KR102075434B1 - Epoxy resin anticorrosive coating compositions, epoxy resin anticorrosive coating films, layered antifouling coating films, antifouling substrates, and methods for production thereof - Google Patents

Abstract

The present invention is a laminated antifouling coating film formed by laminating an epoxy resin anticorrosive coating film and an antifouling coating film. Even if an antifouling coating film is formed on an anticorrosive coating film in a step where the epoxy resin is not sufficiently cured, the decrease in antifouling performance is suppressed and the damage resistance is also increased. An object of the present invention is to provide an excellent laminated antifouling coating film, an epoxy resin anticorrosive coating film, an epoxy resin anticorrosive coating film, a method for producing the same, and the like for forming such a laminated antifouling coating film.
In order to solve the said subject, the epoxy resin anticorrosive coating composition of this invention is an epoxy resin system for forming the said anticorrosive coating film in the laminated antifouling coating film provided by laminating | stacking on the surface of a base material in the order of an anticorrosive coating film and an antifouling coating film from the said substrate side. The anticorrosive coating composition contains an epoxy resin (A), a solid thermoplastic resin (B) and an amine curing agent (C), wherein the solid thermoplastic resin (B) is solid at room temperature, and the content of the solid thermoplastic resin (B). It is 50 mass parts or more with respect to 100 mass parts of solid content of this said epoxy resin (A), It is characterized by the above-mentioned.

Description

Epoxy resin anticorrosive coating compositions, epoxy resin anticorrosive coating films, layered antifouling coating films, antifouling substrates, and methods for production

The present invention relates to a laminated antifouling coating film comprising an epoxy resin anticorrosive coating composition, an epoxy resin anticorrosive coating film, an anticorrosive coating film, and an antifouling coating film laminated thereon, an antifouling material having the laminated antifouling coating film, and a method of manufacturing the same.

Repair paintings are regularly carried out at the bottom of the ship. The coating specification is generally coated with anticorrosive paint after basic treatment such as removal of rust and coating film defects, followed by antifouling paint to prevent anticorrosive and adhesion of marine organisms. In the case of repair coating, it is desired that the anticorrosive coating film and the antifouling coating film are adhered satisfactorily, and that the antifouling property of the anticorrosive coating and the laminated coating film of the antifouling paint formed thereon is good.

As the anticorrosive paint, epoxy resin anticorrosive paint is generally used. There are many literatures on epoxy resin anticorrosive coatings. For example, Patent Literatures 1 to 3 describe epoxy resin anticorrosive coating compositions including vinyl chloride copolymers, and the like. Painting with paint is also described.

In addition, Patent Documents 2 and 3 describe coating of an anticorrosive coating film with an antifouling paint to evaluate dynamic antifouling properties and consumption.

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

In the repair painting work process of ships, the coating interval of anticorrosive paint and antifouling paint is often shortened depending on the adjustment of the ship operation schedule and weather conditions during the painting work. This short coating interval sometimes causes a problem.

From an epoxy resin anticorrosive coating, an anticorrosive coating film is formed by a mechanism in which a curing agent such as an epoxy resin reacts with an amine to cure and dry. In the case where the coating interval between the epoxy resin anticorrosive paint and the antifouling paint is short, the anticorrosive coating film does not have sufficient reaction between a curing agent such as an epoxy resin and an amine when the antifouling paint is applied, and thus an unreacted epoxy resin remains. It was confirmed that when antifouling paint was applied on such an anticorrosive coating film, the unreacted epoxy resin was bleeded into the antifouling paint, resulting in deterioration of the consumption and antifouling properties of the antifouling coating film. When coating is especially performed at low temperature, it was also confirmed that reaction of an epoxy resin and a hardening | curing agent becomes slow, the residual amount in the coating film of an unreacted epoxy resin component increases, and the effect becomes larger.

Moreover, although the coating film formed by laminating | stacking the anticorrosive coating film and antifouling coating film of patent documents 2 and 3 was excellent in dynamic antifouling property, it was confirmed that there exists room for improvement in evaluation of static antifouling property which is a strict evaluation.

In addition, in the coating film of a ship to be repaired and coated, the property that plastic deformation or destruction by external pressure hardly occur (hereinafter referred to as "damage resistance") is also important. In the case of repair painting of a ship, most of the cases are sailed immediately after the completion of painting work due to the loading schedule, and are docked on the inner wall. Therefore, if the ship is moored on the inner wall and the repaired film is deformed and becomes scratchy, the painting work is hard. It becomes this waste. For this reason, the coating film which expresses damage resistance quickly after coating is very preferable.

However, when coating is performed at low temperature, such as copper type, the reactivity of an epoxy resin and a hardening | curing agent falls, The coating film strength of an anticorrosive coating falls, As a result, the damage resistance of a laminated coating film also falls.

As a solution to these problems, it is conceivable to prescribe an epoxy resin anticorrosive coating by simply reducing the epoxy resin composition. However, the paint having such a composition has poor pigment workability and poor leveling property due to the excessive pigment content. It is impossible to form a continuous coating film by lack of resin powder, and the coating film obtained is bad in external appearance, water resistance, and corrosion resistance.

In view of such a problem in the prior art, the present invention is a laminated antifouling coating film formed by laminating an epoxy resin anticorrosive coating film and an antifouling coating film, even when the antifouling coating film is formed on the anticorrosive coating film at a stage where the epoxy resin is not sufficiently cured. Epoxy resin-based anticorrosive coating for forming an epoxy resin-based anticorrosive coating film of a laminated antifouling coating film having suppressed a decrease in antifouling performance (especially antifouling antifouling properties) and excellent damage resistance, an epoxy resin anticorrosive coating film used as an anticorrosive coating film of the laminated antifouling coating film, An object of the present invention is to provide a laminated antifouling coating film and a method for manufacturing the same, and an antifouling coating film having the laminated antifouling coating film and a method of manufacturing the same.

As a result of earnest research by the present inventors in order to solve the said problem, the fall of antifouling performance (especially stationary antifouling property) is suppressed by using comparatively many thermoplastic resins together with an epoxy resin at room temperature in an epoxy resin anticorrosive coating, The present invention has been completed by discovering that an antifouling coating film having excellent damage properties and an antifouling coating film can be formed.

The mechanism of effect expression of the present invention is considered as follows.

In the anticorrosive coating film formed of the epoxy resin anticorrosive coating, the epoxy resin is present in a liquid or semisolid form as long as it is in an unreacted state that does not react with a curing agent such as an amine. When a top coat is applied to the anticorrosive coating film in such a state, a solvent of the topcoat paint penetrates into the anticorrosive coating film, thereby softening the anticorrosive coating film, and unreacted epoxy resin is bleeded into the topcoat film. On the other hand, resin which is solid at normal temperature in an anticorrosive coating film is hard to transfer to a top coat film even if the solvent of a top coat paint penetrates into an anticorrosive coating film. For this reason, when the solid thermoplastic resin is used in combination with the epoxy resin, the amount of the epoxy resin is relatively reduced, which makes it possible to reduce the bleeding component of the unreacted epoxy resin, thereby preventing the antifouling coating film laminated on the anticorrosive coating film. It is thought to improve the damage resistance of a laminated coating film, without degrading performance (especially antifouling antifouling property).

The present invention relates to the following [1] to [23].

[One]

As an epoxy resin anticorrosive coating composition for forming the said anticorrosive coating film in the laminated antifouling coating film provided by laminating | stacking in the order of an anticorrosive coating film and an antifouling coating film from the said substrate side to the base material surface,

An epoxy resin (A), a solid thermoplastic resin (B) and an amine curing agent (C),

The solid thermoplastic resin (B) is solid at room temperature,

The epoxy resin anticorrosive coating composition whose content of the said solid thermoplastic resin (B) is 50 mass parts or more with respect to 100 mass parts of solid content of the said epoxy resin (A).

[2]

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

[3]

Furthermore, the epoxy resin type anticorrosive coating composition which optionally contains a silane coupling agent, When it does not contain a silane coupling agent, the reaction ratio represented by following formula (1), and the silane couple which have reactivity with the said amine-type hardening | curing agent (C) When it contains a ring agent, when it contains the reaction ratio represented by following formula (2), and the silane coupling agent reactive with the said epoxy resin (A), the reaction ratio represented by following formula (3) is respectively 0.3- The epoxy resin anticorrosive coating composition as described in said [1] or [2] which is 0.8.

[4]

The epoxy resin anticorrosive coating composition according to any one of the above [1] to [3], which further contains a pigment (E).

[5]

The epoxy resin anticorrosive coating composition as described in said [4] whose pigment volume concentration (PVC) represented by following formula (4) is 25-50%.

[6]

[1] The solid thermoplastic resin (B) comprises at least one member selected from the group consisting of petroleum resin, chlorinated polyolefin, acrylic resin, butyl acetate resin, styrene resin and vinyl chloride resin. The epoxy resin system anticorrosive coating composition in any one of [5].

[7]

The epoxy resin anticorrosive coating composition according to the above [6], wherein the vinyl chloride resin is a vinyl chloride / vinyl isobutyl ether copolymer.

[8]

Furthermore, the tertiary amine is contained as a hardening accelerator (D), The epoxy resin anticorrosive coating composition in any one of said [1]-[7] characterized by the above-mentioned.

[9]

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

[10]

The epoxy resin anticorrosive coating composition according to the above [9], wherein the adhesion enhancer (F) is a silane coupling agent.

[11]

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

[12]

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

[13]

As an epoxy resin anticorrosive coating film used as the said anticorrosive coating film of the laminated antifouling coating film provided by laminating | stacking on the surface of a base material from the said base material in order of an anticorrosive coating film, an antifouling coating film,

The epoxy resin anticorrosive coating film which is a hardened | cured material of the epoxy resin anticorrosive coating composition in any one of said [1]-[12].

[14]

As an epoxy resin anticorrosive coating film used as the said anticorrosive coating film of the laminated antifouling coating film provided by laminating | stacking on the surface of a base material from the said base material in order of an anticorrosive coating film, an antifouling coating film,

It is made by containing the matrix which contains hardened | cured epoxy resin and solid thermoplastic resin (B),

The solid thermoplastic resin (B) is solid at room temperature,

The epoxy resin anticorrosive coating film whose content of the said solid thermoplastic resin (B) is 7-80 mass%.

[15]

Furthermore, the epoxy resin anticorrosive coating film of the said [14] containing an epoxy resin (A).

[16]

As a method of manufacturing the epoxy resin anticorrosive coating film used as said anticorrosion coating film of the laminated antifouling coating film which is provided by laminating | stacking on the base material surface from the said base material in order of an anticorrosive coating film, an antifouling coating film,

The manufacturing method of the epoxy resin anticorrosive coating film containing the process of hardening | curing the film | membrane which consists of an epoxy resin anticorrosive coating composition in any one of said [1]-[12].

[17]

A laminated antifouling coating film formed by laminating an anticorrosive coating film and an antifouling coating film on the surface of a base material in the order of said anticorrosive coating film, wherein said anticorrosive coating film is an epoxy resin anticorrosive coating film according to any one of [13] to [15].

[18]

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

[19]

As a manufacturing method of the laminated antifouling coating film laminated | stacked and provided in the order of an anticorrosive coating film and an antifouling coating film from the said base material side to the base material surface,

The manufacturing method of the laminated antifouling coating film containing the process of forming the epoxy resin anticorrosive coating film in any one of said [13]-[15], and the process of forming the said antifouling coating film on the surface of the said epoxy resin anticorrosive coating film.

[20]

The antifouling material formed by laminating | stacking the antifouling coating film of said [17] or [18] on the surface of a base material so that the said anticorrosive coating film and said antifouling coating film may be made in order from the said base material side.

[21]

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

[22]

The antifouling material according to the above [20] or [21], wherein the base material is at least one selected from the group consisting of a ship, an offshore structure and a land structure.

[23]

The manufacturing method of the antifouling material containing the process of forming the laminated antifouling coating film as described in said [17] or [18] on the base material surface.

When the anticorrosive coating film is formed of the epoxy resin anticorrosive coating of the present invention in a laminated antifouling coating film formed by laminating the surface of the substrate in the order of the anticorrosive coating film and the antifouling coating film from the substrate side, the resulting anticorrosive coating film contains a curability and a solvent. Since it is excellent in drying property and can suppress bleeding of the unreacted epoxy resin component in an anticorrosive coating film to an antifouling coating film, the fall of the antifouling performance (especially stationary antifouling property) of a laminated antifouling coating film can be suppressed, and a laminated antifouling coating film Can improve the damage resistance.

The present invention is described in more detail below.

[Epoxy Resin  Anticorrosive coating composition ]

The epoxy anticorrosive coating composition of the present invention (hereinafter also referred to simply as the "anticorrosive coating composition") is formed on the surface of the substrate by laminating the anticorrosive coating film in the order of the anticorrosive coating film and the antifouling coating film from the substrate side. An epoxy resin anticorrosive coating composition for forming contains an epoxy resin (A), a solid thermoplastic resin (B), and a curing agent (C).

Each component contained in a composition is demonstrated below and a laminated antifouling coating film is mentioned 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 by ring-opening reaction of one part of the epoxy group are mentioned.

Specifically as said epoxy resin (A), bisphenol-type epoxy resins, such as a bisphenol-type epoxy resin, for example, epichlorohydrin bisphenol A epoxy resin; Bisphenol AD type epoxy resins such as epichlorohydrin-bisphenol AD epoxy resin; Bisphenol F-type epoxy resins, such as the epoxy novolak resin of the structure which epichlorohydrin and bisphenol F (4,4'- methylene bisphenol) reacted; Aromatic epoxy resins such as 3,4-epoxyphenoxy-3 ', 4'-epoxyphenylcarboxymethane; Brominated epoxy resins 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 is brominated; Aliphatic epoxy resins having a structure in which epichlorohydrin and aliphatic dihydric alcohols are reacted; The polyfunctional epoxy resin etc. of the structure which epichlorohydrin and tri (hydroxyphenyl) methane reacted are mentioned.

Among these, a preferable epoxy resin (A) is 1 or more types of epoxy resin chosen from the group which consists of a bisphenol-A epoxy resin, a bisphenol AD epoxy resin, and a bisphenol F-type 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 said epoxy resin (A) (The measurement conditions are the conditions or equivalent conditions when the weight average molecular weight of copolymer (a3) is calculated | required in the Example item mentioned later.) Although it is not determined uniformly also by the coating-hardening conditions (for example, room temperature dry coating or heat drying coating etc.) etc. of the said epoxy resin anticorrosive coating composition, Preferably it is 350-20,000. 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 said epoxy resin (A) becomes like this. Preferably it is 150-1,000 g / eq.

As said epoxy resin (A), the bisphenol-A epoxy resin whose epoxy equivalent is 150-700 g / eq is preferable.

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

As a typical bisphenol A epoxy resin, in the case of a liquid at room temperature, "jER828" (Mitsubishi Chemical Co., Ltd. make, epoxy equivalent 180-190 g / eq, viscosity 12,000-15,000 cPs / 25 degreeC), "E-028- 90X "(Otake Meishin Chemical Co., Ltd. make, 828 type epoxy resin (NV90% of xylene cut product), epoxy equivalent approximately 210 g / eq)," AER260 "(bisphenol A type epoxy resin, Asahi Kasei Epoxy Co., Ltd.) Epoxy equivalent 190 g / eq, NV100%), etc.,

In the case of semisolid form at room temperature, "jER834-X90" (Mitsubishi Chemical Co., Ltd., epoxy equivalent 230-270 g / eq / xylene cut product NV90%), "E-834-85X" (Otake Meishin Chemical ( Note), epoxy equivalent of about 290 ~ 310 g / eq / xylene cut product NV85%), etc.

In the case of the solid form at room temperature, "jER1001-X75" (Mitsubishi Chemical Co., Ltd., epoxy equivalent 600-650 g / eq / xylene cut product NV75%), "E-001-75X" (Otakemecin chemical ( Note), and epoxy equivalent of about 610 to 650 g / eq / xylene cut product NV75%).

The epoxy resin (A) is preferably 5 to 80% by mass, more preferably 10 to 50% by mass in the anticorrosive coating composition.

Solid Thermoplastic Resin (B)

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

When the solid thermoplastic resin (B) is included in the anticorrosive coating composition, the unreacted epoxy resin (A) in the anticorrosive coating film is transferred to an antifouling coating film laminated on the anticorrosive coating film, thereby reducing the antifouling performance (especially antifouling antifouling property). It is possible to suppress or prevent.

The weight average molecular weight measured by GPC of the said solid thermoplastic resin (B) (The detail of a measurement condition is described in the Example item mentioned later) becomes like this. Preferably it is 5,000-100,000, More preferably, it is 20,000-80,000.

As said solid thermoplastic resin (B), it is more preferable that glass transition temperature is 30 degreeC or more.

Examples of the solid thermoplastic resin (B) include chlorinated polyolefins, acrylic resins, butyl acetate resins, styrene resins, and vinyl chloride resins.

Commercially available acrylic resins among these solid thermoplastic resins are those obtained by copolymerizing acrylic acid and esters or derivatives thereof such as Diamond BR106 (manufactured by Mitsubishi Rayon Co., Ltd., Mw = 60,000) and Pararoid B66 (manufactured by Dow Chemical, Mw = 70,000). Solid methacrylic resin etc. which copolymerized solid acrylic resin, methacrylic acid, its ester, or its derivative (s) are mentioned.

As said solid thermoplastic resin (B), a vinyl chloride resin is preferable among the said resins especially in the point that the influence with respect to adhesion with antifouling paint, damage resistance of a coating film, and antifouling property is especially small.

As said vinyl chloride type resin, a vinyl chloride / vinyl isobutyl ether copolymer is further more preferable, and it is more preferable that a glass transition temperature is 30 degreeC or more. As a commercial item of such a vinyl chloride / vinyl isobutyl ether copolymer, "Laroplex LR8829", "Laroplex MP-25" (Mw = 28,000-30,000), "Laroflex MP-35" and "Laroflex" by BASF Corporation MP-45 ”, etc. are mentioned. Moreover, when "Laroflex MP-25" of the said vinyl / vinyl isobutyl ether copolymer prepared the epoxy resin type anticorrosive coating composition, since the raise of the paint viscosity is small and the painting work is excellent, it is especially preferable.

These solid thermoplastic resins can be used individually by 1 type or in combination of 2 or more types.

The amount of the solid thermoplastic resin (B) in the anticorrosive coating composition is transferred to an antifouling coating film in which the unreacted epoxy resin (A) in the anticorrosive coating film is laminated on the anticorrosive coating film, thereby suppressing a decrease in the antifouling performance (particularly antifouling antifouling property) to It is 50 mass parts or more, Preferably it is 60 mass parts or more with respect to 100 mass parts of said epoxy resins (A) from a viewpoint of preventing, The upper limit is preferable from a viewpoint of exhibiting the outstanding anticorrosive property, topability, and dryness to an anticorrosive coating film. Preferably it is 100 mass parts, More preferably, it is 80 mass parts.

Amine  Hardener (C)

The amine curing agent (C) is not particularly limited as long as it contains active hydrogen and reacts with the epoxy resin (A). Aliphatic amines, alicyclic amines, aromatic amines and heterocyclic amines are preferable.

Specific examples of the aliphatic amines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2'-aminoethylamino) propane, triethylene- Bis (trimethylene) hexamine, bis (3-aminoethyl) amine, bishexamethylenetriamine [H ₂ N (CH ₂ ) ₆ NH (CH ₂ ) ₆ NH ₂ ] and bis (cyanoethyl) diethylenetri An amine etc. are mentioned.

Examples of the alicyclic amines include 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, and 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), mensendiamine, etc. are mentioned.

As said aromatic amine, o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2 , 2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 2,2'-dimethyl -4,4'-diaminodiphenylmethane, 2,4-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 ' -Diaminobiphenyl, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene, 2,4,6-tris (3-aminomethylphenylmethylaminomethyl) phenol, and the like.

Examples of the heterocyclic amine include N-methylpiperazine, morpholine, 1,4-bis- (3-aminopropyl) -piperazine, piperazine-1,4-diazacycloheptane, 1- (2'-aminoethyl Piperazine), 1- [2 '-(2 "-aminoethylamino) ethyl] piperazine, 1,11- diazacycloeichoic acid, 1,15- diazacyclooctacoic acid, etc. are mentioned.

Moreover, it is also possible to use the polyamide of these amines, its modified product, epoxy resin addition modified product, and Mannich modified product as said amine-type hardener (C).

The active hydrogen equivalent (amine equivalent) of the amine curing agent (C) is preferably 50 to 1,000 g / eq, more preferably 70 to 500 g / eq.

As the amine-based curing agent (C), for commercial products, lucamide TD966 (manufactured by DIC Corporation, polyamide, active hydrogen equivalent weight 377 g / eq), PA-66 (manufactured by Otake Meishin Chemical Co., Ltd., polyamide, Active hydrogen equivalent 377 g / eq), PA-290 (A) (manufactured by Otakemecin Chemical Co., Ltd., active hydrogen equivalent 277 g / eq), ancaramide 2050 (manufactured by Air Products, polyamide adduct, active Hydrogen equivalent 150 g / eq), NX-4918 (cadolite production, phenalkamine (mannich modified product of cardanol and amine), active hydrogen equivalent 255 g / eq), etc. are mentioned.

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 quantity of the said amine-type hardening | curing agent (C) exists in the said range from the viewpoint of the hardenability of an anticorrosive coating film, the dryness at the time of containing a solvent, and the damage resistance of a laminated anticorrosive coating film.

(Other ingredients)

The epoxy resin anticorrosive coating composition is usually prepared by coating an anticorrosive coating comprising a main component containing the epoxy resin (A) and the solid thermoplastic resin (B) and a curing agent component containing the amine curing agent (C). Immediately before, the said main ingredient and the said hardening | curing agent component are mixed and prepared.

The main ingredient may include a curing accelerator (D), a pigment (E), an adhesion enhancer (F), a solvent (G), an anti-sgging and anti-settling agent (H), a dehydrating agent (stabilizer) (I), or other coating film, if necessary. A component (dispersant, antifoaming agent, leveling agent, etc.) may be mix | blended in the range which does not impair the objective of this invention, A hardening accelerator (D), a solvent (G), etc. can be used for the said hardening | curing agent component as needed. You may mix | blend in the range which does not impair.

Curing Accelerator (D)

Examples of the curing accelerator (D) include tertiary amines, and specific examples of tertiary amines include triethanolamine (N (C ₂ H ₅ OH) ₃ ) and 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), "version samin EH30" (Henkel and kuseuyi Co., Ltd.), "not carmine K-54" (manufactured by Air Products), and the like.

Moreover, as said hardening accelerator (D), an acrylic ester hardening accelerator is also mentioned.

The amount of the curing accelerator (D) in the anticorrosive coating composition increases the curing rate of the epoxy resin (A) by the amine-based curing agent (C), thereby providing excellent adhesion between the anticorrosive coating film and the top coat film, that is, the antifouling coating film. When the non-volatile content of an anticorrosive coating composition is 100 mass%, since the anticorrosive coating film excellent in the flexibility of a coating film is obtained, Preferably it is 0.1-5.0 mass%.

In addition, in this invention, the "non-volatile content of anticorrosive coating composition (or antifouling paint composition)" is the standard (heating temperature: 125 degreeC) of JISK5601 1-2 of the anticorrosive coating composition (or antifouling coating composition mentioned later) of this invention. Heating time: 60 minutes).

Pigment (E)

As said pigment (E), an extender pigment, a coloring pigment, an rust preventive pigment, etc. are mentioned.

Specific examples of extender pigments include barium sulfate, potassium feldspar, barite powder, silica, calcium carbonate, talc, mica, glass flakes, aluminum stearate, and the like.

Specifically as a coloring pigment, a titanium bag, bengal, yellow bengal, carbon black, etc. are mentioned.

As an antirust pigment, aluminum paste, zinc chromate, zinc phosphate, etc. are mentioned. An aluminum paste having a flaky shape in terms of coating film properties (crack resistance, etc.) is preferable.

The amount of the extender pigment in the anticorrosive coating composition is preferably 0.1 to 80 mass% when the nonvolatile content of the anticorrosive coating composition is 100 mass%.

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

The amount of the rust preventive pigment is preferably 0.1 to 50% by mass when the nonvolatile content 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, a silane coupling agent is preferable in view of storage stability of the anticorrosive coating composition.

The silane coupling agent usually has two functional groups in one molecule, and can contribute to the improvement of the adhesion of the anticorrosive coating film to the inorganic substrate, the decrease in the viscosity of the anticorrosive coating composition, and the like. The silane coupling agent is, for example, a formula: X-Si (OR) ₃ [X is a functional group capable of reacting with an organic material (e.g., an amino group, a vinyl group, an epoxy group, a mercapto group, a halogen group and a hydrocarbon group having these groups) (The ether group may be present in this hydrocarbon group.), And OR represents a hydrolyzable group (e.g., methoxy group, ethoxy group).], Preferably, the epoxy resin (A). Or reactive with the amine curing agent (C).

As a specific example of such a silane coupling agent, if it is a commercial item, "KBM403" ((gamma)-glycidoxy propyl trimethoxysilane, the Shin-Etsu Chemical Co., Ltd. product), "silane S-510" (Tosoh Co., Ltd. product) etc. are mentioned. have.

In the case of blending the silane coupling agent, the amount of the silane coupling agent in the anticorrosive coating composition is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass when the nonvolatile content of the anticorrosive coating composition is 100 mass%. %to be. When the silane coupling agent is used in the anticorrosive coating composition in such an amount, the performance such as adhesion of the anticorrosive coating film to be obtained is improved, and the viscosity of the anticorrosive coating composition is lowered to improve coating workability.

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. Can be mentioned.

These solvents are used individually by 1 type or in combination of 2 or more types.

Content of the said solvent (G) in a main 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.

Sagging  Prevention, sedimentation prevention agent (H)

Specific examples of the anti-sagging and anti-settling agent (thixotropic agent) (H) include polyamide wax, polyethylene wax, bentonite-based, and thixotropic agents such as OH-containing nanoparticles (aerosol, resin beads).

Examples of such anti-sagging and anti-settling agents include "Disparon 4200-20" manufactured by Kusumoto Chemicals, "Disparon 6650", and "ASAT-250F" manufactured by Ito Oil Chemicals Co., Ltd. Can be.

The nonvolatile content of the anti-sagging anti-settling agent (H) in the anticorrosive coating composition is preferably 0.1 to 30 mass% when the nonvolatile content of the anticorrosive coating composition is 100 mass%.

Dehydrating agent (Stabilizer) (I)

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

Examples of the dehydrating agent (I) include an inorganic dehydrating agent and an organic dehydrating agent. Preferable examples of the inorganic dehydrating agent include synthetic zeolites, anhydrous gypsum, and hemihydrate gypsum, and as organic dehydrating agents, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane and methyltriethoxy Alkoxysilanes, such as silane, dimethyl diethoxysilane, and trimethylethoxysilane, or polyalkoxysilanes which are its condensate, ortho formate acid ester, such as methyl ortho formate and ethyl ortho formate, are mentioned.

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).

(Anticorrosive coating composition)

The anticorrosive coating composition of this invention contains the above-mentioned epoxy resin (A), solid thermoplastic resin (B), and an amine-type hardening | curing agent (C), and can mix and stir these in accordance with a conventional method, and can prepare it.

(With epoxy resin (A) Amine  Reaction Ratio of Curing Agent (C))

The epoxy resin (A) reacts with the amine curing agent (C) to form a coating film.

In the anticorrosive coating composition of the present invention, when the silane coupling agent is not contained, the reaction ratio represented by the following formula (1), and the amine coupling agent having reactivity with the amine curing agent (C) When containing the reaction ratio represented by (2) and the silane coupling agent which has reactivity with the said epoxy resin (A), the reaction ratio represented by following formula (3) becomes like this. Preferably it is 0.3-0.8, More preferably, Is in the range of 0.4 to 0.7.

In each said formula, "the reactive group equivalent of a silane coupling agent" means the functional group which can react the mass (g) (namely, molecular weight) of 1 mol of silane coupling agents with the organic material contained in 1 molecule of a silane coupling agent (" Reactive groups ". As described above, a silane coupling agent having an amino group or an epoxy group can be used as the reactive group. It is judged whether or not the silane coupling agent is used, and in the case of using it, it is judged whether the silane coupling agent is reactive with the epoxy resin (A) or with the amine curing agent (C) according to the kind of the reactive group, After selecting an appropriate formula by said formula (1)-(3), it is necessary to calculate the reaction ratio by calculating | requiring the reactive group equivalent of a silane coupling agent with respect to each.

When the said reaction ratio is more than the said lower limit, since the said epoxy resin (A) is bridge | crosslinked in many places, an unreacted epoxy resin component becomes difficult to remain | survive, and the obtained anticorrosive coating film is excellent in the drying property in the case of containing curability and a solvent, and lamination | stacking The antifouling coating film has less deterioration of antifouling property (especially political antifouling property) and is excellent in damage resistance.

When the said reaction ratio is below the said upper limit, the unreacted said amine-type hardener (C) is hard to remain | survive in the coating film obtained, and the water resistance fall of a coating film by discoloring unreacted said amine-type hardener (C), discoloration, etc. Problem can be prevented.

( PVC )

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

In addition, the "volume of resins" described in the denominator of Formula (4) is a total volume of an epoxy resin (A), a solid thermoplastic resin (B), an amine-type hardening | curing agent (C), and a hardening accelerator (D).

If PVC is more than the said lower limit, the coating film obtained is excellent in dryness and damage resistance.

When PVC is below the said upper limit, it is possible to prevent the fault that the viscosity of an anticorrosive-paint composition is remarkably high and its coating workability falls, or that the corrosion resistance falls by the generation of the leveling property of a coating film, a pinhole, or the like.

[Epoxy Resin Anticorrosive coating]

The epoxy resin anticorrosive coating film of the present invention (hereinafter also referred to simply as "corrosion coating film") is used as the anticorrosion coating film of a laminated antifouling coating film formed by laminating the surface of the substrate from the substrate side in the order of the anticorrosion coating film and the antifouling coating film. It consists of the matrix which contains hardened | cured epoxy resin and the said solid thermoplastic resin (B) (except hardened | cured material of the said epoxy resin (A).).

The anticorrosive coating film of the present invention is also a cured product of the anticorrosive coating composition of the present invention described above.

The said anticorrosive coating film contains the said solid thermoplastic resin (B) normally in 7-80 mass%, Preferably it is 7-50 mass%, More preferably, it is the ratio of 7-30 mass%. Since the anticorrosive coating film of this invention contains the said solid thermoplastic resin (B) in such a ratio, it shifts to the antifouling coating film by which the unreacted epoxy resin (A) is laminated | stacked on the said anticorrosive coating film, as mentioned above. The fall of antifouling performance (especially stationary antifouling property) can be suppressed.

Moreover, the manufacturing method of the said anticorrosive coating film of this invention includes the process of hardening the film | membrane which consists of an anticorrosive coating composition of this invention. The anticorrosive coating film of the present invention can be produced by the same method as the production method of a conventional epoxy resin-based anticorrosive coating film, except that the anticorrosive coating composition of the present invention is used.

The film thickness (dry film thickness) of the said anticorrosive coating film is about 50-800 micrometers normally.

[Lamination Antifouling coating , Antidote  Etc]

The laminated antifouling coating film of the present invention is a laminated antifouling coating film formed by being laminated on the substrate surface from the base material side in the order of the anticorrosive coating film and the antifouling coating film. The antifouling coating film is a laminated antifouling coating film of the epoxy resin anticorrosive coating film of the present invention described above.

Moreover, the antifouling material of this invention is laminated | stacked on the surface of a base material so that the laminated antifouling coating film of this invention may be in order of the said anticorrosive coating film and the said antifouling coating film from the said base material side.

(Antifouling paint composition)

As the antifouling coating composition for forming an antifouling coating film on the anticorrosive coating film, a conventionally known antifouling coating composition can be cited, and the antifouling coating film generated when the unreacted epoxy resin (A) is transferred from the anticorrosive coating film to the antifouling coating film Hydrolysis type antifouling coating composition is preferable at the point which can suppress the antifouling performance fall especially effectively.

As resin for coating film formation of a hydrolysis-proof antifouling paint, for example

General formula (I):

COO-MO-COR ¹ ... … (I)

A metal salt-containing copolymer having a side chain end group represented by [wherein M represents zinc or copper and R ¹ represents an organic group in formula (I),

General formula (II):

CH ₂ = C (R ² ) -COO-MO-CO-C (R ² ) = CH ₂ . (II)

In the formula (II), M represents zinc or copper, and R ² represents a hydrogen atom or a methyl group. A structural unit derived from a monomer represented by a monomer represented by the monomer represented by another monomer which is copolymerizable with the monomer. A metal salt containing copolymer, and

General formula (III):

R ³ —CH═C (R ⁴ ) —COO-SiR ⁵ R ⁶ R ⁷ . (III)

[In 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, and R ³ represents a hydrogen atom or R ⁸ -O-CO (wherein R ⁸ may independently have a heteroatom). A monovalent organic group having 1 to 20 carbon atoms or a silyl group represented by SiR ⁹ R ¹⁰ R ¹¹ , and R ⁹ , R ¹⁰ and R ¹¹ each independently represent a monovalent organic group having 1 to 20 carbon atoms that may have a hetero atom. The silyl ester containing copolymer containing the structural unit guide | induced from the monomer shown by] and the structural unit derived from the other unsaturated monomer copolymerizable with the said monomer is mentioned.

Antifouling coating compositions using these hydrolyzable resins are preferred because their long-term antifouling properties and long-term coating film properties are stable.

As another unsaturated monomer copolymerizable with the monomer represented by the said General formula (II) or (III), (meth) acrylic acid ester, monocarboxylic acid, dicarboxylic acid, or these half ester (monoester) or di Esters, vinyl esters, and styrenes.

As said unsaturated monomer, (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, for example 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 isobornyl 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) acrylic acid hydroxypropyl ester, (meth) acrylic acid (Meth) acrylic acid esters such as hydroxybutyl ester; Monocarboxylic acids such as (meth) acrylic acid; Dicarboxylic acids such as itaconic acid, maleic acid and succinic acid or their half esters (monoesters) and diesters; Styrenes such as styrene and α-methylstyrene; Vinyl esters such as vinyl acetate and vinyl propionate; These etc. are mentioned, These may use 1 type, or 2 or more types.

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

The antifouling paint composition may be prepared from rosin and / or monocarboxylic acid compound, copper or copper compound, organic antifouling agent, colored pigment, extender pigment, dehydrating agent, plasticizer, pigment dispersant, anti-sgging agent, anti-settling agent, solvent, etc. as necessary. It further contains the component selected.

Rosin  And / or Monocarboxylic acid  compound

Examples of the rosin include rosin such as gum rosin, wood rosin, tall oil rosin, rosin derivatives such as hydrogenated rosin and disproportionated rosin. Rosin is a residue remaining after distillation of pine tree sap, a pine tree sap, and is a natural resin mainly composed of rosin acid (abie acid, palustric acid, isopymaric acid, etc.).

As a monocarboxylic acid compound, aliphatic or alicyclic monocarboxylic acid, these monocarboxylic acid derivatives, or these metal salts are mentioned. Specific examples of the monocarboxylic acid compound include naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versaic acid, trimethylisobutenylcyclohexenecarboxylic acid, stearic acid, hydroxystearic acid, salicylic acid and the like Metal salts; and the like.

Contains by weight (W _A) for a film forming resin and containing a mass ratio of rosin acids and / or monocarboxylic acids containing by weight of an acid compound _{(W B) (W A /} W B) is preferably from 99.9 / 0.1 to 30/70 More preferably, it is 95/5-35/65, More preferably, it is 90/10-40/60. When the content mass ratio is in such a range, there is an effect of increasing the burnability (coating film consumption) in the antifouling coating film, and the antifouling property (particularly antifouling antifouling property) can be improved.

Copper or copper compound

The copper compound may be either an organic or inorganic copper compound, and examples thereof include powdered copper (copper powder), copper nitrous oxide, copper thiocyanate, cupronickel and copper pyrithione.

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

abandonment Antifouling agent

Examples of the organic antifouling agent include metal pyrithiones (except copper pyrithione) such as zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 4-bro Mother-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3carbonitrile, pyridinetriphenylborane, 4-isopropylpyridinediphenylmethylborane, N, N-dimethyl-N '-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2,4,5,6-tetrachloroisophthalnitrile, 2-methylthio-4-tert -Butylamino-6-cyclopropylamino-1,3,5-triazine, medemidine, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, chloromethyl-n-octyldisulfide, N ', N '-Dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2,3-dichloro-N- (2 ', 6'-diethylphenyl) maleimide, 2,3-dicle In the like -N- (2'- ethyl-6'-methylphenyl) maleimide.

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

Coloring pigment

As a coloring pigment, various well-known colored pigments of organic type or inorganic type are mentioned. Carbon black, naphthol red, phthalocyanine blue, etc. are mentioned as an organic coloring pigment. Examples of the inorganic colored pigments include bengal, barite powder, titanium bag, and yellow iron oxide.

The antifouling coating composition may contain a colorant except a color pigment such as a dye together with or instead of the color pigment.

The amount of the colored pigment in the antifouling coating composition is preferably 0.01 to 50 when the nonvolatile content of the antifouling coating composition is set to 100 mass% from the viewpoints of colorability, concealability, exposure discoloration, antifouling property, and water resistance (mechanical characteristics). It is mass%, More preferably, it is 0.1-30 mass%.

Sieving pigment

Examples of the extender pigments include talc, silica, mica, clay, potassium 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. In addition, calcium carbonate and white carbon are used also as an antisettling agent mentioned later, respectively.

The amount of the extender pigment in the antifouling paint composition is preferably 0.1 to 80% by mass when the nonvolatile content of the antifouling paint composition is 100% by mass in terms of water film resistance (mechanical properties), antifouling property, and film hydrolyzability (consumability). More preferably, it is 0.5-70 mass%.

Dehydrating agent

As the dehydrating agent, conventionally known gypsum, tetraethoxysilane and the like can be used.

The amount of the dehydrating agent in the antifouling paint composition is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, when the nonvolatile content of the antifouling paint composition is 100% by mass in view of the effect of preventing the viscosity increase during storage. to be.

Plasticizer

Examples of the plasticizer include chlorinated paraffin (chlorinated paraffin), petroleum resins, ketone resins, TCP (tricresyl phosphate), polyvinyl ethyl ether, dialkyl phthalate, and the like. Coating film water resistance (mechanical characteristics), coating film hydrolyzability (consumability) Among them, chlorinated paraffin (chlorinated paraffin), petroleum resins or ketone resins are preferable.

Specific examples of the chlorinated paraffin include "Toyo Parax 150", "Toyo Parax A-70" (all manufactured by Tosoh Corporation), and the like. Examples of the petroleum resins include C5, C9, styrene, dichloropentadiene and hydrogenated products thereof. As a specific example of petroleum resin, "Quinton 1500", "Quinton 1700" (all are the Nippon-Xeon Corporation make), etc. are mentioned.

The amount of the plasticizer in the antifouling coating composition was 100% by mass in terms of antifouling, coating film water resistance (mechanical characteristics), and the coating film forming resin was hydrolyzable. When it becomes like this. Preferably it is 0.1-80 mass%, More preferably, it is 0.5-70 mass%.

Pigment Dispersant

As a pigment dispersant, various well-known organic or inorganic pigment dispersants are mentioned, for example, an aliphatic amine or organic acids (for example, "Duomin TDO" (made by LION Corporation), "Disperbyk101" (BYK Corporation) Production)).

The amount of the pigment dispersant in the antifouling paint composition is preferably 0.01 to 20% by mass, more preferably 0.1 when the nonvolatile content of the antifouling paint composition is 100% by mass in view of the effect of reducing the viscosity of the coating material and preventing color separation. 10 mass%.

Sagging  Inhibitor

Examples of the anti-sagging agent include amide wax, hydrogenated castor oil wax, polyamide wax, mixtures thereof, synthetic fine silica and the like. Among them, the sagging inhibitor is preferably an amide wax or synthetic fine silica from the viewpoint of storage stability and coating properties of homogeneous / heterogeneous paints.

As a commercial item of a sagging inhibitor, "Disparon A630-20X" (made by Kusumoto Chemicals Co., Ltd.), "ASAT-250F" (made by Ito Oil Chemicals Co., Ltd.), etc. are mentioned.

The amount of the anti-sagging agent in the antifouling coating composition is preferably 0.1 to 50% by mass, more preferably 0.5 when the nonvolatile content of the antifouling coating composition is 100% by mass in view of storage stability and homogeneous / heterogeneous paintability. 30 mass%.

Sedimentation inhibitors

Examples of the antisettling agent include amine salts of Al, Ca, or Zn, polyethylene waxes, polyethylene oxide waxes, and the like. Among them, polyethylene oxide waxes are preferable. Commercially available products of polyethylene oxide wax include "Disparon 4200-20X" (manufactured by Kusumoto Chemicals Co., Ltd.).

The amount of the anti-settling agent in the antifouling coating composition is preferably 0.1 to 50% by mass, more preferably 0.5 when the nonvolatile content of the antifouling coating composition is 100% by mass in view of storage stability and homogeneous / heterogeneous paintability. 30 mass%.

solvent

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

As an organic solvent, Aromatic organic solvents, such as xylene, toluene, and ethylbenzene; Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Aliphatic alcohols having 1 to 10 carbon atoms, preferably about 2 to 5 carbon atoms, such as ethanol, isopropyl alcohol, n-butanol, and isobutanol; Ester solvents such as ethyl acetate and butyl acetate; Etc. can be mentioned. The amount of the solvent in the antifouling coating composition is usually 5 to 80% by mass, preferably 10 to 70% by mass when the amount of the antifouling coating composition is 100% by mass.

(Manufacturing method of laminated antifouling coating film, etc.)

The manufacturing method of the laminated antifouling coating film of this invention includes the process of forming the epoxy resin anticorrosive coating film of this invention, and the process of forming the said antifouling coating film on the surface of the said epoxy resin anticorrosion coating film. Moreover, the manufacturing method of the antifouling material of this invention includes the process of forming the laminated antifouling coating film of this invention on the surface of a base material.

Therefore, the laminated antifouling coating film and the antifouling material of the present invention can be produced by the same method as the conventional method except that the epoxy resin anticorrosive coating film of the present invention is used as the epoxy resin anticorrosive coating film. That is, the epoxy resin anticorrosive coating of the present invention is applied to the surface of the substrate by a conventionally known method and cured to form an epoxy resin anticorrosive coating film, and the antifouling coating composition is applied to the surface of the epoxy resin anticorrosive coating film by a conventionally known method. By hardening, it is possible to manufacture the laminated antifouling coating film or antifouling material of the present invention.

As the base material, a base material which requires corrosion resistance and antifouling property is preferable. Underwater structures such as ships (bottom parts), fishery materials, thermal and nuclear power plant drains, mano roads, submarine tunnels, harbor facilities, canals or waterways And sludge diffusion barriers of various marine civil engineering works, and the like, and base materials include steel, aluminum, wood, and FRP. The laminated antifouling coating film of the present invention formed on the surface of these substrates is excellent in properties (antifouling property, in particular, antifouling property) that prevents the attachment of aquatic organisms such as brown seaweed, barnacle, seaweed, serpula, oyster and large moss insect over a long period of time. .

Although the film thickness (dry film thickness) of the said antifouling coating film is not specifically limited, When a base material is a ship or an underwater structure, it is about 50-2,000 micrometers, for example.

Example

The present invention will be described in more detail based on Examples and Comparative Examples below, but the present invention is not limited to the Examples below.

<Preparation of Metal Salt-Containing Hydrolysis Antifouling Coatings S1 and Silyl Ester-Containing Hydrolysis Antifouling Coatings S2>

(Production of Metal Salt-containing Copolymer (a2) Solution)

[Production Example 1]

85.4 parts by mass of propylene glycol methyl ether (PGM) and 40.7 parts by mass of zinc oxide were added to a four-necked flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer, and the temperature was raised to 75 ° C while stirring.

A mixture consisting 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 by dropping over a constant velocity over 3 hours. After completion of the dropping, the reaction solution became transparent. After stirring for further 2 hours, 36 parts by mass of propylene glycol methyl ether (PGM) was added to obtain a transparent metal salt-containing monomer solution (a1). Solid content of the obtained metal salt containing monomer (a1) solution was 44.8 mass%.

[Production Example 2]

15 mass parts of propylene glycol methyl ether (PGM), 57 mass parts of xylene, and 4 mass parts of ethyl acrylate were added to the four neck flask equipped with the cooler, the thermometer, the dropping funnel, and the stirrer, and it heated up at 100 degreeC, stirring.

Subsequently, 1 mass parts of methyl methacrylate (MMA), 70.2 mass parts of ethyl acrylate (EA), 5.4 mass parts of 2-methoxyethyl acrylate (2-MEA) were obtained by the dripping funnel to the obtained mixture, and obtained by the manufacture example 1. 52 parts by mass of a metal salt-containing monomer (a1) solution, 10 parts by mass of xylene, 1 part by mass of a chain transfer agent ("Nofmer MSD", Japanese fats and oils), azoisobutyronitrile (AIBN, Nippon Hydrazine Industry Co., Ltd.) 2.5 A transparent mixture consisting of 7 parts by weight of 2 parts by weight of 2,2'-azobis- (2-methylbutyronitrile) (AMBN) was subjected to constant dropping over 6 hours. (Hereinafter, this dropping step is also referred to as "dropping step 1".) do.)

After completion of the dropwise addition, 0.5 parts by mass of t-butylperoxy octoate (TBPO) and 7 parts by mass of xylene were added dropwise over 30 minutes, and further stirred for 1 hour and 30 minutes, followed by addition of 4.4 parts by mass of xylene to prepare a light yellow transparent metal salt-containing air. A combined (a2) solution was obtained. Table 2 shows raw materials, properties, and the like of the metal salt-containing copolymer (a2).

(Preparation of the silyl ester-containing copolymer (a3) solution)

[Production Example 3]

Add 53 parts by mass of xylene to a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel, and stir the xylene with a stirrer under a nitrogen atmosphere, and heat it until the xylene temperature in the reaction vessel reaches 85 ° C. under normal pressure. It was. 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) while maintaining the xylene temperature in the reaction vessel And a monomer mixture consisting of 10 parts by mass of BA (butyl acrylate) and 1 part by mass of 2,2'-azobis- (2-methylbutyronitrile) were added into the reaction vessel over 2 hours using a dropping funnel.

Subsequently, 0.5 mass part of t-butylperoxy octoate was further added to the reaction container, and stirring was continued with a stirrer for 2 hours, maintaining the liquid temperature in the reaction container at 85 degreeC 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, and the stirring was stopped when the liquid temperature in the reaction vessel was lowered to 40 ° C. In this way, the silyl ester containing copolymer (a3) containing solution was prepared. Table 3 shows raw materials, properties, 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 characteristics of the metal salt-containing copolymer (a2) and the silyl ester-containing copolymer (a3) were measured by the following method.

(1) Content of heating residue in copolymer solution

1.5 g (X ₁ (g)) of the copolymer solution was maintained for 3 hours under a condition of 1 atm and 108 ° C. in a thermostat, and volatiles were removed to obtain a heated residue (non-volatile content). Subsequently, the amount (X ₂ (g)) of the remaining heating residue (non-volatile content) was measured, and the content rate (%) of the heating residue contained in the (co) polymer solution was calculated based on the following formula.

Content of Heating Residue (%) = X ₂ / X ₁ × 100

(2) the average molecular weight of the 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. Measurement conditions are as follows.

GPC  Condition

Apparatus ： "HLC-8120GPC" (manufactured by Tosoh Corporation)

Column ： "SuperH2000 + H4000" (Toso Corporation make, 6mm (diameter), each 15cm (length))

Eluent ： Tetrahydrofuran (THF)

Flow rate: 0.500 ml / min

Detector: RI column

Thermostat temperature ： 40 ℃

Standard material ： Polystyrene

Sample preparation method: After adding a small amount of calcium chloride to a copolymer solution and dewatering it, the filtrate obtained by filtering with a membrane filter was used as the GPC measurement sample.

(3) viscosity of copolymer solution

The viscosity (unit: mPa * s) of the copolymer solution of 25 degreeC of liquid temperature was measured using the Brookfield viscometer (Tokyo Keiki Co., Ltd. product).

(Preparation of metal salt-containing hydrolyzed antifouling paint S1 and silyl ester-containing hydrolyzed antifouling paint S2)

[Production Example 4]

In a 1,000 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 (0.5 g), zinc omadine (8 g) and Econea (4 g) were combined, and 200 g of glass beads were added and dispersion was performed for 1 hour. Disparon A630-20X (3.0 g) was then added and dispersed for an additional 15 minutes. The metal salt-containing hydrolysis-proof antifouling paint S1 was prepared by filtration through a 60 mesh filter network. Table 5 also shows a list of raw materials.

Production Example 5

The silyl ester-containing hydrolyzed antifouling paint S2 was prepared in the same manner as in Table 4 except that the ingredients were changed.

<Preparation of anticorrosive coating composition>

Example 1

The anticorrosive coating composition was prepared as follows.

(Topic 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) ), Bariko 300W (8 g), mica powder 325 mesh (5 g), Bengala 404 (2 g), Disparon 6650 (1.5 g), KBM403 (0.5 g) are combined, 200 g of glass beads are added Dispersion was carried out for 1 hour. Table 5 also shows a list of raw materials. The dispersion was filtered through a 60 mesh filter net to prepare a main component of the anticorrosive coating.

(Hardener component)

Xylene (5.7 g), luccarmide TD-966 (7 g), and ankamine K-54 (0.3 g) were blended in a 200 ml plastic container, followed by dispersion for 10 minutes. Table 5 also shows a list of raw materials. The dispersion was filtered through a 60 mesh filter net to prepare a curing agent component of the anticorrosive coating.

(Anticorrosive coating composition)

The obtained main component and the hardening | curing agent component were mixed in accordance with a conventional method just before coating, and the anticorrosive coating composition was prepared.

[Examples 2-7, Comparative Examples 1-7]

An anticorrosive coating composition was prepared in the same manner as in Example 1 except that the blending 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) Consumption of laminated antifouling coating

Each of the anticorrosive coating compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were applied to a 50 mm × 50 mm × 1.5 mm hard vinyl chloride plate using an applicator so as to have a dry film thickness of 150 μm. The metal salt-containing hydrolyzed antifouling paint S1 and the silyl ester-containing hydrolyzed antifouling paint S2 were applied with an applicator so as to have a dry film thickness of 100 μm, which was dried at 23 ° C. for 7 days to prepare a test plate having a laminated antifouling coating film. .

The test plate was installed on the side of a rotating drum installed in a thermostatic bath containing 25 ° C seawater, and rotated at 15 knots per hour to measure the total consumption of the antifouling coating film (reduced thickness of the film (μm)) at intervals of one month from the installation.

(2) stationary antifouling properties of the laminated antifouling coating film;

Each anticorrosive coating composition prepared in Examples 1 to 7 and Comparative Examples 1 to 7 was applied to a sandblasted steel sheet of 100 mm × 300 mm × 3.2 mm using an air spray so as to have a dry film thickness of 150 μm. Apply a metal salt-containing hydrolyzed antifouling paint S1 and a silyl ester-containing hydrolyzed antifouling paint S2 with an air spray so that the dry film thickness of the antifouling coating film is 100 μm in one day, and dried it at 23 ° C. for 7 days to form a laminated antifouling coating film. A test plate having was prepared.

The test plate was fixedly immersed in Nagasaki Bay, Nagasaki Prefecture, and the naked eye was attached to the area of attachment of the aquatic organisms (% of the area where the aquatic organisms were attached to 100% of the total area of the antifouling coating film of the test plate) by visual observation. It measured by observation and evaluated based on the following evaluation criteria.

0 ： No adhesion of aquatic organisms

0.5 ： Adhesion area of aquatic organisms is more than 0% and less than 10%

1: Adhesion area of aquatic organisms is more than 10% and less than 20%

2: Adhesion area of aquatic organisms is more than 20% and less than 30%

3: Adhesion area of aquatic organisms is more than 30% and less than 40%

4 ： Adhesion area of aquatic organisms is more than 40% and less than 50%

5: ： Adhesion area of aquatic organisms exceeds 50%

(3) Damage resistance of laminated antifouling coating film

Each anticorrosive coating composition prepared in Examples 1 to 7 and Comparative Examples 1 to 7 was applied to a sandblasted steel sheet having a thickness of 70 mm × 150 mm × 1.6 mm so as to have a dry film thickness of 150 μm. It was left to form an anticorrosive coating film. On the surface of this anticorrosive coating film, a metal salt-containing hydrolyzed antifouling paint S1 or a silyl ester-containing hydrolyzed antifouling paint S2 was applied by air spray so that the dry film thickness of the antifouling coating film was 150 μm, and dried at 5 ° C. The test plate which has a laminated antifouling coating film was produced. 1 day after the start of drying of the antifouling coating film, 2 days and 3 days later, a 30 mm × 30 mm × 10 mm piece of wood is placed in the center on the antifouling film, and 40 kgf / cm ² (3.9 MPa in the vertical direction on the piece. ) Was applied for 20 minutes to observe the state of the surface of the coating film (that is, the degree of deformation of the coating film was measured), and evaluation was performed based on the following evaluation criteria.

5: There is no deformation | transformation of a coating film, and the best state is shown.

4: The deformation | transformation of a coating film is confirmed slightly, but the favorable state is shown.

3, 2, and 1 were found to have significant deformations, in part to the exposure of the steel sheet. The degree of damage (deformation) is increasing in the order of 3, 2, 1.

[Comparative Reference Example]

The following test was done about the antifouling coating film of a single film formed from each of metal salt containing hydrolysis-proof antifouling paint S1 and silyl ester containing hydrolysis-proof antifouling paint S2.

(1) consumption of the antifouling coating film;

Apply a metal salt-containing hydrolyzed antifouling paint S1 or a silyl ester-containing hydrolyzed antifouling paint S2 with an applicator to a 50 mm × 50 mm × 1.5 mm hard vinyl chloride plate using an applicator so that the dry film thickness is 100 μm, This was dried at 23 ° C. for 7 days to prepare a test plate of a single membrane without an anticorrosive coating film.

The test plate was installed on the side of a rotating drum installed in a thermostatic bath containing 25 ° C seawater, and rotated at 15 knots per second to measure the total consumption of the antifouling coating film (reduced thickness (μm)) at intervals of one month.

(2) antifouling property of antifouling coating film;

A metal salt-containing hydrolyzed antifouling paint S1 and a silyl ester-containing hydrolyzed antifouling paint S2 were applied to a hard vinyl chloride plate having a thickness of 100 mm x 300 mm x 3.2 mm with an air spray so that the dry film thickness was 100 m. After drying for 7 days to prepare a test plate having a single membrane antifouling coating film without an anticorrosive coating film.

The test plate having the antifouling coating film of this single film was used in place of the test plate having the laminated antifouling coating film, and the same evaluation as the static antifouling property of the laminated antifouling coating film was performed.

(3) damage resistance of the antifouling coating film;

Apply a metal salt-containing hydrolyzed antifouling paint S1 or a silyl ester-containing hydrolyzed antifouling paint S2 to a dry vinyl thickness of 150 mm by 70 mm x 150 mm x 1.6 mm so as to have a dry film thickness of 150 µm. By drying, a test plate having a single membrane antifouling coating film without an anticorrosive coating film was prepared. The test plate having the antifouling coating film of this single film was used in place of the test plate having the laminated antifouling coating film to evaluate the same damage resistance as that of the laminated antifouling coating film described above.

Claims (23)

As an epoxy resin anticorrosive coating composition for forming the said anticorrosive coating film in the laminated antifouling coating film provided by laminating | stacking in order of the anticorrosive coating film and a hydrolysis-proof antifouling coating film from the said substrate side to the base material surface,
An epoxy resin (A), a solid thermoplastic resin (B) and an amine curing agent (C),
The solid thermoplastic resin (B) is solid at room temperature,
The epoxy resin anticorrosive coating composition whose content of the said solid thermoplastic resin (B) is 50 mass parts or more and 100 mass parts or less with respect to 100 mass parts of solid content of the said epoxy resin (A). The method of claim 1,
The epoxy resin anticorrosive coating composition wherein the epoxy resin (A) is one or two or more selected from the group consisting of bisphenol A, bisphenol AD and bisphenol F. The method of claim 1,
Furthermore, the epoxy resin type anticorrosive coating composition which optionally contains a silane coupling agent, When it does not contain a silane coupling agent, the reaction ratio represented by following formula (1), and the silane couple which have reactivity with the said amine-type hardening | curing agent (C) When it contains a ring agent, when it contains the reaction ratio represented by following formula (2), and the silane coupling agent reactive with the said epoxy resin (A), the reaction ratio represented by following formula (3) is respectively 0.3- 0.8 epoxy resin anticorrosive coating composition.

The method of claim 1,
Furthermore, the epoxy resin type anticorrosive coating composition containing pigment (E). The method of claim 4, wherein
The epoxy resin anticorrosive coating composition whose pigment volume concentration (PVC) represented by following formula (4) is 25-50%.

The method of claim 1,
Epoxy resin-based anticorrosive coating composition, characterized in that the solid thermoplastic resin (B) comprises at least one member selected from the group consisting of acrylic resins and vinyl chloride resins. The method of claim 6,
Epoxy resin-based anticorrosive coating composition, characterized in that the vinyl chloride-based resin is a vinyl chloride / vinyl isobutyl ether copolymer. The method of claim 1,
An epoxy resin anticorrosive coating composition further comprising a tertiary amine as a curing accelerator (D). The method of claim 1,
Furthermore, the epoxy resin type anticorrosive coating composition containing an adhesion promoter (F). The method of claim 9,
Epoxy resin-based anticorrosive coating composition, characterized in that the adhesion enhancer (F) is a silane coupling agent. The method of claim 10,
The epoxy resin anticorrosive coating composition wherein the silane coupling agent is γ-glycidoxypropyltrimethoxysilane. delete As an epoxy resin anticorrosive coating film used as the said anticorrosive coating film of the laminated antifouling coating film provided by laminating | stacking on the surface of a base material from the said base material in order of an anticorrosive coating film,
The epoxy resin anticorrosive coating film which is a hardened | cured material of the epoxy resin anticorrosive coating composition in any one of Claims 1-11. As an epoxy resin type anticorrosive coating film used as said anticorrosive coating film of the laminated antifouling coating film provided by laminating | stacking on the surface of a base material from the said base material in order of an anticorrosive coating film and a hydrolysis-proof antifouling coating film,
It is made by containing the matrix which contains hardened | cured epoxy resin and solid thermoplastic resin (B),
The solid thermoplastic resin (B) is solid at room temperature,
The epoxy resin anticorrosive coating film whose content of the said solid thermoplastic resin (B) is 7-80 mass%. The method of claim 14,
Furthermore, the epoxy resin type anticorrosive coating film containing an epoxy resin (A). As a method of manufacturing the epoxy resin anticorrosive coating film used as said anticorrosion coating film of the laminated antifouling coating film which is provided by laminating | stacking on the base material surface from the said base material in order of an anticorrosive coating film, an antifouling coating film,
The manufacturing method of the epoxy resin anticorrosive coating film containing the process of hardening the film | membrane which consists of an epoxy resin anticorrosive coating composition in any one of Claims 1-11. A laminated antifouling coating film formed by laminating an order of an anticorrosive coating film and an antifouling coating film on a surface of a substrate from the substrate side, wherein the anticorrosive coating film is made of a cured product of the epoxy resin anticorrosive coating composition according to any one of claims 1 to 11. The laminated antifouling coating film which is a film or the epoxy resin anticorrosive coating film of Claim 14 or 15. delete As a manufacturing method of the laminated antifouling coating film laminated | stacked and provided in the order of an anticorrosive coating film and an antifouling coating film from the said base material side to the base material surface,
The process of forming the film which consists of hardened | cured material of the epoxy resin anticorrosive coating composition of any one of Claims 1-11, or the epoxy resin anticorrosive coating film of Claim 14 or 15, and the said epoxy resin anticorrosive coating film A method of manufacturing a laminated antifouling coating film comprising the step of forming the antifouling coating film on the surface of the substrate. The antifouling material formed by laminating | stacking the laminated antifouling coating film of Claim 17 on the surface of a base material so that it may become the order of the said anticorrosive coating film and the said antifouling coating film from the base material side. The method of claim 20,
Antifouling material in contact with sea or fresh water. The method of claim 21,
An antifouling material wherein the substrate is at least one selected from the group consisting of ships, offshore structures and land structures. The manufacturing method of the antifouling material containing the process of forming the laminated antifouling coating film of Claim 17 on the base material surface.