WO2021193082A1 - One-component aqueous coating composition - Google Patents

One-component aqueous coating composition Download PDF

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Publication number
WO2021193082A1
WO2021193082A1 PCT/JP2021/009725 JP2021009725W WO2021193082A1 WO 2021193082 A1 WO2021193082 A1 WO 2021193082A1 JP 2021009725 W JP2021009725 W JP 2021009725W WO 2021193082 A1 WO2021193082 A1 WO 2021193082A1
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Prior art keywords
coating composition
present
mass
resin
water
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PCT/JP2021/009725
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French (fr)
Japanese (ja)
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康人 谷口
昴志 西川
聡 斉藤
山下　智子
晃司 山田
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大日本塗料株式会社
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Publication of WO2021193082A1 publication Critical patent/WO2021193082A1/en

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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a one-component water-based coating composition, and more particularly to a one-component water-based coating composition having excellent adhesion to black-skinned steel.
  • Patent Document 1 In line coating of construction machinery and industrial machinery, adhesiveness and corrosion resistance to various substrates are required, so solvent-based paints with excellent performance have been generally used. However, in recent years, harmful air pollutants and volatile organic compounds have been regulated from the viewpoint of environmental protection, and conversion from solvent-based paints to water-based paints is being considered for line coatings for construction machinery (Patent Document 1). ).
  • Patent Document 2 Japanese Patent Document 2
  • An object of the present invention is to provide a one-component water-based coating composition having excellent adhesion to various substrates including black-skinned steel and having excellent corrosion resistance as a water-based coating material for construction machinery.
  • the object of the present invention has been achieved by the following.
  • the present invention it is possible to provide a one-component water-based coating composition having excellent adhesion to various substrates including black-skinned steel and having excellent corrosion resistance as a water-based coating material for construction machinery.
  • the one-component water-based coating composition of the present invention comprises at least one compound selected from (A) an epoxy ester resin, (B) an acrylic resin, and (C) a drying oil or a polymer of a drying oil. It is characterized by containing.
  • Epoxy ester resin As the epoxy ester resin of the present invention, a normal epoxy ester resin can be used. For example, an adduct of an epoxy resin and an acid such as an aliphatic acid, a reaction product of the adduct with a diisosocyanate compound or a hydroxycarboxylic acid, a vinyl modified product thereof, and the like can be mentioned. In particular, a vinyl-modified epoxy ester resin is preferable.
  • the vinyl-modified epoxy ester resin of the present invention is a vinyl-modified epoxy ester resin having a fatty acid chain to which a vinyl polymer portion is bonded, and the vinyl polymer portion has a terminal carboxyl group-containing structure represented by the following general formula (I). It is a vinyl-modified epoxy ester resin having, and part or all of the terminal carboxyl group-containing structure represented by the following general formula (I) is neutralized with a basic compound.
  • n 1 to 10 and R 1 represents an alkylene group having 2 to 18 carbon atoms.
  • the vinyl-modified epoxy resin described in Japanese Patent No. 3858934 and JP-A-2001-261759 can be preferably used.
  • the epoxy ester resin (A) used in the present invention preferably has a number average molecular weight of 1,000 to 100,000, more preferably a number average molecular weight of 2,000 to 50,000, 2. Those having a number average molecular weight of 000 to 10,000 are more preferable.
  • the softening point (Tm) and the glass transition point (Tg) of the epoxy ester resin (A) of the present invention are not particularly limited and can be selected as needed, but the preferable softening point is ⁇ 20 to 100 ° C., more preferably ⁇ 20. It is about 70 ° C., more preferably ⁇ 10 to 40 ° C.
  • the preferred glass transition point is ⁇ 20 to 100 ° C., more preferably ⁇ 10 to 60 ° C., and even more preferably 0 to 40 ° C.
  • Tm and Tg can be measured by DSC according to JIS K7121-1987.
  • Examples of the (A) epoxy ester resin used in the present invention include those having an acid value of 5 to 100, and among them, those having an acid value of 15 to 40 are preferable, and those having an acid value of 20 to 35 are used. Is more preferable.
  • this (A) epoxy ester resin is used in a state where a part or all of it is neutralized with a basic compound and dispersed in water.
  • the average particle size is 40 to 200 nm, preferably 80 to 150 nm.
  • the average particle size can be measured with a Microtrack particle size analyzer (Microtrack 9340-UPA, manufactured by Nikkiso Co., Ltd.).
  • the epoxy ester resin (A) is preferably an aqueous dispersion having a solid content of 20 to 60% by mass.
  • Examples of the aqueous dispersion of the epoxy ester resin (A) of the present invention include Watersol BM-1000P, CD-540P, EFD-5520, EFD-5530, EFD-5550, EFD-5560, EFD-5570, EFD-5580, EFD-5501P (all manufactured by DIC Corporation) and the like can be obtained as commercial products.
  • the epoxy ester resin (A) of the present invention is contained in an amount of 4 to 16% by mass, preferably 8 to 14% by mass, in the solid content of the one-component water-based coating composition. Is contained in an amount of 5 to 30% by mass, preferably 10 to 25% by mass.
  • the (B) acrylic resin of the present invention contains 30 to 100% by mass of an alkyl (meth) acrylate having 1 to 18 carbon atoms, and other styrene-based monomers (styrene, ⁇ -methylstyrene, etc.), vinyl acetate, and olefin (chloride). It is a resin obtained by copolymerizing vinyl, vinylidene chloride, butadiene, propylene, etc.).
  • alkyl (meth) acrylate having 1 to 18 carbon atoms examples include (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, toluyl (meth) acrylate, and glycidyl (meth).
  • n-butyl (meth) acrylate isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate , N-Heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl Examples include (meth) acrylate.
  • 2-Hydroxyethyl (meth) acrylate with hydroxyl group 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, lactone to 2-hydroxyethyl (meth) attrilate
  • the monomer having a hydroxyl group is preferably 0 to 5% by mass or less.
  • the styrene-based monomer is preferably contained in an amount of 0 to 70% by mass.
  • the number average molecular weight and the weight average molecular weight are values measured by size exclusion chromatography, and polystyrene is used as the standard substance.
  • the acrylic resin (B) of the present invention preferably has a glass transition temperature of ⁇ 50 to 40 ° C., more preferably in the range of ⁇ 30 to 40 ° C., and preferably ⁇ 10 to 40 ° C. More preferred.
  • Tg is the glass transition temperature (K) of the polymer composed of n kinds of monomers
  • Tg (1, 2, i, n) is the glass transition temperature (K) of the homopolymer of each monomer.
  • W (1, 2, i, n) is the mass fraction of each monomer
  • W1 + W2 + ... + Wi + ... + Wn 1.
  • the acrylic resin (B) of the present invention is used as an aqueous dispersion, but after synthesizing the acrylic resin, it is dissolved in an organic solvent and given a shearing force in water to which a surfactant is added to obtain an aqueous dispersion. It can be made into an aqueous dispersion by emulsion polymerization from the beginning.
  • the acrylic resin of the present invention is preferably an aqueous dispersion having a solid content of 20 to 60% by mass, and the aqueous-dispersed acrylic resin described in JP-A-2018-172504 can be used.
  • the aqueous dispersion of the acrylic resin (B) of the present invention preferably has a 50% by volume particle size (D50) in the range of 50 to 300 nm, and more preferably in the range of 50 to 200 nm.
  • the 50% by volume particle size (D50) refers to the 50% particle size (D50) of the volume-based particle size distribution, and is a laser diffraction / scattering type particle size distribution measuring device (for example, SALD-7000: manufactured by Shimadzu Corporation). ) Can be obtained from the particle size distribution measured.
  • the particle size in the present invention is represented by a sphere-equivalent diameter obtained by a laser diffraction / scattering method.
  • the acrylic resin (B) of the present invention is contained in an amount of 4 to 20% by mass, preferably 6 to 15% by mass, and 5 in the solid content of the one-component water-based coating composition. It is contained in an amount of up to 35% by mass, preferably 10 to 25% by mass.
  • drying oil or polymer of drying oil (hereinafter, also referred to as drying oil, etc.)
  • the drying oil of the present invention has an iodine value of 130 or more. It is preferably 140 or more. Further, it has a conjugated double bond in the molecule, and the number of conjugated double bonds in the molecule is 25% or more of the number of double bonds contained in one molecule. The number of conjugated double bonds contained in one molecule of the drying oil is preferably 30% or more, more preferably 50% or more of the total number of double bonds contained in one molecule.
  • the drying oil of the present invention contains an ester of a fatty acid having a conjugated double bond in the molecule.
  • fatty acids having a conjugated double bond include eleostearic acid and octadecadienoic acid.
  • the drying oil of the present invention may contain, for example, a fatty acid having one double bond, a fatty acid having two or more uncoupled double bonds, and a saturated fatty acid in addition to the fatty acid having a conjugated double bond.
  • the fatty acid having one double bond, the fatty acid having two or more unconjugated double bonds, and the saturated fatty acid are not particularly limited.
  • Specific examples of the drying oil of the present invention include dehydrated castor oil and tung oil.
  • Drying oil is not particularly limited in its production. For example, conventionally known ones can be mentioned. Specifically, it can be produced, for example, by dehydrating a drying oil (for example, castor oil) containing a fatty acid ester having a hydroxy group.
  • a drying oil for example, castor oil
  • the dry oil polymer of the present invention is not particularly limited.
  • conventionally known ones can be mentioned.
  • the drying oil can be made into a polymer by applying heat to the drying oil or irradiating it with light.
  • the dry oil polymer of the present invention also includes boiled oil heated by adding an oxidation accelerator such as a metal salt of naphthenic acid.
  • an oxidation accelerator such as a metal salt of naphthenic acid.
  • the drying oil and the polymer of the drying oil can be used alone or in combination of two or more.
  • the drying oil or the like of the present invention contains 0.1 to 3.0% by mass of the one-component water-based coating composition, preferably 1.0 to 2.0% by mass, and is preferably 1.0 to 2.0% by mass. It is contained in the solid content of 0.1 to 5.0% by mass, preferably 1.0 to 3.5% by mass.
  • a metal soap using water as a solvent can be used.
  • the metal component include cobalt, manganese, tin, and lead compounds.
  • the metal component include cobalt, manganese, tin, and lead compounds.
  • metal compounds such as cobalt octylate and zirconium octylate.
  • the curing accelerator (D) is contained in an amount of 0.1 to 1.0% by mass, preferably 0.4 to 0.8% by mass, and is preferably 0.4 to 0.8% by mass of the one-component water-based coating composition. It is contained in the solid content of 0.1 to 0.6% by mass, preferably 0.2 to 0.5% by mass.
  • the non-volatile content is preferably 55 to 73% by mass, more preferably 55 to 65% by mass. Further, in the water-based coating composition of the present invention, the content of the water-dispersible resin in the non-volatile content is preferably 15 to 45% by mass, more preferably 27 to 43% by mass.
  • the coating composition of the present invention preferably has a viscosity of 50 to 200 Pa ⁇ s at a shear rate of 0.1 s-1 and a viscosity of 0.2 to 1 Pa ⁇ s at a shear rate of 1,000 s-1.
  • the viscosity is measured after adjusting the liquid temperature to 23 ° C. using a rheometer ARES manufactured by TA Instruments.
  • the non-volatile component refers to a component excluding volatile components such as water and an organic solvent, and is a component that finally forms a coating film.
  • the coating composition is heated at 130 ° C.
  • the component remaining after drying for 60 minutes is called a non-volatile component.
  • the coating composition of the present invention can be completely water-based, and the proportion of water in the solvent used is preferably 50% by mass or more, most preferably 100% by mass.
  • the solvent is preferably an organic solvent having a polarity that can be mixed with water, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n.
  • the coating composition of the present invention can contain pigments commonly used in the coating industry. Specifically, coloring pigments such as titanium dioxide, iron oxide and carbon black, extender pigments such as silica, talc, mica, calcium carbonate and barium sulfate, aluminum, nickel, chromium, tin, copper, silver, platinum and gold, Examples thereof include bright pigments such as stainless steel and glass flakes. These pigments may be used alone or in combination of two or more.
  • the content of the rust preventive pigment in the non-volatile content is preferably 3 to 10% by mass.
  • the pigment volume concentration in the non-volatile content is preferably 30 to 65% by volume, more preferably 30 to 50% by volume, and even more preferably 30 to 47% by volume. ..
  • the pigment referred to here refers to all the pigments contained in the coating composition, and when a pigment other than the rust preventive pigment is used, the pigment is also included.
  • the pigment volume concentration (PVC: Pigment Volume Concentration) in the non-volatile component can be calculated from the composition and specific gravity of each component constituting the non-volatile component.
  • various resins, pigments, organic solvents, surface conditioners, wetting agents, dispersants, emulsifiers, thickeners, anti-settling agents, anti-skinning agents, and anti-dripping agents can be appropriately blended according to the purpose.
  • Commercially available products can be preferably used as these components.
  • a resin usually used in the coating industry can be exemplified, and specifically, an acrylic resin, a silicone resin, an acrylic silicone resin, a styrene / acrylic copolymer resin, and the like.
  • the coating composition of the present invention can be prepared by mixing various components appropriately selected as necessary.
  • the coating means is not particularly limited, and known coating means such as brush coating, roller coating, iron coating, spatula coating, spray coating and the like can be used.
  • the coating composition of the present invention can particularly preferably coat a steel material having a black skin adhered to the surface as seen on the surface of the steel material (FIG. 1). In FIG. 1, the unevenness existing in the black skin can be confirmed.
  • the base material to which the black skin is attached has a large amount of oil in the gaps between the black skins and the like, and excellent oil level suitability is required.
  • the coating composition of the present invention can also be used for other construction machinery base materials such as aluminum and stainless steel.
  • the base material includes a base material that has been subjected to various surface treatments, for example, an oxidation treatment or a primer treatment, and the old coating film (before coating the coating composition of the present invention) is applied to at least a part of the surface of the base material.
  • a coating film that has already been formed on the surface) may be present.
  • Watersol EFD-5560 Vinyl modified epoxy ester resin dispersion, manufactured by DIC Corporation, NV; 40% by mass.
  • Watersol EFD-5580 Epoxy ester resin dispersion, manufactured by DIC Corporation, NV; 40% by mass -Acronal 295DN: Styrene / acrylic resin dispersion, manufactured by BASF, NV; 50% by mass Acryset PJ-717: Acrylic resin emulsion, manufactured by Nippon Shokubai Co., Ltd., NV; 45% by mass -Yodosol AD201: Styrene / acrylic resin emulsion, manufactured by Henkel Japan Ltd., NV46% by mass -Polysol AP-6750: Styrene / acrylic resin emulsion, manufactured by Showa Denko KK, NV; 45% by mass ⁇ LT boil oil: A mixture of flaxseed oil and tung oil, manufactured by Maruni Oil Co., Ltd.
  • DICNAME3111 Co-based metal soap, manufactured by DIC Co., Ltd.
  • Color pigment MA100, manufactured by Mitsubishi Chemical Co., Ltd.
  • Constituent pigment Sunlight SL-1000, Takehara Chemical Co., Ltd., Dispersant: Disperbyk-190, Big Chemie Japan Co., Ltd., Antifoaming agent: by093, Big Chemie Japan Co., Ltd.
  • Adhesive Tixol K-130B, Kyoeisha Chemical Co., Ltd.
  • Surface conditioner byk-307, Big Chemie Japan Co., Ltd.
  • Formation aid 2,2,4-trimethyl-1,3-pentanediol monoiso Butyrate
  • the measurement / evaluation was performed by the following method. Unless otherwise specified, the measurement and evaluation were carried out in an atmosphere of 23 ° C. and 50% RH. The results are shown in Table 2.
  • ⁇ Coated plate making method 1 (cold rolled steel sheet) ⁇
  • the paints of Examples 1 to 8 and Comparative Examples 1 to 6 were applied to cold-rolled steel sheets (JIS G3141, 150 ⁇ 70 ⁇ 0.8 mm, degreased with a cleaning solvent) polished with water-resistant paper # 180, respectively. Spray coating was performed so that the dry film thickness was 45 ⁇ m.
  • the obtained coating film was dried at 23 ° C. and a 50% RH atmosphere for 1 week to obtain a desired coated plate.
  • the back surface and side surfaces of the obtained coated plate were sealed with polyester tape (manufactured by Nitto Denko KK) and subjected to adhesion test, corrosion resistance test, and water resistance test.
  • ⁇ Coating board making method 2 black-skinned steel sheet
  • the coating films of Examples 1 to 8 and Comparative Examples 1 to 6 were applied to structural steel sheets (black-skinned steel sheets) (JIS G3101, 150 x 70 x 1.6 mm, degreased with a cleaning solvent), respectively.
  • the back surface and side surfaces of the obtained test plate were sealed with polyester tape (manufactured by Nitto Denko KK) and subjected to adhesion test, corrosion resistance test, and water resistance test.
  • ⁇ Adhesion test cross-cut method 100 2 mm wide squares are made on the paint film with a cutter knife, then cellophane tape (manufactured by Nichiban Co., Ltd.) is attached, crimped with a finger, and then the cellophane tape is peeled off at once to remove the remaining squares of the paint film. I counted.
  • the evaluation criteria are as follows. ⁇ : 100/100 ⁇ : 99/100 to 95/100 ⁇ : 94/100 or less
  • Corrosion resistance test (salt spray resistance test) ⁇ Make two scratches on the coated plate with a cutter knife in advance to reach the substrate and meet at an angle of 30 ° with a length of 10 cm.
  • the test plate was tested for 240 hours with a salt spray tester that continuously sprays 5% sodium chloride water at a temperature of 35 ° C. in the tank. Remove from the device and flush the test surface with tap water to remove water. Immediately after that, the corrosion width from scratches on the test surface is measured.
  • the evaluation criteria are as follows. Corrosion width after salt spray (240h) ⁇ : 2mm or less ⁇ : 2-5mm ⁇ : 5 mm or more
  • the one-component water-based paint composition of the present invention has excellent adhesion to various substrates including black-skinned steel, and has corrosion resistance as a water-based paint for construction machinery. Is excellent.

Abstract

The purpose of the present invention is to provide a one-component aqueous coating composition having exceptional adhesiveness to various substrates including mill scale steel, and excellent corrosion resistance as an aqueous coating for construction equipment.　The purpose of the present invention is achieved as described below.　A one-component aqueous coating composition containing at least (A) an epoxy ester resin, (B) an acrylic resin, and (C) at least one compound selected from drying oils and polymers of drying oils.

Description

一液型水性塗料組成物One-component water-based paint composition
　本発明は、一液型水性塗料組成物に関し、詳しくは黒皮鋼材に対する付着力に優れた一液型水性塗料組成物に関する。 The present invention relates to a one-component water-based coating composition, and more particularly to a one-component water-based coating composition having excellent adhesion to black-skinned steel.
　建設機械や産業機械のライン塗装では、種々の基材に対する付着性や耐食性が求められるため、これら性能の優れる溶剤系塗料が一般的に用いられていた。しかし近年では、環境保護の観点から有害大気汚染物質や揮発性有機化合物が規制されており、建機向けのライン塗装においても溶剤系塗料から水系塗料への転換が検討されている（特許文献１）。 In line coating of construction machinery and industrial machinery, adhesiveness and corrosion resistance to various substrates are required, so solvent-based paints with excellent performance have been generally used. However, in recent years, harmful air pollutants and volatile organic compounds have been regulated from the viewpoint of environmental protection, and conversion from solvent-based paints to water-based paints is being considered for line coatings for construction machinery (Patent Document 1). ).
　一方で建設機械や産業機械は部品により鋼材の種類が異なることが多く、鉄やステンレス、アルミニウム等の様々な金属が用いられる。そのため、建設機械用の塗料には、種々の基材に対する付着性が求められるが、従来の建設機械向け水系塗料ではいまだ十分な性能が得られなかった（特許文献２）。 On the other hand, construction machinery and industrial machinery often have different types of steel depending on the parts, and various metals such as iron, stainless steel, and aluminum are used. Therefore, paints for construction machinery are required to have adhesiveness to various base materials, but conventional water-based paints for construction machinery have not yet obtained sufficient performance (Patent Document 2).
特開２０１１－０８４６６３号公報Japanese Unexamined Patent Publication No. 2011-084663 特開２０１８－１７２５０４号公報Japanese Unexamined Patent Publication No. 2018-172504
　中でも、表面にミクロな凹凸が存在する黒皮鋼材（表面に黒色の酸化鉄を残した状態の鋼材）上に塗装する場合、水系塗料は溶剤系塗料と比較して表面張力が高く濡れ広がりにくいため、鋼材との付着性が劣り、早期の剥離や赤錆が生じることがあった。 Above all, when painting on black-skinned steel material (steel material with black iron oxide left on the surface) with micro irregularities on the surface, water-based paint has higher surface tension than solvent-based paint and is less likely to get wet and spread. Therefore, the adhesiveness to the steel material was inferior, and early peeling and red rust may occur.
　本発明は、黒皮鋼材を含む種々の基材に対して優れた付着性を有し、建機向け水性塗料として耐食性に優れた一液型水性塗料組成物を提供することを目的とする。 An object of the present invention is to provide a one-component water-based coating composition having excellent adhesion to various substrates including black-skinned steel and having excellent corrosion resistance as a water-based coating material for construction machinery.
　本発明の目的は、下記によって達成された。 The object of the present invention has been achieved by the following.
１．　少なくとも、
（Ａ）エポキシエステル樹脂、
（Ｂ）アクリル樹脂、および、
（Ｃ）乾性油または乾性油の重合物から選択される少なくとも一種の化合物、
とを含有する一液型水性塗料組成物。
２．　前記一液型水性塗料組成物の固形分中における前記（Ａ）エポキシエステル樹脂の含有量が５～３０質量％である前記１記載の一液型水性塗料組成物。
３．　前記一液型水性塗料組成物の固形分中における前記（Ｃ）乾性油または乾性油の重合物から選択される少なくとも一種の化合物の含有量が０．１～５．０質量％である前記１または２記載の一液型水性塗料組成物。
４．　前記（Ａ）エポキシエステル樹脂が、ビニル変性エポキシエステル樹脂である前記１～３のいずれかに記載の一液型水性塗料組成物。
５．　（Ｄ）酸化促進剤を含有する前記１～４のいずれかに記載の一液型水性塗料組成物。 1. 1. at least,
(A) Epoxy ester resin,
(B) Acrylic resin and
(C) At least one compound selected from a drying oil or a polymer of a drying oil,
A one-component water-based paint composition containing and.
2. The one-component water-based coating composition according to the above 1, wherein the content of the epoxy ester resin (A) in the solid content of the one-component water-based coating composition is 5 to 30% by mass.
3. 3. The content of at least one compound selected from the (C) drying oil or a polymer of the drying oil in the solid content of the one-component water-based coating composition is 0.1 to 5.0% by mass. Alternatively, the one-component water-based coating composition according to 2.
4. The one-component water-based coating composition according to any one of 1 to 3 above, wherein the epoxy ester resin (A) is a vinyl-modified epoxy ester resin.
5. (D) The one-component water-based coating composition according to any one of 1 to 4 above, which contains an oxidation accelerator.
　本発明によれば、黒皮鋼材を含む種々の基材に対して優れた付着性を有し、建機向け水性塗料として耐食性に優れた一液型水性塗料組成物を提供することができる。 According to the present invention, it is possible to provide a one-component water-based coating composition having excellent adhesion to various substrates including black-skinned steel and having excellent corrosion resistance as a water-based coating material for construction machinery.
本発明の黒皮鋼材のミクロな凹凸を示す表面写真である。It is a surface photograph which shows the micro unevenness of the black leather material of this invention.
　以下、本発明の実施形態について詳細に述べる。
＜一液型水性塗料組成物＞
　本発明の一液型水性塗料組成物は、少なくとも、（Ａ）エポキシエステル樹脂、（Ｂ）アクリル樹脂、および、（Ｃ）乾性油または乾性油の重合物から選択される少なくとも一種の化合物、とを含有することを特徴とする。 Hereinafter, embodiments of the present invention will be described in detail.
<One-component water-based paint composition>
The one-component water-based coating composition of the present invention comprises at least one compound selected from (A) an epoxy ester resin, (B) an acrylic resin, and (C) a drying oil or a polymer of a drying oil. It is characterized by containing.
　≪（Ａ）エポキシエステル樹脂≫
　本発明のエポキシエステル樹脂は，通常のエポキシエステル樹脂を使用することができる。例えば、エポキシ樹脂と脂肪族酸などの酸との付加物、さらに該付加物とジイソシアネ－ト化合物やヒドロキシカルボン酸との反応生成物、さらにそのビニル変性物等が挙げられる。特にビニル変性エポキシエステル樹脂であることが好ましい。 ≪ (A) Epoxy ester resin≫
As the epoxy ester resin of the present invention, a normal epoxy ester resin can be used. For example, an adduct of an epoxy resin and an acid such as an aliphatic acid, a reaction product of the adduct with a diisosocyanate compound or a hydroxycarboxylic acid, a vinyl modified product thereof, and the like can be mentioned. In particular, a vinyl-modified epoxy ester resin is preferable.
　本発明のビニル変性エポキシエステル樹脂は、ビニル重合体部分が結合した脂肪酸鎖を有するビニル変性エポキシエステル樹脂であって、ビニル重合体部分が下記一般式（Ｉ）で示される末端カルボキシル基含有構造を有し、かつ、下記一般式（Ｉ）で示される末端カルボキシル基含有構造の一部または全部が塩基性化合物で中和されているビニル変性エポキシエステル樹脂である。 The vinyl-modified epoxy ester resin of the present invention is a vinyl-modified epoxy ester resin having a fatty acid chain to which a vinyl polymer portion is bonded, and the vinyl polymer portion has a terminal carboxyl group-containing structure represented by the following general formula (I). It is a vinyl-modified epoxy ester resin having, and part or all of the terminal carboxyl group-containing structure represented by the following general formula (I) is neutralized with a basic compound.
Figure JPOXMLDOC01-appb-C000001
 ｎは１～１０、Ｒ１は炭素数２～１８のアルキレン基を示す。
Figure JPOXMLDOC01-appb-C000001
 n represents 1 to 10 and R 1 represents an alkylene group having 2 to 18 carbon atoms.
　本発明の（Ａ）エポキシ樹脂は、特許第３８５８９３４号、特開２００１－２６１７５９号に記載のビニル変性エポキシ樹脂を好ましく使用することができる。 As the epoxy resin (A) of the present invention, the vinyl-modified epoxy resin described in Japanese Patent No. 3858934 and JP-A-2001-261759 can be preferably used.
　本発明で使用する（Ａ）エポキシエステル樹脂は、１，０００～１００，０００の数平均分子量を有するものが好ましく、２，０００～５０，０００の数平均分子量を有するものがより好ましく、２，０００～１０，０００の数平均分子量を有するものが更に好ましい。 The epoxy ester resin (A) used in the present invention preferably has a number average molecular weight of 1,000 to 100,000, more preferably a number average molecular weight of 2,000 to 50,000, 2. Those having a number average molecular weight of 000 to 10,000 are more preferable.
　本発明の（Ａ）エポキシエステル樹脂の軟化点（Ｔｍ）やガラス転移点（Ｔｇ）は特に限定されず必要に応じて選択できるが、好ましい軟化点は－２０～１００℃、より好ましくは－２０～７０℃、更に好ましくは－１０～４０℃である。好ましいガラス転移点は－２０～１００℃、より好ましくは－１０～６０℃、さらに好ましくは０～４０℃である。
　Ｔｍ，Ｔｇは、ＪＩＳＫ７１２１-１９８７に準じＤＳＣによって測定することができる。 The softening point (Tm) and the glass transition point (Tg) of the epoxy ester resin (A) of the present invention are not particularly limited and can be selected as needed, but the preferable softening point is −20 to 100 ° C., more preferably −20. It is about 70 ° C., more preferably −10 to 40 ° C. The preferred glass transition point is −20 to 100 ° C., more preferably −10 to 60 ° C., and even more preferably 0 to 40 ° C.
Tm and Tg can be measured by DSC according to JIS K7121-1987.
　本発明で使用する（Ａ）エポキシエステル樹脂は、５～１００の酸価を有するものが挙げられるが、なかでも１５～４０の酸価を有するものが好ましく、２０～３５の酸価を有するものがより好ましい。 Examples of the (A) epoxy ester resin used in the present invention include those having an acid value of 5 to 100, and among them, those having an acid value of 15 to 40 are preferable, and those having an acid value of 20 to 35 are used. Is more preferable.
　本発明においては、この（Ａ）エポキシエステル樹脂は、一部または全部が塩基性化合物で中和されて、水中に分散された状態で使用される。平均粒径は４０～２００ｎｍであり、好ましくは８０～１５０ｎｍである。なお、平均粒径は、マイクロトラック粒度分析計（マイクロトラック９３４０－ＵＰＡ、日機装株式会社製）で測定することができる。
　（Ａ）エポキシエステル樹脂は、固形分として２０～６０質量％の水分散物とすることが好ましい。 In the present invention, this (A) epoxy ester resin is used in a state where a part or all of it is neutralized with a basic compound and dispersed in water. The average particle size is 40 to 200 nm, preferably 80 to 150 nm. The average particle size can be measured with a Microtrack particle size analyzer (Microtrack 9340-UPA, manufactured by Nikkiso Co., Ltd.).
The epoxy ester resin (A) is preferably an aqueous dispersion having a solid content of 20 to 60% by mass.
　本発明の（Ａ）エポキシエステル樹脂の水分散物としては、ウォーターゾールＢＭ－１０００Ｐ、ＣＤ－５４０Ｐ、ＥＦＤ－５５２０、ＥＦＤ－５５３０、ＥＦＤ－５５５０、ＥＦＤ－５５６０、ＥＦＤ－５５７０、ＥＦＤ－５５８０、ＥＦＤ－５５０１Ｐ(以上ＤＩＣ株式会社製)等を市販品として入手することができる。 Examples of the aqueous dispersion of the epoxy ester resin (A) of the present invention include Watersol BM-1000P, CD-540P, EFD-5520, EFD-5530, EFD-5550, EFD-5560, EFD-5570, EFD-5580, EFD-5501P (all manufactured by DIC Corporation) and the like can be obtained as commercial products.
　本発明の（Ａ）エポキシエステル樹脂は、一液型水性塗料組成物の４～１６質量％含有され、８～１４質量％であることが好ましく、一液型水性塗料組成物の固形分中には５～３０質量％含有され、１０～２５質量％であることが好ましい。 The epoxy ester resin (A) of the present invention is contained in an amount of 4 to 16% by mass, preferably 8 to 14% by mass, in the solid content of the one-component water-based coating composition. Is contained in an amount of 5 to 30% by mass, preferably 10 to 25% by mass.
　≪（Ｂ）アクリル樹脂≫
　本発明の（Ｂ）アクリル樹脂は、炭素数１～１８のアルキル（メタ）アクリレートを３０～１００質量％有し、その他スチレン系モノマー（スチレン、α-メチルスチレン等）、酢酸ビニル、オレフィン（塩化ビニル、塩化ビニリデン、ブタジエン、プロピレン等）等を共重合させた樹脂である。 ≪ (B) Acrylic resin ≫
The (B) acrylic resin of the present invention contains 30 to 100% by mass of an alkyl (meth) acrylate having 1 to 18 carbon atoms, and other styrene-based monomers (styrene, α-methylstyrene, etc.), vinyl acetate, and olefin (chloride). It is a resin obtained by copolymerizing vinyl, vinylidene chloride, butadiene, propylene, etc.).
　炭素数１～１８のアルキル（メタ）アクリレートとしては、(メタ)アクリレートや、エチル(メタ)アクリレート、ｎ－プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、トルイル(メタ)アクリレート、グリシジル(メタ)アクリレート、ｎ－ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、ｔ－ブチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、メチルシクロヘキシル(メタ)アクリレート、エチルシクロヘキシル(メタ)アクリレート、シクロヘプチル(メタ)アクリレート、ｎ－ヘプチル(メタ)アクリレート、ｎ－オクチル(メタ)アクリレート、２－エチルヘキシル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ラウリル(メタ)アクリレート、セチル(メタ)アクリレート、ステアリル(メタ)アクリレート等が挙げられる。 Examples of the alkyl (meth) acrylate having 1 to 18 carbon atoms include (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, toluyl (meth) acrylate, and glycidyl (meth). Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate , N-Heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl Examples include (meth) acrylate.
　水酸基を有する２－ヒドロキシエチル(メタ)アクリレート、２－ヒドロキシプロピル(メタ)アクリレート、３－ヒドロキシプロピル(メタ)アクリレート、４－ヒドロキシブチル(メタ)アクリレート、２－ヒドロキシエチル(メタ)アタクリレートへのラクトン付加物、２－ヒドロキシエチル(メタ)アクリレート又は２－ヒドロキシプロピル(メタ)アクリレートへのエチレンオキシドの開環付加物又はプロピレンオキシドの開環付加物、及び２－ヒドロキシエチル(メタ)アクリレート又は２－ヒドロキシプロピル(メタ)アクリレートの２量体又は３量体よりなる群から選択される少なくとも１種のヒドロキシ基含有重合性不飽和モノマーを含むことも好ましい。 2-Hydroxyethyl (meth) acrylate with hydroxyl group, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, lactone to 2-hydroxyethyl (meth) attrilate Additives, ring-opening additions of ethylene oxide or ring-opening additions of propylene oxide to 2-hydroxyethyl (meth) acrylates or 2-hydroxypropyl (meth) acrylates, and 2-hydroxyethyl (meth) acrylates or 2-hydroxys. It is also preferable to include at least one hydroxy group-containing polymerizable unsaturated monomer selected from the group consisting of dimer or trimeric of propyl (meth) acrylate.
　水酸基を有するモノマーは０～５質量％以下であることが好ましい。スチレン系モノマーは、０～７０質量％含有することが好ましい。 The monomer having a hydroxyl group is preferably 0 to 5% by mass or less. The styrene-based monomer is preferably contained in an amount of 0 to 70% by mass.
　なお、本発明において、数平均分子量、重量平均分子量は、サイズ排除クロマトグラフィーで測定した値であり、標準物質にはポリスチレンが使用される。 In the present invention, the number average molecular weight and the weight average molecular weight are values measured by size exclusion chromatography, and polystyrene is used as the standard substance.
　本発明の（Ｂ）アクリル樹脂は、そのガラス転移温度が－５０～４０℃であることが好ましく、－３０～４０℃の範囲内にあることがより好ましく、－１０～４０℃であることが更に好ましい。 The acrylic resin (B) of the present invention preferably has a glass transition temperature of −50 to 40 ° C., more preferably in the range of −30 to 40 ° C., and preferably −10 to 40 ° C. More preferred.
　なお、本発明の（Ｂ）アクリル樹脂において、ガラス転移温度（Ｔｇ）とは、次のＦＯＸ式を用いて計算されるものをいう。
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・＋Ｗｉ／Ｔｇｉ＋・・・＋Ｗｎ／Ｔｇｎ   
上記ＦＯＸ式において、Ｔｇは、ｎ種類のモノマーからなるポリマーのガラス転移温度（Ｋ）であり、Ｔｇ（１、２、ｉ、ｎ）は、各モノマーのホモポリマーのガラス転移温度（Ｋ）であり、Ｗ（１、２、ｉ、ｎ）は、各モノマーの質量分率であり、Ｗ１＋Ｗ２＋・・・＋Ｗｉ＋・・・＋Ｗｎ＝１である。 In the (B) acrylic resin of the present invention, the glass transition temperature (Tg) is calculated by using the following FOX formula.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
In the above FOX equation, Tg is the glass transition temperature (K) of the polymer composed of n kinds of monomers, and Tg (1, 2, i, n) is the glass transition temperature (K) of the homopolymer of each monomer. Yes, W (1, 2, i, n) is the mass fraction of each monomer, and W1 + W2 + ... + Wi + ... + Wn = 1.
　本発明の（Ｂ）アクリル樹脂は、水分散物として使用されるが、アクリル樹脂を合成した後有機溶媒に溶解し、界面活性剤を加えた水中でせん断力を与えることで水分散物とすることができるし、初めから乳化重合によって水分散物とすることもできる。 The acrylic resin (B) of the present invention is used as an aqueous dispersion, but after synthesizing the acrylic resin, it is dissolved in an organic solvent and given a shearing force in water to which a surfactant is added to obtain an aqueous dispersion. It can be made into an aqueous dispersion by emulsion polymerization from the beginning.
　本発明のアクリル樹脂は、固形分として２０～６０質量％の水分散物とすることが好ましく、特開２０１８－１７２５０４号公報等に記載の水分散したアクリル樹脂を使用することができる。 The acrylic resin of the present invention is preferably an aqueous dispersion having a solid content of 20 to 60% by mass, and the aqueous-dispersed acrylic resin described in JP-A-2018-172504 can be used.
　本発明の（Ｂ）アクリル樹脂の水分散物は、５０体積％粒子径（Ｄ５０）が５０～３００ｎｍの範囲内にあることが好ましく、５０～２００ｎｍの範囲内にあることがより好ましい。 The aqueous dispersion of the acrylic resin (B) of the present invention preferably has a 50% by volume particle size (D50) in the range of 50 to 300 nm, and more preferably in the range of 50 to 200 nm.
　本発明において、５０体積％粒子径（Ｄ５０）は、体積基準粒度分布の５０％粒子径（Ｄ５０）を指し、レーザ回折／散乱式粒度分布測定装置（例えばＳＡＬＤ－７０００：株式会社島津製作所社製）を用いて測定される粒度分布から求めることができる。そして、本発明における粒子径は、レーザ回折・散乱法による球相当径で表される。 In the present invention, the 50% by volume particle size (D50) refers to the 50% particle size (D50) of the volume-based particle size distribution, and is a laser diffraction / scattering type particle size distribution measuring device (for example, SALD-7000: manufactured by Shimadzu Corporation). ) Can be obtained from the particle size distribution measured. The particle size in the present invention is represented by a sphere-equivalent diameter obtained by a laser diffraction / scattering method.
　本発明の（Ｂ）アクリル樹脂は、一液型水性塗料組成物の４～２０質量％含有され、６～１５質量％であることが好ましく、一液型水性塗料組成物の固形分中に５～３５質量％含有され、１０～２５質量％であることが好ましい。 The acrylic resin (B) of the present invention is contained in an amount of 4 to 20% by mass, preferably 6 to 15% by mass, and 5 in the solid content of the one-component water-based coating composition. It is contained in an amount of up to 35% by mass, preferably 10 to 25% by mass.
　≪（Ｃ）乾性油または乾性油の重合物（以下、乾性油等ともいう）≫
　本発明の乾性油は、そのヨウ素価が１３０以上である。１４０以上であるのが好ましい。また、分子内に共役二重結合を有し、分子内の共役二重結合の数が、１分子に含まれる二重結合の数の２５％以上である。また、１分子の乾性油に含まれる共役二重結合の数は、１分子に含まれる二重結合の全数の、３０％以上であるのが好ましく、５０％以上であるのがより好ましい。 ≪ (C) Drying oil or polymer of drying oil (hereinafter, also referred to as drying oil, etc.) ≫
The drying oil of the present invention has an iodine value of 130 or more. It is preferably 140 or more. Further, it has a conjugated double bond in the molecule, and the number of conjugated double bonds in the molecule is 25% or more of the number of double bonds contained in one molecule. The number of conjugated double bonds contained in one molecule of the drying oil is preferably 30% or more, more preferably 50% or more of the total number of double bonds contained in one molecule.
　本発明の乾性油は、分子内に共役二重結合を有する脂肪酸のエステルを含む。共役二重結合を有する脂肪酸としては、例えば、エレオステアリン酸、オクタデカジエン酸が挙げられる。 The drying oil of the present invention contains an ester of a fatty acid having a conjugated double bond in the molecule. Examples of fatty acids having a conjugated double bond include eleostearic acid and octadecadienoic acid.
　本発明の乾性油は、共役二重結合を有する脂肪酸のほかに、例えば、二重結合を１個有する脂肪酸、共役していない２個以上の二重結合を有する脂肪酸、飽和脂肪酸を含むことができる。二重結合を１個有する脂肪酸、共役していない２個以上の二重結合を有する脂肪酸、飽和脂肪酸は、それぞれ特に制限されない。本発明の乾性油は、具体的には例えば、脱水ヒマシ油、桐油が挙げられる。 The drying oil of the present invention may contain, for example, a fatty acid having one double bond, a fatty acid having two or more uncoupled double bonds, and a saturated fatty acid in addition to the fatty acid having a conjugated double bond. can. The fatty acid having one double bond, the fatty acid having two or more unconjugated double bonds, and the saturated fatty acid are not particularly limited. Specific examples of the drying oil of the present invention include dehydrated castor oil and tung oil.
　乾性油は、その製造について特に制限されない。例えば、従来公知のものが挙げられる。具体的には、例えば、ヒドロキシ基を有する脂肪酸エステルを含む乾性油（例えば、ヒマシ油。）を脱水することによって、製造することができる。 Drying oil is not particularly limited in its production. For example, conventionally known ones can be mentioned. Specifically, it can be produced, for example, by dehydrating a drying oil (for example, castor oil) containing a fatty acid ester having a hydroxy group.
　本発明の乾性油の重合物については特に制限されない。例えば、従来公知のものが挙げられる。具体的には、例えば、乾性油に、熱を加えること、光を照射することによって乾性油を重合物とすることができる。 The dry oil polymer of the present invention is not particularly limited. For example, conventionally known ones can be mentioned. Specifically, for example, the drying oil can be made into a polymer by applying heat to the drying oil or irradiating it with light.
　本発明の乾性油の重合物には、ナフテン酸金属塩のような酸化促進剤を加え加熱したボイル油も含まれる。乾性油および乾性油の重合物は、それぞれ単独でまたは２種以上を組み合わせて使用することができる。 The dry oil polymer of the present invention also includes boiled oil heated by adding an oxidation accelerator such as a metal salt of naphthenic acid. The drying oil and the polymer of the drying oil can be used alone or in combination of two or more.
　本発明の乾性油等は、一液型水性塗料組成物の０．１～３．０質量％含有され、１．０～２．０質量％であることが好ましく、一液型水性塗料組成物の固形分中に０．１～５．０質量％含有され、１．０～３．５質量％であることが好ましい。 The drying oil or the like of the present invention contains 0.1 to 3.0% by mass of the one-component water-based coating composition, preferably 1.0 to 2.0% by mass, and is preferably 1.0 to 2.0% by mass. It is contained in the solid content of 0.1 to 5.0% by mass, preferably 1.0 to 3.5% by mass.
　≪（Ｄ）硬化促進剤≫
　本発明の硬化促進剤としては、水を溶剤とする金属石鹸を使用することができる。金属成分としては、コバルト、マンガン、錫、鉛化合物等を挙げることができ、例えば、テトライソプロピルチタネート、ジブチル錫ラウレート、ジブチル錫アセテート、ジブチル錫ジオクテート、ナフテン酸コバルト、ナフテン酸鉛、ナフテン酸ジルコニウム、オクチル酸コバルト、オクチル酸ジルコニウム等の金属化合物類等が挙げられる。 ≪ (D) Hardening accelerator ≫
As the curing accelerator of the present invention, a metal soap using water as a solvent can be used. Examples of the metal component include cobalt, manganese, tin, and lead compounds. For example, tetraisopropyl titanate, dibutyltin laurate, dibutyltin acetate, dibutyltin dioctate, cobalt naphthenate, lead naphthenate, zirconium naphthenate, etc. Examples thereof include metal compounds such as cobalt octylate and zirconium octylate.
　（Ｄ）硬化促進剤は、一液型水性塗料組成物の０．１～１．０質量％含有され、０．４～０．８質量％であることが好ましく、一液型水性塗料組成物の固形分中に０．１～０．６質量％含有され、０．２～０．５質量％であることが好ましい。 The curing accelerator (D) is contained in an amount of 0.1 to 1.0% by mass, preferably 0.4 to 0.8% by mass, and is preferably 0.4 to 0.8% by mass of the one-component water-based coating composition. It is contained in the solid content of 0.1 to 0.6% by mass, preferably 0.2 to 0.5% by mass.
　≪塗料組成物≫
　本発明の塗料組成物において、不揮発分の含有量は、５５～７３質量％であることが好ましく、５５～６５質量％であることがより好ましい。また、本発明の水性塗料組成物において、不揮発分中における水分散性樹脂の含有量は、１５～４５質量％であることが好ましく、２７～４３質量％であることがより好ましい。 ≪Paint composition≫
In the coating composition of the present invention, the non-volatile content is preferably 55 to 73% by mass, more preferably 55 to 65% by mass. Further, in the water-based coating composition of the present invention, the content of the water-dispersible resin in the non-volatile content is preferably 15 to 45% by mass, more preferably 27 to 43% by mass.
　本発明の塗料組成物は、せん断速度０．１ｓ－１の粘度が５０～２００Ｐａ・ｓであり、且つせん断速度１，０００ｓ－１の粘度が０．２～１Ｐａ・ｓであることが好ましい。　本発明において、粘度はＴＡインスツルメンツ社製レオメーターＡＲＥＳを用い、液温を２３℃に調整した後測定される。 The coating composition of the present invention preferably has a viscosity of 50 to 200 Pa · s at a shear rate of 0.1 s-1 and a viscosity of 0.2 to 1 Pa · s at a shear rate of 1,000 s-1. In the present invention, the viscosity is measured after adjusting the liquid temperature to 23 ° C. using a rheometer ARES manufactured by TA Instruments.
　なお、不揮発分とは、水や有機溶剤等の揮発する成分を除いた成分を指し、最終的に塗膜を形成することになる成分であるが、本発明においては、塗料組成物を１３０℃で６０分間乾燥させた際に残存する成分を不揮発分という。 The non-volatile component refers to a component excluding volatile components such as water and an organic solvent, and is a component that finally forms a coating film. In the present invention, the coating composition is heated at 130 ° C. The component remaining after drying for 60 minutes is called a non-volatile component.
　本発明の塗料組成物は、完全水系化することも可能であり、使用される溶媒に占める水の割合は、好ましくは５０質量％以上、最も好ましくは１００質量％である。 The coating composition of the present invention can be completely water-based, and the proportion of water in the solvent used is preferably 50% by mass or more, most preferably 100% by mass.
　本発明の塗料組成物が水以外の溶媒を含む場合、その溶媒としては、水と混合し得る極性を持つ有機溶剤が好ましく、例えば、メチルアルコール、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、イソブチルアルコール、ｓｅｃ－ブチルアルコール、ｔ－ブチルアルコール、イソアミルアルコール、ｓｅｃ－アミルアルコール、ｔ－アミルアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、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イソプロピルエーテル、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イソブチルエーテル、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イソプロピルエーテル、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イソブチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、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ｎ－プロピルエーテル、ジプロピレングリコールモノイソプロピルエーテル、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イソブチルエーテル、３－メチル－３－メトキシブタノール、アセトン、メチルエチルケトン、ジエチルケトン等が挙げられる。 When the coating composition of the present invention contains a solvent other than water, the solvent is preferably an organic solvent having a polarity that can be mixed with water, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n. -Butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, isoamyl alcohol, sec-amyl alcohol, t-amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene Glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, diethylene glycol mono n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono n-butyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono n-butyl ether, dipropylene glycol Examples thereof include monoisobutyl ether, 3-methyl-3-methoxybutanol, acetone, methyl ethyl ketone, diethyl ketone and the like.
　本発明の塗料組成物には、塗料業界において通常使用されている顔料を含有することができる。具体的には、二酸化チタン、酸化鉄、カーボンブラック等の着色顔料、シリカ、タルク、マイカ、炭酸カルシウム、硫酸バリウム等の体質顔料、アルミニウム、ニッケル、クロム、錫、銅、銀、白金、金、ステンレス、ガラスフレーク等の光輝顔料等が挙げられる。これら顔料は、一種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 coating composition of the present invention can contain pigments commonly used in the coating industry. Specifically, coloring pigments such as titanium dioxide, iron oxide and carbon black, extender pigments such as silica, talc, mica, calcium carbonate and barium sulfate, aluminum, nickel, chromium, tin, copper, silver, platinum and gold, Examples thereof include bright pigments such as stainless steel and glass flakes. These pigments may be used alone or in combination of two or more.
　その他本発明の塗料組成物に用いる防錆顔料は、公知の材料が使用でき、例えば、亜鉛粉末、酸化亜鉛、メタホウ酸バリウム、珪酸カルシウム、リン酸アルミニウム、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、バナジン酸／リン酸混合顔料等が挙げられる。また、本発明の水性塗料組成物において、不揮発分中における防錆顔料の含有量は、３～１０質量％であることが好ましい。 Other known materials can be used as the rust preventive pigment used in the coating composition of the present invention, for example, zinc powder, zinc oxide, barium metaborate, calcium silicate, aluminum phosphate, aluminum tripolyphosphate, zinc phosphate, phosphite. Zinc acid, potassium phosphite, calcium phosphite, aluminum phosphite, calcium zinc phosphate, zinc aluminum phosphate, zinc phosphate, aluminum phosphate, magnesium phosphate, vanadic acid / phosphoric acid mixed pigment, etc. Be done. Further, in the aqueous coating composition of the present invention, the content of the rust preventive pigment in the non-volatile content is preferably 3 to 10% by mass.
　本発明の塗料組成物において、不揮発分中における顔料体積濃度は３０～６５体積％であることが好ましく、３０～５０体積％にあることがより好ましく、３０～４７体積％であることが更に好ましい。 In the coating composition of the present invention, the pigment volume concentration in the non-volatile content is preferably 30 to 65% by volume, more preferably 30 to 50% by volume, and even more preferably 30 to 47% by volume. ..
　なお、ここでいう顔料とは、塗料組成物中に含まれる全ての顔料を指しており、防錆顔料以外の顔料が使用される場合はその顔料も含まれる。不揮発分中における顔料体積濃度（ＰＶＣ：Ｐｉｇｍｅｎｔ Ｖｏｌｕｍｅ Ｃｏｎｃｅｎｔｒａｔｉｏｎ）は、不揮発分を構成する各成分の組成及び比重から計算により求めることができる。 The pigment referred to here refers to all the pigments contained in the coating composition, and when a pigment other than the rust preventive pigment is used, the pigment is also included. The pigment volume concentration (PVC: Pigment Volume Concentration) in the non-volatile component can be calculated from the composition and specific gravity of each component constituting the non-volatile component.
　≪その他の成分≫
　本発明の塗料組成物には、その他の成分として、各種樹脂、顔料、有機溶剤、表面調整剤、湿潤剤、分散剤、乳化剤、増粘剤、沈降防止剤、皮張り防止剤、たれ防止剤、消泡剤、色分かれ防止剤、レベリング剤、乾燥剤、可塑剤、成膜助剤、防カビ剤、抗菌剤、殺虫剤、光安定化剤、紫外線吸収剤、帯電防止剤及び導電性付与剤等を目的に応じて適宜配合することができる。これら成分は、市販品を好適に使用することができる。 ≪Other ingredients≫
In the coating composition of the present invention, as other components, various resins, pigments, organic solvents, surface conditioners, wetting agents, dispersants, emulsifiers, thickeners, anti-settling agents, anti-skinning agents, and anti-dripping agents , Antifoaming agent, anticoloring agent, leveling agent, desiccant, plasticizer, film forming aid, antifungal agent, antibacterial agent, insecticide, light stabilizer, ultraviolet absorber, antistatic agent and conductivity imparting Agents and the like can be appropriately blended according to the purpose. Commercially available products can be preferably used as these components.
　ここで、その他の成分である樹脂としては、塗料業界において通常使用されている樹脂を例示することができ、具体的には、アクリル樹脂、シリコーン樹脂、アクリルシリコーン樹脂、スチレン・アクリル共重合樹脂、ポリエステル樹脂、ふっ素樹脂、ロジン樹脂、石油樹脂、クマロン樹脂、フェノール樹脂、ウレタン樹脂、メラミン樹脂、尿素樹脂、エポキシ樹脂、セルロース樹脂、キシレン樹脂、アルキド樹脂、脂肪族炭化水素樹脂、ブチラール樹脂、マレイン酸樹脂、フマル酸樹脂、ビニル樹脂、アミン樹脂、ケチミン樹脂等が挙げられる。これらの樹脂を一種単独で用いても良く、二種以上組み合わせて用いてもよい。
　本発明の塗料組成物は、必要に応じて適宜選択される各種成分を混合することによって調製できる。 Here, as the resin as another component, a resin usually used in the coating industry can be exemplified, and specifically, an acrylic resin, a silicone resin, an acrylic silicone resin, a styrene / acrylic copolymer resin, and the like. Polyester resin, fluorine resin, rosin resin, petroleum resin, kumaron resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid Examples thereof include resins, fumaric acid resins, vinyl resins, amine resins, and ketimine resins. These resins may be used alone or in combination of two or more.
The coating composition of the present invention can be prepared by mixing various components appropriately selected as necessary.
　本発明の塗料組成物において、塗装手段は、特に限定されず、既知の塗装手段、例えば、刷毛塗装、ローラー塗装、コテ塗装、ヘラ塗装、スプレー塗装等が利用できる。 In the coating composition of the present invention, the coating means is not particularly limited, and known coating means such as brush coating, roller coating, iron coating, spatula coating, spray coating and the like can be used.
＜塗布基材＞
　本発明の塗料組成物は、鋼材表面に見られるような黒皮が表面に付着した鋼材に対して特に好適に塗装を行うことができる（図１）。図１では、黒皮部に存在する凹凸が確認できる。通常、黒皮が付着した基材は、黒皮の隙間等に油分が多く存在しており、優れた油面適性が求められる。本発明の塗料組成物は、その他アルミニウム、ステンレス等の建機基材に対しても使用することができる。 <Applied base material>
The coating composition of the present invention can particularly preferably coat a steel material having a black skin adhered to the surface as seen on the surface of the steel material (FIG. 1). In FIG. 1, the unevenness existing in the black skin can be confirmed. Usually, the base material to which the black skin is attached has a large amount of oil in the gaps between the black skins and the like, and excellent oil level suitability is required. The coating composition of the present invention can also be used for other construction machinery base materials such as aluminum and stainless steel.
　なお、基材には、各種表面処理、例えば酸化処理やプライマー処理が施された基材が含まれ、基材表面の少なくとも一部に旧塗膜（本発明の塗料組成物の塗装を行う前に既に形成されている塗膜）が存在していてもよい。 The base material includes a base material that has been subjected to various surface treatments, for example, an oxidation treatment or a primer treatment, and the old coating film (before coating the coating composition of the present invention) is applied to at least a part of the surface of the base material. A coating film that has already been formed on the surface) may be present.
　以下に、実施例を挙げて本発明をさらに詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
　≪実施例１～８、比較例１～６の調製≫
　表１に示す配合（数値は質量部である）より、エポキシエステル樹脂水分散物、顔料、分散剤を予め混合した後に、ビーズミルにて分散処理した。この分散処理後の混合物をアクリル樹脂水分散物に撹拌しながら加えた後、その他の原料も同様に撹拌しながら加え、水性塗料組成物（実施例１～８、比較例１～６）を得た。 << Preparation of Examples 1 to 8 and Comparative Examples 1 to 6 >>
From the formulations shown in Table 1 (numerical values are parts by mass), the epoxy ester resin aqueous dispersion, the pigment, and the dispersant were mixed in advance, and then dispersed in a bead mill. The mixture after the dispersion treatment is added to the aqueous dispersion of acrylic resin with stirring, and then other raw materials are also added with stirring in the same manner to obtain water-based coating compositions (Examples 1 to 8 and Comparative Examples 1 to 6). rice field.
　使用した原料の詳細を以下に示す。
・ウォーターゾールＥＦＤ－５５６０：ビニル変性エポキシエステル樹脂ディスパージョン、ＤＩＣ株式会社製、ＮＶ；４０質量％
・ウォーターゾールＥＦＤ－５５８０：エポキシエステル樹脂ディスパージョン、ＤＩＣ株式会社製、ＮＶ；４０質量％
・アクロナール２９５ＤＮ：スチレン・アクリル樹脂ディスパージョン、ＢＡＳＦ社製、ＮＶ；５０質量％
・アクリセットＰＪ－７１７：アクリル樹脂エマルジョン、株式会社日本触媒製、ＮＶ；４５質量％
・ヨドゾールＡＤ２０１：スチレン・アクリル樹脂エマルジョン、ヘンケルジャパン株式会社製、ＮＶ４６質量％
・ポリゾールＡＰ－６７５０：スチレン・アクリル樹脂エマルジョン、昭和電工株式会社製、ＮＶ；４５質量％
・ＬＴボイル油：亜麻仁油と桐油の混合物、マルニ製油社製
・ＤＩＣＮＡＴＥ３１１１：Ｃｏ系金属石鹸、ＤＩＣ株式会社製
・着色顔料：ＭＡ１００、三菱ケミカル株式会社製
・防食顔料：Ｋ-Ｗｈｉｔｅ ♯１４０Ｗ、テイカ株式会社製
・体質顔料：サンライトＳＬ－１０００、竹原化学工業株式会社製
・分散剤：Ｄｉｓｐｅｒｂｙｋ－１９０、ビックケミー・ジャパン株式会社製
・消泡剤：ｂｙｋ－０９３、ビックケミー・ジャパン株式会社製
・増粘剤：チクゾールＫ－１３０Ｂ、共栄社化学株式会社製
・表面調整剤：ｂｙｋ－３０７、ビックケミー・ジャパン株式会社製
・成膜助剤：２，２，４－トリメチル－１，３－ペンタンジオールモノイソブチレート Details of the raw materials used are shown below.
Watersol EFD-5560: Vinyl modified epoxy ester resin dispersion, manufactured by DIC Corporation, NV; 40% by mass.
Watersol EFD-5580: Epoxy ester resin dispersion, manufactured by DIC Corporation, NV; 40% by mass
-Acronal 295DN: Styrene / acrylic resin dispersion, manufactured by BASF, NV; 50% by mass
Acryset PJ-717: Acrylic resin emulsion, manufactured by Nippon Shokubai Co., Ltd., NV; 45% by mass
-Yodosol AD201: Styrene / acrylic resin emulsion, manufactured by Henkel Japan Ltd., NV46% by mass
-Polysol AP-6750: Styrene / acrylic resin emulsion, manufactured by Showa Denko KK, NV; 45% by mass
・ LT boil oil: A mixture of flaxseed oil and tung oil, manufactured by Maruni Oil Co., Ltd. ・ DICNAME3111: Co-based metal soap, manufactured by DIC Co., Ltd. ・ Color pigment: MA100, manufactured by Mitsubishi Chemical Co., Ltd. Constituent pigment: Sunlight SL-1000, Takehara Chemical Co., Ltd., Dispersant: Disperbyk-190, Big Chemie Japan Co., Ltd., Antifoaming agent: by093, Big Chemie Japan Co., Ltd. Adhesive: Tixol K-130B, Kyoeisha Chemical Co., Ltd. ・ Surface conditioner: byk-307, Big Chemie Japan Co., Ltd. ・ Formation aid: 2,2,4-trimethyl-1,3-pentanediol monoiso Butyrate
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例及び比較例において、測定・評価は下記の方法で行った。なお測定・評価は特に断りの無い限り２３℃５０％ＲＨの雰囲気下で行った。結果を表２に示す。 In the examples and comparative examples, the measurement / evaluation was performed by the following method. Unless otherwise specified, the measurement and evaluation were carried out in an atmosphere of 23 ° C. and 50% RH. The results are shown in Table 2.
　≪塗板作成方法１（冷間圧延鋼板）≫
　実施例１～８、比較例１～６の塗料を、各々、耐水ペーパー＃１８０にて研磨済みの冷間圧延鋼板（ＪＩＳ　Ｇ３１４１、１５０×７０×０．８ｍｍ、洗浄溶剤にて脱脂）に、乾燥膜厚が４５μｍとなるようスプレー塗装した。得られた塗膜を２３℃及び５０％ＲＨ雰囲気下で１週間乾燥し、目的とする塗板を得た。得られた塗板の裏面及び側面をポリエステルテープ（日東電工株式会社製）でシールし、付着性試験、耐食性試験、耐水性試験に供した。 ≪Coated plate making method 1 (cold rolled steel sheet) ≫
The paints of Examples 1 to 8 and Comparative Examples 1 to 6 were applied to cold-rolled steel sheets (JIS G3141, 150 × 70 × 0.8 mm, degreased with a cleaning solvent) polished with water-resistant paper # 180, respectively. Spray coating was performed so that the dry film thickness was 45 μm. The obtained coating film was dried at 23 ° C. and a 50% RH atmosphere for 1 week to obtain a desired coated plate. The back surface and side surfaces of the obtained coated plate were sealed with polyester tape (manufactured by Nitto Denko KK) and subjected to adhesion test, corrosion resistance test, and water resistance test.
　≪塗板作成方法２（黒皮鋼板）≫
　実施例１～８、比較例１～６の塗料を、各々、構造用鋼板（黒皮鋼板）（ＪＩＳ　Ｇ３１０１、１５０×７０×１．６ｍｍ、洗浄溶剤にて脱脂）に、得られた塗膜を２３℃及び５０％ＲＨ雰囲気下で１週間乾燥し、目的とする塗板を得た。得られた試験板の裏面及び側面をポリエステルテープ（日東電工株式会社製）でシールし、付着性試験、耐食性試験、耐水性試験に供した。 ≪Coating board making method 2 (black-skinned steel sheet) ≫
The coating films of Examples 1 to 8 and Comparative Examples 1 to 6 were applied to structural steel sheets (black-skinned steel sheets) (JIS G3101, 150 x 70 x 1.6 mm, degreased with a cleaning solvent), respectively. Was dried in an atmosphere of 23 ° C. and 50% RH for 1 week to obtain a desired coated plate. The back surface and side surfaces of the obtained test plate were sealed with polyester tape (manufactured by Nitto Denko KK) and subjected to adhesion test, corrosion resistance test, and water resistance test.
　≪付着性試験　クロスカット法≫
　塗膜にカッターナイフにて２ｍｍ幅のマスを１００個作製し、その後セロハンテープ（ニチバン社製）を貼り付け、指で圧着した後、セロハンテープを一気に引き剥がし、残存する塗膜のマス目を数えた。評価基準は以下の通りとした。
　◎：１００／１００
　○：９９／１００～９５／１００
　×：９４／１００以下 ≪Adhesion test cross-cut method≫
100 2 mm wide squares are made on the paint film with a cutter knife, then cellophane tape (manufactured by Nichiban Co., Ltd.) is attached, crimped with a finger, and then the cellophane tape is peeled off at once to remove the remaining squares of the paint film. I counted. The evaluation criteria are as follows.
⊚: 100/100
◯: 99/100 to 95/100
×: 94/100 or less
　≪耐食性試験（耐塩水噴霧性試験）≫
　塗板に予めカッターナイフにて素地に達する、３０°の角度で交わるよう長さ１０ｃｍの２本のキズを付ける。その試験板を槽内温度３５℃、５％塩化ナトリウム水を連続で噴霧する塩水噴霧試験機にて２４０時間試験を行った。装置から取り出し、水道水で試験面の塩水を粗い流し、水分を取り除く。その後直ちに試験面に付けたキズからの腐食幅を測定する。評価基準は以下の通りとした。
　塩水噴霧(２４０ｈ)後の腐食幅
　◎：２ｍｍ以下
　○：２～５ｍｍ
　×：５ｍｍ以上 ≪Corrosion resistance test (salt spray resistance test) ≫
Make two scratches on the coated plate with a cutter knife in advance to reach the substrate and meet at an angle of 30 ° with a length of 10 cm. The test plate was tested for 240 hours with a salt spray tester that continuously sprays 5% sodium chloride water at a temperature of 35 ° C. in the tank. Remove from the device and flush the test surface with tap water to remove water. Immediately after that, the corrosion width from scratches on the test surface is measured. The evaluation criteria are as follows.
Corrosion width after salt spray (240h) ◎: 2mm or less ○: 2-5mm
×: 5 mm or more
　≪耐水性試験≫
　塗板作製方法１および２で得られた塗板を２０±５℃の水に５０４時間浸漬した後、水洗し、２時間風乾し、塗膜の外観を目視で判定した。
◎：塗膜に割れ、はがれ、ふくれ、錆が無く、著しい変色、つやの変化、軟化等の異常が無い。
〇：塗膜に変色、つやの低下が認められるが、その他の異常はない。
×：塗膜に割れ、はがれ、ふくれ、錆等の異常が発生。 ≪Water resistance test≫
The coated plates obtained in the coated plate preparation methods 1 and 2 were immersed in water at 20 ± 5 ° C. for 504 hours, washed with water, air-dried for 2 hours, and the appearance of the coating film was visually judged.
⊚: There is no cracking, peeling, blistering, or rust on the coating film, and there is no abnormality such as significant discoloration, gloss change, or softening.
〇: Discoloration and loss of gloss are observed in the coating film, but there are no other abnormalities.
X: Abnormalities such as cracks, peeling, swelling, and rust occur in the coating film.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１および表２から明らかなように、本発明の一液型水性塗料組成物は、黒皮鋼材を含む種々の基材に対して優れた付着性を有し、建機向け水性塗料として耐食性に優れている。 As is clear from Tables 1 and 2, the one-component water-based paint composition of the present invention has excellent adhesion to various substrates including black-skinned steel, and has corrosion resistance as a water-based paint for construction machinery. Is excellent.

Claims (5)

  1. 　少なくとも、
    （Ａ）エポキシエステル樹脂、
    （Ｂ）アクリル樹脂、および、
    （Ｃ）乾性油または乾性油の重合物から選択される少なくとも一種の化合物、
    とを含有する一液型水性塗料組成物。     at least,
    (A) Epoxy ester resin,
    (B) Acrylic resin and
    (C) At least one compound selected from a drying oil or a polymer of a drying oil,
    A one-component water-based paint composition containing and.
  2. 　前記一液型水性塗料組成物の固形分中における前記（Ａ）エポキシエステル樹脂の含有量が５～３０質量％である請求項１記載の一液型水性塗料組成物。 The one-component water-based coating composition according to claim 1, wherein the content of the epoxy ester resin (A) in the solid content of the one-component water-based coating composition is 5 to 30% by mass.
  3. 　前記一液型水性塗料組成物の固形分中における前記（Ｃ）乾性油または乾性油の重合物から選択される少なくとも一種の化合物の含有量が０．１～５．０質量％である請求項１または２記載の一液型水性塗料組成物。 The claim that the content of at least one compound selected from the (C) drying oil or the polymer of the drying oil in the solid content of the one-component water-based coating composition is 0.1 to 5.0% by mass. The one-component water-based coating composition according to 1 or 2.
  4. 　前記（Ａ）エポキシエステル樹脂が、ビニル変性エポキシエステル樹脂である請求項１～３のいずれかに記載の一液型水性塗料組成物。 The one-component water-based coating composition according to any one of claims 1 to 3, wherein the (A) epoxy ester resin is a vinyl-modified epoxy ester resin.
  5. 　（Ｄ）酸化促進剤を含有する請求項１～４のいずれかに記載の一液型水性塗料組成物。 (D) The one-component water-based coating composition according to any one of claims 1 to 4, which contains an oxidation accelerator.
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CN114410191A (en) * 2021-12-09 2022-04-29 浙江天女集团制漆有限公司 Low-VOC quick-drying epoxy ester dip-coating primer and preparation method thereof

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JP2000239569A (en) * 1999-02-18 2000-09-05 Kansai Paint Co Ltd Water-based coating composition and article coated with the composition
JP2003064302A (en) * 2001-08-23 2003-03-05 Shinto Paint Co Ltd Aqueous coating composition excellent in rustproofness
JP2006089560A (en) * 2004-09-22 2006-04-06 Hitachi Chem Co Ltd Water-based resin composition and coating material using the same
JP2011168662A (en) * 2010-02-17 2011-09-01 Dic Corp Aqueous resin dispersion and coating material containing the same
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Publication number Priority date Publication date Assignee Title
JPH09263625A (en) * 1996-03-28 1997-10-07 Dainippon Ink & Chem Inc Ordinary temperature-drying type aqueous composition
JP2000239569A (en) * 1999-02-18 2000-09-05 Kansai Paint Co Ltd Water-based coating composition and article coated with the composition
JP2003064302A (en) * 2001-08-23 2003-03-05 Shinto Paint Co Ltd Aqueous coating composition excellent in rustproofness
JP2006089560A (en) * 2004-09-22 2006-04-06 Hitachi Chem Co Ltd Water-based resin composition and coating material using the same
JP2011168662A (en) * 2010-02-17 2011-09-01 Dic Corp Aqueous resin dispersion and coating material containing the same
JP2012224771A (en) * 2011-04-21 2012-11-15 Kansai Paint Co Ltd Aqueous coating composition and coated article

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114410191A (en) * 2021-12-09 2022-04-29 浙江天女集团制漆有限公司 Low-VOC quick-drying epoxy ester dip-coating primer and preparation method thereof

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