JP2872470B2 - Conductive paint for prevention of marine organism adhesion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the prevention of marine organisms from adhering to a ship, a marine / underwater structure, a seawater drainage / drainage facility, a seawater storage tank, a quay, etc. About technology. More specifically, at least a water contact portion of an object in contact with seawater (hereinafter, simply referred to as a "water contact portion")
A conductive layer is provided over the conductive layer, and a direct current is passed through the conductive layer, and the layer is used as an anode to electrolyze seawater to generate chlorine, hypochlorous acid, etc., which are disliked by marine organisms, thereby attaching marine organisms. The present invention relates to a conductive paint for preventing the adhesion of marine organisms used in the formation of the conductive layer in a technique for preventing marine organisms.

[0002]

2. Description of the Related Art Conventionally, a water-contact portion of an object in contact with seawater is coated with an antifouling paint containing an antifouling agent such as an organotin compound, and the leaching antifouling agent is used to prevent marine organisms from adhering. That is being done. However, since the dissolution rate of the antifouling agent cannot be adjusted and the amount of the antifouling agent contained in the paint is limited, repainting work is required. There is a risk of environmental pollution due to elution of the pollutant.

As a technique for preventing the adhesion of marine organisms instead of the antifouling paint, a technique for preventing the adhesion of marine organisms by electrolysis of seawater has been developed.

[0004] More specifically, a conductive layer is provided on a water-contacting portion of an offshore structure via an insulating layer, and the conductive layer is used as an anode, and a cathode is provided at an appropriate distance in seawater. The conductive layer is divided into two or more sections, one part (one or more sections) is used as an anode, and the rest is used as a cathode, and 1 A / m is provided between both electrodes.
Apply a DC current of about ² or less to electrolyze seawater,
The generation of chlorine, hypochlorous acid and the like, which are disliked by marine organisms, in the vicinity of the conductive layer serving as the anode prevents the adhesion.

The conductive layer is provided as a conductive paint film or a composite layer of a conductive paint film and another material. Conventionally, this conductive paint and a conductive layer using the same are as follows. Something like that is known.

(1) An electrically conductive filler made of any one of graphite powder, carbon black, magnetite, manganese dioxide, and platinum group metal is used as an epoxy resin,
A mixture containing 50% or more by volume ratio in a coating material containing any one of an unsaturated polyester resin, an acrylic resin, a phenol resin, and a urethane resin as a matrix
No. 101466).

(2) An electric conductive film made of a conductive filler of a metal such as carbon, magnetite, manganese dioxide, platinum group or the like and an organic binder in which a conductive wire is buried (JP-A-63-103789). No.).

(3) powder of a conductive filler such as nickel, copper, titanium, niobium, magnetite, and manganese dioxide;
Filler, small pieces such as flakes, epoxy resin, vinyl resin, unsaturated polyester resin, acrylic resin, phenol resin, urethane resin, a mixture of organic binders such as vinyl ester epoxy resin is provided in a multilayer,
One in which the specific resistance is gradually increased from the inside to the outside (Japanese Patent Laid-Open No. 64-87791).

[0009]

However, the conductive layer formed by using the above-mentioned conventional conductive paint for preventing marine organisms from adhering is liable to cause seawater to penetrate and diffuse into a coating film constituting the conductive layer. There is a problem that the material is easily deteriorated and damaged by contact with substances such as chlorine and hypochlorous acid generated by the seawater, and the seawater electrolysis resistance is poor.

Specifically, cracking of the coating film, peeling of the coating film, detachment of the conductive filler, erosion of the conductive filler and the conductive wire easily occur, and the conductivity of the conductive layer is reduced. In addition, there is a problem that the prevention of marine organisms from being adhered cannot be maintained for a long period of time over a wide range of the wetted portion.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides a barrier property for preventing permeation and diffusion of seawater and a resistance to electrolysis products of seawater.
It is an object of the present invention to provide a conductive paint for preventing marine organism adhesion which is excellent in seawater electrolysis resistance and can maintain marine organism adhesion in a wide range for a long period of time.

[0012]

Accordingly, the present invention provides a copolymer resin comprising at least the following (A), (B) and (C), wherein (A), (B) and (C) ) Is 70 to 95% by weight, 1 to 10% by weight, 2 to 21% by weight, respectively, and (A) + (B) +
A conductive paint for preventing marine organisms from adhering, characterized in that a copolymer resin containing (C) 95% by weight or more of the whole is used as a binder, and the binder, a conductive filler, and a solvent are contained. (A) Vinyl chloride moiety. (B) a carboxylic acid vinyl ester moiety. (C) A vinyl alcohol moiety resulting from the above (B) by saponification.

The present invention will be described in more detail.

The proportion of the vinyl chloride moiety (A) in the copolymer resin used as the binder is 70 to 95% by weight, preferably 80 to 95% by weight. When this proportion is less than 70% by weight, it is difficult to sufficiently prevent the permeation and diffusion of seawater into the obtained coating film, and the resistance to electrolysis products is reduced, so that the obtained coating film has reduced seawater electrolysis resistance. . Conversely 95
If the amount is more than 10% by weight, the solubility of the copolymer resin in the solvent tends to decrease.

The proportion of the (B) vinyl carboxylate moiety in the copolymer resin used as the binder is from 1 to 1
0% by weight, preferably 1 to 8% by weight. If this proportion is less than 1% by weight, the solubility of the copolymer resin in the solvent tends to decrease. Conversely, if it exceeds 10% by weight, it is difficult to sufficiently prevent permeation and diffusion of seawater into the obtained coating film,
In addition, the resistance to electrolysis products is reduced, so that the resulting coating film has reduced seawater electrolysis resistance.

The proportion of the vinyl carboxylate used in the copolymerization reaction is such that a part of the vinyl carboxylate moiety in the copolymer resin obtained by the copolymerization reaction is converted into a vinyl alcohol moiety by saponification. It is selected in consideration of what is done.

The vinyl carboxylate which forms (B) can be used alone or in combination of two or more. For example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl monochloroacetate, vinyl versatate And the like.

The (C) vinyl alcohol moiety in the copolymer resin used as the binder is formed by saponification of a part of the (B) carboxylic acid vinyl ester moiety in the resin, and the ratio is 2 to 21% by weight. %, Preferably 5
15% by weight. If the content is less than 2% by weight, it becomes difficult to uniformly disperse the conductive filler or the like in the coating material, or it becomes difficult to obtain high reactivity when a crosslinking reaction is performed on the copolymer resin by using a hydroxyl group in a vinyl alcohol portion. It's easy to do.
Conversely, if it exceeds 21% by weight, the solubility of the copolymer resin in the solvent tends to decrease, and the viscosity of the conductive paint increases and the number of hydrophilic groups increases. It becomes difficult to prevent permeation diffusion.

The copolymer resin used as the binder includes:
In addition to the above (A) to (C), another monomer portion (D) copolymerizable with the monomers forming (A) and (B) is 5
It can also be introduced at less than 3% by weight, preferably less than 3% by weight.

The monomer forming (D) will be described. For example, in order to reduce the surface frictional resistance when a coating film is formed, (D) requires a monomer having a silicon atom and a fluorine atom. It is preferably a monomer having
Examples of these monomers include silicon macromonomer (AK-5, AK-30 manufactured by Toa Gosei Chemical Co., Ltd.), 3
-Methacryloxypropyltrimethoxysilane, vinylidene fluoride, vinyl fluoride and the like.

In order to improve the flexibility of the obtained coating film and to prevent the coating film from being cracked or peeled off due to expansion or contraction or vibration of the object to be coated, for example, an alkyl ester having 2 or more carbon atoms is used. Preference is given to alkyl acrylate or methacrylate esters having side chains, alkyl vinyl ethers having alkyl ether side chains having 3 or more carbon atoms, ethylene and the like.

The weight average molecular weight of the copolymer resin used as the binder is preferably 10,000 to 110,000, more preferably 20,000 to 60,000. If the weight average molecular weight is less than 10,000, the strength and durability of the obtained coating film tend to be insufficient, and if it exceeds 110,000, the solvent solubility and coating workability tend to be low.

The copolymer resin used as the binder may be (A), (B) or (A), (B),
It is obtained by copolymerizing a monomer forming (D) and then saponifying the copolymer resin. The method of copolymerization is not particularly limited, and can be, for example, solution polymerization, suspension polymerization, emulsion polymerization, or the like. Specifically, it can be carried out by a usual apparatus, condition, operation, and procedure for performing a polymerization reaction of vinyl chloride. In the polymerization, a polymerization reaction started in a homogeneous system or a heterogeneous system may be changed to a heterogeneous system or a homogeneous system, respectively, in the course of the polymerization.

The saponification can be performed by a known method. For example, the obtained copolymer, in the presence of alcohol, sodium hydroxide, an alkali metal alcoholate, or hydrochloric acid, using a homogeneous or heterogeneous system of the carboxylate vinyl ester portion of the copolymer using sulfuric acid, etc. By saponifying a part of the amount, the copolymer used in the present invention is obtained. It should be noted that there is no problem even if a part of the portion (D) is saponified during the saponification.

The conductive filler is mixed in a form that can be easily dispersed, such as powder, small pieces, or short fibers, and is not particularly limited as long as it is a conductive solid substance. A combination of the above substances or shapes can be used. Specific examples of the substance include carbons such as graphite (natural graphite, artificial graphite), carbon black (gas black such as acetylene black, oil black, naphthalene black, etc.), magnetite, platinum group metals and other conductive metals. And alloys. Among them, carbons are practical in terms of paint stability and cost. In order to reduce the specific resistance of the obtained conductive layer, it is preferable to use a combination of two or more conductive fillers having different average particle sizes.

If the proportion of the conductive filler is too large, the coating workability, coating film forming property, and
The storage stability and the like are reduced, and the barrier properties of the obtained coating film, the retention of the conductive filler, the adhesion to the base, the strength, and the like are reduced. Conversely, if the blending ratio of the conductive filler is too small, it becomes difficult to obtain conductivity when forming a coating film, or blisters occur in part of the coating film during seawater electrolysis. The mixing ratio of the conductive filler may be appropriately selected so that the properties of the conductive paint such as workability of coating and the properties of the obtained coating such as barrier properties are in harmony with the conductivity of the coating. Ratio of conductive filler to the total of conductive filler and binder (X)
Is preferably 5 to 70% by volume. In particular,
When lowering X, it is preferable to use a conductive filler having a high oil absorption such as Ketjen Black, and conversely, when increasing X, a conductive filler having a low oil absorption such as graphite is used. It is preferable to use here,
X is a value represented by the following equation (1).

[0027]

(Equation 1)

The volume of the conductive filler and the volume of the binder are determined by the relationship between the specific gravity and the sample weight, that is, (sample weight)
/ (Specific gravity) Further, the specific gravity of the conductive filler and the specific gravity of the binder is determined as follows. (A) Method of measuring specific gravity of conductive filler Weight of specific gravity bottle W1, weight of specific gravity bottle filled with methanol W2, weight of specific gravity bottle containing conductive filler W3,
Weight of specific gravity bottle containing conductive filler and methanol W4
Were measured at 20 ° C., and the values of W1 to W4 were measured according to JIS K0061 floating measurement method.
From the specific gravity of methanol at ℃, it is determined by the following equation (2).

[0029]

(Equation 2)

(B) Method for measuring the specific gravity of the binder The solid content of the copolymer resin used as the binder is 20% by weight.
Is prepared (usually a mixed solution of equal weights of methyl ethyl ketone and toluene is used as a solvent).
It is cast to a thickness of about m and dried to form a resin film. After measuring the volatile content of this resin film and confirming that it was 2% by weight or less, the weight W5 of the resin film in air and in water at 20 ° C. was determined according to JIS K 0061 Substitution Method 1 ,
W6 is measured and calculated by the following equation (3).

[0031]

(Equation 3)

In the present invention, a non-conductive filler can be contained in order to improve the coating workability, fluidity and abrasion resistance of the resulting coating film.

Examples of the non-conductive filler include titanium oxide, alumina, silica, clay, talc, calcium carbonate, gypsum, Portland cement, alumina cement, stone powder, and synthetic resin insoluble in the solvent used in the present conductive paint. Powders and the like are preferred, and those which do not dissolve during electrolysis of seawater are preferred. When the conductive filler or the non-conductive filler can be used also as a pigment, it can be colored as a filler and a pigment.

When the non-conductive filler is used in combination with the conductive filler, the mixing ratio of the non-conductive filler may be appropriately selected, but the volume ratio of the filler to the total of the filler and the binder (Y) Is preferably 5 to 77% by volume. Here, Y is a value represented by the following equation (4).

[0035]

(Equation 4)

The specific gravity of the non-conductive filler is determined by the same method as the above-described method for measuring the specific gravity of the conductive filler. When Y exceeds 77% by volume, the coating workability, coating film forming property, storage stability, etc. are reduced, and the barrier properties of the obtained coating film, the retention of the conductive filler, the adhesion to the base, the strength, etc. Decrease. On the other hand, when the content is less than 5% by volume, it becomes difficult to obtain conductivity when forming a coating film, or blisters occur in a part of the coating film during seawater electrolysis.

In order not to significantly reduce the conductivity of the obtained coating film, the proportion (Z) of the non-conductive filler in the total amount of the filler represented by the following formula (5) is set to 30% by volume.
It is preferable to set the following.

[0038]

(Equation 5)

The solvent contained in the conductive paint may be any solvent that can dissolve or disperse the copolymer resin used as the above-mentioned binder, and is usually used in combination of one or more organic solvents. . In the case of an emulsion paint, water can also be used. Specifically, for example, methyl ethyl ketone, methyl isobutyl ketone, ketones such as acetone, toluene, aromatics such as xylene, ethyl acetate, esters such as butyl acetate, chain hydrocarbons such as normal hexane, cellosolves, Tetrahydrofuran and the like, and the solvent depends on the properties of the copolymer resin used as the binder, the handleability of the obtained conductive paint, the paintability, the fluidity, the storage stability, the film formability, the drying speed, and the like. One or two or more are arbitrarily selected.

The compounding amount of the solvent in the present conductive paint may be appropriately selected according to the coating method, paintability, storability, handleability, etc. By adjusting the compounding amount of the solvent, the present conductive paint can be used. It can be made into a paste or liquid. It is the same as a general coating material that the coating material can be diluted as needed when painting.

In the present invention, an additive may be further contained as necessary.

The additive may be, for example, a synthetic resin other than the above-described copolymer resin, and an elastomer or a synthetic resin soluble in the solvent of the conductive paint, such as polychloroprene.
Examples include chlorinated polyolefin, vinyl halide resin, epoxy resin, unsaturated polyester resin, phenol resin, melamine resin, and acrylic resin.
As other additives, those generally used in molding of synthetic resins and production of paints may be mentioned. For example, plasticizers, dispersants such as conductive fillers and non-conductive fillers, defoamers, thickeners, flow regulators, anti-settling agents, leveling agents, stabilizers, ultraviolet absorbers, coloring agents, And a soiling agent. Of these, a plasticizer that plasticizes a vinyl chloride resin is preferable. When considering extraction resistance,
Polyester plasticizers are preferred.

The amount of the above-mentioned additives to be added may be a commonly used amount, and is usually 20 parts by weight or less of the active ingredient based on 100 parts by weight of the binder.

The production of the conductive paint can be carried out in the same procedure, under the same conditions and in the same manner as in the production of a general liquid or paste-like paint. After kneading and dispersing the amount of the filler and the total amount of the filler to be used, the remaining amount of the copolymer resin, the solvent, and the like is added, and the mixture is further mixed and dispersed.

The conductive paint of the present invention can be used to obtain a conductive layer by drying the coated film. The coating of the present conductive paint has a thickness of 100 to 1000 μm for the conductive layer.
It is preferable to perform so that When the thickness is less than 100 μm, pinholes are liable to occur. Conversely, when the thickness is 1000 μm or more, workability, cost, and conductivity tend to be disadvantageous. Further, at the time of the above coating, for example, a conductive layer can be obtained by embedding a woven or non-woven fabric of a conductive fiber such as a carbon fiber.

The coating can be performed by one or a combination of two or more of, for example, spray coating, roller coating, brush coating, spatula coating, and iron coating. When the coating range is wide, spray coating or roller coating is suitable, and when using a high-viscosity coating, spatula coating or iron coating is suitable.

In order to prevent the occurrence of coating defects such as pinholes and cracks, it is preferable that the coating be repeated twice or more on the same part. It is preferable to sequentially increase the specific resistance of the conductive layer toward the side. When such a multi-layered conductive layer is formed and a power supply is connected to the innermost layer to perform seawater electrolysis, it is easy to prevent a current density from being concentrated near a power supply connection portion, and a uniform marine area over a wide range is provided. The effect of preventing biofouling is easily obtained.
For example, when the conductive layer is composed of two coating films, a conductive coating compounded so that the volume ratio (X) of the conductive filler is 30 to 70% by volume is used for undercoating, and the volume of the conductive filler is Conductive paint blended so that the ratio (X) is 5 to 45% by volume is used as the top coat, and the top coat is adjusted so that the proportion of the conductive filler is smaller than that of the undercoat, and is applied repeatedly. Is preferably performed.

[0048]

【Example】

Example 1 (1) Production of Copolymer Resin Used as Binder 200 parts by weight of vinyl chloride, 90 parts by weight of vinyl acetate, 560 parts by weight of acetone were placed in a stainless steel autoclave with a stirrer in which oxygen was removed by purging with nitrogen gas or the like. And 1 part by weight of benzoyl peroxide as a polymerization initiator (dissolved in a part of the above-mentioned acetone), and a temperature (liquid temperature) of 58 ° C.
And the polymerization was started under stirring and the following operation was carried out while maintaining the temperature at 58 ° C. to advance the polymerization reaction.

When the temperature of the polymerization reaction system reached 58 ° C. by heating, the polymerization was started, and 40.6 parts by weight of vinyl chloride was continuously added to the polymerization reaction system over 18 hours after the initiation of the polymerization. In addition, twice, 10 hours and 15 hours after the start of the polymerization, 4.5 parts by weight of a solution obtained by dissolving 0.5 parts by weight of benzoyl peroxide in 4 parts by weight of acetone was added to the polymerization reaction system each time. .

When the conversion reached 90%, the mixture was cooled to stop the polymerization reaction, and an acetone solution of the copolymer resin was obtained.
The composition of the copolymer resin was 86% by weight of vinyl chloride and 14% by weight of vinyl acetate.

A methanol solution of sodium hydroxide was added to the obtained copolymer resin solution, and 50 parts by weight of methanol was added to 100 parts by weight of the copolymer resin in the copolymer resin solution.
Sodium hydroxide was added to 1 part by weight, and a saponification reaction was carried out at 45 ° C. while stirring. When the conversion of the vinyl acetate portion to the vinyl alcohol portion reached 60%, the reaction was stopped by cooling, and 500 parts by weight of methanol was added and mixed to precipitate a resin, which was filtered, and the wet cake containing the solvent was removed. Resin was obtained. To the wet cake, 1000 parts by weight of methanol was added to 100 parts by weight of the copolymer resin (in terms of dry resin), and the copolymer resin was washed and filtered. After repeating this washing operation three more times, the solution was drained and dried. The composition (chlorine analysis, IR analysis) of the obtained copolymer resin was 87.1% by weight of vinyl chloride, 7.3% by weight of vinyl acetate, and 5.6% by weight of vinyl alcohol.
The weight average molecular weight (method of converting the value measured by GPC (gel permeation chromatography) into polystyrene) was 49,000.

(2) Production of conductive paint The copolymer resin produced in the above (1) was added to a mixed solvent of equal weights of toluene and methyl isobutyl ketone and dissolved so that the copolymer resin content was 22% by weight. .

270 parts by weight of this copolymer resin solution, 110 parts by weight of conductive filler, and 70 parts by weight of an additive are placed in a 1-liter container, and about 200 ml of glass beads having a diameter of about 5 mm are further placed. The mixture was shake-kneaded for 1 hour with a shaker. Next, 250 parts by weight of the same copolymer resin solution as described above was further added to the kneaded material in this container, and the mixture was shake-mixed with a paint shaker for 15 minutes. As the conductive filler, artificial graphite powder “POG-
80 "(average particle size: 40 m) and" POG-2 "(average particle size: 2 m) were used in equal amounts. In addition, as an additive, in order to impart thixotropic properties and leveling properties to improve coating workability, "Relanit 45" (containing 25% by weight of polyethylene wax and 75% by weight of xylene) manufactured by San Nopco was used.

The obtained conductive coating composition had a nonvolatile content of 35% by weight and a viscosity at 25 ° C. (by a B-type viscometer) of 390.
It was 0 cps.

(3) Preparation of Test Piece for Evaluation of Coating Film As shown in FIG. 1, a transparent acrylic resin plate having a width of 15 cm, a length of 30 cm and a thickness of 0.5 cm was placed on one side of a transparent acrylic resin plate having a width of 13 c.
A copper foil having a length of 26 m and a length of 26 cm and a thickness of 35 μm is attached with a double-sided adhesive tape, and the conductive paint obtained in the above (2) is spray-coated so as to cover the copper foil so as to have a thickness of 350 μm. Thus, a conductive paint film (conductive layer) was provided.

After the coating film was dried at room temperature for 10 days, a lead wire for supplying a direct current was soldered to the copper foil, and the periphery of the copper foil provided with the coating film was covered with a peripheral portion as shown in FIG. Sealing was performed with a putty to obtain a test piece for evaluating a coating film.

(4) Test for Evaluation of Electrolytic Resistance to Seawater of Coating Film As shown in FIG. 2, the test piece for evaluating the coating film obtained in (3) above was placed in an electrolytic tank containing artificial seawater at 25 ° C. The surface area of the coating film in the submerged part directly in contact with artificial seawater is 253 cm
² and was suspended from the water surface such that the conducting wire mounting portion was located above the water surface. On the other hand, a steel sheet soldered with a conducting wire having a width of 15 cm, a length of 30 cm, and a thickness of 0.5 cm, facing the coating surface of the test piece for coating evaluation, was prepared in the same manner as the test specimen for coating evaluation. Was installed.

Using the test piece for evaluating the coating film as an anode and the steel plate as a cathode, a direct current was continuously supplied so as to have a current density of 1 A / m ² to perform electrolysis of artificial seawater.

The number of days until at least one of the following and at least one of the following was first visually confirmed was defined as the seawater electrolysis resistance of the coating film based on the energization start date. Table 2 shows the results.

A dark green to bluish green copper compound is generated on at least one surface of the coating film surface or the back surface side (transparent acrylic resin plate side) of the copper foil.

Defects in the coating film (bulging, cracking, peeling, etc.)
Occurs.

The artificial seawater was prepared by dissolving 2.84 kg of A (powder) and 2 liters of B (liquid) of "Aquamarine" manufactured by Yasu Pharmaceutical Co., Ltd. in ion-exchanged water to make 100 liters.

Examples 2 to 14 and Comparative Examples 1 to 3 Production of paints, preparation of test pieces and coating of coatings were carried out in the same manner as in Example 1 except that copolymer resins having the compositions shown in Table 1 were used as binders. The seawater electrolysis resistance was evaluated. Table 2 shows the results. In addition, in Comparative Example 2, since the coating material gelled, the coating film evaluation test was not performed.

Example 15 17 parts by weight of a conductive filler graphite powder and 17 parts by weight of a non-conductive filler were added to 520 parts by weight of a solution having a copolymer resin content of 22% by weight used in the production of the conductive paint of Example 1. Titanium oxide (rutile type titanium oxide KR-3 manufactured by Titanium Industry Co., Ltd.)
Except for blending 12 parts by weight of 10), the same procedure as in Example 1 was carried out to produce a paint, prepare a test piece, and evaluate seawater electrolysis resistance of the coating film. Table 2 shows the results.

The weight of the filler (graphite powder and titanium oxide) with respect to 100 parts by weight of the binder (copolymer resin) in the paint was 25 parts by weight, and the volume of the filler with respect to the total of the filler and the binder was 25 parts by weight. The ratio (Y) was 11% by volume.

Example 16 Except that 358 parts by weight of a conductive filler graphite powder was blended with 520 parts by weight of a solution containing 22% by weight of a copolymer resin used in the production of the conductive paint of Example 1, In the same manner as in Example 1, production of paint, preparation of test pieces, and evaluation of seawater electrolysis resistance of the coating film were performed. Table 2 shows the results.

Examples 17 to 21 As shown in Table 2, the conductive filler was a combination of graphite powder and acetylene black (“DENKA BLACK” manufactured by Denki Kagaku Kogyo Co., Ltd.), acetylene black alone, magnetite (powder) (Bayer) "Biferox 306")
Example 1 except that magnetite and graphite powder were used alone, and magnetite and acetylene black were used together
Production of paint, preparation of test pieces, and evaluation of seawater electrolysis resistance of the coating film were performed in the same manner as described above. Table 2 shows the results.

Comparative Examples 4 and 5 In the same manner as in Example 1 except that instead of the copolymer resin used in Example 1, an acrylic resin was used as a binder in Comparative Example 4, and an epoxy resin was used as a binder in Comparative Example 5, respectively. Production of paint, preparation of test pieces, and evaluation of seawater electrolysis resistance of the coating film were carried out. Table 2 shows the results.

As the acrylic resin of Comparative Example 4, "Dianal LR-469" manufactured by Mitsubishi Rayon Co., Ltd. was used.
Further, as the epoxy resin of Comparative Example 5, a resin obtained by using "Epicoat 1001" manufactured by Shell Chemical Co., Ltd. and "Versamide 115", a curing agent manufactured by Daiichi Kogyo Seiyaku Co., Ltd., was used.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

The present invention is as described above, and the conductive paint of the present invention is excellent in seawater electrolysis resistance.
When the conductive layer is used, it is possible to prevent the adhesion of marine organisms by electrolysis of seawater over a wide range for a long period of time.

[Brief description of the drawings]

FIG. 1 is a perspective view of a test piece for evaluating a coating film used in Examples and Comparative Examples.

FIG. 2 is an explanatory diagram of a coating film evaluation test performed in Examples and Comparative Examples.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI E02B 1/00 301 E02B 1/00 301A (72) Inventor Motohiro Suzuki 1135 Nakamura, Shibukawa-shi, Gunma Prefecture Electrochemical Co., Ltd. Shibukawa Inside the plant (72) Inventor Minoru Inamura 1135 Nakamura, Shibukawa-shi, Gunma Prefecture Inside the Shibukawa Plant, Electrochemical Industry Co., Ltd. ) Field surveyed (Int.Cl. ⁶ , DB name) C09D 5 / 24,5 / 16,127 / 06 B63B 59/04 E02B 1/00 301 B05D 7/14 B05D 7/24 303

Claims (3)

(57) [Claims] 1. A copolymer resin comprising at least the following (A), (B) and (C), wherein (A), (B),
The ratio of (C) to the whole is 70 to 95% by weight, 1 to 10% by weight, and 2 to 21% by weight, respectively, and (A) + (B) + (C) is 95% by weight or more of the whole. A conductive paint for preventing marine organisms from adhering, comprising a copolymer resin as a binder, and containing the binder, a conductive filler, and a solvent. (A) Vinyl chloride moiety. (B) a carboxylic acid vinyl ester moiety. (C) A vinyl alcohol moiety resulting from the above (B) by saponification. 2. The conductive paint according to claim 1, wherein the volume ratio (X) of the conductive filler to the total of the conductive filler and the binder is 5 to 70% by volume. 3. The conductive paint according to claim 1, wherein the conductive filler is at least one selected from graphite powder and carbon black.