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WO2013140953A1 - Water-based epoxy resin paint composition, anticorrosive painting method, and painted body - Google Patents

Water-based epoxy resin paint composition, anticorrosive painting method, and painted body Download PDF

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Publication number
WO2013140953A1
WO2013140953A1 PCT/JP2013/054770 JP2013054770W WO2013140953A1 WO 2013140953 A1 WO2013140953 A1 WO 2013140953A1 JP 2013054770 W JP2013054770 W JP 2013054770W WO 2013140953 A1 WO2013140953 A1 WO 2013140953A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
coating
water
paint
anticorrosion
Prior art date
Application number
PCT/JP2013/054770
Other languages
French (fr)
Japanese (ja)
Inventor
基弘 山本
秀二 佐野
健一郎 山内
誠 甲斐上
勝也 坂井
千栄 植木
Original Assignee
大日本塗料株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012067704A external-priority patent/JP5296899B1/en
Priority claimed from JP2012070092A external-priority patent/JP5273752B1/en
Priority claimed from JP2012073640A external-priority patent/JP5246977B1/en
Application filed by 大日本塗料株式会社 filed Critical 大日本塗料株式会社
Priority to CN201380011848.8A priority Critical patent/CN104136559A/en
Publication of WO2013140953A1 publication Critical patent/WO2013140953A1/en
Priority to PH12014501710A priority patent/PH12014501710A1/en
Priority to HK15102751.8A priority patent/HK1202301A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2504/00—Epoxy polymers

Definitions

  • the present invention relates to an aqueous epoxy resin coating composition, an anticorrosion coating method, and a coated body, and more particularly to an aqueous epoxy resin coating composition having excellent anticorrosion properties.
  • Patent Document 1 proposes an aqueous anticorrosive paint containing an epoxy resin emulsion and an anticorrosive coating method for applying the aqueous anticorrosive paint on a substrate surface.
  • the water-based anticorrosive paint described in JP-A-2009-149791 cannot be applied to a desired thickness unless the viscosity is appropriate, or a smooth coating film cannot be formed.
  • There have been practical problems such that a thin portion is formed in a part of the coating film and the expected anticorrosive property cannot be obtained.
  • corrosion protection coating various onshore steel structures such as bridges, plants and tanks and marine steel structures have been coated for corrosion protection (hereinafter also referred to as corrosion protection coating).
  • an undercoat paint is applied for the purpose of imparting anticorrosion and rust prevention functions to an object to be coated
  • a topcoat paint having excellent weather resistance is applied for the purpose of maintaining the aesthetic appearance of the object to be coated.
  • an organic solvent-based paint for any paint.
  • Patent Document 2 proposes an aqueous coating composition for anticorrosion coating containing an epoxy resin.
  • the aqueous coating composition described in JP-A-2009-212256 is applied as an undercoat, and the undercoat and overcoat are provided by the anticorrosion coating system as described above.
  • the durability such as weather resistance and corrosion resistance expected for the composite coating film cannot be obtained depending on the type of the top coating material.
  • Patent Document 3 proposes a water-based anticorrosion coating system in which all paints used are water-based paints. In this case, depending on the ultraviolet transmittance of the top-coat paint. Due to the deterioration over time, there was a problem that delamination occurred, for example, delamination between the undercoat film and the topcoat film.
  • the zinc rich paint is generally an inorganic zinc rich paint using an alkyl silicate as a vehicle and an organic zinc rich paint using an epoxy resin as a vehicle, both of which are solvent-based zinc rich paints using an organic solvent. .
  • Patent Document 3 proposes an anticorrosion coating method using an aqueous epoxy resin.
  • the expected anticorrosive property may not be obtained, and when using a water-soluble amine resin as the curing agent, the mixing workability with the main agent is poor, and the pot life is short. There was a problem that painting workability was bad, and there was a problem in practical use.
  • a first object of the present invention is to provide a water-based epoxy resin coating composition that solves the above-mentioned problems of the prior art and is excellent in corrosion resistance.
  • the second object of the present invention is to provide an anticorrosion coating method using such an aqueous epoxy resin coating composition.
  • the third object of the present invention is to solve the above-mentioned problems of the prior art, to improve the mixing workability, to improve the work life and to improve the coating workability, and to the corrosion resistance and impact resistance of the coating film.
  • An object of the present invention is to provide an excellent aqueous epoxy resin coating composition and anticorrosion coating method.
  • a fourth object of the present invention is to provide an anticorrosion coating method capable of solving the problems of the prior art and imparting excellent weather resistance and corrosion resistance. Moreover, the 5th objective of this invention is to provide the coating body obtained by this anticorrosion coating method.
  • the present inventor has used an epoxy resin emulsion and an amine resin emulsion in an aqueous coating composition, and the viscosity of the aqueous coating composition at a specific shear rate is within a specific range.
  • a water-based epoxy resin coating composition having excellent anticorrosion properties was obtained, and that a smooth coating film could be formed by using the water-based epoxy resin coating composition, thereby completing the present invention. It was.
  • the first aqueous epoxy resin coating composition of the present invention comprises a main agent containing an epoxy resin emulsion and a curing agent containing an amine resin emulsion, and has a viscosity of 1 at a shear rate of 0.1 (1 / s).
  • the viscosity is 0.0 to 500 (Pa ⁇ s, 23 ° C.), and the viscosity at a shear rate of 1000 (1 / s) is 0.010 to 1 (Pa ⁇ s, 23 ° C.).
  • the pH of the main agent is 5 to 9
  • the pH of the aqueous epoxy resin coating composition is 7 to 11.
  • the polyamine resin contained in the amine resin emulsion is an adduct-type modified polyamine resin.
  • the first anticorrosion coating method of the present invention is characterized in that the first water-based epoxy resin coating composition is applied onto a surface to be coated.
  • a coating film is formed on the surface to be coated by coating the first aqueous epoxy resin coating composition on the surface to be coated.
  • An aqueous paint other than the aqueous epoxy resin paint composition is applied onto the film.
  • the present inventor uses an amine resin emulsion as a curing agent, and selects a zinc powder having a specific bulk specific gravity, whereby a solvent-based organic zinc rich paint.
  • the present inventors have found that a water-based organic zinc rich paint having coating workability equivalent to that of the coating film and corrosion resistance of the coating film can be obtained, and the present invention has been completed.
  • the second aqueous epoxy resin coating composition of the present invention comprises a main agent (i) containing an epoxy resin emulsion, a curing agent (ii) containing an amine resin emulsion, zinc powder (iii) and / or a phosphate.
  • An aqueous epoxy resin coating composition containing an anticorrosive pigment (iv) The zinc powder (iii) has a bulk specific gravity measured by a natural drop method of 1.0 or more, and a mass ratio of the zinc powder (iii) is 65% by mass or more per total solid mass, The total mass of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 65 to 95% by mass with respect to the total solid mass, and A mass ratio [(iii) / (iv)] of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 100/0 to 70/30.
  • the third anticorrosion coating method of the present invention is characterized in that the second aqueous epoxy resin coating composition is applied.
  • the present inventor as a result of water-based anticorrosion coating system in which all paints used are water-based paints, a multi-component reaction curing type is used for both the undercoat paint and the topcoat paint.
  • the pigment volume concentration of the top coat (Pigment Volume Concentration; hereinafter also referred to as PVC) is lower than the PVC of the base coat, and the UV transmittance of the top coat is controlled within a specific range.
  • PVC Pigment Volume Concentration
  • the present inventors have found that excellent weather resistance equivalent to that of an anticorrosion coating system in which an organic solvent-based paint has been used (that is, an organic solvent-based anticorrosion coating system) can be imparted, and the present invention has been completed.
  • an undercoat is formed by applying a water-based epoxy resin undercoat on the surface to be coated, and then an overcoat is applied by applying the overcoat onto the undercoat.
  • An anticorrosion coating method for forming a coating film characterized by satisfying the following requirements a) to c). a) Both the water-based epoxy resin base coat and the water-based top coat are multi-component reaction curable. b) The water-based top coating has a lower pigment volume concentration than the water-based epoxy resin base coating. c) The top coat film has an ultraviolet transmittance of 0.2% or less.
  • a multi-component reaction curing type water-based intermediate coating material selected from a water-based epoxy resin coating and a water-based urethane resin coating is applied to the undercoat.
  • An intermediate coating film is formed by coating on the coating film.
  • the surface to be coated is subjected to a treatment selected from zinc rich paint treatment, galvanization treatment and metal spraying to form an anticorrosion base.
  • the surface to be coated is the surface of an old paint film.
  • the “old coating film” means a coating film that is formed in advance before the aqueous epoxy resin primer coating is applied in the aqueous anticorrosion coating method of the present invention.
  • the coated body of the present invention is characterized in that a composite coating film is formed on the surface to be coated by the water-based anticorrosion coating method described above.
  • the “composite coating film” refers to a coating film provided with at least a base coating film and a top coating film, and may include an intermediate coating film between the base coating film and the top coating film.
  • an epoxy resin emulsion and an amine resin emulsion are used in the aqueous coating composition, and the viscosity of the coating composition at a specific shear rate is adjusted within a specific range.
  • operativity and anticorrosion property can be provided.
  • a smooth coating film can be formed by coating this aqueous epoxy resin coating composition on the surface to be coated.
  • the main agent and the curing agent can be easily mixed, the pot life is practically long, and the coating workability is high. And an anticorrosion coating composition using the aqueous anticorrosion coating composition, and an anticorrosion coating method using the aqueous anticorrosion coating composition.
  • a multi-component reaction-curable aqueous paint is used for both the undercoat paint and the topcoat paint,
  • the PVC of the top coat lower than the PVC of the base coat and further controlling the ultraviolet transmittance of the top coat within a specific range, excellent weather resistance and corrosion resistance can be imparted.
  • the coating body excellent in a weather resistance and corrosion resistance can be provided by this anticorrosion coating method.
  • the first aqueous epoxy resin coating composition of the present invention comprises a main agent containing an epoxy resin emulsion and a curing agent containing an amine resin emulsion, and has a viscosity at a shear rate of 0.1 (1 / s) of 1.0. It is characterized in that the viscosity at a shear rate of 1000 (1 / s) is 0.010 to 1 (Pa ⁇ s, 23 ° C.).
  • the epoxy resin emulsion and the amine resin emulsion are used in combination, and the viscosity of the aqueous epoxy resin coating composition is within the above specified range.
  • a smooth coating film having excellent anticorrosion properties can be formed.
  • the aqueous epoxy resin coating composition means a coating composition containing an epoxy resin and water.
  • the first aqueous epoxy resin coating composition of the present invention has a viscosity of 1.0 to 500 (Pa ⁇ s, 23 ° C.) at a shear rate of 0.1 (1 / s), and a shear rate of 1000 (1 / s). ) In the range of 0.010 to 1 (Pa ⁇ s, 23 ° C.). The viscosity at a shear rate of 0.1 (1 / s) is less than 1.0 (Pa ⁇ s, 23 ° C.) and the viscosity at a shear rate of 1000 (1 / s) is 0.010 (Pa ⁇ s, 23 ° C.).
  • the viscosity at a shear rate of 0.1 (1 / s) exceeds 500 (Pa ⁇ s, 23 ° C.) and the viscosity at a shear rate of 1000 (1 / s) exceeds 1 (Pa ⁇ s, 23 ° C.). Then, the viscosity becomes too high and the leveling property is deteriorated, so that a portion where the film thickness is partially reduced is formed, and the expected anticorrosive property cannot be obtained.
  • the reason why the viscosity was defined based on two shear rates of 0.1 (1 / s) and 1000 (1 / s) is 0.1 (1 /
  • the shear rate of s) indicates the viscosity of the paint immediately after coating
  • the shear rate of 1000 (1 / s) indicates the viscosity of the paint at the time of painting
  • the viscosity of the paint immediately after coating from the time of painting is sagging and leveling. It is because it correlates with.
  • a method of adjusting the viscosity of the aqueous epoxy resin coating composition of the present invention within the above-specified range for example, a method using a thickener, water or the like can be mentioned.
  • the pH of the main agent is preferably 5 to 9, and the pH of the aqueous epoxy resin coating composition is preferably 7 to 11. If the pH of the main agent and the aqueous epoxy resin coating composition is out of the above specified range, the coating workability may be reduced.
  • the two pH values of the main agent and the aqueous epoxy resin coating composition are specified because the pH of the main agent affects the stability during storage, and the pH of the aqueous epoxy resin coating is determined. This affects the viscosity of the paint.
  • the method etc. which use a pH adjuster etc. are mentioned as a method of adjusting pH of a main ingredient and a water-based epoxy resin coating composition in the above-mentioned specified range.
  • the first aqueous epoxy resin coating composition of the present invention can be obtained by combining a component containing an epoxy resin emulsion and a component containing an amine resin emulsion as a curing agent. In the present invention, this epoxy resin emulsion is used.
  • the component containing is called the main agent.
  • the epoxy resin emulsion means an emulsion in which an epoxy resin is dispersed in an aqueous medium such as water.
  • the epoxy resin constituting the epoxy resin emulsion is not particularly limited as long as it is a resin having at least two epoxy groups in one molecule.
  • it is obtained by reacting a polyhydric alcohol or polyhydric phenol with a halohydrin.
  • Specific examples include bisphenol A type epoxy resins, halogenated bisphenol A type epoxy resins, novolac type epoxy resins, polyglycol type epoxy resins, bisphenol F type epoxy resins, epoxidized oil, and 1,6-hexane.
  • Examples include diol diglycidyl ether and neopentyl glycol diglycidyl ether.
  • bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoints of mechanical durability and corrosion resistance of the coating film, adhesion to the surface to be coated (for example, the surface of the substrate), and the like.
  • these epoxy resins may be used independently and may be used in combination of 2 or more type.
  • the epoxy resin is a resin having at least two epoxy groups in one molecule, and from the viewpoints of finish property, curability, corrosion resistance, etc. of the formed coating film, the epoxy equivalent is usually 100 to 1,000 g / eq is preferable, 160 to 980 g / eq is more preferable, and 160 to 550 g / eq is still more preferable. If the epoxy equivalent is less than 100 g / eq, sufficient film properties may not be obtained. On the other hand, if the epoxy equivalent is greater than 1,000 g / eq, the leveling property at normal temperature is lowered and uniform coating is not possible. A film may not be obtained.
  • the epoxy resin emulsion is not particularly limited, but is prepared by emulsifying the epoxy resin in an aqueous medium such as water by a normal forced emulsification method (a method using an emulsifier and a high-speed stirrer).
  • a normal forced emulsification method a method using an emulsifier and a high-speed stirrer.
  • the emulsifier for example, a polyoxyethylene alkylphenol ether-based nonionic surfactant, a polyether such as a polyoxyethylene / polyoxypropylene block copolymer, or at least the nonionic surfactant and the polyether Examples include adducts of one and a diisocyanate compound. These emulsifiers may be used alone or as a blend of two or more.
  • Epourgeon EA1, 2, 3, 7, 12, 20, 55 and HD2 Nippon NSC company make, brand name
  • Aquatote 205, 510, 3520, 3540, 35201 , 5003, and 5520 (trade name, manufactured by Toto Resin Chemical Co., Ltd.); Yuka Resin KE-002, KE-116, E-1022, KE-301C (trade name, manufactured by Yoshimura Oil Chemical Co., Ltd.); and EM-101-50 ( Adeka's product name).
  • the main agent can contain other compounding agents in addition to the epoxy resin emulsion.
  • the main agent can contain a thickener in order to adjust the viscosity of the main agent and the aqueous epoxy resin coating composition.
  • the thickener is not particularly limited, and known thickeners can be used. Specific examples include inorganic thickeners such as silicate, metal silicate, montmorillonite, organic montmorillonite, colloidal alumina, and the like.
  • Polyacrylic acid thickeners such as polyacrylic acid soda and polyacrylic acid- (meth) acrylic acid ester copolymers; “UH-814N”, “UH-462”, “UH-420”, “UH -472 ",” UH-540 "(above, manufactured by Adeka),” SN thickener 612 ",” SN thickener 621N “,” SN thickener 625N “,” SN thickener 627N “(above, manufactured by San Nopco) Associative thickeners; Fibrin derivative thickeners such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; casein, casein Protein thickeners such as soda and ammonium caseinate; Alginic acid thickeners such as sodium alginate; Polyvinyl thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylbenzyl ether copolymers; Pluronic polyethers and polyether dialkyls Polyether thickeners such
  • the main agent may contain a pH adjuster.
  • the pH adjuster can be used as long as it is generally used in paints, and various nitrogen-containing basic compounds, inorganic acids, organic acids and the like that have been known as neutralizers can be used without any particular limitation.
  • alkylamines such as trimethylamine, triethylamine, tributylamine, triethanolamine, dimethylethanolamine, diethanolamine, monoethanolamine, N-methyldiethanolamine, N, N—
  • examples thereof include alcohol amines such as dimethylethanolamine and ethylpropanolamine, and volatile nitrogen-containing basic compounds such as morpholine and ammonia.
  • examples of inorganic acids include hydrochloric acid, sulfuric acid, and nitric acid
  • organic acids include formic acid and acetic acid.
  • the main agent may contain a commonly used diluent such as a reactive diluent or a non-reactive diluent for the purpose of improving the flexibility of the coating film.
  • a commonly used diluent such as a reactive diluent or a non-reactive diluent for the purpose of improving the flexibility of the coating film.
  • reactive diluents include Cardura E10 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Neotote S (trade name, manufactured by Toto Kasei Co., Ltd.), and Adeka Glycilol ED502 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.).
  • Monofunctional epoxy resins such as
  • examples of the non-reactive diluent include petroleum resins such as Nicanol LLL and coumarone resins. These diluents may be used alone or in combination of two or more.
  • the main agent can contain other coloring pigments, rust preventive pigments, extender pigments, and the like that are generally used in other paints.
  • color pigments, rust preventive pigments and extender pigments include titanium oxide, bengara, yellow iron oxide, carbon black, aluminum tripolyphosphate, zinc phosphate, barium metaborate, calcium carbonate, barium sulfate, talc, clay, mica , Inorganic pigments such as alumina, alum, clay, magnesium hydroxide, and magnesium oxide, phthalocyanine blue, phthalocyanine green, naphthol red, quinacridone red, benzimidazolone yellow, hansa yellow, benzimidazolone orange, and dioxazine violet And organic pigments. These pigments may be used alone or in combination of two or more.
  • the main agent includes a dispersant, an antifoaming agent, an anti-settling agent, an antifungal agent, an antiseptic, an ultraviolet absorber, a light stabilizer, and the like in order to impart various functions to the aqueous epoxy resin coating composition. You may add suitably. Further, in order to promote fusion between the epoxy resin constituting the epoxy resin emulsion and the polyamine resin constituting the amine resin emulsion, an organic solvent can be blended with the main agent.
  • organic solvent examples include ethylene glycol mono n-butyl ether, ethylene glycol mono i-butyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono i-propyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono i-butyl ether, diethylene glycol.
  • Mono n-propyl ether diethylene glycol mono i-propyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol mono i-butyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono i-propyl ether, diethylene glycol diethyl ether
  • glycol ethers such as diethylene glycol dibutyl ether , 2,2,4-trimethyl pentanediol mono-isobutyrate, and 2,2,4-trimethyl pentanediol diisobutyrate and the like. These organic solvents may be used alone or in combination of two or more.
  • the said main ingredient can be prepared by mixing the said epoxy resin emulsion and the various components suitably selected as needed.
  • the 1st water-based epoxy resin coating composition of this invention needs to contain the hardening
  • curing agent containing an amine resin emulsion as a hardening
  • the amine resin emulsion means an emulsion in which the amine resin is dispersed in an aqueous medium such as water, and the amine resin in the present invention contains two or more amino groups in one molecule. Refers to polyamine resin.
  • polyamine resin examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triaminopropane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, and 1,3-bisaminomethylcyclohexane.
  • Aliphatic polyamines such as phenylenediamine, metaxylylenediamine, paraxylylenediamine, and diaminodiphenylmethane; such as polyoxyethylenediamine, polyoxypropylenediamine, triethyleneglycoldiamine, and tripropyleneglycoldiamine
  • aromatic polyamines such as phenylenediamine, metaxylylenediamine, paraxylylenediamine, and diaminodiphenylmethane
  • polyoxyethylenediamine polyoxypropylenediamine
  • triethyleneglycoldiamine triethyleneglycoldiamine
  • tripropyleneglycoldiamine examples include other polyamine compounds and modified polyamine resins obtained by modifying the amino groups of these polyamine resins.
  • modified polyamine resin known methods can be used. Examples of the modification reaction include amidation of an amino group, Mannich reaction of an amino group and a carbonyl compound, addition reaction of an amino group and an epoxy group,
  • a modified polyamine resin in which an epoxy group or the like is added to an amino group is referred to as an adduct type modified polyamine resin
  • an epoxy adduct type modified polyamine resin in which an epoxy group is added to an amino group is preferable from the viewpoint of corrosion resistance.
  • the blending ratio of the curing agent containing the amine resin emulsion constitutes the epoxy resin emulsion contained in the main agent from the viewpoint of the curability and corrosion resistance of the coating film.
  • the active hydrogen of the amine resin constituting the amine resin emulsion is usually in the range of 0.5 to 2.0 equivalents, particularly in the range of 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin. Is preferably within.
  • the curing agent containing the amine resin emulsion includes a compounding agent that can be incorporated into the main agent, for example, a reactive diluent, a non-reactive diluent, a color pigment, an extender pigment, an organic pigment, a thickener, a pH adjuster, You may mix
  • curing agent containing the said amine resin emulsion can be prepared by mixing the said amine resin emulsion and the various components suitably selected as needed.
  • the first aqueous epoxy resin coating composition of the present invention is prepared by using, for example, an apparatus capable of uniformly mixing these components and a curing agent containing the amine resin emulsion, preferably an electric stirrer, etc. It can be prepared by mixing uniformly. Moreover, in order to adjust the viscosity of the aqueous epoxy resin coating composition of the present invention, water may be added after mixing the main agent and the curing agent containing the amine resin emulsion.
  • the first anticorrosion coating method of the present invention is characterized in that the above-mentioned first aqueous epoxy resin coating composition is applied onto the surface to be coated, and the second anticorrosion coating method of the present invention comprises the above-mentioned By coating the first aqueous epoxy resin coating composition on the surface to be coated, a coating film is formed on the surface to be coated, and further, an aqueous solution other than the aqueous epoxy resin coating composition is formed on the coating film. It is characterized by painting a paint. According to the first and second anticorrosion coating methods of the present invention, since the coating film is formed using the first aqueous epoxy resin coating composition, the workability and the anticorrosion property are excellent.
  • the film thickness (dry film thickness) of the coating film formed after drying the aqueous epoxy resin coating composition is usually in the range of 20 to 250 ⁇ m, It is preferably in the range of 30 to 150 ⁇ m. Moreover, it does not restrict
  • the coating environment is not particularly limited, but it is desirable to avoid an extremely low temperature environment such as 0 ° C. or lower or a high temperature environment where the temperature of the surface to be coated is 80 ° C. or higher.
  • the drying time of the aqueous epoxy resin coating composition varies depending on the curing environment conditions such as air temperature and humidity. For example, if the temperature is 23 ° C. and the relative humidity is 50%, a drying time of about 7 days is desirable. However, when the coating composition of the next step is applied repeatedly to form a laminated coating film, the coating is applied without any problem. be able to. In addition, if the formed laminated coating film can exhibit original performance, it will not be limited to this.
  • the surface to be coated is not particularly limited as long as it is a surface that needs to be imparted with anticorrosion, but the surface of a structure such as a bridge or a plant, More specifically, the base material surface which consists of materials, such as a railroad bridge, a road bridge, a gas tank, an oil tank, and carbon steel, such as a steel tower, is mentioned.
  • the first water-based epoxy resin coating composition may be directly coated on the surface to be coated, or the zinc rich paint treatment, galvanization is performed on the surface to be coated.
  • a base having a certain degree of corrosion resistance may be prepared by performing treatment, metal spraying, etc., and then coated on the base. Furthermore, when the state of the aged coating film (old coating film) is healthy, it is possible to paint on it.
  • the first aqueous epoxy resin coating composition can be applied a plurality of times depending on the required anticorrosion performance.
  • the second anticorrosive coating method of the present invention it is necessary to apply a water-based paint other than the water-based epoxy resin paint composition onto the coating film formed of the first water-based epoxy resin paint composition.
  • a top coating having excellent weather resistance as the water-based paint, anticorrosion can be maintained for a long time.
  • various water-based paints can be used as the water-based paint other than the first water-based epoxy resin paint composition, and it is also possible to reapply while changing the type of the water-based paint. For example, before applying the above-mentioned top coat, it is also possible to apply the intermediate coat on the coating film made of the first aqueous epoxy resin paint composition.
  • examples of the intermediate coating include an epoxy resin-based intermediate coating, a modified epoxy resin-based intermediate coating, and a urethane resin-based intermediate coating.
  • examples of the top coating include acrylic resin-based top coating, urethane resin-based top coating, silicone resin-based top coating, and fluororesin-based top coating.
  • the second aqueous epoxy resin coating composition of the present invention comprises a main agent (i) containing an epoxy resin emulsion, a curing agent (ii) containing an amine resin emulsion, a zinc powder (iii) and / or a phosphate-based antibacterial agent.
  • the zinc powder (iii) has a bulk specific gravity measured by a natural drop method of 1.0 or more, and a mass ratio of the zinc powder (iii) is 65% by mass or more per total solid mass,
  • the total mass of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 65 to 95% by mass with respect to the total solid mass
  • a mass ratio [(iii) / (iv)] of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 100/0 to 70/30.
  • the second aqueous epoxy resin coating composition is also referred to as an aqueous anticorrosive coating composition.
  • the second aqueous epoxy resin coating composition (aqueous anticorrosive coating composition) of the present invention comprises a component containing an epoxy resin emulsion, a component containing an amine resin emulsion as a curing agent, a zinc powder and / or a phosphate system. Although obtained by combining with an antirust pigment, in this invention, the component containing this epoxy resin emulsion is called main ingredient.
  • the epoxy resin emulsion means an emulsion in which an epoxy resin is dispersed in an aqueous medium such as water.
  • the “main agent (i) containing an epoxy resin emulsion” used in the second aqueous epoxy resin coating composition of the present invention is the same as that described in the first aqueous epoxy resin coating composition described above. it can. However, in the “main agent (i) containing an epoxy resin emulsion” used in the second aqueous epoxy resin coating composition of the present invention, zinc powder and phosphate-based rust preventive pigment are excluded.
  • the epoxy resin constituting the epoxy resin emulsion is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.
  • the epoxy resin constituting the epoxy resin emulsion preferably has an epoxy equivalent of 160 to 980 g / eq.
  • the epoxy resin constituting the epoxy resin emulsion preferably has a number average molecular weight of 300 to 10,000, more preferably 1,000 to 4,000.
  • the 2nd water-based epoxy resin coating composition of this invention needs to contain the hardening
  • curing agent containing an amine resin emulsion
  • curing agent containing an amine resin emulsion
  • curing agent containing an amine resin emulsion
  • curing agent containing an amine resin emulsion
  • curing agent containing an amine resin emulsion
  • curing agent containing an amine resin emulsion as a hardening
  • the amine resin emulsion means an emulsion in which the amine resin is dispersed in an aqueous medium such as water, and the amine resin in the present invention contains two or more amino groups in one molecule.
  • the “curing agent (ii) containing an amine resin emulsion” used in the second aqueous epoxy resin coating composition of the present invention is the same as that described in the first aqueous epoxy resin coating composition.
  • the 2nd water-based epoxy resin coating composition of this invention needs to contain zinc powder.
  • zinc which has a higher ionization tendency than iron, acts as an anode, and a corrosion-proof current flows from zinc to iron.
  • content of zinc powder (iii) needs to be 65 mass% or more per total solid mass, in order to ensure the corrosion resistance of a coating film.
  • the zinc powder (iii) has a bulk specific gravity of 1.0 or more as measured by the natural drop method. Necessary, and those of 2.0 or more are particularly preferable.
  • the method for calculating the bulk specific gravity of the zinc powder by the natural dropping method is to measure 100 g (m) of zinc powder with an upper pan balance and gradually drop it onto a 200 mL graduated cylinder (minimum scale unit: 2 mL) using a funnel. Gently tilt the graduated cylinder and carefully level the uppermost sample surface without consolidating it, and then read the bulk volume (V0) at that time to the minimum scale unit. Then, bulk specific gravity (g / mL) was computed by m / V0. For the bulk specific gravity in the present invention, an average value of five measurements was adopted.
  • the 2nd water-based epoxy resin coating composition of this invention contains a phosphate type
  • examples of the phosphate-based rust preventive pigment include aluminum phosphate, aluminum tripolyphosphate, zinc phosphate, zinc phosphite, potassium phosphite, Examples thereof include calcium phosphate, aluminum phosphite, zinc calcium phosphate, zinc aluminum phosphate, zinc phosphomolybdate, aluminum phosphomolybdate, magnesium phosphate, and vanadic acid / phosphoric acid mixed pigment.
  • aluminum phosphate and zinc phosphate are preferable from the viewpoint of excellent dispersibility and corrosion resistance.
  • the total mass of the zinc powder (iii) and the phosphate-based anticorrosive pigment (iv) is in the range of 65 to 95% by mass based on the total solid content mass. There must be.
  • the total mass of the phosphate-based anticorrosive pigment (iv) and the zinc powder (iii) is less than 65% by mass with respect to the total solid mass, the anticorrosive property of the coating film cannot be ensured.
  • it exceeds 95 mass% mixing workability
  • the mass ratio [(iii) / (iv)] of the zinc powder (iii) and the phosphate-based anticorrosive pigment (iv) is 100/0. Must be in the range of ⁇ 70/30. When it is out of this range, there is a possibility that the corrosion resistance of the coating film cannot be sufficiently secured, so that the mixing workability is lowered or the coating surface is easily cracked by impact.
  • the second aqueous epoxy resin coating composition of the present invention comprises a main agent (i) containing an epoxy resin emulsion, a curing agent (ii) containing an amine resin emulsion, a zinc powder (iii) and / or a phosphate-based antibacterial agent.
  • a rust pigment iv
  • it can be prepared according to a conventional method. For example, when the phosphate-based anticorrosive pigment (iv) is mixed with the main agent (i) or the curing agent (ii), the phosphate-based emulsion is directly added to the emulsion constituting the main agent (i) or the curing agent (ii).
  • the antirust pigment (iv) is mixed and dispersed with an electric stirrer or the like, or after the phosphate-based antirust pigment (iv) is dispersed in water using a surfactant, the main agent (i ) Or a method of adding a curing agent (ii).
  • the phosphate-based rust preventive pigment (iv) is mixed with the zinc powder (iii), for example, the zinc powder (iii) and the phosphate-based rust preventive pigment (iv) are added to a ball mill and mixed. A method is mentioned.
  • the main component (i) containing the epoxy resin emulsion and the curing agent (ii) containing the amine resin emulsion may be mixed in advance, and then zinc powder (iii) may be mixed, or the main component (i) containing the epoxy resin emulsion and After mixing the zinc powder (iii), a curing agent (ii) containing an amine resin emulsion may be mixed.
  • a curing agent (ii) containing an amine resin emulsion may be mixed.
  • the mixing method it is best to use an electric stirrer, but an apparatus capable of uniformly mixing the paint can be appropriately selected and used.
  • the third anticorrosion coating method of the present invention is characterized in that the above-mentioned second aqueous epoxy resin coating composition is applied.
  • the substrate to which the third anticorrosion coating method of the present invention is applied is not particularly limited as long as it requires anticorrosion, such as carbon steel.
  • the water-based anticorrosive coating composition according to the present invention is applied to the substrate surface so that the dry film thickness is usually in the range of 10 to 200 ⁇ m, preferably 15 to 150 ⁇ m.
  • the coating can be performed by a coating means known per se, for example, air spray, airless spray, brush coating or roller coating.
  • Coating is not limited to one-time coating, and may be divided into multiple coatings as long as the total film thickness is within the range of 10 to 200 ⁇ m.
  • the dry film thickness is less than 10 ⁇ m, the anticorrosion property is not sufficient, which is not preferable.
  • the dry film thickness is greater than 200 ⁇ m, there is a risk of causing problems such as poor adhesion over time.
  • the coating environment is not particularly limited, but it is desirable to avoid an extremely low temperature environment such as 0 ° C. or lower or a high temperature environment where the temperature of the object to be coated is 80 ° C. or higher.
  • the drying time of the coating film depends on the curing environment conditions such as temperature and humidity. For example, if the temperature is 23 ° C. and the relative humidity is 50%, a drying time of about 7 days is desirable. However, when the next coating material is applied repeatedly to form a laminated coating film, it can be applied without any trouble. it can. If the formed laminated coating film can exhibit original performance, it will not be restricted to this.
  • the water-based anticorrosive coating composition according to the present invention is excellent in anticorrosion properties, adhesion to a base material, and the like, it can be used as a primary rust preventive primer or an anticorrosion base.
  • the base coating is formed by coating the base surface with the aqueous anticorrosive coating composition according to the present invention, and then an undercoat is applied, and a topcoat excellent in weather resistance is applied. By doing, anticorrosion property can be maintained over a long period of time.
  • an intermediate paint can be applied between the undercoat paint and the topcoat paint.
  • undercoat paint examples include an epoxy resin-based undercoat paint, a modified epoxy resin-based undercoat paint, and a urethane resin-based undercoat paint.
  • intermediate coating material examples include epoxy resin-based intermediate coating materials, modified epoxy resin-based intermediate coating materials, and urethane resin-based intermediate coating materials.
  • top coating examples include acrylic resin-based top coating, urethane resin-based top coating, silicone resin-based top coating, and fluororesin-based top coating.
  • a conventional solvent-based paint can be obtained by further recoating an aqueous paint other than the aqueous anticorrosive paint composition on a coating film formed by applying the aqueous anticorrosive paint composition according to the present invention to the substrate surface.
  • the amount of organic solvent used can be greatly reduced. Accordingly, the substrate can be protected from corrosion for a long time while maintaining consideration for the environment, and the aesthetic appearance can be maintained.
  • a base coating film is formed by applying a water-based epoxy resin base coating on the surface to be coated, and then a water base top coating is applied on the base coating.
  • the water-based epoxy resin base coat and the water-based top coat are both multi-component reaction curable (requirement a), and the water-based top coat is more than the water-based epoxy resin base coat.
  • the pigment volume concentration (PVC) is low (requirement b), and the top coat film satisfies the three requirements of an ultraviolet transmittance of 0.2% or less (requirement c).
  • the water-based anticorrosion coating method refers to a coating method using a water-based paint among the coating methods aimed at imparting anticorrosion properties.
  • the fourth anticorrosion coating method is referred to as the water-based anticorrosion coating. Also called a method.
  • the fourth anticorrosion coating method (aqueous anticorrosion coating method) of the present invention requires that both the water-based epoxy resin base coat and the water-based top coat are of a multi-component reaction curable type. If these two types of coatings are multi-component reaction curable coatings, a dense cured coating can be obtained, and the effect of shielding corrosion factors will be enhanced. In the case of top coatings, deterioration from ultraviolet rays and the like will be delayed. I can do it.
  • the multi-component reaction curable paint refers to a combination of a main agent containing a resin used as a base material of a coating film and a curing agent containing a component having reactivity with the resin.
  • the water-based top coating material needs to have a lower PVC than the water-based epoxy resin base coating material.
  • the PVC of the water-based top coat is lower than that of the water-based epoxy resin base coat, the followability of the top coat with respect to the base coat is improved, thereby increasing the adhesion between layers over time. Therefore, the weather resistance and corrosion resistance of the composite coating film are improved.
  • the PVC of the water-based top coating is higher than that of the water-based epoxy resin base coating, cracking or peeling may occur in the coating due to deterioration over time.
  • the pigment volume concentration in this invention refers to the ratio (volume%) of the pigment which occupies for paint solid content.
  • the top coat film needs to have an ultraviolet transmittance of 0.2% or less.
  • the UV transmittance of the top coat film exceeds 0.2%, the UV light transmitted through the top coat film causes the surface of the coat film such as the undercoat film or the intermediate coat film to deteriorate, resulting in delamination.
  • the ultraviolet-ray transmittance of the coating film in this invention refers to the transmittance
  • a step of forming a base coating film by applying a water-based epoxy resin base coating on the surface to be coated is performed.
  • an epoxy resin as the base material of the undercoat coating film, excellent anticorrosion properties can be obtained.
  • a water-based epoxy resin undercoat paint means an undercoat paint containing an epoxy resin and water.
  • the surface to be coated is not particularly limited as long as it is a surface that needs to be provided with anticorrosion properties, but more specifically, the surface of a structure such as a bridge or a plant, more specifically, a railway bridge, a road bridge, a gas tank. And base material surfaces made of carbon steel materials such as oil tanks and steel towers.
  • the water-based epoxy resin base coating is not particularly limited except that it is a multi-component reaction curable type and has a higher PVC than the water-based top coating, but is a curing containing an epoxy resin emulsion and an amine resin emulsion. It is preferable to contain an agent.
  • the water-based epoxy resin primer can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating.
  • the epoxy resin emulsion is an emulsion in which the epoxy resin is dispersed in an aqueous medium such as water, and is not particularly limited. It is prepared by emulsifying the epoxy resin in an aqueous medium such as water by a method using a high-speed stirrer or the like.
  • the epoxy resin constituting the epoxy resin emulsion is not particularly limited as long as it is a resin having at least two epoxy groups in one molecule.
  • it is obtained by reacting a polyhydric alcohol or polyhydric phenol with a halohydrin.
  • Specific examples include bisphenol A type epoxy resins, halogenated bisphenol A type epoxy resins, novolac type epoxy resins, polyglycol type epoxy resins, bisphenol F type epoxy resins, epoxidized oil, and 1,6-hexane.
  • Examples include diol diglycidyl ether and neopentyl glycol diglycidyl ether.
  • bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoints of mechanical durability and corrosion resistance of the coating film, adhesion to the surface to be coated (for example, the surface of the substrate), and the like.
  • these epoxy resins may be used independently and may be used in combination of 2 or more type.
  • Epourgeon EA1, 2, 3, 7, 12, 20, 55 and HD2 Nippon NSC company make, brand name
  • Aquatote 205, 510, 3520, 3540, 35201 , 5003, and 5520 (trade name, manufactured by Toto Resin Chemical Co., Ltd.); Yuka Resin KE-002, KE-116, E-1022, KE-301C (trade name, manufactured by Yoshimura Oil Chemical Co., Ltd.); and EM-101-50 ( Adeka's product name).
  • the main agent may contain a commonly used diluent such as a reactive diluent and a non-reactive diluent for the purpose of improving the flexibility of the coating film.
  • a commonly used diluent such as Cardura E10 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Neotote S (trade name, manufactured by Toto Kasei Co., Ltd.), and Adeka Glycilol ED502 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.).
  • Monofunctional epoxy resins such as
  • examples of the non-reactive diluent include petroleum resins such as Nicanol LLL and coumarone resins. These diluents may be used alone or in combination of two or more.
  • the said main ingredient can be prepared by mixing the said epoxy resin emulsion and the various components suitably selected as needed.
  • the amine resin emulsion constituting the curing agent is an emulsion in which an amine resin is dispersed in an aqueous medium such as water.
  • the amine resin means two or more amino groups in one molecule.
  • a polyamine resin containing Examples of the polyamine resin include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triaminopropane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, and 1,3-bisaminomethylcyclohexane.
  • Aliphatic polyamines such as phenylenediamine, metaxylylenediamine, paraxylylenediamine, and diaminodiphenylmethane; such as polyoxyethylenediamine, polyoxypropylenediamine, triethyleneglycoldiamine, and tripropyleneglycoldiamine
  • aromatic polyamines such as phenylenediamine, metaxylylenediamine, paraxylylenediamine, and diaminodiphenylmethane
  • polyoxyethylenediamine polyoxypropylenediamine
  • triethyleneglycoldiamine triethyleneglycoldiamine
  • tripropyleneglycoldiamine examples include other polyamine compounds and modified polyamine resins obtained by modifying the amino groups of these polyamine resins.
  • modified polyamine resin known methods can be used. Examples of the modification reaction include amidation of an amino group, Mannich reaction of an amino group and a carbonyl compound, addition reaction of an amino group and an epoxy group,
  • a modified polyamine resin in which an epoxy group or the like is added to an amino group is referred to as an adduct type modified polyamine resin
  • an epoxy adduct type modified polyamine resin in which an epoxy group is added to an amino group is preferable from the viewpoint of corrosion resistance.
  • curing agent can be prepared by mixing the said amine resin emulsion and the various components suitably selected as needed.
  • the main agent and / or the curing agent may contain other coloring pigments, rust preventive pigments, extender pigments, and the like that are generally used for paints.
  • color pigments, rust preventive pigments and extender pigments include titanium oxide, bengara, yellow iron oxide, carbon black, aluminum tripolyphosphate, zinc phosphate, barium metaborate, calcium carbonate, barium sulfate, talc, clay, mica , Inorganic pigments such as alumina, alum, clay, magnesium hydroxide, and magnesium oxide, phthalocyanine blue, phthalocyanine green, naphthol red, quinacridone red, benzimidazolone yellow, hansa yellow, benzimidazolone orange, and dioxazine violet And organic pigments. These pigments may be used alone or in combination of two or more.
  • the main agent and / or curing agent has a thickener, a dispersant, an antifoaming agent, an anti-settling agent, an antifungal agent, an antiseptic, and an ultraviolet absorber for imparting various functions to the water-based epoxy resin primer. Or a light stabilizer etc. may be added suitably.
  • a light stabilizer etc. may be added suitably.
  • organic solvent examples include ethylene glycol mono n-butyl ether, ethylene glycol mono i-butyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono i-propyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono i-butyl ether, diethylene glycol.
  • Mono n-propyl ether diethylene glycol mono i-propyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol mono i-butyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono i-propyl ether, diethylene glycol diethyl ether
  • glycol ethers such as diethylene glycol dibutyl ether , 2,2,4-trimethyl pentanediol mono-isobutyrate, and 2,2,4-trimethyl pentanediol diisobutyrate and the like. These organic solvents may be used alone or in combination of two or more.
  • the blending ratio of the curing agent containing the amine resin emulsion is the epoxy group 1 of the epoxy resin constituting the epoxy resin emulsion contained in the main agent from the viewpoint of the curability of the coating film and the corrosion resistance. It is preferable that the active hydrogen of the amine resin constituting the amine resin emulsion is usually in the range of 0.5 to 2.0 equivalents with respect to equivalents.
  • the film thickness (dry film thickness) of the undercoat film formed after the application of the water-based epoxy resin undercoat is usually in the range of 20 to 250 ⁇ m, and in the range of 30 to 150 ⁇ m. Is preferably within.
  • the method for applying the water-based epoxy resin primer is not particularly limited, and known coating means such as air spray coating, airless spray coating, brush coating, or roller coating can be used. In addition, it is also possible to use these coating means a plurality of times and repeatedly apply the water-based epoxy resin primer.
  • the coating environment is not particularly limited, but it is desirable to avoid an extremely low temperature environment such as 0 ° C.
  • the drying time of the water-based epoxy resin undercoat varies depending on the curing environment conditions such as temperature and humidity. For example, if the temperature is 23 ° C. and the relative humidity is 50%, a drying time of about 7 days is desirable. However, when the next coating material is applied repeatedly to form a laminated coating film, it can be applied without any trouble. it can. In addition, if the formed laminated coating film can exhibit original performance, it will not be limited to this.
  • a step of forming a topcoat film by applying an aqueous topcoat onto the undercoat film is then performed.
  • the above-mentioned water-based top coating is a multi-component reaction curable type, and is particularly limited as long as the PVC is lower than the water-based epoxy resin base coating and the UV transmittance of the formed top coating is 0.2% or less.
  • water-based urethane resin paints, water-based fluororesin paints and the like are preferable.
  • the aqueous urethane resin paint includes, for example, a main agent containing a dispersion or emulsion in which an acrylic resin having a plurality of hydroxyl groups per molecule is dispersed in an aqueous medium such as water, and one isocyanate per molecule. And a curing agent containing an isocyanate resin having a group or a polyisocyanate resin having a plurality of isocyanate groups in one molecule.
  • the water-based urethane resin coating can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating, and after the coating, a curing reaction is started and a coating film is formed.
  • the water-based fluororesin coating material includes, for example, a main agent containing a dispersion or emulsion in which a fluororesin having a plurality of hydroxyl groups per molecule is dispersed in an aqueous medium such as water, and one isocyanate per molecule. And a curing agent containing an isocyanate resin having a group or a polyisocyanate resin having a plurality of isocyanate groups in one molecule.
  • the aqueous fluororesin coating material can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating, and after the coating, a curing reaction is started and a coating film is formed.
  • Examples of the dispersion or emulsion obtained by dispersing the acrylic resin include Bernock WE-301, WE-304, WE-306, WE-310, and WD-551 (trade name, manufactured by DIC).
  • Examples of the dispersion or emulsion obtained by dispersing the fluororesin include Lumiflon FE-4200, FE-4300, FE-4400, FE-4500 (trade name, manufactured by Asahi Glass Co., Ltd.), and the like.
  • the water-based top coat (specifically, water-based urethane resin paint and water-based fluororesin paint) can be blended with the water-based epoxy resin base coat, for example, coloring pigment, extender pigment, organic pigment, thickener.
  • a dispersant, an antifoaming agent, an anti-settling agent, an antifungal agent, an antiseptic, an ultraviolet absorber, a light stabilizer, an organic solvent and the like may be blended as necessary.
  • the film thickness (dry film thickness) of the top coat film formed after applying the water-based top coat is usually within the range of 10 to 200 ⁇ m, and within the range of 20 to 100 ⁇ m. Preferably there is.
  • the method for applying the water-based top coating is not particularly limited, and known coating means such as air spray coating, airless spray coating, brush coating, or roller coating can be used.
  • the coating is not limited to one time, and the coating may be performed in a plurality of times as long as the total film thickness is in the range of 10 to 200 ⁇ m.
  • the same conditions as those described for the water-based epoxy resin undercoating can be applied to the coating environment and drying time of the water-based top coating.
  • the surface to be coated is preferably subjected to a treatment selected from zinc rich paint treatment, galvanizing treatment and metal spraying to form an anticorrosion base.
  • a treatment selected from zinc rich paint treatment, galvanizing treatment and metal spraying to form an anticorrosion base.
  • a zinc rich paint means the coating material containing high concentration zinc, and the water-based zinc rich paint which uses water as a solvent is suitable.
  • the water-based epoxy resin undercoat paint is applied on the anti-corrosion base.
  • the surface to be coated may be the surface of an old paint film.
  • the water-based epoxy resin primer can be directly applied on the surface of the coating film.
  • a multi-component reaction curing type water-based intermediate coating is applied onto the base coating to form an intermediate coating.
  • the composite coating film in which the intermediate coating film is incorporated between the undercoating film and the top coating film can be expected to have various functions in the intermediate coating film, for example, to improve the finished appearance of the top coating film. Is possible.
  • the water-based top coating composition is applied onto the intermediate coating film.
  • the aqueous intermediate coating is not particularly limited as long as it is a multi-component reaction curable type, but an aqueous epoxy resin coating and an aqueous urethane resin coating are preferable.
  • the above-mentioned water-based epoxy resin undercoat can be used for the water-based epoxy resin paint
  • the above-mentioned water-based urethane resin paint that can be used as a water-based top coat can be used for the water-based urethane resin paint.
  • the coated body of the present invention is characterized in that a composite coating film is formed on the surface to be coated by the above-described fourth anticorrosion coating method (aqueous anticorrosion coating method).
  • a composite coating film such as a structure such as a bridge or a plant, is excellent in weather resistance and corrosion resistance.
  • ⁇ first water-based epoxy resin coating composition and first and second anticorrosion coating methods >> ⁇ Production Example 1-1> 11 parts of ion-exchanged water is added to the mixer, and 1 part of the dispersant, 0.3 part of the antifoaming agent, 10 parts of titanium oxide, 7 parts of aluminum tripolyphosphate, 20 parts of precipitated barium sulfate, and kaolin clay 8 Portions were gradually added under a stirring environment, and after completion of the addition, mixing was performed until the particle size became 50 ⁇ m or less. Next, 40 parts of the epoxy resin emulsion and 4 parts of ethylene glycol mono-n-butyl ether were gradually added to the mixer in a stirring environment, followed by stirring for 10 minutes to prepare the main agent 1-1.
  • Tables 1 and 2 below show the formulation of the main ingredients 1-1 to 1-6 and the formulation of the curing agents 1-1 to 1-2.
  • the main agents 1-2 to 1-6 were mixed according to the formulation shown in Table 1, and the main agent 1 except that the pH was adjusted with 25% aqueous ammonia or 1N hydrochloric acid as necessary.
  • -1 was prepared in the same manner as in Production Example 1-1.
  • Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-2 Aqueous epoxy resin coating compositions having the formulations shown in Tables 3 to 4 below were prepared, and the pH, viscosity, sagging property, workability, and anticorrosion properties of the aqueous epoxy resin coating composition were measured and evaluated. The results are shown in Tables 3-4.
  • ⁇ Looseness> A tin plate placed on a vertical surface is coated with a water-based epoxy resin paint composition or an organic solvent-based epoxy resin paint so that the theoretical dry film thickness is 60 ⁇ m by brushing.
  • the dry film thickness was measured using an electromagnetic film thickness meter SM-1000 manufactured by Sanko Electronic Laboratory.
  • ⁇ The minimum dry film thickness when the coated surface is measured at 10 points is 48 ⁇ m or more.
  • X The minimum dry film thickness when the coated surface was measured at 10 points was less than 48 ⁇ m.
  • ⁇ Coating workability> A water-based epoxy resin coating composition or an organic solvent-based epoxy resin coating was applied to the tinplate by brush coating or roller coating, and the coating workability was evaluated according to the following criteria. ⁇ : The coating composition spreads uniformly and the finish of the coated surface is good. X: The coating composition does not spread uniformly and the finish of the coated surface is poor.
  • ⁇ Anti-corrosion> As a test plate, a grid blasted steel plate (150 ⁇ 70 ⁇ 3.2 mm) having a base adjustment degree of ISO 8501-1 Sa2.5 was used, and an air spray was used on both sides of the test plate to obtain a dry film thickness of 55. A water-based epoxy resin coating composition or an organic solvent-based epoxy resin coating was applied so as to have a thickness of ⁇ 65 ⁇ m, and dried for 7 days under the conditions of 23 ° C. and 50% relative humidity to prepare a test piece. In accordance with JIS K5600-7-9, the degree of rust and swelling generated on the test piece after 120 cycles of the test piece under the cycle D test conditions of Appendix 1 was evaluated according to the following criteria.
  • A There is no abnormality such as rust or swelling on the surface of the test piece 2 mm or more away from the cut part.
  • ⁇ There is no abnormality such as rust and swelling on the surface of the test piece 4 mm or more away from the cut part.
  • X Rust and swelling occur on the surface of the test piece 4 mm or more away from the cut part.
  • Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-5 As the test plate, a grid blasted steel plate (150 ⁇ 70 ⁇ 3.2 mm) having a base adjustment degree of ISO 8501-1 Sa2.5 was used. In accordance with the formulation shown in Table 5 and Table 6 below, a main agent containing an epoxy resin emulsion and a curing agent containing an amine resin emulsion are mixed, and then zinc powder and phosphate rust preventive pigment are mixed as necessary. A water-based anticorrosive coating composition was prepared. In addition, when using a phosphate type
  • the obtained water-based anticorrosive coating composition is previously diluted with water to adjust to an appropriate coating viscosity, and applied to both surfaces of the test plate using an air spray so that the dry film thickness becomes 70 to 80 ⁇ m.
  • a test piece was prepared by drying for 7 days under conditions of 23 ° C. and 50% relative humidity. These test pieces were subjected to the following evaluation test, and the results are shown in Tables 5 and 6.
  • ⁇ Mixing workability> The aqueous anticorrosive coating composition was mixed with an electric stirrer for 1 minute, then allowed to stand for 5 minutes, filtered through an 80 mesh wire mesh, and the degree of residue generation was evaluated based on the following criteria. ⁇ : There is no residue. X: There is a residue.
  • (Note 1) to (Note 10) used in Tables 5 and 6 are as follows.
  • (Note 1) Bisphenol A type epoxy resin emulsion, resin solid content 55%, epoxy equivalent 495 g / eq, (trade name: Eporation EA55, manufactured by NSC Japan)
  • (Note 2) Bisphenol A type epoxy resin emulsion, resin solid content 62%, epoxy equivalent 200 g / eq, (trade name: Eporation HD2, manufactured by NSC Japan)
  • ⁇ 4th anticorrosion coating method and painted body >> ⁇ Production Example 3-1> 11 parts of ion-exchanged water is added to a mixer, and 1 part of a dispersant, 0.3 part of an antifoaming agent, 10 parts of titanium oxide, 5 parts of aluminum tripolyphosphate, 20 parts of precipitated barium sulfate, and kaolin clay 8 Portions were gradually added under a stirring environment, and after completion of the addition, mixing was performed until the particle size became 50 ⁇ m or less. Next, 45 parts of the epoxy resin emulsion and 4 parts of ethylene glycol mono-n-butyl ether were gradually added to the mixer in a stirring environment and stirred for 10 minutes to prepare the main agent of the undercoat paint 3-1. Undercoating paint 3-1 was prepared by mixing 12 parts of amine resin emulsion as a curing agent with the main agent immediately before coating.
  • Table 7 shows the formulation of the undercoat paints 3-1 to 3-2 and the intermediate coat paint.
  • the undercoat paint 3-2 and the intermediate coat paint were prepared in the same manner as in Production Example 3-1, except that the compounding agents were blended according to the formulation shown in Table 7.
  • Topcoat paint 3-1 to 3-2 Table 8 below shows the formulation of top coat paints 3-1 and 3-2.
  • the top coat 3-2 was prepared in the same manner as in Production Example 3-2 except that the compounding agent was blended according to the formulation shown in Table 8.
  • Example 9 shows the materials used (the materials used are marked with “ ⁇ ”).
  • the base grading degree is ISO 8501-1 Sa2.5 grid blasted steel plate (150 ⁇ 70 ⁇ 3.2 mm) or galvanized steel plate SGH400 ZC Z27 (150 ⁇ 70) specified in JIS G 3302 ⁇ 2.3 mm) was used.
  • Example 3-2 an undercoat paint was applied to both sides of the test plate using an air spray so that the dry film thickness was 55 to 65 ⁇ m, and dried for one day under the conditions of 23 ° C. and 50% relative humidity. Formed.
  • Example 3-2 an intermediate coating was then applied on the two undercoat films formed on both sides of the test plate using air spray so that the dry film thickness was 25 to 35 ⁇ m. And dried at 23 ° C. and 50% relative humidity for 1 day to form an intermediate coating film.
  • Example 3-1 On the two undercoat films formed on both surfaces of the test plate, in Example 3-2, The top coat was applied to the two intermediate coats formed on each of the two undercoats using air spray so that the dry film thickness was 25 to 35 ⁇ m.
  • the test piece provided with the composite coating film was produced by drying for 7 days under conditions of relative humidity. The corrosion resistance and weather resistance of these test pieces were evaluated according to the following methods. The results are shown in Table 9.
  • ⁇ Anti-corrosion> In accordance with JIS K5600-7-1, the test piece was subjected to salt spray for 500 hours according to the medium-resistant salt spray property, and then the degree of occurrence of rust, swelling, etc. generated on the test piece was evaluated according to the following criteria.
  • X Rust and swelling occur on the surface of the test piece 3 mm or more away from the cut part.

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Abstract

A first aspect of the present invention pertains to a water-based epoxy resin paint composition with excellent anticorrosive properties, and in further detail pertains to a water-based epoxy resin paint composition comprising a main agent containing an epoxy resin emulsion, and a curing agent containing an amine resin emulsion, wherein the viscosity at a shear rate of 0.1 (1/s) is 1.0 to 500 (Pa·s, 23°C), and the viscosity at a shear rate of 1000 (1/s) is 0.010 to 1 (Pa·s, 23°C).

Description

水性エポキシ樹脂塗料組成物、防食塗装方法、及び塗装体Water-based epoxy resin coating composition, anticorrosion coating method, and coated body
　本発明は、水性エポキシ樹脂塗料組成物、防食塗装方法、及び塗装体に関し、特には、防食性に優れる水性エポキシ樹脂塗料組成物に関するものである。 The present invention relates to an aqueous epoxy resin coating composition, an anticorrosion coating method, and a coated body, and more particularly to an aqueous epoxy resin coating composition having excellent anticorrosion properties.
　従来、有機溶剤系エポキシ樹脂塗料による下塗りは、その品質が日本工業規格等において規格化されており、橋梁やプラント等の構造物に防食性を付与する目的として広く使用されている。 Conventionally, undercoating with an organic solvent-based epoxy resin paint has been standardized in quality according to Japanese Industrial Standards, and is widely used for the purpose of imparting corrosion resistance to structures such as bridges and plants.
　しかしながら、近年、大気汚染防止や省資源等の観点から、従来の有機溶剤系エポキシ樹脂塗料から水性エポキシ樹脂塗料への転換が強く要望されるようになってきている。 However, in recent years, there has been a strong demand for switching from conventional organic solvent-based epoxy resin paints to water-based epoxy resin paints from the viewpoint of preventing air pollution and saving resources.
　例えば、特開２００９－１４９７９１号公報（特許文献１）には、エポキシ樹脂エマルジョンを含む水性防食塗料と、該水性防食塗料を基材面に塗装する防食塗装方法とが提案されている。しかしながら、特開２００９－１４９７９１号公報に記載の水性防食塗料には、その粘性が適当でないと、該水性防食塗料を所望の厚みに塗り付けることができなかったり、平滑な塗膜が形成されず、塗膜の一部に薄い箇所が生じたり、期待される防食性が得られなかったりといった実用上の問題が存在していた。 For example, Japanese Patent Application Laid-Open No. 2009-149791 (Patent Document 1) proposes an aqueous anticorrosive paint containing an epoxy resin emulsion and an anticorrosive coating method for applying the aqueous anticorrosive paint on a substrate surface. However, the water-based anticorrosive paint described in JP-A-2009-149791 cannot be applied to a desired thickness unless the viscosity is appropriate, or a smooth coating film cannot be formed. There have been practical problems such that a thin portion is formed in a part of the coating film and the expected anticorrosive property cannot be obtained.
　ところで、従来、橋梁、プラント及びタンク等の各種陸上鋼構造物や海洋鋼構造物には、防食目的としての塗装（以下、防食塗装ともいう）が施されている。 By the way, conventionally, various onshore steel structures such as bridges, plants and tanks and marine steel structures have been coated for corrosion protection (hereinafter also referred to as corrosion protection coating).
　一般に、防食塗装では、被塗装物に防食・防錆機能を付与する目的として下塗り塗料が適用されると共に、被塗装物の美観保持を目的として耐候性に優れた上塗り塗料が適用されている。このような防食塗装システムでは、いずれの塗料にも有機溶剤系塗料を使用することが一般的であった。 Generally, in anticorrosion coating, an undercoat paint is applied for the purpose of imparting anticorrosion and rust prevention functions to an object to be coated, and a topcoat paint having excellent weather resistance is applied for the purpose of maintaining the aesthetic appearance of the object to be coated. In such an anticorrosion coating system, it is common to use an organic solvent-based paint for any paint.
　しかしながら、近年、大気汚染防止や省資源等の観点から、有機溶剤系塗料から水性塗料への転換が強く要望されるようになってきており、使用する全ての塗料を水性塗料に転換した水性防食塗装システムが求められている。 However, in recent years, there has been a strong demand for switching from organic solvent-based paints to water-based paints from the viewpoints of air pollution prevention and resource saving, and water-based anticorrosion that converts all paints used to water-based paints. There is a need for a painting system.
　特開２００９－２２１２５６号公報（特許文献２）には、エポキシ樹脂を含む防食塗装用の水性塗料組成物が提案されている。しかしながら、防食性を付与するために、特開２００９－２２１２５６号公報に記載の水性塗料組成物を下塗り塗料として適用した上で、上述のような防食塗装システムによって下塗り塗膜及び上塗り塗膜を備える複合塗膜を形成した場合、上塗り塗料の種類によっては複合塗膜に期待される耐候性や防食性等の耐久性が得られないという課題があった。 Japanese Unexamined Patent Application Publication No. 2009-212256 (Patent Document 2) proposes an aqueous coating composition for anticorrosion coating containing an epoxy resin. However, in order to impart anticorrosion properties, the aqueous coating composition described in JP-A-2009-212256 is applied as an undercoat, and the undercoat and overcoat are provided by the anticorrosion coating system as described above. When the composite coating film is formed, there is a problem that the durability such as weather resistance and corrosion resistance expected for the composite coating film cannot be obtained depending on the type of the top coating material.
　また、特開２００８－２７２６６６号公報（特許文献３）には、使用される全ての塗料が水性塗料である水性防食塗装システムが提案されているものの、この場合、上塗り塗料の紫外線透過率によっては経年劣化によって、層間剥離、例えば下塗り塗膜と上塗り塗膜間での剥離が生じるという課題があった。 Japanese Patent Application Laid-Open No. 2008-272666 (Patent Document 3) proposes a water-based anticorrosion coating system in which all paints used are water-based paints. In this case, depending on the ultraviolet transmittance of the top-coat paint. Due to the deterioration over time, there was a problem that delamination occurred, for example, delamination between the undercoat film and the topcoat film.
　また、橋梁、プラント及びタンク等の各種陸上鋼構造物や海洋鋼構造物には、従来から、防食目的として亜鉛粉末を多く含有したいわゆるジンクリッチペイントが広く塗装されている。 Also, various onshore steel structures such as bridges, plants and tanks, and marine steel structures have been conventionally coated with so-called zinc rich paint containing a large amount of zinc powder for the purpose of corrosion protection.
　ジンクリッチペイントは、アルキルシリケートをビヒクルとする無機ジンクリッチペイントとエポキシ樹脂をビヒクルとする有機ジンクリッチペイントが一般的であり、これらは、いずれも有機溶剤を使用した溶剤系ジンクリッチペイントであった。 The zinc rich paint is generally an inorganic zinc rich paint using an alkyl silicate as a vehicle and an organic zinc rich paint using an epoxy resin as a vehicle, both of which are solvent-based zinc rich paints using an organic solvent. .
　しかしながら、近年、大気汚染防止や省資源等の観点から水もしくは水に少量の有機溶剤を併用した水系ジンクリッチペイントへの転換が強く要望されるようになってきている。例えば、特開２００８－２７２６６６号公報（特許文献３）には、水性エポキシ樹脂を用いた防食塗装方法が提案されている。しかしながら、亜鉛粉末の種類によっては期待される防食性が得られない場合があり、また、硬化剤に水溶性アミン樹脂を用いた時に主剤との混合作業性が悪く、更に、可使時間が短く塗装作業性が悪いという課題があり、実用上問題があった。 However, in recent years, there has been a strong demand for switching to water-based zinc rich paint that uses water or a small amount of an organic solvent in combination with water in order to prevent air pollution and save resources. For example, Japanese Unexamined Patent Application Publication No. 2008-272666 (Patent Document 3) proposes an anticorrosion coating method using an aqueous epoxy resin. However, depending on the type of zinc powder, the expected anticorrosive property may not be obtained, and when using a water-soluble amine resin as the curing agent, the mixing workability with the main agent is poor, and the pot life is short. There was a problem that painting workability was bad, and there was a problem in practical use.
特開２００９－１４９７９１号公報JP 2009-149791 A 特開２００９－２２１２５６号公報JP 2009-212256 A 特開２００８－２７２６６６号公報JP 2008-272666 A
　そこで、本発明の第１の目的は、上記従来技術の問題を解決し、防食性に優れる水性エポキシ樹脂塗料組成物を提供することにある。また、本発明の第２の目的は、かかる水性エポキシ樹脂塗料組成物を用いた防食塗装方法を提供することにある。 Therefore, a first object of the present invention is to provide a water-based epoxy resin coating composition that solves the above-mentioned problems of the prior art and is excellent in corrosion resistance. The second object of the present invention is to provide an anticorrosion coating method using such an aqueous epoxy resin coating composition.
　更に、本発明の第３の目的は、上記従来技術の問題を解決し、混合作業性が良く及び可使時間が長く塗装作業性が良好であり、並びに塗膜の防食性及び耐衝撃性に優れる水性エポキシ樹脂塗料組成物及び防食塗装方法を提供することにある。 Furthermore, the third object of the present invention is to solve the above-mentioned problems of the prior art, to improve the mixing workability, to improve the work life and to improve the coating workability, and to the corrosion resistance and impact resistance of the coating film. An object of the present invention is to provide an excellent aqueous epoxy resin coating composition and anticorrosion coating method.
　また更に、本発明の第４の目的は、上記従来技術の問題を解決し、優れた耐候性及び防食性を付与することが可能な防食塗装方法を提供することにある。また、本発明の第５の目的は、かかる防食塗装方法によって得られる塗装体を提供することにある。 Furthermore, a fourth object of the present invention is to provide an anticorrosion coating method capable of solving the problems of the prior art and imparting excellent weather resistance and corrosion resistance. Moreover, the 5th objective of this invention is to provide the coating body obtained by this anticorrosion coating method.
　本発明者は、上記目的を達成するために鋭意検討した結果、水性塗料組成物にエポキシ樹脂エマルジョンとアミン樹脂エマルジョンとを使用し、特定のずり速度における水性塗料組成物の粘度を特定の範囲内に調整することによって、防食性に優れる水性エポキシ樹脂塗料組成物が得られ、また、該水性エポキシ樹脂塗料組成物の使用により平滑な塗膜をも形成できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventor has used an epoxy resin emulsion and an amine resin emulsion in an aqueous coating composition, and the viscosity of the aqueous coating composition at a specific shear rate is within a specific range. By adjusting to, it was found that a water-based epoxy resin coating composition having excellent anticorrosion properties was obtained, and that a smooth coating film could be formed by using the water-based epoxy resin coating composition, thereby completing the present invention. It was.
　即ち、本発明の第１の水性エポキシ樹脂塗料組成物は、エポキシ樹脂エマルジョンを含む主剤とアミン樹脂エマルジョンを含む硬化剤とを含んでなり、ずり速度０．１（１／ｓ）における粘度が１．０～５００（Ｐａ・ｓ、２３℃）であり、ずり速度１０００（１／ｓ）における粘度が０．０１０～１（Ｐａ・ｓ、２３℃）であることを特徴とする。 That is, the first aqueous epoxy resin coating composition of the present invention comprises a main agent containing an epoxy resin emulsion and a curing agent containing an amine resin emulsion, and has a viscosity of 1 at a shear rate of 0.1 (1 / s). The viscosity is 0.0 to 500 (Pa · s, 23 ° C.), and the viscosity at a shear rate of 1000 (1 / s) is 0.010 to 1 (Pa · s, 23 ° C.).
　本発明の第１の水性エポキシ樹脂塗料組成物の好適例においては、前記主剤のｐＨが５～９であり、且つ前記水性エポキシ樹脂塗料組成物のｐＨが７～１１である。 In a preferred example of the first aqueous epoxy resin coating composition of the present invention, the pH of the main agent is 5 to 9, and the pH of the aqueous epoxy resin coating composition is 7 to 11.
　本発明の第１の水性エポキシ樹脂塗料組成物の他の好適例においては、アミン樹脂エマルジョン中に含まれるポリアミン樹脂が、アダクトタイプの変性ポリアミン樹脂である。 In another preferred embodiment of the first aqueous epoxy resin coating composition of the present invention, the polyamine resin contained in the amine resin emulsion is an adduct-type modified polyamine resin.
　また、本発明の第１の防食塗装方法は、上記第１の水性エポキシ樹脂塗料組成物を被塗装面上に塗装することを特徴とする。 The first anticorrosion coating method of the present invention is characterized in that the first water-based epoxy resin coating composition is applied onto a surface to be coated.
　更に、本発明の第２の防食塗装方法は、上記第１の水性エポキシ樹脂塗料組成物を被塗装面上に塗装することによって、該被塗装面上に塗膜を形成し、更に、該塗膜上に、該水性エポキシ樹脂塗料組成物以外の水性塗料を塗装することを特徴とする。 Furthermore, in the second anticorrosion coating method of the present invention, a coating film is formed on the surface to be coated by coating the first aqueous epoxy resin coating composition on the surface to be coated. An aqueous paint other than the aqueous epoxy resin paint composition is applied onto the film.
　次に、本発明者は、上記目的を達成するために鋭意検討した結果、硬化剤としてアミン樹脂エマルジョンを使用し、特定のかさ比重を有する亜鉛粉末を選択することで、溶剤系有機ジンクリッチペイントと同等の塗装作業性や塗膜の防食性を有する水系有機ジンクリッチペイントが得られることを見出し、本発明を完成させるに至った。 Next, as a result of intensive studies to achieve the above-mentioned object, the present inventor uses an amine resin emulsion as a curing agent, and selects a zinc powder having a specific bulk specific gravity, whereby a solvent-based organic zinc rich paint. The present inventors have found that a water-based organic zinc rich paint having coating workability equivalent to that of the coating film and corrosion resistance of the coating film can be obtained, and the present invention has been completed.
　即ち、本発明の第２の水性エポキシ樹脂塗料組成物は、エポキシ樹脂エマルジョンを含む主剤（ｉ）と、アミン樹脂エマルジョンを含む硬化剤（ｉｉ）と、亜鉛粉末（ｉｉｉ）及び／又はリン酸塩系防錆顔料（ｉｖ）とを含有する水性エポキシ樹脂塗料組成物であって、
　該亜鉛粉末（ｉｉｉ）は、自然落下法によって測定されるかさ比重が１．０以上であり、該亜鉛粉末（ｉｉｉ）の質量比が、全固形分質量あたり６５質量％以上であり、
　該亜鉛粉末（ｉｉｉ）と該リン酸塩系防錆顔料（ｉｖ）の合計質量が、全固形分質量あたり６５～９５質量％にあり、且つ、
　該亜鉛粉末（ｉｉｉ）と該リン酸塩系防錆顔料（ｉｖ）の質量比［（ｉｉｉ）／（ｉｖ）］が、１００／０～７０／３０である
　ことを特徴とする。 That is, the second aqueous epoxy resin coating composition of the present invention comprises a main agent (i) containing an epoxy resin emulsion, a curing agent (ii) containing an amine resin emulsion, zinc powder (iii) and / or a phosphate. An aqueous epoxy resin coating composition containing an anticorrosive pigment (iv),
The zinc powder (iii) has a bulk specific gravity measured by a natural drop method of 1.0 or more, and a mass ratio of the zinc powder (iii) is 65% by mass or more per total solid mass,
The total mass of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 65 to 95% by mass with respect to the total solid mass, and
A mass ratio [(iii) / (iv)] of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 100/0 to 70/30.
　また、本発明の第３の防食塗装方法は、上記第２の水性エポキシ樹脂塗料組成物を塗装することを特徴とする。 The third anticorrosion coating method of the present invention is characterized in that the second aqueous epoxy resin coating composition is applied.
　次に、本発明者は、上記目的を達成するために鋭意検討した結果、使用される全ての塗料が水性塗料である水性防食塗装システムにおいて、下塗り塗料及び上塗り塗料の両方に多液反応硬化型の水性塗料を使用し、上塗り塗料の顔料容積濃度（Ｐｉｇｍｅｎｔ　Ｖｏｌｕｍｅ　Ｃｏｎｃｅｎｔｒａｔｉｏｎ；以下、ＰＶＣともいう）を下塗り塗料のＰＶＣより低くし、更に上塗り塗膜の紫外線透過率を特定の範囲内に制御することによって、有機溶剤系塗料が使用されていた防食塗装システム（即ち、有機溶剤系防食塗装システム）と同等の優れた耐候性を付与できることを見出し、本発明を完成させるに至った。 Next, as a result of intensive investigations to achieve the above object, the present inventor, as a result of water-based anticorrosion coating system in which all paints used are water-based paints, a multi-component reaction curing type is used for both the undercoat paint and the topcoat paint. The pigment volume concentration of the top coat (Pigment Volume Concentration; hereinafter also referred to as PVC) is lower than the PVC of the base coat, and the UV transmittance of the top coat is controlled within a specific range. Thus, the present inventors have found that excellent weather resistance equivalent to that of an anticorrosion coating system in which an organic solvent-based paint has been used (that is, an organic solvent-based anticorrosion coating system) can be imparted, and the present invention has been completed.
　即ち、本発明の第４の防食塗装方法は、被塗装面上に水性エポキシ樹脂下塗り塗料を塗布して下塗り塗膜を形成し、その後、該下塗り塗膜上に水性上塗り塗料を塗布して上塗り塗膜を形成する防食塗装方法であって、下記ａ）～ｃ）の要件を満たすことを特徴とする。
　ａ）前記水性エポキシ樹脂下塗り塗料及び前記水性上塗り塗料の両方が、多液反応硬化型である。
　ｂ）前記水性上塗り塗料は、前記水性エポキシ樹脂下塗り塗料よりも顔料容積濃度が低い。
　ｃ）前記上塗り塗膜は、紫外線透過率が０．２％以下である。 That is, in the fourth anticorrosion coating method of the present invention, an undercoat is formed by applying a water-based epoxy resin undercoat on the surface to be coated, and then an overcoat is applied by applying the overcoat onto the undercoat. An anticorrosion coating method for forming a coating film, characterized by satisfying the following requirements a) to c).
a) Both the water-based epoxy resin base coat and the water-based top coat are multi-component reaction curable.
b) The water-based top coating has a lower pigment volume concentration than the water-based epoxy resin base coating.
c) The top coat film has an ultraviolet transmittance of 0.2% or less.
　本発明の第４の防食塗装方法の好適例においては、前記水性上塗り塗料を塗布する前に、水性エポキシ樹脂塗料及び水性ウレタン樹脂塗料から選ばれる多液反応硬化型の水性中塗り塗料を前記下塗り塗膜上に塗布し、中塗り塗膜が形成されている。 In a preferred example of the fourth anticorrosion coating method of the present invention, before applying the water-based top coating material, a multi-component reaction curing type water-based intermediate coating material selected from a water-based epoxy resin coating and a water-based urethane resin coating is applied to the undercoat. An intermediate coating film is formed by coating on the coating film.
　本発明の第４の防食塗装方法の他の好適例において、前記被塗装面には、ジンクリッチペイント処理、亜鉛メッキ処理及び金属溶射から選ばれる処理が施され、防食下地が形成されている。 In another preferred embodiment of the fourth anticorrosion coating method of the present invention, the surface to be coated is subjected to a treatment selected from zinc rich paint treatment, galvanization treatment and metal spraying to form an anticorrosion base.
　本発明の第４の防食塗装方法の他の好適例においては、前記被塗装面の少なくとも一部が、旧塗膜の表面であることを特徴とする。なお、「旧塗膜」とは、本発明の水性防食塗装方法において、水性エポキシ樹脂下塗り塗料が塗布される前に予め形成されている塗膜を意味する。 In another preferred embodiment of the fourth anticorrosion coating method of the present invention, at least a part of the surface to be coated is the surface of an old paint film. The “old coating film” means a coating film that is formed in advance before the aqueous epoxy resin primer coating is applied in the aqueous anticorrosion coating method of the present invention.
　また、本発明の塗装体は、上記の水性防食塗装方法によって被塗装面上に複合塗膜が形成されていることを特徴とする。なお、「複合塗膜」とは、少なくとも下塗り塗膜及び上塗り塗膜を備える塗膜を指し、下塗り塗膜と上塗り塗膜の間に中塗り塗膜を備える場合もある。 Further, the coated body of the present invention is characterized in that a composite coating film is formed on the surface to be coated by the water-based anticorrosion coating method described above. The “composite coating film” refers to a coating film provided with at least a base coating film and a top coating film, and may include an intermediate coating film between the base coating film and the top coating film.
　本発明の第１の水性エポキシ樹脂塗料組成物によれば、水性塗料組成物にエポキシ樹脂エマルジョンとアミン樹脂エマルジョンとを使用し、特定のずり速度における塗料組成物の粘度を特定の範囲内に調整することによって、作業性及び防食性に優れる水性エポキシ樹脂塗料組成物を提供することができる。また、かかる水性エポキシ樹脂塗料組成物を被塗装面上に塗装することによって、平滑な塗膜を形成することができる。 According to the first aqueous epoxy resin coating composition of the present invention, an epoxy resin emulsion and an amine resin emulsion are used in the aqueous coating composition, and the viscosity of the coating composition at a specific shear rate is adjusted within a specific range. By doing, the water-based epoxy resin coating composition excellent in workability | operativity and anticorrosion property can be provided. Moreover, a smooth coating film can be formed by coating this aqueous epoxy resin coating composition on the surface to be coated.
　本発明の第２の水性エポキシ樹脂塗料組成物及び第３の防食塗装方法によれば、主剤と硬化剤を容易に混合することが可能で、可使時間が実用上十分に長く、塗装作業性や塗膜の防食性及び耐衝撃性に優れる水性防食塗料組成物及び該水性防食塗料組成物を用いた防食塗装方法を提供することができる。 According to the second aqueous epoxy resin coating composition and the third anticorrosive coating method of the present invention, the main agent and the curing agent can be easily mixed, the pot life is practically long, and the coating workability is high. And an anticorrosion coating composition using the aqueous anticorrosion coating composition, and an anticorrosion coating method using the aqueous anticorrosion coating composition.
　本発明の第４の防食塗装方法によれば、使用される全ての塗料が水性塗料である水性防食塗装システムにおいて、下塗り塗料及び上塗り塗料の両方に多液反応硬化型の水性塗料を使用し、上塗り塗料のＰＶＣを下塗り塗料のＰＶＣより低くし、更に上塗り塗膜の紫外線透過率を特定の範囲内に制御することによって、優れた耐候性及び防食性を付与することができる。また、かかる防食塗装方法によって、耐候性及び防食性に優れる塗装体を提供することができる。 According to the fourth anticorrosive coating method of the present invention, in a waterborne anticorrosive coating system in which all paints used are aqueous paints, a multi-component reaction-curable aqueous paint is used for both the undercoat paint and the topcoat paint, By making the PVC of the top coat lower than the PVC of the base coat and further controlling the ultraviolet transmittance of the top coat within a specific range, excellent weather resistance and corrosion resistance can be imparted. Moreover, the coating body excellent in a weather resistance and corrosion resistance can be provided by this anticorrosion coating method.
＜＜第１の水性エポキシ樹脂塗料組成物＞＞
　以下に、本発明の第１の水性エポキシ樹脂塗料組成物を詳細に説明する。本発明の第１の水性エポキシ樹脂塗料組成物は、エポキシ樹脂エマルジョンを含む主剤とアミン樹脂エマルジョンを含む硬化剤とを含んでなり、ずり速度０．１（１／ｓ）における粘度が１．０～５００（Ｐａ・ｓ、２３℃）であり、ずり速度１０００（１／ｓ）における粘度が０．０１０～１（Ｐａ・ｓ、２３℃）であることを特徴とする。本発明によれば、エポキシ樹脂エマルジョンとアミン樹脂エマルジョンを組み合わせて使用した上で、水性エポキシ樹脂塗料組成物の粘度が上述の特定した範囲内にあるため、作業性及び防食性に優れており、防食性に優れる平滑な塗膜を形成することができる。なお、水性エポキシ樹脂塗料組成物とは、エポキシ樹脂及び水を含有する塗料組成物を意味する。 << first aqueous epoxy resin coating composition >>
Below, the 1st water-based epoxy resin coating composition of this invention is demonstrated in detail. The first aqueous epoxy resin coating composition of the present invention comprises a main agent containing an epoxy resin emulsion and a curing agent containing an amine resin emulsion, and has a viscosity at a shear rate of 0.1 (1 / s) of 1.0. It is characterized in that the viscosity at a shear rate of 1000 (1 / s) is 0.010 to 1 (Pa · s, 23 ° C.). According to the present invention, the epoxy resin emulsion and the amine resin emulsion are used in combination, and the viscosity of the aqueous epoxy resin coating composition is within the above specified range. A smooth coating film having excellent anticorrosion properties can be formed. The aqueous epoxy resin coating composition means a coating composition containing an epoxy resin and water.
　本発明の第１の水性エポキシ樹脂塗料組成物は、ずり速度０．１（１／ｓ）における粘度が１．０～５００（Ｐａ・ｓ、２３℃）であり、ずり速度１０００（１／ｓ）における粘度が０．０１０～１（Ｐａ・ｓ、２３℃）であることを要する。ずり速度０．１（１／ｓ）における粘度が１．０（Ｐａ・ｓ、２３℃）未満であり且つずり速度１０００（１／ｓ）における粘度が０．０１０（Ｐａ・ｓ、２３℃）未満であると、粘度が低くなりすぎ、所定の膜厚が得られず、期待される防食性が得られない。一方、ずり速度０．１（１／ｓ）における粘度が５００（Ｐａ・ｓ、２３℃）を超えて且つずり速度１０００（１／ｓ）における粘度が１（Ｐａ・ｓ、２３℃）を超えると、粘度が高くなりすぎ、レベリング性が悪化するため、膜厚が部分的に薄くなる箇所ができ、期待される防食性が得られない。 The first aqueous epoxy resin coating composition of the present invention has a viscosity of 1.0 to 500 (Pa · s, 23 ° C.) at a shear rate of 0.1 (1 / s), and a shear rate of 1000 (1 / s). ) In the range of 0.010 to 1 (Pa · s, 23 ° C.). The viscosity at a shear rate of 0.1 (1 / s) is less than 1.0 (Pa · s, 23 ° C.) and the viscosity at a shear rate of 1000 (1 / s) is 0.010 (Pa · s, 23 ° C.). If it is less than 1, the viscosity becomes too low, the predetermined film thickness cannot be obtained, and the expected anticorrosive property cannot be obtained. On the other hand, the viscosity at a shear rate of 0.1 (1 / s) exceeds 500 (Pa · s, 23 ° C.) and the viscosity at a shear rate of 1000 (1 / s) exceeds 1 (Pa · s, 23 ° C.). Then, the viscosity becomes too high and the leveling property is deteriorated, so that a portion where the film thickness is partially reduced is formed, and the expected anticorrosive property cannot be obtained.
　なお、本発明の水性エポキシ樹脂塗料組成物において、０．１（１／ｓ）と１０００（１／ｓ）の２つのずり速度を基準にして粘度を規定した理由は、０．１（１／ｓ）のずり速度が塗装直後の塗料の粘性を指し、１０００（１／ｓ）のずり速度が塗装時の塗料の粘性を指し、この塗装時から塗装直後の塗料の粘性がタレ性及びレベリング性に相関しているからである。また、本発明の水性エポキシ樹脂塗料組成物の粘度を上述の特定した範囲内に調整する方法としては、例えば、増粘剤、水等を使用する手法が挙げられる。 In the water-based epoxy resin coating composition of the present invention, the reason why the viscosity was defined based on two shear rates of 0.1 (1 / s) and 1000 (1 / s) is 0.1 (1 / The shear rate of s) indicates the viscosity of the paint immediately after coating, the shear rate of 1000 (1 / s) indicates the viscosity of the paint at the time of painting, and the viscosity of the paint immediately after coating from the time of painting is sagging and leveling. It is because it correlates with. Moreover, as a method of adjusting the viscosity of the aqueous epoxy resin coating composition of the present invention within the above-specified range, for example, a method using a thickener, water or the like can be mentioned.
　本発明の第１の水性エポキシ樹脂塗料組成物は、上記主剤のｐＨが５～９であり且つ該水性エポキシ樹脂塗料組成物のｐＨが７～１１であることが好ましい。主剤及び水性エポキシ樹脂塗料組成物のｐＨが上記の特定した範囲から外れると、塗装作業性が低下するおそれがある。なお、本発明の水性エポキシ樹脂塗料組成物において、主剤と水性エポキシ樹脂塗料組成物の２つのｐＨを規定した理由は、主剤のｐＨが貯蔵時の安定性に影響し、水性エポキシ樹脂塗料のｐＨが塗料の粘性に影響するからである。また、主剤及び水性エポキシ樹脂塗料組成物のｐＨを上述の特定した範囲内に調整する方法としては、ｐＨ調整剤等を使用する手法等も挙げられる。 In the first aqueous epoxy resin coating composition of the present invention, the pH of the main agent is preferably 5 to 9, and the pH of the aqueous epoxy resin coating composition is preferably 7 to 11. If the pH of the main agent and the aqueous epoxy resin coating composition is out of the above specified range, the coating workability may be reduced. In the aqueous epoxy resin coating composition of the present invention, the two pH values of the main agent and the aqueous epoxy resin coating composition are specified because the pH of the main agent affects the stability during storage, and the pH of the aqueous epoxy resin coating is determined. This affects the viscosity of the paint. Moreover, the method etc. which use a pH adjuster etc. are mentioned as a method of adjusting pH of a main ingredient and a water-based epoxy resin coating composition in the above-mentioned specified range.
＜エポキシ樹脂エマルジョンを含む主剤＞
　本発明の第１の水性エポキシ樹脂塗料組成物は、エポキシ樹脂エマルジョンを含む成分と、硬化剤としてのアミン樹脂エマルジョンを含む成分とを組み合わせることによって得られるが、本発明においては、このエポキシ樹脂エマルジョンを含む成分を主剤という。なお、エポキシ樹脂エマルジョンとは、エポキシ樹脂が水等の水性媒体中で分散してなる乳濁液を意味する。 <Main agent containing epoxy resin emulsion>
The first aqueous epoxy resin coating composition of the present invention can be obtained by combining a component containing an epoxy resin emulsion and a component containing an amine resin emulsion as a curing agent. In the present invention, this epoxy resin emulsion is used. The component containing is called the main agent. The epoxy resin emulsion means an emulsion in which an epoxy resin is dispersed in an aqueous medium such as water.
　上記エポキシ樹脂エマルジョンを構成するエポキシ樹脂は、１分子中に少なくとも２個のエポキシ基を有する樹脂である限り、特に限定されないが、例えば、多価アルコール又は多価フェノールとハロヒドリンとを反応させて得られるものであり、具体例としては、ビスフェノールＡ型エポキシ樹脂、ハロゲン化ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、ポリグリコール型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、エポキシ化油、１，６－ヘキサンジオールジグリシジルエーテル及びネオペンチルグリコールジグリシジルエーテル等が挙げられる。これらの中でも、塗膜の機械的耐久性や防食性、被塗装面（例えば基材表面）との付着性等の観点から、ビスフェノールＡ型エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂が好ましい。なお、これらエポキシ樹脂は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The epoxy resin constituting the epoxy resin emulsion is not particularly limited as long as it is a resin having at least two epoxy groups in one molecule. For example, it is obtained by reacting a polyhydric alcohol or polyhydric phenol with a halohydrin. Specific examples include bisphenol A type epoxy resins, halogenated bisphenol A type epoxy resins, novolac type epoxy resins, polyglycol type epoxy resins, bisphenol F type epoxy resins, epoxidized oil, and 1,6-hexane. Examples include diol diglycidyl ether and neopentyl glycol diglycidyl ether. Among these, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoints of mechanical durability and corrosion resistance of the coating film, adhesion to the surface to be coated (for example, the surface of the substrate), and the like. In addition, these epoxy resins may be used independently and may be used in combination of 2 or more type.
　また、上記エポキシ樹脂は、１分子中に少なくとも２個のエポキシ基を有する樹脂であり、形成される塗膜の常温における仕上がり性、硬化性、及び防食性等の観点から、通常、エポキシ当量は１００～１，０００ｇ／ｅｑが好ましく、１６０～９８０ｇ／ｅｑがより好ましく、１６０～５５０ｇ／ｅｑが更に好ましい。エポキシ当量が１００ｇ／ｅｑ未満では、十分な塗膜物性が得られないおそれがあり、一方でエポキシ当量が１，０００ｇ／ｅｑより大きい場合には、常温でのレベリング性が低下し、均一な塗膜が得られないおそれがある。 In addition, the epoxy resin is a resin having at least two epoxy groups in one molecule, and from the viewpoints of finish property, curability, corrosion resistance, etc. of the formed coating film, the epoxy equivalent is usually 100 to 1,000 g / eq is preferable, 160 to 980 g / eq is more preferable, and 160 to 550 g / eq is still more preferable. If the epoxy equivalent is less than 100 g / eq, sufficient film properties may not be obtained. On the other hand, if the epoxy equivalent is greater than 1,000 g / eq, the leveling property at normal temperature is lowered and uniform coating is not possible. A film may not be obtained.
　上記エポキシ樹脂エマルジョンは、特に制限されないが、通常の強制乳化方式（乳化剤及び高速攪拌機等を使用する方式）によって、水等の水性媒体中でエポキシ樹脂を乳化させることにより調製される。ここで、乳化剤としては、例えば、ポリオキシエチレンアルキルフェノールエーテル系ノニオン界面活性剤、ポリオキシエチレン・ポリオキシプロピレンブロック共重合体等のポリエーテル類、或いは該ノニオン界面活性剤及び該ポリエーテル類の少なくとも一方とジイソシアネート化合物との付加物等が挙げられる。なお、これら乳化剤は、１種単独でも、２種以上のブレンドとして用いてもよい。また、エポキシ樹脂エマルジョンの市販品としては、例えば、エポルジョンＥＡ１、２、３、７、１２、２０、５５及びＨＤ２（日本ＮＳＣ社製、商品名）；アクアトート２０５、５１０、３５２０、３５４０、３５２０１、５００３、及び５５２０（東都レジン化工社製、商品名）；ユカレジンＫＥ－００２、ＫＥ－１１６、Ｅ－１０２２、ＫＥ－３０１Ｃ（吉村油化学社製、商品名）；及びＥＭ－１０１－５０（アデカ社製、商品名）が挙げられる。 The epoxy resin emulsion is not particularly limited, but is prepared by emulsifying the epoxy resin in an aqueous medium such as water by a normal forced emulsification method (a method using an emulsifier and a high-speed stirrer). Here, as the emulsifier, for example, a polyoxyethylene alkylphenol ether-based nonionic surfactant, a polyether such as a polyoxyethylene / polyoxypropylene block copolymer, or at least the nonionic surfactant and the polyether Examples include adducts of one and a diisocyanate compound. These emulsifiers may be used alone or as a blend of two or more. Moreover, as a commercial item of an epoxy resin emulsion, for example, Epourgeon EA1, 2, 3, 7, 12, 20, 55 and HD2 (Nippon NSC company make, brand name); Aquatote 205, 510, 3520, 3540, 35201 , 5003, and 5520 (trade name, manufactured by Toto Resin Chemical Co., Ltd.); Yuka Resin KE-002, KE-116, E-1022, KE-301C (trade name, manufactured by Yoshimura Oil Chemical Co., Ltd.); and EM-101-50 ( Adeka's product name).
　上記主剤は、上記エポキシ樹脂エマルジョンの他にも他の配合剤を含有することができる。具体的に、上記主剤は、主剤や水性エポキシ樹脂塗料組成物の粘性を調整するため、増粘剤を含有することができる。上記増粘剤としては、特に制限されず、公知の増粘剤が使用できるが、具体例としては、ケイ酸塩、金属ケイ酸塩、モンモリロナイト、有機モンモリロナイト、コロイド状アルミナ等の無機系増粘剤；ポリアクリル酸ソーダ、ポリアクリル酸－（メタ）アクリル酸エステル共重合体等のポリアクリル酸系増粘剤；「ＵＨ－８１４Ｎ」、「ＵＨ－４６２」、「ＵＨ－４２０」、「ＵＨ－４７２」、「ＵＨ－５４０」（以上、アデカ社製）、「ＳＮシックナー６１２」、「ＳＮシックナー６２１Ｎ」、「ＳＮシックナー６２５Ｎ」、「ＳＮシックナー６２７Ｎ」（以上、サンノプコ社製）等のウレタン会合型増粘剤；カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチルセルロース等の繊維素誘導体系増粘剤；カゼイン、カゼイン酸ソーダ、カゼイン酸アンモニウム等のタンパク質系増粘剤；アルギン酸ソーダ等のアルギン酸系増粘剤；ポリビニルアルコール、ポリビニルピロリドン、ポリビニルベンジルエーテル共重合体等のポリビニル系増粘剤；プルロニックポリエーテル、ポリエーテルジアルキルエステル、ポリエーテルジアルキルエーテル、ポリエーテルエポキシ変性物等のポリエーテル系増粘剤；ビニルメチルエーテル－無水マレイン酸共重合体の部分エステル等の無水マレイン酸共重合体系増粘剤；ポリアミドアミン塩等のポリアミド系増粘剤等が挙げられる。これら増粘剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The main agent can contain other compounding agents in addition to the epoxy resin emulsion. Specifically, the main agent can contain a thickener in order to adjust the viscosity of the main agent and the aqueous epoxy resin coating composition. The thickener is not particularly limited, and known thickeners can be used. Specific examples include inorganic thickeners such as silicate, metal silicate, montmorillonite, organic montmorillonite, colloidal alumina, and the like. Agents: Polyacrylic acid thickeners such as polyacrylic acid soda and polyacrylic acid- (meth) acrylic acid ester copolymers; “UH-814N”, “UH-462”, “UH-420”, “UH -472 "," UH-540 "(above, manufactured by Adeka)," SN thickener 612 "," SN thickener 621N "," SN thickener 625N "," SN thickener 627N "(above, manufactured by San Nopco) Associative thickeners; Fibrin derivative thickeners such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; casein, casein Protein thickeners such as soda and ammonium caseinate; Alginic acid thickeners such as sodium alginate; Polyvinyl thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylbenzyl ether copolymers; Pluronic polyethers and polyether dialkyls Polyether thickeners such as esters, polyether dialkyl ethers, and polyether epoxy modified products; Maleic anhydride copolymer thickeners such as partial esters of vinyl methyl ether-maleic anhydride copolymer; Polyamidoamine salts, etc. And polyamide thickeners. These thickeners may be used alone or in combination of two or more.
　また、上記主剤は、ｐＨ調整剤を含有してもよい。ｐＨ調整剤は、塗料に一般的に使用されるものであれば使用でき、以前より中和剤として公知の各種含窒素塩基性化合物、無機酸、有機酸等が特に制限なく利用できる。具体的には、例えば、各種含窒素塩基性化合物として、トリメチルアミン、トリエチルアミン、トリブチルアミン等のアルキルアミン類、トリエタノールアミン、ジメチルエタノールアミン、ジエタノールアミン、モノエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、エチルプロパノールアミン等のアルコールアミン類、モルホリン、アンモニア等の揮発性含窒素塩基性化合物が挙げられる。また無機酸としては、塩酸、硫酸、硝酸等が挙げられ、有機酸としては、蟻酸、酢酸等が挙げられる。これらｐＨ調整剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In addition, the main agent may contain a pH adjuster. The pH adjuster can be used as long as it is generally used in paints, and various nitrogen-containing basic compounds, inorganic acids, organic acids and the like that have been known as neutralizers can be used without any particular limitation. Specifically, for example, as various nitrogen-containing basic compounds, alkylamines such as trimethylamine, triethylamine, tributylamine, triethanolamine, dimethylethanolamine, diethanolamine, monoethanolamine, N-methyldiethanolamine, N, N— Examples thereof include alcohol amines such as dimethylethanolamine and ethylpropanolamine, and volatile nitrogen-containing basic compounds such as morpholine and ammonia. Examples of inorganic acids include hydrochloric acid, sulfuric acid, and nitric acid, and examples of organic acids include formic acid and acetic acid. These pH adjusters may be used alone or in combination of two or more.
　更に、上記主剤は、塗膜の可撓性を向上させる目的として、反応性希釈剤や非反応性希釈剤等の一般的に使用される希釈剤を含有してもよい。反応性希釈剤としては、例えば、カージュラＥ１０（油化シェルエポキシ社製、商品名）、ネオトートＳ（東都化成社製、商品名）、及びアデカグリシロールＥＤ５０２（旭電化工業社製、商品名）等の１官能性エポキシ樹脂が挙げられる。一方、非反応性希釈剤としては、例えば、ニカノールＬＬＬ等の石油樹脂及びクマロン樹脂等が挙げられる。これら希釈剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Furthermore, the main agent may contain a commonly used diluent such as a reactive diluent or a non-reactive diluent for the purpose of improving the flexibility of the coating film. Examples of reactive diluents include Cardura E10 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Neotote S (trade name, manufactured by Toto Kasei Co., Ltd.), and Adeka Glycilol ED502 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.). Monofunctional epoxy resins such as On the other hand, examples of the non-reactive diluent include petroleum resins such as Nicanol LLL and coumarone resins. These diluents may be used alone or in combination of two or more.
　また更に、上記主剤は、その他塗料に一般的に使用される着色顔料、防錆顔料及び体質顔料等を特に制限無く含有することができる。着色顔料、防錆顔料及び体質顔料の具体例としては、酸化チタン、ベンガラ、黄色酸化鉄、カーボンブラック、トリポリリン酸アルミニウム、リン酸亜鉛、メタホウ酸バリウム、炭酸カルシウム、硫酸バリウム、タルク、クレー、マイカ、アルミナ、ミョウバン、白土、水酸化マグネシウム、及び酸化マグネシウム等の無機顔料や、フタロシアニンブルー、フタロシアニングリーン、ナフトールレッド、キナクリドンレッド、ベンズイミダゾロンイエロー、ハンザイエロー、ベンズイミダゾロンオレンジ、及びジオキサジンバイオレット等の有機顔料が挙げられる。これら顔料は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Furthermore, the main agent can contain other coloring pigments, rust preventive pigments, extender pigments, and the like that are generally used in other paints. Specific examples of color pigments, rust preventive pigments and extender pigments include titanium oxide, bengara, yellow iron oxide, carbon black, aluminum tripolyphosphate, zinc phosphate, barium metaborate, calcium carbonate, barium sulfate, talc, clay, mica , Inorganic pigments such as alumina, alum, clay, magnesium hydroxide, and magnesium oxide, phthalocyanine blue, phthalocyanine green, naphthol red, quinacridone red, benzimidazolone yellow, hansa yellow, benzimidazolone orange, and dioxazine violet And organic pigments. These pigments may be used alone or in combination of two or more.
　更にまた、上記主剤には、水性エポキシ樹脂塗料組成物に各種機能を付与するため、分散剤、消泡剤、沈降防止剤、防カビ剤、防腐剤、紫外線吸収剤、又は光安定剤等が適宜添加されてもよい。また、エポキシ樹脂エマルジョンを構成するエポキシ樹脂とアミン樹脂エマルジョンを構成するポリアミン樹脂との融着を促進するため、上記主剤には、有機溶剤を配合することも可能である。有機溶剤としては、例えば、エチレングリコールモノｎ－ブチルエーテル、エチレングリコールモノｉ－ブチルエーテル、エチレングリコールモノｎ－プロピルエーテル、エチレングリコールモノｉ－プロピルエーテル、ジエチレングリコールモノｎ－ブチルエーテル、ジエチレングリコールモノｉ－ブチルエーテル、ジエチレングリコールモノｎ－プロピルエーテル、ジエチレングリコールモノｉ－プロピルエーテル、ジプロピレングリコールモノｎ－ブチルエーテル、ジプロピレングリコールモノｉ－ブチルエーテル、ジプロピレングリコールモノｎ－プロピルエーテル、ジプロピレングリコールモノｉ－プロピルエーテル、ジエチレングリコールジエチルエーテル、及びジエチレングリコールジブチルエーテル等のグリコールエーテル類、２，２，４－トリメチルペンタンジオールモノイソブチレート、及び２，２，４－トリメチルペンタンジオールジイソブチレート等が挙げられる。これら有機溶剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Furthermore, the main agent includes a dispersant, an antifoaming agent, an anti-settling agent, an antifungal agent, an antiseptic, an ultraviolet absorber, a light stabilizer, and the like in order to impart various functions to the aqueous epoxy resin coating composition. You may add suitably. Further, in order to promote fusion between the epoxy resin constituting the epoxy resin emulsion and the polyamine resin constituting the amine resin emulsion, an organic solvent can be blended with the main agent. Examples of the organic solvent include ethylene glycol mono n-butyl ether, ethylene glycol mono i-butyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono i-propyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono i-butyl ether, diethylene glycol. Mono n-propyl ether, diethylene glycol mono i-propyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol mono i-butyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono i-propyl ether, diethylene glycol diethyl ether And glycol ethers such as diethylene glycol dibutyl ether , 2,2,4-trimethyl pentanediol mono-isobutyrate, and 2,2,4-trimethyl pentanediol diisobutyrate and the like. These organic solvents may be used alone or in combination of two or more.
　なお、上記主剤は、上記エポキシ樹脂エマルジョンと、必要に応じて適宜選択される各種成分とを混合することにより調製できる。 In addition, the said main ingredient can be prepared by mixing the said epoxy resin emulsion and the various components suitably selected as needed.
＜アミン樹脂エマルジョンを含む硬化剤＞
　本発明の第１の水性エポキシ樹脂塗料組成物は、硬化剤として、アミン樹脂エマルジョンを含む硬化剤を含むことを要する。ここで、アミン樹脂エマルジョンとは、アミン樹脂が水等の水性媒体中で分散してなる乳濁液を意味し、本発明におけるアミン樹脂とは、１分子中に２個以上のアミノ基を含有するポリアミン樹脂を指す。上記ポリアミン樹脂としては、例えば、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、トリアミノプロパン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、イソホロンジアミン、及び１，３－ビスアミノメチルシクロヘキサン等の脂肪族ポリアミン；フェニレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、及びジアミノジフエニルメタン等の芳香族ポリアミン；ポリオキシエチレンジアミン、ポリオキシプロピレンジアミン、トリエチレングリコールジアミン、及びトリプロピレングリコールジアミン等の他のポリアミン化合物と、これらポリアミン樹脂のアミノ基を変性してなる変性ポリアミン樹脂とが挙げられる。なお、上記ポリアミン樹脂の変性には、既知の方法が利用でき、変性反応の例としては、アミノ基のアミド化、アミノ基とカルボニル化合物のマンニッヒ反応、アミノ基とエポキシ基の付加反応等が挙げられる。ここで、アミノ基にエポキシ基等が付加したタイプの変性ポリアミン樹脂をアダクトタイプの変性ポリアミン樹脂といい、防食性の観点から、アミノ基にエポキシ基が付加したエポキシアダクトタイプの変性ポリアミン樹脂が好ましい。 <Curing agent containing amine resin emulsion>
The 1st water-based epoxy resin coating composition of this invention needs to contain the hardening | curing agent containing an amine resin emulsion as a hardening | curing agent. Here, the amine resin emulsion means an emulsion in which the amine resin is dispersed in an aqueous medium such as water, and the amine resin in the present invention contains two or more amino groups in one molecule. Refers to polyamine resin. Examples of the polyamine resin include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triaminopropane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, and 1,3-bisaminomethylcyclohexane. Aliphatic polyamines; aromatic polyamines such as phenylenediamine, metaxylylenediamine, paraxylylenediamine, and diaminodiphenylmethane; such as polyoxyethylenediamine, polyoxypropylenediamine, triethyleneglycoldiamine, and tripropyleneglycoldiamine Examples include other polyamine compounds and modified polyamine resins obtained by modifying the amino groups of these polyamine resins. For modification of the polyamine resin, known methods can be used. Examples of the modification reaction include amidation of an amino group, Mannich reaction of an amino group and a carbonyl compound, addition reaction of an amino group and an epoxy group, and the like. It is done. Here, a modified polyamine resin in which an epoxy group or the like is added to an amino group is referred to as an adduct type modified polyamine resin, and an epoxy adduct type modified polyamine resin in which an epoxy group is added to an amino group is preferable from the viewpoint of corrosion resistance. .
　本発明の第１の水性エポキシ樹脂塗料組成物において、アミン樹脂エマルジョンを含む硬化剤の配合割合は、塗膜の硬化性及び防食性等の観点から、主剤中に含まれるエポキシ樹脂エマルジョンを構成するエポキシ樹脂のエポキシ基１当量に対して、アミン樹脂エマルジョンを構成するアミン樹脂の活性水素が、通常０．５～２．０当量の範囲内であり、特に０．６～１．２当量の範囲内であるのが好ましい。 In the first aqueous epoxy resin coating composition of the present invention, the blending ratio of the curing agent containing the amine resin emulsion constitutes the epoxy resin emulsion contained in the main agent from the viewpoint of the curability and corrosion resistance of the coating film. The active hydrogen of the amine resin constituting the amine resin emulsion is usually in the range of 0.5 to 2.0 equivalents, particularly in the range of 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin. Is preferably within.
　また、上記アミン樹脂エマルジョンを含む硬化剤には、主剤にも配合できる配合剤、例えば反応性希釈剤、非反応性希釈剤、着色顔料、体質顔料、有機顔料、増粘剤、ｐＨ調整剤、分散剤、消泡剤、沈降防止剤、防カビ剤、防腐剤、紫外線吸収剤、光安定剤、有機溶剤等を必要に応じて配合してもよい。 In addition, the curing agent containing the amine resin emulsion includes a compounding agent that can be incorporated into the main agent, for example, a reactive diluent, a non-reactive diluent, a color pigment, an extender pigment, an organic pigment, a thickener, a pH adjuster, You may mix | blend a dispersing agent, an antifoamer, an antisettling agent, an antifungal agent, an antiseptic | preservative, a ultraviolet absorber, a light stabilizer, an organic solvent, etc. as needed.
　なお、上記アミン樹脂エマルジョンを含む硬化剤は、上記アミン樹脂エマルジョンと、必要に応じて適宜選択される各種成分とを混合することにより調製できる。 In addition, the hardening | curing agent containing the said amine resin emulsion can be prepared by mixing the said amine resin emulsion and the various components suitably selected as needed.
＜第１の水性エポキシ樹脂塗料組成物の調製＞
　本発明の第１の水性エポキシ樹脂塗料組成物は、上記主剤と、上記アミン樹脂エマルジョンを含む硬化剤とを、例えば、これらの成分を均一に混合できる装置、好ましくは電動攪拌機等を用いて、均一に混合することにより調製できる。また、本発明の水性エポキシ樹脂塗料組成物の粘度を調整するため、上記主剤と、上記アミン樹脂エマルジョンを含む硬化剤とを混合した後に、水を加えてもよい。 <Preparation of first aqueous epoxy resin coating composition>
The first aqueous epoxy resin coating composition of the present invention is prepared by using, for example, an apparatus capable of uniformly mixing these components and a curing agent containing the amine resin emulsion, preferably an electric stirrer, etc. It can be prepared by mixing uniformly. Moreover, in order to adjust the viscosity of the aqueous epoxy resin coating composition of the present invention, water may be added after mixing the main agent and the curing agent containing the amine resin emulsion.
＜＜第１及び第２の防食塗装方法＞＞
　次に、本発明の第１及び第２の防食塗装方法について詳細に説明する。本発明の第１の防食塗装方法は、上述の第１の水性エポキシ樹脂塗料組成物を被塗装面上に塗装することを特徴とし、また、本発明の第２の防食塗装方法は、上述の第１の水性エポキシ樹脂塗料組成物を被塗装面上に塗装することによって、該被塗装面上に塗膜を形成し、更に、該塗膜上に、該水性エポキシ樹脂塗料組成物以外の水性塗料を塗装することを特徴とする。本発明の第１及び第２の防食塗装方法によれば、上述の第１の水性エポキシ樹脂塗料組成物を用いて塗膜を形成しているため、作業性及び防食性に優れる。 << First and second anticorrosion coating method >>
Next, the first and second anticorrosion coating methods of the present invention will be described in detail. The first anticorrosion coating method of the present invention is characterized in that the above-mentioned first aqueous epoxy resin coating composition is applied onto the surface to be coated, and the second anticorrosion coating method of the present invention comprises the above-mentioned By coating the first aqueous epoxy resin coating composition on the surface to be coated, a coating film is formed on the surface to be coated, and further, an aqueous solution other than the aqueous epoxy resin coating composition is formed on the coating film. It is characterized by painting a paint. According to the first and second anticorrosion coating methods of the present invention, since the coating film is formed using the first aqueous epoxy resin coating composition, the workability and the anticorrosion property are excellent.
　本発明の第１及び第２の防食塗装方法において、上記水性エポキシ樹脂塗料組成物を乾燥した後に形成される塗膜の膜厚（乾燥膜厚）は、通常２０～２５０μｍの範囲内であり、３０～１５０μｍの範囲内であるのが好ましい。また、上記水性エポキシ樹脂塗料組成物の塗装方法としては、特に制限されず、既知の塗装手段、例えば、エアスプレー塗装、エアレススプレー塗装、刷毛塗り、又はローラー塗り等が利用できる。なお、塗装環境は、特に制限されるものではないが、０℃以下のような極端な低温環境や被塗装表面の温度が８０℃以上のような高温環境は避けることが望ましい。水性エポキシ樹脂塗料組成物の乾燥時間は、気温や湿度等の養生環境条件によって異なる。例えば、気温２３℃、相対湿度５０％の条件であれば７日間程度の乾燥時間が望ましいが、積層塗膜を形成するために次工程の塗料組成物を塗り重ねる場合には、支障なく塗り重ねることができる。なお、形成された積層塗膜が、本来の性能を発揮できるのであれば、これに限定されない。 In the first and second anticorrosion coating methods of the present invention, the film thickness (dry film thickness) of the coating film formed after drying the aqueous epoxy resin coating composition is usually in the range of 20 to 250 μm, It is preferably in the range of 30 to 150 μm. Moreover, it does not restrict | limit especially as a coating method of the said water-based epoxy resin coating composition, A well-known coating means, for example, air spray coating, airless spray coating, brush coating, or roller coating, etc. can be utilized. The coating environment is not particularly limited, but it is desirable to avoid an extremely low temperature environment such as 0 ° C. or lower or a high temperature environment where the temperature of the surface to be coated is 80 ° C. or higher. The drying time of the aqueous epoxy resin coating composition varies depending on the curing environment conditions such as air temperature and humidity. For example, if the temperature is 23 ° C. and the relative humidity is 50%, a drying time of about 7 days is desirable. However, when the coating composition of the next step is applied repeatedly to form a laminated coating film, the coating is applied without any problem. be able to. In addition, if the formed laminated coating film can exhibit original performance, it will not be limited to this.
　本発明の第１及び第２の防食塗装方法において、被塗装面としては、防食性の付与が必要な表面であれば特に制限されるものではないが、橋梁やプラント等の構造物の表面、より具体的には、鉄道橋、道路橋、ガスタンク、石油タンク、鉄塔等の炭素鋼等の材料からなる基材表面が挙げられる。 In the first and second anticorrosion coating methods of the present invention, the surface to be coated is not particularly limited as long as it is a surface that needs to be imparted with anticorrosion, but the surface of a structure such as a bridge or a plant, More specifically, the base material surface which consists of materials, such as a railroad bridge, a road bridge, a gas tank, an oil tank, and carbon steel, such as a steel tower, is mentioned.
　本発明の第１及び第２の防食塗装方法においては、上記第１の水性エポキシ樹脂塗料組成物を被塗装面上に直接塗装してもよいし、被塗装面にジンクリッチペイント処理、亜鉛メッキ処理、金属溶射等を施し、ある程度の防食性がある下地を準備してから、該下地の上に塗装してもよい。更に、経年した塗膜（旧塗膜）の状態が健全である場合には、その上に塗装することも可能である。 In the first and second anticorrosion coating methods of the present invention, the first water-based epoxy resin coating composition may be directly coated on the surface to be coated, or the zinc rich paint treatment, galvanization is performed on the surface to be coated. A base having a certain degree of corrosion resistance may be prepared by performing treatment, metal spraying, etc., and then coated on the base. Furthermore, when the state of the aged coating film (old coating film) is healthy, it is possible to paint on it.
　本発明の第１及び第２の防食塗装方法においては、必要とされる防食性能に応じて、上記第１の水性エポキシ樹脂塗料組成物を複数回塗り重ねることも可能である。 In the first and second anticorrosion coating methods of the present invention, the first aqueous epoxy resin coating composition can be applied a plurality of times depending on the required anticorrosion performance.
　本発明の第２の防食塗装方法によれば、上記第１の水性エポキシ樹脂塗料組成物による塗膜上に、該水性エポキシ樹脂塗料組成物以外の水性塗料を塗装することを要するが、例えば、該水性塗料として、耐候性に優れる上塗り塗料を使用することにより、防食性を長期に亘って維持することができる。また、上記第１の水性エポキシ樹脂塗料組成物以外の水性塗料には、種々の水性塗料を使用でき、該水性塗料の種類を変更しながら塗り重ねることも可能である。例えば、上述の上塗り塗料を塗装する前に、上記第１の水性エポキシ樹脂塗料組成物による塗膜上に、中塗り塗料を塗装することも可能である。中塗り塗料としては、例えば、エポキシ樹脂系中塗り塗料、変性エポキシ樹脂系中塗り塗料、及びウレタン樹脂系中塗り塗料等が挙げられる。また、上塗り塗料としては、例えば、アクリル樹脂系上塗り塗料、ウレタン樹脂系上塗り塗料、シリコーン樹脂系上塗り塗料、及びフッ素樹脂系上塗り塗料等が挙げられる。 According to the second anticorrosive coating method of the present invention, it is necessary to apply a water-based paint other than the water-based epoxy resin paint composition onto the coating film formed of the first water-based epoxy resin paint composition. By using a top coating having excellent weather resistance as the water-based paint, anticorrosion can be maintained for a long time. Moreover, various water-based paints can be used as the water-based paint other than the first water-based epoxy resin paint composition, and it is also possible to reapply while changing the type of the water-based paint. For example, before applying the above-mentioned top coat, it is also possible to apply the intermediate coat on the coating film made of the first aqueous epoxy resin paint composition. Examples of the intermediate coating include an epoxy resin-based intermediate coating, a modified epoxy resin-based intermediate coating, and a urethane resin-based intermediate coating. Further, examples of the top coating include acrylic resin-based top coating, urethane resin-based top coating, silicone resin-based top coating, and fluororesin-based top coating.
＜＜第２の水性エポキシ樹脂塗料組成物＞＞
　以下に、本発明の第２の水性エポキシ樹脂塗料組成物を詳細に説明する。本発明の第２の水性エポキシ樹脂塗料組成物は、エポキシ樹脂エマルジョンを含む主剤（ｉ）と、アミン樹脂エマルジョンを含む硬化剤（ｉｉ）と、亜鉛粉末（ｉｉｉ）及び／又はリン酸塩系防錆顔料（ｉｖ）とを含有する水性エポキシ樹脂塗料組成物であって、
　該亜鉛粉末（ｉｉｉ）は、自然落下法によって測定されるかさ比重が１．０以上であり、該亜鉛粉末（ｉｉｉ）の質量比が、全固形分質量あたり６５質量％以上であり、
　該亜鉛粉末（ｉｉｉ）と該リン酸塩系防錆顔料（ｉｖ）の合計質量が、全固形分質量あたり６５～９５質量％にあり、且つ、
　該亜鉛粉末（ｉｉｉ）と該リン酸塩系防錆顔料（ｉｖ）の質量比［（ｉｉｉ）／（ｉｖ）］が、１００／０～７０／３０である
　ことを特徴とする。なお、本明細書においては、上記第２の水性エポキシ樹脂塗料組成物を水性防食塗料組成物とも称する。 << second aqueous epoxy resin coating composition >>
Below, the 2nd water-based epoxy resin coating composition of this invention is demonstrated in detail. The second aqueous epoxy resin coating composition of the present invention comprises a main agent (i) containing an epoxy resin emulsion, a curing agent (ii) containing an amine resin emulsion, a zinc powder (iii) and / or a phosphate-based antibacterial agent. An aqueous epoxy resin coating composition containing a rust pigment (iv),
The zinc powder (iii) has a bulk specific gravity measured by a natural drop method of 1.0 or more, and a mass ratio of the zinc powder (iii) is 65% by mass or more per total solid mass,
The total mass of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 65 to 95% by mass with respect to the total solid mass, and
A mass ratio [(iii) / (iv)] of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 100/0 to 70/30. In the present specification, the second aqueous epoxy resin coating composition is also referred to as an aqueous anticorrosive coating composition.
＜エポキシ樹脂エマルジョンを含む主剤（ｉ）＞
　本発明の第２の水性エポキシ樹脂塗料組成物（水性防食塗料組成物）は、エポキシ樹脂エマルジョンを含む成分と、硬化剤としてのアミン樹脂エマルジョンを含む成分と、亜鉛粉末及び／又はリン酸塩系防錆顔料とを組み合わせることによって得られるが、本発明においては、このエポキシ樹脂エマルジョンを含む成分を主剤という。なお、エポキシ樹脂エマルジョンとは、エポキシ樹脂が水等の水性媒体中で分散してなる乳濁液を意味する。 <Main agent containing epoxy resin emulsion (i)>
The second aqueous epoxy resin coating composition (aqueous anticorrosive coating composition) of the present invention comprises a component containing an epoxy resin emulsion, a component containing an amine resin emulsion as a curing agent, a zinc powder and / or a phosphate system. Although obtained by combining with an antirust pigment, in this invention, the component containing this epoxy resin emulsion is called main ingredient. The epoxy resin emulsion means an emulsion in which an epoxy resin is dispersed in an aqueous medium such as water.
　本発明の第２の水性エポキシ樹脂塗料組成物に使用される「エポキシ樹脂エマルジョンを含む主剤（ｉ）」は、上述した第１の水性エポキシ樹脂塗料組成物において説明したものと同一のものが使用できる。但し、本発明の第２の水性エポキシ樹脂塗料組成物に使用される「エポキシ樹脂エマルジョンを含む主剤（ｉ）」においては、亜鉛粉末及びリン酸塩系防錆顔料が除かれる。 The “main agent (i) containing an epoxy resin emulsion” used in the second aqueous epoxy resin coating composition of the present invention is the same as that described in the first aqueous epoxy resin coating composition described above. it can. However, in the “main agent (i) containing an epoxy resin emulsion” used in the second aqueous epoxy resin coating composition of the present invention, zinc powder and phosphate-based rust preventive pigment are excluded.
　なお、上記水性防食塗料組成物において、上記エポキシ樹脂エマルジョンを構成するエポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂であることが好ましい。また、上記水性防食塗料組成物において、上記エポキシ樹脂エマルジョンを構成するエポキシ樹脂は、エポキシ当量が１６０～９８０ｇ／ｅｑであることが好ましい。更に、上記水性防食塗料組成物において、上記エポキシ樹脂エマルジョンを構成するエポキシ樹脂は、数平均分子量が３００～１０，０００であることが好ましく、１，０００～４，０００であることが更に好ましい。 In the water-based anticorrosion coating composition, the epoxy resin constituting the epoxy resin emulsion is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. In the water-based anticorrosive coating composition, the epoxy resin constituting the epoxy resin emulsion preferably has an epoxy equivalent of 160 to 980 g / eq. Further, in the water-based anticorrosive coating composition, the epoxy resin constituting the epoxy resin emulsion preferably has a number average molecular weight of 300 to 10,000, more preferably 1,000 to 4,000.
＜アミン樹脂エマルジョンを含む硬化剤（ｉｉ）＞
　本発明の第２の水性エポキシ樹脂塗料組成物は、硬化剤として、アミン樹脂エマルジョンを含む硬化剤を含むことを要する。ここで、アミン樹脂エマルジョンとは、アミン樹脂が水等の水性媒体中で分散してなる乳濁液を意味し、本発明におけるアミン樹脂とは、１分子中に２個以上のアミノ基を含有するポリアミン樹脂を指す。即ち、本発明の第２の水性エポキシ樹脂塗料組成物に使用される「アミン樹脂エマルジョンを含む硬化剤（ｉｉ）」は、上述した第１の水性エポキシ樹脂塗料組成物において説明したものと同一のものが使用できる。但し、本発明の第２の水性エポキシ樹脂塗料組成物に使用される「エポキシ樹脂エマルジョンを含む主剤（ｉ）」においては、亜鉛粉末及びリン酸塩系防錆顔料が除かれる。 <Hardening agent containing amine resin emulsion (ii)>
The 2nd water-based epoxy resin coating composition of this invention needs to contain the hardening | curing agent containing an amine resin emulsion as a hardening | curing agent. Here, the amine resin emulsion means an emulsion in which the amine resin is dispersed in an aqueous medium such as water, and the amine resin in the present invention contains two or more amino groups in one molecule. Refers to polyamine resin. That is, the “curing agent (ii) containing an amine resin emulsion” used in the second aqueous epoxy resin coating composition of the present invention is the same as that described in the first aqueous epoxy resin coating composition. Things can be used. However, in the “main agent (i) containing an epoxy resin emulsion” used in the second aqueous epoxy resin coating composition of the present invention, zinc powder and phosphate-based rust preventive pigment are excluded.
＜亜鉛粉末（ｉｉｉ）＞
　本発明の第２の水性エポキシ樹脂塗料組成物は、亜鉛粉末を含むことを要する。亜鉛粉末を多く含有するジンクリッチペイントを鋼材に塗装した場合、その塗膜が水分に触れると、鉄よりもイオン化傾向の大きい亜鉛が陽極となり亜鉛から鉄に向かって防食電流が流れ、鉄は腐食から守られる。ここで、亜鉛粉末（ｉｉｉ）の含有量は、塗膜の防食性を確保するため、全固形分質量あたり６５質量％以上である必要がある。 <Zinc powder (iii)>
The 2nd water-based epoxy resin coating composition of this invention needs to contain zinc powder. When zinc rich paint containing a large amount of zinc powder is applied to steel, when the coating film comes into contact with moisture, zinc, which has a higher ionization tendency than iron, acts as an anode, and a corrosion-proof current flows from zinc to iron. Protected from. Here, content of zinc powder (iii) needs to be 65 mass% or more per total solid mass, in order to ensure the corrosion resistance of a coating film.
　塗料中での分散性、混合時の作業性及び塗膜の防食性等の点から、亜鉛粉末（ｉｉｉ）は、自然落下法によって測定されるかさ比重が１．０以上のものであることが必要であり、特に２．０以上のものが好ましい。ここで、亜鉛粉末の自然落下法によるかさ比重の算出法は、亜鉛粉末１００ｇ（ｍ）を上皿天秤にて測り取り、漏斗を用いて２００ｍＬメスシリンダー（最小目盛単位：２ｍＬ）へ徐々に落下させ、メスシリンダーを静かに傾け最上部の試料面を圧密せずに注意深く平らに均した後、その時点のかさ体積（Ｖ０）を最小目盛単位まで読み取る。その後、ｍ／Ｖ０によってかさ比重（ｇ／ｍＬ）を算出した。本発明におけるかさ比重は、５回測定の平均値を採用した。 From the viewpoints of dispersibility in the paint, workability during mixing, and corrosion resistance of the coating film, the zinc powder (iii) has a bulk specific gravity of 1.0 or more as measured by the natural drop method. Necessary, and those of 2.0 or more are particularly preferable. Here, the method for calculating the bulk specific gravity of the zinc powder by the natural dropping method is to measure 100 g (m) of zinc powder with an upper pan balance and gradually drop it onto a 200 mL graduated cylinder (minimum scale unit: 2 mL) using a funnel. Gently tilt the graduated cylinder and carefully level the uppermost sample surface without consolidating it, and then read the bulk volume (V0) at that time to the minimum scale unit. Then, bulk specific gravity (g / mL) was computed by m / V0. For the bulk specific gravity in the present invention, an average value of five measurements was adopted.
＜リン酸塩系防錆顔料（ｉｖ）＞
　本発明の第２の水性エポキシ樹脂塗料組成物は、リン酸塩系防錆顔料を含むことが好ましい。亜鉛粉末とリン酸塩系防錆顔料を組み合わせることによって、亜鉛粉末を単独で使用した場合と比べて、塗膜の防食性を向上させることができる。 <Phosphate rust preventive pigment (iv)>
It is preferable that the 2nd water-based epoxy resin coating composition of this invention contains a phosphate type | system | group antirust pigment. By combining the zinc powder and the phosphate-based anticorrosive pigment, the corrosion resistance of the coating film can be improved as compared with the case where the zinc powder is used alone.
　本発明の第２の水性エポキシ樹脂塗料組成物において、リン酸塩系防錆顔料としては、例えば、リン酸アルミニウムや、トリポリリン酸アルミニウム、リン酸亜鉛、亜リン酸亜鉛、亜リン酸カリウム、亜リン酸カルシウム、亜リン酸アルミニウム、リン酸亜鉛カルシウム、リン酸亜鉛アルミニウム、リンモリブデン酸亜鉛、リンモリブデン酸アルミニウム、リン酸マグネシウム及びバナジン酸／リン酸混合顔料等が挙げられる。特に、分散性及び防食性が優れているという点からリン酸アルミニウム及びリン酸亜鉛が好ましい。 In the second aqueous epoxy resin coating composition of the present invention, examples of the phosphate-based rust preventive pigment include aluminum phosphate, aluminum tripolyphosphate, zinc phosphate, zinc phosphite, potassium phosphite, Examples thereof include calcium phosphate, aluminum phosphite, zinc calcium phosphate, zinc aluminum phosphate, zinc phosphomolybdate, aluminum phosphomolybdate, magnesium phosphate, and vanadic acid / phosphoric acid mixed pigment. In particular, aluminum phosphate and zinc phosphate are preferable from the viewpoint of excellent dispersibility and corrosion resistance.
　本発明の第２の水性エポキシ樹脂塗料組成物においては、亜鉛粉末（ｉｉｉ）とリン酸塩系防錆顔料（ｉｖ）の合計質量が、全固形分質量あたり６５～９５質量％の範囲内である必要がある。リン酸塩系防錆顔料（ｉｖ）と亜鉛粉末（ｉｉｉ）の合計質量が、全固形分質量あたり６５質量％未満の場合は、塗膜の防食性を確保することができない。一方、９５質量％を超える場合は、混合作業性が低下したり、衝撃によって塗面に割れが発生し易くなり、また、基材との付着性が十分に得られないことがある。 In the second aqueous epoxy resin coating composition of the present invention, the total mass of the zinc powder (iii) and the phosphate-based anticorrosive pigment (iv) is in the range of 65 to 95% by mass based on the total solid content mass. There must be. When the total mass of the phosphate-based anticorrosive pigment (iv) and the zinc powder (iii) is less than 65% by mass with respect to the total solid mass, the anticorrosive property of the coating film cannot be ensured. On the other hand, when it exceeds 95 mass%, mixing workability | operativity falls, it becomes easy to generate | occur | produce a crack in a coating surface by an impact, and adhesiveness with a base material may not fully be obtained.
　本発明の第２の水性エポキシ樹脂塗料組成物においては、更に、亜鉛粉末（ｉｉｉ）とリン酸塩系防錆顔料（ｉｖ）の質量比［（ｉｉｉ）／（ｉｖ）］が、１００／０～７０／３０の範囲内である必要がある。この範囲を外れる場合は、塗膜の防食性を十分に確保できない恐れがあり、混合作業性が低下したり、衝撃によって塗面に割れが発生し易くなる。 In the second aqueous epoxy resin coating composition of the present invention, the mass ratio [(iii) / (iv)] of the zinc powder (iii) and the phosphate-based anticorrosive pigment (iv) is 100/0. Must be in the range of ~ 70/30. When it is out of this range, there is a possibility that the corrosion resistance of the coating film cannot be sufficiently secured, so that the mixing workability is lowered or the coating surface is easily cracked by impact.
＜第２の水性エポキシ樹脂塗料組成物の調製＞
　本発明の第２の水性エポキシ樹脂塗料組成物は、エポキシ樹脂エマルジョンを含む主剤（ｉ）と、アミン樹脂エマルジョンを含む硬化剤（ｉｉ）と、亜鉛粉末（ｉｉｉ）及び／又はリン酸塩系防錆顔料（ｉｖ）とを組み合わせることによって得られるが、常法に従って調製が可能である。例えば、主剤（ｉ）又は硬化剤（ｉｉ）にリン酸塩系防錆顔料（ｉｖ）を混合する場合には、主剤（ｉ）又は硬化剤（ｉｉ）を構成するエマルジョンに直接リン酸塩系防錆顔料（ｉｖ）を混合し、電動撹拌機等で分散させる方法や、界面活性剤を用いて水にリン酸塩系防錆顔料（ｉｖ）を分散させた後、ここに、主剤（ｉ）又は硬化剤（ｉｉ）を投入する方法が挙げられる。また、亜鉛粉末（ｉｉｉ）にリン酸塩系防錆顔料（ｉｖ）を混合する場合には、例えば、ボールミルに亜鉛粉末（ｉｉｉ）とリン酸塩系防錆顔料（ｉｖ）を投入し混合する方法が挙げられる。 <Preparation of second aqueous epoxy resin coating composition>
The second aqueous epoxy resin coating composition of the present invention comprises a main agent (i) containing an epoxy resin emulsion, a curing agent (ii) containing an amine resin emulsion, a zinc powder (iii) and / or a phosphate-based antibacterial agent. Although obtained by combining with a rust pigment (iv), it can be prepared according to a conventional method. For example, when the phosphate-based anticorrosive pigment (iv) is mixed with the main agent (i) or the curing agent (ii), the phosphate-based emulsion is directly added to the emulsion constituting the main agent (i) or the curing agent (ii). The antirust pigment (iv) is mixed and dispersed with an electric stirrer or the like, or after the phosphate-based antirust pigment (iv) is dispersed in water using a surfactant, the main agent (i ) Or a method of adding a curing agent (ii). In addition, when the phosphate-based rust preventive pigment (iv) is mixed with the zinc powder (iii), for example, the zinc powder (iii) and the phosphate-based rust preventive pigment (iv) are added to a ball mill and mixed. A method is mentioned.
　本発明による水性防食塗料組成物の混合方法の一例を以下に示す。予め、エポキシ樹脂エマルジョンを含む主剤（ｉ）とアミン樹脂エマルジョンを含む硬化剤（ｉｉ）を混合した後に、亜鉛粉末（ｉｉｉ）を混合してもよいし、エポキシ樹脂エマルジョンを含む主剤（ｉ）と亜鉛粉末（ｉｉｉ）を混合した後に、アミン樹脂エマルジョンを含む硬化剤（ｉｉ）を混合してもよい。いずれにしても、塗装直前に主剤（ｉ）、硬化剤（ｉｉ）及び亜鉛粉末（ｉｉｉ）を混合する必要がある。混合する方法としては、電動撹拌機を用いるのが最善であるが、塗料を均一に混合できる能力のある装置を適切に選択し、使用することができる。 An example of the mixing method of the water-based anticorrosive coating composition according to the present invention is shown below. The main component (i) containing the epoxy resin emulsion and the curing agent (ii) containing the amine resin emulsion may be mixed in advance, and then zinc powder (iii) may be mixed, or the main component (i) containing the epoxy resin emulsion and After mixing the zinc powder (iii), a curing agent (ii) containing an amine resin emulsion may be mixed. In any case, it is necessary to mix the main agent (i), the curing agent (ii) and the zinc powder (iii) immediately before coating. As the mixing method, it is best to use an electric stirrer, but an apparatus capable of uniformly mixing the paint can be appropriately selected and used.
＜＜第３の防食塗装方法＞＞
　次に、本発明の第３の防食塗装方法について詳細に説明する。本発明の第３の防食塗装方法は、上述の第２の水性エポキシ樹脂塗料組成物を塗装することを特徴とする。 << Third anticorrosion coating method >>
Next, the third anticorrosion coating method of the present invention will be described in detail. The third anticorrosion coating method of the present invention is characterized in that the above-mentioned second aqueous epoxy resin coating composition is applied.
　本発明の第３の防食塗装方法が適用される基材としては、例えば、炭素鋼等のように防食を必要とするものであれば、特に制限されるものではない。 The substrate to which the third anticorrosion coating method of the present invention is applied is not particularly limited as long as it requires anticorrosion, such as carbon steel.
　本発明に係る水性防食塗料組成物は、乾燥膜厚で通常１０～２００μｍ、好ましくは１５～１５０μｍの範囲内となるようにして上記基材面に塗装される。その塗装は、それ自体既知の塗装手段、例えば、エアスプレー、エアレススプレー、刷毛塗り又はローラー塗り等で行なうことができる。 The water-based anticorrosive coating composition according to the present invention is applied to the substrate surface so that the dry film thickness is usually in the range of 10 to 200 μm, preferably 15 to 150 μm. The coating can be performed by a coating means known per se, for example, air spray, airless spray, brush coating or roller coating.
　塗装は、１回塗りに限定されず、合計膜厚が１０～２００μｍの範囲内であれば、複数回に分割して塗装してもよい。乾燥膜厚が１０μｍ未満の場合は、防食性が十分でないため好ましくなく、一方、乾燥膜厚が２００μｍより厚膜の場合は、経年で付着不良等の不具合を起こす恐れがある。 Coating is not limited to one-time coating, and may be divided into multiple coatings as long as the total film thickness is within the range of 10 to 200 μm. When the dry film thickness is less than 10 μm, the anticorrosion property is not sufficient, which is not preferable. On the other hand, when the dry film thickness is greater than 200 μm, there is a risk of causing problems such as poor adhesion over time.
　塗装環境は、特に制限されるものではないが、０℃以下のような極端な低温環境や被塗物温度が８０℃以上のような高温環境は避けることが望ましい。 The coating environment is not particularly limited, but it is desirable to avoid an extremely low temperature environment such as 0 ° C. or lower or a high temperature environment where the temperature of the object to be coated is 80 ° C. or higher.
　塗膜の乾燥時間は、気温や湿度といった養生環境条件によって異なる。例えば、気温２３℃、相対湿度５０％の条件であれば７日間程度の乾燥時間が望ましいが、積層塗膜を形成するために次工程の塗料を塗り重ねる場合には、支障なく塗り重ねることができる。形成された積層塗膜が、本来の性能を発揮できるのであれば、これに限らない。 The drying time of the coating film depends on the curing environment conditions such as temperature and humidity. For example, if the temperature is 23 ° C. and the relative humidity is 50%, a drying time of about 7 days is desirable. However, when the next coating material is applied repeatedly to form a laminated coating film, it can be applied without any trouble. it can. If the formed laminated coating film can exhibit original performance, it will not be restricted to this.
　本発明に係る水性防食塗料組成物は、防食性や基材との付着性等に優れているため、一次防錆プライマーや防食下地として使用することができる。例えば、防食下地として使用する場合には、本発明に係る水性防食塗料組成物を基材面に塗装し塗膜を形成後、下塗り塗料を塗装し、更に、耐候性に優れた上塗り塗料を塗装することで、防食性を長期に亘り維持することができる。ただし、下塗り塗料と上塗り塗料の間に、中塗り塗料を塗装することも可能である。下塗り塗料としては、例えば、エポキシ樹脂系下塗り塗料、変性エポキシ樹脂系下塗り塗料及びウレタン樹脂系下塗り塗料等が挙げられる。また、中塗り塗料としては、例えば、エポキシ樹脂系中塗り塗料、変性エポキシ樹脂系中塗り塗料及びウレタン樹脂系中塗り塗料等が挙げられる。更に、上塗り塗料としては、例えば、アクリル樹脂系上塗り塗料、ウレタン樹脂系上塗り塗料、シリコーン樹脂系上塗り塗料及びフッ素樹脂系上塗り塗料等が挙げられる。 Since the water-based anticorrosive coating composition according to the present invention is excellent in anticorrosion properties, adhesion to a base material, and the like, it can be used as a primary rust preventive primer or an anticorrosion base. For example, when used as an anticorrosion substrate, the base coating is formed by coating the base surface with the aqueous anticorrosive coating composition according to the present invention, and then an undercoat is applied, and a topcoat excellent in weather resistance is applied. By doing, anticorrosion property can be maintained over a long period of time. However, an intermediate paint can be applied between the undercoat paint and the topcoat paint. Examples of the undercoat paint include an epoxy resin-based undercoat paint, a modified epoxy resin-based undercoat paint, and a urethane resin-based undercoat paint. Examples of the intermediate coating material include epoxy resin-based intermediate coating materials, modified epoxy resin-based intermediate coating materials, and urethane resin-based intermediate coating materials. Furthermore, examples of the top coating include acrylic resin-based top coating, urethane resin-based top coating, silicone resin-based top coating, and fluororesin-based top coating.
　特に、本発明に係る水性防食塗料組成物を基材面に塗装して形成された塗膜上に、更に、該水性防食塗料組成物以外の水性塗料を塗り重ねることにより、従来の溶剤系塗料と比較して大幅に有機溶剤の使用量を削減することが可能となった。これによって、環境に対して配慮しつつ基材を長期に亘って腐食から保護し、美観を維持することができる。 In particular, a conventional solvent-based paint can be obtained by further recoating an aqueous paint other than the aqueous anticorrosive paint composition on a coating film formed by applying the aqueous anticorrosive paint composition according to the present invention to the substrate surface. As a result, the amount of organic solvent used can be greatly reduced. Accordingly, the substrate can be protected from corrosion for a long time while maintaining consideration for the environment, and the aesthetic appearance can be maintained.
＜＜第４の防食塗装方法＞＞
　次に、本発明の第４の防食塗装方法を詳細に説明する。本発明の第４の防食塗装方法は、被塗装面上に水性エポキシ樹脂下塗り塗料を塗布して下塗り塗膜を形成し、その後、該下塗り塗膜上に水性上塗り塗料を塗布して上塗り塗膜を形成する防食塗装方法であって、前記水性エポキシ樹脂下塗り塗料及び前記水性上塗り塗料の両方が多液反応硬化型であり（要件ａ）、前記水性上塗り塗料は、前記水性エポキシ樹脂下塗り塗料よりも顔料容積濃度（ＰＶＣ）が低く（要件ｂ）、前記上塗り塗膜は、紫外線透過率が０．２％以下である（要件ｃ）という３つの要件を満たすことを特徴とする。上記３つの要件ａ～ｃを満たす水性防食塗装方法であれば、被塗装面に優れた耐候性及び防食性を付与することができる。ここで、水性防食塗装方法とは、防食性の付与を目的とした塗装方法のうち、水性塗料を用いた塗装方法を指し、本明細書においては、上記第４の防食塗装方法を水性防食塗装方法とも称する。 << 4th anticorrosion painting method >>
Next, the fourth anticorrosion coating method of the present invention will be described in detail. In the fourth anticorrosion coating method of the present invention, a base coating film is formed by applying a water-based epoxy resin base coating on the surface to be coated, and then a water base top coating is applied on the base coating. The water-based epoxy resin base coat and the water-based top coat are both multi-component reaction curable (requirement a), and the water-based top coat is more than the water-based epoxy resin base coat. The pigment volume concentration (PVC) is low (requirement b), and the top coat film satisfies the three requirements of an ultraviolet transmittance of 0.2% or less (requirement c). If the water-based anticorrosion coating method satisfies the above three requirements a to c, excellent weather resistance and anticorrosion properties can be imparted to the surface to be coated. Here, the water-based anticorrosion coating method refers to a coating method using a water-based paint among the coating methods aimed at imparting anticorrosion properties. In the present specification, the fourth anticorrosion coating method is referred to as the water-based anticorrosion coating. Also called a method.
　本発明の第４の防食塗装方法（水性防食塗装方法）は、上記水性エポキシ樹脂下塗り塗料及び上記水性上塗り塗料の両方が多液反応硬化型であることを要する。これら２種の塗料が多液反応硬化型の塗料であれば、緻密な硬化塗膜が得られ、腐食因子を遮蔽する効果が高くなるとともに、上塗り塗料の場合には紫外線等からの劣化を遅らせることが出来る。なお、多液反応硬化型の塗料とは、塗膜の母材として使用される樹脂を含む主剤と、該樹脂に対する反応性を有する成分を含む硬化剤とを組み合わせたものを指す。 The fourth anticorrosion coating method (aqueous anticorrosion coating method) of the present invention requires that both the water-based epoxy resin base coat and the water-based top coat are of a multi-component reaction curable type. If these two types of coatings are multi-component reaction curable coatings, a dense cured coating can be obtained, and the effect of shielding corrosion factors will be enhanced. In the case of top coatings, deterioration from ultraviolet rays and the like will be delayed. I can do it. The multi-component reaction curable paint refers to a combination of a main agent containing a resin used as a base material of a coating film and a curing agent containing a component having reactivity with the resin.
　また、本発明の水性防食塗装方法において、上記水性上塗り塗料は、上記水性エポキシ樹脂下塗り塗料よりもＰＶＣが低いことを要する。水性上塗り塗料のＰＶＣが水性エポキシ樹脂下塗り塗料よりも低い場合、下塗り塗膜に対する上塗り塗膜の追従性が改善され、これにより、経時での層間の密着性が高くなる。そのため、複合塗膜の耐候性や防食性が向上する。一方、水性上塗り塗料のＰＶＣが水性エポキシ樹脂下塗り塗料よりも高い場合には、経年劣化により塗膜に割れやはがれが発生する場合がある。なお、本発明における顔料容積濃度とは、塗料固形分中に占める顔料の割合（体積％）を指す。 Further, in the water-based anticorrosion coating method of the present invention, the water-based top coating material needs to have a lower PVC than the water-based epoxy resin base coating material. When the PVC of the water-based top coat is lower than that of the water-based epoxy resin base coat, the followability of the top coat with respect to the base coat is improved, thereby increasing the adhesion between layers over time. Therefore, the weather resistance and corrosion resistance of the composite coating film are improved. On the other hand, when the PVC of the water-based top coating is higher than that of the water-based epoxy resin base coating, cracking or peeling may occur in the coating due to deterioration over time. In addition, the pigment volume concentration in this invention refers to the ratio (volume%) of the pigment which occupies for paint solid content.
　更に、本発明の水性防食塗装方法においては、上記上塗り塗膜は、紫外線透過率が０．２％以下であることを要する。上塗り塗膜の紫外線透過率が０．２％を超えると、上塗り塗膜を透過した紫外線によって、下塗り塗膜や中塗り塗膜等の塗膜表面の劣化が起こり、層間剥離が生じる。なお、本発明における塗膜の紫外線透過率とは、波長３８０ｎｍの光線を塗膜に当てたときの透過率（％）を指す。 Furthermore, in the water-based anticorrosive coating method of the present invention, the top coat film needs to have an ultraviolet transmittance of 0.2% or less. When the UV transmittance of the top coat film exceeds 0.2%, the UV light transmitted through the top coat film causes the surface of the coat film such as the undercoat film or the intermediate coat film to deteriorate, resulting in delamination. In addition, the ultraviolet-ray transmittance of the coating film in this invention refers to the transmittance | permeability (%) when a light beam with a wavelength of 380 nm is applied to a coating film.
　本発明の水性防食塗装方法は、まず、被塗装面上に水性エポキシ樹脂下塗り塗料を塗布して下塗り塗膜を形成する工程が行われる。下塗り塗膜の母材にエポキシ樹脂を用いることで、優れた防食性が得られる。なお、水性エポキシ樹脂下塗り塗料とは、エポキシ樹脂及び水を含有する下塗り塗料を意味する。 In the water-based anticorrosive coating method of the present invention, first, a step of forming a base coating film by applying a water-based epoxy resin base coating on the surface to be coated is performed. By using an epoxy resin as the base material of the undercoat coating film, excellent anticorrosion properties can be obtained. In addition, a water-based epoxy resin undercoat paint means an undercoat paint containing an epoxy resin and water.
　上記被塗装面としては、防食性の付与が必要な表面であれば特に制限されるものではないが、橋梁やプラント等の構造物の表面、より具体的には、鉄道橋、道路橋、ガスタンク、石油タンク、鉄塔等の炭素鋼等の材料からなる基材表面が挙げられる。 The surface to be coated is not particularly limited as long as it is a surface that needs to be provided with anticorrosion properties, but more specifically, the surface of a structure such as a bridge or a plant, more specifically, a railway bridge, a road bridge, a gas tank. And base material surfaces made of carbon steel materials such as oil tanks and steel towers.
　上記水性エポキシ樹脂下塗り塗料は、多液反応硬化型であり且つ上記水性上塗り塗料よりもＰＶＣが高いことを除き特に制限されるものではないが、エポキシ樹脂エマルジョンを含む主剤とアミン樹脂エマルジョンを含む硬化剤とを含むことが好ましい。この場合、上記水性エポキシ樹脂下塗り塗料は、主剤と硬化剤とを、例えば、これらの成分を均一に混合できる装置、好ましくは電動攪拌機等を用いて、均一に混合することにより調製できる。また、主剤と硬化剤を混合する時期は、塗装の直前が好ましい。 The water-based epoxy resin base coating is not particularly limited except that it is a multi-component reaction curable type and has a higher PVC than the water-based top coating, but is a curing containing an epoxy resin emulsion and an amine resin emulsion. It is preferable to contain an agent. In this case, the water-based epoxy resin primer can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating.
　上記水性エポキシ樹脂下塗り塗料において、エポキシ樹脂エマルジョンは、エポキシ樹脂が水等の水性媒体中で分散してなる乳濁液であり、特に制限されるものではないが、通常の強制乳化方式（乳化剤及び高速攪拌機等を使用する方式）によって、水等の水性媒体中でエポキシ樹脂を乳化させることにより調製される。 In the above-mentioned water-based epoxy resin primer, the epoxy resin emulsion is an emulsion in which the epoxy resin is dispersed in an aqueous medium such as water, and is not particularly limited. It is prepared by emulsifying the epoxy resin in an aqueous medium such as water by a method using a high-speed stirrer or the like.
　上記エポキシ樹脂エマルジョンを構成するエポキシ樹脂は、１分子中に少なくとも２個のエポキシ基を有する樹脂である限り、特に限定されないが、例えば、多価アルコール又は多価フェノールとハロヒドリンとを反応させて得られるものであり、具体例としては、ビスフェノールＡ型エポキシ樹脂、ハロゲン化ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、ポリグリコール型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、エポキシ化油、１，６－ヘキサンジオールジグリシジルエーテル及びネオペンチルグリコールジグリシジルエーテル等が挙げられる。これらの中でも、塗膜の機械的耐久性や防食性、被塗装面（例えば基材表面）との付着性等の観点から、ビスフェノールＡ型エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂が好ましい。なお、これらエポキシ樹脂は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、エポキシ樹脂エマルジョンの市販品としては、例えば、エポルジョンＥＡ１、２、３、７、１２、２０、５５及びＨＤ２（日本ＮＳＣ社製、商品名）；アクアトート２０５、５１０、３５２０、３５４０、３５２０１、５００３、及び５５２０（東都レジン化工社製、商品名）；ユカレジンＫＥ－００２、ＫＥ－１１６、Ｅ－１０２２、ＫＥ－３０１Ｃ（吉村油化学社製、商品名）；及びＥＭ－１０１－５０（アデカ社製、商品名）が挙げられる。 The epoxy resin constituting the epoxy resin emulsion is not particularly limited as long as it is a resin having at least two epoxy groups in one molecule. For example, it is obtained by reacting a polyhydric alcohol or polyhydric phenol with a halohydrin. Specific examples include bisphenol A type epoxy resins, halogenated bisphenol A type epoxy resins, novolac type epoxy resins, polyglycol type epoxy resins, bisphenol F type epoxy resins, epoxidized oil, and 1,6-hexane. Examples include diol diglycidyl ether and neopentyl glycol diglycidyl ether. Among these, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoints of mechanical durability and corrosion resistance of the coating film, adhesion to the surface to be coated (for example, the surface of the substrate), and the like. In addition, these epoxy resins may be used independently and may be used in combination of 2 or more type. Moreover, as a commercial item of an epoxy resin emulsion, for example, Epourgeon EA1, 2, 3, 7, 12, 20, 55 and HD2 (Nippon NSC company make, brand name); Aquatote 205, 510, 3520, 3540, 35201 , 5003, and 5520 (trade name, manufactured by Toto Resin Chemical Co., Ltd.); Yuka Resin KE-002, KE-116, E-1022, KE-301C (trade name, manufactured by Yoshimura Oil Chemical Co., Ltd.); and EM-101-50 ( Adeka's product name).
　上記主剤は、上記エポキシ樹脂エマルジョンの他、塗膜の可撓性を向上させる目的として、反応性希釈剤や非反応性希釈剤等の一般的に使用される希釈剤を含有してもよい。反応性希釈剤としては、例えば、カージュラＥ１０（油化シェルエポキシ社製、商品名）、ネオトートＳ（東都化成社製、商品名）、及びアデカグリシロールＥＤ５０２（旭電化工業社製、商品名）等の１官能性エポキシ樹脂が挙げられる。一方、非反応性希釈剤としては、例えば、ニカノールＬＬＬ等の石油樹脂及びクマロン樹脂等が挙げられる。これら希釈剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In addition to the epoxy resin emulsion, the main agent may contain a commonly used diluent such as a reactive diluent and a non-reactive diluent for the purpose of improving the flexibility of the coating film. Examples of reactive diluents include Cardura E10 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Neotote S (trade name, manufactured by Toto Kasei Co., Ltd.), and Adeka Glycilol ED502 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.). Monofunctional epoxy resins such as On the other hand, examples of the non-reactive diluent include petroleum resins such as Nicanol LLL and coumarone resins. These diluents may be used alone or in combination of two or more.
　なお、上記主剤は、上記エポキシ樹脂エマルジョンと、必要に応じて適宜選択される各種成分とを混合することにより調製できる。 In addition, the said main ingredient can be prepared by mixing the said epoxy resin emulsion and the various components suitably selected as needed.
　上記硬化剤を構成するアミン樹脂エマルジョンとは、アミン樹脂が水等の水性媒体中で分散してなる乳濁液であり、ここで、アミン樹脂とは、１分子中に２個以上のアミノ基を含有するポリアミン樹脂である。上記ポリアミン樹脂としては、例えば、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、トリアミノプロパン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、イソホロンジアミン、及び１，３－ビスアミノメチルシクロヘキサン等の脂肪族ポリアミン；フェニレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、及びジアミノジフエニルメタン等の芳香族ポリアミン；ポリオキシエチレンジアミン、ポリオキシプロピレンジアミン、トリエチレングリコールジアミン、及びトリプロピレングリコールジアミン等の他のポリアミン化合物と、これらポリアミン樹脂のアミノ基を変性してなる変性ポリアミン樹脂とが挙げられる。なお、上記ポリアミン樹脂の変性には、既知の方法が利用でき、変性反応の例としては、アミノ基のアミド化、アミノ基とカルボニル化合物のマンニッヒ反応、アミノ基とエポキシ基の付加反応等が挙げられる。ここで、アミノ基にエポキシ基等が付加したタイプの変性ポリアミン樹脂をアダクトタイプの変性ポリアミン樹脂といい、防食性の観点から、アミノ基にエポキシ基が付加したエポキシアダクトタイプの変性ポリアミン樹脂が好ましい。 The amine resin emulsion constituting the curing agent is an emulsion in which an amine resin is dispersed in an aqueous medium such as water. Here, the amine resin means two or more amino groups in one molecule. Is a polyamine resin containing Examples of the polyamine resin include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triaminopropane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, and 1,3-bisaminomethylcyclohexane. Aliphatic polyamines; aromatic polyamines such as phenylenediamine, metaxylylenediamine, paraxylylenediamine, and diaminodiphenylmethane; such as polyoxyethylenediamine, polyoxypropylenediamine, triethyleneglycoldiamine, and tripropyleneglycoldiamine Examples include other polyamine compounds and modified polyamine resins obtained by modifying the amino groups of these polyamine resins. For modification of the polyamine resin, known methods can be used. Examples of the modification reaction include amidation of an amino group, Mannich reaction of an amino group and a carbonyl compound, addition reaction of an amino group and an epoxy group, and the like. It is done. Here, a modified polyamine resin in which an epoxy group or the like is added to an amino group is referred to as an adduct type modified polyamine resin, and an epoxy adduct type modified polyamine resin in which an epoxy group is added to an amino group is preferable from the viewpoint of corrosion resistance. .
　なお、上記硬化剤は、上記アミン樹脂エマルジョンと、必要に応じて適宜選択される各種成分とを混合することにより調製できる。 In addition, the said hardening | curing agent can be prepared by mixing the said amine resin emulsion and the various components suitably selected as needed.
　また、上記主剤及び／又は硬化剤は、その他塗料に一般的に使用される着色顔料、防錆顔料及び体質顔料等を特に制限無く含有することができる。着色顔料、防錆顔料及び体質顔料の具体例としては、酸化チタン、ベンガラ、黄色酸化鉄、カーボンブラック、トリポリリン酸アルミニウム、リン酸亜鉛、メタホウ酸バリウム、炭酸カルシウム、硫酸バリウム、タルク、クレー、マイカ、アルミナ、ミョウバン、白土、水酸化マグネシウム、及び酸化マグネシウム等の無機顔料や、フタロシアニンブルー、フタロシアニングリーン、ナフトールレッド、キナクリドンレッド、ベンズイミダゾロンイエロー、ハンザイエロー、ベンズイミダゾロンオレンジ、及びジオキサジンバイオレット等の有機顔料が挙げられる。これら顔料は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 In addition, the main agent and / or the curing agent may contain other coloring pigments, rust preventive pigments, extender pigments, and the like that are generally used for paints. Specific examples of color pigments, rust preventive pigments and extender pigments include titanium oxide, bengara, yellow iron oxide, carbon black, aluminum tripolyphosphate, zinc phosphate, barium metaborate, calcium carbonate, barium sulfate, talc, clay, mica , Inorganic pigments such as alumina, alum, clay, magnesium hydroxide, and magnesium oxide, phthalocyanine blue, phthalocyanine green, naphthol red, quinacridone red, benzimidazolone yellow, hansa yellow, benzimidazolone orange, and dioxazine violet And organic pigments. These pigments may be used alone or in combination of two or more.
　更に、上記主剤及び／又は硬化剤には、水性エポキシ樹脂下塗り塗料に各種機能を付与するため、増粘剤、分散剤、消泡剤、沈降防止剤、防カビ剤、防腐剤、紫外線吸収剤、又は光安定剤等が適宜添加されてもよい。また、エポキシ樹脂エマルジョンを構成するエポキシ樹脂とアミン樹脂エマルジョンを構成するポリアミン樹脂との融着を促進するため、上記主剤及び／又は硬化剤には、有機溶剤を配合することも可能である。有機溶剤としては、例えば、エチレングリコールモノｎ－ブチルエーテル、エチレングリコールモノｉ－ブチルエーテル、エチレングリコールモノｎ－プロピルエーテル、エチレングリコールモノｉ－プロピルエーテル、ジエチレングリコールモノｎ－ブチルエーテル、ジエチレングリコールモノｉ－ブチルエーテル、ジエチレングリコールモノｎ－プロピルエーテル、ジエチレングリコールモノｉ－プロピルエーテル、ジプロピレングリコールモノｎ－ブチルエーテル、ジプロピレングリコールモノｉ－ブチルエーテル、ジプロピレングリコールモノｎ－プロピルエーテル、ジプロピレングリコールモノｉ－プロピルエーテル、ジエチレングリコールジエチルエーテル、及びジエチレングリコールジブチルエーテル等のグリコールエーテル類、２，２，４－トリメチルペンタンジオールモノイソブチレート、及び２，２，４－トリメチルペンタンジオールジイソブチレート等が挙げられる。これら有機溶剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Further, the main agent and / or curing agent has a thickener, a dispersant, an antifoaming agent, an anti-settling agent, an antifungal agent, an antiseptic, and an ultraviolet absorber for imparting various functions to the water-based epoxy resin primer. Or a light stabilizer etc. may be added suitably. Moreover, in order to accelerate | stimulate melt | fusion of the epoxy resin which comprises an epoxy resin emulsion, and the polyamine resin which comprises an amine resin emulsion, it is also possible to mix | blend an organic solvent with the said main ingredient and / or a hardening | curing agent. Examples of the organic solvent include ethylene glycol mono n-butyl ether, ethylene glycol mono i-butyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono i-propyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono i-butyl ether, diethylene glycol. Mono n-propyl ether, diethylene glycol mono i-propyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol mono i-butyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono i-propyl ether, diethylene glycol diethyl ether And glycol ethers such as diethylene glycol dibutyl ether , 2,2,4-trimethyl pentanediol mono-isobutyrate, and 2,2,4-trimethyl pentanediol diisobutyrate and the like. These organic solvents may be used alone or in combination of two or more.
　上記水性エポキシ樹脂下塗り塗料において、アミン樹脂エマルジョンを含む硬化剤の配合割合は、塗膜の硬化性及び防食性等の観点から、主剤中に含まれるエポキシ樹脂エマルジョンを構成するエポキシ樹脂のエポキシ基１当量に対して、アミン樹脂エマルジョンを構成するアミン樹脂の活性水素が、通常０．５～２．０当量の範囲内であるのが好ましい。 In the water-based epoxy resin undercoat paint, the blending ratio of the curing agent containing the amine resin emulsion is the epoxy group 1 of the epoxy resin constituting the epoxy resin emulsion contained in the main agent from the viewpoint of the curability of the coating film and the corrosion resistance. It is preferable that the active hydrogen of the amine resin constituting the amine resin emulsion is usually in the range of 0.5 to 2.0 equivalents with respect to equivalents.
　本発明の水性防食塗装方法において、上記水性エポキシ樹脂下塗り塗料を塗布した後に形成される下塗り塗膜の膜厚（乾燥膜厚）は、通常２０～２５０μｍの範囲内であり、３０～１５０μｍの範囲内であるのが好ましい。また、上記水性エポキシ樹脂下塗り塗料の塗装方法としては、特に制限されず、既知の塗装手段、例えば、エアスプレー塗装、エアレススプレー塗装、刷毛塗り、又はローラー塗り等が利用できる。なお、これら塗装手段を複数回利用し、水性エポキシ樹脂下塗り塗料を塗り重ねることも可能である。また、塗装環境は、特に制限されるものではないが、０℃以下のような極端な低温環境や被塗装表面の温度が８０℃以上のような高温環境は避けることが望ましい。水性エポキシ樹脂下塗り塗料の乾燥時間は、気温や湿度等の養生環境条件によって異なる。例えば、気温２３℃、相対湿度５０％の条件であれば７日間程度の乾燥時間が望ましいが、積層塗膜を形成するために次工程の塗料を塗り重ねる場合には、支障なく塗り重ねることができる。なお、形成された積層塗膜が、本来の性能を発揮できるのであれば、これに限定されない。 In the water-based anticorrosive coating method of the present invention, the film thickness (dry film thickness) of the undercoat film formed after the application of the water-based epoxy resin undercoat is usually in the range of 20 to 250 μm, and in the range of 30 to 150 μm. Is preferably within. The method for applying the water-based epoxy resin primer is not particularly limited, and known coating means such as air spray coating, airless spray coating, brush coating, or roller coating can be used. In addition, it is also possible to use these coating means a plurality of times and repeatedly apply the water-based epoxy resin primer. The coating environment is not particularly limited, but it is desirable to avoid an extremely low temperature environment such as 0 ° C. or less or a high temperature environment where the temperature of the surface to be coated is 80 ° C. or more. The drying time of the water-based epoxy resin undercoat varies depending on the curing environment conditions such as temperature and humidity. For example, if the temperature is 23 ° C. and the relative humidity is 50%, a drying time of about 7 days is desirable. However, when the next coating material is applied repeatedly to form a laminated coating film, it can be applied without any trouble. it can. In addition, if the formed laminated coating film can exhibit original performance, it will not be limited to this.
　本発明の水性防食塗装方法は、次いで、下塗り塗膜上に水性上塗り塗料を塗布して上塗り塗膜を形成する工程が行われる。 In the water-based anticorrosive coating method of the present invention, a step of forming a topcoat film by applying an aqueous topcoat onto the undercoat film is then performed.
　上記水性上塗り塗料は、多液反応硬化型であり、水性エポキシ樹脂下塗り塗料よりもＰＶＣが低く、且つ形成される上塗り塗膜の紫外線透過率が０．２％以下である限り特に制限されるものではないが、水性ウレタン樹脂塗料、水性フッ素樹脂塗料等が好ましい。 The above-mentioned water-based top coating is a multi-component reaction curable type, and is particularly limited as long as the PVC is lower than the water-based epoxy resin base coating and the UV transmittance of the formed top coating is 0.2% or less. However, water-based urethane resin paints, water-based fluororesin paints and the like are preferable.
　上記水性ウレタン樹脂塗料は、例えば、１分子中に複数の水酸基を有するアクリル樹脂が水等の水性媒体中で分散してなる分散液又は乳濁液を含む主剤と、１分子中に１つのイソシアネート基を有するイソシアネート樹脂又は１分子中に複数のイソシアネート基を有するポリイソシアネート樹脂を含む硬化剤とからなる。この場合、上記水性ウレタン樹脂塗料は、主剤と硬化剤とを、例えば、これらの成分を均一に混合できる装置、好ましくは電動攪拌機等を用いて、均一に混合することにより調製できる。また、主剤と硬化剤を混合する時期は、塗装の直前が好ましく、塗装後に硬化反応を開始し、塗膜が形成される。 The aqueous urethane resin paint includes, for example, a main agent containing a dispersion or emulsion in which an acrylic resin having a plurality of hydroxyl groups per molecule is dispersed in an aqueous medium such as water, and one isocyanate per molecule. And a curing agent containing an isocyanate resin having a group or a polyisocyanate resin having a plurality of isocyanate groups in one molecule. In this case, the water-based urethane resin coating can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating, and after the coating, a curing reaction is started and a coating film is formed.
　上記水性フッ素樹脂塗料は、例えば、１分子中に複数の水酸基を有するフッ素樹脂が水等の水性媒体中で分散してなる分散液又は乳濁液を含む主剤と、１分子中に１つのイソシアネート基を有するイソシアネート樹脂又は１分子中に複数のイソシアネート基を有するポリイソシアネート樹脂を含む硬化剤とからなる。この場合、上記水性フッ素樹脂塗料は、主剤と硬化剤とを、例えば、これらの成分を均一に混合できる装置、好ましくは電動攪拌機等を用いて、均一に混合することにより調製できる。また、主剤と硬化剤を混合する時期は、塗装の直前が好ましく、塗装後に硬化反応を開始し、塗膜が形成される。 The water-based fluororesin coating material includes, for example, a main agent containing a dispersion or emulsion in which a fluororesin having a plurality of hydroxyl groups per molecule is dispersed in an aqueous medium such as water, and one isocyanate per molecule. And a curing agent containing an isocyanate resin having a group or a polyisocyanate resin having a plurality of isocyanate groups in one molecule. In this case, the aqueous fluororesin coating material can be prepared by uniformly mixing the main agent and the curing agent using, for example, an apparatus capable of uniformly mixing these components, preferably an electric stirrer. Further, the timing of mixing the main agent and the curing agent is preferably immediately before coating, and after the coating, a curing reaction is started and a coating film is formed.
　なお、上記アクリル樹脂が分散してなる分散液又は乳濁液としては、バーノックＷＥ－３０１、ＷＥ－３０４、ＷＥ－３０６、ＷＥ－３１０、ＷＤ－５５１（ＤＩＣ社製、商品名）等が挙げられ、上記フッ素樹脂が分散してなる分散液又は乳濁液としては、ルミフロンＦＥ－４２００、ＦＥ－４３００、ＦＥ－４４００、ＦＥ－４５００（旭硝子社製、商品名）等が挙げられ、イソシアネート樹脂又はポリイソシアネート樹脂としては、バーノックＤＮＷ－５５００、ＤＮＷ－６０００（ＤＩＣ社製、商品名）、デュラネートＷＢ４０－１００、ＷＴ２０－１００、ＷＴ３０－１００、ＷＥ５０－１００（旭化成ケミカルズ社製、商品名）等が挙げられる。これら配合剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Examples of the dispersion or emulsion obtained by dispersing the acrylic resin include Bernock WE-301, WE-304, WE-306, WE-310, and WD-551 (trade name, manufactured by DIC). Examples of the dispersion or emulsion obtained by dispersing the fluororesin include Lumiflon FE-4200, FE-4300, FE-4400, FE-4500 (trade name, manufactured by Asahi Glass Co., Ltd.), and the like. Or as polyisocyanate resin, Bernock DNW-5500, DNW-6000 (manufactured by DIC, trade name), Duranate WB40-100, WT20-100, WT30-100, WE50-100 (trade name, manufactured by Asahi Kasei Chemicals), etc. Is mentioned. These compounding agents may be used alone or in combination of two or more.
　また、上記水性上塗り塗料（具体的には水性ウレタン樹脂塗料及び水性フッ素樹脂塗料）には、上記水性エポキシ樹脂下塗り塗料にも配合できる配合剤、例えば着色顔料、体質顔料、有機顔料、増粘剤、分散剤、消泡剤、沈降防止剤、防カビ剤、防腐剤、紫外線吸収剤、光安定剤、有機溶剤等を必要に応じて配合してもよい。 In addition, the water-based top coat (specifically, water-based urethane resin paint and water-based fluororesin paint) can be blended with the water-based epoxy resin base coat, for example, coloring pigment, extender pigment, organic pigment, thickener. A dispersant, an antifoaming agent, an anti-settling agent, an antifungal agent, an antiseptic, an ultraviolet absorber, a light stabilizer, an organic solvent and the like may be blended as necessary.
　本発明の水性防食塗装方法において、上記水性上塗り塗料を塗布した後に形成される上塗り塗膜の膜厚（乾燥膜厚）は、通常１０～２００μｍの範囲内であり、２０～１００μｍの範囲内であるのが好ましい。また、上記水性上塗り塗料の塗装方法としては、特に制限されず、既知の塗装手段、例えば、エアスプレー塗装、エアレススプレー塗装、刷毛塗り、又はローラー塗り等が利用できる。なお、塗装は、１回に限定されず、合計膜厚が１０～２００μｍの範囲内にあれば、複数回に分けて塗装を行ってもよい。また、上記水性上塗り塗料の塗装環境や乾燥時間については、水性エポキシ樹脂下塗り塗料について記載したものと同じ条件が適用できる。 In the water-based anticorrosion coating method of the present invention, the film thickness (dry film thickness) of the top coat film formed after applying the water-based top coat is usually within the range of 10 to 200 μm, and within the range of 20 to 100 μm. Preferably there is. The method for applying the water-based top coating is not particularly limited, and known coating means such as air spray coating, airless spray coating, brush coating, or roller coating can be used. The coating is not limited to one time, and the coating may be performed in a plurality of times as long as the total film thickness is in the range of 10 to 200 μm. The same conditions as those described for the water-based epoxy resin undercoating can be applied to the coating environment and drying time of the water-based top coating.
　本発明の水性防食塗装方法において、上記被塗装面には、ジンクリッチペイント処理、亜鉛メッキ処理及び金属溶射から選ばれる処理が施され、防食下地が形成されていることが好ましい。上記水性エポキシ樹脂下塗り塗料を塗布する前に、かかる処理を施すことによって、防食性を更に向上させることができる。なお、ジンクリッチペイントとは、高濃度の亜鉛を含有する塗料を意味し、水を溶媒とする水性ジンクリッチペイントが好適である。なお、被塗装面に防食下地が形成されているため、水性エポキシ樹脂下塗り塗料は、該防食下地の上に塗布されることになる。 In the water-based anticorrosion coating method of the present invention, the surface to be coated is preferably subjected to a treatment selected from zinc rich paint treatment, galvanizing treatment and metal spraying to form an anticorrosion base. By applying such treatment before applying the water-based epoxy resin primer, the anticorrosion can be further improved. In addition, a zinc rich paint means the coating material containing high concentration zinc, and the water-based zinc rich paint which uses water as a solvent is suitable. In addition, since the anti-corrosion base is formed in the to-be-coated surface, the water-based epoxy resin undercoat paint is applied on the anti-corrosion base.
　また、本発明の水性防食塗装方法においては、上記被塗装面の少なくとも一部が、旧塗膜の表面であってもよい。例えば、基材面上に予め形成した塗膜が経年しても、その状態が健全であれば、該塗膜の表面上に、上記水性エポキシ樹脂下塗り塗料を直接塗布することができる。 Moreover, in the water-based anticorrosion coating method of the present invention, at least a part of the surface to be coated may be the surface of an old paint film. For example, even if the coating film previously formed on the substrate surface is aged, if the state is healthy, the water-based epoxy resin primer can be directly applied on the surface of the coating film.
　更に、本発明の水性防食塗装方法においては、上記水性上塗り塗料を塗布する前に、多液反応硬化型の水性中塗り塗料を上記下塗り塗膜上に塗布し、中塗り塗膜が形成されていることが好ましい。このように下塗り塗膜と上塗り塗膜の間に中塗り塗膜が組み込まれた複合塗膜は、中塗り塗膜に各種機能を期待でき、例えば、上塗り塗膜の仕上がり外観を向上させることも可能である。なお、下塗り塗膜上に中塗り塗膜が形成されているため、水性上塗り塗料は、該中塗り塗膜上に塗布されることになる。上記水性中塗り塗料は、多液反応硬化型である限り特に制限されるものではないが、水性エポキシ樹脂塗料及び水性ウレタン樹脂塗料等が好ましい。なお、上記水性エポキシ樹脂塗料には、上述の水性エポキシ樹脂下塗り塗料が使用でき、また、上記水性ウレタン樹脂塗料には、水性上塗り塗料として使用できる上述の水性ウレタン樹脂塗料が使用できる。 Furthermore, in the water-based anticorrosive coating method of the present invention, before applying the water-based top coating, a multi-component reaction curing type water-based intermediate coating is applied onto the base coating to form an intermediate coating. Preferably it is. Thus, the composite coating film in which the intermediate coating film is incorporated between the undercoating film and the top coating film can be expected to have various functions in the intermediate coating film, for example, to improve the finished appearance of the top coating film. Is possible. In addition, since the intermediate coating film is formed on the undercoat coating film, the water-based top coating composition is applied onto the intermediate coating film. The aqueous intermediate coating is not particularly limited as long as it is a multi-component reaction curable type, but an aqueous epoxy resin coating and an aqueous urethane resin coating are preferable. In addition, the above-mentioned water-based epoxy resin undercoat can be used for the water-based epoxy resin paint, and the above-mentioned water-based urethane resin paint that can be used as a water-based top coat can be used for the water-based urethane resin paint.
＜塗装体＞
　次に、本発明の塗装体を詳細に説明する。本発明の塗装体は、上述の第４の防食塗装方法（水性防食塗装方法）によって被塗装面上に複合塗膜が形成されていることを特徴とする。複合塗膜を備えた物体、例えば橋梁やプラント等の構造物は、耐候性及び防食性に優れる。 <Coated body>
Next, the coated body of the present invention will be described in detail. The coated body of the present invention is characterized in that a composite coating film is formed on the surface to be coated by the above-described fourth anticorrosion coating method (aqueous anticorrosion coating method). An object provided with a composite coating film, such as a structure such as a bridge or a plant, is excellent in weather resistance and corrosion resistance.
　以下、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。なお、下記例中、「部」及び「％」は、それぞれ「質量部」及び「質量％」を意味する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.
＜＜第１の水性エポキシ樹脂塗料組成物、並びに第１及び第２の防食塗装方法＞＞
＜製造例１－１＞
　混合機に、イオン交換水を１１部投入し、これに分散剤１部、消泡剤０．３部、酸化チタン１０部、トリポリリン酸アルミニウム７部、沈降性硫酸バリウム２０部、及びカオリンクレー８部を撹拌環境下で除々に投入し、投入完了後、粒度が５０μｍ以下になるまで混合した。次いで、混合機に、エポキシ樹脂エマルジョン４０部、及びエチレングリコールモノｎ－ブチルエーテル４部を撹拌環境下で徐々に投入し、１０分間撹拌を行い、主剤１－１を調製した。 << first water-based epoxy resin coating composition and first and second anticorrosion coating methods >>
<Production Example 1-1>
11 parts of ion-exchanged water is added to the mixer, and 1 part of the dispersant, 0.3 part of the antifoaming agent, 10 parts of titanium oxide, 7 parts of aluminum tripolyphosphate, 20 parts of precipitated barium sulfate, and kaolin clay 8 Portions were gradually added under a stirring environment, and after completion of the addition, mixing was performed until the particle size became 50 μm or less. Next, 40 parts of the epoxy resin emulsion and 4 parts of ethylene glycol mono-n-butyl ether were gradually added to the mixer in a stirring environment, followed by stirring for 10 minutes to prepare the main agent 1-1.
＜製造例１－２＞
　混合機に、アミン樹脂エマルジョンを６２部投入し、これにイオン交換水３８部を撹拌環境下で徐々に投入し、１０分間撹拌を行い、硬化剤１－２を調製した。 <Production Example 1-2>
62 parts of the amine resin emulsion was added to the mixer, and 38 parts of ion-exchanged water was gradually added to the mixer in a stirring environment, followed by stirring for 10 minutes to prepare a curing agent 1-2.
＜主剤１－１～１－６及び硬化剤１－１～１－２＞
　以下の表１及び表２には、主剤１－１～１－６の配合処方及び硬化剤１－１～１－２の配合処方を示す。なお、主剤１－２～１－６は、表１に示す処方に従って配合剤を配合し、必要に応じて２５％アンモニア水又は１Ｎ塩酸を用いてｐＨの調製を行った以外は、上記主剤１－１の製造例１－１と同様にして、調製された。 <Main agents 1-1 to 1-6 and curing agents 1-1 to 1-2>
Tables 1 and 2 below show the formulation of the main ingredients 1-1 to 1-6 and the formulation of the curing agents 1-1 to 1-2. The main agents 1-2 to 1-6 were mixed according to the formulation shown in Table 1, and the main agent 1 except that the pH was adjusted with 25% aqueous ammonia or 1N hydrochloric acid as necessary. -1 was prepared in the same manner as in Production Example 1-1.
＜実施例１－１～１－８及び比較例１－１～１－２＞
　以下の表３～４に示す配合処方の水性エポキシ樹脂塗料組成物を調製し、該水性エポキシ樹脂塗料組成物のｐＨ、粘度、たるみ性、作業性及び防食性を測定及び評価した。結果を表３～４に示す。 <Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-2>
Aqueous epoxy resin coating compositions having the formulations shown in Tables 3 to 4 below were prepared, and the pH, viscosity, sagging property, workability, and anticorrosion properties of the aqueous epoxy resin coating composition were measured and evaluated. The results are shown in Tables 3-4.
＜参考例１－１＞
　参考例として、市販の有機溶剤系エポキシ樹脂塗料のエポニックス＃３０下塗（大日本塗料社製）を使用した。 <Reference Example 1-1>
As a reference example, a commercially available organic solvent-based epoxy resin paint, Eponics # 30 undercoat (Dainippon Paint Co., Ltd.) was used.
＜ｐＨ測定＞
　主剤及び水性エポキシ樹脂塗料組成物のｐＨをホリバ社製ｐＨ　ＭＥＴＥＲ　Ｄ－５２を用いて測定した。 <PH measurement>
The pH of the main agent and the aqueous epoxy resin coating composition was measured using pH METER D-52 manufactured by Horiba.
＜粘度測定＞
　２３℃における水性エポキシ樹脂塗料組成物について、ＴＡインスツルメンツ社製レオメーターＡＲＥＳを用い、ずり速度０．１（１／ｓ）における粘度及びずり速度１０００（１／ｓ）における粘度を測定した。 <Viscosity measurement>
With respect to the aqueous epoxy resin coating composition at 23 ° C., the viscosity at a shear rate of 0.1 (1 / s) and the viscosity at a shear rate of 1000 (1 / s) were measured using a rheometer ARES manufactured by TA Instruments.
＜たるみ性＞
　垂直面に設置したブリキ板に、刷毛塗りにて、理論乾燥膜厚が６０μｍとなるように、水性エポキシ樹脂塗料組成物又は有機溶剤系エポキシ樹脂塗料を塗装し、形成される塗膜のたるみ性を下記の基準に従って評価した。なお、乾燥膜厚は、サンコウ電子研究所社製　電磁膜厚計ＳＭ－１０００を用いて測定された。
　○：塗付面を１０点測定したときの最低乾燥膜厚が４８μｍ以上。
　×：塗付面を１０点測定したときの最低乾燥膜厚が４８μｍ未満。 <Looseness>
A tin plate placed on a vertical surface is coated with a water-based epoxy resin paint composition or an organic solvent-based epoxy resin paint so that the theoretical dry film thickness is 60 μm by brushing. Was evaluated according to the following criteria. The dry film thickness was measured using an electromagnetic film thickness meter SM-1000 manufactured by Sanko Electronic Laboratory.
○: The minimum dry film thickness when the coated surface is measured at 10 points is 48 μm or more.
X: The minimum dry film thickness when the coated surface was measured at 10 points was less than 48 μm.
＜塗装作業性＞
　ブリキ板に、刷毛塗り及びローラー塗りにて、水性エポキシ樹脂塗料組成物又は有機溶剤系エポキシ樹脂塗料を塗装し、塗装作業性を下記の基準に従って評価した。
　○：塗料組成物が均一に広がり、塗付面の仕上がりがよい。
　×：塗料組成物が均一に広がらず、塗付面の仕上がりが悪い。 <Coating workability>
A water-based epoxy resin coating composition or an organic solvent-based epoxy resin coating was applied to the tinplate by brush coating or roller coating, and the coating workability was evaluated according to the following criteria.
○: The coating composition spreads uniformly and the finish of the coated surface is good.
X: The coating composition does not spread uniformly and the finish of the coated surface is poor.
＜防食性＞
　試験板として、素地調整程度がＩＳＯ　８５０１－１　Ｓａ２．５のグリッドブラスト処理鋼板（１５０×７０×３．２ｍｍ）を用い、該試験板の両面に、エアスプレーを用いて、乾燥膜厚が５５～６５μｍになるように、水性エポキシ樹脂塗料組成物又は有機溶剤系エポキシ樹脂塗料を塗装し、２３℃、５０％相対湿度の条件にて７日間乾燥させ、試験片を作製した。該試験片をＪＩＳ　Ｋ５６００－７－９に準じて、付属書１のサイクルＤの試験条件で、１２０サイクル曝した後の試験片に生じたサビ、フクレの発生程度を下記の基準に従って評価した。
　◎：カット部から２ｍｍ以上離れた試験片表面にサビ、フクレ等の異常が無い。
　○：カット部から４ｍｍ以上離れた試験片表面にサビ、フクレ等の異常が無い。
　×：カット部から４ｍｍ以上離れた試験片表面にサビ、フクレが発生。 <Anti-corrosion>
As a test plate, a grid blasted steel plate (150 × 70 × 3.2 mm) having a base adjustment degree of ISO 8501-1 Sa2.5 was used, and an air spray was used on both sides of the test plate to obtain a dry film thickness of 55. A water-based epoxy resin coating composition or an organic solvent-based epoxy resin coating was applied so as to have a thickness of ˜65 μm, and dried for 7 days under the conditions of 23 ° C. and 50% relative humidity to prepare a test piece. In accordance with JIS K5600-7-9, the degree of rust and swelling generated on the test piece after 120 cycles of the test piece under the cycle D test conditions of Appendix 1 was evaluated according to the following criteria.
A: There is no abnormality such as rust or swelling on the surface of the test piece 2 mm or more away from the cut part.
○: There is no abnormality such as rust and swelling on the surface of the test piece 4 mm or more away from the cut part.
X: Rust and swelling occur on the surface of the test piece 4 mm or more away from the cut part.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上記表１～表４中に用いた（注１）～（注６）は、下記の通りである。
（注１）Ｄｉｓｐｅｒｂｙｋ－１９０（ビックケミー・ジャパン社製）
（注２）ＢＹＫ－０９３（ビックケミー・ジャパン社製）
（注３）エポルジョンＥＡ５５（日本ＮＳＣ；樹脂固形分５５％、エポキシ当量４９５ｇ／ｅｑ）
（注４）フジキュアーＦＸＳ－９１８－ＦＡ（Ｔ＆Ｋ　ＴＯＫＡ社製；エポキシアダクトタイプの変性ポリアミン樹脂、樹脂固形分６０％）
（注５）エポルジョンＥＢ－３（日本ＮＳＣ社製；ポリアミドアミン、樹脂固形分７５％）
（注６）主剤中に含まれるエポキシ樹脂エマルジョンを構成するエポキシ樹脂のエポキシ基１当量に対するアミン樹脂エマルジョンを構成するアミン樹脂の活性水素の当量を示す。 (Note 1) to (Note 6) used in Tables 1 to 4 are as follows.
(Note 1) Disperbyk-190 (by Big Chemie Japan)
(Note 2) BYK-093 (by Big Chemie Japan)
(Note 3) Epochon EA55 (Japan NSC; resin solid content 55%, epoxy equivalent 495 g / eq)
(Note 4) Fuji Cure FXS-918-FA (manufactured by T & K TOKA; epoxy adduct type modified polyamine resin, resin solid content 60%)
(Note 5) Eporation EB-3 (NSC Japan; polyamidoamine, resin solids 75%)
(Note 6) Indicates the equivalent amount of active hydrogen of the amine resin constituting the amine resin emulsion to one equivalent of the epoxy group of the epoxy resin constituting the epoxy resin emulsion contained in the main agent.
＜＜第２の水性エポキシ樹脂塗料組成物、及び第３の防食塗装方法＞＞
＜実施例２－１～２－８及び比較例２－１～２－５＞
　試験板としては、素地調整程度がＩＳＯ　８５０１－１　Ｓａ２．５のグリッドブラスト処理鋼板（１５０×７０×３．２ｍｍ）を用いた。下記表５及び表６に示す配合処方に従い、エポキシ樹脂エマルジョンを含む主剤とアミン樹脂エマルジョンを含む硬化剤を混合し、その後、必要に応じて亜鉛粉末やリン酸塩系防錆顔料を混合して水性防食塗料組成物を調製した。なお、リン酸塩系防錆顔料を使用する場合は、事前に亜鉛粉末と電動撹拌にて混合してから使用した。 «Second aqueous epoxy resin coating composition and third anticorrosion coating method»
<Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-5>
As the test plate, a grid blasted steel plate (150 × 70 × 3.2 mm) having a base adjustment degree of ISO 8501-1 Sa2.5 was used. In accordance with the formulation shown in Table 5 and Table 6 below, a main agent containing an epoxy resin emulsion and a curing agent containing an amine resin emulsion are mixed, and then zinc powder and phosphate rust preventive pigment are mixed as necessary. A water-based anticorrosive coating composition was prepared. In addition, when using a phosphate type | system | group anticorrosive pigment, it mixed and used by zinc powder and electric stirring beforehand.
　次に、得られた水性防食塗料組成物を予め水で希釈して適切な塗装粘度に調整し、乾燥膜厚が７０～８０μｍになるようにエアスプレーを用いて試験板の両面に塗布し、２３℃、５０％相対湿度の条件にて７日間乾燥させ、試験片を作製した。これらの試験片を下記の評価試験に供し、その結果を表５及び表６に示す。 Next, the obtained water-based anticorrosive coating composition is previously diluted with water to adjust to an appropriate coating viscosity, and applied to both surfaces of the test plate using an air spray so that the dry film thickness becomes 70 to 80 μm. A test piece was prepared by drying for 7 days under conditions of 23 ° C. and 50% relative humidity. These test pieces were subjected to the following evaluation test, and the results are shown in Tables 5 and 6.
＜混合作業性＞
　水性防食塗料組成物を電動撹拌機にて１分間混合後、５分間静置し、８０メッシュの金網でろ過し、残渣の発生程度を下記の基準に基づいて評価した。
　○：残渣が無い。
　×：残渣がある。 <Mixing workability>
The aqueous anticorrosive coating composition was mixed with an electric stirrer for 1 minute, then allowed to stand for 5 minutes, filtered through an 80 mesh wire mesh, and the degree of residue generation was evaluated based on the following criteria.
○: There is no residue.
X: There is a residue.
＜可使時間＞
　ＪＩＳ　Ｋ５６００－２－６に準じて、下記の基準に基づいて評価した。
　○：５時間後エアスプレーにより塗装が可能。
　×：５時間後エアスプレーにより塗装が不可能。 <Pot life>
In accordance with JIS K5600-2-6, evaluation was performed based on the following criteria.
○: Paintable by air spray after 5 hours.
X: Painting is impossible by air spray after 5 hours.
＜防食性＞
　ＪＩＳ　Ｋ５６００－７－１の耐中性塩水噴霧性に準じて、塩水噴霧に５００時間曝した後の試験片に生じたサビ及びフクレの発生程度を下記の基準に基づいて評価した。
　◎：カット部から１ｍｍ以上離れた試験片表面に赤サビ及びフクレ等の異常が無い。
　○：カット部から３ｍｍ以上離れた試験片表面に赤サビ及びフクレ等の異常が無い。
　×：カット部から３ｍｍ以上離れた試験片表面に赤サビ及びフクレが発生。 <Anti-corrosion>
According to JIS K5600-7-1's medium-resistant salt spray properties, the degree of rust and swelling generated on the test piece after exposure to salt water for 500 hours was evaluated based on the following criteria.
A: There is no abnormality such as red rust and swelling on the surface of the test piece 1 mm or more away from the cut part.
◯: There is no abnormality such as red rust and swelling on the surface of the test piece 3 mm or more away from the cut part.
X: Red rust and swelling are generated on the surface of the test piece 3 mm or more away from the cut part.
＜耐衝撃性＞
　ＪＩＳ　Ｋ－５６００－５－３の６（２００６）デュポン式耐衝撃性試験に準じて、落錘質量５００ｇ、撃心の尖端直径１／２インチの条件で試験を行い、塗膜に損傷を生じない最大落錘高さ（ｃｍ）を表示する。なお、５０ｃｍを最大値とする。 <Impact resistance>
In accordance with 6 (2006) DuPont impact resistance test of JIS K-5600-5-3, the test was conducted under the conditions of a falling weight mass of 500 g and a pointed diameter of the impact point of 1/2 inch, resulting in damage to the coating film. No maximum drop weight height (cm) is displayed. Note that 50 cm is the maximum value.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　上記表５及び表６中に用いた（注１）～（注１０）は、下記の通りである。
（注１）ビスフェノールＡ型エポキシ樹脂エマルジョン、樹脂固形分５５％、エポキシ当量４９５ｇ／ｅｑ、（商品名：エポルジョンＥＡ５５、日本ＮＳＣ社製）
（注２）ビスフェノールＡ型エポキシ樹脂エマルジョン、樹脂固形分６２％、エポキシ当量２００ｇ／ｅｑ、（商品名：エポルジョンＨＤ２、日本ＮＳＣ社製）
（注３）ビスフェノールＦ型エポキシ樹脂エマルジョン、樹脂固形分　７０％、エポキシ当量２００ｇ／ｅｑ、（商品名：ＪＥＲ　Ｗ８７３５Ｒ７０、三菱化学社製）
（注４）変性脂肪族ポリアミン系樹脂エマルジョン、樹脂固形分５６％、（商品名：フジキュアーＦＸＳ－９１８－ＦＡ、Ｔ＆Ｋ　ＴＯＫＡ社製）
（注５）変性ポリアミドアミン（水溶性）、樹脂固形分６０％、（商品名：ＪＥＲキュア
　ＷＤ１１Ｍ６０、三菱化学社製）
（注６）亜鉛粉末Ａ：平均粒子径４μｍ、かさ比重２．５
（注７）亜鉛粉末Ｂ：平均粒子径７μｍ、かさ比重３．１
（注８）亜鉛粉末Ｃ：平均粒子径８μｍ、かさ比重０．９
（注９）トリポリリン酸アルミニウム（商品名：ＣＡ６５０、テイカ社製）
（注１０）リン酸亜鉛（商品名：ＰＷ２、キクチカラー社製） (Note 1) to (Note 10) used in Tables 5 and 6 are as follows.
(Note 1) Bisphenol A type epoxy resin emulsion, resin solid content 55%, epoxy equivalent 495 g / eq, (trade name: Eporation EA55, manufactured by NSC Japan)
(Note 2) Bisphenol A type epoxy resin emulsion, resin solid content 62%, epoxy equivalent 200 g / eq, (trade name: Eporation HD2, manufactured by NSC Japan)
(Note 3) Bisphenol F type epoxy resin emulsion, resin solid content 70%, epoxy equivalent 200 g / eq, (trade name: JER W8735R70, manufactured by Mitsubishi Chemical Corporation)
(Note 4) Modified aliphatic polyamine resin emulsion, resin solid content 56%, (trade name: Fujicure FXS-918-FA, manufactured by T & K TOKA)
(Note 5) Modified polyamidoamine (water-soluble), resin solid content 60%, (trade name: JER Cure WD11M60, manufactured by Mitsubishi Chemical Corporation)
(Note 6) Zinc powder A: average particle diameter 4 μm, bulk specific gravity 2.5
(Note 7) Zinc powder B: average particle diameter 7 μm, bulk specific gravity 3.1
(Note 8) Zinc powder C: average particle diameter 8 μm, bulk specific gravity 0.9
(Note 9) Aluminum tripolyphosphate (trade name: CA650, manufactured by Teica)
(Note 10) Zinc phosphate (trade name: PW2, manufactured by Kikuchi Color)
＜＜第４の防食塗装方法、及び塗装体＞＞
＜製造例３－１＞
　混合機に、イオン交換水を１１部投入し、これに分散剤１部、消泡剤０．３部、酸化チタン１０部、トリポリリン酸アルミニウム５部、沈降性硫酸バリウム２０部、及びカオリンクレー８部を撹拌環境下で除々に投入し、投入完了後、粒度が５０μｍ以下になるまで混合した。次いで、混合機に、エポキシ樹脂エマルジョン４５部、及びエチレングリコールモノｎ－ブチルエーテル４部を撹拌環境下で徐々に投入し、１０分間撹拌を行い、下塗り塗料３－１の主剤を調製した。この主剤に硬化剤としてアミン樹脂エマルジョン１２部を塗装直前に混合し、下塗り塗料３－１を調製した。 << 4th anticorrosion coating method and painted body >>
<Production Example 3-1>
11 parts of ion-exchanged water is added to a mixer, and 1 part of a dispersant, 0.3 part of an antifoaming agent, 10 parts of titanium oxide, 5 parts of aluminum tripolyphosphate, 20 parts of precipitated barium sulfate, and kaolin clay 8 Portions were gradually added under a stirring environment, and after completion of the addition, mixing was performed until the particle size became 50 μm or less. Next, 45 parts of the epoxy resin emulsion and 4 parts of ethylene glycol mono-n-butyl ether were gradually added to the mixer in a stirring environment and stirred for 10 minutes to prepare the main agent of the undercoat paint 3-1. Undercoating paint 3-1 was prepared by mixing 12 parts of amine resin emulsion as a curing agent with the main agent immediately before coating.
＜下塗り塗料３－１～３－２及び中塗り塗料＞
　以下の表７には、下塗り塗料３－１～３－２及び中塗り塗料の配合処方を示す。なお、下塗り塗料３－２及び中塗り塗料は、表７に示す処方に従って配合剤を配合した以外は、製造例３－１と同様にして、調製された。 <Undercoat paint 3-1 to 3-2 and intermediate paint>
Table 7 below shows the formulation of the undercoat paints 3-1 to 3-2 and the intermediate coat paint. The undercoat paint 3-2 and the intermediate coat paint were prepared in the same manner as in Production Example 3-1, except that the compounding agents were blended according to the formulation shown in Table 7.
＜製造例３－２＞
　混合機に、イオン交換水８部を投入し、これに分散剤１部、及び酸化チタン２５部を撹拌環境下で除々に投入し、投入完了後、粒度が１０μｍ以下になるまで混合した。次いで、混合機に、アクリルポリオール樹脂エマルジョン６０部、ジエチレングリコールジｎ－ブチルエーテル４部、紫外線吸収剤０．５部、増粘剤１部、及び消泡剤０．５部を撹拌環境下で徐々に投入し、１０分間撹拌を行い、上塗り塗料３－１の主剤を調製した。この主剤にイソシアネート樹脂１０部を塗装直前に混合し、上塗り塗料３－１を調製した。 <Production Example 3-2>
8 parts of ion-exchanged water was added to the mixer, and 1 part of the dispersant and 25 parts of titanium oxide were gradually added in a stirring environment. After completion of the addition, mixing was performed until the particle size became 10 μm or less. Next, 60 parts of an acrylic polyol resin emulsion, 4 parts of diethylene glycol di-n-butyl ether, 0.5 part of an ultraviolet absorber, 1 part of a thickening agent, and 0.5 part of an antifoaming agent are gradually added to a mixer in a stirring environment. The mixture was stirred for 10 minutes to prepare the main agent of the top coat paint 3-1. The main coating was mixed with 10 parts of an isocyanate resin immediately before coating to prepare a top coat paint 3-1.
＜上塗り塗料３－１～３－２＞
　以下の表８には、上塗り塗料３－１～３－２の配合処方を示す。なお、上塗り塗料３－２は、表８に示す処方に従って配合剤を配合した以外は、製造例３－２と同様にして、調製された。 <Topcoat paint 3-1 to 3-2>
Table 8 below shows the formulation of top coat paints 3-1 and 3-2. The top coat 3-2 was prepared in the same manner as in Production Example 3-2 except that the compounding agent was blended according to the formulation shown in Table 8.
　なお、表７及び表８は、更に顔料容積濃度の設計値及び紫外線透過率を示しているが、これらの値は、以下の方法で算出される。 In addition, although Table 7 and Table 8 have shown the design value and ultraviolet-ray transmittance of the pigment volume concentration further, these values are computed with the following method.
＜顔料容積濃度＞
　塗料の顔料容積濃度（体積％）は、以下の式によって算出された。
　顔料容積濃度　＝　（顔料の体積）／　（塗料固形分の体積）　×　１００
　塗料固形分の体積　＝　樹脂の体積　＋　顔料の体積 <Pigment volume concentration>
The pigment volume concentration (volume%) of the paint was calculated by the following formula.
Pigment volume concentration = (Pigment volume) / (Paint solids volume) × 100
Volume of paint solids = Resin volume + Pigment volume
＜紫外線透過率＞
　ポリプロピレン板上に、乾燥膜厚が２５～３５μｍになるようエアスプレーを用いて、上塗り塗料を塗布し、２３℃、５０％相対湿度の条件にて７日間乾燥させ、その後、ポリプロピレン板から乾燥塗膜を剥がし、上塗り塗料の単離膜を作製した。次に、得られた単離膜の波長３８０ｎｍにおける紫外線透過率を島津製作所社製の紫外可視近赤外分析光度計ＵＶ３１００ＰＣを用いて測定した。 <Ultraviolet transmittance>
On the polypropylene plate, apply a top coat using air spray so that the dry film thickness is 25 to 35 μm, and dry for 7 days at 23 ° C. and 50% relative humidity. The film was peeled off to produce an isolated film for the top coat. Next, the ultraviolet transmittance at a wavelength of 380 nm of the obtained isolated membrane was measured using an ultraviolet-visible near-infrared analytical photometer UV3100PC manufactured by Shimadzu Corporation.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　上記表７及び表８中に用いた（注１）～（注８）は、下記の通りである。
（注１）Ｄｉｓｐｅｒｂｙｋ－１９０（ビックケミー・ジャパン社製）
（注２）ＢＹＫ－０９３（ビックケミー・ジャパン社製）
（注３）エポルジョンＥＡ５５（日本ＮＳＣ社製；樹脂固形分５５％、エポキシ当量４９５ｇ／ｅｑ）
（注４）フジキュアーＦＸＳ－９１８－ＦＡ（Ｔ＆Ｋ　ＴＯＫＡ社製；エポキシアダクトタイプの変性ポリアミン樹脂、樹脂固形分５６％）
（注５）バーノックＷＥ－３０１（ＤＩＣ社製；樹脂固形分４５％）
（注６）ＴＩＮＵＶＩＮ１１３０（ＢＡＳＦジャパン社製）
（注７）プライマルＲＭ－８Ｗ（ローム＆ハース社製）
（注８）バーノックＤＮＷ－６０００（ＤＩＣ社製；樹脂固形分１００％） (Note 1) to (Note 8) used in Tables 7 and 8 are as follows.
(Note 1) Disperbyk-190 (by Big Chemie Japan)
(Note 2) BYK-093 (by Big Chemie Japan)
(Note 3) Epourgeon EA55 (NSC Japan, resin solid content 55%, epoxy equivalent 495 g / eq)
(Note 4) Fuji Cure FXS-918-FA (manufactured by T & K TOKA; epoxy adduct type modified polyamine resin, resin solid content 56%)
(Note 5) Vernock WE-301 (manufactured by DIC; resin solid content 45%)
(Note 6) TINUVIN 1130 (manufactured by BASF Japan)
(Note 7) Primal RM-8W (Rohm & Haas)
(Note 8) Vernock DNW-6000 (manufactured by DIC; resin solid content 100%)
（実施例３－１～３－３及び比較例３－１～３－２）
　以下の表９には、使用した材料を示す（使用した材料には「○」が付けられている）。なお、試験板としては、素地調整程度がＩＳＯ　８５０１－１　Ｓａ２．５のグリッドブラスト処理鋼板（１５０×７０×３．２ｍｍ）又はＪＩＳ　Ｇ　３３０２に規定する亜鉛めっき鋼鈑ＳＧＨ４００　ＺＣ　Ｚ２７（１５０×７０×２．３ｍｍ）のいずれかを用いた。 (Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-2)
Table 9 below shows the materials used (the materials used are marked with “◯”). In addition, as a test plate, the base grading degree is ISO 8501-1 Sa2.5 grid blasted steel plate (150 × 70 × 3.2 mm) or galvanized steel plate SGH400 ZC Z27 (150 × 70) specified in JIS G 3302 × 2.3 mm) was used.
　まず、試験板の両面に、乾燥膜厚が５５～６５μｍになるようエアスプレーを用いて、下塗り塗料を塗布し、２３℃、５０％相対湿度の条件にて１日間乾燥させ、下塗り塗膜を形成させた。実施例３－２においては、次に、試験板の両面に形成された２枚の下塗り塗膜上に、乾燥膜厚が２５～３５μｍになるようエアスプレーを用いて、中塗り塗料を塗布し、２３℃、５０％相対湿度の条件にて１日間乾燥させ、中塗り塗膜を形成させた。最後に、実施例３－１及び３－３並びに比較例３－１～３－２においては、試験板の両面に形成された２枚の下塗り塗膜上に、実施例３－２においては、２枚の下塗り塗膜それぞれの上に形成された２枚の中塗り塗膜上に、乾燥膜厚が２５～３５μｍになるようエアスプレーを用いて、上塗り塗料を塗布し、２３℃、５０％相対湿度の条件にて７日間乾燥させ、複合塗膜を備えた試験片を作製した。これら試験片の防食性及び耐候性を以下の方法に従い評価した。結果を表９に示す。 First, an undercoat paint was applied to both sides of the test plate using an air spray so that the dry film thickness was 55 to 65 μm, and dried for one day under the conditions of 23 ° C. and 50% relative humidity. Formed. In Example 3-2, an intermediate coating was then applied on the two undercoat films formed on both sides of the test plate using air spray so that the dry film thickness was 25 to 35 μm. And dried at 23 ° C. and 50% relative humidity for 1 day to form an intermediate coating film. Finally, in Examples 3-1 and 3-3 and Comparative Examples 3-1 and 3-2, on the two undercoat films formed on both surfaces of the test plate, in Example 3-2, The top coat was applied to the two intermediate coats formed on each of the two undercoats using air spray so that the dry film thickness was 25 to 35 μm. The test piece provided with the composite coating film was produced by drying for 7 days under conditions of relative humidity. The corrosion resistance and weather resistance of these test pieces were evaluated according to the following methods. The results are shown in Table 9.
＜防食性＞
　ＪＩＳ　Ｋ５６００－７－１の耐中性塩水噴霧性に準じて、試験片を塩水噴霧に５００時間さらし、その後、該試験片に生じたサビ、フクレ等の発生程度を下記の基準に従って評価した。
　◎：カット部から１ｍｍ以上離れた試験片表面にサビ、フクレ等の異常が無い。
　○：カット部から３ｍｍ以上離れた試験片表面にサビ、フクレ等の異常が無い。
　×：カット部から３ｍｍ以上離れた試験片表面にサビ、フクレが発生。 <Anti-corrosion>
In accordance with JIS K5600-7-1, the test piece was subjected to salt spray for 500 hours according to the medium-resistant salt spray property, and then the degree of occurrence of rust, swelling, etc. generated on the test piece was evaluated according to the following criteria.
A: There is no abnormality such as rust or swelling on the surface of the test piece 1 mm or more away from the cut part.
○: There is no abnormality such as rust and swelling on the surface of the test piece 3 mm or more away from the cut part.
X: Rust and swelling occur on the surface of the test piece 3 mm or more away from the cut part.
＜耐候性＞
　ＪＩＳ　Ｋ５６００－７－７の促進耐候性及び促進耐光性（キセノンランプ法）のサイクルＡに準じて、１０００時間照射した後の試験片の光沢保持率を算出し、また、該試験片に生じた割れ、はがれ、フクレ等の発生を下記の基準に従って評価した。なお、光沢保持率は、ＢＹＫガードナー社製の光沢計ＢＹＫガードナー・マイクロ－グロスによって照射前後の光沢値を測定し、以下の式によって算出された。
　光沢保持率（％）＝　照射後の光沢値／照射前の光沢値×１００
　○：光沢保持率が７０％以上で、且つ割れ、はがれ、フクレ等の異常がない。
　×：光沢保持率が７０％未満、若しくは割れ、はがれ、フクレが発生。 <Weather resistance>
In accordance with cycle A of accelerated weather resistance and accelerated light resistance (xenon lamp method) of JIS K5600-7-7, the gloss retention of the test piece after 1000 hours of irradiation was calculated, and also occurred in the test piece. The occurrence of cracking, peeling, swelling, etc. was evaluated according to the following criteria. The gloss retention was calculated by the following equation after measuring the gloss value before and after irradiation with a gloss meter BYK Gardner Micro-Gloss manufactured by BYK Gardner.
Gloss retention (%) = Gloss value after irradiation / Gloss value before irradiation × 100
○: Gloss retention is 70% or more, and there is no abnormality such as cracking, peeling or swelling.
X: The gloss retention is less than 70%, or cracking, peeling, and swelling are generated.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009

Claims (14)

  1. 　エポキシ樹脂エマルジョンを含む主剤とアミン樹脂エマルジョンを含む硬化剤とを含んでなり、ずり速度０．１（１／ｓ）における粘度が１．０～５００（Ｐａ・ｓ、２３℃）であり、ずり速度１０００（１／ｓ）における粘度が０．０１０～１（Ｐａ・ｓ、２３℃）であることを特徴とする水性エポキシ樹脂塗料組成物。 It comprises a main agent containing an epoxy resin emulsion and a curing agent containing an amine resin emulsion, and has a viscosity of 1.0 to 500 (Pa · s, 23 ° C.) at a shear rate of 0.1 (1 / s). An aqueous epoxy resin coating composition having a viscosity at a speed of 1000 (1 / s) of 0.010 to 1 (Pa · s, 23 ° C.).
  2. 　前記主剤のｐＨが５～９であり、且つ前記水性エポキシ樹脂塗料組成物のｐＨが７～１１であることを特徴とする請求項１に記載の水性エポキシ樹脂塗料組成物。 The aqueous epoxy resin coating composition according to claim 1, wherein the pH of the main agent is 5 to 9, and the pH of the aqueous epoxy resin coating composition is 7 to 11.
  3. 　アミン樹脂エマルジョン中に含まれるポリアミン樹脂が、アダクトタイプの変性ポリアミン樹脂であることを特徴とする請求項１に記載の水性エポキシ樹脂塗料組成物。 2. The aqueous epoxy resin coating composition according to claim 1, wherein the polyamine resin contained in the amine resin emulsion is an adduct-type modified polyamine resin.
  4. 　請求項１～３のいずれかに記載の水性エポキシ樹脂塗料組成物を被塗装面上に塗装することを特徴とする防食塗装方法。 An anticorrosion coating method comprising coating the aqueous epoxy resin coating composition according to any one of claims 1 to 3 on a surface to be coated.
  5. 　請求項１～３のいずれかに記載の水性エポキシ樹脂塗料組成物を被塗装面上に塗装することによって、該被塗装面上に塗膜を形成し、更に、該塗膜上に、該水性エポキシ樹脂塗料組成物以外の水性塗料を塗装することを特徴とする防食塗装方法。 A coating film is formed on the surface to be coated by coating the aqueous epoxy resin coating composition according to any one of claims 1 to 3 on the surface to be coated, and further, An anticorrosion coating method characterized by coating a water-based paint other than an epoxy resin paint composition.
  6. 　エポキシ樹脂エマルジョンを含む主剤（ｉ）と、アミン樹脂エマルジョンを含む硬化剤（ｉｉ）と、亜鉛粉末（ｉｉｉ）及び／又はリン酸塩系防錆顔料（ｉｖ）とを含有する水性エポキシ樹脂塗料組成物であって、
    　該亜鉛粉末（ｉｉｉ）は、自然落下法によって測定されるかさ比重が１．０以上であり、該亜鉛粉末（ｉｉｉ）の質量比が、全固形分質量あたり６５質量％以上であり、
    　該亜鉛粉末（ｉｉｉ）と該リン酸塩系防錆顔料（ｉｖ）の合計質量が、全固形分質量あたり６５～９５質量％にあり、且つ、
    　該亜鉛粉末（ｉｉｉ）と該リン酸塩系防錆顔料（ｉｖ）の質量比［（ｉｉｉ）／（ｉｖ）］が、１００／０～７０／３０である
    　ことを特徴とする水性エポキシ樹脂塗料組成物。     An aqueous epoxy resin coating composition containing a main agent (i) containing an epoxy resin emulsion, a curing agent (ii) containing an amine resin emulsion, and zinc powder (iii) and / or a phosphate-based antirust pigment (iv) A thing,
    The zinc powder (iii) has a bulk specific gravity measured by a natural drop method of 1.0 or more, and a mass ratio of the zinc powder (iii) is 65% by mass or more per total solid mass,
    The total mass of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 65 to 95% by mass with respect to the total solid mass, and
    A water-based epoxy resin paint characterized in that the mass ratio [(iii) / (iv)] of the zinc powder (iii) and the phosphate anticorrosive pigment (iv) is 100/0 to 70/30 Composition.
  7. 　前記主剤（ｉ）に含まれるエポキシ樹脂が、ビスフェノールＡ型又はビスフェノールＦ型エポキシ樹脂であり、該エポキシ樹脂のエポキシ当量が１６０～９８０ｇ／ｅｑであることを特徴とする請求項６に記載の水性エポキシ樹脂塗料組成物。 The aqueous resin according to claim 6, wherein the epoxy resin contained in the main agent (i) is a bisphenol A type or bisphenol F type epoxy resin, and the epoxy equivalent of the epoxy resin is 160 to 980 g / eq. Epoxy resin coating composition.
  8. 　請求項６又は７に記載の水性エポキシ樹脂塗料組成物を塗装することを特徴とする防食塗装方法。 An anticorrosion coating method, wherein the aqueous epoxy resin coating composition according to claim 6 or 7 is applied.
  9. 　請求項６又は７に記載の水性エポキシ樹脂塗料組成物を塗装して得られた塗膜上に、更に、該防食塗料組成物以外の水性塗料を塗装することを特徴とする請求項８に記載の防食塗装方法。 The water-based paint other than the anticorrosive paint composition is further applied onto the coating film obtained by applying the water-based epoxy resin paint composition according to claim 6 or 7. Anti-corrosion painting method.
  10. 　被塗装面上に水性エポキシ樹脂下塗り塗料を塗布して下塗り塗膜を形成し、その後、該下塗り塗膜上に水性上塗り塗料を塗布して上塗り塗膜を形成する防食塗装方法であって、下記ａ）～ｃ）の要件を満たすことを特徴とする防食塗装方法。
    　ａ）前記水性エポキシ樹脂下塗り塗料及び前記水性上塗り塗料の両方が、多液反応硬化型である。
    　ｂ）前記水性上塗り塗料は、前記水性エポキシ樹脂下塗り塗料よりも顔料容積濃度が低い。
    　ｃ）前記上塗り塗膜は、紫外線透過率が０．２％以下である。     An anticorrosion coating method in which a water-based epoxy resin base coat is applied on a surface to be coated to form a base coat, and then a water base coat is applied on the base coat to form a top coat. An anticorrosion coating method characterized by satisfying the requirements of a) to c).
    a) Both the water-based epoxy resin base coat and the water-based top coat are multi-component reaction curable.
    b) The water-based top coating has a lower pigment volume concentration than the water-based epoxy resin base coating.
    c) The top coat film has an ultraviolet transmittance of 0.2% or less.
  11. 　前記水性上塗り塗料を塗布する前に、水性エポキシ樹脂塗料及び水性ウレタン樹脂塗料から選ばれる多液反応硬化型の水性中塗り塗料を前記下塗り塗膜上に塗布し、中塗り塗膜が形成されていることを特徴とする請求項１０に記載の防食塗装方法。 Before applying the water-based top coat, a multi-component reaction curing type water-based intermediate coat selected from a water-based epoxy resin paint and a water-based urethane resin paint is applied onto the base coat to form an intermediate coat. The anticorrosion coating method according to claim 10, wherein:
  12. 　前記被塗装面には、ジンクリッチペイント処理、亜鉛メッキ処理及び金属溶射から選ばれる処理が施され、防食下地が形成されていることを特徴とする請求項１０に記載の防食塗装方法。 11. The anticorrosion coating method according to claim 10, wherein the surface to be coated is subjected to a treatment selected from a zinc rich paint treatment, a galvanizing treatment and a metal spraying to form an anticorrosion base.
  13. 　前記被塗装面の少なくとも一部が、旧塗膜の表面であることを特徴とする請求項１０に記載の防食塗装方法。 11. The anticorrosion coating method according to claim 10, wherein at least a part of the surface to be coated is a surface of an old coating film.
  14. 　請求項１０～１３のいずれかに記載の防食塗装方法によって被塗装面上に複合塗膜が形成された塗装体。 A coated body in which a composite coating film is formed on a surface to be coated by the anticorrosion coating method according to any one of claims 10 to 13.
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