JPWO2018221266A1 - Epoxy resin anticorrosion coating composition, anticorrosion coating, laminated antifouling coating, and antifouling substrate, and methods for producing these - Google Patents

Abstract

[Problem] Epoxy resin system having good adhesion to a hydrolyzable antifouling paint containing a large amount of rosin even when the anticorrosion paint and the antifouling paint are coated at intervals, and having excellent low-temperature drying property and anticorrosion property. To provide an anticorrosion paint, a laminated antifouling coating film, a method for producing the same, and the like. [Solution] An epoxy resin (A), a thermoplastic resin (B), a rosin (C), and a curing agent (D) are contained, and the content of the thermoplastic resin (B) is the epoxy resin ( It is 35 parts by mass or more based on 100 parts by mass of A), and the content of the rosins (C) is 5 parts by mass based on 100 parts by mass of the epoxy resin (A) and the thermoplastic resin (B). The epoxy resin anticorrosion coating composition is about 30 parts by mass.

Description

  The present invention relates to an epoxy resin anticorrosion coating composition, and more particularly, an epoxy resin anticorrosion coating composition useful for forming an anticorrosion coating film in a laminated antifouling coating film comprising an anticorrosion coating film and an antifouling coating film, TECHNICAL FIELD The present invention relates to a coating film, a laminated antifouling coating film comprising the anticorrosion coating film and an antifouling coating film laminated thereon, an antifouling substrate having the laminated antifouling coating film, and a method for producing these.

  Conventionally, a metal base material such as steel is used for many (large) steel structures such as ships and underwater structures. These structures are coated with anticorrosion paint to prevent corrosion by seawater. Furthermore, an antifouling paint that prevents the adhesion of aquatic organisms such as barnacles and seaweed is applied as the topcoat paint.

As the anticorrosion paint, an epoxy resin anticorrosion paint is generally used.
There are many documents relating to epoxy resin anticorrosive paints. For example, Patent Document 1 discloses an anticorrosion paint composition containing an epoxy resin, an alicyclic amine, and an acrylate monomer, and Patent Document 2 discloses an epoxy resin heavy anticorrosion paint containing a vinyl chloride resin or the like. ing. It is described in these documents that after coating the anticorrosion paint, a topcoat paint (antifouling paint) was applied to evaluate the adhesion between the anticorrosion coating film and the topcoat film. As the antifouling paint, it is currently mainstream to use a hydrolyzable antifouling paint which has a good long-term antifouling performance.

  Further, Patent Document 3 is composed of an organosilicon compound having an aminoalkyl group and an alkoxy group and a compound having an oxirane ring, and is suitable for rust prevention of copper, copper alloys, and chromate-plated metal. It is described that by adding one or more kinds selected from rosins or derivatives thereof, terpene resins and petroleum resins to the metal rust preventive composition, the rust preventive property is more effectively improved.

International Publication No. 2006/016625 JP, 11-333374, A JP-A-60-221472

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

Describing the coating of a ship here, in the ship building process, the interval between application of the anticorrosion paint and application of the antifouling paint (hereinafter also referred to as "painting interval") due to weather conditions, the coating process, and the like. May be longer. A coating film formed from a hydrolysis-type antifouling paint having a high rosin content has a problem that the coating film hardness is high and it is difficult to adhere to the undercoating anticorrosion coating film. Therefore, in order to secure sufficient adhesion, it is necessary to apply the antifouling paint before the coating film hardness increases, that is, it is necessary to set the coating interval short, and the coating process control at the coating site becomes tight. Especially in summer when the temperature is high, there is a case where the allowable coating interval is one day. Also, if the coating work is stopped due to rainfall or the like and the allowable coating interval is exceeded, the anticorrosion paint will be reapplied and the antifouling paint will be applied later, which will be a return work, which is economically and time negative. ..
As a countermeasure against the above, it is strongly desired to develop an anticorrosion paint capable of forming an anticorrosion coating film having sufficient adhesiveness even if the coating interval becomes long.

  In order to solve the above problems, the inventors of the present invention have earnestly studied, and by using a thermoplastic resin and a rosin in an epoxy resin-based anticorrosion coating, the antifouling coating film has a high rosin content. It has been found that the adhesiveness of the anticorrosion coating film to the antifouling coating film (hereinafter, also simply referred to as “adhesion property of anticorrosion coating film” or “adhesion property”) is improved even if it is formed from.

The mechanism of the effect expression of the present invention is considered as follows.
Epoxy resin-based anticorrosion paint forms an anticorrosion coating film by a mechanism in which an epoxy resin reacts with a curing agent such as amine, and is cured and dried. The surface of the anticorrosion coating film is softened by the solvent contained in the antifouling coating material 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 to the antifouling coating.

  The curing reaction of the anticorrosion paint progresses with the passage of time. The hardness of the coating film increases as time passes, and the solvent resistance of the coating film also improves. Therefore, if a long period of time elapses before the antifouling paint is applied after the anticorrosion coating is formed, the softening of the anticorrosion coating by the solvent in the antifouling coating is prevented, and the anticorrosion coating and the antifouling coating do not interact with each other. There is a phenomenon that the adhesiveness is insufficient and the adhesiveness cannot be expressed. Particularly when the antifouling coating film is formed from an antifouling coating material with a high rosin content, the hardness and brittleness of the rosin increases the coating film hardness, and the rosin component migrates to the interface with the anticorrosion coating material. However, it is difficult to secure the adhesiveness because the tendency to lower the adhesiveness becomes stronger.

  In the present invention, by using the rosin (C) in combination with the anticorrosive paint containing the thermoplastic resin (B), the solvent resistance of the anticorrosive coating after drying and curing is the same as that of the usual rosin (C) -free resin. Since it is lower than that of the anticorrosion coating, even if the coating interval is long, the anticorrosion coating is easily dissolved by the solvent of the top antifouling coating and the adhesiveness is easily exhibited. Furthermore, when the antifouling paint contains rosins, the rosins in the antifouling paint migrate to the interface with the anticorrosion coating, and the affinity between the anticorrosion coating containing rosin and the antifouling coating is improved. It is considered that the above results synergistically significantly improve the adhesion.

  Furthermore, in the case of anticorrosion paints containing an epoxy resin and a curing agent, conventionally, in order to improve the adhesiveness, it was general to apply a formulation such as reducing the reaction ratio. There arises a problem that the low temperature drying property and the anticorrosion property are deteriorated. The present invention eliminates such a trade-off relationship and secures adhesion to a coating film formed from a hydrolyzable antifouling paint having a high rosin content without impairing low-temperature drying property and anticorrosion property. Can be established.

Furthermore, the present inventors have found that if the rosin is excessively added to the anticorrosion paint, the anticorrosion property of the anticorrosion coating is rather deteriorated.
The present inventors have completed the present invention based on these findings. The present invention is as follows.

[1]
Contains an epoxy resin (A), a thermoplastic resin (B) (however, excluding rosins (C)), rosins (C), and a curing agent (D),
The content of the thermoplastic resin (B) is 35 parts by mass or more based on 100 parts by mass of the epoxy resin (A),
An epoxy resin anticorrosion coating composition in which the content of the rosin (C) is 5 to 30 parts by mass with respect to 100 parts by mass of the total 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 anticorrosion coating composition according to [1] above.

[3]
The epoxy resin-based anticorrosive coating composition according to the above [1] or [2], which further contains a 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 coating composition / (volume of resins in anticorrosion coating composition + volume of pigment in anticorrosion coating composition) x 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 anticorrosion coating composition according to any one of the above [1] to [4].

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

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

[8]
A substrate with an anticorrosion coating, which comprises the substrate and the anticorrosion coating of [7] provided on the surface of the substrate.

[9]
The method has a step of coating the substrate with the epoxy resin anticorrosive coating composition according to any one of [1] to [6], and a step of curing the coated anticorrosive coating composition to form an anticorrosive coating film. A method for producing a substrate with an anticorrosion coating.

[10]
A laminated antifouling coating film, which is provided by laminating the anticorrosion coating film of [7] and the antifouling coating film in this order from the substrate side on the surface of the substrate.

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

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

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

[14]
An antifouling obtained by laminating the laminated antifouling coating film of any one of [10] to [12] on the surface of a base material in the order of the anticorrosion coating film and the antifouling coating film from the base material side. Soil base material.

[15]
The antifouling substrate of [14], which comes into contact with seawater or fresh water.

[16]
The antifouling substrate of [14] or [15], wherein the substrate is at least one selected from the group consisting of ships, underwater structures, and fishing gear.

[17]
A method for producing an antifouling substrate, comprising the step of forming the laminated antifouling coating film according to any one of [10] to [12] on the surface of the substrate.

  According to the epoxy resin anticorrosion coating composition of the present invention, an anticorrosion coating film having excellent anticorrosion properties can be formed. This anticorrosion coating is a laminated antifouling coating formed by laminating an anticorrosion coating and an antifouling coating on the surface of the substrate in this order from the side of the substrate, and has excellent adhesion even if the coating interval is long. In particular, the antifouling coating film is formed of a hydrolyzable antifouling coating material having a high rosin content and has excellent adhesiveness even when the coating interval is long.

  The epoxy resin anticorrosive 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 the examples.

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

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

  As the main component, if necessary, the pigment (E), the curing accelerator (F), the adhesion enhancer (G), the plasticizer (H), the solvent (I), the anti-sagging agent or the anti-settling agent (J). , A dehydrating agent (stabilizer) (K), or other coating film-forming components (dispersing agent, defoaming agent, leveling agent, etc.) may be added within a range that does not impair the object of the present invention, If necessary, a curing accelerator (F), a solvent (I), or the like may be added to the curing agent component as long as the object of the present invention is not impaired.

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

  In the present invention, the term "nonvolatile components of the anticorrosion coating composition (or antifouling coating composition)" means JIS K5601-1-2 of the anticorrosion coating composition (or the antifouling coating composition described later) of the present invention. It is the 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 formed by 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, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, alicyclic ring. Examples thereof include group epoxy resins and epoxidized oil-based epoxy resins. Specific examples of such epoxy resin (A) include, for example, bisphenol A type epoxy resin such as epichlorohydrin-bisphenol A resin; 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 novolac resin; aromatic such as 3,4-epoxyphenoxy-3 ′, 4′-epoxyphenylcarboxymethane Epoxy resin; epichlorohydrin-bisphenol A 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 aliphatic dihydric alcohol Aliphatic epoxy resin with a structure reacted with; polyfunctional epoxy resin with a structure reacted with epichlorohydrin and tri (hydroxyphenyl) methane; bisphenol type epoxy resin with dimer acid (dimer of unsaturated fatty acid) A modified dimer acid-modified epoxy resin; a hydrogenated epoxy resin having a structure in which an aromatic ring in a bisphenol type epoxy resin is hydrogenated, and the like.

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

  The said epoxy resin (A) can be used individually by 1 type or in combination of 2 or more types. Weight average molecular weight of the epoxy resin (A) measured by GPC (gel permeation chromatography) (measurement conditions are the conditions described in the column "(2) Average molecular weight of copolymer" of the example described later or this) Is the same as the above condition), but is not generally determined depending on the coating and curing conditions of the epoxy resin anticorrosion coating composition (eg, normal dry coating or baking coating), but preferably 350 to 20, 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 (according to JIS K7236) of the epoxy resin (A) is preferably 150 to 1,000 g / eq.
The epoxy resin (A) is preferably a bisphenol A type epoxy resin having an epoxy equivalent of 150 to 700 g / eq.

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

As a typical bisphenol A type epoxy resin, when it is liquid at room temperature, "jER (registered trademark) 828" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 to 200 g / eq, NV 100%), "E-028" is used. -90X "(manufactured by Ohtake Meishin Chemical Co., Ltd., 828 type epoxy resin, nonvolatile content epoxy equivalent 180 to 200 g / eq, xylene cut product NV90%)," AER260 "(bisphenol A type epoxy resin, Asahi Kasei Epoxy Co., Ltd.) , Epoxy equivalent 190 g / eq, NV 100%) and the like,
For those that are semi-solid at room temperature, "jER834-X90" (Mitsubishi Chemical Co., Ltd., nonvolatile epoxy equivalent 230-270 g / eq, xylene cut product NV90%), "E-834-85X" (Otake Meishin Chemical Co., Ltd.) Co., Ltd., nonvolatile epoxy equivalent of about 230 to 270 g / eq, xylene cut product NV85%), and the like.
In the solid state at room temperature, "jER1001-X75" (Mitsubishi Chemical Co., Ltd., non-volatile epoxy equivalent 450-500 g / eq, xylene cut product NV75%), "E-001-75X" (Otake Meishin Chemical ( Non-volatile epoxy equivalent of about 450 to 500 g / eq, xylene cut product NV75%) and the like.

As other epoxy resins and modified epoxy resins, "jER807" (manufactured by Mitsubishi Chemical Corporation, bisphenol F-type diglycidyl ether resin, epoxy equivalent 160 to 175 g / eq, NV 100%), "Flep 60" (polysulfide modified) Epoxy resin, manufactured by Toray Fine Chemical Co., Ltd., epoxy equivalent 280 g / eq, NV100%, "YD-172-X75" (dimer acid modified epoxy resin, Kokuto Kagaku Co., Ltd., nonvolatile epoxy equivalent 600-700 g). / Eq, xylene cut product NV75%), "Epiclon 5300-70" (Novolac type epoxy resin, manufactured by DIC Corporation, nonvolatile epoxy equivalent 300 to 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 resin, ketone resin, chlorinated polyolefin, acrylic resin, butyl acetate resin, styrene resin, vinyl chloride resin and the like. When the anticorrosion coating film formed from the anticorrosion coating composition is coated with an antifouling coating material containing an organic solvent, as described in Patent Document 2 ([0045]), the thermoplastic resin (B) is It is dissolved by the organic solvent in the antifouling paint to improve the adhesion of the anticorrosion coating to the antifouling coating.

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

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

As the thermoplastic resin (B), one having a glass transition temperature of 30 ° C. or higher is more preferable.
As the thermoplastic resin (B), among the above resins, a vinyl chloride resin is preferable because it has little influence on the adhesion to 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 one having a glass transition temperature of 30 ° C. or higher is more preferable. Commercially available products of such vinyl chloride / vinyl isobutyl ether copolymer 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. In addition, among the vinyl / vinyl isobutyl ether copolymers, "Laroflex MP-25" is particularly preferable because the viscosity of the paint when the epoxy resin anticorrosive paint composition is prepared is small and the workability is excellent. .

  As the above-mentioned other thermoplastic resins (B), as commercially available products of acrylic resin, “Dianal BR106” (manufactured by Mitsubishi Chemical Corporation, Mw = 60,000), “Paraloid B66” (manufactured by Dow Chemical Co., Mw) = 70,000) and the like, and an acrylic resin copolymerized with acrylic acid and its ester or its derivative, a methacrylic resin copolymerized with methacrylic acid and its ester or its derivative, and the like.

  These thermoplastic resins may be used alone or in combination of two or more. The amount of the thermoplastic resin (B) in the anticorrosion coating composition is determined 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. From the viewpoint of suppressing or preventing the deterioration of the antifouling performance (particularly static antifouling property) by shifting to another antifouling coating film, and optionally from the viewpoint of further drying property, the epoxy resin (A) 100. 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 from the viewpoint of exhibiting excellent anticorrosion properties, topcoating properties, and drying properties of the anticorrosion coating film, the upper limit thereof is set. Is preferably 100 parts by mass, more preferably 90 parts by mass.

Rosin (C)
By mixing a predetermined amount of rosin (C) into the epoxy resin anticorrosion coating composition, the drying property of the anticorrosion coating is improved, and the antifouling coating of the anticorrosion coating (particularly, an organic solvent containing a large amount of rosins It becomes possible to significantly improve the adhesion to the antifouling coating film formed from the mold antifouling paint.

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

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

Curing agent (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, Cresol novolac resins, phenol novolac 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, From the viewpoint of the adhesion of the anticorrosion coating film and the drying property of the anticorrosion coating composition, an amine-based curing agent that is a compound having two or more amino groups in one molecule is particularly preferable. Examples of the compound constituting the amine 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 Mannich modified products. Things etc. are mentioned.

Specifically, as the aliphatic amine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2'-aminoethylamino) propane, triethylene-bis (trimethylene) hexamine, bis (3-aminoethyl) amine, bis hexamethylene triamine _{[H 2 N (CH 2)} 6 NH (CH 2) 6 NH 2], and bis (cyanoethyl) diethylenetriamine, and the like.

  Examples of the alicyclic amine include 4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexylamine, norbornanediamine (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 menthene. Diamine and the like can be mentioned.

  Examples of the aromatic amine include o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis (4). -Aminophenyl) propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4- Examples include diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis (aminomethyl) naphthalene, and bis (aminoethyl) naphthalene. Be done.

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

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 Corporation, polyamide, nonvolatile active hydrogen equivalent 226 g / eq NV60%), "PA-66" (Akira Otake) New Chemical Co., Ltd., polyamide, nonvolatile content active hydrogen equivalent 226g / eq NV60%), "PA-290 (A)" (Otake Meiji Shin Chemical Co., Ltd., nonvolatile content active hydrogen equivalent 166g / eq NV60%) , "Ancamide 2050" (manufactured by Air Products, polyamide adduct, active hydrogen equivalent 150 g / eq NV100%), "NX-4918" (manufactured by Cardlight, phenalkamine (Mannich modified product of cardanol and amine) adduct, non-volatile component 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, and 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 curability of the anticorrosion coating film and drying property when a solvent is included.

Pigment (E )
Examples of the pigment (E) include extender pigments, coloring pigments, and rust preventive pigments.
Specific examples of extender pigments include barium sulfate, potassium feldspar, barite powder, silica, calcium carbonate, talc, mica, glass flakes, and aluminum stearate. Specific examples of the color pigment include titanium white (titanium oxide), red petals, yellow red 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 scale-like mica or aluminum paste in terms of coating film physical properties and anticorrosion properties.

  The amount of the extender pigment in the anticorrosion coating composition is preferably 0.1 to 80% by mass, when the nonvolatile content of the anticorrosion coating composition is 100% by mass. The amount of the coloring pigment is preferably 0.1 to 50 mass% when the nonvolatile content of the anticorrosion coating composition is 100 mass%. The amount of the rust-preventive pigment is preferably 0.1 to 50% by mass, when the amount of nonvolatile components in the anticorrosion coating composition is 100% by mass.

Curing accelerator (F)
Examples of the curing accelerator (F) include tertiary amines. Specific examples of the tertiary amine include triethanolamine (N (C ₂ H ₅ OH) ₃ ), dialkylaminoethanol ([CH _{3 (CH 2) n] 2} NCH 2 OH, n: repetition), triethylenediamine (1,4-diazabicyclo (2,2,2) octane), 2,4,6-tris (dimethylaminomethyl) phenol ( _{C 6 H 5 -CH 2 N (} CH 3) 2), "Basamin EH30" manufactured (BASF Japan Ltd.), and "Ancamine K-54" (manufactured by air Products Co., Ltd.).

Examples of the curing accelerator (F) also include acrylic acid ester curing accelerators.
The amount of the curing accelerator (F) in the anticorrosion coating composition enhances the rate of curing of the epoxy resin (A) with the curing agent (D), so that the anticorrosion coating film and the top coating film, that is, the antifouling coating film. Since the anticorrosion coating film having excellent adhesion to the film and excellent flexibility of the anticorrosion coating film is obtained, when the nonvolatile content of the anticorrosion coating composition is 100% by mass, preferably 0.1 to 5% by mass. Is.

Adhesion enhancer (G)
Examples of the adhesion enhancer (G) include organic acids, chelating agents, and silane coupling agents. Among them, the silane coupling agent is preferable from the viewpoint 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 and the reduction of the viscosity of the anticorrosion coating composition. The silane coupling agent may be, for example, a compound represented by 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 Represents a hydrocarbon group having a group (this hydrocarbon group may have an ether bond or the like), 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” if they are commercially available products. (Manufactured by Chisso Corporation) 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 nonvolatile content of the anticorrosion coating composition is 100% by mass. It is mass%, more preferably 0.5 to 5 mass%. When the silane coupling agent is used in the anticorrosion coating composition in such an amount, the performance such as the adhesion of the obtained anticorrosion coating film is improved, and the viscosity of the anticorrosion coating composition is lowered to improve the coating workability. ..

Plasticizer (H)
Examples of the plasticizer (H) include chlorinated paraffin (chlorinated paraffin), TCP (tricresyl phosphate), polyvinyl ethyl ether, dialkyl phthalate, and the like, and from the viewpoint of coating film water resistance (mechanical properties), Among them, chlorinated paraffin (chlorinated paraffin) and polyvinyl ethyl ether are preferable.
The non-volatile content of the plasticizer (H) in the anticorrosion coating composition is preferably 0.1 to 20 mass% when the non-volatile content of the anticorrosion coating composition is 100 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 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-sagging or anti-settling agent (J)
Specific examples of the anti-sagging or anti-settling agent (thixotropic agent) (J) include polyamide wax, polyethylene wax, bentonite type, OH-containing nanoparticles (erogel, resin beads) and the like.

Examples of such an anti-sagging agent or an anti-settling agent (J) include "Disparon 4200-20" and "Disparon 6650" manufactured by Kusumoto Kasei Co., Ltd. and "A-S-A T-250F" manufactured by Ito Oil Co., Ltd. , "A-S-A T-55-20BX" and the like.
The non-volatile content of the anti-sagging or anti-settling agent (J) in the anticorrosion coating composition is preferably 0.1 to 30 mass% when the non-volatile content of the anticorrosion coating composition is 100 mass%. ..

Dehydrating agent (stabilizer) (K)
The anticorrosion coating composition of the present invention can have further excellent long-term storage stability by adding a dehydrating agent (stabilizer) (K) as necessary.
Examples of the dehydrating agent (K) include an inorganic dehydrating agent and an organic dehydrating agent. The inorganic dehydrating agent is preferably synthetic zeolite, anhydrous gypsum or hemihydrate gypsum, and the organic dehydrating agent is preferably tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, or methyltri. Examples thereof include alkoxysilanes such as ethoxysilane, dimethyldiethoxysilane, and trimethylethoxysilane, or polyalkoxysilanes which are condensates thereof, and alkyl orthoformate alkyl esters such as methyl orthoformate and ethyl orthoformate.
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).

(Anticorrosion coating composition)
The anticorrosion coating composition according to the present invention contains the above-mentioned epoxy resin (A), thermoplastic resin (B), rosin (C), curing agent (D), and optionally other components. These can be prepared by mixing and stirring them 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 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 compounding amount and the equivalent are g and g / eq, respectively.)

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

  When the reaction ratio is equal to or more than the lower limit value, the epoxy resin (A) is cross-linked at many places, so that the unreacted epoxy resin component is less likely to remain, and the resulting anticorrosion coating film has curability and solvent. When it contains, the laminated antifouling coating film has little deterioration in antifouling property (particularly static antifouling property).

  When the reaction ratio is less than or equal to the upper limit value, the unreacted curing agent (D) is unlikely to remain in the resulting coating film, and the unreacted curing agent (D) draws in water, resulting in coating. Problems such as deterioration of water resistance of the film and discoloration can be prevented.

(PVC)
The nonvolatile content of the anticorrosion coating composition of the present invention is preferably 25 to 50%, more preferably 30 to 45%, as the pigment volume concentration (hereinafter also referred to as "PVC") defined by the following formula (2). is there.
Pigment volume concentration (%)
= Volume of pigment in anticorrosion coating composition / (volume of resins in anticorrosion coating composition + volume of pigment in anticorrosion coating composition) x 100 ... Formula (2)

Further, the “volume of resin” described in the denominator of the formula (2) means an epoxy resin (A), a thermoplastic resin (B), a rosin (C), a curing agent (D) and a curing accelerator ( It is the total volume of F) and the plasticizer (H).
When the PVC is at least the lower limit value, the resulting coating film has excellent dryness.
When the PVC is less than the above upper limit, the viscosity of the anticorrosion coating composition is remarkably high and the coating workability is deteriorated, or the anticorrosion property is deteriorated due to deterioration of the leveling property of the coating film or occurrence of pinholes. You can prevent problems.

[Corrosion-proof coating, substrate with anti-corrosion coating]
The anticorrosion coating film according to the present invention comprises a cured product of the above-mentioned epoxy resin anticorrosion coating composition according to the present invention.
The anticorrosion coating film according to the present invention includes an epoxy resin cured product, the thermoplastic resin (B) (excluding the cured product of the epoxy resin (A) and the rosin (C)), and the rosin. It also comprises a matrix containing (C).

  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 the rosin (C) is usually 1.0 to 7.0. % By mass, preferably 1.5 to 6.0% by mass. Since the anticorrosive coating film according to the present invention contains the thermoplastic resin (B) and the rosins (C) in such a proportion, it has excellent adhesion to various topcoat paints, and the topcoat paint is particularly an antifouling paint. In the case of, it is preferably used. 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 rosin (C) in a predetermined amount, it has excellent film-forming properties at low temperatures (for example, 5 ° C) and excellent low-temperature drying properties. ..
The anticorrosion coating film according to the present invention is preferably used as the anticorrosion coating film of a laminated antifouling coating film formed by laminating an anticorrosion coating film and an antifouling coating film in this order from the substrate side on the substrate surface. .. The anticorrosion coating film according to the present invention has excellent adhesion to the antifouling coating film in the laminated antifouling coating film when the antifouling coating film is formed from an organic solvent type antifouling coating material containing a large amount of rosin. However, it has excellent adhesion.

The base material with an anticorrosion coating 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 a 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 a method similar to the conventional method for producing an anticorrosion coating film, 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, it is possible to reduce the amount of diluting solvent and ensure good workability in coating.
The thickness of the anticorrosion coating film (dry film thickness) is usually about 50 to 800 μm.

[Laminate 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 a substrate from the side of the substrate in the order of the anticorrosion coating film and the antifouling coating film, wherein the anticorrosion coating film is It is a laminated antifouling coating film which is the anticorrosion coating film according to the present invention described above.
Further, the antifouling substrate according to the present invention, the laminated antifouling coating film according to the present invention is laminated on the substrate surface in the order of the anticorrosion coating film, the antifouling coating film from the substrate side. It will be done.

(Antifouling paint composition)
Examples of the antifouling coating composition for overcoating the anticorrosion coating to form an antifouling coating film include conventionally known antifouling coating compositions.

Examples of the antifouling paint composition include hydrolyzable antifouling paint compositions, and as the coating film forming resin of the hydrolyzable antifouling paint composition, a hydrolyzable resin, for example,
An acrylic resin or a polyester resin, represented by the general formula (I):
COO-M-O-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-M-O-CO-C (R 2) = CH 2 ··· (II)
[M in the formula (II) represents zinc or copper, and R ² represents a hydrogen atom or a methyl group. ]
And a metal salt-containing copolymer containing a structural unit derived from a monomer represented by 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)
[In the formula (III), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ , R ⁶ and R ⁷ each independently represent a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom. R ³ is a hydrogen atom or R ⁸ —O—CO (wherein R ⁸ is independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or SiR ⁹ R ¹⁰ R ¹¹ Represents a silyl group, and R ⁹ , R ¹⁰ and R ¹¹ each independently represent a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
Examples thereof include a silyl ester-containing copolymer containing a constitutional unit derived from the monomer represented by and a constitutional unit derived from another unsaturated monomer copolymerizable with the monomer.

Antifouling coating compositions using these hydrolyzable resins are preferable because they are stable in long-term antifouling properties and long-term coating film properties.
As the other unsaturated monomer copolymerizable with the monomer represented by the general formula (II) or the general formula (III), (meth) acrylic acid esters, monocarboxylic acids, dicarboxylic acids or these Half ester (monoester), diester, 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, (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, ( (Meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid hydroxybutyl ester and other (meth) acrylic acid esters; (meth) acrylic acid and other monocarboxylic acids; itaconic acid, maleic acid, succinic acid and other dicarboxylic acids or These half esters (monoesters) and diesters; styrenes such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; and the like, and these may be used alone or in combination of two or more. May be.

  The amount of the resin for forming a coating film in the antifouling coating composition is preferably 5 to 50% by mass, from the viewpoint of coating film physical properties, when the nonvolatile content of the antifouling coating composition is 100% by mass. More preferably, it is 5 to 30 mass%.

  The antifouling coating composition is, if necessary, a rosin and / or a monocarboxylic acid compound, copper or a copper compound, an organic antifouling agent, a pigment, a dehydrating agent, a plasticizer, a pigment dispersant, an anti-sagging agent or an anti-settling agent. , 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, and hydrogenated rosins, rosin derivatives such as disproportionated rosins, and their esters and metal salts. Be done. Rosin is a residue that remains after the distillation of pine resin, which is the sap of a pine plant, and is a natural resin that contains rosin acid (avietic acid, parastolic acid, isopimaric acid, etc.) as its main component.

  Examples of the monocarboxylic acid compound include aliphatic or alicyclic monocarboxylic acids, their monocarboxylic acid derivatives, and their metal salts. 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 total content mass of the coating film containing the mass of the resin for forming (W _A) and rosins and monocarboxylic acid compound (W _B) and containing a weight ratio of (W _A / W _B) is preferably 99.9 / 0 1 to 30/70, more preferably 95/5 to 35/65, and further preferably 90/10 to 40/60. When the content ratio by mass is within such a range, the antifouling coating film has an effect of enhancing the scouring property (coating film wearability), and the antifouling property (particularly static antifouling property) can be improved.

In order to improve stationary antifouling property and long-term antifouling property, the composition containing a large amount of rosin and / or monocarboxylic acid compound is particularly desirable for ships with many long-term berths and ships operating on routes with severe fouling conditions. For example, (W _A / W _B is more than 70/30) is preferably used, but when an antifouling paint having such a composition is applied to an anticorrosion coating film, the conventional anticorrosion paint shows a marked decrease in adhesion. There is a tendency. However, since the anticorrosion coating composition of the present invention can form an anticorrosion coating film having good adhesion to an antifouling paint, even if an antifouling paint having a large rosin content as in the above range is used, high adhesion can be obtained. Can be demonstrated.

Copper or copper compound The copper compound may be any organic or inorganic copper compound, for example, powdery copper (copper powder), cuprous oxide, copper thiocyanate, cupronickel, copper pyrithione, etc. Is mentioned.

  The amount of copper or a copper compound (total amount of copper and copper compound) in the antifouling coating composition is 100% by mass of the nonvolatile content of the antifouling coating composition from the viewpoint of long-term antifouling property. , Preferably 0.1 to 90% by mass, more preferably 0.5 to 80% by mass.

Organic antifouling agents Examples of organic antifouling agents include metal pyrithiones such as zinc 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, pyridinetriphenylborane, 4-isopropylpyridinediphenylmethylborane, 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 medetomidine), bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, Chloromethyl-n-octyl disulfide, N ', N'-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2,3-dichloro Examples include -N- (2 ', 6'-diethylphenyl) maleimide and 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) maleimide.

  The amount of the organic antifouling agent in the antifouling coating composition is 100% by mass of the nonvolatile content of the antifouling coating composition from the viewpoint of long-term antifouling property and maintenance of coating film water resistance (maintenance of mechanical properties). %, The content is preferably 0.1 to 90% by mass, 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, hiding the undercoat, and for adjusting the coating film to an appropriate strength.
Examples of the pigment include talc, mica, clay, potassium feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, zinc sulfide and the like. Examples include pigments, rouge, titanium white (titanium oxide), yellow rouge, carbon black, naphthol red, phthalocyanine blue, and the like, with talc and zinc oxide being preferred. These pigments may be used alone or in combination of two or more. Calcium carbonate and white carbon are also used as anti-settling agents described later, respectively.

  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, but in the nonvolatile 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 or 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 nonvolatile content of the antifouling coating composition is 100% by mass, from the viewpoint of the effect of preventing a viscosity increase during storage. It is mass%, more preferably 0.1 to 20 mass%.

Examples of the plasticizer include chlorinated paraffin (chlorinated paraffin), TCP (tricresyl phosphate), polyvinyl ethyl ether, dialkyl phthalate, and the like. Coating film water resistance (mechanical properties), coating film hydrolyzability ( Among these, chlorinated paraffin (chlorinated paraffin) and polyvinyl ethyl ether are preferable from the viewpoint of (consumability).

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

  The amount of the plasticizer in the antifouling coating composition is antifouling property, coating film water resistance (mechanical properties), and if the film forming resin is a hydrolyzable resin, coating film hydrolyzability (consumable) From this viewpoint, when the nonvolatile content of the antifouling coating composition is 100% by mass, it is preferably 0.1 to 80% by mass, more preferably 0.5 to 70% by mass.

Pigment Dispersant Examples of the pigment dispersant include various known organic or inorganic pigment dispersants. Examples thereof include aliphatic amines and organic acids (for example, “Rheomix TDO” (Lion Specialty Chemicals Co., Ltd.). Manufactured by Big Chemie Japan Co., Ltd.).

  The amount of the pigment dispersant in the antifouling coating composition is preferably 0.1% from the viewpoint of the effect of reducing the viscosity of the coating and the effect of preventing color separation, when the amount of the nonvolatile content of the antifouling coating composition is 100% by mass. The content 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 agent or an anti-settling agent (thixotropic agent) for the purpose of adjusting the viscosity of the coating composition.

  As an anti-sagging agent or an anti-settling agent, an organic clay wax (a stearate salt of Al, Ca or Zn, a lecithin salt, an alkyl sulfonate, etc.), an organic wax (polyethylene wax, polyethylene oxide wax, amide wax, polyamide) Wax, hydrogenated castor oil wax, etc.), a mixture of an organic clay wax and an organic wax, and synthetic fine powder silica.

As the anti-sagging agent or the anti-settling agent, a commercially available product may be used, and for example, "Disparlon 305", "Disparlon 4200-20", "Disparlon A630-20X", "Disparlon 6900-20X" manufactured by Kusumoto Kasei Co., Ltd. , "A-S-A D-120", "A-S-A T-250F" manufactured by Ito Oil Co., Ltd., and the like.
The anti-sagging agent or the anti-settling agent may be used alone or in combination of two or more.

  When the antifouling coating composition of the present invention contains an anti-sagging agent or an 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 / different type coating composition. When the amount is 100% by mass, it is preferably 0.1 to 50% by mass, more preferably 0.3 to 30% by mass.

The solvent antifouling coating composition may optionally contain a solvent such as water or an organic solvent in order to improve dispersibility and adjust the viscosity of the composition. From the viewpoint of enhancing the adhesion to the antifouling coating film of the anticorrosion coating film according to the present invention, the solvent is an organic solvent, specifically an organic compound capable of softening the anticorrosion coating film according to the present invention near its surface. 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; aliphatic compounds such as ethanol, isopropyl alcohol, n-butanol and isobutanol (having 1 to 1 carbon atoms). 10, preferably about 2 to 5) monohydric alcohols; ester 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.

(Method for producing laminated antifouling coating film, etc.)
The method for producing a laminated antifouling coating film according to the present invention comprises a step of curing the film made of the epoxy resin anticorrosion coating composition according to the present invention to form the anticorrosion coating film, and the surface of the anticorrosion coating film as described above. It includes a step of forming an antifouling coating film. The method for producing an antifouling substrate according to the present invention includes the step of forming the laminated antifouling coating film according to the present invention on the surface of the substrate.

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

  The base material is preferably a base material required to have anticorrosion and antifouling properties in water, for example, thermal power, underwater structures such as water supply and drainage ports of nuclear power plants, coastal roads, seabed tunnels, port facilities, canals, waterways. Such as various sludge diffusion prevention membranes for various marine civil engineering works such as ships, vessels (eg ship bottom), fishing gear (eg floats, buoys), and other base materials that come into contact with seawater or fresh water. Examples of the material include steel, aluminum and FRP. The laminated antifouling coating film of the present invention formed on the surface of these base materials has a property (antifouling property, which prevents adhesion of aquatic organisms such as Ulva, Barnacle, Aonori, Serpra, oyster, and Bedbug for long periods of time. Especially excellent in static stain resistance.

As the base material, in order to remove rust, oil and fat, water, dust, slime, salt and the like, and in order to improve the adhesion of the resulting anticorrosion coating, the base material surface is treated as necessary (for example, Blast treatment (ISO8501-1 Sa2 1/2), power tool treatment, friction method, treatment for removing oil and dust by degreasing) may be performed, and in view of corrosion resistance, weldability, or shearing property of the base material, If necessary, a thin film-forming coating material such as a conventionally known primary anticorrosive coating material (shop primer), or other primer material may be applied and dried on the surface of the base material. Moreover, you may use the base material with a deterioration antifouling coating film as a base material for the purpose of repair painting.
The film thickness (dry film thickness) of the antifouling coating film is not particularly limited, but when the substrate 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 coating composition>
[Example 1]
The anticorrosion coating composition was prepared as follows.

(Main ingredient)
5 parts by mass of MIBK (methyl isobutyl ketone), 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 gum rosin in a poly container. Part, TTK talc 15 parts by mass, Varico # 300W 15 parts by mass, Unisper PG-K10 10 parts by mass, titanium white R-930 0.5 parts by mass, valve stem 404 1 part by mass, AS- 4 parts by mass of AT-55-20BX and 0.5 parts by mass of KBM-403 were blended, glass beads were added, and a dispersion operation was performed for 1 hour by a conventional method. Table 1 shows a list of raw materials. The obtained dispersion liquid was filtered through a 60-mesh filter net to prepare the main component of the anticorrosion paint.

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

(Anticorrosion coating composition)
The obtained main agent component and curing agent component were mixed by a conventional method immediately before coating 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 coating composition>
[Production of Copolymer Solution Containing Metal Salt (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 were charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction tube, and a heating / cooling jacket, and stirred while stirring 75 The temperature was raised to ° C. Subsequently, a mixture of 43.1 parts by weight of methacrylic acid, 36.1 parts by weight of acrylic acid, and 5.0 parts by weight of water was added dropwise at a constant rate over 3 hours from a dropping device. 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 liquid containing the metal salt-containing monomer (a1).

<Production Example 1: Production of metal salt-containing copolymer solution (A1)>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introducing tube, and a heating / cooling jacket, 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. Was charged, and the temperature was raised to 100 ± 5 ° C. with stirring. While maintaining the same temperature, from the dropping device, 52.0 parts by mass of a reaction solution containing the metal salt-containing monomer (a1) obtained in Preparation Example 1 in the reaction vessel, 1.0 part by mass of methyl methacrylate, 66.2 parts by mass of ethyl acrylate, 5.4 parts by mass of 2-methoxyethyl acrylate, and 2.5 parts by mass of a polymerization initiator (2,2′-azobisisobutyronitrile), a polymerization initiator (2,2 ′). -Azobis (2-methylbutyronitrile)) 7.0 parts by mass, chain transfer agent ("NOFMER MSD" (manufactured by NOF CORPORATION)) 1.0 parts by mass, and xylene 10.0 parts by mass for 6 hours. It dripped over. After the dropping was completed, 0.5 parts by mass of a polymerization initiator (t-butylperoxyoctoate (TBPO)) and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 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 addition, in the table, the theoretical blending amount (parts by mass) of each monomer is described.

(Production of silyl ester-containing copolymer solution (A2))
[Production Example 2]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introducing tube and a dropping funnel was charged with 67 parts by mass of xylene, and, under a nitrogen atmosphere, while stirring xylene with the stirrer, under normal pressure, the content of the reaction vessel in the reaction vessel was adjusted. It heated until the temperature of xylene became 85 degreeC. While maintaining the temperature of xylene in the reaction vessel at 85 ° C., 50 parts by mass of TIPSMA (triisopropylsilyl methacrylate), 30 parts by mass of MEMA (2-methoxyethyl methacrylate), and 10 parts by mass of MMA (methyl methacrylate), 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-butylperoxyoctoate was further added to the reaction container, and stirring was continued with a stirrer for 2 hours while maintaining the liquid temperature in the reaction container at 85 ° C. under normal pressure. Then, after raising the liquid temperature in the reaction vessel from 85 ° C. to 110 ° C. and heating it for 1 hour, 14 parts by mass of xylene was added to the reaction vessel to lower the liquid temperature in the reaction vessel to 40 ° C. The stirring was stopped when it became. Thus, the silyl ester-containing copolymer solution (A2) was prepared. Table 4 shows raw materials, characteristics and the like 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 respective properties 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 copolymer solution 1.5 g (X ₁ (g)) of the copolymer solution was kept 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 (X ₂ (g)) of the remaining heating residue (nonvolatile content) was measured, and the content (%) of the heating residue contained in the copolymer solution was calculated based on the following formula.
Content of heating residue (%) = X ₂ / X ₁ × 100

(2) Average Molecular Weight of Copolymer The average molecular weight (number average molecular weight (Mn) or weight average molecular weight (Mw)) of the copolymer was measured using GPC (gel permeation chromatography) under the following conditions. The measurement conditions are as follows.
GPC conditions Device: "HLC-8120GPC" (manufactured by Tosoh Corporation)
Column: "TSKgel Super H2000" and "TSKgel Super H4000" are connected (both manufactured by Tosoh Corporation, 6 mm (inner diameter) x 15 cm (length))
Eluent: Tetrahydrofuran (THF)
Flow rate: 0.500 ml / min
Detector: RI
Column constant temperature bath temperature: 40 ℃
Standard substance: Polystyrene sample preparation method: A small amount of calcium chloride was added to the copolymer solution for dehydration, and the residue was filtered with a membrane filter to give a filter 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.).

(Production of Hydrolyzable Antifouling Paint S1 Containing Metal Salt and Hydrolyzable Antifouling Paint S2 and S3 Containing Silyl Ester)
[Production Example 3]
3. In a poly container, xylene 9.5 parts by mass, metal salt-containing copolymer solution (A1) solution 20 parts by mass, gum rosin 6.5 parts by mass, ethyl silicate 28 0.5 parts by mass, zinc oxide 4. 0 parts by mass, TTK talc 4.0 parts by mass, titanium white R-930 2.0 parts by mass, valve stem 404 2.0 parts by mass, kappa omazine 2.0 parts by mass, cuprous oxide NC- 48 parts by mass of 301 and 0.5 parts by mass of A-S-A-D-120 were mixed, glass beads were added, and a dispersion operation was performed for 1 hour by a conventional method. Then, 1.0 part by mass of Disparlon A630-20X was added, and the dispersion operation was further performed for 15 minutes. The obtained dispersion liquid was filtered through a 60-mesh filter mesh to prepare a metal salt-containing hydrolyzable antifouling paint S1. Table 1 shows a list of raw materials.

[Production 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 Main Component and Mixture (Coating Composition) Each of the main component and the curing agent component is maintained at 23 ° C., the viscosity of the main component, and the mixture obtained by mixing the main component and the curing component. Viscosity was measured using a viscometer VT-04F (manufactured by Rion Co., Ltd.) No. 1 rotor (unit: dPa · s).

(2) Spray atomization property The main ingredient component and the curing agent component are kept at 23 ° C., the main ingredient component and the curing agent component are mixed, and the resulting mixture is sprayed with an air spray to 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 by 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).
B: When the mixed paint was applied to the base material by air spray, the mixed paint was not sprayed as fine particles (in the form of mist), and the spray pattern spreads, but the pattern looks like streaks ( Poor atomization).
C: When the base material was coated with the mixed coating material by using an air spray, the mixed coating material was not sprayed as fine particles (in a mist state), the spray pattern was not spread at all, and coating was impossible (no atomization). ).

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

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

Specifically, the test needle moves from the movement start position a to the position b where the glass plate 2 is no longer visible at the trace of the test needle in the schematic drawing 1 looking down on the glass plate 2 on which the coating film 1 is formed. The time required to do so is defined as a semi-curing time, and the test needle moves from the movement start position a to a position c at which the test needle slides on the surface of the coating film and the trace of the test needle is not completely attached to the surface of the coating film. The time required for was set as the complete curing time.
The drying property was judged to be practically acceptable if the complete curing time at 5 ° C. was less than 24 hours.

(4) Anticorrosion 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 performed as follows. Each of the anticorrosion coating compositions obtained in Examples and Comparative Examples was dried on a blast-treated steel plate (hereinafter also referred to as “test plate”) having dimensions of 150 mm × 70 mm × 1.6 mm (thickness) to form a dry film. A test plate with an anticorrosion coating was prepared by spray-coating to 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. This test plate with anticorrosion coating was immersed in 3% salt water at 40 ° C., and the appearance of the anticorrosion coating after 30 days and 60 days from the start of immersion was visually evaluated according to the following criteria.
(Evaluation criteria)
A: No blisters, cracks, rust, peeling, and hue change.
B: Blisters, cracks, rust, peeling, and some defects (changes) in any of the hues.
C: Blisters, cracks, rust, peeling, or change in hue is clearly observed.

<Electrical anticorrosion test>
A zinc anode was connected to a test plate with an anticorrosion coating 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 days after immersion in 3% salt water at 40 ° C. The appearance of the anticorrosion coating film after day was visually evaluated according to the same criteria as above for the salt water resistance test.

<Salt spray test>
Based on JIS K5600-7-1, a test plate with an anticorrosion coating film prepared in the same manner as the salt water resistance test was continuously sprayed with a solution having a salt water concentration of 5% under the condition of 35 ° C., 30 The appearance of the anticorrosion coating film after day and after 60 days was visually evaluated according to the same criteria as described above in the salt water resistance test.
The results of the above tests are listed in Table 6.

(5) Adhesion between anticorrosion coating film and antifouling coating film Each of the anticorrosion coating compositions of Examples and Comparative Examples was dried on a sandblast plate (150 mm × 70 mm × 1.6 mm) so that the dry film thickness was 150 μm. After coating, a cured coating film was formed, and immediately thereafter, the sandblast plate with the cured coating film was exposed to the south with the cured coating film side facing upward at an angle of 45 ° with respect to the ground.

Then, each of the antifouling paint compositions of the above Production Examples 3 to 5 was placed on a test plate exposed to the outdoors under the above-mentioned conditions for 1 day, 4 days, or 7 days (on the surface of a cured coating film formed from an anticorrosion paint). Was coated 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, to prepare a laminated antifouling coating film test plate.
The resulting laminated antifouling coating film-coated test plate was immersed in 40 ° C. artificial seawater, and the adhesion between the anticorrosion coating film and the antifouling coating film 30 days and 60 days after the start of immersion was determined based on the following evaluation criteria. Evaluated.

(Adhesion evaluation method)
Using an NT cutter, put 4 cuts in each length and width at 4 mm intervals on the antifouling coating surface of the laminated antifouling coating test plate to create 9 squares, and the coating was created. Cellotape (registered trademark) was pressure-bonded to the surface and then quickly peeled off to observe squares. Next, in the case where the area of the 9 squares is 100%, the ratio of the area (peeling area) of the coating film peeled between the anticorrosion coating film and the antifouling coating film in the squares after the peeling operation (%) ) Was calculated and the adhesion 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 A 100 mm × 300 mm × 3.2 mm sandblasted steel plate was air-sprayed with each anticorrosion coating composition of Examples and Comparative Examples so as to have a dry film thickness of 150 μm. The antifouling paint S1 is applied with a spray interval of 1 day by air spraying 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 form a laminated antifouling coating film. A test plate with a membrane was prepared.

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

1 ... Coating film 2 ... Glass plate 3 ... Trace of test needle passing a ... Test needle start position b ... Position where glass plate is no longer visible c ... Test needle slides on coating film surface, test needle on coating film surface The position where the trace of

Claims (17)

Contains an epoxy resin (A), a thermoplastic resin (B) (however, excluding rosins (C)), rosins (C), and a curing agent (D),
The content of the thermoplastic resin (B) is 35 parts by mass or more based on 100 parts by mass of the epoxy resin (A),
An epoxy resin anticorrosion coating composition in which the content of the rosin (C) is 5 to 30 parts by mass with respect to 100 parts by mass of the total 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 anticorrosion coating composition according to claim 1, which is   The epoxy resin anticorrosive coating composition according to claim 1 or 2, further comprising a pigment (E). The epoxy resin 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 coating composition / (volume of resins in anticorrosion coating composition + volume of pigment in anticorrosion coating composition) x 100 ... Formula (2)   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 anticorrosion coating composition according to any one of claims 1 to 4.   The epoxy resin anticorrosive coating composition according to claim 5, wherein the thermoplastic resin (B) contains a vinyl chloride resin, and the vinyl chloride resin is a vinyl chloride / vinyl isobutyl ether copolymer. ..   An anticorrosive coating film comprising a cured product of the epoxy resin anticorrosive coating composition according to any one of claims 1 to 6.   A substrate with an anticorrosion coating, comprising the substrate and the anticorrosion coating according to claim 7 provided on the surface of the substrate.   A step of applying the epoxy resin-based anticorrosion coating composition according to any one of claims 1 to 6 to a substrate, and a step of curing the applied anticorrosion coating composition to form an anticorrosion coating film. A method for producing a base material having an anticorrosion coating film.   A laminated antifouling coating film, which is provided by stacking the anticorrosion coating film and the antifouling coating film according to claim 7 in this order on the surface of the substrate.   The laminated antifouling coating film according to claim 10, wherein the antifouling coating film is a hydrolysis-type antifouling coating film.   The laminated antifouling coating film according to claim 11, wherein the hydrolysis-type antifouling coating film contains a rosin.   A method for producing a laminated antifouling coating film, which is provided by laminating an anticorrosion coating film and an antifouling coating film in this order on the surface of a substrate from the side of the substrate, and the method according to claim 1. Of a laminated antifouling coating film, comprising the steps of curing a film made of the epoxy resin-based anticorrosion coating composition to form the anticorrosion coating film, and 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 10 to 12 is laminated on the surface of a 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 14, which comes into contact with seawater or fresh water.   The antifouling substrate according to claim 14 or 15, wherein the substrate is at least one selected from the group consisting of ships, underwater structures, and fishing gear.   A method for producing an antifouling substrate, comprising the step of forming the laminated antifouling coating film according to any one of claims 10 to 12 on the surface of the substrate.

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