JPH11209658A - Underwater antifouling coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating agent which is excellent in long-term storage stability and in long-term prevention of the growth of marine organisms by incorporating a metal ester compd. and an antifouling agent into the same. SOLUTION: The metal ester compd. incorporated is a reaction product of (A) a compd. of formula I, (B) a compd. selected from among rosin, rosin derivs. having carboxyl groups, and org. compds. having at least one monobasic acid group, and (C) a di- or tri-valent metal compd. In formula I, X is a group of formula II or III; n is 0-15; m is 0 or higher; R<1> and R<2> are each alkyl, alkoxy, or aryl; R<3> is R<1> , R<2> or a group of formula IV (wherein Y is a group of formula II or III; and p is 0-15); and R<4> and R<5> are each R<1> , R<2> or a group of formula V (wherein q is 0 or higher; and R<6> to R<10> are each alkyl, alkoxy or aryl). The metal ester compd. used usually has a wt. average mol.wt. of 500-100,000 and is used as a soln. in a solvent or as a synthetic soln. as it is. Further incorporation of a surface lubricant into the coating agent is pref.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater antifouling coating for preventing organisms from adhering to the surface of an underwater object.

[0002]

2. Description of the Related Art Conventionally, ship bottoms, buoys, fishing nets (cultured nets such as hamachi and scallops, salmon fixed nets, etc.) immersed in seawater, undersea pollution prevention sheets, various suction and drain pipes for cooling, etc. Barnacles, serpula,
Various obstacles have been caused by adhesion of mussels, algae and the like. It is well known that anti-fouling paints and underwater anti-fouling coatings called fishing net anti-fouling agents are applied to the surface of seawater immersions in order to prevent fouling by such organisms. This underwater antifouling coating agent is roughly classified into the following two types (a) and (b). (A) An antifouling agent such as an organotin copolymer or cuprous oxide which has an effect of preventing adhesion to living organisms and is slightly soluble in seawater. For example, paints using an organotin compound as an antifouling agent are disclosed in JP-B-40-21426, JP-B-44-9579, and JP-B-46-133.
No. 92, Japanese Patent Publication No. 49-20481, Japanese Patent Publication No. 5
These are disclosed in, for example, JP-A-11-11647 and JP-B-52-48170. (B) A paint which does not use an antifouling agent and does not dissolve in seawater, and is typified by silicone rubber utilizing the water-repellent physical properties of the coating film surface.

[0003] For example, Japanese Patent Publication No. 53-35974 discloses a composition using a vulcanized silicone rubber as a paint, and Japanese Patent Application Laid-Open No. Sho 51-96830 discloses a method having a hydroxyl terminal group. Oligomeric silicone
The use of a mixture of rubber and silicone oil is shown. Further, JP-A-53-79980 discloses that
Mixtures of vulcanized silicone rubber and metal-free, silicon-free, flowable organic compounds are shown. Furthermore, Japanese Patent Publication No. 60-3433 discloses an oligomer-like room temperature-curable silicone rubber (for example, KE45TS, KE44RTV, etc., of Shin-Etsu Chemical Co., Ltd.).
And a liquid paraffin or petrolatum mixed with a marine organism adhesion preventing paint. Furthermore, fairness 5
Japanese Patent No. -60503 discloses an underwater antifouling coating comprising a silicone acrylic copolymer. These conventionally known underwater antifouling coating agents can be used depending on the purpose because they can exhibit the performance according to the type thereof, but all have the following disadvantages, and improvement of these is desired. It is rare.

[0004] First, in the underwater antifouling coating agent (a), the organic tin group bonded to the resin is hydrolyzed in seawater, thereby depleting the coating film and maintaining the activity of the coating film surface. Further, the hydrolyzed organic tin compound also functions as an antifouling agent, so that the adhesion of marine organisms can be prevented for a long time. However, organotin compounds are highly accumulative in the environment, and their use is regulated due to concerns about environmental pollution. In addition, the underwater antifouling coating agent of the above (b) is designed to prevent the adhesion of underwater organisms to the coating surface by utilizing the slipperiness of the surface of silicone rubber or silicone acrylic resin. However, there is an advantage that there is no elution component which may cause water pollution as in the underwater antifouling coating agent (a).
Since the silicone rubber or silicone acrylic copolymer forming the coating does not show solubility in seawater, reactivation of the deteriorated coating surface after aging is inhibited, and as a result, long-term antifouling power is maintained. There was a difficult problem.

[0005]

SUMMARY OF THE INVENTION Under the above circumstances, the present invention aims to prevent long-term storage stability and long-term marine organism adhesion prevention performance in order to prevent organisms from adhering to the surface of objects in the sea. An object of the present invention is to provide an underwater antifouling coating agent excellent in water resistance.

[0006]

The present inventors have conducted intensive studies on the above points, and as a result, have found that they have no toxicity like organotin compounds and which are derived from an organosilyl group or an organosiloxy group which contributes to antifouling performance. By using a metal ester compound that imparts a hydrolytic property to the surface slip property at the same time, it is found that a coating film having antifouling activity can always be obtained, and it does not have the above-mentioned disadvantages, and exhibits antifouling performance for a long time A new underwater antifouling coating was successfully obtained. That is, the present invention is [1] an underwater antifouling coating agent containing a metal ester compound which is a reaction product of the following (A), (B) and (C), and (D) an antifouling agent. (A) The following general formula (1)

[0007]

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[Where X in the formula is

[0009]

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Wherein n is an integer from 0 to 15;
Is a real number of 0 or more; R ¹ and R ² are each a group selected from an alkyl group, an alkoxyl group and an aryl group; R ³ is a group similar to R ¹ and R ² and Equation (4)

[0011]

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(Where Y represents the above formula (2) or (3), and p represents an integer of 0 to 15) and is a group selected from the group consisting of ⁴ and R ⁵ are the same groups as R ¹ and R ² and the following general formula (5)

[0013]

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(Where q is a real number greater than or equal to 0, R ⁶
To R ^8, R ⁹ , and R ¹⁰ are all groups selected from the group consisting of alkyl groups, alkoxyl groups, aryl groups, and substituted aryl groups, and may be the same or different groups. A) selected from the group consisting of organosiloxy groups represented by the following formulas, and R ⁴ and R ⁵ may be the same or different from each other]. A) a compound selected from the group consisting of rosin, a rosin derivative having a carboxylic acid, and an organic compound having at least one monobasic acid, and (C) a compound of a divalent or trivalent metal. Still further, the present invention provides the aforementioned [1]
The present invention also provides an underwater antifouling coating containing the metal ester compound of the above, an antifouling agent and a surface lubricant.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In order to obtain an underwater antifouling coating composition of the present invention, a compound represented by the above formula (A) represented by the general formula (1) is used. In the general formulas (1) and (5), m and q are the number of repetitions of the organosiloxy group, and can be a real number of 0 or more, but usually it is preferably up to about 1,000. Since the organosiloxy group is introduced by dehydration condensation or addition reaction, the compound A is usually a mixture of organosiloxy groups having different numbers of repetitions. Therefore, the above m and q values should be expressed as their average values (av.m) and (av.q), and the reason why they are expressed as the real numbers is also for this reason. From this viewpoint, the average values (av.m) and (av.q) are used in the examples described later. Such a compound A is easily available as a commercial product. As a synthesis example, a method of adding a polyorganosiloxane having a silane group at one or both ends to an organic acid having one double bond can be given.

In the organosilyl group or organosiloxy group represented by the general formula (1) or (5) in the compound A as an essential component of the present invention, R ¹ , R ²
And R ^{6 to} R ¹⁰ may be the same or different groups. Specifically, methyl, ethyl, n-
Linear alkyl groups such as propyl, n-butyl, heptyl, pentyl, octyl, decyl, octadecyl;
Branched alkyl groups such as isopropyl, isobutyl, s-butyl and t-butyl; cyclic alkyl groups such as cyclohexyl group; aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group and naphthyl group or substituted aryl thereof And the like. Examples of the substituted aryl group include a halogen atom, an aryl group substituted with an alkyl group having up to about 18 carbon atoms, an acyl group, a nitro group, or an amino group. R ³ is a group similar to R ¹ and R ² described above, or a carboxylic acid or sulfonic acid having an alkylene chain having 0 to 15 carbon atoms. Specific examples of the above R ¹ and R ² and the carboxylic acid system include, for example, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl, carboxypentyl, carboxyhexyl, carboxyoctyl, carboxyoctadecyl, and the like. Examples of the acid system include a sulfoxymethyl, sulfoxyethyl, sulfoxypropyl, sulfoxybutyl, sulfoxypentyl, sulfoxyhexyl, sulfoxyoctyl, sulfoxyoctadecyl group and the like.

In order to obtain the underwater antifouling coating composition of the present invention, it is selected from the group consisting of rosin, which is the compound shown in the above (B), a rosin derivative having a carboxylic acid, and an organic compound having at least one monobasic acid. The compound to be used is used. For example, rosin includes tall rosin, gum rosin, wood rosin and the like. Examples of the rosin derivative having a carboxylic acid include hydrogenated rosin, maleated rosin obtained by reacting rosin with maleic anhydride, and polymerized rosin. Examples of the organic compound having at least one monobasic acid include, for example, acetic acid, propionic acid, butenoic acid, octylic acid, benzoic acid, salicylic acid, lactic acid, abietic acid, naphthenic acid, caprylic acid, and capric acid. , Lauric acid, myristic acid, palmitic acid, stearic acid, cerotic acid, montanic acid,
Melic acid, lauroleic acid, oleic acid, vaccenic acid, gadolinic acid, whale oil acid, shark oil acid, diuniperic acid,
Examples include succinic acid, valeric acid, malonic acid, phthalic acid, nicotinic acid, and cyclohexanecarboxylic acid. Examples of the sulfonic acids include butanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, 4-toluenedisulfonic acid and the like; thiocarboxylic acids include hexanethioic acid, hexanedithioic acid, 1-piperidinecarbodithioic acid, dithiobenzoic acid, and the like; carbamates include diethyldithiocarbamic acid, dibutyldithiocarbamic acid, and the like. And other various organic acids such as organic phosphoric acid and organic carbamic acid.

The divalent or trivalent metal compound shown in the above (C) is used to obtain the underwater antifouling coating composition of the present invention. For example, Group II (Mg, Ca, Zn, Sr, Ba, etc.), Group III (Al, Sc, Ga, Y, In, Tl, etc.), Group IV (Si, Ti, Zr, Ge, etc.), Group V (V , As, Nb, Sb, etc.), VI group (Cr, Se, M
o, W, etc.), Group VII (Mn, Tc, Re, etc.), VIII
Or trivalent compounds of metals such as group III (Fe, Co, Ni, Ru, Rh, Pd, etc.), for example, oxides such as zinc oxide, copper oxide, iron oxide, nickel oxide, manganese oxide; iron chloride Halides such as copper chloride, zinc chloride, aluminum chloride, calcium chloride, magnesium chloride, zinc bromide, and aluminum bromide; hydroxides such as aluminum hydroxide, copper hydroxide, iron hydroxide, and zinc hydroxide; sulfuric acid Sulfates such as copper, zinc sulfate, nickel sulfate, aluminum sulfate, and lead sulfate; and nitrates such as copper nitrate, zinc nitrate, and aluminum nitrate.

As the metal ester compound used in the underwater antifouling coating composition of the present invention, the above-mentioned compounds (A), (B) and (C) are used. (A) is 5 to 80% by weight, preferably 10 to 70% by weight, compound (B) is 5 to 70% by weight, preferably 10 to 60% by weight, and compound (C) is 5 to 70% by weight, preferably Use 10-60% by weight. In this case, one or more of each compound may be used. The reaction conditions for reacting the components (A), (B) and (C) include ordinary reactions, for example, (A), (B) and (C).
Can be mixed with or without a solvent in the above-mentioned predetermined ratio and stirred and mixed at room temperature or at a temperature higher than room temperature.

Examples of the organic solvent which can be used in producing the metal ester compound include aromatic hydrocarbon solvents such as xylene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ethyl acetate and butyl acetate. Ester solvents, alcohol solvents such as isopropyl alcohol and butyl alcohol, ether solvents such as dioxane and diethyl ether, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and cellosolve solvents such as methyl cellosolve, ethyl cellosolve and cellosolve acetate. Or a mixed solvent thereof.

In the underwater antifouling coating composition of the present invention,
The weight average molecular weight of the metal ester compound which is a reaction product of (A), (B) and (C) is 500 to 100,0.
00, preferably 700 to 90,000. When the weight-average molecular weight is less than 500, it is difficult to form a film that can withstand use, and when the weight-average molecular weight exceeds 100,000, hydrophobicity increases, and the originally required proper hydrolyzability cannot be obtained. Long-term stabilization of antifouling performance cannot be achieved. Incidentally, the compound (A), (B) or (C) may be contained.

In the underwater antifouling agent of the present invention, the above-mentioned metal ester compound is contained in a solvent, or when the above-mentioned metal ester compound is synthesized using a solvent, the synthesis solution is used as it is. Can be.
At that time, the amount of the organic solvent used in the total amount of the metal ester compound and the organic solvent is generally 5 to 95% by weight, preferably 5 to 90% by weight, more preferably 10 to 70% by weight.

In the underwater antifouling coating composition of the present invention, component (D), which is used as one of the other essential components, is an antifouling agent, which includes a wide variety of conventionally known antifouling agents. Roughly speaking, there are inorganic compounds, organic compounds containing metals, and organic compounds containing no metals. Examples of the inorganic compound include cuprous oxide, copper powder, copper compounds such as cuprous thiocyanate, copper carbonate, copper chloride, and copper sulfate, zinc sulfate, zinc oxide, nickel sulfate, and a copper-nickel alloy. .

Examples of the organic compound containing a metal include an organic copper compound, an organic nickel compound, an organic zinc compound and the like, and also include maneb, manceb,
Propineb can also be used. Examples of organic copper compounds include oxine copper, copper nonylphenolsulfonate, copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, copper bis (pentachlorophenolate), and copper pyrithione. Nickel-based compounds include nickel acetate, nickel dimethyldithiocarbamate, and the like, and organic zinc-based compounds include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylenebisdithiocarbamate.

Examples of the organic compound containing no metal include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compounds, and triazines. System compounds and others. As N-trihalomethylthiophthalimide,
Examples of N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, and dithiocarbamic acids include bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ammonium ethylenebis (dithiocarbamate), and milneb. .

As the N-arylmaleimide, N-arylmaleimide
(2,4,6-trichlorophenyl) maleimide, N-
4-tolylmaleimide, N-3-chlorophenylmaleimide, N- (4-n-butylphenyl) maleimide, N
-(Anilinophenyl) maleimide, N- (2,3-xylyl) maleimide and the like. As the 3-substituted amino-1,3-thiazolidine-2,4-dione, 3
-Benzylideneamino-1,3-thiazolidine-2,4
-Dione, 3- (4-methylbenzylideneamino)-
1,3-thiazolidine-2,4-dione, 3- (2-hydroxybenzylideneamino) -1,3-thiazolidine-2,4-dione, 3- (4-dimethylaminobenzylideneamino) -1,3-thiazolidine -2,4-dione, 3- (2,4-dichlorobenzylideneamino)-
1,3-thiazolidine-2,4-dione and the like.

Examples of the dithiocyano compound include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene.
-Methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine and the like. Other metal-free organic compounds include 2,
4,5,6-tetrachloroisophthalonitrile, N, N
-Dimethyl-N ^, -dichlorophenylurea, 4,5-dichloro-2-n-octyl-isothiazolin-3-one, N, N-dimethyl-N ^, -phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram Disulfide, 3-iodo-2-propynylbutyl carbamate, 2- (methoxycarbonylamino) benzimidazole, 2,3,5,6-tetrachloro-4
-(Methylsulfonyl) pyridine, diiodomethylparatolylsulfone, phenyl (bispyridine) bismuth dichloride, 2- (4-thiazolyl) benzimidazole, triphenylboronpyridine and the like.

In the present invention, one or more of the above-mentioned various antifouling agents are selected and used. The amount of the antifouling agent used is determined by the ratio of the antifouling agent to the solid content of the paint. It is 0.1 to 80% by weight, preferably 1 to 70% by weight, more preferably 1 to 60% by weight. If the proportion of the antifouling agent is less than 0.1% by weight, the antifouling effect cannot be expected, and if it exceeds 80% by weight, defects such as cracks and peeling are liable to occur in the formed coating film, and the effective antifouling property is obtained. Is difficult to obtain.

The underwater antifouling coating composition of the present invention preferably further contains a surface lubricant. Those usable as such a surface lubricating agent include various substances known to impart a lubricating property to the surface of the coating film. A typical example is JIS-K223.
Petroleum wax specified in No. 5, liquid paraffin specified in JIS-K2231, 5500 at 25 ° C.
A silicone oil having a kinematic viscosity of 0 centistokes or less, a fatty acid having 8 or more carbon atoms and a ester thereof having a melting point of -5 ° C. or more, an organic amine having an alkyl group or an alkenyl group having 12 to 20 carbon atoms, and 60,000 at 26 ° C. Examples include polybutene having a kinematic viscosity of less than centistokes.

As a specific example of the above, JIS-K22
35 of 120P, 125P, 130P, 135P, 14
Paraffin wax such as 0P, 145P, 150P, 155P, 150M, 160M of JIS-K2235,
Microcrystalline Wax such as 170M, 180M, 190M, and JIS-K2235 No. 1,
No. 3, No. 4, etc. and petroleum wax such as petrolatum.

As a specific example of the above, ISOVG1
0, ISOVG15, ISOVG32, ISOVG6
8, each equivalent of ISOVG100, and the like.

Examples of the above examples include KF96L-0.65 and KF96L- made by Shin-Etsu Chemical Co., Ltd.
2.0, KF96-30, KF96-100, KF96
H-50000, KF965, KF50, KF54, K
F69, FL100, trade names TSF440, TSF410, TSF4440, TSF manufactured by Toshiba Silicone Co., Ltd.
431, TSF433, TSF404, TFA420
0, YF3860, YF3818, YF3965, YF
3841, YF3953, TSF451, TSF400
0, FQF501, trade names SH200, SH510, SH353 manufactured by Dow Corning Toray Silicone Co., Ltd.
1, SH230, FS1265 and the like. The above silicone oil is most commonly dimethyl silicone oil, but other methyl phenyl silicone oil, polyether silicone oil, cyclic polysiloxane oil, alkyl-modified silicone oil, methyl chlorinated phenyl silicone oil, Other materials such as fatty acid-modified silicone oil and fluorosilicone oil may be used.

Specific examples of the above include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, serotinic acid, montanic acid, melicic acid, lauroleic acid, oleic acid, vaccenic acid, and gadolinic acid. , Whale oil, shark oil, diuniperic acid, and the like. Further, as esters of these carboxylic acids,
Stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, seryl cellulose, myristyl palmitate, merisil meliseate, whale wax, beeswax, carnauba wax, montan wax, insect white Wax, tristearin, tolpalmitin, triolein, myristodilaurin, caprylo lauromyristin, stearopalmitolein, monostearin, monopalmitin, distearin, dipalmitin, tallow, lard, horse tallow, sheep tallow, cod Examples include liver oil, coconut oil, palm oil, wood wax, kapok oil, cocoa butter, china butter, and lippe butter.

Further, specific examples of the above include dodecylamine, tetradodecylamine, hexadecylamine, octadecylamine, oleylamine, tallowalkylamine, cocoalkylamine, soybean oilalkylamine, didodecylamine, ditallow hydrogenated alkyl. Amine,
Dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine, octadecyldimethylamine and the like can be mentioned.

As a specific example of the above, Nippon Oil & Fats Co., Ltd.
Registered trademark Nissan Polybutene 0N, 06N, 015
N, 3N, 5N, 10N, 30N, 200N, 0SH,
06SH, 015SH, 3SH, 5SH, 10SH, 3
0SH, 200SH and the like.

In the underwater antifouling coating composition of the present invention, one or more of the above-mentioned various surface lubricants can be selected and used. It is set in an appropriate range in consideration of the performance of the compound such as drying property and adhesion, and the antifouling performance. Generally, the amount of the surface lubricant used in the total amount of the metal ester compound and the surface lubricant is 1 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 3% by weight.
5% by weight.

The underwater antifouling coating composition of the present invention thus constituted includes, for example, coloring agents such as pigments and dyes such as titanium dioxide, red iron oxide, zinc oxide and talc; water binders; Paraffin, dioctyl phthalate, tricresyl phosphate and other plasticizers, UV absorbers such as benzophenone-based compounds and benzotriazole-based compounds, anti-segregation agents, anti-settling agents, defoamers, silanols, polysiloxanes, alkoxysilanes And various kinds of additives and various solvents can be appropriately blended.

To form an antifouling coating on the surface of an object to be immersed in seawater using the underwater antifouling coating agent of the present invention,
For example, after applying the coating agent as a solution to the surface of the object by an appropriate means, it may be dried at room temperature or under heating to volatilize and remove the organic solvent. A film with good performance can be easily formed. Since the above-mentioned metal ester compounds used in the present invention all have an organosilyl group or an organosiloxy group derived from the compound (A), they impart a strong surface slip property to the formed film. Therefore, the coating itself has a function of physically preventing the attachment of marine organisms.

[0039]

The underwater antifouling coating composition of the present invention can be used for underwater structures such as ship bottoms, fishing nets and cooling water pipes which need to prevent underwater biofouling, and for preventing the spread of sludge in marine civil engineering works. The underwater antifouling coating itself has good long-term storage stability, and its coating has a uniform hydrolytic property without change over time even after long-term immersion, and has excellent marine organism adhesion prevention performance over a long period of time. Can last.

[0040]

Next, the present invention will be described specifically with reference to Production Examples, Examples and Comparative Examples of metal ester compounds. In addition, the part in an example is a weight part, and molecular weight is polystyrene conversion weight average molecular weight by GPC. Further, the compound (A) (A1 to A8) used in the production example is represented by the aforementioned general formula (1),
A compound represented by the general formula (1):
N, X, p, Y, m (av.m), q (a) in (5)
v. q) and R ^{1 to} R ¹⁰ are as shown in Table 1 below.

[0041]

[Table 1]

(Note in Table 1) (* 1)

[0043]

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(* 2)

[0045]

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(* 3)

[0047]

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(* 4)

[0049]

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(* 5)

[0051]

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Production Examples 1-4 Solvent a, compound (A), compound (B) and metal compound (C) were charged into a flask equipped with a stirrer in the proportions shown in Table 2 below, and a predetermined reaction was carried out with stirring. The temperature was raised to the temperature, and after the temperature was raised, the temperature was maintained at the same temperature for a predetermined time. After the reaction,
The precipitate was removed by filtration, and the metal ester compound solution I was removed.
~ IV.

Production Examples 5 to 8 Into a flask equipped with a stirrer, the solvent a, the compound (A) and the metal compound (C) were charged in the proportions shown in the following Table 2, and the mixture was heated to a predetermined reaction temperature while stirring. After the temperature was raised, a mixture of the compound (B) and the solvent b was dropped for a predetermined time, and after the completion of the drop, the mixture was kept at the same temperature for a predetermined time. After completion of the reaction, the precipitate was removed by filtration to obtain metal ester compound solutions V to VIII.

[0054]

[Table 2]

(Note of Table 2) (* 1) MIBK: methyl isobutyl ketone (* 2) Weight average molecular weight: weight average molecular weight of metal ester compound (× 103) (* 3) Symbol: symbol of metal ester compound solution

Examples 1 to 11 Using the metal ester compound solutions I to VIII, the following Table 3
Each component was mixed according to the composition shown in Table 1 (the numerical values in the table are% by weight) and mixed and dispersed with a homomixer of 2,000 rpm to prepare 11 kinds of antifouling underwater coating agents. In the ingredients, Petrolatum No. 1 is petroleum wax according to JIS K2235, and ISOVG10 is a liquid paraffin according to JIS K2231. The silicone oil having a trade name of TSF433 is manufactured by Toshiba Silicone Co., Ltd. Nissan Polybutene 06N is a polybutene manufactured by NOF Corporation. Also, Oil Blue 2N
[Orient Chemical Co., Ltd.] is a dye, and DISPARON A630-20X [Kusumoto Kasei Co., Ltd.] and AERILIL 300 [Nippon AERILIL CO., LTD.] Are anti-sagging agents. is there.

Comparative Example 1 KE45 was used instead of the metal ester compound solutions I to VIII.
Except that TS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd .; oligomeric, room-temperature-curable silicone rubber, 50% by weight in toluene solution) was used in the same manner as in Examples 1 to 11, except for the composition shown in Table 3 below. A water-based antifouling coating was prepared.

Comparative Example 2 The same composition as in Examples 1 to 11 was used, except that the organotin copolymer solution (a) was used instead of the metal ester compound solutions I to VIII, and had the composition shown in Table 3 below. An underwater antifouling coating was prepared. The above-mentioned organotin copolymer solution (a)
Was manufactured as follows. First, 30 parts of xylene was charged into a flask equipped with a stirrer, and the temperature was raised to 80 ° C. while introducing nitrogen gas while stirring. Next, methyl methacrylate 4
A mixture of 0 parts, 20 parts of octyl acrylate, 40 parts of tributyltin methacrylate, and 0.5 part of azobisisobutyronitrile as a polymerization catalyst was dropped in 2 hours, and kept at that temperature for 1 hour after completion of the dropping. To complete the polymerization. The weight average molecular weight of the obtained copolymer is a transparent xylene 50% by weight solution of 9000.

[0059]

[Table 3]

(Note in Table 3) (* 1) Amount of surface lubricant used (% by weight in terms of solid content) =
(Surface lubricant) / [(Surface lubricant) + (metal ester compound)] × 100

Next, with respect to the metal ester compound solutions I to VIII prepared in Production Examples, the weight loss of the coating film and the solvent resolubility of the coating film were measured by the following methods. The underwater antifouling coatings of Examples 1 to 11 and Comparative Examples 1 and 2 were subjected to a storage stability test and an antifouling performance test by the following methods to evaluate the performance. These results were as shown in Tables 4 and 5 below.

<Measurement of Weight Loss of Coating and Measurement of Solvent Resolubility of Coating> Metal ester compound solutions I to VIII were applied to a transparent glass plate, dried, and the weight of the coating was measured. , And washed with fresh water every three months to remove salt in seawater. After sufficiently dried, the weight of the remaining film was measured again. And to check the uniform solubility,
The following calculation was performed to determine the dissolution uniformity value α. α = (dissolved amount in the previous period) / (dissolved amount in the previous period)
Since there was no change in the solvent-soluble content of the residual metal ester compound after 12 months using the initial composition solvent in Production Example, the soluble content of the residual metal ester compound in the initial composition solvent after 12 months was measured. . From this value, the re-dissolution rate β (%) was determined by the following equation. Re-dissolution rate β (%) = (weight of soluble portion of residual coating in initial composition solvent after 12 months) / (total weight of coating after 12 months)
× 100

<Storage Stability Test> 200 cc of each underwater antifouling coating agent was placed in a 250 cc mayonnaise bottle, which was then sealed with a lid. This was stored in a thermo-hygrostat at a temperature of 70 ° C. and a humidity of 75%, and the viscosity of each sample was increased two weeks later.
Storage stability was determined. When the rate of increase from the initial viscosity is less than 10%, ○ when the rate is 10% or more and less than 100%, Δ, 100
% Or more was evaluated as x.

<Anti-fouling performance test> Each underwater anti-fouling coating agent was coated on a sandblasted steel sheet with a tar vinyl-based rust-preventive paint in advance, and the coated film (100 × 200 × 1 mm) was coated on both sides with a dry film thickness. The coating was performed twice by spray coating so as to have a thickness of 120 μm on one side, and dried for one week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% to prepare a test piece. The test piece was immersed in seawater for 24 months in Yura Bay, Hyogo Prefecture, and the ratio of the occupied area (adhered area) of the attached organisms on the test coating was measured over time.

[0065]

[Table 4]

(Note) (* 1) α1 = [(coating dry weight after immersion for 3 months g) − (coating dry weight after immersion for 6 months g)] / [(initial coating dry weight g) −
(Dry weight of coating after immersion for 3 months g)] (* 2) α2 = [(Dry weight of coating after immersion for 6 months g)-(Dry weight of coating for immersion after 9 months)] / [(Dry weight of coating after immersion for 3 months) g)-(coating dry weight after 6 months immersion)] (* 3) α3 = [(coating dry weight after 9 months immersion)-(coating dry weight after 12 months immersion)] / [(6 months after immersion) Coating dry weight g)-(Coating dry weight after immersion for 9 months g)]

[0067]

[Table 5]

(Note) (* 1) Antifouling performance: Indicates the area (%) of organisms attached.

As is clear from the results in Table 4 above, Examples 1 to 5 obtained from the metal ester compound solutions I to VIII were used.
The coating of each underwater antifouling coating of Example 11 had a uniform dissolution uniformity value α1 to α3 of 0.97 to 1.
In the range of 03, the uniform solubility is high, the solubility does not peak even with time, and good performance is shown. Further, the re-dissolution rate β measurement with the initial composition solvent shows that the time-dependent film is almost the same as the initial film. This indicates that hydrolysis occurred from the coating surface, and only the hydrolyzed coating surface was uniformly dissolved. On the other hand, in the silicone rubber shown in Comparative Example 1, the solubility of the film was not observed, and the resolubility by the solvent was not measured. In addition, in the coating obtained from the organotin copolymer solution shown in Comparative Example 2, the dissolution uniformity value α decreased with time, indicating that the coating became more and more difficult to dissolve. This means that the re-dissolution rate β (%) of the aged film with the initial composition solvent after 12 months is as low as 76%, so that the hydrolysis in the film precedes and the insoluble after hydrolysis on the surface of the remaining film. Ingredients remain,
This indicates that stable solubility was not obtained.

In Examples 1 to 11, both the storage stability and the antifouling performance were very good, as is clear from the results shown in Table 5. On the other hand, in the silicone rubber shown in Comparative Example 1, gelation occurred in the storage stability test, and further, in the antifouling performance, biofouling was observed after 6 months, and after 12 months, the biofouling was completely adhered, and underwater protection was observed. Insufficient results were shown as a soil coating. In addition, the organotin copolymer solution shown in Comparative Example 2 did not gel in the storage stability test, but showed a tendency to thicken, and the antifouling performance was 1%.
Two months later, biofouling was observed, indicating poor results.

Claims (2)

[Claims] An underwater antifouling coating composition comprising a metal ester compound which is a reaction product of the following (A), (B) and (C) and (D) an antifouling agent. (A) The following general formula (1) [Where X in the formula is Wherein n is an integer of 0 to 15, m is a real number of 0 or more, and R ¹ and R ² are groups selected from an alkyl group, an alkoxyl group, and an aryl group; ³ is the same group as R ¹ and R ² and the following general formula (4) (Where Y represents the above formula (2) or (3), and p represents an integer of 0 to 15), and is a group selected from the group consisting of groups represented by R ⁴ and R ^{4 5} is the same group as R ¹ and R ² and the following general formula (5) (Where q is a real number of 0 or more, R ^{6 to} R ⁸ and R
⁹ and R ¹⁰ are each a group selected from the group consisting of an alkyl group, an alkoxyl group, an aryl group and a substituted aryl group, which may be the same or different from each other). A group selected from the group consisting of organosiloxy groups, and R ⁴ and R ⁵ may be the same or different from each other.)
(B) a compound selected from the group consisting of rosin, a rosin derivative having a carboxylic acid, and an organic compound having at least one monobasic acid; and (C) a compound of a divalent or trivalent metal. 2. An underwater antifouling coating agent comprising the metal ester compound according to claim 1, an antifouling agent, and a surface lubricant.