JP6990241B2 - Epoxy resin-based anticorrosion paint composition, anticorrosion coating film, laminated antifouling coating film, antifouling base material, and manufacturing method thereof. - Google Patents

Description

The present invention relates to an epoxy resin-based anticorrosion coating composition, and more particularly, an epoxy resin-based anticorrosion coating composition and an anticorrosion coating material useful for forming an anticorrosion coating film in a laminated anticorrosion coating film composed of an anticorrosion coating film and an antifouling coating film. The present invention relates to a coating film, a laminated antifouling coating film composed of the anticorrosion coating film and an antifouling coating film laminated on the coating film, an antifouling base material having the laminated antifouling coating film, and a method for producing these.

Conventionally, many (large) steel structures such as ships and underwater structures use metal base materials such as steel materials. These structures are painted with anticorrosive paint to prevent corrosion by seawater. Further, an antifouling paint that prevents aquatic organisms such as barnacles and seaweeds from adhering is applied as a top coat.

As the anticorrosion paint, an epoxy resin-based anticorrosion paint is generally used.
There are many documents on epoxy resin-based anticorrosion paints. For example, Patent Document 1 discloses an anticorrosion coating composition containing an epoxy resin, an alicyclic amine, and an acrylate monomer, and Patent Document 2 discloses an epoxy resin heavy anticorrosion coating material containing a vinyl chloride resin or the like. ing. These documents describe that after the anticorrosion paint was applied, the topcoat paint (antifouling paint) was applied and the adhesion between the anticorrosion coating film and the topcoat coating film was evaluated. As the antifouling paint, it is currently the mainstream to use a hydrolyzable antifouling paint having good long-term antifouling performance.

Further, Patent Document 3 comprises an organic silicon compound having an aminoalkyl group and an alkoxy group, and a compound having an oxylan ring, which is suitable for rust prevention of copper, a copper alloy, and a metal coated with a chromate plating film. It is described that the rust preventive property is more effectively improved by blending one or more selected from rosins or derivatives thereof, terpene resin and petroleum resin into the metal rust preventive composition.

International Publication No. 2006/016625 Japanese Unexamined Patent Publication No. 11-333374 Japanese Unexamined Patent Publication No. 60-221472

Many hydrolyzable antifouling paints contain rosin in order to promote the elution of the antifouling agent and to improve the wearability of the coating film. In particular, for ships with slow speeds and ships with irregular operating conditions and long-term mooring, hydrolyzed antifouling paints with a relatively high rosin content are used for the purpose of improving antifouling performance. There is.

Here, to explain the painting of a ship, in the ship construction process, due to the weather conditions, the painting process, etc., the interval from the application of the anticorrosion paint to the application of the antifouling paint (hereinafter also referred to as "painting interval"). May be longer. The coating film formed from the hydrolyzable antifouling paint having a high rosin content has a problem that the hardness of the coating film is high and it is difficult to adhere to the anticorrosion coating film of the undercoat. Therefore, in order to ensure sufficient adhesion, it is necessary to apply the antifouling paint before the hardness of the coating film becomes high, that is, it is necessary to set the coating interval short, and the coating process control at the coating site becomes tight. Especially in the hot summer, there are cases where the allowable painting interval is one day. In addition, if the painting work is stopped due to rainfall or the like and the allowable painting interval is exceeded, the anticorrosion paint is repainted again, and then the antifouling paint is applied. ..
As a countermeasure for the above, it is strongly desired to develop an anticorrosion paint capable of forming an anticorrosion coating film having sufficient adhesion even if the coating interval is long.

In order to solve the above problem, the present inventors have conducted diligent research, and found that the antifouling coating film contains a large amount of rosin by using a thermoplastic resin and rosins in combination in an epoxy resin-based anticorrosion paint. It has been found that the adhesiveness of the anticorrosion coating film to the antifouling coating film (hereinafter, also simply referred to as "adhesiveness of the anticorrosion coating film" or "adhesiveness") is improved even if it is formed from.

The mechanism of expression of the effect of the present invention is considered as follows.
The epoxy resin-based anticorrosion paint forms an anticorrosion coating film by a mechanism in which the epoxy resin reacts with a curing agent such as amine to cure and dry. The surface of the anticorrosion coating film is softened by the solvent contained in the antifouling paint to be applied thereafter, and the adhesion between the anticorrosion coating film and the antifouling coating film is developed. As described in Patent Document 2 ([0045]), the thermoplastic resin (B) is dissolved by the solvent in the antifouling paint to improve the adhesion of the anticorrosion coating film to the antifouling coating film.

The curing reaction of the anticorrosion paint progresses over time. As time passes, the hardness of the coating film increases, and the solvent resistance of the coating film also improves. Therefore, if a long period of time elapses from the formation of the antifouling coating film to the application of the antifouling paint, the softening of the anticorrosion coating film by the solvent in the antifouling paint is hindered, and the mutual between the anticorrosion coating film and the antifouling coating film There is a phenomenon that the adhesiveness is insufficient and the adhesiveness cannot be developed. In particular, when the antifouling coating film is formed from an antifouling paint having a high rosin content, the hardness of the rosin and the brittleness of the rosin increase the hardness of the coating film, and the rosin component is transferred to the interface with the anticorrosion paint. It was difficult to secure the adhesiveness because the tendency to reduce the adhesiveness became stronger.

In the present invention, by using the rosins (C) in combination with the anticorrosion paint containing the thermoplastic resin (B), the solvent resistance of the anticorrosion coating after drying and curing is normal without containing the rosins (C). Since it is lower than the anticorrosion coating film, the anticorrosion coating film is easily dissolved by the solvent of the antifouling paint of the top coat even if the coating interval is long, and the adhesiveness is easily developed. Further, when the antifouling paint contains rosins, the rosins in the antifouling paint migrate to the interface with the anticorrosion coating film, and the affinity between the anticorrosion coating film containing rosin and the antifouling coating film is improved. Therefore, it is considered that the adhesiveness is significantly improved in a synergistic effect.

Furthermore, in anticorrosion paints containing epoxy resins and curing agents, it has been common to apply a prescription such as reducing the reaction ratio in order to improve the adhesiveness, but such a prescription has been used. There is a problem that low temperature drying property and corrosion resistance are lowered. The present invention eliminates such a trade-off relationship, secures adhesion to a coating film formed from a hydrolyzable antifouling paint having a high rosin content, without impairing low-temperature drying property and corrosion resistance. You can establish a prescription to do.

Furthermore, the present inventors have found that if rosins are excessively blended in the anticorrosion paint, the anticorrosion property of the anticorrosion coating film is rather deteriorated.
The present inventors have completed the present invention based on these findings. The present invention is as follows.

[1]
It contains an epoxy resin (A), a thermoplastic resin (B) (excluding rosins (C)), rosins (C), and a curing agent (D).
The content of the thermoplastic resin (B) is 35 parts by mass or more with respect to 100 parts by mass of the epoxy resin (A).
An epoxy resin-based anticorrosion coating composition having a content of the rosins (C) of 5 to 30 parts by mass with respect to a total of 100 parts by mass of the epoxy resin (A) and the thermoplastic resin (B).

[2]
The epoxy resin (A) is one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol F type epoxy resin, and a modified epoxy resin obtained by modifying these epoxy resins. The epoxy resin-based anticorrosion coating composition according to the above [1].

[3]
The epoxy resin-based anticorrosion coating composition according to the above [1] or [2], further containing the pigment (E).

[4]
The epoxy resin-based anticorrosion coating composition according to the above [3], wherein the pigment volume concentration (PVC) represented by the following formula (2) is 25 to 50%.
Pigment volume concentration (%)
= Volume of pigment in anticorrosion paint composition / (Volume of resins in anticorrosion paint composition + Volume of pigment in anticorrosion paint composition) × 100 ... Formula (2)

[5]
The thermoplastic resin (B) contains at least one selected from the group consisting of petroleum resin, ketone resin, chlorinated polyolefin, acrylic resin, butyl acetate resin, styrene resin, and vinyl chloride resin. The epoxy resin-based anticorrosion coating composition according to any one of the above [1] to [4].

[6]
The epoxy resin-based anticorrosion coating composition according to the above [5], wherein the thermoplastic resin (B) contains a vinyl chloride-based resin, and the vinyl chloride-based resin is a vinyl chloride / vinyl isobutyl ether copolymer.

[7]
An anticorrosion coating film comprising a cured product of the epoxy resin-based anticorrosion coating composition according to any one of [1] to [6].

[8]
A base material with an anticorrosion coating film having the base material and the anticorrosion coating film of the above [7] provided on the surface of the base material.

[9]
The substrate has a step of applying the epoxy resin-based anticorrosion coating composition according to any one of [1] to [6], and a step of curing the painted anticorrosion coating composition to form an anticorrosion coating film. A method for manufacturing a base material with an anticorrosion coating.

[10]
A laminated antifouling coating film provided on the surface of the base material in the order of the anticorrosion coating film and the antifouling coating film of the above [7] from the base material side.

[11]
The laminated antifouling coating film according to the above [10], wherein the antifouling coating film is a hydrolysis type antifouling coating film.

[12]
The laminated antifouling coating film according to the above [11], wherein the hydrolysis type antifouling coating film contains rosins.

[13]
A method for producing a laminated antifouling coating film, which is formed by laminating an anticorrosion coating film and an antifouling coating film on the surface of the base material in this order from the base material side, according to any one of the above [1] to [6]. A method for producing a laminated antifouling coating film, which comprises a step of curing a film made of an epoxy resin-based anticorrosion coating film to form the anticorrosion coating film and a step of forming the antifouling coating film on the surface of the anticorrosion coating film. ..

[14]
The laminated antifouling coating film according to any one of [10] to [12] is laminated on the surface of the base material in the order of the anticorrosion coating film and the antifouling coating film from the base material side. Dirty substrate.

[15]
The antifouling base material of the above [14] that comes into contact with seawater or fresh water.

[16]
The antifouling base material according to the above [14] or [15], wherein the base material is at least one selected from the group consisting of a ship, an underwater structure, and a fishing gear.

[17]
A method for producing an antifouling base material, which comprises a step of forming the laminated antifouling coating film according to any one of [10] to [12] on the surface of the base material.

According to the epoxy resin-based anticorrosion coating composition according to the present invention, it is possible to form an anticorrosion coating film having excellent anticorrosion properties. This anticorrosion coating film is a laminated anticorrosion coating film provided on the surface of the base material in the order of the anticorrosion coating film and the antifouling coating film from the base material side, and has excellent adhesion even if the coating interval is long. In particular, the antifouling coating film is formed of a hydrolyzable antifouling paint having a high rosin content, and has excellent adhesion even when the coating interval is long.

The epoxy resin-based anticorrosion coating composition according to the present invention is further excellent in low-temperature drying property and coating workability.

FIG. 1 is a diagram for explaining a method for evaluating dryness in Examples.

Hereinafter, the present invention will be described in more detail.
[Epoxy resin-based anticorrosion paint composition]
The epoxy resin-based anticorrosion coating composition according to the present invention (hereinafter, also simply referred to as “anticorrosion coating composition”) includes an epoxy resin (A), a thermoplastic resin (B), rosins (C), and a curing agent (D). ) Is contained.

The epoxy resin-based anticorrosion coating composition usually contains a main agent component containing the epoxy resin (A), the thermoplastic resin (B) and the rosins (C), and a curing agent (D). An anticorrosion paint composed of an agent component is prepared, and is prepared by mixing the main agent component and the curing agent component immediately before painting.

The main ingredient may include a pigment (E), a curing accelerator (F), an adhesion enhancer (G), a plasticizer (H), a solvent (I), a sagging preventive agent or an anti-settling agent (J), if necessary. , Dehydrating agent (stabilizer) (K), or other coating film-forming component (dispersant, defoaming agent, leveling agent, etc.) may be blended as long as the object of the present invention is not impaired. If necessary, the curing agent component may contain a curing accelerator (F), a solvent (I), or the like, as long as the object of the present invention is not impaired.

Hereinafter, each component contained in the composition will be described.
In addition, "(meth) acrylic ((meth) acryl)" is a general term for acrylic (acryl) and methacryl (methacryl).

Further, in the present invention, the "nonvolatile component of the anticorrosion paint composition (or antifouling paint composition)" refers to JIS K5601-1-2 of the anticorrosion paint composition (or antifouling paint composition described later) of the present invention. It is a heating residue measured according to the standard (heating temperature: 125 ° C., heating time: 60 minutes).

Epoxy resin (A)
Examples of the epoxy resin (A) include polymers or oligomers containing two or more epoxy groups in one molecule, and polymers or oligomers produced by a ring-opening reaction of a part of the epoxy groups.

Examples of the epoxy resin (A) include bisphenol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, and oil ring. Examples thereof include group epoxy resins and epoxidized oil-based epoxy resins. Specific examples of such an epoxy resin (A) include, for example, a bisphenol A type epoxy resin such as epichlorohydrin-bisphenol A resin; a bisphenol AD type epoxy resin such as epichlorohydrin-bisphenol AD resin; epichloro. Bisphenol F type epoxy resin such as hydrin-bisphenol F resin; phenol novolac epoxy resin such as epichlorohydrin-phenol novolak resin; aromatics such as 3,4-epoxyphenoxy-3', 4'-epoxyphenylcarboxymethane Epoxy resin; Epichlorohydrin-bisphenol A A brominated epoxy resin having a structure in which at least a part of hydrogen atoms bonded to the benzene ring in the epoxy resin is bromine-substituted; epichlorohydrin and an aliphatic dihydric alcohol An aliphatic epoxy resin with a reaction structure; a polyfunctional epoxy resin with a structure in which epichlorohydrin and tri (hydroxyphenyl) methane are reacted; a bisphenol type epoxy resin with dimer acid (a dimer of unsaturated fatty acid) Modified dimer acid-modified epoxy resin; hydrogenated epoxy resin having a structure in which an aromatic ring in a bisphenol type epoxy resin is hydrogenated can be mentioned.

Among these, the preferable epoxy resin (A) is at least one selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol F type epoxy resin, and a modified epoxy resin obtained by modifying these bisphenol type epoxy resins. A kind of epoxy resin, and a particularly preferable epoxy resin (A) is a bisphenol A type epoxy resin.

The epoxy resin (A) can be used alone or in combination of two or more. Weight average molecular weight measured by GPC (gel permeation chromatography) of the epoxy resin (A) (measurement conditions are the conditions described in the column of "(2) Average molecular weight of copolymer" of Examples described later or this. The conditions are the same as those of It is 000. The viscosity (25 ° C.) of the epoxy resin (A) is preferably 12,000 mPa · s or less, and more preferably 10,000 mPa · s or less.

The epoxy equivalent of the epoxy resin (A) (according to JIS K7236) is preferably 150 to 1,000 g / eq.
As the epoxy resin (A), a bisphenol A type epoxy resin having an epoxy equivalent of 150 to 700 g / eq is preferable.

When two or more kinds of epoxy resins are used in combination, the weight average molecular weight and the epoxy equivalent of the epoxy resin (A) are the weight average molecular weight and the epoxy equivalent of the two or more kinds of epoxy resins as a whole.

Typical bisphenol A type epoxy resins that are liquid at room temperature are "jER (registered trademark) 828" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180-200 g / eq, NV100%), "E-028". -90X "(manufactured by Otake Meishin Kagaku Co., Ltd., 828 type epoxy resin, non-volatile component epoxy equivalent 180-200 g / eq, xylene cut product NV90%)," AER260 "(bisphenol A type epoxy resin, Asahi Kasei Epoxy Co., Ltd.) , Epoxy equivalent 190g / eq, NV100%), etc.
For semi-solid products at room temperature, "jER834-X90" (Mitsubishi Chemical Corporation, non-volatile epoxy equivalent 230-270 g / eq, xylene-cut product NV90%), "E-834-85X" (Otake Akira Shinkagaku) Co., Ltd., non-volatile epoxy equivalent about 230-270 g / eq, xylene-cut product NV85%), etc.
For solids at room temperature, "jER1001-X75" (Mitsubishi Chemical Corporation, non-volatile epoxy equivalent 450-500g / eq, xylene-cut product NV75%), "E-001-75X" (Otake Akira Shinkagaku) Co., Ltd., non-volatile epoxy equivalent of about 450 to 500 g / eq, xylene-cut product NV75%) and the like.

Other epoxy resins and modified epoxy resins include "jER807" (manufactured by Mitsubishi Chemical Corporation, bisphenol F type diglycidyl ether resin, epoxy equivalent 160-175 g / eq, NV100%), "Flep 60" (polysulfide modified). Epoxy resin, manufactured by Toray Fine Chemicals Co., Ltd., epoxy equivalent approx. 280 g / eq, NV100%), "YD-172-X75" (dimeric acid-modified epoxy resin, manufactured by Kokuto Kagaku Co., Ltd., non-volatile epoxy equivalent 600-700 g) / Eq, xylene cut product NV75%), "Epiclon 5300-70" (Novolak type epoxy resin, manufactured by DIC Co., Ltd., non-volatile epoxy equivalent 300-340 g / eq, xylene / isobutyl alcohol cut product NV70%) and the like. ..
The epoxy resin (A) is preferably contained in the anticorrosion coating composition in an amount of 5 to 80% by mass, more preferably 7 to 50% by mass.

Thermoplastic resin (B) (excluding rosins (C))
Examples of the thermoplastic resin (B) include petroleum resins, ketone resins, chlorinated polyolefins, acrylic resins, butyl acetate resins, styrene resins, vinyl chloride resins and the like. When the anticorrosion coating film formed from the anticorrosion coating composition is coated with an antifouling paint containing an organic solvent, the thermoplastic resin (B) is used as described in Patent Document 2 ([0045]). It is dissolved by the organic solvent in the antifouling paint and improves the adhesion of the anticorrosion coating film to the antifouling coating film.

The thermoplastic resin (B) is preferably a solid resin at room temperature (23 ° C.). Solid at room temperature means that the shape is maintained even if it is left at room temperature and pressure (23 ° C., 1 atm) for one day. When the thermoplastic resin (B) is a solid resin at room temperature (23 ° C.), the unreacted epoxy resin (A) in the anticorrosion coating film becomes an antifouling coating film laminated on the anticorrosion coating film. It is possible to suppress or prevent the transition and deterioration of its antifouling performance (particularly static antifouling property).

Weight average molecular weight of the thermoplastic resin (B) measured by GPC (measurement conditions are the conditions described in the column of "(2) Average molecular weight of copolymer" of Examples described later or equivalent conditions. ) Is preferably 5,000 to 100,000, more preferably 20,000 to 80,000.

The thermoplastic resin (B) preferably has a glass transition temperature of 30 ° C. or higher.
As the thermoplastic resin (B), among the above-mentioned resins, a vinyl chloride resin is particularly preferable because it has little influence on the adhesion to the antifouling paint and the antifouling property of the coating film.

As the vinyl chloride resin, a vinyl chloride / vinyl isobutyl ether copolymer is more preferable, and a resin having a glass transition temperature of 30 ° C. or higher is more preferable. Commercially available products of such vinyl chloride / vinyl isobutyl ether copolymers include "Laroflex LR8829" and "Laroflex MP-25" (Mw = 28,000 to 30,000) manufactured by BASF Japan Ltd. ), "Laroflex MP-35", "Laroflex MP-45" and the like. Further, among the vinyl / vinyl isobutyl ether copolymers, "Laloflex MP-25" is particularly preferable because the increase in the viscosity of the coating material is small when the epoxy resin-based anticorrosion coating composition is prepared and the coating workability is excellent. ..

As the other thermoplastic resin (B), "Dianal BR106" (manufactured by Mitsubishi Chemical Co., Ltd., Mw = 60,000) and "Paraloid B66" (manufactured by Dow Chemical Co., Ltd., Mw) are commercially available acrylic resins. Examples thereof include an acrylic resin obtained by copolymerizing acrylic acid with an ester thereof or a derivative thereof, a methacrylic resin obtained by copolymerizing methacrylic acid with an ester thereof or a derivative thereof, and the like.

These thermoplastic resins can be used alone or in combination of two or more. The amount of the thermoplastic resin (B) in the anticorrosion coating composition is from the viewpoint of adhesion of the anticorrosion coating, and the unreacted epoxy resin (A) in the anticorrosion coating is laminated on the anticorrosion coating. The epoxy resin (A) 100 is from the viewpoint of suppressing or preventing the transition to the antifouling coating film and lowering the antifouling performance (particularly the static antifouling property), and optionally further the drying property. It is 35 parts by mass or more, preferably 50 parts by mass or more, more preferably 60 parts by mass or more with respect to parts by mass, and the upper limit thereof is from the viewpoint of exhibiting excellent anticorrosion property, top coat property and drying property in the anticorrosion coating film. Is preferably 100 parts by mass, more preferably 90 parts by mass.

Rosin (C)
By blending a predetermined amount of rosins (C) in the epoxy resin-based anticorrosion coating composition, the drying property of the anticorrosion coating film is improved, and the antifouling coating film of the anticorrosion coating film (particularly, an organic solvent containing a large amount of rosins) is used. It is possible to significantly improve the adhesiveness to the antifouling coating film (antifouling coating film formed from the mold antifouling paint).

Examples of the rosins (C) include rosins such as gum rosin, wood rosin and tall oil rosin, rosin derivatives such as hydrogenated rosin and disproportionated rosin, and esters and metal salts thereof. In particular, it is preferable to use rosins such as gum rosin, wood rosin, and tall oil rosin from the viewpoint of high adhesiveness improving effect.

The content of the rosins (C) is 5 to 30 parts by mass, preferably 10 to 25 parts by mass with respect to 100 parts by mass in total of the epoxy resin (A) and the thermoplastic resin (B). be. If it is less than 5 parts by mass, the adhesiveness and drying property of the anticorrosion coating film tend to be inferior. When it exceeds 30 parts by mass, the viscosity of the mixture obtained by mixing the curing agent component with the main agent component (that is, the anticorrosion coating composition) is large, the coating workability is lowered, and the drying property and the anticorrosion property are also lowered. There's a problem.

Hardener (D)
The curing agent (D) is not particularly limited as long as it contains active hydrogen and reacts with the epoxy resin (A). For example, polyamines, polyamide resins, imines, phenol novolac resins, and the like. Examples thereof include cresol novolak resins, phenol novolak resins having an aliphatic hydrocarbon group having 4 to 18 carbon atoms as a substituent on the aromatic nucleus, polycarboxylic acids, polycarboxylic acid anhydrides, imidazoles, dicyandiamides and the like. In particular, from the viewpoint of the adhesiveness of the anticorrosion coating film and the drying property of the anticorrosion coating composition, an amine-based curing agent which is a compound having two or more amino groups in one molecule is preferable. The compounds constituting the amine-based curing agent include aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines, and polyamides of these amines, modified products thereof, epoxy resin adduct-modified products, and Mannig-modified compounds. Things and the like can be mentioned.

Specifically, the aliphatic amines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2'-aminoethylamino) propane, and triethylene-bis. Examples thereof include (trimethylene) hexamine, bis (3-aminoethyl) amine, bishexamethylenetriamine [H ₂ N (CH ₂ ) ₆ NH (CH ₂ ) ₆ NH ₂ ], and bis (cyanoethyl) diethylenetriamine.

Examples of the alicyclic amine include 4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, and norbornandiamine (NBDA / 2,5- and 2,6-bis (NBDA / 2,5- and 2,6-bis). Aminomethyl) -bicyclo [2,2,1] heptane), bis (aminomethyl) cyclohexane, diaminodicyclohexylmethane, isophoronediamine (IPDA / 3-aminomethyl-3,5,5-trimethylcyclohexylamine), and mensen Examples include diamine.

Examples of the aromatic amine include o-xylylene diamine, m-xylylene diamine (MXDA), p-xylylene diamine, phenylenediamine, naphthylene diamine, diaminodiphenylmethane, diaminodiethylphenylmethane and 2,2-bis (4). -Aminophenyl) Propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4- Diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene and the like. Will be.

Examples of the heterocyclic amine include N-methylpiperazine, morpholin, 1,4-bis- (3-aminopropyl) -piperazine, piperazine-1,4-diazacycloheptane, 1- (2'-aminoethylpiperazine). , 1- [2'-(2 "-aminoethylamino) ethyl] piperazine, 1,11-diazacycloeicosan, 1,15-diazacyclooctacosane and the like.

The active hydrogen equivalent (amine equivalent) of the curing agent (D) is preferably 50 to 1000 g / eq, more preferably 70 to 500 g / eq.
As the curing agent (D), if it is a commercially available product, "laccamide TD-966" (manufactured by DIC Co., Ltd., polyamide, non-volatile active hydrogen equivalent 226 g / eq NV60%), "PA-66" (Akira Otake). Shinkagaku Co., Ltd., polyamide, non-volatile active hydrogen equivalent 226 g / eq NV60%), "PA-290 (A)" (Otake Akira Shinkagaku Co., Ltd., non-volatile active hydrogen equivalent 166 g / eq NV60%) , "Ancamide 2050" (manufactured by Air Products, polyamide adduct, active hydrogen equivalent 150 g / eq NV100%), "NX-4918" (manufactured by Cardlite, phenalkamine (Mannig modified product of cardanol and amine) adduct, non-volatile content activity Hydrogen equivalent 204 g / eq NV 80%) and the like.

The amount of the curing agent (D) in the anticorrosion coating composition is preferably 10 to 100 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the epoxy resin (A). It is preferable that the amount of the curing agent (D) is in the above range from the viewpoint of the curability of the anticorrosion coating film and the drying property when a solvent is contained.

Pigment (E )
Examples of the pigment (E) include extender pigments, coloring pigments, and rust preventive pigments.
Specific examples of the extender pigment include barium sulfate, potassium feldspar, barite powder, silica, calcium carbonate, talc, mica, glass flakes, and aluminum stearate. Specific examples of the coloring pigment include titanium white (titanium oxide), petals, yellow petals, carbon black and the like. Examples of the rust preventive pigment include aluminum paste, zinc chromate, zinc phosphate and the like. Among these pigments, it is preferable to add mica and aluminum paste, which are scaly in terms of coating film physical characteristics and corrosion resistance.

The amount of the extender pigment in the anticorrosion coating composition is preferably 0.1 to 80% by mass, where the amount of the non-volatile content of the anticorrosion coating composition is 100% by mass. The amount of the coloring pigment is preferably 0.1 to 50% by mass, where the amount of the non-volatile content of the anticorrosion coating composition is 100% by mass. The amount of the rust-preventive pigment is preferably 0.1 to 50% by mass, where the non-volatile content of the anticorrosive coating composition is 100% by mass.

Curing accelerator (F)
Examples of the curing accelerator (F) include tertiary amines, and specific examples of the tertiary amines include triethanolamine (N (C ₂ H ₅ OH) ₃ ) and dialkylaminoethanol ([CH). ₃ (CH ₂ ) _n ] ₂ NCH ₂ OH, n: number of repetitions), triethylenediamine (1,4-diazabicyclo (2,2,2) octane), 2,4,6-tris (dimethylaminomethyl) phenol ( C ₆ H ₅ -CH ₂ N (CH ₃ ) ₂ ), "Versamine EH30" (manufactured by BASF Japan Co., Ltd.), "Ancamin K-54" (manufactured by Air Products Co., Ltd.) and the like.

Further, as the curing accelerator (F), an acrylic acid ester-based curing accelerator can also be mentioned.
The amount of the curing accelerator (F) in the anticorrosion coating composition increases the rate of curing of the epoxy resin (A) by the curing agent (D), and the anticorrosion coating film and the topcoat coating film, that is, the antifouling coating. Since an anticorrosion coating film having excellent adhesion to the film and excellent flexibility of the anticorrosion coating film can be obtained, the amount of the non-volatile content of the anticorrosion coating composition is preferably 100% by mass, preferably 0.1 to 5% by mass. Is.

Adhesion enhancer (G)
Examples of the adhesion strengthening agent (G) include organic acids, chelating agents, silane coupling agents and the like, and among them, the silane coupling agent is preferable in terms of storage stability of the anticorrosion coating composition.

The silane coupling agent usually has two kinds of functional groups in one molecule, and can contribute to the improvement of the adhesive force of the anticorrosion coating film to the inorganic substrate, the decrease of the viscosity of the anticorrosion coating composition, and the like. The silane coupling agent is, for example, the formula: X-Si (OR) ₃ [X is a functional group capable of reacting with an organic material (eg, amino group, vinyl group, epoxy group, mercapto group, halogeno group, and these. It represents a hydrocarbon group having a group (an ether bond or the like may be present in this hydrocarbon group), and OR represents a hydrolyzable group (eg, methoxy group, ethoxy group). ], And preferably has reactivity with the epoxy resin (A) or the curing agent (D).

Specific examples of such a silane coupling agent include "KBM-403" (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and "silane S-510" as commercial products. (Manufactured by Chisso Co., Ltd.) and the like.

When the silane coupling agent is blended, the amount of the silane coupling agent in the anticorrosion coating composition is preferably 0.1 to 10 when the amount of the non-volatile content of the anticorrosion coating composition is 100% by mass. It is by mass, more preferably 0.5 to 5% by mass. When the silane coupling agent is used in the anticorrosion coating composition in such an amount, the performance such as the adhesiveness of the obtained anticorrosion coating film is improved, the viscosity of the anticorrosion coating composition is lowered, and the coating workability is improved. ..

Plasticizer (H)
Examples of the plasticizer (H) include chlorinated paraffin (chlorinated paraffin), TCP (tricresyl phosphate), polyvinyl ethyl ether, dialkylphthalate and the like, and these are mentioned from the viewpoint of water resistance (mechanical properties) of the coating film. Of these, chlorinated paraffin (chlorinated paraffin) and polyvinyl ethyl ether are preferable.
The amount of the non-volatile content of the plasticizer (H) in the anticorrosion coating composition is preferably 0.1 to 20% by mass, where the amount of the non-volatile content of the anticorrosion coating composition is 100% by mass.

Solvent (I)
Examples of the solvent (I) include xylene, toluene, methyl isobutyl ketone (MIBK), methoxypropanol, methyl ethyl ketone (MEK), butyl acetate, n-butanol, isobutanol, isopropyl alcohol (IPA) and the like.
These solvents may be used alone or in combination of two or more.
The content of the solvent (I) in the main agent component is, for example, 0.1 to 80% by mass, and the content of the solvent (I) in the curing agent component is, for example, 0.1 to 80% by mass. ..

Anti-sauce or anti-settling agent (J)
Specific examples of the anti-sagging or anti-settling agent (variable agent) (J) include polyamide wax, polyethylene wax, bentonite-based particles, and OH-containing nanoparticles (erosil, resin beads).

Examples of such anti-sagging or sedimentation inhibitor (J) include "Disparon 4200-20" and "Disparon 6650" manufactured by Kusumoto Kasei Co., Ltd. and "AS-A T-250F" manufactured by Itoh Oil Chemicals Co., Ltd. , "AS-A T-55-20BX" and the like.
The amount of the non-volatile content of the anti-sagging or anti-sedimenting agent (J) in the anti-corrosion coating composition is preferably 0.1 to 30% by mass when the amount of the non-volatile content of the anti-corrosion coating composition is 100% by mass. ..

Dehydrating agent (stabilizer) (K)
The anticorrosion coating composition of the present invention can obtain even better long-term storage stability by adding a dehydrating agent (stabilizer) (K) as needed.
Examples of the dehydrating agent (K) include an inorganic dehydrating agent and an organic dehydrating agent. The inorganic dehydrating agent preferably includes synthetic zeolite, anhydrous gypsum or hemihydrate gypsum, and the organic dehydrating agent preferably includes tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, and methyltri. Examples thereof include alkoxysilanes such as ethoxysilane, dimethyldiethoxysilane, and trimethylethoxysilane, or polyalkoxysilanes which are condensates thereof, and orthosilicate alkyl esters such as methyl orthosilicate and ethyl orthosilicate.
The amount of the dehydrating agent (K) in the anticorrosion coating composition is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin (A).

(Anti-corrosion paint composition)
The anticorrosion coating composition according to the present invention contains the above-mentioned epoxy resin (A), thermoplastic resin (B), rosins (C), curing agent (D), and optionally other components. , These can be prepared by mixing and stirring according to a usual method.

(Reaction ratio of epoxy resin (A) and curing agent (D))
The epoxy resin (A) reacts with the curing agent (D) to form a coating film.
In the anticorrosion coating composition according to the present invention, the reaction ratio represented by the following formula (1) is preferably in the range of 0.3 to 1.0, more preferably 0.4 to 0.9.

（上記式（１）において、配合量および当量の単位は、それぞれｇおよびｇ／ｅｑである。）

(In the above formula (1), the units of the blending amount and the equivalent amount are g and g / eq, respectively.)

Here, the "other components having reactivity with the epoxy resin (A)" and the "other components having reactivity with the curing agent (D)" in the above formula (1) are the epoxy resin (A), respectively. Alternatively, a component having a functional group (hereinafter, also referred to as “reactive group”) that reacts with the curing agent (D), specifically, the silane coupling agent, an acrylic acid ester as a curing accelerator (F), or the like. Refers to the components of. Further, the "functional group equivalent of other components" means the mass (g) per functional group in 1 mol of these components (that is, the molecular weight of the other components / the number of the functional groups in one molecule). As the silane coupling agent, as described above, a silane coupling agent having an amino group or an epoxy group as a reactive group can be used. It is determined whether or not to use the silane coupling agent, and if it is used, whether or not the silane coupling agent has reactivity with the epoxy resin (A) depends on the type of the reactive group, and the curing agent (D). It is determined whether or not it has reactivity with respect to, and the reaction ratio is calculated from the above formula (1).

When the reaction ratio is equal to or higher than the lower limit, the epoxy resin (A) is crosslinked at many points, so that unreacted epoxy resin components are less likely to remain, and the obtained anticorrosion coating film is curable and solvent. The laminated antifouling coating material has excellent drying property, and the antifouling property (particularly the static antifouling property) is less deteriorated.

When the reaction ratio is not more than the upper limit value, the unreacted curing agent (D) is unlikely to remain in the obtained coating film, and the unreacted curing agent (D) attracts water to apply the coating. It is possible to prevent problems such as deterioration of water resistance of the film and discoloration.

(PVC)
The non-volatile content of the anticorrosion coating composition of the present invention has a pigment volume concentration (hereinafter, also referred to as “PVC”) defined by the following formula (2), preferably 25 to 50%, more preferably 30 to 45%. be.
Pigment volume concentration (%)
= Volume of pigment in anticorrosion paint composition / (Volume of resins in anticorrosion paint composition + Volume of pigment in anticorrosion paint composition) × 100 ... Formula (2)

The "volume of resins" described in the denominator of the formula (2) refers to the epoxy resin (A), the thermoplastic resin (B), the rosins (C), the curing agent (D), and the curing accelerator ( F) is the total volume of the plasticizer (H).
When the PVC is at least the above lower limit value, the obtained coating film is excellent in drying property.
When PVC is not more than the above upper limit value, the viscosity of the anticorrosion coating composition is remarkably high and the coating workability is deteriorated, or the leveling property of the coating film is deteriorated or pinholes are generated and the anticorrosion property is deteriorated. It is possible to prevent problems.

[Anti-corrosion coating film, base material with anti-corrosion coating film]
The anticorrosion coating film according to the present invention comprises a cured product of the epoxy resin-based anticorrosion coating composition according to the present invention described above.
The anticorrosion coating film according to the present invention includes a cured epoxy resin, the thermoplastic resin (B) (excluding the cured product of the epoxy resin (A) and the rosins (C)), and the rosins. It also contains a matrix containing (C) and.

The anticorrosion coating film contains the thermoplastic resin (B) in an amount of usually 7 to 80% by mass, preferably 7 to 30% by mass, and contains the rosins (C) in an amount of usually 1.0 to 7.0. It contains% by mass, preferably 1.5 to 6.0% by mass. Since the anticorrosion coating film according to the present invention contains the thermoplastic resin (B) and rosins (C) in such a proportion, it has excellent adhesion to various topcoat paints, and the topcoat paint is particularly an antifouling paint. It is preferably used in the case of. When the anticorrosion coating film according to the present invention is used, as described above, a laminated antifouling coating film having good adhesion between the anticorrosion coating film and the antifouling coating film is formed even if the coating interval is long. It becomes possible to do.

Since the anticorrosion coating composition of the present invention contains the thermoplastic resin (B) and the rosins (C) in a predetermined amount, it is excellent in film forming property at low temperature (for example, 5 ° C.) and excellent in low temperature drying property. ..
The anticorrosion coating film according to the present invention is preferably used as the anticorrosion coating film of the laminated anticorrosion coating film provided on the surface of the base material in the order of the anticorrosion coating film and the antifouling coating film from the base material side. .. The anticorrosion coating film according to the present invention has excellent adhesion to the antifouling coating film in the laminated antifouling coating film, and the antifouling coating film may be formed from an organic solvent type antifouling paint containing a large amount of rosin. However, it has excellent adhesion.

Further, the base material with an anticorrosion coating film according to the present invention comprises a base material and the anticorrosion coating film of the present invention formed on the surface of the base material.
Further, the method for producing the anticorrosion coating film according to the present invention includes a step of curing the film made of the anticorrosion coating composition according to the present invention. The anticorrosion coating film according to the present invention can be produced by the same method as the conventional anticorrosion coating film production method except that the anticorrosion coating composition according to the present invention is used as the anticorrosion coating material.

Since the anticorrosion coating composition of the present invention has a low coating viscosity, the amount of diluting solvent can be reduced and good coating workability can be ensured.
The thickness (dry film thickness) of the anticorrosion coating film is usually about 50 to 800 μm.

[Laminated antifouling coating film, antifouling base material, etc.]
The laminated antifouling coating film according to the present invention is a laminated antifouling coating film provided on the surface of the base material in the order of the anticorrosion coating film and the antifouling coating film from the base material side, and the anticorrosion coating film is provided. It is a laminated antifouling coating film which is the anticorrosion coating film according to the present invention described above.
Further, in the antifouling base material according to the present invention, the laminated antifouling coating film according to the present invention is laminated on the surface of the base material in the order of the anticorrosion coating film and the antifouling coating film from the base material side. Being done.

(Anti-fouling paint composition)
Examples of the antifouling coating composition for forming the antifouling coating film by overcoating the anticorrosion coating film include conventionally known antifouling coating compositions.

Examples of the antifouling paint composition include a hydrolyzable antifouling paint composition, and examples of the resin for forming a coating film of the hydrolyzable antifouling paint composition include a hydrolyzable resin, for example.
Acrylic resin or polyester resin, general formula (I):
COO-MO-COR ¹ ... (I)
[M in the formula (I) represents zinc or copper, and R ¹ represents an organic group. ]
A metal salt-containing copolymer having a side chain terminal group represented by
General formula (II):
CH ₂ = C (R ² ) -COO-MO-CO-C (R ² ) = CH ₂ ... (II)
[M in formula (II) represents zinc or copper, and R ² represents a hydrogen atom or methyl group. ]
A metal salt-containing copolymer containing a structural unit derived from a monomer represented by the above and a structural unit derived from another unsaturated monomer copolymerizable with the monomer, and a general formula. (III):
R ³ -CH = C (R ⁴ ) -COO-SiR ⁵ R ⁶ R ⁷ ... (III)
[R ⁴ in formula (III) represents a hydrogen atom or a methyl group, and R ⁵ , R ⁶ and R ⁷ each have a monovalent organic group having 1 to 20 carbon atoms which may independently have a heteroatom. Shown, R ³ is a hydrogen atom or R ⁸ -O-CO (where R ⁸ is a monovalent organic group with 1 to 20 carbon atoms or Si R ⁹ R ¹⁰ R ¹¹ that may independently have a heteroatom. R ⁹ , R ¹⁰ and R ¹¹ each represent a monovalent organic group having 1 to 20 carbon atoms which may independently have a heteroatom). ]
Examples thereof include a silyl ester-containing copolymer containing a structural unit derived from the monomer represented by the above-mentioned monomer and a structural unit derived from another unsaturated monomer copolymerizable with the monomer.

An antifouling coating composition using these hydrolyzable resins is preferable because it is stable in long-term antifouling property and long-term coating film physical properties.
Other unsaturated monomers that can be copolymerized with the monomer represented by the general formula (II) or the general formula (III) include (meth) acrylic acid esters, monocarboxylic acids, dicarboxylic acids or these. Examples thereof include half esters (monoesters), diesters, vinyl esters, and styrenes.

Examples of the unsaturated monomer include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and (meth) acrylic acid. Lauryl ester, (meth) acrylic acid tridecyl ester, (meth) acrylic acid stearyl ester, (meth) acrylic acid allyl ester, (meth) acrylic acid cyclohexyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid iso Bornyl ester, (meth) acrylic acid methoxyalkyl ester, (meth) acrylic acid ethoxyalkyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid hydroxyethyl ester, ( (Meta) acrylic acid esters such as (meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid hydroxybutyl ester; monocarboxylic acids such as (meth) acrylic acid; dicarboxylic acids such as itaconic acid, maleic acid, succinic acid or These half esters (monoesters) and diesters; styrenes such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; etc., and these may be used alone or in combination of two or more. May be.

The amount of the coating film forming resin in the antifouling coating composition is preferably 5 to 50% by mass, where the amount of the non-volatile content of the antifouling coating composition is 100% by mass from the viewpoint of the physical characteristics of the coating film. More preferably, it is 5 to 30% by mass.

The antifouling coating composition may contain rosins and / or monocarboxylic acid compounds, copper or copper compounds, organic antifouling agents, pigments, dehydrating agents, plasticizers, pigment dispersants, anti-sagging or anti-settling agents, if necessary. , And a component selected from a solvent and the like.

Examples of rosins and / or monocarboxylic acid compound rosins include rosins such as gum rosin, wood rosin and tall oil rosin, rosin derivatives such as hydrogenated rosin and disproportionated rosin, and esters and metal salts thereof. Will be. Rosin is a residue left after distilling pine fat, which is the sap of pine plants, and is a natural resin containing rosin acid (avietic acid, palastolic acid, isopimaric acid, etc.) as a main component.

Examples of the monocarboxylic acid compound include aliphatic or alicyclic monocarboxylic acids, monocarboxylic acid derivatives thereof, and metal salts thereof. Specific examples of the monocarboxylic acid compound include naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, stearic acid, hydroxystearic acid, salicylic acid, and metal salts thereof. Can be mentioned.

The content mass ratio ( _WA / _WB ) of the content mass ( _WA ) of the coating film forming resin and the total content mass ( _WB ) of the rosins and the monocarboxylic acid compound is preferably 99.9 / 0. .1 to 30/70, more preferably 95/5 to 35/65, and even more preferably 90/10 to 40/60. When the content mass ratio is in such a range, the antifouling coating film has an effect of enhancing the grindability (coating film wearability), and the antifouling property (particularly, the static antifouling property) can be improved.

For vessels with many long-term berths and vessels operating on routes with severe fouling conditions, the composition containing a large amount of rosins and / or monocarboxylic acid compounds in order to improve static antifouling property and long-term antifouling property (in order to improve static antifouling property and long-term antifouling property). For example, ( _WA / _WB ) is more than 70/30) is preferably used, but when an antifouling paint having such a composition is applied to an anticorrosion coating, the adhesiveness of the conventional anticorrosion coating is significantly reduced. There is a tendency. However, since the anticorrosion coating composition of the present invention can form an anticorrosion coating film having good adhesion to the antifouling paint, even if an antifouling paint having a high rosin content as described above is used, high adhesion is achieved. It can be demonstrated.

Copper or Copper Compound The copper compound may be any organic or inorganic copper compound, for example, powdered copper (copper powder), cuprous oxide, copper thiosianate, cupronickel, copper pyrithione and the like. Can be mentioned.

The amount of copper or copper compound (total amount of copper and copper compound) in the antifouling coating composition is assumed to be 100% by mass based on the non-volatile content of the antifouling coating composition from the viewpoint of long-term antifouling property. It is preferably 0.1 to 90% by mass, more preferably 0.5 to 80% by mass.

Organic antifouling agent Examples of the organic antifouling agent include metal pyrithions such as disulfide pyrithione (excluding copper pyrithione), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and 4-bromo-. 2- (4-Chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, pyridinetriphenylboran, 4-isopropylpyridinediphenylmethylboran, N, N-dimethyl-N'-(3, 4-Dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2,4,5,6-tetrachloroisophthalonitrile, 2-methylthio-4-tert-butylamino-6-cyclopropylamino -1,3,5-triazine, (+/-) -4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (also known as medetomidin), bisdimethyldithiocarbamoyl disulfide bisdithiocarbamate, Chloromethyl-n-octyldisulfide, N', N'-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthium disulfide, zinc dimethyldithiocarbamate, zincethylenebisdithiocarbamate, 2,3-dichloro Examples thereof include -N- (2', 6'-diethylphenyl) maleimide, 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide and the like.

The amount of the organic antifouling agent in the antifouling coating composition is 100% by mass of the non-volatile content of the antifouling coating composition from the viewpoint of long-term antifouling property and maintenance of water resistance of the coating film (maintenance of mechanical properties). %, It is preferably 0.1 to 90% by mass, and more preferably 0.5 to 80% by mass.

Pigment The antifouling coating composition may contain a pigment for the purpose of coloring the coating film or concealing the base, and for the purpose of adjusting the coating film to an appropriate strength.
Pigments include, for example, talc, mica, clay, potash, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, zinc sulfide and the like. Pigments, petals, titanium white (titanium oxide), yellow petals, carbon black, naphthol red, phthalocyanine blue and the like, with talc and zinc oxide being preferred. These pigments can be used alone or in combination of two or more. Calcium carbonate and white carbon are also used as sedimentation inhibitors, which will be described later.

When the antifouling coating composition of the present invention contains a pigment, the content thereof is determined by a desired viscosity according to the coating form of the coating composition and the like, and the content thereof is determined by the non-volatile content of the coating composition. It is preferably 0.01 to 80% by mass, more preferably 0.1 to 70% by mass.

Dehydrating agent As the dehydrating agent, conventionally known gypsum, tetraethoxysilane and the like can be used.
The amount of the dehydrating agent in the antifouling coating composition is preferably 0.01 to 30 when the amount of the non-volatile content of the antifouling coating composition is 100% by mass from the viewpoint of the effect of preventing the increase in viscosity during storage. It is by mass, more preferably 0.1 to 20% by mass.

Plasticizer Examples of the plasticizer include chlorinated paraffin (chlorinated paraffin), TCP (tricresyl phosphate), polyvinyl ethyl ether, dialkyl phthalate, etc., and have water resistance (mechanical properties) of the coating film and hydrolysis property of the coating film ( From the viewpoint of consumability), among these, chlorinated paraffin (chlorinated paraffin) and polyvinyl ethyl ether are preferable.

Specific examples of chlorinated paraffin include "Toyoparax 150" and "Toyoparax A-70" (both manufactured by Tosoh Corporation). Specific examples of polyvinyl ethyl ether include "Lutner M-40" (manufactured by BASF Japan Ltd., polyvinyl methyl ether), "Lutner A-25" (manufactured by BASF Japan Ltd., polyvinyl ethyl ether), and "Lutner I". -60 "(manufactured by BASF Japan Ltd., polyvinyl isobutyl ether) and the like.

The amount of the plasticizer in the antifouling paint composition is antifouling property, water resistance of the coating film (mechanical property), and if the resin for forming the coating film is a hydrolyzable resin, the coating film is hydrolyzable (consumable). From this point of view, assuming that the amount of the non-volatile content of the antifouling coating composition is 100% by mass, it is preferably 0.1 to 80% by mass, and more preferably 0.5 to 70% by mass.

Pigment Dispersant Examples of the pigment dispersant include various known organic or inorganic pigment dispersants, for example, aliphatic amines or organic acids (for example, "Leomix TDO" (Lion Specialty Chemical Co., Ltd.). (Manufactured by), "Disperbyk-101" (manufactured by Big Chemie Japan Co., Ltd.)).

The amount of the pigment dispersant in the antifouling paint composition is preferably 0. From the viewpoint of the paint viscosity reducing effect and the color separation preventing effect, the non-volatile content of the antifouling paint composition is preferably 100% by mass. It is 01 to 20% by mass, more preferably 0.1 to 10% by mass.

Anti-sagging or anti-settling agent The antifouling coating composition of the present invention may contain an anti-sagging or anti-settling agent (disturbing agent) for the purpose of adjusting the viscosity of the coating composition.

Organic clay waxes (stearate salts of Al, Ca or Zn, lecithin salts, alkyl sulfonates, etc.) and organic waxes (polyethylene wax, oxide polyethylene wax, amido wax, polyamide, etc.) can be used as anti-sagging or anti-settling agents. Wax, hydrogenated castor oil wax, etc.), a mixture of organic clay wax and organic wax, synthetic fine powder silica, etc. may be mentioned.

Commercially available products may be used as the anti-sagging or sedimentation inhibitor, for example, "Disparon 305", "Disparon 4200-20", "Disparon A630-20X", "Disparon 6900-20X" manufactured by Kusumoto Kasei Co., Ltd. , "AS-AD-120", "AS-A T-250F" manufactured by Itoh Oil Chemicals Co., Ltd., and the like.
The sagging prevention or sedimentation inhibitor may be used alone or in combination of two or more.

When the antifouling coating composition of the present invention contains a sagging preventive or anti-settling agent, the content thereof is a non-volatile content of the antifouling coating composition from the viewpoint of storage stability and recoatability of the same type / dissimilar paint. When the amount of the above is 100% by mass, it is preferably 0.1 to 50% by mass, and more preferably 0.3 to 30% by mass.

The solvent antifouling coating composition may contain a solvent such as water or an organic solvent, if necessary, in order to improve the dispersibility and adjust the viscosity of the composition. From the viewpoint of enhancing the adhesion of the anticorrosion coating film according to the present invention to the antifouling coating film, the solvent is an organic solvent, specifically, the anticorrosion coating film according to the present invention can be softened in the vicinity of the surface thereof. Solvents are preferred.

Examples of the organic solvent include aromatic organic solvents such as xylene, toluene and ethylbenzene; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and aliphatic solvents such as ethanol, isopropyl alcohol, n-butanol and isobutanol (1 to 1 to carbon atoms). 10. (Preferably about 2 to 5) monohydric alcohols; ester-based solvents such as ethyl acetate and butyl acetate; and the like. The amount of the solvent in the antifouling coating composition is usually 5 to 80% by mass, preferably 10 to 70% by mass, when the amount of the antifouling coating composition is 100% by mass.

(Manufacturing method of laminated antifouling coating film, etc.)
The method for producing a laminated antifouling coating film according to the present invention includes a step of curing a film made of the epoxy resin-based anticorrosion coating film according to the present invention to form the anticorrosion coating film, and the above-mentioned on the surface of the anticorrosion coating film. It includes a step of forming an antifouling coating film. Further, the method for producing an antifouling base material according to the present invention includes a step of forming a laminated antifouling coating film according to the present invention on the surface of the base material.

Therefore, the laminated antifouling coating film and the antifouling base material according to the present invention are produced by the same method as the conventional method except that the epoxy resin-based anticorrosion coating composition according to the present invention is used as the epoxy resin-based anticorrosion coating material. be able to. That is, the epoxy resin-based anticorrosive coating composition according to the present invention is applied to the surface of the base material by a conventionally known method and cured to form an anticorrosion coating film, and the antifouling coating composition is formed on the surface of the anticorrosion coating film. The laminated antifouling coating film or antifouling base material according to the present invention can be produced, preferably by applying the antifouling coating composition containing the above-mentioned organic solvent by a conventionally known method and curing it.

As the base material, a base material that is required to have anticorrosion and antifouling properties in water is preferable. Examples include various base materials that come into contact with seawater or fresh water such as sludge diffusion prevention films for various marine civil engineering works, ships (eg, bottom of ships), fishing gear (eg, floats, buoys), etc. Examples of the material include steel, aluminum, FRP and the like. The laminated antifouling coating film of the present invention formed on the surface of these base materials has a property of preventing the adhesion of aquatic organisms such as sea lettuce, barnacle, green laver, cellula, oyster, and bugula neritina for a long period of time (antifouling property, Especially excellent in static antifouling property).

As the substrate, the surface of the substrate is treated (for example, for example) in order to remove rust, oil, moisture, dust, slime, salt and the like, and to improve the adhesion of the obtained anticorrosion coating film, if necessary. It may be blasted (ISO8501-1 Sa2 1/2), power tool treatment, friction method, treatment to remove oil and dust by degreasing), and from the viewpoint of corrosion resistance, weldability, or shearability of the substrate, it may be used. If necessary, the surface of the base material may be coated with a thin film forming paint such as a conventionally known primary rust preventive paint (shop primer) or other primer and dried. Further, for the purpose of repair coating, a substrate with a deteriorated antifouling coating film may be used as the substrate.
The film thickness (dry film thickness) of the antifouling coating film is not particularly limited, but when the base material is a ship or an underwater structure, it is, for example, about 50 to 2000 μm.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.
<Preparation of anticorrosion paint composition>
[Example 1]
The anticorrosion paint composition was prepared as follows.

(Main ingredient)
In a plastic container, 5 parts by mass of MIBK (methylisobutylketone), 4 parts by mass of n-butanol, 14 parts by mass of xylene, 12 parts by mass of jER1001-X75, 6 parts by mass of Laroflex MP-25, and 1 part by mass of gumrosin. 15 parts by mass of TTK talc, 15 parts by mass of Varico # 300W, 10 parts by mass of Unisper PG-K10, 0.5 part by mass of titanium white R-930, 1 part by mass of valve handle 404, AS- 4 parts by mass of AT-55-20BX and 0.5 part by mass of KBM-403 were blended, glass beads were added, and a dispersion operation was carried out for 1 hour by a conventional method. A list of raw materials is shown in Table 1. The obtained dispersion was filtered through a 60-mesh filtration net to prepare the main component of the anticorrosion paint.

(Curing agent component)
In a plastic container, 2.5 parts by mass of xylene, 1.4 parts by mass of n-butanol, 6 parts by mass of lacamide TD-966, and 0.1 parts by mass of ancamine K-54 were mixed and dispersed for 10 minutes by a conventional method. The operation was performed. A list of raw materials is shown in Table 1. The obtained dispersion was filtered through a 60-mesh filtration net to prepare a curing agent component for an anticorrosion paint.

(Anti-corrosion paint composition)
The obtained main agent component and the curing agent component were mixed by a conventional method immediately before painting to prepare an anticorrosion coating composition.

[Examples 2 to 12, Comparative Examples 1 to 6]
An anticorrosion coating composition was prepared in the same manner as in Example 1 except that the composition of the main agent component and the curing agent component was changed as shown in Table 2.

<Preparation of antifouling paint composition>
[Manufacturing of metal salt-containing copolymer solution (A1)]
In producing the metal salt-containing copolymer, first, the metal salt-containing monomer (a1) was prepared as follows.

<Preparation Example 1: Preparation of Metal Salt-Containing Monomer (a1)>
85.4 parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide are placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction tube, and a heating / cooling jacket, and 75 by mass while stirring. The temperature was raised to ° C. Subsequently, a mixture consisting of 43.1 parts by mass of methacrylic acid, 36.1 parts by mass of acrylic acid, and 5.0 parts by mass of water was dropped from the dropping device at a constant velocity over 3 hours. After completion of the dropping, the mixture was further stirred for 2 hours, and then 36.0 parts by mass of propylene glycol monomethyl ether was added to obtain a reaction solution containing the metal salt-containing monomer (a1).

<Production Example 1: Production of Metal Salt-Containing Copolymer Solution (A1)>
15.0 parts by mass of propylene glycol monomethyl ether, 57.0 parts by mass of xylene and 4.0 parts by mass of ethyl acrylate in a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen introduction tube, and heating / cooling jacket. Was charged, and the temperature was raised to 100 ± 5 ° C. with stirring. While maintaining the same temperature, 52.0 parts by mass of the reaction solution containing the metal salt-containing monomer (a1) obtained in Preparation Example 1 and 1.0 part by mass of methyl methacrylate in the reaction vessel from the dropping device. 66.2 parts by mass of ethyl acrylate, 5.4 parts by mass of 2-methoxyethyl acrylate, 2.5 parts by mass of polymerization initiator (2,2'-azobisisobutyronitrile), polymerization initiator (2,2' -Azobis (2-methylbutyronitrile) 7.0 parts by mass, chain transfer agent ("Nofmer MSD" (manufactured by Nichiyu Co., Ltd.)) 1.0 part by mass, and xylene 10.0 parts by mass for 6 hours. Dropped over. After completion of the dropping, 0.5 part by mass of the polymerization initiator (t-butylperoxyoctate (TBPO)) and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and after further stirring for 1 hour and 30 minutes, xylene was added. 4.4 parts by mass was added to prepare a pale yellow transparent metal salt-containing copolymer solution (A1) containing the metal salt-containing copolymer.
Table 3 shows the composition of the monomers used and the characteristic values of the metal salt-containing copolymer solution (A1). In the table, the theoretical compounding amount (part by mass) of each monomer is described.

(Production of silyl ester-containing copolymer solution (A2))
[Manufacturing Example 2]
67 parts by mass of xylene was charged in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube and a dropping funnel, and while stirring xylene with a stirrer in a nitrogen atmosphere, the inside of the reaction vessel was subjected to normal pressure. It was heated until the temperature of xylene reached 85 ° C. While maintaining the temperature of xylene in the reaction vessel at 85 ° C., 50 parts by mass of TIPSMA (triisopropylsilylmethacrylate), 30 parts by mass of MEMA (2-methoxyethylmethacrylate), 10 parts by mass of MMA (methylmethacrylate), and BA. A monomer mixture consisting of 10 parts by mass of (butyl acrylate) and 1 part by mass of AMBN (2,2'-azobis- (2-methylbutyronitrile)) was added into the reaction vessel over 2 hours using a dropping funnel. did.

Next, 0.5 part by mass of t-butyl peroxyoctate was further added to the reaction vessel, and stirring was continued with a stirrer for 2 hours while maintaining the liquid temperature in the reaction vessel at 85 ° C. under normal pressure. Then, the liquid temperature in the reaction vessel is raised from 85 ° C. to 110 ° C. and heated for 1 hour, and then 14 parts by mass of xylene is added into the reaction vessel to lower the liquid temperature in the reaction vessel, and the liquid temperature becomes 40 ° C. Stirring was stopped when it became. In this way, a silyl ester-containing copolymer solution (A2) was prepared. Table 4 shows the raw materials, properties, etc. of the silyl ester-containing copolymer solution (A2).

<Characteristic evaluation of metal salt-containing copolymer solution (A1) and silyl ester-containing copolymer solution (A2)>
The above-mentioned characteristics of the metal salt-containing copolymer solution (A1) and the silyl ester-containing copolymer solution (A2) were measured by the following methods.

(1) Content of heating residue in the copolymer solution 1.5 g (X ₁ (g)) of the copolymer solution is held in a constant temperature bath under the conditions of 1 atm and 108 ° C. for 3 hours. The volatile matter was removed to obtain a heating residue (nonvolatile matter). Next, the amount of the remaining heating residue (nonvolatile content) (X ₂ (g)) was measured, and the content rate (%) of the heating residue contained in the copolymer solution was calculated based on the following formula.
Content of heating residue (%) = X ₂ / X ₁ x 100

(2) Average Molecular Weight of Copolymer The average molecular weight of the copolymer (number average molecular weight (Mn) or weight average molecular weight (Mw)) was measured using GPC (gel permeation chromatography) under the following conditions. The measurement conditions are as follows.
GPC conditions
Equipment: "HLC-8120GPC" (manufactured by Tosoh Corporation)
Column: "TSKgel SuperH2000" and "TSKgel SuperH4000" are connected (both manufactured by Tosoh Corporation, 6 mm (inner diameter) x 15 cm (length))
Eluent: Tetrahydrofuran (THF)
Flow velocity: 0.500 ml / min
Detector: RI
Column constant temperature bath temperature: 40 ° C
Standard substance: Polystyrene sample preparation method: A small amount of calcium chloride was added to the copolymer solution, dehydrated, and then filtered through a membrane filter, and the obtained filter was used as a GPC measurement sample.

(3) Viscosity of Copolymer Solution The viscosity (unit: mPa · s) of the copolymer solution at a liquid temperature of 25 ° C. was measured using a B-type viscometer [manufactured by Tokyo Keiki Co., Ltd.].

(Manufacturing of metal salt-containing hydrolyzable antifouling paint S1 and silyl ester-containing hydrolyzable antifouling paints S2 and S3)
[Manufacturing Example 3]
In a plastic container, 9.5 parts by mass of xylene, 20 parts by mass of a metal salt-containing copolymer solution (A1) solution, 6.5 parts by mass of gumrosin, 0.5 parts by mass of ethyl silicate 28, and 4. by mass of zinc oxide. 0 parts by mass, TTK talc 4.0 parts by mass, titanium white R-930 2.0 parts by mass, valve handle 404 2.0 parts by mass, copper omadin 2.0 parts by mass, copper oxide NC- 48 parts by mass of 301 and 0.5 parts by mass of ASAD-120 were blended, glass beads were added, and a dispersion operation was carried out for 1 hour by a conventional method. Then, 1.0 part by mass of Disparon A630-20X was added, and a dispersion operation was further carried out for 15 minutes. The obtained dispersion was filtered through a 60-mesh filtration net to prepare a metal salt-containing hydrolyzable antifouling paint S1. A list of raw materials is shown in Table 1.

[Manufacturing Examples 4 and 5]
The silyl ester-containing hydrolyzable antifouling paints S2 and S3 were prepared in the same manner as in Production Example 3 except that the composition of each component was changed as shown in Table 5.

<Evaluation of anticorrosion paint>
(1) Viscosity of the main agent component and the mixture (paint composition) The viscosity of the main agent component and the mixture obtained by mixing the main agent component and the curing agent component while keeping each of the main agent components and the curing agent component at 23 ° C. The viscosity was measured using a No. 1 rotor of Viscometer VT-04F (manufactured by Rion Co., Ltd.), which is a viscometer (unit: dPa · s).

(2) Spray atomization property Keep each of the main agent component and the curing agent component at 23 ° C., mix the main agent component and the curing agent component, spray the obtained mixture with an air spray, and confirm the spread of the spray pattern. , The spray atomization property was evaluated according to the following criteria.
(Evaluation criteria)
A: When the base material was coated with the mixed paint using an air spray, the mixed paint was sprayed as fine particles (in the form of mist), and the spray pattern was a uniform pattern without causing streaks or the like. (Good atomization property).
B: When the base material is coated with the mixed paint using an air spray, the mixed paint is not sprayed as fine particles (in the form of mist), and the spray pattern spreads, but it looks like a streak (streak pattern). Poor atomization property).
C: When the base material is coated with the mixed paint using an air spray, the mixed paint is not sprayed as fine particles (in the form of mist), the spray pattern does not spread at all, and painting is impossible (does not atomize). ).

(3) Drying property Each of the anticorrosion coating compositions is applied to a glass plate of 348 mm × 25 mm × 2 mm (thickness) with a film applicator so that the dry coating film thickness becomes 150 μm, and RC is performed at a temperature of 5 ° C. Using a mold drying time recorder (manufactured by Coating Tester Co., Ltd.), the time until the coating film was semi-cured or completely cured was measured.

In this drying property test, the test needle of the RC type drying time recorder was slowly moved at a constant speed on the coating film immediately after the anticorrosion paint composition was applied on the glass plate, so that the test needle passed. The state of the coating film was determined from the traces, and the time from immediately after the coating film was formed to semi-curing or complete curing was determined.

Specifically, the test needle moves from the movement start position a to the position b where the glass plate 2 cannot be seen in the trace of the test needle in the schematic diagram 1 overlooking the glass plate 2 on which the coating film 1 is formed. The time required for this is defined as the semi-curing time, and the test needle moves from the movement start position a to the position c where the test needle slides on the coating film surface and no trace of the test needle is completely left on the coating film surface. The time required for this was taken as the complete curing time.
It was judged that there is no practical problem in terms of drying property if the complete curing time at 5 ° C. is less than 24 hours.

(4) Anticorrosion resistance of anticorrosion paint <Salt water resistance test>
The salt water resistance of the anticorrosion coating film was measured according to JIS K5600-6-1. Specifically, it was carried out as follows. Each of the anticorrosion coating compositions obtained in Examples and Comparative Examples was coated with a dry film on a blasted steel sheet having dimensions of 150 mm × 70 mm × 1.6 mm (thickness) (hereinafter, also referred to as “test plate”). A test plate with an anticorrosion coating was prepared by spray-coating the test plate so as to have a thickness of about 250 μm and drying the spray-coated test plate in an atmosphere of 23 ° C. and 50% RH for 7 days. Using this test plate with an anticorrosion coating film, the test plate was immersed in 3% salt water at 40 ° C., and the appearance of the anticorrosion coating film 30 days and 60 days after the start of immersion was visually evaluated according to the following criteria.
(Evaluation criteria)
A: No change in blisters, cracks, rust, peeling, or hue.
B: Some defects (changes) are observed in any of blisters, cracks, rust, peeling, and hue.
C: Any of blisters, cracks, rust, peeling, and changes in hue are clearly observed.

<Electrical corrosion protection test>
A zinc anode was connected to a test plate with an anticorrosion coating film prepared in the same manner as in the salt water resistance test so that the electric current density was 5 mA / m ² or less, and after 30 days and 60 after immersion in 3% salt water at 40 ° C. The appearance of the anticorrosion coating film after a day was visually evaluated according to the same criteria as in the salt water resistance test.

<Salt spray test>
A solution with a salt water concentration of 5% was continuously sprayed on a test plate with an anticorrosion coating film prepared in the same manner as in the salt water resistance test in accordance with JIS K5600-7-1 under the condition of 35 ° C. The appearance of the anticorrosion coating film after 1 day and 60 days was visually evaluated according to the same criteria as in the salt water resistance test.
The results of the above tests are shown in Table 6.

(5) Adhesion between anticorrosion coating film and antifouling coating film On a sandblast plate (150 mm × 70 mm × 1.6 mm), each of the anticorrosion coating compositions of Examples and Comparative Examples has a dry film thickness of 150 μm. It was applied to form a cured coating film, and then immediately outdoors, the sandblasted plate with the cured coating film was exposed at an angle of 45 ° to the ground facing south with the cured coating film side facing up.

Then, on the test plate exposed outdoors for 1 day, 4 days or 7 days under the above-mentioned conditions (on the surface of the cured coating film formed from the anticorrosion paint), each of the antifouling paint compositions of Production Examples 3 to 5 above. Was applied using an applicator to a dry film thickness of 100 μm, and dried at 23 ° C. for 7 days to form an antifouling coating film, thereby producing a test plate with a laminated antifouling coating film.
The obtained test plate with a laminated antifouling coating film is immersed in artificial seawater at 40 ° C., and the adhesion between the anticorrosion coating film and the antifouling coating film 30 days and 60 days after the start of immersion is based on the following evaluation criteria. Evaluated.

(Adhesion evaluation method)
Using an NT cutter, make 9 squares by making 4 cuts in each of the vertical and horizontal directions at 4 mm intervals on the antifouling coating surface of the test plate with a laminated antifouling coating film, and the coating film on which the squares were created was created. After crimping cellophane tape (registered trademark) on the surface, it was quickly peeled off and the squares were observed. Next, when the area of the nine squares is 100%, the ratio (%) of the area (peeling area) of the coating film peeled between the layers of the anticorrosion coating film and the antifouling coating film in the squares after the peeling operation. ) Was calculated, and the adhesiveness was evaluated based on the following evaluation criteria. The results are shown in Table 7.
(Evaluation criteria)
0: The delamination area of the coating film is less than 5%.
1: The delamination area of the coating film is 5% or more and less than 25%.
2: The delamination area of the coating film is 25% or more and less than 50%.
3: The delamination area of the coating film is 50% or more.

(6) Antifouling property of laminated antifouling coating film Air spray is applied to a sandblasted steel plate of 100 mm × 300 mm × 3.2 mm so that each of the anticorrosion coating compositions of Examples and Comparative Examples has a dry film thickness of 150 μm. The antifouling paint S1 is applied with an air spray so that the dry film thickness of the antifouling coating film is 100 μm, and this is dried at 23 ° C. for 7 days to achieve a laminated antifouling coating. A test plate having a membrane was prepared.

The above test plate is statically immersed in Nagasaki Bay, Nagasaki Prefecture, and the area where aquatic organisms adhere to the area where aquatic organisms adhere to 100% of the total area of the antifouling coating film of the test plate every month after immersion. Area ratio (%)) was visually measured and evaluated based on the following evaluation criteria. The results are shown in Table 8.
(Evaluation criteria)
0: No attachment of aquatic organisms.
0.5: Adhesion area of aquatic organisms exceeds 0% and is 10% or less.
1: The area of aquatic organisms attached is more than 10% and 20% or less.
2: The area of aquatic organisms attached is more than 20% and less than 30%.
3: The area of aquatic organisms attached is more than 30% and 40% or less.
4: The adhered area of aquatic organisms exceeds 40% and 50% or less.
5: The attached area of aquatic organisms exceeds 50%.

1 ... Coating film 2 ... Glass plate 3 ... Traces of the test needle passing a ... Position where the test needle starts moving b ... Position where the glass plate is no longer visible c ... The test needle slides on the surface of the coating film and the test needle is on the surface of the coating film The position where the trace of

Claims (16)

It contains an epoxy resin (A), a thermoplastic resin (B) (excluding rosins (C)), rosins (C), and a curing agent (D).
The thermoplastic resin (B) contains at least one selected from the group consisting of petroleum resin, ketone resin, chlorinated polyolefin, acrylic resin, butyl acetate resin, styrene resin, and vinyl chloride resin.
The content of the thermoplastic resin (B) is 35 parts by mass or more with respect to 100 parts by mass of the epoxy resin (A).
An epoxy resin-based anticorrosion coating composition having a content of the rosins (C) of 5 to 30 parts by mass with respect to a total of 100 parts by mass of the epoxy resin (A) and the thermoplastic resin (B). The epoxy resin (A) is one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol F type epoxy resin, and a modified epoxy resin obtained by modifying these epoxy resins. The epoxy resin-based anticorrosion coating composition according to claim 1. The epoxy resin-based anticorrosion coating composition according to claim 1 or 2, further comprising a pigment (E). The epoxy resin-based anticorrosion coating composition according to claim 3, wherein the pigment volume concentration (PVC) represented by the following formula (2) is 25 to 50%.
Pigment volume concentration (%)
= Volume of pigment in anticorrosion paint composition / (Volume of resins in anticorrosion paint composition + Volume of pigment in anticorrosion paint composition) × 100 ... Formula (2) The invention according to any one of claims 1 to 4, wherein the thermoplastic resin (B) contains a vinyl chloride resin, and the vinyl chloride resin is a vinyl chloride / vinyl isobutyl ether copolymer. Epoxy resin-based anticorrosion coating composition. An anticorrosion coating film comprising a cured product of the epoxy resin-based anticorrosion coating composition according to any one of claims 1 to 5 . A base material with an anticorrosion coating film having the base material and the anticorrosion coating film according to claim 6 provided on the surface of the base material. A step of applying the epoxy resin-based anticorrosion coating composition according to any one of claims 1 to 5 to a substrate, and a step of curing the coated anticorrosion coating composition to form an anticorrosion coating film. A method for manufacturing a base material with an anticorrosion coating. A laminated antifouling coating film provided on the surface of a base material in the order of the anticorrosion coating film and the antifouling coating film according to claim 6 from the base material side. The laminated antifouling coating film according to claim 9 , wherein the antifouling coating film is a hydrolysis type antifouling coating film. The laminated antifouling coating film according to claim 10 , wherein the hydrolysis type antifouling coating film contains rosins. The method for producing a laminated antifouling coating film, which is formed by laminating an anticorrosion coating film and an antifouling coating film on the surface of the base material in this order from the base material side, according to any one of claims 1 to 5 . Production of a laminated antifouling coating film including a step of curing a film made of the epoxy resin-based anticorrosion coating film to form the anticorrosion coating film and a step of forming the antifouling coating film on the surface of the anticorrosion coating film. Method. The laminated antifouling coating film according to any one of claims 9 to 11 is laminated on the surface of the base material in the order of the anticorrosion coating film and the antifouling coating film from the base material side. Antifouling base material. The antifouling substrate according to claim 13 , which comes into contact with seawater or fresh water. The antifouling base material according to claim 13 or 14 , wherein the base material is at least one selected from the group consisting of a ship, an underwater structure, and a fishing gear. A method for producing an antifouling base material, which comprises the step of forming the laminated antifouling coating film according to any one of claims 9 to 11 on the surface of the base material.

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