JPH083484A - Antifouling paint composition - Google Patents

Abstract

PURPOSE:To provide a coating composition which prevents effectively for a long time the surfaces of the outer plate of the bottom of a ship, an underwater structure, a fishnet, etc., from being fouled by various marine life and is excellent in safety, health and environmental protection. CONSTITUTION:This composition is an antifouling coating material containing, as a binder, a resin having a group represented by the following formula at the terminal of a side chain: -CO-O-M-O-Si-(R)3 (wherein M is zinc or copper; Rs, which may be the same or different from each other, are each hydrogen, a halogen, hydroxyl, an organic group, an organo(poly)siloxane group, silyl, mercapto or a substituted derivative thereof).

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling coating composition containing a metal-containing resin that hydrolyzes in seawater as a binder.

[0001]

2. Description of the Related Art The bottom skin of a ship below sea level,
Various types of marine organisms adhere to the surface of marine structures and fishing nets, which hinders efficient operation of ships.
In marine structures and fishing nets, problems such as a markedly shortened service life occur, and as a countermeasure, underwater antifouling paint compositions containing various antifouling agents are used. As a typical antifouling paint that has been conventionally used, a vehicle component consisting of a seawater-insoluble resin such as vinyl resin, alkyd resin, and chlorinated rubber and seawater-soluble rosin is used as an antifouling agent. Dissolved matrix type antifouling paints, and dissolved matrix type antifouling paints that use a copolymer having a triorganotin-containing monomer that gradually hydrolyzes in seawater as a constituent component as a vehicle component, and an antifouling agent as necessary. There is. However, the antifouling agent is eluted together with rosin in seawater, and the insoluble matrix antifouling paint exhibiting an antifouling effect cannot be expected to have a stable antifouling effect for a long period of time, and the rosin and the antifouling agent are eluted. After that, since the resin component insoluble in seawater remains as a coating film and forms a skeleton structure, there is a drawback that friction resistance between seawater and the coated surface increases, speed decreases, fuel consumption increases, etc. especially when applied to a ship. . On the other hand, the dissolving matrix type antifouling paint has an antifouling effect, but has problems in health and safety and environmental conservation.

Recently, an antifouling paint containing a hydrolyzable polyester resin and a water-insoluble resin as vehicle components, which does not use an organic tin-containing resin, has been developed as an intermediate type between the above two paints (Japanese Patent Publication No. Hei 3). -46501, JP-A-4-23020, etc.). This antifouling paint has a vehicle component of a single condensate of an oxyacid such as lactic acid and a water-insoluble resin, and does not contain organic tin.
Although it is a paint that is excellent in terms of environmental protection, since it uses a water-insoluble resin in combination, like the insoluble matrix antifouling paint, a resin component that is insoluble in seawater remains as a coating film, forming a skeleton structure. was there. Therefore, an antifouling paint using only a single condensate of oxyacid as a vehicle component has been considered, but when the condensate becomes a high molecular weight at a level of tens of thousands or more, it is dissolved only in a special organic solvent such as chloroform. Since it does not dissolve in normal paint organic solvents, it has drawbacks in paintability and workability. On the other hand, when the molecular weight is reduced to 10,000 or less, it dissolves in normal paint organic solvents, but in seawater. However, the hydrolysis rate was too high, and the hydrolysis rate could not be adjusted. Therefore, the long-term antifouling effect could not be obtained.

[0003]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of conventional antifouling paints such as those mentioned above and enables the use of bottom skins of ships below sea level, marine structures, fishing nets and the like. An object of the present invention is to provide a coating composition which can effectively prevent various marine organisms from adhering to the surface for a long period of time and is excellent in safety and health and environmental protection.

[0004]

Means for Solving the Problems As a result of research to overcome such a situation, the present inventors have found that other specific metal-containing resin can be used as a binder without containing organotin. The present invention has been completed based on the finding that a coating composition having a long-term antifouling property and excellent safety and health and environmental protection can be obtained. That is, the present invention
Provided is an antifouling coating composition using as a binder a resin having a group represented by the following formula (I) at the end of the side chain. —CO—O—M—O—Si (R) ₃ (wherein M represents a zinc or copper atom; R is the same or different group, and is a hydrogen atom, a halogen atom, a hydroxyl group, an organic group , An organo (poly) siloxane group,
A silyl group, a mercapto group, or a substitution product thereof is shown. ) As the material group, an alkyl group, an aryl group,
Representative examples include an alkenyl group, an alkoxyl group, a phenoxyl group, an acyl group, and a substitution product thereof. Hereinafter, the present invention will be described in detail.

The binder constituting the coating composition of the present invention is
It is synthesized by various methods, but in particular, the acid value is 40 to 3
It is synthesized by introducing a group represented by the formula (I) into a resin having a carboxyl group-containing ordinary coating resin such as an acrylic resin or a polyester resin of 50 to 60, preferably 60 to 300 as a base resin. Binders are preferred. When the acid value of the base resin is smaller than the above range, the introduction amount of the group represented by the formula (I) tends to be small, and the long-term antifouling property tends to decrease, while when it is larger than the above range, the coating composition obtained can be improved. The physical properties of the film tend to deteriorate, and cracks and the like tend to occur.

The acrylic resin as the base resin is appropriately combined with various polymerizable unsaturated monomers so that the resulting acrylic resin has an acid value within the above range, for example, 80
It is produced by reacting at ˜180 ° C. for 2 to 10 hours. Examples of the polymerizable unsaturated monomer used here include (meth)
Acrylic acid, crotonic acid, maleic acid, itaconic acid, phthalic acid, citraconic acid and other polymerizable unsaturated carboxylic acids or their acid anhydrides; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 -(Meth) acrylic acid esters such as ethylhexyl (meth) acrylate and lauryl (meth) acrylate; aromatic vinyl monomers such as styrene and vinyltoluene; hydroxy groups such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate Vinyl monomer containing; glycidyl group-containing vinyl monomer such as glycidyl (meth) acrylate, methylglycidyl (meth) acrylate; perfluorocyclohexyl (meth) acrylate, propyl perfluorooctanesulfonamide ethyl (meth) ac Rate, vinyl fluoride, fluorine-containing vinyl monomers such as vinylidene fluoride diethyl (meth) acrylamide, (meth) nitrogen-containing vinyl monomers such as acrylamide, vinyl ethyl ether, vinyl ether monomers such as vinyl ether; vinyl acetate,
Vinyl esters such as vinyl benzoate; Others (meth) acrylic acid chloride, vinyl chloride, vinylidene chloride,
(Meth) acrylonitrile and the like.

The polyester resin used here is a polybasic acid or a polyhydric alcohol with an acid anhydride thereof, and if necessary, benzoic acid, and one base as a molecular weight modifier such as various animal and vegetable oil fatty acids. 180 to 2 while dehydrating in the presence or absence of a catalyst in combination with an acid.
It is manufactured by reacting by heating at a temperature of 30 ° C. Examples of the polybasic acid or its acid anhydride used in the production of this polyester resin include oxalic acid, succinic acid, succinic anhydride,
Linear polybasic acids such as adipic acid, azelaic acid and sebacic acid or acid anhydrides thereof; phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride,
Hexahydrophthalic acid, hexahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, cyclohexanedicarboxylic acid, and other aromatic basic acids or their anhydrides; maleic acid There are unsaturated polybasic acids such as maleic anhydride, fumaric acid and itaconic acid, or acid anhydrides thereof, and examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butanediol,
There are 1,6-hexanediol, diethylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A, bisphenol dihydroxypropyl ether, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and cyclohexanedimethanol. Other examples of the base resin include epoxy resin, acrylic modified epoxy resin, acrylic modified polyester resin, alkyd resin, and fluororesin. Particularly in the present invention, an acrylic resin is preferable because it has excellent adhesiveness when repeatedly applied to the old antifouling coating film formed from the coating material of the present invention.

In order to introduce the group represented by the above formula (I) into these base resins, the following compounds are used. (i) Zinc or copper oxides, chlorides, hydroxides, sulfides or these and acetic acid, lactic acid, butyric acid, propionic acid,
(Meth) acrylic acid, oxalic acid, valeric acid, enanthic acid, cyclohexanecarboxylic acid, propiolic acid, zinc salts or copper salts of organic basic acids that are reaction products with organic basic acids such as glycolic acid (hereinafter collectively referred to as (Ii) Ethyl orthosilicate, silanol, silanediol, silanetriol, disilanehexol, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and other silane compounds; represented by the following formula: Siloxane compound: (R) ₃ Si-O- (Si (R) ₂ -O-) _n -Si (R) ₃ or (R) ₃ Si-O- (
Si (R) ₂ -O-) _m- (Si (R) ₂ -0-) _n -Si (R) ₃ (wherein R is the same or different, at least one is a hydroxyl group or an alkoxy group) And the remainder is a hydrogen atom, a halogen atom, a mercapto group, or a material group such as an alkyl group, an aryl group, an alkenyl group, an alkoxyl group, a phenoxyl group, an acyl group or a substitution product thereof; m and n are , 0 or an integer of 1 or more.);

DC6-2230, DC3037, DC3
074, SH6018, SR2402, QP8-531
4 (all are trade names of Toray Dow Corning Silicone Co., Ltd.) and other known silicone intermediates having a hydroxyl group or an alkoxy group; Compound (hereinafter collectively referred to as "silicon compound"). The binder of the present invention is preferably prepared by heating and reacting the metal compound (i) and the silicon compound (ii) in a solvent in the presence or absence of a catalyst at a temperature of about 70 to 200 ° C. It can be produced by heating the reaction product and the base resin containing a carboxyl group at a temperature of about 110 ° C to 200 ° C. Alternatively, it is also possible to react the base resin containing the carboxyl group with the metal compound (i), and then react the silicon compound (ii) to produce the binder of the present invention. is there.

The above-described production method is a method of introducing the group represented by the above formula (I) into the base resin, but as another method, the polymerizable unsaturated carboxylic acid or its acid anhydride and the metal can be used. A method of reacting the compound (i) and then copolymerizing it with another polymerizable unsaturated monomer, and further reacting the silicon compound (ii) to produce a binder, or the metal compound (i) and silicon. The compound (ii) is reacted, then the reaction product is reacted with the polymerizable unsaturated carboxylic acid or an acid anhydride thereof, and further copolymerized with another polymerizable unsaturated monomer to produce a binder. The method or the like may be used.

The binder thus obtained is water-repellent while the group represented by the formula (I) is gradually hydrolyzed in seawater and the group remains unhydrolyzed. Since it has an effect, it has a long-term stable antifouling effect due to the synergistic effect of both. In order to exert such an antifouling effect, the content of zinc or copper atom in the group represented by the formula (I) is 1 to 20% by weight, and particularly preferably 1. A range of 5 to 15% by weight is suitable. Incidentally, if the amount of zinc or copper atoms is less than the above range, the antifouling effect is reduced, and conversely if the amount is too much, the amount of hydrolysis is too large and the coating film is likely to disappear in an early period, resulting in long-term antifouling property. It tends to decrease.

The weight average molecular weight of the binder resin varies depending on the kind of the resin, but is usually 2,000 to 150,0.
A value of 00, preferably 5,000 to 50,000, is suitable.
When the weight average molecular weight is smaller than the above range, the drying property and various physical properties of the resulting coating film tend to be deteriorated, while when it is larger than the above range, the storage stability of the coating composition tends to be deteriorated. The binder resin thus obtained is a solvent such as an aromatic solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as ethyl acetate, butyl acetate or cellosolve acetate. Dilute to a desired resin concentration with an alcohol solvent such as butyl alcohol or an ether solvent such as dioxane or tetrahydrofuran, and use it as a vehicle component of an antifouling paint. The antifouling coating composition of the present invention contains the resin solution as a vehicle component, and further, if necessary, a known antifouling agent, a copper compound of a monovalent organic acid having 5 to 18 carbon atoms, a solvent, a color pigment, and a constitution. Pigment, rosin,
It is composed of various additives such as a plasticizer, an antifoaming agent, an antisettling agent, and a leveling agent.

The antifouling agent used as necessary in the present invention is not particularly limited, but as an example,
Cuprous oxide, basic copper carbonate, copper thiocyanate, copper hydroxide, cuprous rhodanate, manganese ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino- s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethylchlorophenylurea, zinc ethylene bisdithiocarbamate, 4,5-
Dichloro-2-N-octyl-3 (2H) inchazolone, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N'-phenyl (N-fluorodichloromethylthio) sulfamide, tetramethylthiuram disulfide, 2, There are 4,6-trichlorophenylmaleimide, 2-pyridinethiol-1-oxide zinc salt and the like, and these can be used alone or in combination.

The copper compound of a monovalent organic acid having 5 to 18 carbon atoms, which is optionally used in the present invention, is typically a monovalent organic acid having 5 to 18 carbon atoms, a hydroxide of copper, or an oxide. Or the like, or a direct method of dehydration and filtration, or a monovalent organic acid having 5 to 18 carbon atoms into a water-soluble salt such as a sodium salt, and a water-soluble salt of copper, for example, a sulfate or a nitrate. Alternatively, it is produced by a metathesis method in which a carbonate or the like is added, an ion exchange reaction called metathesis is carried out, and further washing with water, dehydration and filtration are carried out. As the monovalent organic acid having 5 to 18 carbon atoms, valeric acid, caproic acid, caprylic acid, undecyl acid, lauric acid, myristic acid, stearic acid, undecylenic acid, linoleic acid, versatic acid (manufactured by Shell Chemical Co., Ltd. ), Equacid-9, -10 (manufactured by Idemitsu Petroleum Co., Ltd.), neodecanoic acid (manufactured by Exxon Chemical Co., Ltd.)
Various fatty acids such as, and synthetic fatty acids can be mentioned.

The solvent used in the present invention as needed is the same as the solvent for the resin. The coloring pigments, extender pigments, rosins, plasticizers, various additives and the like used as necessary in the present invention are the same as those used in ordinary antifouling paints. When the antifouling coating composition of the present invention is prepared, the resin is 15 to 60% by weight, preferably 20 to 40% by weight, the antifouling agent is 0 to 45% by weight, preferably 10 to 40% by weight, a monovalent organic acid. It is suitable to add the copper compound of 0 to 20% by weight, preferably 1 to 10% by weight, and the solvent (solvent) 20 to 70% by weight, preferably 30 to 50% by weight. When the amount of the resin is less than the above range, the coating film strength and the like tend to decrease, while when it is too large, the coating workability and the like tend to deteriorate. The antifouling coating composition of the present invention is prepared by mixing and dispersing the above resin and other components in a batch or by dividing and mixing with a usual coating production apparatus such as a ball mill and a disperser. The antifouling coating composition of the present invention thus prepared, as it is, or after adjusting the viscosity with a solvent, by airless spray coating, air spray coating, roller coating, brush coating, etc., to a ship or marine structure, etc., dried. It is preferable to apply a film having a thickness of about 30 to 300 μm, preferably 80 to 200 μm later.

[0016]

According to the present invention, the long-term antifouling property is almost the same as that of the dissolution matrix type antifouling paint containing the organic tin-containing resin as the vehicle component, and the hydrolysis rate of the coating film can be controlled. A coating film formed from the coating material of the present invention has excellent adhesion when repainted, that is, excellent recoatability, and does not contain an organic tin-containing resin. A groundbreaking antifouling paint was obtained.

[0017]

EXAMPLES The present invention will now be described in more detail by way of examples. In the examples, "parts" and "%" are shown based on weight. <Preparation of base resin varnish A> In a separable flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe,
After adding 80 parts of xylene and 20 parts of n-butanol and raising the reaction temperature to a reflux temperature (100 to 110 ° C.), 48.2 parts of ethyl acrylate, 19.7 parts of 2-ethylhexyl acrylate, under a nitrogen gas atmosphere, A mixture of 32.1 parts of acrylic acid and 1.5 parts of azobisisobutyronitrile was added dropwise over 3 hours, and after 30 minutes from the end of addition, 30
0.2 parts of azobisisobutyronitrile and 7 parts of xylene were added every 3 minutes, and the reaction was continued for 2 hours. The obtained base resin varnish A has a solid content of 45.1% and an acid value (solid content).
It was 250 and the weight average molecular weight was 10,200. <Preparation of Base Resin Varnish B> In the method for preparing base resin varnish A, the mixed solution was mixed with n-butyl acrylate 70.0
Parts, n-butyl methacrylate 7.0 parts, methacrylic acid 2
The reaction was carried out in the same manner except that the mixture was changed to 3.0 parts and 1.0 part of azobisisobutyronitrile, and the solid content was 45.0%, the acid value (solid content) was 150, and the weight average molecular weight was 21. Three
A base resin varnish B of No. 00 was prepared.

<Preparation of Base Resin Varnish C> In the method for preparing base resin varnish A, the mixed solution was prepared by mixing 14.7 parts of methyl methacrylate, 75.0 parts of ethyl acrylate, 10.3 parts of acrylic acid and azobisisobutyrate. Ronitrile was changed to a mixed solution consisting of 0.7 parts and the reaction was carried out in the same manner except that the reaction temperature was changed to 90 ° C., solid content 44.9%, acid value (solid content) 80 weight average molecular weight 35,500 A base resin varnish C of was prepared. <Preparation of Metal-Containing Intermediate Varnish D> In a separable flask equipped with a stirrer, a thermometer, a cooling tube with a water divider, and a nitrogen introducing tube, 15.0 parts of xylene and a silicone intermediate [“S
H6018 "(trade name of Toray Dow Corning Silicone Co., Ltd.); average molecular weight 1,600, hydroxyl group content 6.4%]
217.2 parts and 53.1 parts of 2-ethylhexyl alcohol were added, and the reaction temperature was 120 ° C to 14 ° C under a nitrogen gas atmosphere.
At 0 ° C., 6.6 parts of condensed water were removed and cooled. Next, 29.7 parts of zinc acetate and 300 parts of xylene were added, and the reaction temperature was 12
Performing deacetic acid reaction while raising from 0 ℃ to 140 ℃,
The amount of deacetic acid was quantified, and the reaction was terminated at the reaction rate of 50% as zinc acetate, and the mixture was cooled. The solid content of the obtained metal-containing intermediate varnish D was 48.3%.

<Preparation of Metal-Containing Intermediate Varnish E> 400.0 parts of xylene, 158.0 parts of dimethyldiethoxysilane, 103.6 parts of copper hydroxide and 2 in the separable flask.
-Ethylhexyl alcohol 138.4 parts was added, the reaction was performed under a nitrogen gas atmosphere at a reaction temperature of 80 ° C to 130 ° C while removing ethanol, the amount of ethanol removed was quantified, and the reaction rate as dimethyldiethoxysilane was 90%. At that point, the reaction was terminated and the mixture was cooled. The solid content of the obtained metal-containing intermediate varnish E was 46.5%. <Preparation of Metal-Containing Intermediate Varnish F> In the separable flask, 15.0 parts of xylene and a silicone intermediate [“SH
6018 "(trade name of Toray Dow Corning Silicone Co., Ltd.)] 219.0 parts and 53.4 parts of 2-ethylhexyl alcohol were added, and the reaction temperature was 120 ° C. under a nitrogen gas atmosphere.
At 140 ° C., 6.6 parts of condensed water was removed and cooled. Next, 27.3 parts of copper acetate and 300 parts of xylene were added, and the deacetic acid reaction was carried out while raising the reaction temperature from 120 ° C to 140 ° C. The amount of deacetic acid was quantified, and the reaction end point was determined when the reaction rate as copper acetate was 50%. , Cooled. The solid content of the obtained metal-containing intermediate varnish F was 49.0%.

<Preparation of Metal-Containing Resin Varnish M-1> The base resin varnish A100 was placed in a separable flask equipped with a stirrer, a thermometer, a cooling pipe with a water diverter, and a nitrogen introducing pipe.
Parts, metal-containing intermediate D857 parts and xylene 288 parts were added, and the reaction temperature was adjusted to the reflux temperature (118
The temperature was raised to 140 ° C.) to carry out the deacetic acid reaction, and the reaction end point was reached when the deacetic acid amount reached 10.8 parts (reaction rate 90%). During the reaction, acetic acid was dissolved in the solvent, so the reaction was sometimes carried out while removing the solvent and replenishing the removed amount of xylene. The obtained metal-containing resin varnish M-1 had a solid content of 37.8% and a resin weight average molecular weight of 15,
300, Zn content in the resin was 3%, and Si content was 5.1%.

<Preparation of metal-containing resin varnish M-2> 100 parts of base resin varnish A in the separable flask,
2.6 parts of the metal-containing intermediate varnish E12 and 53 parts of xylene were added, and the reaction temperature was adjusted to the reflux temperature (11
(8-140 ℃), the dehydration reaction is performed and the dehydration amount 3.
The reaction end point was reached when the amount reached 2 parts (reaction rate 89%). The obtained metal-containing resin varnish M-2 had a solid content of 38.4%,
Weight average molecular weight of resin 28,700, Cu content of resin 12.9
%, And the Si amount was 5.7%. <Preparation of Metal-Containing Resin Varnish M-3> 100 parts of the base resin varnish C, 39 parts of the metal-containing intermediate E and 32 parts of xylene were placed in the separable flask, and the reaction temperature was set to a reflux temperature (118 to 140) under a nitrogen gas atmosphere. (° C) to dehydration reaction, dehydration amount 1.0 parts (reaction rate 87%)
The reaction end point was reached. The obtained metal-containing resin varnish M-3 had a solid content of 38.2%, a weight average molecular weight of the resin of 39,800, a Cu content of the resin of 6.5%, and a Si content of 2.9%.

<Preparation of Metal-Containing Resin Varnish M-4> Base resin varnish B100 was placed in the separable flask.
Parts, metal-containing intermediate F505 parts and xylene 185 parts were added and the reaction temperature was adjusted to the reflux temperature (118
Up to 140 ° C) to carry out deacetic acid reaction and deacetic acid amount 6.
The end point of the reaction was when the content reached 5 parts (reaction rate 90%). During the reaction, acetic acid was dissolved in the solvent, so the reaction was sometimes carried out while removing the solvent and replenishing the removed amount of xylene. Obtained metal-containing resin varnish M-4
Is a solid content of 38.5%, the weight average molecular weight of the resin is 25,10
0, the amount of Cu in the resin was 2.7%, and the amount of Si was 4.7%.

[Examples 1 to 4 and Comparative Examples 1 and 2] The composition components shown in Table 1 were kneaded and dispersed to produce the antifouling paints of Examples 1 to 4 and Comparative Examples 1 and 2. Each of these antifouling paints,
A steel plate coated with anticorrosion paint was air-spray coated to a dry film thickness of 150 μm and dried. When the obtained test plate was subjected to an antifouling test and a film thickness reduction test, the results shown in Tables 2 and 3 were obtained, respectively.
The test was performed based on the following method. <Antifouling test method> In Toba Bay, Toba City, Mie Prefecture, a test plate was submerged in the sea, and the appearance of the coating film was observed. Evaluation criterion 5: No deposit was observed on the test plate. 4: Adhesion of thin slime is recognized on the test plate. 3: Thick slime adhered to the test plate. 2: Adhesion of large animals and plants is slightly observed. 1: Large attachment of large animals and plants is observed. <Test Method for Measuring Film Thickness Reduction> A test plate was attached to a rotor having a peripheral speed of 15 knots and rotated in the sea to measure the degree of film thickness reduction every three months. The numerical values in Table 4 are the difference (unit: μm) between the initial film thickness measured with a micrometer and the film thickness measured every 3 months.

[0024]

[Table 1] Table 1 (Unit: parts by weight) Example ratio Comparative example Composition 1 2 3 4 1 2 Metal-containing resin varnish M-1 59.5 〃 M-2 58.6 〃 M-3 58.9 〃 M-4 58.4 Rosin 15 Vinyl chloride resin varnish (solid content 50%) 20 Organic tin methacrylate copolymer varnish Note 1) 45 Chlorinated paraffin 5 Cuprous oxide 35 35 35 35 35 35 Talc 5 5 5 5 5 5 5 Valve handle 3 3 3 3 3 3 Xylene 10 10 10 10 12 15 Methyl isobutyl ketone 2 2 2 2 ──────────────────────────────────── Note 1) Varnish of tributyltin methacrylate / methyl methacrylate (65/35) copolymer with a solid content of 50%

[0025]

[Table 2] Table 2 (results of antifouling test) Number of soaking months 3 6 9 12 18 24 30 36 Example 1 5 5 5 5 5 5 5 5 5 2 5 5 5 5 5 5 5 5 5 5 3 5 5 5 5 5 5 5 5 5 4 5 5 5 5 5 5 5 5 5 5 comparison Example 1 5 5 5 5 5 5 5 5 5 2 4 4 3 2 1 1 1 1 1

[0026]

[Table 3] Table 3 (result of film thickness reduction measurement test) Number of soaking months 3 6 9 12 Example 1 25 53 80 104 2 27 50 70 98 3 18 33 50 70 4 21 40 63 88 Comparative example 1 16 40 68 90 2 5 6 8 9

As is clear from the test results of Tables 2 and 3, the coating materials of Examples 1 to 4 of the present invention have the organotin-based dissolution matrix of Comparative Example 1 which has been conventionally considered to have a safety and health problem. It had almost the same antifouling properties as the type antifouling paint.
Further, it can be seen that the reduction amount of the film thickness is almost uniform and the solubility of the coating film can be controlled. On the other hand, Comparative Example 2, which is an insoluble matrix antifouling paint, had a poor long-term antifouling property. Further, in Examples 1 to 4, the test plate after 12 months of the film thickness reduction measurement test was washed with water and dried, and the same paint was again applied on the old coating film in the same manner and dried, and then the test was conducted. The plate was attached to a rotor with a peripheral speed of 15 knots, rotated in the sea, and the state of the coating film after 6 months was observed. As a result, no peeling of the coating film was observed and recoatability was excellent.

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[Procedure amendment]

[Submission date] July 29, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

<Preparation of Metal-Containing Intermediate Varnish E> 400.0 parts of xylene, 158.0 parts of dimethyldiethoxysilane, 103.6 parts of copper hydroxide and 138.4 parts of 2-ethylhexyl alcohol in the separable flask. In a nitrogen gas atmosphere at a reaction temperature of 80 ° C. to 130 ° C.
The reaction was carried out while removing ethanol with, the amount of ethanol removed was quantified, the reaction end point was reached when the reaction rate as dimethyldiethoxysilane was 90%, and the reaction was cooled. The solid content of the obtained metal-containing intermediate varnish E was 46.5%. <Preparation of Metal-Containing Intermediate Varnish F> 15.0 parts of xylene and silicone intermediate [“S
H6018 "(trade name of Toray Dow Corning Silicone Co., Ltd.)] 219.3 parts and 53.4 parts of 2-ethylhexyl alcohol were added, and the reaction temperature was 1 under a nitrogen gas atmosphere.
At 20 ° C. to 140 ° C., 6.6 parts of condensed water was removed and cooled. Next, 27.3 parts of copper acetate and 300 parts of xylene were added, and a deacetic acid reaction was carried out while raising the reaction temperature from 120 ° C to 140 ° C, and the amount of deacetic acid was quantified. , Cooled. The solid content of the obtained metal-containing intermediate varnish F was 49.0%.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

<Preparation of Metal-Containing Resin Varnish M-1> A base resin varnish A100 was placed in a separable flask equipped with a stirrer, a thermometer, a cooling pipe with a water divider, and a nitrogen introducing pipe.
Parts, metal-containing intermediate D857 parts and xylene 288 parts were added, and the reaction temperature was adjusted to the reflux temperature (118
The temperature was raised to ˜140 ° C.) to carry out the deacetic acid reaction, and the reaction end point was reached when the deacetic acid amount reached 10.8 parts (reaction rate 90%). During the reaction, acetic acid was dissolved in the solvent, so the reaction was sometimes carried out while removing the solvent and replenishing the removed amount of xylene. The obtained metal-containing resin varnish M-1 had a solid content of 37.8% and a resin weight average molecular weight of 1
5,300, the amount of Zn in the resin was 3%, and the amount of Si was 17.3 %.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

<Preparation of Metal-Containing Resin Varnish M-4> Base resin varnish B100 was placed in the separable flask.
Parts, metal-containing intermediate F505 parts and xylene 185 parts were added and the reaction temperature was adjusted to the reflux temperature (118
The temperature was raised to 140 ° C.) to carry out the deacetic acid reaction, and the reaction end point was reached when the amount of deacetic acid reached 6.5 parts (reaction rate 90%). During the reaction, acetic acid was dissolved in the solvent, so the reaction was sometimes carried out while removing the solvent and replenishing the removed amount of xylene. The resulting metal-containing resin varnish M-4 had a solid content of 38.5% and a resin weight average molecular weight of 2
5,100, Cu amount 2.7% in resin, Si amount 16.1
%Met.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuyoshi Tsuneda 1-981 Shimonagata, Nishinasuno-machi, Nasu-gun, Tochigi Prefecture (72) Inventor Yoshiyuki Iwase 68-27 Nishi-Toyama, Nishinasuno-cho, Nasu-gun, Tochigi Prefecture (72) Inventor Tomohisa Nitta 3-1172-4 Shimonagata, Nishinasuno-cho, Nasu-gun, Tochigi Prefecture Co-op Cherry A102

Claims (2)

[Claims] 1. An antifouling coating composition comprising as a binder a resin having a group represented by the following formula at the end of the side chain. —CO—O—M—O—Si (R) ₃ (wherein M represents a zinc or copper atom; R is the same or different group, and is a hydrogen atom, a halogen atom, a hydroxyl group, an organic group , An organo (poly) siloxane group,
A silyl group, a mercapto group, or a substitution product thereof is shown. ) 2. The antifouling coating composition according to claim 1, wherein the resin is an acrylic resin or a polyester resin.