JP3498563B2 - Underwater antifouling coating - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an underwater antifouling coating agent for preventing organisms from adhering to the surface of objects in the sea.

[0002]

2. Description of the Related Art Ship bottoms, buoys, fishing nets (aquaculture nets such as yellowtail and scallops, stationary nets for salmon), sea pollution control sheets, various intake and drainage pipes for cooling, etc. There are barnacles, serpra,
Various obstacles are caused by the attachment of mussels and algae. It is well known that an antifouling paint or an underwater antifouling coating agent called a fishing net antifouling agent is applied to the surface of the seawater soaked product in order to prevent the stains from being caused by those organisms. This underwater antifouling coating agent is roughly classified into the following two types (a) and (b). (B) An antifouling agent such as an organotin copolymer or cuprous oxide that has an effect of preventing adhesion to living organisms and is slightly soluble in seawater. For example, for coatings using an organic tin compound as an antifouling agent, JP-B-40-21426, JP-B-44-9579 and JP-B-46-133.
92, Japanese Patent Publication No. 49-20491, Japanese Patent Publication No. 5
It is disclosed in Japanese Patent Publication No. 1-111647 and Japanese Patent Publication No. 52-48170. (B) A paint that does not dissolve in seawater without using an antifouling agent, and is represented by silicone rubber that utilizes the physical properties of the water repellent property of the coating film surface.

For example, Japanese Examined Patent Publication (Kokoku) No. 53-35974 discloses that a vulcanized silicone rubber is used as a paint, and Japanese Laid-Open Patent Publication No. 51 (1996) -96830 has a hydroxyl end group. Oligomer-like silicone
A mixture of rubber and silicone oil is shown. Furthermore, Japanese Patent Laid-Open No. 53-79980 discloses that
A mixture of vulcanized silicone rubber and a flowable organic compound containing no metal and no silicon is shown. Further, Japanese Patent Publication No. 60-3433 discloses an oligomeric room temperature curable silicone rubber (for example, Shin-Etsu Chemical Co., Ltd., trade name KE45TS, KE44RTV, etc.).
And a fluid paraffin or petrolatum mixed marine anti-fouling paint. Further fairness 5
JP-A-60503 discloses an underwater antifouling coating agent comprising a silicone-acrylic copolymer. These conventionally known underwater antifouling coating agents are used properly according to the purpose because they can exhibit the performance according to their type, but all have the drawbacks described below, and improvement thereof is desired. It is rare.

First, in the underwater antifouling coating agent (a), the organic tin group bonded to the resin is hydrolyzed in seawater to consume the coating film and maintain the activity of the coating film surface. In addition, since the hydrolyzed organotin compound also functions as an antifouling agent, the adhesion of marine organisms can be prevented for a long period of time. However, organotin compounds have high accumulation in the environment, and their use is regulated because of concern over environmental pollution. Further, the above-mentioned (b) underwater antifouling coating agent is one which prevents the adhesion of aquatic organisms to the coating surface by utilizing the slipperiness of the surface of silicone rubber or silicone acrylic resin. It has the advantage that there is no elution component that may cause water pollution like the underwater antifouling coating agent of (a) above.
Since the silicone rubber or silicone acrylic copolymer forming the above coating does not exhibit 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]

Under the above circumstances, the present invention is intended 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. It is an object of the present invention to provide an underwater antifouling coating agent having excellent properties.

[0006]

Means for Solving the Problems As a result of intensive studies on the above points, the present inventors have found that an organosilyl group or an organosiloxy group derived from an organosilyl group or organosiloxy group, which is not toxic like organotin compounds and contributes to antifouling performance, is provided. It was found that a coating film having antifouling activity can always be obtained by using a metal ester compound having hydrolyzability at the same time as surface slipperiness, and exhibits antifouling performance for a long time without the above-mentioned defects. We succeeded in obtaining a new antifouling coating in water. That is, the present invention is [1] an underwater antifouling coating material 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]

[Chemical 5]

[However, X in the formula is

[0009]

[Chemical 6]

Where n is an integer from 0 to 15 and m
Is a real number of 0 or more, R ¹ and R ² are both groups selected from an alkyl group, an alkoxyl group, and an aryl group, and R ³ is the same group as R ¹ and R ² and the following general groups: Formula (4)

[0011]

[Chemical 7]

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

[0013]

[Chemical 8]

(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 or a substituted aryl group, which may be the same or different from each other. A group selected from the group consisting of organosiloxy groups represented by the formula (1), and R ⁴ and R ⁵ may be the same or different from each other], ) 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 divalent or trivalent metal compound. Furthermore, the present invention provides the above [1].
There is also provided an underwater antifouling coating agent containing the metal ester compound of 1), an antifouling agent, and a surface lubricant.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In order to obtain the underwater antifouling coating material of the present invention, the compound represented by the above general formula (1) (A) is used. In the general formulas (1) and (5), m and q are the repeating numbers of the organosiloxy group and can be a real number of 0 or more, but it is usually 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 the organosiloxy groups having different repeating numbers. Therefore, the above-mentioned m and q values should be expressed as their average values (av.m) and (av.q), and this is why they are expressed as the real numbers. From this point of view, in the following examples, the average values (av.m) and (av.q) are used. Such a compound A is easily available as a commercial product. As a synthesis example, there is a method of adding a polyorganosiloxane having a silane group at one end or both ends to an organic acid having one double bond.

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

In order to obtain the underwater antifouling coating material of the present invention, it is selected from the group consisting of rosin which is a compound shown in (B) above, a rosin derivative having a carboxylic acid and an organic compound having at least one monobasic acid. Used compounds. Examples of rosin include tall rosin, gum rosin, and wood rosin. Examples of the rosin derivative having a carboxylic acid include hydrogenated rosin, maleated rosin obtained by reacting rosin with maleic anhydride, and polymerized rosin. Further, as the organic compound having at least one monobasic acid, for example, carboxylic acid-based acetic acid, propionic acid, butenoic acid, octylic acid, benzoic acid, salicylic acid, lactic acid, abietic acid, naphthenic acid, caprylic acid, capric acid. , Lauric acid, myristic acid, palmitic acid, stearic acid, cerotic acid, montanic acid,
Melic acid, lauroleic acid, oleic acid, vaccenic acid, gadoleic acid, whale oil acid, shark oil acid, diuniperic acid,
Examples include succinic acid, valeric acid, malonic acid, phthalic acid, nicotinic acid, cyclohexanecarboxylic acid, and sulfonic acid-based compounds include butanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, 2, 4-toluene disulfonic acid and the like, thiocarboxylic acid-based hexanethioic acid, hexanedithioic acid, 1-piperidinecarbodithioic acid, dithiobenzoic acid and the like, carbamic acid-based diethyldithiocarbamic acid, dibutyldithiocarbamic acid, etc. Other examples include various organic acids such as organic phosphoric acid and organic carbamic acid.

In order to obtain the underwater antifouling coating material of the present invention, the compound of the divalent or trivalent metal shown in the above (C) is used. 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.), Group VI (Cr, Se, M
o, W, etc.), Group VII (Mn, Tc, Re, etc.), VIII
Divalent or trivalent compounds of metals such as group (Fe, Co, Ni, Ru, Rh, Pd, etc.), for example, oxides such as zinc oxide, copper oxide, iron oxide, nickel oxide, manganese oxide; iron chloride , Copper chloride, zinc chloride, aluminum chloride, calcium chloride, magnesium chloride, zinc bromide, aluminum bromide and other halides; aluminum hydroxide, copper hydroxide, iron hydroxide, zinc hydroxide and other hydroxides; sulfuric acid Examples thereof include sulfates such as copper, zinc sulfate, nickel sulfate, aluminum sulfate, and lead sulfate; 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 compounds (A), (B) and (C) as described above are used. The amount of the compound used is the ratio of the solid content to the compound. (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, compound (C) is 5 to 70% by weight, preferably Use from 10 to 60% by weight. At that time, one kind or two or more kinds of each compound may be used. The reaction conditions for reacting the components (A), (B) and (C) are usual reactions such as (A), (B) and (C).
Each of the components can be mixed with the above-mentioned predetermined ratios with or without a solvent, and stirred and mixed at room temperature or a temperature of room temperature or higher.

Examples of the organic solvent that can be used when producing the above 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 solvent, alcohol solvent such as isopropyl alcohol, butyl alcohol, ether solvent such as dioxane and diethyl ether, ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, cellosolve solvent such as methyl cellosolve, ethyl cellosolve and cellosolve acetate And the like, or a mixed solvent thereof.

Used 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 coating that can be used, and when the weight average molecular weight exceeds 100,000, the hydrophobicity becomes large, and proper hydrolyzability that is originally required cannot be obtained. Antifouling performance cannot be stabilized for a long period of time. The compound (A), (B) or (C) may be contained.

Further, in the underwater coating antifouling agent of the present invention, the above metal ester compound is contained in a solvent, or when the above metal ester compound is synthesized using a solvent, the synthetic solution is used as it is. You can
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 agent of the present invention, the component (D) used as another one of the essential components is an antifouling agent, and widely known ones are conventionally included. Broadly classified, there are inorganic compounds, organic compounds containing metals, and organic compounds containing no metals. Examples of the inorganic compound include cuprous oxide, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, copper compounds such as copper sulfate, zinc sulfate, zinc oxide, nickel sulfate, and copper-nickel alloy. .

Examples of the organic compound containing a metal include organic copper compounds, organic nickel compounds and organic zinc compounds, and other compounds such as manneb, manceb,
Propineb can also be used. Examples of the organic copper-based compound include oxine copper, copper nonylphenol sulfonate, copper bis (ethylenediamine) -bis (dodecylbenzene sulfonate), copper acetate, copper naphthenate, bis (pentachlorophenolic acid) copper, and copper pyrithione. Examples of nickel compounds include nickel acetate and nickel dimethyldithiocarbamate, and examples of organic zinc compounds include zinc acetate, zinc carbamate, zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylenebisdithiocarbamate.

Examples of the metal-free organic compound include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compound and triazine. System compounds and others. As N-trihalomethylthiophthalimide,
Examples thereof include N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide, and examples of dithiocarbamic acid include bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ethylenebis (dithiocarbamate) ammonium, and millneb. .

Examples of N-arylmaleimides include N-
(2,4,6-Trichlorophenyl) maleimide, N-
4-tolylmaleimide, N-3-chlorophenylmaleimide, N- (4-n-butylphenyl) maleimide, N
Examples thereof include-(anilinophenyl) maleimide and N- (2,3-xylyl) maleimide. As 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 can be mentioned.

Examples of the dithiocyano compound include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene, and examples of the triazine compound include 2
-Methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine and the like, respectively. Other organic compounds containing no metal 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
Examples thereof include-(methylsulfonyl) pyridine, diiodomethylparatolylsulfone, phenyl (bispyridine) bismuth dichloride, 2- (4-thiazolyl) benzimidazole, and triphenylboron pyridine.

In the present invention, one or more kinds of antifouling agents are selected and used from the above-mentioned various antifouling agents. The amount of the antifouling agent used in the coating solid content is 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 likely to occur in the formed coating film, resulting in an effective antifouling property. Is difficult to obtain.

The underwater antifouling coating material of the present invention preferably further contains a surface slip agent. Examples of the surface slippery agent that can be used include various substances known to impart slipperiness to the coating surface. As a representative example, JIS-K223
Petroleum wax specified in No. 5, fluid paraffin specified in JIS-K2231, 5500 at 25 ° C.
Silicone oil having a kinematic viscosity of 0 centistokes or less, fatty acid having 8 or more carbon atoms and its ester having a melting point of -5 ° C or more, 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 not more than centistokes.

As a specific example of the above, JIS-K22
35 120P, 125P, 130P, 135P, 14
Paraffin wax such as 0P, 145P, 150P, 155P, 150M, 160M of JIS-K2235,
170M, 180M, 190M, etc. microcrystalline wax, and JIS-K2235 No. 1, 2
Petroleum waxes such as No. 3, No. 4, and No. 4 petrolatum.

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

Specific examples of the above include KF96L-0.65 and KF96L- manufactured 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 Toray Dow Corning Silicone Co., Ltd.
1, SH230, FS1265 and the like. The above-mentioned 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, higher grade 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, cerotic acid, montanic acid, melissic acid, laureleic acid, oleic acid, vaccenic acid, gadoleic acid. , Whale oil acid, shark oil acid, diuniperic acid and the like. Further, as the ester of these carboxylic acids,
Stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, ceryl cerotate, myricyl palmitate, melisyl melissate, whale wax, beeswax, carnauba wax, montan wax, musk white Wax, tristearin, tolpalmitin, triolein, myristodilaurin, caprylolauromyristin, stearopalmitoolein, monostearin, monopalmitin, distearin, dipalmitin, beef tallow, lard, horse fat, sheep fat, cod Liver oil, coconut oil, palm oil, wood wax, kapok oil, cacao butter, Chinese fat, illipe fat and the like can be mentioned.

Further, specific examples of the above include dodecylamine, tetradodecylamine, hexadecylamine, octadecylamine, oleylamine, tallow alkylamine, cocoalkylamine, soybean oil alkylamine, didodecylamine, ditallow hydrogenated alkyl. Amine,
Examples thereof include dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine and octadecyldimethylamine.

Specific examples of the above include Nippon Oil & Fats Co., Ltd.
Registered trademarks of Nissan Polybutene 0N, 06N, 015
N, 3N, 5N, 10N, 30N, 200N, 0SH,
06SH, 015SH, 3SH, 5SH, 10SH, 3
Examples include 0SH and 200SH.

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, and the amount thereof is the above-mentioned metal ester. It is set in an appropriate range in consideration of performance such as drying property and adhesion property of the compound and further antifouling property. 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%.
It is 5% by weight.

Examples of the underwater antifouling coating composition of the present invention having such a constitution include colorants such as pigments and dyes such as titanium dioxide, rouge, zinc oxide and talc, water binders, anti-sagging agents and chlorine. Plasticizers such as denatured paraffin, dioctyl phthalate, tricresyl phosphate, UV absorbers such as benzophenone compounds and benzotriazole compounds, color separation inhibitors, antisettling agents, defoamers, silanols, polysiloxanes, alkoxysilanes Various additives such as the above, various solvents, and the like can be appropriately mixed.

To form an antifouling film on the surface of an object to be immersed in seawater using the underwater antifouling coating agent of the present invention,
For example, the above coating agent as a solution may be applied to the surface of the object by an appropriate means, and then dried at room temperature or under heating to volatilize and remove the organic solvent. By this method, the surface of the object is uniformly soil-resistant. A film having good performance can be easily formed. The metal ester compounds used in the present invention each have an organosilyl group or an organosiloxy group derived from the compound (A), and thus impart a strong surface slipperiness to the coating film formed. Therefore, this film itself has a function of physically preventing the adhesion of marine organisms.

[0039]

INDUSTRIAL APPLICABILITY The underwater antifouling coating material of the present invention is used for the bottom of a ship, which is required to prevent biological contamination in the sea, underwater structures such as fishing nets and cooling water pipes, and for preventing sludge diffusion in marine civil engineering work. The underwater antifouling coating itself has good long-term storage stability, and even after long-term immersion, the coating has a uniform hydrolysis property that does not change over time, and has excellent marine organism adhesion prevention performance over a long period of time. Can last.

[0040]

EXAMPLES Next, the present invention will be specifically described with reference to production examples of metal ester compounds, examples and comparative examples. In the examples, parts are parts by weight and molecular weights are polystyrene-equivalent weight average molecular weights by GPC. In addition, the compound (A) (A1 to A8) used in Production Examples is represented by the 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]

[Chemical 9]

(* 2)

[0045]

[Chemical 10]

(* 3)

[0047]

[Chemical 11]

(* 4)

[0049]

[Chemical 12]

(* 5)

[0051]

[Chemical 13]

Production Examples 1 to 4 A flask equipped with a stirrer was charged with the solvent a, the compound (A), the compound (B) and the metal compound (C) at the compounding ratios shown in Table 2 below, and a predetermined reaction was carried out while stirring. The temperature was raised to the temperature, and after the temperature was raised, the temperature was maintained for the predetermined time. After the reaction,
The precipitate is removed by filtration, and the metal ester compound solution I
Got IV.

Production Examples 5-8 A flask equipped with a stirrer was charged with the solvent a, the compound (A) and the metal compound (C) in the mixing ratios shown in Table 2 below, and the temperature was raised to a predetermined reaction temperature while stirring. After the temperature was raised, a mixed solution of the compound (B) and the solvent b was dropped for a predetermined time, and after the dropping, the temperature was kept at the same temperature for a predetermined time. After the reaction was completed, the precipitate was removed by filtration to obtain metal ester compound solutions V to VIII.

[0054]

[Table 2]

(Notes to 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 metal ester compound solutions I to VIII, the following Table 3
Each component was mixed according to the blending composition shown in Table 1 (the numerical values in the table are% by weight) and mixed and dispersed by a homomixer at 2,000 rpm to prepare 11 kinds of underwater antifouling coating agents. Among the blended components, Petrolatum No. 1 is a petroleum wax of JISK2235, and ISOVG10 is a fluid paraffin of JISK2231. The silicone oil with the trade name TSF433 is manufactured by Toshiba Silicone Co., Ltd. Further, registered trademark Nissan Polybutene 06N is polybutene manufactured by NOF CORPORATION. Also, oil blue 2N
[Orient Chemical Co., Ltd. product name] is a dye, Desparon A630-20X [Kusumoto Kasei Co., Ltd. product name] and Aerozil 300 [Japan Aerogel Co., Ltd. product name] are all 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 of Shin-Etsu Chemical Co., Ltd .; oligomeric room temperature curable silicone rubber 50% by weight toluene solution] was used, the same composition as shown in Table 3 below was used in the same manner as in Examples 1 to 11. An underwater antifouling coating agent was prepared.

Comparative Example 2 Except that the organotin copolymer solution (a) was used in place of the metal ester compound solutions I to VIII, the composition was as shown in Table 3 below in the same manner as in Examples 1 to 11. An underwater antifouling coating was prepared. The above 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 parts of azobisisobutyronitrile as a polymerization catalyst was added dropwise over 2 hours, and the temperature was maintained for 1 hour after the completion of the addition. Then, the polymerization was completed. The obtained copolymer is a transparent 50% by weight xylene solution having a weight average molecular weight of 9000.

[0059]

[Table 3]

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

Next, with respect to the metal ester compound solutions I to VIII prepared in the Production Examples, the weight loss measurement of the coating and the solvent re-solubility measurement of the coating were carried out by the following methods. Further, with respect to each of the underwater antifouling coatings of Examples 1 to 11 and Comparative Examples 1 and 2, a storage stability test and an antifouling performance test were performed by the methods described below, and the performance was evaluated. These results were as shown in Tables 4 and 5 below.

<Measurement of weight loss of coating film and measurement of solvent resolubility of coating film> Metal ester compound solutions I to VIII were applied to a transparent glass plate, dried, and the weight of the coating film was measured. Was immersed in water, washed with fresh water every 3 months to remove salt in seawater, sufficiently dried, and then the weight of the remaining film was measured again. And to confirm the uniform solubility,
The following calculation was performed to determine the dissolution uniform value α. α = (dissolved amount in the previous period) / (dissolved amount in the current period) If hydrolysis is constantly performed from the surface of the film,
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 after 12 months in the initial composition solvent was measured. . From this value, the redissolution rate β (%) was calculated by the following formula. Re-dissolution rate β (%) = (weight of soluble component in initial composition solvent of residual coating 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 mayonnaise bottle having a capacity of 250 cc, and the lid was sealed. This is stored in a thermo-hygrostat at a temperature of 70 ° C and a humidity of 75%, and the viscosity increase of each sample after 2 weeks
Storage stability was determined. When the increase rate is less than 10% from the initial viscosity ○, When 10% or more and less than 100% △, 100
When it was more than%, it was evaluated as ×.

<Anti-fouling performance test> Each underwater anti-fouling coating was applied to a sandblasted steel sheet with a tar vinyl anticorrosive paint in advance on both sides of a coated plate (100 x 200 x 1 mm) to give a dry film thickness. Spray coating was applied twice to 120 μm on one side and drying was performed for 1 week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% to prepare a test piece. This test piece was immersed in seawater for 24 months in Yura Bay, Hyogo Prefecture, and the ratio of the area occupied by adherent organisms (adhered area) on the test film was measured over time.

[0065]

[Table 4]

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

[0067]

[Table 5]

(Note) (* 1) Antifouling performance: Indicates the area (%) on which organisms adhere.

As is clear from the results of Table 4 above, Examples 1 to 1 obtained from the metal ester compound solutions I to VIII
The coating film of each of the underwater antifouling coating compositions of Example 11 has a uniform dissolution value α1 to α3 of 0.97 to 1.
In the range of 03, the uniform solubility is high, the solubility does not reach a peak over time, and excellent performance is exhibited. Further, the re-dissolution rate β measurement with the initial composition solvent shows that the aged film is almost the same as the initial film. This means that hydrolysis did not occur, 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 coating film was not found, and the resolubility in the solvent was not measured. Further, in the coating film obtained from the organotin copolymer solution shown in Comparative Example 2, the dissolution uniform value α decreases with time, which indicates that it gradually becomes difficult to dissolve. This is because the redissolving rate β (%) of the initial composition solvent of the aged film after 12 months was as low as 76%, so that hydrolysis in the film preceded and insolubility after hydrolysis on the surface of the remaining film. The ingredients remain,
It shows that stable solubility is not obtained.

Further, as is clear from the results of Table 5, Examples 1 to 11 were very good in both storage stability and antifouling performance. On the other hand, in the silicone rubber shown in Comparative Example 1, gelation occurred in the storage stability test, and even in the antifouling property, biological adhesion was observed after 6 months, and after 12 months, full adhesion was observed. It showed poor results as a stain coating agent. In the storage stability test, the organotin copolymer solution shown in Comparative Example 2 did not gel, but showed a tendency to increase in viscosity.
Biofouling was observed after 2 months, indicating poor results.

Front page continued (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 5/16 C09D 5/14 A01N 25/24 A01N 55/00-55/10 C09D 7/12 C09D 183/00-183 / 16

Claims (2)

(57) [Claims] 1. An underwater antifouling coating material 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): [However, X in the formula is Wherein n is an integer of 0 to 15, m is a real number of 0 or more, R ¹ and R ² are both groups selected from an alkyl group, an alkoxyl group and an aryl group, and R ³ is a group similar to R ¹ and R ² and the following general formula (4): (Wherein Y represents the formula (2) or the formula (3), and p represents an integer of 0 to 15), and R ⁴ or R is a group selected from the group consisting of ⁵ is a group similar to R ¹ and R ² and the following general formula (5): (However, in the formula, 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 or a substituted aryl group, and may be the same or different groups 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 divalent or trivalent metal compound. 2. An underwater antifouling coating agent containing the metal ester compound according to claim 1, an antifouling agent, and a surface lubricant.