-methyl-bicyclo[2,2,2]2 octenyl'' around acid [Compound A-7a] (MW: 208), propyl 3 fluorenyl ring [2, 2, 2] 2-octenyl-carboxylic acid [Compound A-7b] (MW: 208), etc. 2-ring-type acid or the like. 36 316720 1333947 Maleic acid monomethyl, formula (8) ^]: 丨2_methoxyxylpropenyl)-5,6-dimethyl-4-cyclohexene formed by the reaction of all °-ocimene and heart 2-Π Alkene-1 -carboxyl 1 =, _: 266), [then: 丨2, yl-"2-methyl-1 ShuJw 5' bis dimethyl + cyclohexene mono carboxy carboxylic acid methyl ester} [compound : 2 (6) and other single ring type (four) and so on. (10) is the abbreviation for the weight of the moir (five). Compounds such as Yanhai (the ring-like retardation usually produces a mixture of various isomers) due to the difficulty of isolation, and the mixture of isomers as an anti-fouling coating: excellent characteristics, for example, can be suppressed In the coatings and coatings, the coatings have excellent adhesion and plasticity, and most of them are used in the form of these mixtures. The synthesis of these cyclic acids can be carried out using the well-known Diels-Al. When the synthesis is carried out, a known catalyst such as a solid acid may be used as necessary. The reaction product may be used without purification, or may be purified by a method such as recrystallization or recrystallization. ..., the cyclic carboxylic acid The acid can be synthesized by reacting a conjugated diene compound with an unsaturated carboxylic acid and a ruthenium P. The reaction of the conjugated diene compound with an unsaturated carboxylic acid can be used as a catalyst, and the catalyst can be enumerated as an activity. In the above reaction, in the conjugated diene compound and the unsaturated carboxy oxime, for example, the amount of the conjugated diene compound and the unsaturated carboxy oxime is 0 01 to 2 = 里 / β 敕乜〇. 05 to 〇· 5 wt% activity White clay catalyst; reaction temperature: 60 to 10 Torr (TC, preferably 7 〇 to 9 (temperature of rc; reaction time: preferably 60 Βτ is preferably η to 4 〇 hours; pressure to 1 〇 atmosphere 316720 37 The reaction product of the cyclic carboxylic acid (usually a mixture of isomers) of the present invention can be obtained by a reaction under pressure of preferably 9 to 5 atm. The reaction product can be purified as described above. It can be used as it is, if necessary, by removing insoluble matter by filtration, and distilling off low-boiling substances such as unreacted materials (compared to the desired cyclic carboxylic acid of the present invention, usually the unreacted material has a low boiling point). It is purified by well-known rectification, vacuum distillation, recrystallization, solvent fractionation, and the like.

38 316720 1333947

CPD MAA

Compound A-2 (M*: 152)

k \

Basil

COOH

Compound A-4a

Compound A-4b (Mw: 222) 39 316720 1333947

Geranene

COOH

Alpha-water order dilute Compound A-7a (Mw: 208) Compound A-7b (Ww: 208) 40 316720 1333947

Bellerol

Among the above-mentioned cyclic carboxylic acids, the numbers (2), (3), (5) and (8) are particularly preferable from the viewpoints of the antifouling property of the obtained antifouling coating film and the appropriate depletion property. Among the cyclic carboxylic acids, the numbers (3), (4), (5), (6), (7), and (8) are novel substances. Further, for example, in the carboxylic acid [Compound A-1] (or [Compound A-2]] represented by the above formula (1) (or the formula (2)), the (meth)acrylic acid is used as the raw material of the cyclopentane. The addition direction/position of the olefin (CPD) or the formation of the internal structure/external structure, and the following four isomers exist respectively.

41 316720 1333947 The same applies to the production examples of carboxylic acids (AD-1) and (AD-3) described later. Further, when Al 1 o-ocimene is used as the raw material for the preparation of the above-mentioned retarded acid, the allo-ocimene itself is a mixture of the following three isomers.

Allo-ocimene (2) Into the ocimene (3) Therefore, as shown in the above formula (3), the following 24 isomers can be considered in the [Compound Α-3] (carboxylic acid). The same applies to the production examples of the carboxylic acids (AD-4) to (AD-5) described later.

42 316720 1333947

43 316720 1333947

The compounding agent for an antifouling coating of the present invention comprises a cyclic acid, a cyclic carboxylic acid derivative (excluding a metal salt), a cyclic carboxylic acid, which is formed by an addition reaction of the above unsaturated carboxylic acid and a conjugated dilute compound. In the case of the above-mentioned cyclic carboxylic acid derivative constituting the compounding agent for the antifouling paint, a compound such as a cyclic carboxylic acid can be mentioned. , hydrazine, hydride, heterogeneous 'heat treated material, ethylene 44 316720 1333947 ether adduct, Michael (Michae 丨) plus and so on. The compound or the Diels-Alder adduct may specifically be exemplified by an ester of an alcohol, an ester of an aryl cyclic carboxylic acid of a cyclic carboxylic acid (cyclic carboxylic acid ester), a ring type. The hydrocarbon acid and the carbon number 丨 to ^, preferably 1 to 8, more specifically, a hydrocarbon ester such as a cyclic aryl alcohol ester. The carbamide of the cyclic carboxylic acid (cyclic formula with Λ β 4 1^, absorbing 3 dishes ^ ‘

For example, a carboxylic acid having a % carboxylic acid and a carbon number of 1 to 18, and an amine having a weight of 1 to 8 may be exemplified by, for example, calcined hydrazine. A guanamine containing a hydrocarbon group such as a carbaryl amine. For example, in the case of a hydride of a sulphuric acid, a compound obtained by hydrogen addition of a -carbon double bond or a hydrazine ring of a ring (4) molecule may be hydrogen-added. The compound obtained by the ring. Examples of the heat-treated product of the cyclic acid repellent include, for example, an inert gas in which a cyclic carboxylic acid is obtained by heat treatment at 250 to 35 (TC). When the heat treatment is performed, a reaction occurs between molecules of the cyclic carboxylic acid. Further, the heterogeneous compound may be obtained from the cyclic carboxylic acid derivative of the present invention. The vinyl ether adduct of the carboxylic acid of the formula is a carboxyl group of the cyclic carboxylic acid. a vinyl ether having a hydrocarbon group such as an alkyl group or an aryl group having a carbon number of 丨18, preferably 1 to 8. The vinyl ether adducts are, for example, those disclosed in Japanese Patent Laid-Open Publication No. 2001-262076 Manufactured by the disclosed method. The carboxylic acid addition product of a cyclic carboxylic acid may, for example, be an activity of a carbon number of 1 to 18, preferably 1 to 8, such as a malonic acid ester, an ethyl acetate, or a cyanoacetate. Sub-45 316720 1333947 A compound formed by the addition reaction of a methyl compound with a polarized (; p〇larized) carbon-n-double bond in a cyclic carboxylic acid (or its ester). The carboxyl group of the bond may be exemplified by a compound which is itself added by the mic. The Diels-Alder adduct of the cyclic carboxylic acid may be enumerated as a compound formed by adding a carbon number of 4 to 50, preferably 4 to 20, to a carbon-bonded double bond of the cyclic ticker acid. The novel (b) metal salt of a cyclic olefinic acid of the present invention is a formula [ v] or [VI] • The monocarboxylic acid metal salt obtained by reacting a monocarboxylic acid with a metal compound is generally represented by the formula (〇〇: "(RC00)xM" (RC〇〇 represents a cyclic carboxylic acid) Residue, Μ indicates that the metal atom 'X indicates the valence of the metal atom.) However, the above formula (α) may also be bonded to a ligand such as water, an acid or a base, or the like, and further, as a metal salt. The metal and the carboxylic acid (more preferably the carboxyl group in the carboxylic acid) are not limited to being constituted by an equivalent ratio (number of metal equivalents / number of carboxylic acid equivalents = 1/1), and may be excessive metal equivalent ratio (number of metal equivalents / carboxylic acid equivalent) a carboxylic acid metal salt having a number of carboxylic acid metal excess salts, or an opposite metal equivalent ratio thereof. (Also, regarding the semantic meaning of the carboxylic acid metal excess salt, please refer to the inventor of the present invention. Japanese Patent Application Laid-Open No. 2002-97406, the entire disclosure of which is incorporated herein by reference. The metal salt of the living may, for example, be a cyclic carboxylic acid or a cyclic carboxylic acid derivative (excluding a metal salt), and a metal such as zinc, dance, copper, bismuth, ing, bell, brocade or a metal containing the metal atom. A metal salt formed by the reaction of a compound, wherein a metal salt of zinc or copper is preferred from the viewpoint of coating film dissipability and stain resistance. 46 3] 6720 acid metal salt can be used, and fusion 13 0 Various methods are produced, for example, by the following complex melting method, direct method, etc. [Deterolysis method]: The decomposition method is based on the sodium salt of the acid-inducing metal (copper sulfate, etc.) Method salt, purified by solution, etc., to produce acid metal [Hyun melting method] The smelting method is to heat the metal oxide and the carrier carboxylic acid, and to remove the lanthanum... The field removes water or acetic acid to obtain a metal carboxylate salt, and the water is removed by evaporation or the like. In the medium, the azeotropic [direct method] method can be used to directly react the metal and (4) acid to obtain the metal salt of the metal salt, which can also be used in the manufacturing process of the coating. It is easy to prepare such a mixture of several acids. For example, the zinc salt of the acid-repellent zinc salt can be easily obtained by oxidation. In the far-reaching method, in advance, the presence of the solvent for the carboxylic acid and the zinc white paint is required. The well-known method of mixing and mixing is made... ", the various components to be combined with the composition of the coating composition of mUl, etc., ::= is a salt) The composition in the composition (anti-fouling coating) / 望 涂 涂 316 720 720 720 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 In the method, in order to increase the rate of formation of the metal salt, water may be added, and in order to remove water formed by the reaction and water to be added, a dehydrating agent is known. use. Appropriately, the compatibility of these components (1) with the self-grinding antifouling cold copolymer (8) described in the following, especially the Shi Xi (4) copolymer, is better than == points (1) and (8) When the antifouling coating composition is formed into a coating film, the '., the member has a moderate solubility in seawater, and has excellent characteristics such as coating film consumption and stain resistance. Long juice to the following hydrolyzable self-polishing antifouling coating for the antifouling coating composition of the present invention (8) (non-volatile part), especially β 夕 烧 vinegar copolymer (non-volatile part) ), in terms of the parts by weight, the content of the compounding agent (1) for the antifouling coating is. .11300 parts by weight;;: 〇〇 〇〇 〇〇 更 更 更 更 更 更 更 更 更 ' 更 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' The hydrolysis rate of the decomposable resin coating film can be appropriately adjusted, and the anti-fouling property of the coating film for a long period of time is good, especially in a high-range or static environment, which is excellent in anti-fouling performance. The above-mentioned antifouling coating compounding agent (4)' is usually a UU9G by weight component in the anti-staining excluding chest weight part, and is preferably used in an amount of from 1 to 50 parts by weight. ▲The same as the anti-fouling paint fine. The anti-fouling coating composition of the present invention contains the above-mentioned anti-fouling paint with 316720 48 1333947 (A) or (AD), and is used together with the self-polishing anti-fouling paint. The antifouling coating composition such as the polymerization f is excellent in that it does not substantially contain an antifouling agent having a large environmental load such as a tin compound, and as a result, a coating film which is adversely affected by the environment can be formed. However, in the coating film, the antifouling coating compounding agent (A) which functions as a hydrolysis regulator or an auxiliary agent, and the copolymer of the self-polishing antifouling coating contained in the coating film (8) The hydrolysis rate is well controlled, the consumption rate of the coating film is stable for a long time (certain), the dissolution rate of the antifouling agent is also excellent, and the long-term anti-fouling property is excellent, and it is suitable for high fouling. Ships operating in the sea, or underwater structures, fishing gear, fishing nets, etc. used in a static environment. A copolymerized anti-cold coating for a body-coating type of anti-cold coating, a self-polishing antifouling coating (4) copolymer of the coating film forming component (8) can be used as a polymerizable unsaturated buffer acid-based metal salt-based copolymer (and And "or a polymerizable unsaturated carboxylic acid metal compound-based copolymer (B_b) containing a component unit derived from a polymerizable unsaturated metallurgical compound directly bonded to a metal atom). The former polymerizable unsaturated carboxylic acid hydroxy metal salt-based copolymer (Ba) 'is preferably a (meth)acrylic acid hydroxy metal salt-based copolymerization of the latter "containing a direct bond to the entire ^ (). a poly-human unsaturated (tetra) metal compound-based copolymer derived from a polymerizable unsaturated ruthenic acid metal compound of the atomic group (i〇H) of the atomic group (ie, preferably a bond containing no bond) a (meth)acrylic acid metal salt-based copolymer (ii) bonded to a metal atom (hydr〇xyl curry). 3] 6720 49 1333947 The above (meth) propylene hydrazine hydroxy metal salt copolymerization (i), can be used = such as Japanese Patent Special Open 8-209 A tree L(10)Μ disclosed in Japanese Laid-Open Patent Publication No. Hei 9-286933, (wherein, RP: a base resin, a zinc atom of a divalent metal atom, a copper atom), etc. Further, the above-mentioned copolymer (ii) ), that is, a (meth)acrylic metal compound-based copolymer (Π) bonded to a metal atom hydroxy 1 gr〇up, which can be used by the inventor of the present invention. The (meth)acrylic acid metal salt-based copolymer disclosed in the [_6] to [_9] towel of the Japanese Patent Publication No. 323209, or the [〇〇15] to [〇] of the Japanese Patent Laid-Open No. Hei. 〇44] In the resin disclosed in the present invention, the polymerizable unsaturated carboxylic acid hydroxy metal salt copolymer is preferably a polymerizable unsaturated carboxylic acid represented by the following formula in the molecule. a copolymer of the main constituent units,

Formula: R]-C00M-0H-------[JJ =[1], 'R1 means CH2=C(CH3)_, (3)2=CH_, dirty, ΓΓΓ (called organic with unsaturated bond) The base may also form a genus of genus or vinegar. Μ represents a metal atom, for example, zn, Cub J ii. The above-mentioned copolymer (1) is desirably contained in a unit of (meth)acrylic acid; ) Aromatic base metal salt ° (4) 疋 3 ^ base) acrylic acid copolymerized by a base metal salt (= 3 atomic atoms preferred her), steel ((5); in addition, bismuth is zinc (曱 dipropylene diyl) acrylic acid The component unit (methyl) propane-based zinc salt-based copolymer derived from the base metal salt is desirable because of the physical properties of the coating film 316720 50 1333947. In this January, there is no direct bonding to the metal atom. The (meth)acrylic metal compound-based copolymer (ii) of the radical group may be a copolymer of a component unit derived from a polymerizable unsaturated acid-lowering metal compound having no molecular formula in the following formula: V-COO-MU-------[Π] {where [Π], R] means CH2=c(ch〇_, ch2=ch_, h〇〇c_ch=ch_, HOOC CH C(CH3) - the middle-of-the-none has an organic bond that is not saturated The base, Lu-(10) oxime may also form a metal salt or a g. M represents a metal atom, preferably a metal atom other than ^ 'L represents an organic residue "" 2 represents a burning base (preferably C The group may also have a substituent. The organic residue may also be one of organic acids derived from the novel ring of the present invention. a dilute acid compound (7), an organic residue of the novel bicyclic dilute acid compound [VI] of the present invention, wherein L and / may be the same or different. n represents the number of valences of the metal M. Preferably, the copolymer (ii) is a copolymer containing a component soap fraction derived from a metal compound of a (meth)acrylic acid which is directly bonded to a hydroxyl group of the atom, and particularly the metal atom is Zn. Cu, preferably contains: a copolymer having a component unit derived from a (meth) propyl salt of a zinc or copper base. A copper. The auto-grinding type used in the present invention. a copolymer (8) for stain coating, preferably a (meth)propionate metal salt-based copolymer having a loading component The long-term water-soluble coating film gives long-term anti-J properties, and the (f-based) acrylic acid metal compound-based copolymer can be exemplified by 51 3] 6720 (3) state 47-single monomer (mercapto group) "Alternative monomer" (B) of a metal acrylate compound ("(())) (=) = genus (meth) acrylate metal compound (a): two ' to 99.99% by weight Λ 曰〇 曰〇 曰〇 5 5 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共The amount, that is, the content is % by weight, preferably 98 to 50% by weight (only, the total of (曱) + (B) is 100% by weight). Further, in the present invention, the (meth)acrylic acid metal compound is a human or a polymerizable unsaturated carboxylic acid hydroxymetalate-based copolymer, and the like. The term "糸" (for example, a (meth)acrylic acid metal compound), such as when the copolymer is produced, the essential component used is "00" (for example, a base) - a metal acrylate compound) or organisms. The like is not limited, and it is not limited to be used in the maximum amount or 50% by weight or more of the components to be used. The metal M constituting the above-mentioned (fluorenyl)acrylic acid metal compound may be exemplified by a group of gold (manufactured by the group), and may be exemplified by a metal having a valence of 2 or more. Preferably, the 211 and Cu 〇 曱 曱 丙烯酸 丙烯酸 丙烯酸 为 为 为 为 为 为 为 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合 合'For example, when the ruthenium is a metal atom other than S1 such as Cu, Zn or Mg, the (meth)acrylic acid metal compound (monomer) is represented by the following formula (B-11): 316720 52 1333947 ------ (B-ll)

COO-M-L

[In the formula (B-U), Ri, M, L, n& are respectively the same as the formula [u. In particular, in the formula (B-ll), 'R is the same as the above-mentioned formula. Μ indicates that the above-mentioned metals other than Si such as Cu, Zn, and Mg, and 4 R, which may be the same or different, are the same as the above. The organic group, preferably an acid residue (-〇C〇R2), n is the same as above. In the above formula (Β-11), when L is a carboxylic acid residue (_〇c〇R2), these groups

The carboxylic acid (H〇c〇r2) obtained by the derivative may be in the form of a chain, or may have an alicyclic ring, an aromatic ring or the like, and may be exemplified by a carboxylic acid which is mainly monovalent: propionic acid, valeric acid, oleic acid, or sub Oleic acid, linolenic acid, stearic acid, versatic carbonic acid (versatic), abietic acid (acid contained in turpentine), naphthetkacid, (meth)acrylic acid, benzoic acid, The above novel cycloolefincarboxylic acid compound [v], novel dicycloolefincarboxylic acid compound [VI], etc. of the present invention. The (indenyl)acrylic acid metal compound represented by the above formula (Bl 1) is specifically For example: Zinc methacrylate: [(CH2=C(CH3)-COO-)2Zn], zinc acrylate: [(CKH-COO-hZn], magnesium methacrylate: [(CH2=C(CH3)-C00 -) 2Mg], magnesium acrylate · [(CH2=CH-COO-) 2Mg], bismuth propylene hydride copper: [(CH2=C(CH3)-COO-)2Cu], copper acrylate: [(CH2= CH-C00-)2Cu], zinc decyl phthalate: [(CH2=C(CH3)-C00-)((C3H7)3C-C00-)Zn], zinc acrylate carbonate··[(CH2 =CH-COO-)((C3H7)3C-COO-)Zn], cyclodextrin acid zinc methacrylate··[(CH2=C(CH3)-C00-)(naphthenic acid Base) Zn], naphthenic acid propylene 53 316720 1333947 Zinc acid: [(CH^CH-COO-) (naphthenic acid residue) Zn], benzoic acid methyl propionate zinc: [(CH2=C(CH3) )-C00-)((C6H〇-C00-)Zn], zinc benzoate acid: [(CH2=CH-C00-)((C6H5)-C00_)Zn], benzoic acid magnesium methacrylate: [(CH2 =C(CH3)-C00-)((C6H5)_C00-)Mg], magnesium methacrylate: [(CH2=CH-C00-)((C3H7)3C-C00-)Mg] 'Tetracarbonate Copper acrylate: [(CH2=C(CH3)-COO-)((C3H7)3C-COO-)Cu], benzoic acid methyl propyl sulfonium steel [ [CH2=C(CH3)-C00-) ((C6H5)-C00-)Cu], ring acid acid copper methacrylate · [(CH2=C(CH3)-COO-) (naphthenic acid residue) Cu], naphthenic acid copper ·· (CH2=CH_C00_) (naphthenic acid residue) cu] or the like hydrate. The other monomer J (B) which can be copolymerized with the above (indenyl) propionate metal compound (A), Examples of the aliphatic group, the alicyclic group, and the aromatic group include a (meth) acrylate, a vinyl monomer having a hydroxyl group and/or an amine group, and the like. In the "other monomer", the (mercapto) acrylate may specifically be, for example, decyl (meth) acrylate, ethyl (meth) acrylate or n-propyl (meth) acrylate. Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Lauryl (meth)acrylate, stearic acid (meth) propionate, condensed glycine (meth) acrylate, (meth) acrylate 2 曱 曱 乙 S (fluorenyl) acrylic acid cyclohexamethylene, (meth)acrylic acid isobornyl alicyclic monomer; aromatic monomers such as (meth)acrylic acid benzene vinegar, (meth)acrylic acid benzoate Wait. 316720 54 1333947 "Other monomers" (B) copolymerizable with the above (indenyl) metal acrylate (曱), a vinyl monomer having a hydroxyl group and/or an amine group (B) = a hydroxyl group and/or Any one of the amine groups may be one or more, and may be a monomer or a 2 to 3 volume or the like. Specifically, for example, (mercapto)acrylic acid 2 -ethethacetic acid, (mercapto)acrylic acid 2-perylene group may be mentioned. A propyl ester, (mercapto)acrylic acid 3_ mercaptoacetic acid, 2-hydroxybutyl (meth)acrylic acid ester or the like has one hydroxyl group. Other examples include an adduct of 2-hydroxyethyl acrylate and ethylene oxide, propylene oxide, γ-butyrolactone, ε-butyrolactone, etc.; 2-hydroxyethyl (meth)acrylate (a 2- to 3-volume of 2-acrylic acrylic acid 2-propanol vinegar; a monomer having a plurality of radicals such as (meth)acrylic acid glycerin or the like; a monomer having an amine group (B), which may be Any of the first to second amine groups such as (meth) acrylamide, butyl methacrylate (mercapto) acrylate, and the like; Dimethylaminoethyl acrylate, ethylaminoethyl (meth)acrylate, diammonium propyl (meth) acrylate, dimethylaminobutyl (meth) acrylate (methyl) Dibutylaminoethyl acrylate, diammonium ethyl (decyl) acrylamide, dimethylaminopropyl (decyl) acrylamide, etc. Other examples are vinylpyrrolidone, vinyl pyridine, vinyl hydrazine. a heterocyclic group such as azole, a basic monomer, etc. Other examples include, for example, (meth)acrylic acid, itaconic acid, maleic acid, succinic acid, and the like, and the like Derived cool class; styrene, vinyl benzene, (X-methyl styrene, (methyl) acrylonitrile, ethyl acetate vinegar, vinyl vine acetate, etc.. 3 hai (meth) acrylate metal compound ( Single body (A) and "other monomer" (B) can be used in combination or in combination of two or more. 55 316720 1333947 S Xuan soap body (曱) and (B) are carbon-carbon unsaturated bonds The junction portion is copolymerized to form a (meth)acrylic acid metal compound-based copolymer. In the copolymer, the component units (曱) and (B) derived from the Shai Temple monomer (曱) and (B) may be Random or block configuration, usually in a random configuration. The monomer (曱) and (B) copolymerized (mercapto) propionate metal compound copolymer The weight average molecular weight (Mw) is usually 丨, 〇〇〇 to about 100,000 'glass transition temperature 7 bogey _20. 〇 to + 1 〇〇. 〇 around. » The (fluorenyl) acrylate metal compound copolymer The solid content of the resin is usually from 1 to 99% by weight, preferably from 10 to 7% by weight, more It is contained in the antifouling coating composition in an amount of 15 to 50% by weight. The anti-fouling coating composition contains the same amount of the (meth)acrylic acid metal compound-based copolymer, and has a sufficient antifouling effect. Further, the (meth)acrylic acid metal compound is a total amount of the compound of the (meth)acrylic acid compound, and the total amount of the components other than the solvent is 100 parts by weight based on the antifouling coating composition. It is usually preferred to contain i to 99 parts by weight, preferably 1 to 7 parts by weight, of the summer. The (meth)acrylic metal compound is a copolymer, and when it is contained in the antifouling coating composition in the above range, The surface of the coating film has a long-term stability and is excellent in the consumption resistance and the stain resistance. The above-mentioned (meth)acrylic acid metal compound-based copolymer can be referred to Japanese Patent Publication No. Hei 7-64985, and JP-A-4-8(4) Japanese Laid-Open Patent Publication No. Hei-4-80269, JP-A-4-80270, JP-A-63-12_8, JP-A-2013 (E), H.S.A.特开平3]6720 56 1333947 HM58 It is easily manufactured by a method such as No. 547 and JP-A-H2572. These (indenyl) metal acrylate-based copolymers can be produced, for example, by any of the following methods (1) to (4). The method is a (meth)acrylic acid metal compound (曱), and (meth)acrylic acid 2-methoxyethyl ester (meth) copolymerizable with the metal compound (monomer) The other monomer (B) such as decyl acrylate is mixed with an organic solvent, and is present in the presence of a radical polymerization initiator such as butyl peroxyoctanoate or azobisisobutyronitrile (AIBN) at 6 to 18 Torr. The above copolymer can be formed by performing a solution polymerization at a temperature of r for 5 to 14 hours. The second method is a carboxylic acid (A-1) containing an unsaturated double bond such as (mercapto)acrylic acid, and a monomer (ethyl) and a saturated aliphatic carboxylic acid metal compound copolymerizable with the monomer. a saturated alicyclic carboxylic acid metal compound or an aromatic carboxylic acid metal compound (C) is mixed with an organic solvent, and is a radical polymerization initiator such as a third butyl peroxyoctanoate or an azobisisobutyronitrile (octa(3)... In the presence of 'solution polymerization at a temperature of 60 to 1801 for 5 to 14 hours, the above-mentioned copolymer can be formed. The second method firstly uses a carboxylic acid (A-1) containing an unsaturated double bond such as (fluorenyl)acrylic acid. And the monomer (the other monomer (B) copolymerized with the methyl-ruthenium is mixed with an organic solvent, and is a radical polymerization initiator such as a third butyl peroxylate or an azobisisobutyronitrile (ruthenium). In the presence of the solution, it is subjected to solution polymerization at a temperature of from 6 Torr to 18 Torr for 5 to 14 hours, and a copolymer having a carboxyl group derived from the above-mentioned unsaturated double bond carboxylic acid (曱_丨) at the side of the side chain is formed. Secondly, the copolymer can be guided on the carboxyl group of the copolymer. a metal carboxylic acid compound such as copper acetate (Cu) such as copper acetate, and a bond 316720 57 1333947 attached to the metal atom 而' to introduce a human acid residue at the end of the side chain (-0C0R2'R2 is the same as above) The terminal acid (1) propionic acid, valeric acid, oleic acid, sub-(iv) and other acids (10) (10), R2 are the same as above) and water (pure water) are placed in the counter-instrument' at a temperature of 6G to 18G °C, and react! After 10 hours, the temperature is raised to 120 14 (TC, and the by-product acetic acid or the like is separated and removed, and the side chain 〆COO M Ln ' Μ, Ln is the same as described above.) The hydrolyzable (meth) propylene fosphate metal compound is introduced. The fourth method is the same as the third method described above, and the (meth)acrylic acid»etc. contains a double acid and a double bond (曱_n and can be copolymerized with the monomer (A-D copolymerization a) , the single limb (B) is mixed with an organic solvent, and in the presence of a free radical polymerization initiator such as peroxyoctanoic acid octane = azobisisobutyronitrile (AIBN), polyfluorene is formed at the end of the side chain having the above a copolymer of a carboxyl group containing an unsaturated double bond carboxylic acid (曱_玉). Subsequently, the copolymerization is carried out. A metal oxide such as zinc oxide (zinc white) of a metal atom such as Ζ (Ζη) may be introduced into the carboxyl group of the copolymer, and a _ bond, a ruthenium metal atom, may be at the end of the side chain. A carboxylic acid such as propionic acid, valeric acid, oleic acid or sulfite S, and water (pure water) of a terminal group (L) such as a carboxylic acid residue (COOR, R is the same as above) are introduced into the reactor. 〇 〇 〇 〇 〇 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' (Μ, Ln is the same as above) of a hydrolyzable (mercapto)acrylic metal compound-based copolymer. Alkyl ester-based copolymer (b2)> Next, the above-mentioned copolymer (b) is a polymerizable unsaturated carboxylic acid.矽 58 58 316720 1333947 West I 糸 copolymer case. When the M is Si, in the formula [II], n = 3, showing a polymerizable unsaturated carboxylic acid decyl ester (monomer), (B-12) formula (B-12): R^COO-Si- La -

[In the formula (B-12), r· is the same as the above [n], and represents an organic group; 匕 may be the same or different and each represents a carbon number of 1 to 2 5 , preferably 1 to 2 Å, more preferably 1 to 1 10 may have a divergent bond-like m-alkyl aromatic fumes (preferably a phenyl group), and any of the alkyl-alkyl alkoxy groups of the same alkyl group as described above, and the groups may have a substituent]. Therefore, the polymerizable unsaturated carboxylic acid decyl ester-based copolymer is a copolymer having a molecular weight derived from the above-mentioned polymerizable unsaturated carboxylic acid decyl ester in the molecule. That is, R1 represents CH2=C (CH3). ), -CH2=CH-, H00C-CH=CH-, _c-ch=c(ch3)-, an organic group containing an unsaturated bond, and H ru can also form a metal salt or ester. L, that is, L, L2, L3 may be the same or different 'respectively represent a hydrogen atom; a carbon number of 1 to 25, preferably 1 to 20, more preferably 1 to 1 可 may have a branched chain alkyl group; An alkyl group; an aromatic hydrocarbon group, preferably a stupid group. Any one of the alkylalkyl alkoxy groups of the same alkyl group as described above (the groups may have a substituent) 'preferably, L1, L2, L3 may be The same or different, respectively, represents a carbon number! to &, preferably from 1 to 20, more preferably from 1 to 18, still more preferably from 1 to 1 Torr, particularly preferably from 2 to 6, which may have divergent chain alkanes. a base; preferably a carbon number of 3 to 1 Torr, more preferably 316720 59 1333947 2 to 8 of a cycloalkyl group; any of the phenyl groups which may have a substituent. The 荨L may be the same as or different from R. , the copolymer (8) is a molecule An unsaturated polymer of the following formula [IIIA], and a copolymer of a component unit derived from an unsaturated monomer copolymerizable therewith. Formula: R]-coo-Si (lI, l2, l3)--------[ΙΠΑ] (R丨, L丨, l2, l3 in the formula [im] are the same as above. Again, three seven, also PLL, L and In the following formula [ΠΙ], R, 2, r13, and r are the same.) Hereinafter, the polymerizable unsaturated carboxylic acid containing the component unit derived from the polymerizable unsaturated carboxylic acid decyl ester (B-12) will be described in detail. A decyl ester-based copolymer (B2) (also referred to as a decyl ester copolymer). The decyl ester copolymer (B2) used in the present invention contains a component unit derived from a polymerizable unsaturated carboxylic acid decyl ester. The polymerizable acid decane ruthenium component 覃仂 polymerizable unsaturated carboxylic acid decyl ester may, for example, be an unsaturated monocarboxylic acid such as acrylic acid or mercaptoacrylic acid, itaconic acid, maleic acid, fumaric acid or citric acid dicaprylic acid. a decyl ester of an α,β-unsaturated dicarboxylic acid or the like, and a sulfonate of an α, a conjugated to a non-saturated bis-acidic acid. The component unit derived from the ester is preferably a unit of a decyl (meth) acrylate represented by the following formula [III]. 316720 60 1333947 CH(R°) CRnCO^SiR) 2R13R14 _ In the formula [m], R represents A hydrogen atom or _C00H, preferably a chlorine atom (H) '-COOH can form a metal salt or an ester; Rn means that the two cores may be the same or different from each other, and each represents an alkyl group having a gas number of hits (ie, a carbon number of 1). To 25, preferably more preferably ^ to ... more preferably mo, particularly preferably having a divergence: a bond-like alkyl group), a cycloalkyl group having the same carbon number as above (i.e., preferably having a carbon number of 3) An alkylene group (preferably a phenyl group) having 6 to a carbon atoms which may have a substituent, and a alkyl group having the same carbon number as described above Any of the oxy groups. Further, the substituent of the chlorine atom which may be substituted with an aromatic hydrocarbon group such as a phenyl group may be an alkyl group, an aryl group or a halogen. The (meth) decyl methacrylate derived from the unit of the (decyl) decyl acrylate (system) is represented by the following formula (ln~a). Formula (ΠΙ-aO): CH(R°)

II CR "COOS iR l2R % 】4 ... 仰·3〇) The formula (ΙΠ-aO) is the same as R〇 in the above formula [ίπ], indicating a hydrogen atom or C00H, and Li Weijia is a hydrogen atom (η); ρη Like the above-mentioned formula 6] 316720 1333947, it represents a hydrogen atom or a fluorenyl group; R]2, R, 3, R" and R12, R'3, and RU in the above formula [in] may be the same or different from each other. And each of the hydrogen atom, the alkyl group, the cycloalkyl group, the phenyl group which may have a substituent, and the alkyl decyloxy group which are the same as the above. The (mercapto) decyl acrylate (III_a 〇), specifically, trimethyl methacrylate (meth) acrylate, triethyl sulfonium hydride, tripropyl acrylate Hydrazinyl ester, triisopropyl carbaryl (meth) acrylate, tributyl sulfonate (meth) acrylate, tri-b-butyl decyl (meth) acrylate, (methyl) Triisobutyl decyl acrylate, etc. r]2, rU and R are the same decyl (meth) acrylate; (meth)acrylic acid di-t-butyl decyl decyl ester, (meth) acrylate second butyl R1 such as dimethyl decyl ester, dimethyl propyl methacrylate (meth) acrylate, monodecyl propyl propyl (meth) acrylate, decyl ethyl propyl methacrylate (meth) acrylate 2. A decyl (meth) acrylate or the like which is partially or completely different from each other in Rls and RH. The above decyl (meth)acrylates can be used in combination.

Among the decyl (meth) acrylates, Ru & R" are independently 1 to 18 carbon atoms such as methyl, ethyl, n- and i-propyl, and second, third and isobutyl groups. Preferably, R>2 is preferably a divalent alkyl group or a ground-based group. R13 and R14 may be the same or different from f. Further, the total carbon number of R, 2, RU& R is 5 Preferably, it is about 21. The decyl acrylate is considered to be easy to synthesize a (decyl) decyl acrylate copolymer or by using the (mercapto) decyl acrylate copolymer. The film-forming property, storage stability, ease of control of self-polishing, etc. of the antifouling coating composition, etc., is preferably carried out using (meth) propyl 62 316720 1333947 diisopropyl decyl sulphate, (fluorenyl) triisobutyl decyl acrylate 'di-t-butyl methyl decyl (meth) acrylate, second butyl decyl methacrylate (meth) acrylate, (mercapto) acrylic three _ second Butyl decyl ester.

The present invention preferably has both (a) a component unit derived from a polymerizable unsaturated carboxylic acid decane oxime and (b) a polar group-containing (fluorenyl) acrylate-derived knive unit. Further, the unit of the component (b) is not necessarily contained in the copolymer of the sulphuric acid ester. The component unit derived from a (thio) acrylate having a polar group is not particularly limited as long as it is a component derived from a (meth) acrylate monomer having a polar group, and is preferably a formula [IV] below. ] The unit of ingredients shown. CH(R°) ----[IV] cr15cozr]6

(8) In [ί5[Ιν], R° represents a gas atom or ~C00H, preferably a hydrogen atom (8), R f represents a hydrogen atom or a methyl group; z represents an oxygen atom or _nr17, and an oxygenogen of 8 is R, 6 a polyalkylene glycol group represented by a hydroxyalkyl group which may have a substituent, a hydroxy ring = soil h, (R180) nH (only, the ruler 18 is an alkyl group: an integer of 2 to 5 Å) or a formula: The filament group 1 di-base shown by r (only 'RX is an integer of 1 to (10) when the exfoliation group is a burnt group); when Ζ is a paste, R" means a dentate, a silk, an amine group, Substituted amine 316720 63 1333947 Any alkyl group substituted with a fluorenyl group or an alkoxy group, and R, 6 represents a hydrogen atom. The carbon number of the hydroxyalkyl group in the above formula Πν] is preferably from 18 to more preferably from 2 to 9; the carbon number of the above hydroxycycloalkyl group is preferably from 3 to 1 Torr, more preferably from 3 to 8. The carbon number of the alkylene group in the above polyalkylene glycol group is preferably from 丨 to 8, more preferably 2, and the carbon number of the alkylene group in the alkoxy diol group is preferably from 1 to 8, more preferably It is 2 to 4, and the carbon number of the alkyl group is 1 to 8'. More preferably, the thio group may form a ring structure. The substituted amine group can be exemplified by a carbon number of 丨 to 64 |

Or a dialkylamine group, and the alkoxy group of the hexyl group of 6 to 6 may be mentioned. The unsaturated single system derived from the inverse J to the saturated body component unit (8) is represented by the following formula (IV a). CH(R°) 〇Va) CR15C〇2RJ6 [Formula ma), R represents a hydrogen atom ( H); R15 is the same as the above formula nv] hmg is the same as the argon atom, and represents the hydrogen atom 啖 methyl group; Z is the same as the above formula [1¥], and the second is the same as the sub-frame 7 m 1 *, When the oxygen atom or -NR17, Z is a milk atom, Rl6 represents a hydroxyalkyl group having a substituent, a hydroxy ring group or an integer represented by the formula (R 〇) nH representing an integer of 2 to 50 or式·咖^基(Quasi-R is the county day, Ρχ(R 〇)nR is not alkoxypolyalkylene (only r is alkyl, number); two conditions I蚪' η means 1 to When 100 is complete, and Ζ is -NR)·7, this _1, Χ can not be replaced by dentate, hydroxyl, amine, substituted amine 316720 64 1333947 based on either the brewing base or the alkoxy group. R16 represents a hydrogen atom.] When the unsaturated monomer (IV-a) and Z in the formula (IV-a) are oxygen atoms, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are mentioned. , 2, propyl acrylate, 2-hydroxypropyl methacrylate, methacrylic acid 3 Gas via propyl acetate, 3-phenoxy-2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, acrylic acid 2-butadiene, 2-hydroxybutyrate methacrylate, 6-hydroxyhexyl acrylate , 1,4-cyclohexanedonol monoacrylate, polyethylene glycol monomethacrylate (n=2), polyethylene glycol monomethacrylate (n=4), poly(methacrylic acid) poly(ethylene) Glycol ester (n=5), polyethylene glycol monomethacrylate (n=8), polyethylene glycol oxime (n=l〇), polyethylene glycol monomethacrylate ( n=l5), polypropylene glycol monomethacrylate (n=5), polypropylene glycol monomethacrylate (n-9), monodecyl propylene glycol (n=12), bismuth acrylate Oxygen, monodecyl decyl acrylate polyethylene glycol ester (n=45), etc. In the above formula (IV-a), when Z is -NR] 7, specifically, it can be listed

For example, N-methylol acrylamide, N_foxymercapto acrylamide, N-ethoxymercapto acrylamide, N'N-dimethylaminopropyl acrylamide, N, N_ Methylaminopropylmethacrylamide, diacetone acrylamide, and the like. These unsaturated monomers (IV-a) can be used singly or in combination of two or more kinds. Among the unsaturated monomers (IV-a), a hydroxyl group-containing monomer is preferred, and in the monomer containing a warp group, an acrylic acid 2-(4), methacrylic acid 2_butyl acetate material can be used. It is excellent in an anti-fouling coating film having a moderate dissolution property. The king A and monomer component units (V) decyl ester copolymers are usually in the above unit (4) and the above-mentioned units of 316720 65 1333947 ί (8). It also contains unsaturated monomer component units (C). The unsaturated single-biliary forming unit (c) is a component unit different from any of the above-mentioned component units (a) and (b). 'Unsaturated monomer component (C)-derived unsaturated monomer (cj)' is specifically mentioned, for example, methyl (meth)acrylate, (meth) propylene gs s (methyl) Acrylic acid, such as (meth)acrylic acid vinegar; styrene such as styrene, vinyl, and α-methylstyrene; vinyl acetate, vinyl benzoate, vinyl propionate, butyric acid Essence of Ethyl citrate; crotonic acid (crotonic acid) esters, itaconate esters, fumarates, maleic acid, etc.; among them, '(mercapto) acrylic acid vinegar , styrene and ethyl esters can be prepared with an anti-fouling coating film with moderate film strength. The above unsaturated monomers may be used in combination or in combination of two or more. In the present invention, the polymerizable unsaturated carboxylic acid decyl ester component unit (a) contains a polar ruthenyl (methyl) propyl group in an amount of 20 to 80% by weight, preferably 3 to 7 % by weight. The unit of the rare acid ester component is from 〇 to 4% by weight, preferably from 0.01 to 20% by weight, and the other unsaturated monomer component unit (<:) is from 5 to 80% by weight, preferably from 10 to 6〇% by weight ((a) + (b) + (c) = ι〇〇重里/.) is contained in the decyl ester copolymer (B2), in terms of coating strength and consumability good. The decyl ester copolymer (B2) has a weight average molecular weight (Mw) of 200,000 or less, preferably 5,000 to 10,000, as measured by gel permeation chromatography (GPC), and is blended with the decyl ester copolymer ( B2) The ease of preparation of the antifouling coating, the storage stability of the antifouling coating produced, the coating operation, the consumption speed of the antifouling coating 66 316720 1333947, and the crack resistance.

, (为2) decyl acrylate copolymer (B2), which is a decyl acrylate (3 丨) represented by formula (III aO), 2 〇 to 8 〇% by weight, The unsaturated monomer (M) represented by the above formula (IV-a) is 〇 to 4% by weight, and other unsaturated monomers (cl) 5 copolymerizable with the above monomers (1), aQ) and (Iv_a) are 80% by weight (only, (al) + (M) + (cl) = 1% by weight), in the presence of a radical polymerization initiator, solution polymerization, bulk polymerization, emulsification, σ suspension polymerization, etc. Various methods are used for random polymerization. At the time of the polymerization, a chain shifting agent or the like can be used. The radical polymerization initiator may be a conventionally known azo compound, a peroxide or the like, and an azo compound, and specific examples thereof include 2,2'-azobisisobutyl nitrile and 2, 2,-azobis(2-mercaptobutyronitrile), 2, 2, azobis(2,4-dimercapto valeronitrile), etc.; peroxides such as benzoquinone peroxide, acetic acid Third butyl ester _ oxide, octyl octanoate peroxide, cumyl hydroperoxide, third butyl peroxide, butyl butyl butyl peroxide, isopropyl carbonate Tributyl ester peroxide, tert-butyl hydroperoxide, persulfate (potassium salt, ammonium salt), and the like. For example, the above-mentioned exemplified Wei-based compound, etc., which are disclosed in [〇〇77] to [0086] of JP-A-2002-206069, may be used. 67 316720 1333947 Ο Ο

II II hsch2—co (〇2Η4〇)2— c — ch2sh o :

II CH30(C2H40)22C-C2H4SH (Μ-2) ο ο (M-l)

II II HSC2H4-CO~(C2H4C〇4-c-c2h4sh

ο ο II II HSC2H4-CO(C2H40)19—C 〇2H4SH (Μ-3)

CH3(OC3H6)1〇(OC2H4)32'HN—C II S

(Μ-7) Call H4〇C 2H4-HN-r 〇-c——NH~C3He0(C2H40)2C3H6-HN—C_

II s

S II

Ch3oc2h, occh2sh

CH3O(C2H40),0(CsHeO)5CCH2SH HSCjH,C0(C3H60)10CC2H4SH 0 0 68 1333947 Ο

ο O(C3H6O)10CCH2SH ο

CH2OC2H4OCC2H4SH ch3ch2——c—CH2OC2H4OCC2H4SH ch2oc2h4occ2h4sho

o II 9H2〇(CH2CH20)4QCCH2SH: 9 HSCH200(CH2CH20)4CH2-$—CH20(CH2CH20)4-CCH2SH 9 ch2〇i H2-c— < CH20(CH2CH20)4〇CCH2SH δ

O(CH2CH2〇)10-CCH2SH o HSC2H4CO(CHCH2〇)20 ch3

o 0(CH2CHO)2cjCC2H4SH ch3 ch3 . 〇 ^ -〇(C2H40)10(CH2CHO)i〇-CC2H4SH CHg

SH (^.5) (Further, in the production example (s 8) of the polymer (copolymer) described later, '316?2〇69 poly(η=4) ethylene glycol double (3 using the above a chain shifting agent of the formula (Μ-1), wherein the polymer is used in an antifouling coating, and in the above various polymerization methods, a solution polymerization method in which polymerization is carried out in an organic solvent The bulk polymerization method is preferably a good solvent used in the solution polymerization, and examples thereof include aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as hexan and gamma; and vinegar such as acetic acid and butyl vinegar. ; an alcohol such as isopropyl alcohol or butanol; a ketone such as a dimethyl ketone or an ether; a ketone such as methyl ethyl fluorenone or methyl isobutyl ketone; or a combination of two or more of these solvents. Ester copolymer η^9-·η In the middle of the month, the shixi burning g曰 copolymer (Β2) can be used as a decyl acrylate component containing the following formula (ΠΙ-a). Magic: CR20COOSiR2 W ...-(in-a)

(In the formula (ni~a), 'R° represents a hydrogen atom or -COOH (preferably a hydrogen atom (Η)), P represents a hydrogen atom or a fluorenyl group; and R22 independently represents a carbon number of 1 to 10, respectively. An alkyl group, a substituted phenyl group or a trimethyl decyloxy group 'R23 represents an alkyl group having 1 to 18 carbon atoms which may have a ring structure or a divergence, a substituted phenyl group or a carbon number of 6 to 10.曱 矽 矽 氧基 氧基 , 及 及 及 及 及 曱 曱 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 In III-b), R° represents a hydrogen atom or -C〇〇H (preferably a hydrogen atom (H)) 'R2° represents a hydrogen atom or a methyl group; and R24 and R25 each independently represent a carbon number of 3 to 10 Divalent or cycloalkyl, R26 represents a straight-bonding group having a carbon number of 1 to 10, a divalent or carbonic group having a carbon number of 3 to 10, a substituted alkyl group or a trimethyl decyloxy group having a carbon number of 6 to 1 Å. Base) a decyl ester copolymer of (meth) propylene. Hereinafter, each component unit (d), (e), and (f) constituting the (meth)acrylic acid sulphate copolymer (B2 1) will be described in order. (mercapto) decyl acrylate component (d)

(曱) decyl acrylate component (d) is represented by the following formula (III_a ° J

CH(R») 〇〇SiR2W3 ... Lu a) Formula (III-main-λτ (Η)), R2〇* - ^, non-虱 atom or -C〇〇H (preferably hydrogen number 1 to 1) 〇 (preferably A; soil, R is a linear (tetra), a ketyl group, an ethyl group, a benzyloxy group which independently represents a carbon-substituted benzene λ/more material 1 to 6). Propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, 3] 672 〇 71 1333947 n-octyl, n-decyl, n-decyl. Substituents which can replace the hydrogen atom in the above-mentioned stupid group can be enumerated a base group, a halogen, etc. R23 represents a carbon group having a ring structure or a divergence of 1 to 18 (preferably i to 12' or more preferably 1 to 9), and has a carbon number of 6 to 1 Torr (preferably 6). To the phenyl or trimethyl hydroxyoxy group: "(CH3)3Si". The alkyl group such as hydrazine is in addition to the above-exemplified linear alkyl group;

Misfiring: propyl, isobutyl, t-butyl, tert-butyl, neopentyl aliquots a% hexyl, ethylidene norbornene, etc. having an alicyclic structure (cyclohexane hydrazine, norbornane ring) An alicyclic alkyl group or the like. Among these, R2]'R22 and R23 may be the same or different, preferably methyl JL propyl, n-butyl, n-hexyltrimethyldecyloxy, especially methyl, n-propyl, n-butyl Base and n-hexyl are preferred. / (Methyl phthalate (4) component unit (4) derived (methyl) decyl acrylate (dl), expressed by the following formula (ΙΙΙ-a-l).

CR20COOSiR21R22R23 — m) Formula (in Πΐ-aD, RD, R2D & ^ to R23 are the same as R0, Π... to r23 in the above formula (III_a) which is not in the above-mentioned component unit (4). Member (methyl) acrylate sand The ester (ΠΙ-al), and the body, for example, trimethyl decyl (meth) acrylate, 72 3] 6720 丄 333947 (mercapto) propionate diethyl sulphate | Base) propylene fine di-n-propyl catechus, tri-n-butyl decane (meth) acrylate, (mercapto) di-n-pentyl sulphate, succinic acid, tri-n-hexyl (meth) acrylate矽 醋 vinegar, tri-n-heptyl decane (Mercapto) acrylate, tri-n-octyl decyl (meth) acrylate, di-n-decyl sulfonate (Mercapto) R2!, R22 and R23 such as mercapto decyl ester are phase (aliphatic) decyl acrylates of the aliphatic group; and [5] (methylene) propyl triacetate R2HR23 is the same aromatic or decane-based (meth)acrylic acid decyl ester; (, methyl) Monomethyl-n-propyl sulfonate acrylate; isopropyl didecyl decyl acrylate; di-n-butyl-isobutyl sulphate (meth) acrylate; (methyl) N-hexyl-didecyl decyl acrylate; (butyl) butyl phthalic acid (meth) acrylate; (mercapto) acrylic acid monodecyl di-n-propyl decane vinegar; (methyl) Methyl ethyl n-propyl acrylate acrylate g-type; (meth)acrylic acid ethyl norbornyl dimethyl decyl ester; (meth)acrylic acid trimethyl decyloxy-dimethyl decyl ester ( CH2 = c (CH3)C00Si(CHa)2(0Si(CH3)3)^CH2= CHCOOSi (CHs)2 (OS! (CH3)3), etc. R21, R22 and some or all of them are dissimilar aliphatic (A

7S 316720 1333947 base) decyl acrylates and the like. In the present invention, the decyl (meth) acrylate (Ιπ-ad) may be used singly or in combination of two or more kinds. ((meth)acrylic acid sulphonate component unit (e)) The (meth)acrylic acid decyl ester component unit (e) is represented by the following formula (丨丨丨-b). CH(R°)

| -(ΠΙ-b) CR20CO〇SiR2W6 Formula (ΙΙΙ-b) in 'R. Represents a hydrogen atom or _c〇〇H (preferably a hydrogen atom (H)), R2° represents a hydrogen atom or a fluorenyl group; and ^4 and R25 independently represent a carbon number of 3 to 10 (preferably 3 to 8). The divalent alkyl group or a cycloalkyl group having a carbon number of 3 to ι〇 (; preferably 3 to 9). The above-mentioned divalent alkyl group may be the same as the above formula (m_a), such as a divalent alkyl group such as isopropyl 'isobutyl group, second butyl group, tert-butyl group or neopentyl group. The above cycloalkyl group may, for example, be a cyclohexyl group or an ethylidene norbornyl group. 2 6 R represents a linear alkyl group having 1 to 10 carbon atoms (preferably 1 to 8, more preferably 1 to 6), a divalent or cycloalkyl group having 3 to 1 Å (preferably 3 to 9) carbon atoms. Or a substituted phenyl or tridecyldecyloxy group of 6 to 1 Torr (preferably 6 to 8). The linear alkyl group, the divalent or cycloalkyl group, the stupid group and the like in R26 may, specifically, be the same as those described above. 5 Hai, etc. 'R 4, p and r26 may also be the same or different handles, the same 74 316720 1333947 with isopropyl, second butyl, isobutyl, preferably isopropyl, second butyl The base is good. Further, when some or all of R, R and R26 are different, R24 and r25 may be the same or different from each other, and R24& R25 is preferably isopropyl, isobutyl, second butyl or second butyl. R26 is preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl or tridecyldecyloxy. Such a (meth) decyl methacrylate component (e) derived (mercapto) decyl acrylate (el) is represented by the following formula (abbreviation), CH (R°) (ΙΠ-bl) CR20COOSiR24R25R26 In the formula (ΙΙΙ-bl), R°, R2D, r25 and r26 are the same as those of the above formula (III), and R°, 0, R24, r25 and r26 in the above formula (III). Such a decyl (meth) acrylate (ΠΙ-bl), specifically, a trimethyl sulfonate (meth) acrylate, a triisobutyl (meth) acrylate , R25 and R26 are the same (mercapto) decyl acrylate of (meth)acrylic acid tributyl butyl sulphate; (mercapto) propane acid diisopropyl-cyclohexyl sulphate , (mercapto) propionate diisopropyl-phenyl sinter, (methyl) acrylic acid monoisopropyl-trimethyl oxalate sulphur, 75 316720 1333947 (mercapto) acrylic acid Dibutyl-decyl decyl ester, (diyl) acrylic acid di-tert-butyl-ethyl sulphuric acid ester, (mercapto) propyl ketoic acid, one brother, one butyl, bis- fluorenyl曱 旨 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 R 、 R R R R R R R R R R R R R R R . In the present invention, such (fluorenyl) decyl acrylate (111 _b-1) may be used singly or in combination of two or more kinds. Among such (mercapto) decyl acrylates, the ease of synthesis of the (mercapto) acrylonitrile ester copolymer is particularly considered, or the use of such a (meth) acrylate The film-forming property, storage stability, and self-polish control of the stain coating composition are easy, and the (meth)acrylic acid decyl ester (ΙΠ-bl) is selected from (meth)acrylic acid. Triterpene sulphuric acid ester, triethyl decyl (meth) acrylate, tri-n-propyl decyl (meth) acrylate, tri-n-butyl decyl (meth) acrylate, n-hexyl (meth) acrylate - Dimercaptoalkyl ester, n-octyl-didecyl decyl (decyl) acrylate, isopropyl-didecyl decyl (decyl) acrylate, ethyl norbornyl (indenyl) acrylate Pyridyl ester, trimethyl decyloxy dimethyl methoxide (meth) acrylate, bis(tridecyl hydroxyoxy) fluorenyl acetonate, (meth) acrylate (trimethyl sulphate oxy) shixi (four) of any kind or two kinds of 316720 76 1333947 on 'and (mercapto) decyl acrylate ( III-bl) is selected from the group consisting of triisopropyl decyl (meth) acrylate, triisobutyl decyl (mercapto) acrylate, tributyl decyl (meth) acrylate, (mercapto) acrylate Second butyl-fluorenyl sulphate, (diyl) diisopropyl-tridecyl decyloxy decyl acrylate, (mercapto) acrylic acid di-tert-butyl-trimethyl sulphate Any one or two or more kinds of the base sulphuric acid esters are preferably used in combination. Furthermore, (meth)acrylic acid sulphuric vinegar (ΠΙ-bl) in the (indenyl) acrylic acid. Di-n-butyl sulphide and (indenyl) acrylate stone smelting g (ΠΙ The combination of (meth)acrylic acid triisopropyl rock in the -bl) is preferably used in combination. Φ (unsaturated monomer component unit (f)), saturated monomer component unit (f), and the above component unit (d) and the above-mentioned forming unit (e) constitute a (fluorenyl) decyl acrylate copolymer of the present invention. a component which is different from any of the above-mentioned component units (4) and (e), such a saturated monomer component (1) derived unsaturated monomer ((1), which can be listed as a formula (IV-a) (b) the (meth) acrylate containing a polar group or the unsaturated monomer (ci) derived from the above unit (4). The monomer 'specifically' may be as曱基)Acrylic acid, (Mercapto) acrylic acid B, (fluorenyl) acrylic acid _, different... Third Dingku, (A 316720 77 1333947) 2-ethylhexyl acrylate and (fluorenyl) acrylic acid Hydrophobic (fluorenyl) acrylates such as cyclohexyl ester; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ) 4-hydroxybutyl acrylate, 2-methoxyethyl (meth) acrylate, alkoxy polyethylene glycol mono(decyl) propylene Hydrophilic (meth) acrylates such as acid esters and alkoxy polypropylene glycol mono(meth)acrylates; styrenes such as styrene, vinyl benzene, and α-mercapto styrene; ethylene acetate, benzene Vinyl esters such as vinyl phthalate, vinyl propionate and vinyl butyrate; organic carboxylic acid esters such as itaconate group and maleate group; among them, (meth) acrylates and styrene And the organic carboxylic acid vinyl esters can be obtained with an anti-fouling coating film having a moderate film strength. The use of hydrophilic (meth) acrylates can enhance the consumption of the coating film, and propylene oxime can also be used for this purpose. A hydrophilic comonomer such as an amine derivative. The unsaturated monomer (Π) may be used singly or in combination of two or more kinds. The (meth) acrylate sulphuric acid ester copolymer of the present invention comprises the above ( The methyl (meth) acrylate component (d) is 〇 5 to 5 〇 by weight (preferably 0.5 to 25% by weight), and the above (indenyl) decyl methacrylate component (e) is 10 to 70. % by weight (preferably 30 to 65% by weight), and unsaturated monomers other than the above (d) and (e) The fraction (f) is an amount of 2 to 7 wt% (preferably 3 to 60 wt% ((dH(e) + (f) = 100 wt%)) to prevent cracking and coating of the coating film. 78 316720 1333947 is suitable for the peeling resistance, film strength, and consumability. The weight of the (meth) methacrylate acrylate copolymer (B2-i) measured by gel permeation chromatography (GPC) The average molecular weight (Mw) is 200,000 or less, more than 3,000 to 10,000, more preferably 5 to 100, and particularly preferably 5 to 80,000, and it is desirable to match the The ease of preparation of the antifouling paint of the decyl acrylate copolymer, the coating workability of the obtained antifouling paint, the consumption speed of the antifouling paint, and the crack resistance.矽 矽 酯 共 囔诰 _ 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种 此种〇 5 to 50% by weight, the above formula (丨丨丨-丨) indicates that (meth)acrylic acid decane is (el) 10 to 70% by weight, and is copolymerized with the above monomers (di) and (ei) Other unsaturated monomers (丄1) 20 to 7 wt% (only, (dlH(el) + (fi) = 100 wt%, in the presence of free radicals (radic(1) polymerization: in the presence of Various methods, such as polymerization, emulsion polymerization, suspension polymerization, etc., can be carried out by random (rand〇m) polymerization. When the above polymerization is carried out, a chain shifting agent as described above can be used. The base polymerization initiator can be a conventional one. Knowing the azo compound, the total amount of the product, etc., can be exemplified by, for example, 2, 2, azobispyrene: splenic porphyrin (2~mercaptobutyronitrile), 2, 2 Nitrogen bis(2,4-difluorenyl valeronitrile), etc. r π 匕 匕 匕 匕 匕 匕 匕 匕 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯 曱醯Propylene Peroxide, first octagonal emulsion, benzoic acid tert-butyl peroxide, isopropyl carbonate 316720 79 1333947 persulfate (slanted second s s-peroxide, third τ-based hydroperoxide, When the above polymer is used in the antifouling paint, the above various polymerization methods are preferably a solution polymerization method and a bulk polymerization method in which polymerization is carried out in an organic solvent, and the organic solvent used in the solution polymerization may be a toluene. , dimethyl stupid hydrocarbons; aliphatic hydrocarbons such as hexane and heptane; vinegar such as ethyl acetate and butyl vinegar; alcohols such as isopropyl alcohol and butanol. A ketone such as methyl ethyl ketone or decyl isobutyl ketone, etc. These solvents may be used in combination of two or more kinds. The antifouling coating composition of the present invention contains the above-mentioned antifouling coating compounding agent. (Α) and a self-grinding antifouling coating copolymer (8) as an essential component, and a preferred component (Α) usually contains 〇1 to 8〇% by weight, preferably □5〇 by weight (four), and a component. (B) is usually a ratio of α6〇% by weight, preferably 3 to 40% by weight. The components (Α) and (Β) are contained in the antifouling coating composition or the antifouling coating film in the same amount, and the coating film prepared is a good adjustment of the hydrolysis rate of the contained component (Α) in the long term. Anti-fouling property, excellent anti-fouling performance in high-contamination sea area or in a static environment. Further, the total of the components (1) and the component (8) contained in the antifouling coating composition ((ah(b))igg parts by weight The compounding agent (1) for the antifouling coating is usually 0.01 to 90 parts by weight, preferably 0.1 to 75 parts by weight, and the total amount of the component (B) (nonvolatile portion) is a residual amount, that is, usually It is preferably from 1 9 to 99.99 parts by weight, preferably from 25 to 99 parts by weight, in terms of the stain resistance of the coating film, moderate coating film consuming properties, and coating film properties. 316720 80 1333947 If the composition of the antifouling coating contains such a component (1) and the component (8), since the storage stability of the crucible is good, and the coating film is not easily cracked, the hydrolysis speed of the coating is well controlled, and the antifouling property and Among the antifouling properties, it is excellent in antifouling property and long-term antifouling property in a fouling environment, and has an antifouling coating film having moderate hardness.

The antifouling coating composition of the present invention may further contain various additions, that is, the antifouling coating composition of the present invention, the above-mentioned antifouling (IV) compounding agent CA) and the above-mentioned self-abrasive antifouling coating copolymer. (8) Bamboo is an essential component 'In addition to the components (1) and (8), it may contain anti-fouling (C) (especially (C) copper and/or steel compounds, (2) organic antifouling agent), oxy zinc white, Dehydrating agent (8), drip prevention and sedimentation preventive agent's dissolution-promoting component (F), coloring, base pigment, and other pigments, propylene glycol-based tree, and polyalkylene-based test (vinyl Various additives such as plastics (H) such as (G), plasticizers such as chlorinated paraffin, defoamers, color preventive agents, leveling agents, and solvents, etc. [Anti-fouling agent (C)] The antifouling agent (C) may be either inorganic or organic, and may be widely used in the past. In the present invention, copper and/or copper compounds are particularly used. (C1 and organic antifouling agent (C2) are preferred. The antifouling coating of the present invention will be described below. The copper and/or copper compound (pyrithiQne) _, f organic copper compound contained in the product is the same as the f organic copper compound. The following is the same.) 316720 8] 1333947 The copper compound (C1) used in the present invention may be an inorganic copper compound. Any of the inorganic copper compounds may, for example, be cuprous oxide, copper thiocyanate (copper thiocyanate, copper rodone), basic copper sulfate, copper chloride, copper oxide, or the like. Preferably, cuprous oxide or copper thiocyanate (rhodan copper) is used. Such a copper compound may be used in place of copper or copper, or may be used in combination of two or more kinds. Copper and/or copper compound (C1) is used herein. The antifouling coating composition of the invention is usually contained in an amount of from 1 to 7 % by weight, preferably from 3 to 65 % by weight, based on 100% by weight. Further, the self-polishing type contained in the antifouling coating composition Antifouling coating. The copolymer (B) (nonvolatile portion), preferably 100 parts by weight relative to the decyl ester copolymer (B) (nonvolatile portion), the copper and/or copper compound (C1) is usually The total amount is preferably from 3 to 1400 parts by weight, preferably from 1 to 1300 parts by weight. When the copper and/or copper compound is contained in the composition of the antifouling paint in this range, the antifouling coating excellent in stain resistance can be formed. In the present invention, the organic antifouling agent (C2) can be used simultaneously. The copper and/or copper compound (ci) may also be substituted for the copper and/or copper compound (C1) as an antifouling agent. For the organic antifouling agent (C2), for example, a pyrithione or an organic copper compound may be used. Etc., especially the copper pyrithione type. Metal bismuth thiones can be exemplified by sodium pyridinium salts such as sodium, magnesium, calcium, barium, aluminum, copper, zinc, iron, lead, etc. Among the above metal pyrithiones, copper pyrithione and zinc pyrithione are preferred, and copper pyrithione is preferred. 316720 82 1333947 Organic copper compounds include, for example, copper acetate and oxygen-containing copper (〇▲ coppejO, copper nonylphenolsulfonate, bis(ethylenediamine)-bis(dodecylbenzenesulfonate) copper, nai至至重量重量优选优选优选优选的优选的优选的优选的优选的优选为为1. a ratio of 5 to 25% by weight. Further, the copolymer (8) (nonvolatile portion) of the self-polishing antifouling coating contained in the antifouling coating composition is preferably copolymerized with g| The amount of the organic antifouling agent is usually from 0.3 to 3 parts by weight, preferably from 2 to 2 parts by weight, based on 1 part by weight of the total amount of the organic antifouling agent. Further, the pyrithione-based compound and the following antifouling agent may be contained, or the following antifouling agent (other anti-drug agent) may be contained in place of the pyrithione-based compound. Various antifouling agents, specifically, for example, bis(dimethylthiocarbamate) disulfide (tetramethyl) Thiuram disulfide), carbamate-based compound (eg zinc monodecyldithiocarbamate, 2-extended ethyl bis(dithiocarbamic acid) manganese), 2, 4, 5, 6-four Chloroisophthalonitrile, N,N-didecyldiphenylphenylurea 2A &yl 4-secondbutylamine碁_6_cyclopropylamine碁_s_trimorphine, 4' 5-one gas- 2-n-octyl-4-isothiazoline-3-yl ketone, 2, 4, 6-trisylphenylmaleimide, pyridine-triphenylborane, amine-triphenylborane, etc. In the invention, the antifouling agent may be used in combination with two or more kinds of acridinethione compounds (metal pyrithione) such as zinc pyrithione copper pyrithione. For example, 'pyridylthione can be used. Copper and/or zinc pyrithione in combination with 4, 5-monox-2-n-octyl-4-isothiazolin-3-one. Further, the copper and/or contained in the antifouling coating composition Or the total content of various antifouling agents such as copper compound 316720 83 1333947 (Π) and organic antifouling agent (C2), and the antifouling agent and film forming property used for preparing the antifouling paint composition; Type or ship formed by coating these antifouling coating compositions The type (the sea navigation outside the ship - the use of the sea in the sea, the use of the sea, the wood, the steel, etc.), etc., and the co-polymer (B) (non-volatile part) of the self-polishing antifouling coating ( It is preferably 100 parts by weight of the decane-based copolymer (B) (nonvolatile portion), and the total amount of the antifouling agent is usually contained in an amount of up to 1400 parts by weight, preferably 20 to 1 300 parts by weight. When the total amount of the antifouling agent is within the above range, the cracking property is excellent and the stain resistance is excellent. 〃 For example, copper pyrithione and cuprous oxide (CU2〇) are used in combination as an anti-coating composition. In the antifouling coating composition, the copolymer (8) (non-volatile part) for the self-polishing antifouling coating in the antifouling coating composition (preferably the Shixiyuan vinegar-based copolymer (B) (not) Volatile portion)) 1 part by weight, copper pyrithione content of 2 to 200 parts by weight, for the same copolymer (B) (nonvolatile portion) 1 part by weight, the cuprous oxide The content is about 1 to 13 parts by weight. [Zinc Oxide (Zinc White) (〇)] The antifouling paint composition of the present invention may also contain zinc oxide (zinc white) (D). In combination with the anti-fouling coating composition of the zinc oxide, the strength of the obtained coating film is improved, and the polishing property of the coating film can be effectively controlled. Further, the content of the zinc oxide in the antifouling coating composition is usually from 至. 5 to 35 ϊ %, preferably from 1 to 25% by weight, from the viewpoint of consumption-degree adjustment and film hardness adjustment. . Further, the co-polymer (8) (non-volatile portion) (preferably a decyl ester-based copolymer (8) (non-volatile portion)) of the anti-fouling coating for the self-polishing 3] 6720 84 1333947 is used. The zinc oxide is usually contained in the antifouling paint composition in an amount of from 5 to 1200 parts by weight, preferably from 4 to 6 parts by weight, per part by weight. [Inorganic dehydrating agent (E)] The antifouling coating composition of the present invention may be blended with an inorganic or organic dehydrating agent J, preferably an inorganic dehydrating agent (inorganic dehydrating agent (8)). The antifouling coating composition with the dehydrating agent can improve the storage stability. The dehydrating agent 'specifically' may, for example, be anhydrous gypsum (CaS〇d, synthetic shale-based adsorbent (trade name: molecular sieve (m〇1 coffee! sz (four)), etc.), original formic acid methyl vinegar, orthoacetic acid methyl vinegar, etc. The original vinegar, the shackle acid cool, the Shixi acid vinegar and the purpose category (trade name: Adi Tib T1 (transliteration), etc., particularly preferably water gypsum, molecular sieve as an inorganic dehydrating agent (8). The dehydrating agent can be 1 Use of such a dehydrating agent, especially an inorganic dehydrating agent, for the above-mentioned autogenous grinding: a copolymer for coating (8) (non-volatile part) (preferably a thorough: paste (not Volatile portion)) (10) parts by weight, usually in combination with 2 parts to 2 parts by weight, preferably 0.2 to 50 parts by weight. ^ "This inorganic dehydrating agent" in the antifouling coating composition, wanted The content of the inorganic dehydrating agent having a negative dehydration property of 0.01 to 2% by weight, preferably from 〇" to 8% by weight, of the stain coating composition. The antifouling coating composition of the present invention may further contain a dissolution promoting component 316720 85 1333947 (F) (however, the above component (B) is not contained in Promoting component (F), such as rosin, rosin derivatives, organic carboxylic acids, and organic carboxylic acid metal salts, etc. rosin has gel rosin, wood rosin, high oil rosin (tall oil rosin), etc., any of them may be used in the present invention. The rosin derivatives may, for example, be heterogeneous rosin, low melting point uneven rosin, hydrogenated rosin, polymeric rosin, maleated turpentine, aldehyde modified rosin , polyoxyalkylene ester of rosin, reduced rosin (rosin alcohol), rosin metal salt (steel salt, zinc salt, salt, etc.), rosin amine, etc. The rosin and its derivatives may be one or a combination The organic acid retardation may, for example, be a fatty acid having a carbon number of about 5 to 30, a synthetic fatty acid or a naphthoic acid, and examples of the organic (tetra) metal salt include a Cu salt and a salt.

Mg salt, Ca salt, and the like. The organic acid metal salt can be used as an organic acid metal. It is also possible to use a salt of an organic rebel and a metal equivalent in an equivalence ratio or an equivalent ratio. These elution-promoting components may be used singly or in combination of two or more kinds.

When the coating composition contains such a dissolution promoting component, the antifouling coating is preferably contained in an amount of from 1 to 3 parts by weight, more preferably in parts by weight, more preferably in parts by weight. 5 to 15 parts by weight. From the coating film: 乂 1 inch water risk This view 'the ratio of the dissolution promoting component is suitable for the site.' Sr coating composition contains auto-grinding anti-fouling coating = non-volatile part Π is better The amount of the copolymerization component is a total amount of the elution-promoting component and is _part by weight, preferably 2 to 300 parts by weight. 316720 86 1333947 When the elution-promoting component is present in the antifouling coating composition in this range, it is excellent in stain resistance and coating film dissipating property. [Vinyl ether-based (co)polymer (G)] A vinyl ether-based (co)polymer having a vinyl ether component unit and improving the crack resistance, peeling resistance, and dissolution rate stability of the obtained coating film. It also acts as a coating film forming component. The above-mentioned vinyl ether-based (co)polymer, specifically, for example, a polyethylene-based test, a polyethylene ethyl-polyethylene isopropyl light, a dimethyl ether or the like can be exemplified. Hey. The vinyl ether-based (co)polymer (G) is preferably present in an amount of from 2 to 5 parts by weight based on the anti-fouling coating composition i 重量 by weight. The co-polymer (8) (non-volatile portion) of the self-polishing f antifouling coating contained in the antifouling coating composition is preferably one part by weight of the vinegar copolymer (B) (nonvolatile portion). Preferably, the dissolution promoting ingredient juice is contained in an amount of from 0.3 to 60 parts by weight, preferably from 6 to 4 parts by weight. When the vinyl ether-based (co)polymer is present in the composition in this range, it is excellent in stability of the leafiness of the vine. , · soil, in turtles, peeling resistance and dissolution rate γ use a variety of polymers containing hydrophilic groups to replace ethylene _ (4)

Li is either used in conjunction with a vinyl lanthanide (co)polymer. These include the same effects as (methoxy) polyethylene glycol mono(methyl) propylene di-Si, and the like each of the oxyalkyl) polyalkylene glycol mono(10)) propylene fosphate polymers. ~ and ethane (total) 316720 87 1333947 [plasticizer ου] The plasticizer is orthophosphate, gasified paraffin, titanate, adipate, etc. Usually, a plasticizer for coatings can be used. These plasticizers can be used in combination of the above. When the plasticizer is blended with the plasticizer, the plasticizer is blended in the antifouling paint composition in an amount of, for example, G.1 to 1 G% by weight. 〇*These plasticizers can improve the crack resistance of the cold pancreas (also referred to as the antifouling coating film in the present specification) formed by the obtained antifouling coating composition, and use the gas fossil mouse in the plastic rut Or squamous acid vinegar (D (8) and other scallops δ ～ 0 - the weathered stone can be linear or divergent, liquid at room temperature ^ can be solid (powder > chlorinated stone Sacrifice can be cited by Dongsuo (10) Qing Company: "East Paras 150" and "East Parass _7〇" #. The present invention makes it possible to appropriately combine and use such gas-vaporized waxes having different gas contents and carbon numbers. • ion 2) Plasticizer When using such vaporized paraffin, it is usually necessary to contain U5 to 20 parts by weight, preferably 〇··15 parts by weight, in the reset f of the antifouling coating composition. The self-polishing coating material polymer (8) (non-volatile portion) contained in the antifouling coating composition is preferably one part by weight of the "non-volatile portion of the material", and the chlorinated butterfly is preferably contained; M weight A, &amp; good 2 to 4G parts by weight. And the chlorinated stone soil in the ^ dry circumference k 'coat film crack inhibition effect, film strength and resistance to damage (rush And (H) the plasticizer is used in the amount of 0.05 to 20 parts by weight, preferably 〇1 to 15 parts by weight, in the anti-fouling coating composition 316720 88 1333947 100 parts by weight. The copolymer (8) (non-volatile portion) of the auto-polishing antifouling coating contained in the antifouling coating composition is preferably a material containing a component unit derived from the polymerizable unsaturated acid sand (4) (4) 100 parts by weight of the polymer (nonvolatile portion), the orthophosphate preferably contains 丨 to 5 parts by weight, preferably 2 to 40 parts by weight. When orthophosphate is contained as the plasticizer (H), It is possible to accelerate the coating film and to reduce the consumability of the coating film. / <Other components> The antifouling coating composition of the present invention may contain a drip prevention, a precipitation preventive agent, and a coloring pigment in addition to the above components. Various pigments such as a base pigment, an acrylic resin other than the above-mentioned vinyl ether (co)polymer, and the like, and various additives such as a resin, an antifoaming agent, a color separation preventing agent, and a leveling agent are as follows. Drip prevention • Shen; Temple preventive agent]

The drip prevention and precipitation inhibitor can be blended in an arbitrary amount to a known person. Examples of such drip prevention and precipitation inhibitors include salts such as stearates of A1, Ca, and Zn, salts of lecithin salts and alkyl sulfonates, and polyethylene waxes. Hydrogenated castor oil (cast〇r 〇il) wax music, polyamidamine wax system and a mixture of the two, synthetic fine powder cerium oxide, oxidized polyethylenic wax, etc., preferably using hydrogenated castor oil wax system, synthetic fine powder Oxide oxide, oxidized polyethylene wax. Such dripping prevention and precipitation preventing agents are exemplified by the product name "DISPARL0N 89 316720 1333947 A-603-20X" and "DISPARLON 4200-20, 箄 f·古" inch Φ. [Pigment, solvent] The pigment can be used in the well-known organic system, helmet ((4) white, red iron oxide, organic red color; pigments also include various coloring agents such as dyes. Temple). Further, the crack resistance of the film in which the form of the pigment is needle-like, flat, or scaly can be further increased. The solvent can be blended with, for example, an aliphatic system, an aromatic system (for example: = ), a lanthanide system, a system I, a laboratory, etc., which are generally used in antifouling coatings. The solvent contained in the substance may be used to prepare a solvent which can be used in the polymerization of the above polymerizable unsaturated (tetra) metal compound. σ [Various Resins] Examples of various resins include acrylic acid (ugly) conjugates, acrylic vinegar (co)polymers, and mercaptoacrylic acid (co)polymers 1 lenone (co)polymers. 2-hydroxyethyl acrylate (co)polymer diacid resin. Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The ^ ^ / 7^i Qq 斤 'C total) polymer disclosed in the Gazette 'Special Note 〇 〇 〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 ( ( ( ( ( ( ~ ~ 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 In the antifouling coating composition of the present invention. [Production of Antifouling Coating Composition] The antifouling coating composition of the present invention can be suitably produced by a conventionally known method of 316720 90 1333947, for example, a compounding agent (A) for an antifouling coating, and an autogenous grinding type antifouling coating. Copolymer (B), and optionally antifouling agent (c) (especially (C1) copper and / or copper compound, (C2) organic antifouling agent, etc.), (])) zinc oxide, (E Dehydrating agent (for example: anhydrite, molecule _), (趵 dissolution promoting component, (g) vinyl ether (co)polymer, (Η) plasticizer, dripping prevention, precipitation inhibitor, pigment, solvent, etc. 'Add or dispose, mix, disperse, etc. together or in any order. The anti-fouling coating composition is a liquid-like one, and it satisfies the adhesion, durability, and anti-fouling of anti-fouling coatings. All kinds of properties require performance. r The above anti-fouling coating composition, in water, water structures (also known as marine structures) (such as atomic power plant water supply and drainage B), Gulf Coast roads, submarine tracks, riding equipment , canals, water materials, various materials, civil engineering, etc. For the surface of various shaped ItL substrates such as ships and fishing gears (9) such as ropes and fishing nets, the coatings are coated and hardened one to several times, and the two-cracking and anti-fouling coatings are coated with antifouling coatings. Or the sea ocean and H reading composition can be directly applied to the surface of the ship or the substrate 2, or can be applied to the surface of the ship or marine structure which is first made of rust inhibitor, primer or the like. In addition, the anti-fouling coating (4) of the present invention may be coated by self-use of the anti-fouling coating of the present invention by coating the coating with the conventional coating or by using the antifouling coating composition of the present invention. On it. There is no particular limitation on the resistance of the ship to the surface of the ship and the surface of the marine structure. For example, [the effect of the invention] 316720 91 The fouling hydrolysis rate according to the present invention is good control and resistance. Excellent in sex and long-term antifouling'The coating film is not easily cracked and has moderateness: ΐ2: = anti-fouling coating film with excellent balance of properties and storage stability. The coating is also provided with a coating film having such excellent characteristics and a ship or underwater structure 'fishing gear or fishing net with the coating film. Further, the invention provides an antifouling method which uses such antifouling coatings with little possibility. [Embodiment] [The invention] The present invention is not limited by the following description, and the present invention is more specifically described by way of examples. In addition, in the following examples, comparative examples, and the like, "parts" means weight. The measurement conditions of IR and MS are as follows. &lt;IR measurement conditions> Perkins

One. "FT-IR" Spectrum method manufactured by Perkin-Elmer: neat method, using KBr plate. Measurement conditions &gt; "5973MSD" manufactured by Agilent. Determination method: EI method. <Production of cyclopentadiene from thermal decomposition of dicyclopentadiene> In a reaction vessel equipped with a stirrer, a dehydrator and a condenser, and a heating and cooling jacket 316720 92 1333947 (jacket), a bicyclodequinone is placed. 600 parts of a olefin was heated and stirred at 160 to 170 ° C for 8 hours to obtain 400 parts of cyclopentadiene. [Production Example of Compounding Agent for Antifouling Coatings] <Manufacture of Compounding Agent (AD-1) for Antifouling Coatings> Acrylic acid (AA) is placed in a reaction vessel equipped with a stirrer, a condenser, and a heating and cooling jacket. 720 copies, from 25t to 35. (: 660 parts of cyclopentadiene (CPD) was dropped with stirring for 2 hours. After the dropwise addition, the mixture was stirred at room temperature for 2 hours to obtain a GC (gas chromatography) 93% purity antifouling coating compounding agent (AD). -1) ° The IR spectrum of the compounding agent for antifouling paint (AD-1) is shown in Fig. 1. The compounding agent for antifouling paint (AD-1) is equivalent to the ring rebellion as shown in the above formula (1). The acid "Compound A-1" is the aforementioned mixture of isomers.

Compound (A-1)

<Manufacture of compounding agent for antifouling paint (AD-2)> In a reaction container equipped with a mixer, a condenser, and a heating and cooling jacket, the compounding agent for the antifouling coating is placed.

Activated white clay of acid catalyst 2. 7 parts, heated and stirred at 70 ° C for 40 minutes, made 93 316720 1333947 to obtain a compound with anti-fouling coating of brown solid with a molecular weight of about 1 600 [AD-2 :

The polyester monocarboxylic acid produced by the self-addition of Michael addition in the presence of an acid catalyst (AD-1). The IR spectrum of the antifouling coating compound (AD-2) is shown in Fig. 2 <Manufacture of compounding agent for antifouling coating (AD-3)> It is equipped with a mixer, a condenser, and a heating and cooling jacket. In the reaction capacity, 860 parts of thioglycolic acid (MAA) and 792 parts of cyclopentaphene were placed, and 4 (TC was heated and stirred for 24 hours to obtain a GC (gas chromatography) purity 80% antifouling coating. Agent [AD-3(A-2)]:

The IR spectrum of the compounding agent for antifouling coating (AD-3) is shown in Fig. 3, and the MS spectrum is shown in Fig. 4. The compounding agent for antifouling paint (AD-3) corresponds to the cyclic carboxylic acid "Compound A-2" represented by the above formula (2), and is the above-mentioned mixture of isomers. Further, the mixture can obtain an IR spectrum with reproducible reproducibility. <Manufacture of compounding agent for antifouling paint (AD-4)> 316720 94 1333947 960 parts of all lo-ocimene in the reaction capacity equipped with a mixer, condenser and heating and cooling jacket 525 parts of thiol-propanoid acid and 0.5 parts of hydroquinone monomethyl ether were stirred at 401 for 24 hours. Thereafter, the unreacted raw materials were distilled off under reduced pressure to obtain 220 parts of a compounding agent (AD-4) for an antifouling paint in the form of a brown viscous liquid. The IR spectrum of the compounding agent for antifouling coating (AD-4) is shown in Fig. 5. The compounding agent for antifouling paint (AD-4) corresponds to the above formula (3) (that is, the cyclic carboxylic acid "compound a-3" represented by the following formula (3):

Compound A-3a (Mw: 222) 3 Compound A-3b (Mw: 222) is a mixture of the above-mentioned isomers. &lt;Production of Compounding Agent for Antifouling Coatings (AD-5)> 1016 parts of alio-〇cimene were placed in a reaction vessel equipped with a mixer, a condenser, and a heating and cooling jacket. 540 parts of acrylic acid, activated clay, 9 parts and hydroquinone monomethyl ether 1. 〇 parts, heated and stirred at 90 ° C for 24 hours, the reaction is finished. Thereafter, the object was purified by distillation under reduced pressure (160 to 170 ° C / 2 mmHg) to obtain 1 055 parts of a compound (AD-5) for a yellow transparent liquid antifouling paint. Thereafter, the antifouling coating was cured by a compounding agent (AD-5) at room temperature and 95 316720 1333947.

The melting point of the compounding agent (AD-5) for crystallization of the antifouling coating is determined by DSC to be 58 ° C. The IR spectrum of the compounding agent for antifouling coating (AD-5) is shown in Fig. 6 and its MS spectrum is shown. Shown in Figure 7. The compounding agent for antifouling paint (AD-5) corresponds to the cyclic carboxylic acid "Compound A-3" represented by the above formula (3), and is the above-mentioned mixture of isomers. <Manufacture of compounding agent for antifouling paint (AD-6)> In a reaction vessel equipped with a stirrer, a condenser, and a heating and cooling jacket, 1 030 parts of myrcene and 470 parts of methacrylic acid were placed. 5 parts of hydroquinone monodecyl ether and heating and stirring at 90 ° C for 8 hours to complete the reaction. Thereafter, the unreacted raw materials were distilled off under reduced pressure to obtain 890 parts of a compound (AD-6) for an antifouling paint in the form of a brown viscous liquid. The IR spectrum of the compounding agent for antifouling paint (AD-6) is shown in Fig. 8. The compounding agent for antifouling paint (AD-6) corresponds to the cyclic carboxylic acid "Compound A-5" represented by the above formula (5) (that is, the following formula (5)):

96 316720 1333947 is the aforementioned mixture of isomers. <Manufacture of compounding agent for antifouling paint (AD-7)> 1070 parts of my rcene, methacrylic acid 506, placed in a reaction medium equipped with a mixer, a condenser, and a heating and cooling jacket. A portion, 0.9 parts of activated clay and 1. hydrazine monohydrocarbyl ether were stirred and heated at 9 Torr for 16 hours to complete the reaction. Thereafter, the object was purified by distillation under reduced pressure (yield: 6 〇 to 17 〇t &gt; c /2 mmHg) to obtain 861 parts of a compounding agent (AD-7) for a yellow transparent liquid antifouling paint. The IR spectrum of the antifouling coating compound (AD-7) is shown in Fig. 9, and the MS spectrum is shown in Fig. 1. The compounding agent for antifouling paint (AD-7) corresponds to the cyclic carboxylic acid "Compound A-5" represented by the above formula (5), and is the above-mentioned mixture of isomers. <Manufacture of compounding agent for antifouling paint (AD-8)> In the reaction vessel equipped with a mixer, a condenser, and a heating and cooling jacket, 953 parts of all l〇-ocimene were placed, Malay 867 parts of monomethyl sulphate and 1 part of hydroquinone monodecyl ether were used in 4 〇. (: The mixture was heated and stirred for 24 hours to complete the reaction. Thereafter, the unreacted raw material was distilled off under reduced pressure to obtain 1450 parts of a compounding agent (AD-8) for an antifouling paint in the form of a yellow transparent viscous liquid. The IR spectrum of AD-8 is shown in Fig. 11. The MS spectrum is shown in Fig. 12. The compounding agent for antifouling paint (AD-8) corresponds to the cyclic carboxylic acid represented by the following formula (8). Isomer mixture 97 316720 1333947 Belulene

_&lt;Production Example of Copolymer] <Production of Copolymer (S-1)> In a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction tube, and a heating and cooling jacket, 100 parts of toluene was heated and stirred under a nitrogen stream at a temperature of 85 ° C. While maintaining the same temperature, in the reaction vessel, 50 parts of triisopropyl acrylate, 50 parts of hydrazino acrylate, and 50 parts of polymerization initiator 2, 2 were dropped from the dropping device by a dropping device for 2 hours. A mixture of 1 - azobisisobutyronitrile. After stirring for 4 hours at the same temperature, 0. 4 parts of 2,2'-azobisisobutyronitrile was added, and the mixture was stirred at the same temperature for 4 hours to obtain a colorless transparent copolymer (S-1) solution. . The weight of the copolymer (S-1) obtained by heating (the residual amount of heating after drying for 3 hours in a hot air dryer at 105 ° C) is 51. 2 weight ° / 〇, viscosity at 25 ° C For 408 cps, the number average molecular weight (?n) determined by GPC was 6618, and the weight average molecular weight (Mw) was 19434. The measurement conditions of GPC are as follows. [GPC measurement conditions] 98 316720 1333947 Apparatus: HLC-8120GPC manufactured by Tosoh Corporation. Pipe column: Super H2000+H4000 manufactured by Tosoh Corporation. 6mm, I. D. 15cm ° Dissolution: T H F (tetrahydrofurfuran).

Flow rate: 0. 50 Om 1 / mi n. / ‘ J detector: RI. Column temperature bath temperature: 40 ° C. , <Production of Copolymer (S-2) to Co-polymer (S-8)> &gt; In the production of the above-mentioned copolymer (S-1), in addition to changing the copolymerization according to Table 1, The copolymer (S-2) to the copolymer (S-8) was polymerized in the same manner as above except for the monomer-containing component, and the properties (physical properties) of the copolymer (solution) were measured in the same manner as above. The results are combined and shown in Table 1. <Production of Copolymer (S-9)> (Manufacturing procedure of monomer (K-1)) Propylene glycol is placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a heating, and a cooling jacket. 85.4 parts of monodecyl ether (solvent) and 40. 7 parts of zinc oxide were heated to 75 ° C with stirring. Then, a mixture of 4 parts of hydrazino acrylate, 36.1 parts of acrylic acid, and 5.0 parts of water was added dropwise from the dropping device at a temperature of 3 hours. After further stirring at the same temperature for 2 hours, 30.0 parts of propylene glycol monodecyl ether was added to complete the reaction to obtain a monomer solution (K-1). (Manufacture of copolymer S-9) propylene glycol monodecyl ether is placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen guide 99 316720 1333947 into a tube, and a heating and cooling jacket. , , - 曱 57 57 · 0 parts and 4 parts of ethyl acrylate, under nitrogen flow y, 10 (heating and stirring under the temperature of TC. Maintain the same temperature, within the reaction capacity) by a drop device dripping a 6-hour period a acrylonitrile-based styrene acetophenone 66. 2 parts, a 2-methoxy ethoxy acrylate group of 5.4 parts, a monomer solution (κ_1) prepared by the above production example, 52 parts of diphenylbenzene 2, 2,-azobisisobutanin 2,5,2,2,-azobisindenyl butyronitrile a mixture of 7 parts, after which a mixture of tert-butyl peroctoate (peroctoate) and 7 parts of xylene was dropped during 30 minutes, and then heated and stirred at the same temperature for 1 hour and 30 minutes. Adding 4 parts of diphenylbenzene to prepare a pale yellow transparent copolymer (S-9) solution. The heating residual amount of the obtained copolymer (S-9) solution ( 1〇5. In the hot air dryer, the remaining amount of heating after drying for 3 hours is 45.6 wt%, and the Gardner viscosity at 25 C is γ. (Also, the copolymer adsorbs on the official In the column, the copolymer cannot be accurately molecularly determined by Gpc.) [Preparation Example of Antifouling Coating Composition] (Examples 1 to 24, Comparative Examples 1 to 7) The composition shown in Tables 2 to 4 The compounding component 'is placed in a paint shaker using glass beads as a medium (mixed dispersion medium), and after 2 hours, it is filtered by a loo mesh filter to obtain a desired antifouling property. Coating composition. The storage stability of the antifouling coating composition after storage for 2 months at room temperature was evaluated by 〇〇316720 1333947. The evaluation results are shown in Tables 2 to 4. Storage stability and storage stability Evaluation, the viscosity of the coating (anti-fouling coating composition), the viscosity of the garment, and the viscosity after storage for 2 months (the Ku value of 25 ° C measured by the stormer viscosimeter), For comparison, the increase is based on the following Benchmark evaluation (Evaluation criteria) 5. The increase in viscosity is less than 1〇4. The increase in viscosity is 1 〇 or more and 2 〇 or less 3. The increase in viscosity is 2〇 or more and 30 or less 2: The increase in viscosity is 3〇 or more Ϊ : None The fluidity, the inability to measure the Ku value, and the evaluation of the static stain resistance, the degree of consumption, and the state of the coating film of the coating film using the antifouling coating composition were as follows. I The results are shown in Table 2 to Table. 4. (Standing anti-fouling test) After sandblasting (sandblast;) steel plate with a size of 100 mm &gt;&lt; 300 mm x 2 mm (thickness), after coating the epoxy-based zinc-rich primer with a dry film thickness of 20 μm, The modified epoxy-based anticorrosive coating was applied with a dry film thickness of 200 μηι, and the test antifouling coating composition shown in Table 2 to Table 4 above was coated with a dry film thickness of ΜΟμηι every other day to prepare a test plate. . From the test raft set up in Nagasaki Bay, Japan, the test panel is suspended at a depth of about lm. 'After 24 months, the micro organism (sma) is evaluated! 】 〇] 3] 6720 1333947 Serpula, etc. ) Attached to the test creatures) (Barnaus, test plate area. (Evaluation criteria) 5 : Not attached 4 : Less than 5% of adhesion 3 : 5% or more and 15% or less of adhesion 2 : 15% or more and 40% or less Attachment 1: Attachment of 40% or more (Evaluation of film consumption and film state) (曱) Evaluation of film consumption in a disc-shaped sandblasted steel plate with a diameter of 300 mm and a thickness of 3 mm, with a dry film thickness of 20 μm After applying epoxy-based zinc-rich primer, dry the next day:

After the film thickness was 20 Ομπι, the epoxy-based anticorrosive coating was applied and dried in the room for 7 days. After L, a test plate was prepared by radially coating a radial anti-fouling coating composition in the radial direction of the center of the circle of the disc-shaped sandblasted steel plate using a coater having a gap of 500 μm. (In addition, the coater is substantially a box-shaped container having a foot length (gap) of 500 ,, and a paint outlet is provided at the bottom of the container, and the S is placed on the steel plate to be coated, and the paint is stored. The coating device is moved in a set direction on the steel sheet, and the coating material can be coated with a thickness corresponding to the gap when the paint flows out from the outlet B. The test « was set on the motor, and was continuously rotated for 2 months at a peripheral speed of 15 knots (sea knot/hour) in a thermostatic bath in which the sea was hung, and the degree of consumption near the circumference (reduction in film thickness) was measured. 316720 】 02 1333947 (Evaluation Criteria) 5 : Confirmation of no abnormality in the coating film 4 : Confirmation of slight cracks in the part 3 : Confirm that there are fine cracks in the whole 2 : Confirm that there are obvious cracks in the part 1 : Confirm that all the turtles are obvious The compound name and the manufacturing and selling unit of the compounding component indicated by the trade name or the like used in the following table are as follows. Difficult (1) "WW rosin": Chinese-made turpentine (2) High-oil turpentine: trade name "HATALL r-X" (Hirima Chemical Co., Ltd.) (3) Rodin Copper: Sakamoto Chemical Industry Co., Ltd. (4) "Anhydrous Gypsum Dl": manufactured by Noritake Co., Ltd., II iCaSCh, white powder, average particle size 15μιη (5) "DISPARLON 4200-20": oxidized polyethylene oxide, Nanben Huayu Company's '2〇% dioxin benzene paste (6) "DISPARLON Α 630-20 Χ": Aliphatic guanamine soil, made by Nanben Chemical Company, 20% diterpene benzene paste. 1333947 ool 5

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Table 2 Examples of compounding ingredients (represented by S) 1 2 3 4 5 6 7 8 9 10 rs-1 \ 22 S-2 } 16 Solution S-3/ 22 18 22 18 22 22 22 22 W S-5 V S -6 i&gt; S-7 S-8 S-9 anti-fouling AD-1 2 coating AB=2. 5 with AD-31 2 4 mixture AD-4i 2 4 2 AD-5 2 AD-6 2 η AD- 7 2 WW turpentine high oil turpentine gasified cuprous 45 45 45 45 45 45 45 45 45 45 anti-pyridine thiol-1- - copper oxide built '3 3 3 3 3 3 3 3 3 3 dirt 4, 5 -diqi-2-n-octyl-isothiazole #-3-ketone 2, 4, 5, 6-tetraisomeric nitrile L 2-methylthio-4-t-butylamine true &gt;-6- Cyclopropyl tombstone tomb _ S-tripa N-(2,4,6-three-infant base) Maleidinide D-pyridyl-triphenylborane Rodin copper-titanium white 2 2 2 2 2 2 2 2 2 2 iron oxide red anhydrous sarcophagus D-1 1 1 1 1 1 1 1 1 1 1 zinc white 6 6 6 6 6 6 6 6 6 6 talc DISPARL ON 4200-20 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 DISPARLON A603-20X 4 4 4 4 4 4 4 4 4 4 Dimethyl 13.5 16.5 13.5 15.5 13.5 15.5 13.5 13.5 13.5 13.5 Total 100 100 100 100 100 100 100 100 100 100 Evaluation of storage stability 5 5 5 5 5 5 5 5 5 5 Result Antifouling 4 4 4 5 5 5 5 5 5 5 Consumption 8 9 11 15 12 16 15 16 13 15 Flag state 5 5 5 4 5 5 5 5 5 5 105 316720 1333947

Table 3 Compatibilities. (Parts by weight) Example 11 12 13 14 15 16 17 18 19 20 Copolymer solution S-1 18 S-2 S-3 S-4 18 S-5 22 18 22 S-6 22 S-7 22 S-8 22 18 S-9 35 Formulation for antifouling coating AD-1 AD - 2 AD-3 AD-4 AD-5 2 2 4 Z 2 4 4 AD-6 2 4 AD-7 2 WW Songyue 1 high oil turpentine antifouling agent vaporized cuprous 45 45 45 45 45 45 45 45 45 45 2-pyridine thiol-1-' copper oxide salt 3 3 3 3 3 3 3 4, 5-two gas - 2-n-octyl-isothiazol-3-one 3 3 2, 4, 5, 6-tetrachloroiso-5 2-methylthio-4-indanetriamine-6-cyclopropylamino- S-three tillage N-(2,4,6-three gas stupid) maleic imine pyridine-triphenyl borane dithiocyanate copper titanium dioxide 2 2 2 2 2 2 2 2 2 2 iron oxide red Anhydrous stone bone D-1 1 1 1 1 1 1 1 1 1 1 Zinc white 6 6 6 6 6 6 6 6 6 6 Talc DJSPARLON 42 00-20 1.5 1.5 1.5 1.5 1.5 1,5 1.5 1.5 1.5 1.5 DISPARLON A603-20X 4 4 4 4 4 4 4 4 4 4 Dimethyl 0.5 13.5 15.5 13.5 13.6 13.5 13.5 15.5 15.5 13.5 Total 100 100 100 100 100 100 100 100 100 100 Evaluation results Storage stability 5 5 5 5 5 5 5 5 5 5 Antifouling property 4 5 5 5 5 5 5 5 5 5 浈 Consumption 31 20 28 19 18 17 25 30 10 18 Coating state · 5 5 5 5 5 5 5 5 5 5 106 316720 1333947

Table 4 Heterogeneous application examples [injury indication] 21 22 23 24 1 2 3 4 5 6 7 Copolymer solution S-1 26 • 26 S^3 26 22 22 22 S-5 22 30 S=6 1= 7 18 S=8 40 35 Formulation agent for antifouling paint AD1! AD-2 — ~~ AD^ AI&gt;4 AD-5 2 6 2 AD-6 AD-7 — 4 (4) Rosin 2 2 High oil turpentine. 2 Resistance Sulphur oxide molybdenum 45 45 50 45 45 45 45 45 40 40 t pyridine thiol-1- bismuth copper salt 1 3 3 3 3 3 dicyan-2-oxoyl-isothiazole €-3-玥2 3 3 2, 4, 5, 6-tetraazaisophthalonitrile 2-methylthio-4-third cavyl-6-cyclopropylamino-S-three tillage 5 m 4,6-three gas stupid ) maleimide 5 pyridine-tridecylborane 5 copper disulfide 15 titanium white 2 2 2 1 2 2 2 2 2 2 2 gasified iron red 2 1 anhydrous stone bone D-1 1 1 1 1 1 1 1 1 1 Zinc White 6 6 6 6 6 6 6 6 6 6 Talc 2 DISPARLON 4200-20 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 DISPARLON A603-20X 4 4 4 4 4 ά 4 4 4 4 4 Dimethyl hydrazine 13.5 11.5 25.5 U.5 11.5 11.5 11.5 13.5 13.5 3.5 6.5 Total 100 100 100 100 100 100 100 100 100 100 100 Evaluation results Storage stability 5 5 5 5 5 5 5 5 5 5 5 Anti-fouling 5 5 5 5 1 1 1 3 2 1 2 Consumption 25 18 39 14 4 5 5 7 6 17 20 Coating state 5 5 5 5 5 5 5 4 3 5 5 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a compounding agent (AD-1) for an antifouling paint used in an example or a comparative example of the present invention. IR spectrum. 〇7 316720 1333947 Fig. 2 is a view showing an IR spectrum of a compounding agent (AD-2) for an antifouling coating used in Examples of the present invention or a comparative example. Fig. 3 is a chart showing the IR spectrum of the compounding agent for antifouling coating (AD-3) used in the examples of the invention or the comparative examples. Fig. 4 is a view showing the MS spectrum of the compounding agent for antifouling coating (AD-3) used in the examples of the invention or the comparative examples. The fifth graph is not an IR spectrum of the compounding agent for antifouling coating (AD-4) used in the known examples or comparative examples of the present invention. Fig. 6 is a chart showing the composition of the compound for antifouling coatings (AD-5, Compound A-3) used in the examples or comparative examples of the present invention. Fig. 7 is a chart showing the enthalpy spectrum of the compounding agent for antifouling coatings (AD-5, compound^3) used in the examples or comparative examples of the present invention. Fig. 8 is a view showing an IR spectrum of a compounding agent (AD-6) for an antifouling coating according to an embodiment of the present invention or a comparative use. Fig. 9 is a chart showing the IR spectrum of the compounding agent for antifouling coating (AD-7) used in the examples or comparative examples of the present invention. Fig. 10 is a view showing the MS spectrum of the compounding agent for antifouling paint (AD-7) used in the examples or comparative examples of the present invention. Fig. 11 is a chart showing the IR spectrum of the compounding agent for antifouling paint (AD-8) used in the examples of the invention or the comparative examples. Fig. 12 is a view showing the MS spectrum of the compounding agent for antifouling paint (AD-8) used in the examples or comparative examples of the present invention. [Main component symbol description] There is no component symbol in this case. 316720 108

Claims (1)

j^3947 Patent Application No. 94102858, Patent Application Range·· 告 ' 1.~ A compounding agent for antifouling coatings, which is a dicycloolefin represented by the following formula: [VI] Any one or more of a carboxylic acid or a salt thereof: (COO)mR^ (cooyi8 CV] {in the formula [v], R1 represents a hydrogen atom, a 3-methyl-2-butenyl group or a 2_ τ-propenyl group, and when R represents a hydrogen atom, R2 represents 4_曱. The base _3_penta R represents a hydrogen atom, when the methyl group is not a 3-methyl-2-butenyl group, the methyl group of the R2 is a methyl group, and the ring metal of R3 represents a hydrogen atom, 1^Table 7^2-methyl group + propyl group R2 represents a hydrogen atom, R3, κ represents a methyl group; R and R respectively represent a hydrogen atom or an alkyl group having a carbon number of 1 to 丨0; :, n: not a number of 0 or 1 (only when 'm, n are different) 〇); represents a hydrogen atom or a hydrocarbon group; respectively, when M is 〇, 'R7 is a hydrogen atom, when 10 is 1, R7 is a hydrogen atom or a hydrocarbon group, and when R is a zero, R8 is a ruthenium atom. , (Revised) 316720 109 1333947 Patent No. 941〇2858 (August 8, 1999) 'R8 is a hydrogen atom or a base (only 'R7, R8 are not the same In the formula "1", any of 'RUj y6 represents an isopropyl group, and when &lt;A&gt; R is an isopropyl group, when η is 1 a hydrocarbon group); • » · « [VI R , R13 represents a hydrogen atom, Rl4 represents a fluorenyl group, and ^ R represents a hydrogen atom or a carbon number of 1 to 1 Å, respectively, and the knives 18 are not 〇 or 1 (only 'm, n is not 〇), and R represents a hydrogen atom or Hydrocarbyl group, k, 1 is 0, R21, R2° represent a hydrogen atom, and i R represents a hydrogen atom or an alkyl group having a carbon number of (7), respectively. When m is 0, R17 is a hydrogen atom, and m is 1 k ' Ri7 Is a hydrogen atom or a nicotine group, when the above is..., IT is a hydrogen atom, when η is 1, when p丨8 is a hydrocarbon group); 4 is a wind atom or a nicotine group (only, R17 and R18 are different &lt;β&gt; R is isopropyl (Revised) 316720 110 1333947 Patent Application No. 94102858 (March 8, 1999) R, R12矣-Production K is not a hydrogen atom Rl3 represents a methyl group, R represents a hydrogen atom, and R represents hydrogen. An atom or an alkyl group having a carbon number of 1 to 10, m and η respectively represent 〇, and R and R18 represent a hydrogen atom, ^1 is not denoted by 〇 or 1 (except that k and 1 are not 〇 at the same time), R and R respectively represent a hydrogen atom or a hydrocarbon group, and R and R22 respectively represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. When k is 〇, it is a hydrogen atom, and when k is 1, 'R19 is a hydrogen atom or a hydrocarbon group. When 1 is 0, f is a hydrogen atom, and when 1 is 1, 'R2° is a hydrogen atom or a hydrocarbon group. 19 and R2. They are not simultaneously a hydrocarbon group)}. 2. The compounding agent for antifouling paint according to item 1 of the patent application, wherein the ring ketone acid represented by the formula _ [V] is represented by the following formula [Va], [Vb], [Vc] or [Vd] (Only 'omitting the hydrogen atoms bonded to carbon atoms in various formulas'): (Revised) 316720 111 1333947 Patent Application No. 94102858 (March 8, 9 September) 3. An antifouling coating composition comprising: (A) a compounding agent for antifouling coatings according to claim 1 or 2, and a copolymer of bismuth (B) self-grinding antifouling coating . 4. The antifouling coating composition of claim 3, which additionally contains the antifouling agent (C). 5. A composition for an antifouling coating according to item 4 of the patent application, which contains copper or a copper compound (C1) as an antifouling agent (C). 6. The antifouling coating composition of claim 4, which contains the organic antifouling agent (C2) as the antifouling agent (C) (except for copper or copper compounds (C1)). 7. The antifouling coating composition of claim 5, which contains an organic antifouling agent (2) (only copper) as an antifouling agent (C) of the patent application No. 94, 720, pp. Or steel; [: except for the month 8 a). • The anti-fouling coating composition of any of items 3 to 7 of the patent application of the patent. The co-polymer (8) for the auto-grinding type anti-material coating is a polymerizable unsaturated carboxylic acid hydroxymetalate-based copolymer. 9. The antifouling coating composition of claim 8 wherein the self-grinding antifouling coating copolymer (B) is a polymerizable unsaturated citric acid having no molecular weight in the molecule. a copolymer of a single W group derived from a base metal ruthenium ·· f-COO-M-OH.........[ I ] {Form [Π, R1 is CH2=C(CH 〇-, CH2=CH-, H00C-CH=CH-, h〇〇c-ch=c(10)3)_ represents an organic group containing an unsaturated bond, _c_ may also form a metal salt or ester, and Μ represents a metal atom} . 10. The antifouling coating composition of claim 9, wherein the self-grinding antifouling coating co-polymer (Β) has a molecular (metal)-acrylic acid-containing metal salt A copolymer of derived constituent units. Soil 11_, as in the anti-fouling coating composition of claim 10, wherein the self-polymerized anti-fouling coating copolymer (β) has a hydroxyzinc salt of /methyl) acrylate in the molecule or A copolymer of constituent units derived from a copper salt. 12. The antifouling coating composition according to any one of claims 3 to 7, wherein the self-grinding antifouling coating copolymer (β) contains: no bond to the metal atom Polymeric Unsaturated Metallic Compounds Derived from Metallic Compounds Polymeric Unsaturated Citrate Metals (Revised) 316720 113 1333947 Patent Application No. 94102858 • (March 8, 1999) Compound System Copolymer . 13. The antifouling coating composition according to claim 2, wherein the self-polymerizing antifouling coating copolymer (B) has a polymerizable unsaturated carboxylic acid represented by the formula [11] in the molecule. The copolymer type of the component unit derived from the acid hydroxy metal compound: f-COO-M-Ln... (II) {In the formula [11], R1 is CH2=C(CH3)- , CH2=CH-, H00C-CH=CH-, H00C-CH=C(CH3)- represents an organic group containing an unsaturated bond, -C00H can also form a metal salt or ester, Μ represents a metal atom, and l represents The organic acid residue "-0C0R2" (R2 represents an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group or an aralkyl group which may have a substituent), and η represents the number of valences of the metal ruthenium}. 14. The antifouling coating composition of claim 13, wherein the self-grinding antifouling coating co-polymer (Β) has a hydroxyl group in the molecule which is not bonded to a metal atom. a copolymer of constituent units derived from a metal acrylate compound. 15. The antifouling coating composition of claim 14, wherein the self-grinding antifouling coating co-polymer (Β) has a matrix in which no bond to zinc or copper atoms is contained in the molecule. a copolymer of constituent units derived from a zinc (meth) acrylate or a copper salt. 16. The antifouling coating composition of claim 15, wherein the self-grinding antifouling coating copolymer (Β) is a polymerizable unsaturated acid-lowering metal salt copolymer, the polymerizable unsaturated The metal carboxylate copolymer is a copolymer of a (meth)acrylic acid salt or a copper salt monomer (A) and a monomer which can be copolymerized with the monomer (Revised) 316,720, 114, patent application No. 94,102,858. The body (6) is copolymerized, (in March 3, 2, the (methyl) acrylate zinc salt or the copper salt monomer (7), the composition of the street is 2 to 50 1% by weight, and other copolymerizable The unit of the monomer (1) is 5〇 to 98% by weight (component unit (component unit (b) = 100% by weight). 17·If you apply for the third to seventh item The viscous paint composition, wherein the self-polymerizing antifouling coating copolymer (8) is a polymerizable unsaturated carboxylic acid decyl ester-based copolymer, such as the antifouling coating composition of claim 17 of the patent application, wherein The self-polymerizing antifouling coating copolymer (8) has an insufficient content in the molecule represented by the formula [IIIA]共 (4) g|monomer and copolymerizable unsaturated monomer derived from the copolymer unit: V-COO- Si〇A2L3).........[ΙΠΑ] {Form [IIIA ]t, R1 is CH2=C(CH3)-, CH2=CH_, hooc-ch-ch-, _c_ch=c(CH3)4, which contains an unsaturated bond, an organic group, and _C00H may also form a metal salt or The esters, L1, L2, and L3, may be the same or different and each independently represent a hydrogen atom, a silk, a ring-based group, an aromatic hydrocarbon group, an aralkyl group or an alkyl-decyloxy group, and these groups may have a substituent}. 19. The antifouling coating composition according to claim 18, wherein the self-polymerizing antifouling coating copolymer (8) is (mercapto) acrylonitrile and can be copolymerized therewith. a copolymer obtained by copolymerizing a saturated monomer. 20. An antifouling coating film which is obtained by the antifouling coating according to any one of claims 3 to 19 (Revised) 316720 1333947. The composition of the composition. ϋ410ί858 财利申申申(March 8, 9 9) A coated film coated ship coated with any of the coatings in the range of items 3 to 19. 'It is characterized by It is formed by the application of the special antifouling coating composition 22. The coated film is coated with the k-sum structure in the summer, which is characterized by the application of the patent range from 3rd to 7th ji to 19 Any of the coatings formed by the anti-fouling coating of any one of the items. It is characterized in that it is formed by the composition of the antifouling coating which is applied for by the application. A coated film coated fishing tool is a coating film applicator of any of items 3 to 19. 24. A coated film coated fishing net characterized by being coated with a coating film formed from the antifouling coating composition of any of items 3 to 19 of the Shenjing Patent Range. 25. A method for resisting contamination of a ship or underwater structure, characterized in that the surface of the ship or underwater structure is formed by an antifouling coating composition of any one of claims 3 to W of the patent application. Coating film applicator. 26. An antifouling method for a fishing gear or a fishing net, characterized in that the surface of the fishing net is coated with a coating film formed by any two of claims 3 to 19 of the patent application = antifouling coating composition . 27. The use of a cyclic hydrazine carboxylic acid represented by the following formula [V] or a salt of a dicycloolefin carboxylic acid represented by the following [vi] or a salt thereof, for use in the manufacture of an antifouling coating: (Revised) 316720 116 1333947 Patent Application No. 94102858 (March 8, 2009) In the formula [乂], R1 represents a hydrogen atom, a 3-methyl-2-butanyl group or a 2-mercapto-1-propenyl group, and when R1 represents a hydrogen atom, R2 represents a 4-methyl-3-pentyl group. The dilute base 'R3, R4 represents a hydrogen atom, R1 represents a 3-methyl-2_butyl group, R2 represents a fluorenyl group, R and R4 represent a hydrogen atom, and R1 represents a 2-methyl-1-propenyl group, R2 Represents a hydrogen atom, R3, and R4 represent a fluorenyl group; R5 and R6 each represent a hydrogen atom or an alkyl group having 1 to 1 carbon atom; m and n respectively represent a number of 0 or 1 (except that m and n are not 0 at the same time) R7 and R8 each represent a hydrogen atom or a hydrocarbon group; when m is 0, R7 is a negative atom, and when m is 1, R7 is a hydrogen atom or a hydrocarbon group, and when η is 0, R8 is a hydrogen atom, and when η is 1 , R8 is a hydrogen atom or a hydrocarbon group (except that R7 and R8 are not hydrocarbon groups at the same time)}; 117 (Revised) 316720 /R22 3fj ®ί^—(COO)^20 -(COO^Ri? Rl\〇〇C) Ir^L· R16 7s pl2 K RJI A In the formula [VI], w: &lt;a&gt; When R11 is isopropyl, *table-isomeric, R, RI3 represents a hydrogen atom, Rl4 represents a methyl group, R15 , IT separately sounds a knife, not the atom or carbon number] m, n respectively, the table i 〇 alkyl, j clothing 〇 or 1 (only, m R and R18 respectively indicate that the dry gas tower is not 〇 at the same time) 彳 clothing does not 虱 atom or hydrocarbon group, k, 1 is 〇, R21, R2 ° represents a hydrogen atom, i: R respectively When a hydrogen atom or a carbon number is 1 to 1 〇, when m is 0, R17 is a hydrogen atom, and when the alkyl group ''1' is 1, p17 is up to &gt; K is a halogen atom or a hydrocarbon group, and when the above 〇 is 0, R18 is A hydrogen atom, when Π is 1, R 8 is a ruthenium atom or a hydrocarbon group (only, ρ, 7 is a hydrocarbon group); Κ and R18 are different &lt;B&gt; When R16 is isopropyl, r11, p! 2 矣K represents no hydrogen atom, R13 represents a methyl group, Rl4 represents a hydrogen atom, (Repaired JE) 316720 118 1333947. Patent Application No. 94102858 (March 8, 9 9) • R15 represents a hydrogen atom or a carbon number 1 to 10 alkyl, m, η represent 0, respectively; • R17, R18 represent 氲 atoms, 'k, 1 respectively represent 0 or 1 (only, k, 1 are not 0), R19, R2° respectively Represents a hydrogen atom or a hydrocarbon group, and R21 and R22 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and when k is 0, R19 is a hydrogen atom, and when k is 1, R19 is a hydrogen atom or a hydrocarbon group, 1 is 0, R2 ° is a hydrogen atom, a is 1, R2 ° is a hydrogen atom or a hydrocarbon group (provided that when, R19 and R2 ° is different hydrocarbon group)}. 119 (amendment) 316720