JP2017132960A - Epoxy resin-based anticorrosive coating composition, epoxy resin-based anticorrosive coated film, laminate antifouling coated film, antifouling substrate, and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate antifouling coated film by laminating an epoxy resin-based anticorrosive coated film and an antifouling coated film, suppressing reduction of antifouling performance even when the antifouling coated film is formed on an anticorrosive coated film in a step where an epoxy resin is not cured sufficiently and excellent in damage resistance, an epoxy resin-based anticorrosive coating for forming the laminate antifouling coated film, an epoxy resin-based anticorrosive coated film and a manufacturing method therefor.SOLUTION: There is provided an epoxy resin-based anticorrosive coating composition for forming an anticorrosive coated film in a laminate antifouling coated film arranged by laminating an anticorrosive coated film and an antifouling coated film on a surface of a substrate in this order from the substrate side, containing an epoxy resin (A), a solid thermoplastic resin (B) and an amine-based curing agent, where the solid thermoplastic resin (B) is solid at a normal temperature and the content of the solid thermoplastic resin (B) is 50 pts.mass or more based on 100 pts.mass of a solid component of the epoxy resin (A).SELECTED DRAWING: None

Description

  The present invention has an epoxy resin anticorrosion coating composition, an epoxy resin anticorrosion coating, a laminated antifouling coating comprising the anticorrosive coating and an antifouling coating laminated thereon, and the laminated antifouling coating The present invention relates to an antifouling substrate and methods for producing them.

  Repair painting is regularly performed on the bottom of the ship that is submerged in the seawater of the ship. The coating specification is generally to apply anti-corrosion paint after ground treatment such as removing rust and paint film defects, and then apply anti-fouling paint to prevent corrosion and adhesion of marine organisms. It is. In the repair coating, it is required that the anticorrosion coating film and the antifouling coating film adhere well, and that the multilayer coating film of the anticorrosion coating film and the antifouling coating film formed thereon has a good antifouling property. The

As the anticorrosion paint, an epoxy resin anticorrosion paint is generally used.
There are many documents related to epoxy resin-based anticorrosion paints. For example, Patent Documents 1 to 3 describe an epoxy resin-based anticorrosion paint composition containing a vinyl chloride copolymer and the like, and an anticorrosion coating formed from this paint composition. It is also described that the membrane is painted with a hydrolyzable antifouling paint.
Furthermore, Patent Documents 2 and 3 describe that an anticorrosive coating was applied with an antifouling paint, and the dynamic antifouling property and the degree of wear were evaluated.

International Publication No. 2006/016625 Japanese Patent Laid-Open No. 10-259351 JP-A-11-333374

  In the ship repair painting process, the interval between the anticorrosion paint and the antifouling paint is often shortened due to adjustment of the ship operation schedule and weather conditions during the painting work. That short paint interval can cause problems.

  From the epoxy resin-based anticorrosive coating, an anticorrosive coating film is formed by a mechanism in which the epoxy resin reacts with a curing agent such as amine to cure and dry. When the coating interval between the epoxy resin anticorrosion paint and the antifouling paint is short, the anticorrosion coating does not sufficiently react with the curing agent such as amine and amine, and the unreacted epoxy resin remains. It is in a state to do. When antifouling paint is applied on such anticorrosive paint, unreacted epoxy resin bleeds (transfers) to antifouling paint, and the effect of the antifouling paint is reduced. It was confirmed. In particular, when the coating is performed at a low temperature, it was confirmed that the reaction between the epoxy resin and the curing agent becomes slow, and the residual amount of the unreacted epoxy resin component in the coating film increases, which further increases the effect. .

  Furthermore, the coating film formed by laminating an anticorrosion coating film and an antifouling coating film described in Patent Documents 2 and 3 is excellent in dynamic antifouling properties, but is a more rigorous evaluation. In the evaluation of soiling, it was confirmed that there was room for improvement.

  In addition, the nature of the paint film of ships to be repair-painted that hardly undergoes plastic deformation or destruction due to external pressure (hereinafter referred to as “damage resistance”) is also regarded as important. In ship repair painting, in most cases, the ship sails immediately after the completion of the painting work due to the cargo schedule, etc., and berths at the quay, but the ship touches the quay and the repaired paint film deforms. If it gets scratched, the painting work will be spoiled. Therefore, a coating film that exhibits damage resistance immediately after coating is very preferable.

  However, when painting is performed at a low temperature such as in winter, the reactivity between the epoxy resin and the curing agent decreases, so the coating strength of the anticorrosion coating decreases, and as a result, the damage resistance of the laminated coating also decreases. End up.

  As a solution to these problems, a formulation such as simply reducing the epoxy resin composition to an epoxy resin-based anticorrosive paint can be considered. The coating film obtained has poor appearance, water resistance and anticorrosion properties due to poor properties, poor leveling, and inability to form a continuous coating film due to lack of resin content.

  In view of such problems in the prior art, the present invention is a laminated antifouling coating film obtained by laminating an epoxy resin anticorrosive coating film and an antifouling coating film, and the epoxy resin is not sufficiently cured. Even if the anti-stain coating is formed on the anti-corrosion coating, the deterioration of the anti-proof performance (especially stationary anti-stain property) is suppressed, and the anti-stain coating film has excellent damage resistance. Epoxy resin anticorrosion coating for forming epoxy resin anticorrosion coating, epoxy resin anticorrosion coating used as anticorrosion coating for laminated antifouling coating, laminated antifouling coating and production method thereof, and It aims at providing the antifouling coating film which has a lamination antifouling coating film, and its manufacturing method.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and in an epoxy resin anticorrosive coating, a relatively large amount of a thermoplastic resin solid at room temperature is used together with an epoxy resin, so that antifouling performance (particularly static It was found that a laminated antifouling coating film of an anticorrosion coating film and an antifouling coating film, which was suppressed in deterioration of the (stain resistance) and was excellent in damage resistance, and completed the present invention.

The mechanism of the effects of the present invention is considered as follows.
In the anticorrosive coating film formed from the epoxy resin-based anticorrosive coating, the epoxy resin exists in a liquid or semi-solid state when it is in an unreacted state that has not reacted with a curing agent such as an amine. When the top coating is applied to the anticorrosion coating in such a state, the solvent of the top coating penetrates into the anticorrosion coating, the anticorrosion coating softens, and the unreacted epoxy resin bleeds (transfers) to the top coating. . On the other hand, a resin that is solid at room temperature in the anticorrosion coating film is difficult to transfer to the topcoating film even if the solvent of the topcoating material penetrates into the anticorrosion coating film. For these reasons, when a solid thermoplastic resin is used in combination with an epoxy resin, the amount of the epoxy resin is relatively reduced, so that the bleed component of the unreacted epoxy resin can be reduced. It is considered that the antifouling performance (particularly static antifouling property) of the antifouling coating film laminated on the coating film is not lowered and the damage resistance of the laminated coating film is improved.

The present invention relates to the following [1] to [23].
[1]
An epoxy resin anticorrosion coating composition for forming the anticorrosion coating in a laminated antifouling coating provided on the surface of the substrate in the order of the anticorrosion coating and the antifouling coating from the substrate side, ,
Containing an epoxy resin (A), a solid thermoplastic resin (B), and an amine-based curing agent (C);
The solid thermoplastic resin (B) is solid at room temperature,
An epoxy resin anticorrosive coating composition, wherein the content of the solid thermoplastic resin (B) is 50 parts by mass or more with respect to 100 parts by mass of the solid content of the epoxy resin (A).

[2]
The epoxy resin anticorrosive coating composition according to the above [1], wherein the epoxy resin (A) is one or more selected from the group consisting of bisphenol A, bisphenol AD and bisphenol F.

[3]
Furthermore, it is an epoxy resin anticorrosion coating composition optionally containing a silane coupling agent, and when it does not contain a silane coupling agent, the reaction ratio represented by the following formula (1) is such that the amine curing agent ( When a silane coupling agent having reactivity with respect to C) is contained, the reaction ratio represented by the following formula (2) is a silane coupling agent having reactivity with respect to the epoxy resin (A). When contained, the epoxy resin anticorrosive coating composition according to the above [1] or [2], wherein the reaction ratio represented by the following formula (3) is 0.3 to 0.8, respectively.

[4]
The epoxy resin anticorrosive coating composition according to any one of [1] to [3], further containing a pigment (E).

[5]
The epoxy resin anticorrosive coating composition according to the above [4], wherein the pigment volume concentration (PVC) represented by the following formula (4) 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) Formula (4)

[6]
The solid thermoplastic resin (B) includes at least one selected from the group consisting of petroleum resins, chlorinated polyolefins, acrylic resins, butyl acetate resins, styrene resins, and vinyl chloride resins. The epoxy resin anticorrosive coating composition according to any one of the above [1] to [5].

[7]
The epoxy resin anticorrosive coating composition as described in [6] above, wherein the vinyl chloride resin is a vinyl chloride / vinyl isobutyl ether copolymer.

[8]
The epoxy resin anticorrosive coating composition according to any one of [1] to [7], further comprising a tertiary amine as a curing accelerator (D).

[9]
The epoxy resin anticorrosive coating composition according to any one of the above [1] to [8], further comprising an adhesion enhancer (F).

[10]
The epoxy resin anticorrosive coating composition as described in [9] above, wherein the adhesion enhancing agent (F) is a silane coupling agent.

[11]
The epoxy resin anticorrosive coating composition according to [10] above, wherein the silane coupling agent is γ-glycidoxypropyltrimethoxysilane.

[12]
The epoxy resin anticorrosive coating composition according to any one of [1] to [11], wherein the antifouling coating film is a hydrolyzable antifouling coating film.

[13]
An epoxy resin anticorrosion coating used as the anticorrosion coating of the antifouling coating provided on the substrate surface in the order of the anticorrosion coating and the antifouling coating from the substrate side,
An epoxy resin anticorrosion coating film, which is a cured product of the epoxy resin anticorrosion coating composition according to any one of [1] to [12].

[14]
An epoxy resin anticorrosion coating used as the anticorrosion coating of the antifouling coating provided on the substrate surface in the order of the anticorrosion coating and the antifouling coating from the substrate side,
Comprising a matrix comprising a cured epoxy resin and a solid thermoplastic resin (B);
The solid thermoplastic resin (B) is solid at room temperature,
An epoxy resin anticorrosive coating film having a content of the solid thermoplastic resin (B) of 7 to 80% by mass.

[15]
Furthermore, the epoxy resin anticorrosion coating film according to [14], further containing an epoxy resin (A).

[16]
It is a method for producing an epoxy resin anticorrosion coating used as the anticorrosion coating of a laminated antifouling coating provided on the substrate surface in the order of the anticorrosion coating and the antifouling coating from the substrate side. And
The manufacturing method of the epoxy resin type anti-corrosion coating film including the process of hardening the film | membrane which consists of an epoxy resin type anti-corrosion coating composition in any one of said [1]-[12].

[17]
A laminated antifouling coating film provided on the surface of the substrate in the order of the anticorrosion coating film and the antifouling coating film from the substrate side, wherein the anticorrosion coating film is any one of the above [13] to [15] A laminated antifouling coating film, which is the epoxy resin anticorrosion coating film described in 1.

[18]
The laminated antifouling coating film according to the above [17], wherein the antifouling coating film is a hydrolyzable antifouling coating film.

[19]
A method for producing a laminated antifouling coating film, which is provided by laminating in the order of the anticorrosion coating film and the antifouling coating film from the substrate side on the substrate surface,
Laminated antifouling comprising the step of forming the epoxy resin-based anticorrosive coating film according to any one of the above [13] to [15] and the step of forming the antifouling coating film on the surface of the epoxy resin-based anticorrosive coating film A method for producing a coating film.

[20]
The antifouling film obtained by laminating the laminated antifouling coating film according to [17] or [18] on the surface of the base material so that the anticorrosion coating film and the antifouling coating film are arranged in this order from the base material side. Base material.

[21]
The antifouling substrate according to the above [20], which is in contact with seawater or fresh water.

[22]
The antifouling substrate according to the above [20] or [21], wherein the substrate is at least one selected from the group consisting of ships, marine structures, and land structures.

[23]
A method for producing an antifouling substrate, comprising a step of forming the laminated antifouling coating film according to [17] or [18] on the surface of the substrate.

  It is obtained by forming an anticorrosion coating from the epoxy resin-based anticorrosion coating of the present invention in a laminated antifouling coating provided on the surface of the substrate in the order of the anticorrosion coating and the antifouling coating from the substrate side. The anti-corrosion coating has excellent curability and drying when it contains a solvent, and it can suppress bleeding of unreacted epoxy resin components in the anti-corrosion coating to the anti-fouling coating. It is possible to suppress a decrease in (especially stationary antifouling property) and to improve the damage resistance of the laminated antifouling coating film.

Hereinafter, the present invention will be described in more detail.
[Epoxy resin anticorrosion coating composition]
The epoxy resin-based anticorrosive coating composition according to the present invention (hereinafter also simply referred to as “anticorrosive coating composition”) is laminated on the substrate surface in the order of the anticorrosion coating and the antifouling coating from the substrate side. An epoxy resin-based anticorrosion coating composition for forming the anticorrosion coating film in a laminated antifouling coating film, comprising an epoxy resin (A), a solid thermoplastic resin (B), and a curing agent (C) ing.
Hereinafter, each component contained in the composition will be described, and the laminated antifouling coating film will be described later.

Epoxy resin (A)
As said epoxy resin (A), the polymer or oligomer which contains two or more epoxy groups in 1 molecule, and the polymer or oligomer produced | generated by the ring-opening reaction of the one part of the epoxy group are mentioned.

  Specific examples of the epoxy resin (A) include bisphenol type epoxy resins, for example, bisphenol A type epoxy resins such as epichlorohydrin-bisphenol A epoxy resin; bisphenol AD type epoxy resins such as epichlorohydrin-bisphenol AD epoxy resin; epichlorohydrin. And bisphenol F type epoxy resin such as epoxy novolac resin having a structure in which bisphenol F (4,4′-methylenebisphenol) is reacted; aromatic such as 3,4-epoxyphenoxy-3 ′, 4′-epoxyphenylcarboxymethane Epoxy resin; Brominated epoxy resin having a structure in which at least a part of the hydrogen atoms bonded to the benzene ring in the epichlorohydrin-bisphenol A epoxy resin are substituted with bromine; epichlorohydrin and fat Dihydric alcohol and aliphatic epoxy resins of the reaction structure; and epichlorohydrin and tri (hydroxyphenyl) polyfunctional epoxy resins of the methane and the reaction structure and the like.

  Among these, a preferable epoxy resin (A) is at least one epoxy resin selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol AD type epoxy resin, and a bisphenol F type epoxy resin epoxy resin.

The said epoxy resin (A) can be used individually by 1 type or in combination of 2 or more types.
The weight average molecular weight measured by GPC (gel permeation chromatography) of the epoxy resin (A) (measurement conditions are the conditions when the weight average molecular weight of the copolymer (a3) is determined in the column of Examples described later, or Is equivalently determined) depending on the coating curing conditions of the epoxy resin anticorrosive coating composition (eg, normally dry coating or baking coating), etc., but is not generally determined, but preferably 350 to 20,000. It is. Moreover, the viscosity (25 degreeC) of the said epoxy resin (A) becomes like this. Preferably it is 12,000 cPs or less, More preferably, it is 10,000 cPs or less.

The epoxy equivalent (based on 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.

  In addition, the weight average molecular weight and epoxy equivalent of the said epoxy resin (A) in the case of using in combination of 2 or more types of epoxy resins are the weight average molecular weight and epoxy equivalent as a whole of 2 or more types of epoxy resins.

As a typical bisphenol A type epoxy resin, in a liquid form at room temperature, “jER828” (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180 to 190 g / eq, viscosity 12,000 to 15,000 cPs / 25 ° C.), “E-028-90X” (made by Akira Ohtake Shin Chemical Co., Ltd., 828 type epoxy resin (xylene cut product NV 90%), epoxy equivalent of about 210 g / eq), “AER260” (bisphenol A type epoxy resin, Asahi Kasei Epoxy ( Co., Ltd.), epoxy equivalent 190 g / eq, NV 100%), etc.
For semi-solid materials at room temperature, “jER834-X90” (Mitsubishi Chemical Corporation, epoxy equivalent 230-270 g / eq / xylene cut product NV 90%), “E-834-85X” (Otake Akira Shin Chemical Co., Ltd.) ), Epoxy equivalent of about 290 to 310 g / eq / xylene cut product NV85%), etc.
For solids at room temperature, "jER1001-X75" (Mitsubishi Chemical Corporation, epoxy equivalent 600-650 g / eq / xylene cut product NV75%), "E-001-75X" (Otake Akira Shin Chemical Co., Ltd.) And epoxy equivalent of about 610 to 650 g / eq / xylene cut product NV75%).
The epoxy resin (A) is preferably contained in the anticorrosion coating composition in an amount of 5 to 80% by mass, more preferably 10 to 50% by mass.

Solid thermoplastic resin (B)
The said solid thermoplastic resin (B) is solid resin at normal temperature (23 degreeC). Solid at room temperature means that the shape is maintained even after standing for 1 day at room temperature and normal pressure (23 ° C., 1 atm).

  When the solid thermoplastic resin (B) is contained in the anticorrosion paint composition, the unreacted epoxy resin (A) in the anticorrosion paint film moves to an antifouling paint film laminated on the anticorrosion paint film. It is possible to suppress or prevent the antifouling performance (especially stationary antifouling property) from being lowered.

  The weight average molecular weight of the solid thermoplastic resin (B) measured by GPC (details of measurement conditions are described in the Examples section described later) is preferably 5,000 to 100,000, more preferably 20,000-80,000.

As said solid thermoplastic resin (B), what has a glass transition temperature of 30 degreeC or more is more preferable.
Examples of the solid thermoplastic resin (B) include chlorinated polyolefin, acrylic resin, butyl acetate resin, styrene resin, and vinyl chloride resin.

  Among these solid thermoplastic resins, acrylic resins such as Dianaal BR106 (Mw = 60,000 manufactured by Mitsubishi Rayon Co., Ltd.) and Paraloid B66 (manufactured by Dow Chemical, Mw = 70,000) are commercially available as acrylic resins. Examples thereof include a solid acrylic resin obtained by copolymerizing an acid and an ester thereof or a derivative thereof, and a solid methacrylic resin obtained by copolymerizing a methacrylic acid and an ester thereof or a derivative thereof.

As the solid thermoplastic resin (B), among the above resins, a vinyl chloride-based resin is particularly preferable in that it has little influence on adhesion to an antifouling paint, damage resistance of a coating film, and antifouling property. .
The vinyl chloride resin is more preferably a vinyl chloride / vinyl isobutyl ether copolymer, and more preferably a glass transition temperature of 30 ° C. or higher. Commercially available products of such a vinyl chloride / vinyl isobutyl ether copolymer include “Laroflex LR8829”, “Laloflex MP-25” (Mw = 28,000-30,000), “Laro” manufactured by BASF. Flex MP-35 "," Laroflex MP-45 ", etc. can be mentioned. Further, among the vinyl / vinyl isobutyl ether copolymers, “Laroflex MP-25” is particularly preferable because when the epoxy resin anticorrosive coating composition is prepared, the increase in the viscosity of the coating is small and the coating workability is excellent. .
These solid thermoplastic resins can be used singly or in combination of two or more.

  The amount of the solid thermoplastic resin (B) in the anticorrosion coating composition is shifted to an antifouling coating film in which the unreacted epoxy resin (A) in the anticorrosion coating film is laminated on the anticorrosion coating film. From the viewpoint of suppressing or preventing the antifouling performance (especially stationary antifouling property) from being reduced, it is 50 parts by mass or more, preferably 60 parts by mass or more with respect to 100 parts by mass of the epoxy resin (A). The upper limit is preferably 100 parts by mass, more preferably 80 parts by mass, from the viewpoint of exhibiting excellent anticorrosive properties, top coatability, and drying properties for the anticorrosive coating film.

Amine-based curing agent (C)
The amine curing agent (C) is not particularly limited as long as it contains active hydrogen and reacts with the epoxy resin (A). An aliphatic amine, an alicyclic amine, an aromatic amine, and Heterocyclic amines are preferred.

Specifically, the aliphatic amine includes ethylenediamine, diethylenetriamine, triethylenetetramine, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2′-aminoethylamino) propane, triethylene-bis. Examples 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, 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 mensen Examples include diamines.

  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- Diaminobiphenyl, 2,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene, and 2, 4,6-Tris (3-aminomethylphenylmethyl) Aminomethyl) phenol, and the like.

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

Furthermore, polyamides of these amines and modified products thereof, modified epoxy resin adducts, modified Mannich products can also be used as the amine curing agent (C).
The active hydrogen equivalent (amine equivalent) of the amine curing agent (C) is preferably 50 to 1000 g / eq, more preferably 70 to 500 g / eq.

  As said amine type hardening | curing agent (C), if it is a commercial item, racamide TD966 (DIC Corporation make, polyamide, active hydrogen equivalent 377g / eq), PA-66 (Otake Akira Shin Chemical Co., Ltd. make, polyamide) , Active hydrogen equivalent 377 g / eq), PA-290 (A) (manufactured by Akira Ohtake Shin Chemical Co., Ltd., active hydrogen equivalent 277 g / eq), ancamide 2050 (manufactured by Air Products, polyamide adduct, active hydrogen equivalent 150 g / eq) ), NX-4918 (manufactured by Cardlite, phenalkamine (Mannich modified product of cardanol and amine) adduct, active hydrogen equivalent of 255 g / eq), and the like.

  The amount of the amine curing agent (C) in the anticorrosive 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 amine-based curing agent (C) is in the above range from the viewpoints of curability of the anticorrosion coating film and drying properties when a solvent is included, and damage resistance of the laminated anticorrosion coating film.

(Other ingredients)
The epoxy resin-based anticorrosive coating composition is usually composed of a main component containing the epoxy resin (A) and the solid thermoplastic resin (B), and an amine-based curing agent containing the amine-based curing agent (C) ( An anticorrosion paint comprising a curing agent component containing C) is prepared, and the main component component and the curing agent component are mixed immediately before coating.

  The main component includes a curing accelerator (D), a pigment (E), an adhesion strengthening agent (F), a solvent (G), an anti-sagging / anti-settling agent (H), and a dehydrating agent (stabilizer) as necessary. ) (I), or other coating film forming components (dispersant, antifoaming agent, leveling agent, etc.) may be blended within a range that does not impair the object of the present invention. If necessary, a curing accelerator (D), a solvent (G), or the like may be blended within a range that does not impair the object of the present invention.

Curing accelerator (D)
Examples of the curing accelerator (D) 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: repeating number), 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 Henkel Hakusui Co., Ltd.), “Ancamine K-54” (manufactured by Air Products) and the like.

Moreover, as said hardening accelerator (D), an acrylic ester type hardening accelerator is also mentioned.
The amount of the curing accelerator (D) in the anticorrosive coating composition increases the speed of curing of the epoxy resin (A) by the amine-based curing agent (C). Since an anticorrosion coating film excellent in adhesion to a dirty coating film and excellent in anticorrosion coating film can be obtained, preferably 0.1 to 5 when the nonvolatile content of the anticorrosion coating composition is 100% by mass. 0.0% by mass.

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

Pigment (E )
Examples of the pigment (E) include extender pigments, colored pigments, and rust preventive pigments.
Specific examples of extender pigments include barium sulfate, potassium feldspar, barite powder, silica, tankal, talc, mica, glass flakes, and aluminum stearate.

Specific examples of the color pigment include titanium white, red rose, yellow red rose, and carbon black.
Examples of the rust preventive pigment include aluminum paste, zinc chromate, and zinc phosphate. A scale-like aluminum paste is preferable in terms of physical properties of the coating film (such as crack resistance).

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 color pigment is preferably 0.1 to 50% by mass when the amount of nonvolatile components of the anticorrosive coating composition is 100% by mass.
The amount of the anticorrosive pigment is preferably 0.1 to 50% by mass when the amount of nonvolatile components of the anticorrosive coating composition is 100% by mass.

Adhesion enhancer (F)
Examples of the adhesion enhancer (F) include organic acids, chelating agents, silane coupling agents, and the like, and among them, silane coupling agents are preferable from the viewpoint of storage stability of the anticorrosive coating composition.

The silane coupling agent usually has two types of functional groups in one molecule, and can contribute to an improvement in the adhesion of the anticorrosion coating film to the inorganic substrate, a decrease in the viscosity of the anticorrosion coating composition, and the like. The silane coupling agent has, 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, halogen group, and these 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). It is preferably represented by the epoxy resin (A) or the amine curing agent (C).

  Specific examples of such a silane coupling agent include “KBM403” (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and “Silane S-510” (Chisso) as commercial products. Etc.).

  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 0.5 mass%, More preferably, it is 0.5-5 mass%. When the silane coupling agent is used in the anticorrosion coating composition in such an amount, performance such as adhesion of the resulting anticorrosion coating film is improved, and the viscosity of the anticorrosion coating composition is lowered, and the coating workability is improved. .

Solvent (G)
Examples of the solvent (G) 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 are used alone or in combination of two or more.
Content of the said solvent (G) in a main ingredient component is 0.1-80 mass%, for example, and content of the said solvent (G) in a hardening | curing agent component is 0.1-80 mass%, for example. .

Anti-sagging / Anti-settling agent (H)
Specific examples of the anti-sagging and anti-settling agent (thixotropic agent) (H) include thixotropic agents such as polyamide wax, polyethylene wax, bentonite, and OH-containing nanoparticles (erological and resin beads). It is done.

Examples of such an anti-sagging and anti-settling agent include “Disparon 4200-20” and “Dispalon 6650” manufactured by Enomoto Kasei Co., Ltd., “ASAT-250F” manufactured by Ito Seiyaku Co., Ltd., and the like.
The amount of non-volatile content of the anti-sagging and anti-settling agent (H) in the anti-corrosion coating composition is preferably 0.1 to 30% by mass when the amount of non-volatile content of the anti-corrosion coating composition is 100% by mass. .

Dehydrating agent (stabilizer) (I)
The anticorrosive coating composition of the present invention can obtain further excellent long-term storage stability by adding a dehydrating agent (stabilizer) (I) as necessary.

Examples of the dehydrating agent (I) include inorganic dehydrating agents and organic dehydrating agents. The inorganic dehydrating agent is preferably synthetic zeolite, anhydrous gypsum or hemihydrate gypsum, and the organic dehydrating agent is preferably tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltride. Examples include alkoxysilanes such as ethoxysilane, dimethyldiethoxysilane, and trimethylethoxysilane or polyalkoxysilanes that are condensates thereof, and orthoformate alkyl esters such as methyl orthoformate and ethyl orthoformate.
The amount of the dehydrating agent (I) in the anticorrosive 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-described epoxy resin (A), solid thermoplastic resin (B), and amine-based curing agent (C), and these are mixed and stirred according to a usual method. Can be prepared.

(Reaction ratio between epoxy resin (A) and amine curing agent (C))
The epoxy resin (A) reacts with the amine curing agent (C) to form a coating film.
In the anticorrosion coating composition according to the present invention, when the silane coupling agent is not included, the reaction ratio represented by the following formula (1) is a silane having reactivity with the amine-based curing agent (C). When the coupling agent is contained, the reaction ratio represented by the following formula (2) is the following formula (3) when the silane coupling agent having reactivity with the epoxy resin (A) is contained. Is preferably in the range of 0.3 to 0.8, more preferably 0.4 to 0.7.

  The “reactive group equivalent of the silane coupling agent” in the above formulas means an organic property in which 1 mol of the silane coupling agent (ie, molecular weight) is contained in one molecule of the silane coupling agent. It is a value divided by the number of functional groups that can react with the material (hereinafter also referred to as “reactive groups”). As described above, a silane coupling agent having an amino group or an epoxy group as a reactive group can be used as the silane coupling agent. It is determined whether or not to use a silane coupling agent, and when used, depending on the type of reactive group, whether the silane coupling agent has reactivity with the epoxy resin (A), an amine curing agent ( C) is determined whether it has reactivity, and after selecting an appropriate formula from the above formulas (1) to (3), the reactive group equivalent of the silane coupling agent is obtained for each, and the reaction ratio is determined. It is necessary to calculate.

  When the reaction ratio is equal to or higher than the lower limit, the epoxy resin (A) is cross-linked at a number of locations, so that an unreacted epoxy resin component hardly remains, and the resulting anticorrosive coating film has a curability and a solvent. When it contains, the laminated antifouling coating film has little deterioration of antifouling property (especially stationary antifouling property) and is excellent in damage resistance.

  If the reaction ratio is less than or equal to the upper limit, the unreacted amine curing agent (C) hardly remains in the resulting coating film, and the unreacted amine curing agent (C) attracts moisture. Therefore, problems such as a decrease in water resistance of the coating film and discoloration can be prevented.

(PVC)
The pigment volume concentration (hereinafter also referred to as “PVC”) defined by the following formula (4) of the nonvolatile content of the anticorrosive coating composition of the present invention is preferably 25 to 50%, more preferably 30 to 45%. 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) × 100 (4)

In addition, the “volume of resins” described in the denominator of the formula (4) means the epoxy resin (A), the solid thermoplastic resin (B), the amine-based curing agent (C), and the curing accelerator (D). The total volume.
When the PVC is equal to or higher than the lower limit, the resulting coating film is excellent in drying properties and damage resistance.
If the PVC is less than or equal to the above upper limit value, the viscosity of the anticorrosive coating composition is remarkably high, and the coating workability decreases, or the corrosion resistance decreases due to a decrease in coating leveling or pinholes. A malfunction can be prevented.

[Epoxy resin anticorrosion coating]
The epoxy resin-based anticorrosion coating film according to the present invention (hereinafter also simply referred to as “anticorrosion coating film”) is provided on the substrate surface by laminating the anticorrosion coating film and the antifouling coating film in this order from the substrate side. It is an anticorrosion coating film used as the anticorrosion coating film of a laminated antifouling coating film, which is an epoxy resin cured product and the solid thermoplastic resin (B) (excluding the cured product of the epoxy resin (A)). It contains the matrix formed by containing.

The anticorrosion coating film according to the present invention is also a cured product of the above-described anticorrosion coating composition according to the present invention.
The said anticorrosion coating film contains the said solid thermoplastic resin (B) normally in 7-50 mass%, Preferably in the ratio of 7-30 mass%. Since the anticorrosion coating film according to the present invention contains the solid thermoplastic resin (B) at such a ratio, the unreacted epoxy resin (A) is laminated on the anticorrosion coating film as described above. It can suppress that it transfers to an antifouling coating film and the antifouling performance (especially stationary antifouling property) of an antifouling coating film falls.

Moreover, the manufacturing method of the said anticorrosion coating film which concerns on this invention includes the process of hardening the film | membrane which consists of an anticorrosion coating composition which concerns on this invention. The said anticorrosion coating film which concerns on this invention can be manufactured by the method similar to the manufacturing method of the conventional epoxy resin type anticorrosion coating film except the point which uses the anticorrosion coating composition which concerns on this invention as an anticorrosion coating.
The thickness of the anticorrosion coating film (dry film thickness) is usually about 50 to 800 μm.

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

(Anti-fouling paint composition)
Examples of the antifouling coating composition for overcoating the anticorrosive coating to form an antifouling coating include conventionally known antifouling coating compositions, and the unreacted epoxy resin (A Hydrolyzable antifouling paint composition is preferable in that the deterioration of the antifouling performance of the antifouling coating film caused by shifting to the antifouling coating film can be particularly effectively suppressed.

As a resin for forming a coating film of a hydrolyzable antifouling paint, for example,
Formula (I):
COO-MO-COR ¹ (I)
[M in 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 Formula (II) represents zinc or copper, and R ² represents a hydrogen atom or a methyl group. ]
A metal salt-containing copolymer comprising a structural unit derived from a monomer represented by the formula: and a structural unit derived from another unsaturated monomer capable of copolymerizing 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 independently represents 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 (where 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 . And R ⁹ , R ¹⁰ and R ¹¹ each independently represents a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom. ]
And a silyl ester-containing copolymer containing a structural unit derived from a monomer represented by the formula (1) and a structural unit derived from another unsaturated monomer that can be copolymerized with the monomer.
Antifouling paint compositions using these hydrolyzable resins are preferred because they are stable with long-term antifouling properties and long-term coating film 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 And 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, (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 methoxy ester, (meth) acrylic acid ethoxy ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid hydroxyethyl ester, (meth) Acry (Meth) acrylic esters such as hydroxypropyl ester of acid, hydroxybutyl ester of (meth) acrylic acid; monocarboxylic acids such as (meth) acrylic acid; dicarboxylic acids such as itaconic acid, maleic acid and succinic acid, or a half thereof Examples include esters (monoesters) and diesters; styrenes such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; and these may be used alone or in combination of two or more. .

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

  The antifouling coating composition may be prepared from rosins and / or monocarboxylic acid compounds, copper or copper compounds, organic antifouling agents, colored pigments, extender pigments, dehydrating agents, plasticizers, pigment dispersants, and anti-sagging as required. And a component selected from an agent, an anti-settling agent and a solvent.

Examples of rosins and / or monocarboxylic acid compound rosins include rosins such as gum rosin, wood rosin and tall oil rosin, and rosin derivatives such as hydrogenated rosin and disproportionated rosin. Rosin is a residue that remains after distillation of the pine sap, which is the sap of a pine plant, and is a natural resin mainly composed of rosin acid (eg, abietic acid, parastolic acid, isopimaric acid).

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

Containing the mass of the coating film containing the mass of the resin for forming (W _A) and the rosin and / or monocarboxylic acid compound (W _B) and containing a weight ratio of (W _A / W _B) is preferably 99.9 / 0 0.1-30 / 70, more preferably 95 / 5-35 / 65, and still more preferably 90 / 10-40 / 60. When the content mass ratio is in such a range, there is an effect of improving the scouring property (coating wearability) in the antifouling coating film, and the antifouling property (particularly, stationary antifouling property) can be improved.

Copper or copper compound The copper compound may be any organic or inorganic copper compound, such as powdered copper (copper powder), cuprous oxide, copper thiocyanate, cupronickel, copper pyrithione, etc. Is mentioned.

  From the viewpoint of long-term antifouling properties, the amount of copper or copper compound in the antifouling coating composition is 100% by mass from the viewpoint of long-term antifouling properties. , Preferably it is 0.1-90 mass%, More preferably, it is 0.5-80 mass%.

Organic antifouling agents include, for example, metal pyrithiones (excluding copper pyrithione) such as zinc pithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo- 2- (4-Chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3carbonitrile, pyridine triphenylborane, 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, medetomidine, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate Chloromethyl-n-octyl disulfide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkyltyramium disulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2,3- Examples include dichloro-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 masses of the nonvolatile content of the antifouling coating composition from the viewpoint of long-term antifouling properties and maintaining water resistance of the coating film (maintaining mechanical properties). %, Preferably 0.1 to 90% by mass, more preferably 0.5 to 80% by mass.

Examples of the color pigment include various known organic or inorganic color pigments. Examples of organic coloring pigments include carbon black, naphthol red, and phthalocyanine blue. Examples of the inorganic coloring pigment include bengara, barite powder, titanium white, and yellow iron oxide.

The antifouling paint composition may contain a colorant other than the color pigment, such as a dye, together with the color pigment or instead of the color pigment.
The amount of the color pigment in the antifouling coating composition is determined from the viewpoint of coloring property, hiding property, exposure discoloration property, antifouling property, and coating film water resistance (mechanical properties). When the amount is 100 mass%, it is preferably 0.01 to 50 mass%, more preferably 0.1 to 30 mass%.

Examples of the extender pigment extender pigments such as talc, silica, mica, clay, feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate and the like . Among these, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar, and zinc oxide are preferable. Calcium carbonate and white carbon are also used as an anti-settling agent or a matting agent, which will be described later.

  The amount of extender in the antifouling coating composition is non-volatile in the antifouling coating composition from the viewpoints of water resistance (mechanical characteristics), antifouling properties, and hydrolyzability (consumability) of the coating film. When the amount of the minute is 100% by mass, it is preferably 0.1 to 80% by mass, more preferably 0.5 to 70% by mass.

As the dehydrating agent 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 nonvolatile content of the antifouling coating composition is 100% by mass from the viewpoint of preventing the increase in viscosity during storage. It is 0.1 mass%, More preferably, it is 0.1-20 mass%.

Plasticizers Plasticizers include chlorinated paraffin (chlorinated paraffin), petroleum resins, ketone resins, TCP (tricresyl phosphate), polyvinyl ethyl ether, dialkyl phthalate, etc. ), Among these, chlorinated paraffin (chlorinated paraffin), petroleum resins or ketone resins are preferable from the viewpoint of coating film hydrolyzability (consumable).

  Specific examples of the chlorinated paraffin include “Toyoparax 150” and “Toyoparax A-70” (both manufactured by Tosoh Corporation). Examples of petroleum resins include C5, C9, styrene, dichloropentadiene, and hydrogenated products thereof. Specific examples of petroleum resins include “Quinton 1500” and “Quinton 1700” (both manufactured by Nippon Zeon Co., Ltd.).

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

The pigment dispersant pigment dispersant, known organic or inorganic various pigments dispersants include, for example, aliphatic amines or organic acids (e.g., manufactured by "Duomeen TDO" (LION (Ltd.)), "Disperbyk101 (By BYK Co., Ltd.)).

  The amount of the pigment dispersant in the antifouling paint composition is preferably from the viewpoint of the effect of reducing the viscosity of the paint and the effect of preventing color separation when the nonvolatile content of the antifouling paint composition is 100% by mass. It is 01-20 mass%, More preferably, it is 0.1-10 mass%.

The anti-sagging agent sagging agents, amide wax, hydrogenated castor oil wax, and polyamide wax, mixtures thereof, synthetic particulate silica and the like. Among these, from the viewpoint of storage stability and coatability of the same / different kinds of paints, the sagging agent is preferably amide wax or synthetic finely divided silica.

Examples of commercially available sagging agents include “Disparon A630-20X” (manufactured by Enomoto Kasei Co., Ltd.) and “ASAT-250F” (manufactured by Ito Seiyaku Co., Ltd.).
The amount of the anti-sagging agent in the antifouling paint composition is preferably 100% by mass from the viewpoint of storage stability and the coating property of the same / different kinds of paints with the nonvolatile content of the antifouling paint composition being 100% by mass. Is 0.1 to 50% by mass, more preferably 0.5 to 30% by mass.

Anti- settling agents Anti- settling agents include amine salts of Al, Ca or Zn, polyethylene waxes, oxidized polyethylene waxes, etc. Among them, oxidized polyethylene waxes are preferred. As a commercially available product of oxidized polyethylene-based wax, “DISPARON 4200-20X” (manufactured by Enomoto Kasei Co., Ltd.) can be mentioned.

  The amount of the anti-settling agent in the antifouling coating composition is preferably 100% by mass from the viewpoint of storage stability and the coating properties of the same / different types of coatings with the nonvolatile content of the antifouling coating composition being 100% by mass. Is 0.1 to 50% by mass, more preferably 0.5 to 30% by mass.

The solvent antifouling paint composition may contain a solvent such as water or an organic solvent, if necessary, in order to improve dispersibility or adjust the viscosity of the composition.

  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; aliphatics such as ethanol, isopropyl alcohol, n-butanol, and isobutanol (having 1 to 3 carbon atoms). 10 and 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.

(Production method of laminated antifouling coating film)
The method for producing a laminated antifouling coating film according to the present invention comprises the steps of forming an epoxy resin anticorrosion coating film according to the present invention, and forming the antifouling coating film on the surface of the epoxy resin anticorrosion coating film. Contains. Moreover, the manufacturing method of the antifouling substrate according to the present invention includes a 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 a method similar to the conventional method except that the epoxy resin anticorrosion coating film according to the present invention is used as the epoxy resin anticorrosion coating film. be able to. That is, the epoxy resin-based anticorrosive paint according to the present invention is applied to the surface of the base material by a conventionally known method and cured to form an epoxy resin-based anticorrosive coating. The laminated antifouling coating film or antifouling substrate according to the present invention can be produced by applying and curing the antifouling paint composition by a conventionally known method.

  The base material is preferably a base material that is required to have anticorrosion and antifouling properties in water, such as a ship (such as the bottom of a ship), fishery materials, underwater structures such as water supply / drainage ports of thermal power / nuclear power plants, gulf roads, seabeds. Examples include a sludge diffusion prevention film for various civil engineering works such as tunnels, harbor facilities, canals or waterways, and examples of the base material include steel, aluminum, wood, and FRP. The laminated antifouling coating film of the present invention formed on the surface of these base materials has a characteristic (antifouling property, anti-fouling property, anti-fouling property, anti-fouling property, Especially excellent in antifouling property).

  Although the film thickness (dry film thickness) of the antifouling coating film is not particularly limited, it is, for example, about 50 to 2000 μm when the substrate is a ship or an underwater structure.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
<Preparation of hydrolyzable antifouling paint S1 containing metal salt and hydrolyzable antifouling paint S2 containing silyl ester>
(Production of metal salt-containing copolymer (a2) solution)
[Production Example 1]
A four-necked flask equipped with a cooler, thermometer, dropping funnel and stirrer was charged with 85.4 parts by mass of propylene glycol methyl ether (PGM) and 40.7 parts by mass of zinc oxide, and the temperature was raised to 75 ° C. while stirring. did.

  Subsequently, a mixture of 50.0 parts by mass of methacrylic acid (MAA), 36.1 parts by mass of acrylic acid (AA), and 5 parts by mass of water was added to the milky white mixture obtained at a constant speed over 3 hours. It was dripped. After completion of the dropping, the reaction solution became transparent. After further stirring for 2 hours, 36 parts by mass of propylene glycol methyl ether (PGM) was added to obtain a transparent metal salt-containing monomer solution (a1). The solid content of the obtained metal salt-containing monomer (a1) solution was 44.8% by mass.

[Production Example 2]
A four-necked flask equipped with a condenser, thermometer, dropping funnel and stirrer was charged with 15 parts by mass of propylene glycol methyl ether (PGM), 57 parts by mass of xylene and 4 parts by mass of ethyl acrylate, and the temperature was raised to 100 ° C. while stirring. Warm up.

  Subsequently, from the dropping funnel, 1 part by mass of methyl methacrylate (MMA), 70.2 parts by mass of ethyl acrylate (EA), 5.4 parts by mass of 2-methoxyethyl acrylate (2-MEA), and production example are added to the obtained mixture. 52 parts by weight of the metal salt-containing monomer (a1) solution obtained in 1, 10 parts by weight of xylene, 1 part by weight of a chain transfer agent (“NOFMER MSD”, manufactured by NOF Corporation), azoisobutyronitrile (AIBN, A transparent mixture composed of 2.5 parts by mass of Nippon Hydrazine Kogyo Co., Ltd. and 7 parts by weight of 2,2′-azobis- (2-methylbutyronitrile) (AMBN) was added dropwise at a constant rate over 6 hours. (Hereinafter, this dropping step is also referred to as “dropping step 1”.)

  After completion of dropping, 0.5 parts by mass of t-butyl peroctoate (TBPO) and 7 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 4.4 parts by mass of xylene was added. A pale yellow transparent metal salt-containing copolymer (a2) solution was obtained. Table 2 shows the raw materials, characteristics, and the like of the metal salt-containing copolymer (a2).

(Manufacture of silyl ester-containing copolymer (a3) solution)
[Production Example 3]
Into a reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen introduction tube and dropping funnel, 53 parts by mass of xylene was charged, and the xylene was stirred with a stirrer under a nitrogen atmosphere, while maintaining the pressure in the reaction vessel at normal pressure. The xylene was heated until the temperature reached 85 ° C. 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), 10 parts by mass of MMA (methyl methacrylate), and BA A monomer mixture consisting of 10 parts by weight of (butyl acrylate) and 1 part by weight of 2,2′-azobis- (2-methylbutyronitrile) was added to the reaction vessel using a dropping funnel over 2 hours.

  Next, 0.5 parts by mass of t-butyl peroxyoctoate 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. And after raising the liquid temperature in reaction container from 85 degreeC to 110 degreeC and heating for 1 hour, 14 mass parts of xylene is added in reaction container, the liquid temperature in reaction container is reduced, and liquid temperature is 40 degreeC. At that time, stirring was stopped. Thus, a silyl ester-containing copolymer (a3) -containing solution was prepared. Table 3 shows the raw materials, characteristics, and the like of the silyl ester-containing copolymer (a3).

(Characteristic evaluation of metal salt-containing copolymer (a2) and silyl ester-containing copolymer (a3))
The above-mentioned properties of the metal salt-containing copolymer (a2) and the silyl ester-containing copolymer (a3) were measured by the following methods.
(1) Content of heated residue in copolymer solution 1.5 g of copolymer solution (X ₁ (g)) was held in a thermostatic bath at 1 atm and 108 ° C. for 3 hours. Volatiles were removed to obtain a heating residue (nonvolatile content). 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 (co) polymer solution was calculated based on the following formula: did.
Heat residue content (%) = 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 Apparatus: "HLC-8120GPC" (manufactured by Tosoh Corporation)
Column: “Super H2000 + H4000” (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length))
Eluent: Tetrahydrofuran (THF)
Flow rate: 0.500 ml / min
Detector: RI
Column bath temperature: 40 ° C
Standard substance: Polystyrene sample preparation method: A small amount of calcium chloride was added to the copolymer solution for dehydration, and the filtrate obtained by filtration through a membrane 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.].

(Production of metal salt-containing hydrolyzable antifouling paint S1 and silyl ester-containing hydrolyzable antifouling paint S2)
[Production Example 4]
In a 1000 ml plastic container, xylene (16 g), metal salt-containing copolymer (a2) solution (37 g), zinc oxide (20 g), TTK talc (10 g), Bengala 404 (1.5 g), Nova Palm Red F5RK (0 0.5 g), zinc omadin (8 g), and econea (4 g) were added, and 200 g of glass beads were added and dispersed for 1 hour. Thereafter, Disparon A630-20X (3.0 g) was added and dispersed for another 15 minutes. The mixture was filtered through a 60 mesh filter screen to prepare a metal salt-containing hydrolyzable antifouling paint S1. Table 5 shows a list of raw materials.

[Production Example 5]
A silyl ester-containing hydrolyzable antifouling paint S2 was similarly prepared except that the blending components were changed as shown in Table 4.

<Preparation of anticorrosion coating composition>
[Example 1]
An anticorrosive coating composition was prepared as follows.
(Main ingredient)
In a 1000 ml plastic container, MIBK (3 g), N-butyl alcohol (3 g), xylene (17 g), jER1001-X75 (16 g), Laroflex MP-25 (6 g), TTK talc (25 g), Varico 300W (8 g) Mica powder 325 mesh (5 g), Bengala 404 (2 g), Disparon 6650 (1.5 g), KBM403 (0.5 g) were added, and 200 g of glass beads were added and dispersed for 1 hour. Table 5 shows a list of raw materials. The dispersion was filtered through a 60-mesh filter screen to prepare the main component of the anticorrosion paint.

(Curing agent component)
Xylene (5.7 g), raccamide TD-966 (7 g) and ancamine K-54 (0.3 g) were blended in a 200 ml plastic container and dispersed for 10 minutes. A list of raw materials is shown in Table 5. The dispersion was filtered through a 60-mesh filter screen to prepare a curing agent component for the anticorrosion paint.

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

[Examples 2-7, Comparative Examples 1-7]
An anticorrosion coating composition was prepared in the same manner as in Example 1 except that the composition of the main component and the curing agent component was changed as shown in Table 6.

<Production and evaluation of laminated antifouling coating film>
(1) Consumability of laminated antifouling coating film Each anticorrosion coating composition prepared in Examples 1 to 7 and Comparative Examples 1 to 7 was applied to a hard vinyl chloride plate of 50 mm x 50 mm x 1.5 mm using an applicator. Apply each to a dry film thickness of 150 μm, and with a coating interval of 1 day, apply a metal salt-containing hydrolyzable antifouling paint S1 and a silyl ester-containing hydrolyzable antifouling paint S2 to a dry film thickness of 100 μm with an applicator. This was applied and dried at 23 ° C. for 7 days to prepare a test plate having a laminated antifouling coating film.

  The above test plate is installed on the side of a rotating drum installed in a thermostatic bath containing 25 ° C. seawater, rotated at a peripheral speed of 15 knots, and the cumulative consumption of the antifouling coating every month from installation (thickness reduction amount) (Μm)).

(2) Static antifouling property of laminated antifouling coating film;
Each of the anticorrosive coating compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 7 was applied to a 100 × 300 × 3.2 mm sandblasted steel plate using an air spray so that the dry film thickness was 150 μm. Apply the metal salt-containing hydrolyzable antifouling paint S1 and the silyl ester-containing hydrolyzable antifouling paint S2 with an air spray so that the dry film thickness of the antifouling coating film is 100 μm. A test plate having a laminated antifouling coating film was prepared by drying at 23 ° C. for 7 days.

The test plate is immersed in Nagasaki Bay, Nagasaki Prefecture, and the aquatic organism adhesion area every month after immersion (of the part where aquatic organisms adhere to the total area of 100% of the antifouling coating on the test plate) The area ratio (%) was measured visually and evaluated based on the following evaluation criteria.
0: No attachment of aquatic organisms 0.5: Attachment area of aquatic organisms exceeds 0% and 10% or less 1: Attachment area of aquatic organisms exceeds 10% and 20% or less 2: Attachment area of aquatic organisms is 20% Exceeding 30% or less 3: Adhering area of aquatic organisms exceeding 30% to 40% or less 4: Adhering area of aquatic organisms exceeding 40% to 50% or less 5: Adhering area of aquatic organisms exceeding 50%

(3) Damage resistance of laminated antifouling coating film Each of the anticorrosion coating compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 7 is applied by air spray to a 70 mm × 150 × 1.6 mm sandblasted steel sheet. The film was applied to a dry film thickness of 150 μm and left at 5 ° C. for 1 day to form an anticorrosion coating film. On the surface of the anti-corrosion coating, the metal salt-containing hydrolyzable antifouling paint S1 or the silyl ester-containing hydrolyzable antifouling paint S2 is applied to the surface of the anticorrosive coating with a spray interval of 1 day. It applied so that it might become, and it dried at 5 degreeC and produced the test plate which has a lamination | stacking antifouling coating film. One day, two days, and three days after the start of drying of the antifouling coating film, a 30 mm × 30 mm × 10 mm piece of wood is placed in the center of the antifouling coating and 40 kgf / cm ² (vertically from above the piece of wood. A pressure of 3.9 MPa) was applied for 20 minutes, the state of the coating film surface was observed (that is, the degree of deformation of the coating film was measured), and evaluation was performed based on the following evaluation criteria.
5: The coating film is not deformed and shows the best state.
4: Although a deformation | transformation of a coating film is recognized a little, it has shown the favorable state.
3, 2, and 1 are considerably deformed, and the steel sheet is partially exposed. The degree of damage (deformation) increases in the order of 3, 2, and 1.

[Comparative reference example]
The following tests were carried out on single-layer antifouling coating films formed from each of the metal salt-containing hydrolyzable antifouling paint S1 and the silyl ester-containing hydrolyzable antifouling paint S2.

(1) Consumability of antifouling coating film;
A metal salt-containing hydrolyzable antifouling paint S2 or a silyl ester-containing hydrolyzable antifouling paint S2 is applied to a hard vinyl chloride plate of 50 mm × 50 mm × 1.5 mm using an applicator. And dried at 23 ° C. for 7 days to produce a single-film test plate having no anticorrosion coating.

  The test plate is installed on the side of a rotating drum installed in a thermostatic bath containing 25 ° C. seawater, rotated at a peripheral speed of 15 knots, and the cumulative consumption of antifouling coating every month (thickness reduction (μm) )) Was measured.

(2) Static antifouling property of the antifouling coating film;
Apply a metal salt-containing hydrolyzable antifouling paint S1 and a silyl ester-containing hydrolyzable antifouling paint S2 to a 100 x 300 x 3.2 mm rigid vinyl chloride plate by air spray so that the dry film thickness is 100 μm. This was dried at 23 ° C. for 7 days to prepare a test plate having a single antifouling coating without an anticorrosion coating.
The test plate having the single antifouling coating film was used in place of the test plate having the laminated antifouling coating film, and the same evaluation as the stationary antifouling property of the laminated antifouling coating film was performed.

(3) Damage resistance of the antifouling coating film;
Apply a metal salt-containing hydrolyzable antifouling paint S1 or a silyl ester-containing hydrolyzable antifouling paint S2 to a hard vinyl chloride plate of 70 mm x 150 x 1.6 mm with air spray so that the dry film thickness is 150 μm. A test plate having a single antifouling coating without an anticorrosive coating was prepared by drying at 5 ° C. Damage The test plate having the single antifouling coating film was used in place of the test plate having the laminated antifouling coating film, and the same evaluation as the above-mentioned damage resistance of the laminated antifouling film was performed.

Claims (23)

An epoxy resin anticorrosion coating composition for forming the anticorrosion coating in a laminated antifouling coating provided on the surface of the substrate in the order of the anticorrosion coating and the antifouling coating from the substrate side, ,
Containing an epoxy resin (A), a solid thermoplastic resin (B), and an amine-based curing agent (C);
The solid thermoplastic resin (B) is solid at room temperature,
An epoxy resin anticorrosive coating composition, wherein the content of the solid thermoplastic resin (B) is 50 parts by mass or more with respect to 100 parts by mass of the solid content of the epoxy resin (A).   The epoxy resin anticorrosive coating composition according to claim 1, wherein the epoxy resin (A) is one or more selected from the group consisting of bisphenol A, bisphenol AD, and bisphenol F. Furthermore, it is an epoxy resin anticorrosion coating composition optionally containing a silane coupling agent, and when it does not contain a silane coupling agent, the reaction ratio represented by the following formula (1) is such that the amine curing agent ( When a silane coupling agent having reactivity with respect to C) is contained, the reaction ratio represented by the following formula (2) is a silane coupling agent having reactivity with respect to the epoxy resin (A). 3. The epoxy resin anticorrosive coating composition according to claim 1, wherein when contained, the reaction ratio represented by the following formula (3) is 0.3 to 0.8, respectively.
  Furthermore, the epoxy resin type anticorrosion coating composition as described in any one of Claims 1-3 containing a pigment (E). The epoxy resin anticorrosive coating composition according to claim 4, wherein the pigment volume concentration (PVC) represented by the following formula (4) 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) Formula (4)   The solid thermoplastic resin (B) includes at least one selected from the group consisting of petroleum resins, chlorinated polyolefins, acrylic resins, butyl acetate resins, styrene resins, and vinyl chloride resins. The epoxy resin anticorrosive coating composition according to any one of claims 1 to 5.   The epoxy resin anticorrosive coating composition according to claim 6, wherein the vinyl chloride resin is a vinyl chloride / vinyl isobutyl ether copolymer.   Furthermore, tertiary amine is contained as a hardening accelerator (D), The epoxy resin type anticorrosion coating composition as described in any one of Claims 1-7 characterized by the above-mentioned.   Furthermore, the epoxy resin type anticorrosion coating composition as described in any one of Claims 1-8 containing an adhesion | attachment reinforcement | strengthening agent (F).   The epoxy resin-based anticorrosive coating composition according to claim 9, wherein the adhesion enhancing agent (F) is a silane coupling agent.   The epoxy resin anticorrosive coating composition according to claim 10, wherein the silane coupling agent is γ-glycidoxypropyltrimethoxysilane.   The epoxy resin anticorrosive coating composition according to any one of claims 1 to 11, wherein the antifouling coating film is a hydrolyzable antifouling coating film. An epoxy resin anticorrosion coating used as the anticorrosion coating of the antifouling coating provided on the substrate surface in the order of the anticorrosion coating and the antifouling coating from the substrate side,
An epoxy resin-based anticorrosive coating film, which is a cured product of the epoxy resin-based anticorrosive coating composition according to any one of claims 1 to 12. An epoxy resin anticorrosion coating used as the anticorrosion coating of the antifouling coating provided on the substrate surface in the order of the anticorrosion coating and the antifouling coating from the substrate side,
Comprising a matrix comprising a cured epoxy resin and a solid thermoplastic resin (B);
The solid thermoplastic resin (B) is solid at room temperature,
An epoxy resin anticorrosive coating film having a content of the solid thermoplastic resin (B) of 7 to 80% by mass.   Furthermore, the epoxy resin-type anticorrosion coating film of Claim 14 containing an epoxy resin (A). It is a method for producing an epoxy resin anticorrosion coating used as the anticorrosion coating of a laminated antifouling coating provided on the substrate surface in the order of the anticorrosion coating and the antifouling coating from the substrate side. And
The manufacturing method of the epoxy resin type anti-corrosion coating film including the process of hardening the film | membrane which consists of an epoxy resin type anti-corrosion coating composition as described in any one of Claims 1-12.   It is a laminated antifouling coating film provided on the surface of the substrate in the order of the anticorrosion coating film and the antifouling coating film from the substrate side, and the anticorrosion coating film is according to any one of claims 13 to 15. A laminated antifouling coating film, which is the epoxy resin anticorrosion coating described.   The laminated antifouling coating film according to claim 17, wherein the antifouling coating film is a hydrolyzable antifouling coating film. A method for producing a laminated antifouling coating film, which is provided by laminating in the order of the anticorrosion coating film and the antifouling coating film from the substrate side on the substrate surface,
A laminated antifouling coating comprising the step of forming the epoxy resin-based anticorrosive coating according to any one of claims 13 to 15 and the step of forming the antifouling coating on the surface of the epoxy resin-based anticorrosive coating. A method for producing a membrane.   The antifouling base material by which the laminated antifouling coating film of Claim 17 or 18 is laminated | stacked on the base-material surface so that it may become the order of the said anticorrosion coating film and the said antifouling coating film from the said base material side.   The antifouling substrate according to claim 20, which is in contact with seawater or fresh water.   The antifouling substrate according to claim 20 or 21, wherein the substrate is at least one selected from the group consisting of ships, marine structures, and land structures.   A method for producing an antifouling substrate comprising a step of forming the laminated antifouling coating film according to claim 17 or 18 on the surface of the substrate.