WO2011118792A1 - Composition de revêtement aqueuse et procédé pour la formation d'un film de revêtement - Google Patents

Composition de revêtement aqueuse et procédé pour la formation d'un film de revêtement Download PDF

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Publication number
WO2011118792A1
WO2011118792A1 PCT/JP2011/057408 JP2011057408W WO2011118792A1 WO 2011118792 A1 WO2011118792 A1 WO 2011118792A1 JP 2011057408 W JP2011057408 W JP 2011057408W WO 2011118792 A1 WO2011118792 A1 WO 2011118792A1
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Prior art keywords
epoxy
aqueous
water
resin
coating composition
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PCT/JP2011/057408
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English (en)
Japanese (ja)
Inventor
克彦 庄
宗夫 今村
崇宏 雲林院
照久 畑中
Original Assignee
日本ペイント株式会社
日本ペイントマリン株式会社
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Application filed by 日本ペイント株式会社, 日本ペイントマリン株式会社 filed Critical 日本ペイント株式会社
Priority to SG2012071205A priority Critical patent/SG184263A1/en
Priority to KR1020127023902A priority patent/KR101656912B1/ko
Priority to CN201180010254.6A priority patent/CN102770499B/zh
Priority to JP2012507102A priority patent/JP5543581B2/ja
Publication of WO2011118792A1 publication Critical patent/WO2011118792A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • 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
    • 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
    • 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
    • C09D5/022—Emulsions, e.g. oil in water
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

  • the present invention relates to a water-based coating composition and a coating film forming method.
  • a solvent-type paint containing an epoxy resin and a polyamine compound is used as an anticorrosion paint.
  • a water-based paint for example, a water-soluble polyamine resin blended with various pigments and additives as a main agent, and further includes an epoxy resin emulsion and an acrylic silicon resin emulsion containing a glycidyl group and an alkoxysilyl group.
  • An aqueous paint is mentioned (patent document 1).
  • the present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide an aqueous coating composition capable of forming a coating film having excellent low-temperature curability and excellent corrosion resistance. There is.
  • the aqueous coating composition of the present invention comprises an aqueous epoxy polyamine resin (A) having one or more primary amino groups and / or secondary amino groups in the molecule, and one or more (meth) acryloyl in the molecule.
  • An aqueous coating composition comprising a group-containing compound (B) and an alkoxysilane compound (C), the amino group of the aqueous epoxy polyamine resin (A) and the (meth) acryloyl group of the compound (B) Equivalent ratio ((meth) acryloyl group / amino group) is 0.7 to 2.5, and the content of the alkoxysilane compound (C) is 0. 0 in the solid content of the aqueous coating composition. 2% by mass to 5% by mass.
  • the aqueous coating composition is a two-component aqueous coating composition
  • the main coating liquid contains the aqueous epoxy polyamine resin (A)
  • the curing agent is the compound (B) and an alkoxysilane compound.
  • C is included.
  • the said water-based epoxy-type polyamine resin (A) is a water dispersion type.
  • the amino group equivalent of the aqueous epoxy polyamine resin (A) is 100 to 3000.
  • the aqueous epoxy polyamine resin (A) is obtained by amine-modifying an epoxy resin, and the epoxy equivalent of the epoxy resin is 180 to 3800.
  • the aqueous coating composition of the present invention is an aqueous epoxy polyamine obtained by amine-modifying an epoxy resin (a1) having an epoxy equivalent of 400 to 1500 as the aqueous epoxy polyamine resin (A).
  • the mass ratio a1 / a2 between the epoxy resin (a1) and the epoxy resin (a2) is 8/2 to 2/8.
  • the aqueous epoxy polyamine resin (A) is obtained by neutralizing the amino group of the epoxy polyamine resin with an acid, and the neutralization rate during the neutralization is 10% to 70%. is there.
  • the viscosity in 25 degreeC of the said compound (B) is 3000 mPa * s or less.
  • the aqueous coating composition of the present invention further comprises a pigment, and the pigment volume concentration of the pigment is 20% to 50%.
  • the coating-film formation method is provided. In this coating film forming method, the aqueous coating composition is applied to form a coating film. In a preferred embodiment, the coating film forming method of the present invention further forms a top coat layer by applying a top coat.
  • the aqueous coating composition of the present invention comprises an aqueous epoxy polyamine resin (A) having one or more primary amino groups and / or second amino groups in the molecule, and one or more (meth) acryloyl groups in the molecule.
  • A aqueous epoxy polyamine resin
  • B alkoxysilane compound
  • C alkoxysilane compound
  • the aqueous coating composition of the present invention comprises an aqueous epoxy polyamine resin (A) having one or more primary amino groups and / or second amino groups in the molecule, and one or more in the molecule.
  • the (meth) acryloyl group-containing compound (B) and the alkoxysilane compound (C) are included.
  • the aqueous coating composition of the present invention can form a coating film by mixing the aqueous epoxy polyamine resin (A) and the compound (B) to advance the curing reaction of these compounds.
  • the water-based coating composition of the present invention is excellent in low-temperature curability. Moreover, the water-based coating composition of this invention can form the coating film which is excellent in adhesiveness with a base material by including the alkoxysilane compound (C). Such excellent adhesion can be obtained even when a coating film is formed at a low temperature.
  • the aqueous coating composition of the present invention is preferably a two-component aqueous coating composition comprising a main coating liquid and a curing agent.
  • the main component coating liquid contains the water-based epoxy polyamine resin (A)
  • the curing agent contains the compound (B) and the alkoxysilane compound (C).
  • the aqueous coating composition of the present invention comprises (1) diluting the compound (B) with an organic solvent before mixing the aqueous epoxy polyamine resin (A) and the compound (B).
  • An emulsifier is mixed with B), or the compound (B) is emulsified or dispersed with a dispersant, an emulsifier or an aqueous resin, or (3) a dispersion of a resin different from the aqueous epoxy polyamine resin (A) is mixed with the compound (B).
  • the aqueous epoxy polyamine resin (A) and the compound (B) can be mixed without using a special mixing apparatus, and an aqueous coating composition having excellent dispersibility can be obtained.
  • the aqueous epoxy polyamine resin (A) and the compound (B) can be reacted with each other efficiently.
  • the compound (B) (2) is mixed with an emulsifier, or the compound (B) is emulsified or dispersed with a dispersant, an emulsifier or an aqueous resin, the compound (B) is regarded as a non-dangerous substance. It can be handled.
  • Examples of the organic solvent used when diluting the compound (B) with an organic solvent include ethylene glycol monobutyether and diethylene glycol monobutyl ether.
  • an emulsifier or an aqueous resin for example, a nonionic emulsifier, an anionic emulsifier, or the like is used.
  • a nonionic emulsifier include polyoxyethylene alkylphenol ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester and the like.
  • anionic emulsifier examples include dodecylbenzene sulfonate, dialkyl succinate sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl diphenyl ether disulfonate, and the like.
  • dispersant examples include polyacrylic acid sodium salt, ammonium salt of half ester of styrene maleic acid copolymer, and the like. As said aqueous resin, the soda salt of polyacrylic acid ester etc. are mentioned, for example.
  • Examples of the dispersion when the compound (B) is dispersed in a resin dispersion different from the aqueous epoxy polyamine resin (A) include an acrylic resin emulsion and dispersion, a urethane resin emulsion and dispersion, and the like. Is mentioned.
  • the content of the aqueous epoxy polyamine resin (A) as a solid content is preferably 5% by mass to 95% by mass and more preferably 10% by mass to 90% by mass with respect to the total solid content of the aqueous coating composition. % By mass.
  • the content of the compound (B) is preferably 2% by mass to 30% by mass and more preferably 5% by mass to 25% by mass with respect to the total solid content of the aqueous coating composition.
  • the equivalent ratio of the amino group of the aqueous epoxy polyamine resin (A) to the (meth) acryloyl group of the compound (B) ((meth) acryloyl group / amino group) is 0.7 to 2.5, Preferably, it is 0.8 to 2.0.
  • the equivalent ratio is less than 0.7, the low temperature curability of the aqueous coating composition may be lowered.
  • exceeding 2.5 there exists a possibility that the adhesiveness of the coating film obtained may fall.
  • the content of the alkoxysilane compound (C) is 0.2% by mass to 5% by mass, preferably 0.3% by mass to 3% by mass, with respect to the total solid content of the aqueous coating composition. More preferably, it is 0.5 mass% to 2 mass%. If the content of the alkoxysilane compound (C) is in such a range, it is possible to obtain an aqueous coating composition that is excellent in adhesion to the substrate and as a result can form a coating film exhibiting excellent anticorrosion properties. it can. Note that even if the content of the alkoxysilane compound (C) is more than 5% by mass, there is no further improvement in adhesion, but rather the curability (particularly low temperature curability) of the coating film may be lowered.
  • the aqueous coating composition of the present invention may further contain a pigment.
  • the viscosity of the aqueous coating composition can be increased, and the film thickness obtained by one coating can be increased.
  • the number of coatings can be reduced, it is possible to obtain an aqueous coating composition that is excellent in coating workability and can form a coating film exhibiting sufficient corrosion resistance.
  • the pigment examples include extender pigments such as precipitated barium sulfate, clay, talc, and mica; colored pigments such as titanium dioxide and carbon black; and rust preventive pigments such as zinc phosphate.
  • extender pigments such as precipitated barium sulfate, clay, talc, and mica
  • colored pigments such as titanium dioxide and carbon black
  • rust preventive pigments such as zinc phosphate.
  • the pigment volume concentration of the pigment in the aqueous coating composition is preferably 20% to 50%, more preferably 25% to 45%, and particularly preferably 30% to 40%. When the pigment volume concentration is less than 20%, the effect of containing the pigment may not be sufficiently obtained. When the pigment volume concentration is more than 50%, the coating film appearance may be deteriorated.
  • the pigment volume concentration can be obtained by calculation from the blending mass of the pigment and the specific gravity of each component in the paint.
  • the water-based coating composition of the present invention may contain water, a solvent, an additive and the like.
  • the solvent include glycol solvents such as ethylene glycol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether; xylene, Aromatic solvents such as Solvesso 100, Solvesso 150, Solvesso 200; hydrocarbon solvents such as mineral spirits; 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name “manufactured by Chisso Corporation” CS-12 "), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (manufactured by Chisso, trade name” CS-16 "), diethyl adipate And ester
  • the additive include a dispersant, a viscosity modifier, a curing catalyst, a surface modifier, an antifoaming agent, a plasticizer, a film-forming aid, an ultraviolet absorber, and an antioxidant.
  • water, solvent and / or additive are added to the main coating liquid or curing agent before mixing the main coating liquid and the curing agent. Alternatively, it may be added after mixing the main coating liquid and the curing agent. Whether water, a solvent and / or an additive is added to the main coating liquid or the curing agent can be determined depending on the expected function and properties.
  • Aqueous epoxy polyamine resin (A) The aqueous coating composition of the present invention includes an aqueous epoxy polyamine resin (A) having one or more primary amino groups and / or secondary amino groups in the molecule.
  • aqueous is a concept including “water-soluble” and “water-dispersed”.
  • the aqueous epoxy polyamine resin (A) is water-dispersed. If the water-dispersed aqueous epoxy polyamine resin (A) is used, an aqueous coating composition capable of forming a coating film excellent in water resistance can be obtained. Further, if the water-based epoxy polyamine resin (A) is water-dispersed, it can be easily mixed with the compound (B), and the water-based epoxy polyamine resin (A) and the compound (B) are rapidly mixed. It is possible to obtain an aqueous coating composition having a long pot life by suppressing the progress of the reaction and appropriately adjusting the reactivity.
  • the water-based epoxy polyamine resin (A) is a water-dispersed type
  • the water-based paint composition before coating is difficult to contact the water-based epoxy polyamine resin (A) and the compound (B).
  • the reaction does not proceed easily even at room temperature, and the storage and coating properties are good.
  • the dispersion medium for example, water
  • the aqueous epoxy polyamine resin (A) and the compound (B) are easily brought into contact with each other, and the curing reaction proceeds even at a low temperature. Can be formed.
  • the aqueous epoxy polyamine resin (A) can be obtained, for example, by modifying an epoxy resin with an amine. Moreover, when the epoxy-type polyamine resin obtained by amine-modifying an epoxy resin is not aqueous, for example, it is made aqueous by neutralizing the amino group of the epoxy-type polyamine resin with an acid to form an aqueous epoxy-type polyamine resin ( A) can be obtained.
  • epoxy resin Any appropriate epoxy resin can be used. Bisphenol A type epoxy resins or bisphenol F type epoxy resins are preferred, and bisphenol A type epoxy resins are particularly preferred.
  • the epoxy equivalent of the epoxy resin can be determined according to the desired film properties. It is preferably 180 to 3800, more preferably 400 to 3200, and particularly preferably 700 to 3200. If the epoxy equivalent of an epoxy resin is such a range, the coating film which is excellent in water resistance, corrosion resistance, and water-resistant adhesiveness can be obtained. When the epoxy equivalent of the epoxy resin is less than 180, the initial rainfall resistance of the resulting coating film may be lowered. On the other hand, if it exceeds 3,800, the epoxy-based polyamine resin may cause phase separation without being dispersed in water, and the coating composition may not be made water-based, and an aqueous coating composition having sufficient water-resistant adhesion can be obtained. There is a risk of not.
  • initial rain resistance means water resistance at the initial stage of curing of a coating film, specifically, at a stage where a coating film that is not completely cured but has no stickiness is formed. .
  • initial rainfall resistance is inferior, if the coated film is exposed to rain before the coated film is completely cured, the coated film may be cracked or blistered.
  • Water-based paint compositions that can form a coating with high initial rainfall resistance are particularly effective for applications to outdoor coatings that may be exposed to rainfall after application and before the coating is fully cured It is.
  • the epoxy resin is an epoxy resin (a1) having an epoxy equivalent of 400 to 1500. If the aqueous epoxy polyamine resin (A1) obtained by amine-modifying such an epoxy resin (a1) is used, an aqueous coating composition capable of forming a coating film excellent in water-resistant adhesion can be obtained.
  • the epoxy equivalent of the epoxy resin (a1) is more preferably 600 to 1400, and particularly preferably 800 to 1300.
  • the epoxy resin is an epoxy resin (a2) having an epoxy equivalent of 2000 to 3200.
  • an aqueous epoxy polyamine resin (A2) obtained by amine modification of such an epoxy resin (a2) an aqueous coating composition capable of forming a coating film excellent in initial rainfall resistance can be obtained.
  • the epoxy equivalent of the epoxy resin (a2) is more preferably 2200 to 3000.
  • the epoxy resin may be used in combination of two or more epoxy resins.
  • the epoxy resin there may be used those obtained by chain extension by using a reaction between an active hydrogen-containing compound capable of reacting with an epoxy group and an epoxy group to increase the molecular weight or modify the molecular weight.
  • an active hydrogen-containing compound capable of reacting with an epoxy group and an epoxy group to increase the molecular weight or modify the molecular weight.
  • the active hydrogen-containing compound include bifunctional compounds such as dimer acid, diamine, and polyether polyol.
  • the epoxy resin a resin to which a fatty acid is added before amine modification can be used.
  • a resin to which a fatty acid is added before amine modification can be used.
  • it is possible to reduce the reactivity by introducing a soft component into the resin or reducing the number of epoxy groups to reduce the number of amine-modified sites.
  • the epoxy polyamine resin can be obtained by modifying the epoxy resin by any appropriate modification method.
  • the modification method include a method of adding a first amino group-containing polyamine to an epoxy resin and a method of adding a ketiminated amino group-containing compound to an epoxy resin.
  • the epoxy polyamine resin thus obtained has one or more primary amino groups and / or secondary amino groups and secondary hydroxyl groups in the molecule.
  • the epoxy-based polyamine resin has a functional group such as an epoxy group, an acid anhydride group, an acid halogen group, or an isocyanate group in a part of the first amino group, the second amino group, and / or the hydroxyl group of the epoxy-based polyamine resin. It may be a resin obtained by reacting a compound.
  • the physical properties of the resulting coating film are adjusted by including an aqueous product of an epoxy polyamine resin reacted with a compound having such a functional group. Can do.
  • the method of adding the first amino group-containing polyamine to the epoxy resin means that the first amino group of the first amino group-containing polyamine is reacted with the epoxy group of the epoxy resin to form a second amino group, As a result, the epoxy polyamine resin having the second amino group is produced.
  • Examples of the first amino group-containing polyamine include diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine. These may be used alone or in combination.
  • the method of adding the ketiminized amino group-containing compound to the epoxy resin means that the ketimine group is hydrolyzed after reacting the ketiminized amino group-containing compound and the epoxy resin, thereby the first amino group. As a result, the epoxy-based polyamine resin having the first amino group is produced.
  • secondary amines such as diethanolamine, methylethanolamine, and diethylamine may coexist.
  • the ketiminated amino group-containing compound can be obtained by reacting a first amino group-containing compound with a ketone.
  • first amino group-containing compound include first amino group-containing polyamines such as diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine; aminoethylethanolamine, methylaminopropylamine, ethylaminoethylamine, and the like. It is done. These may be used alone or in combination.
  • the ketone include methyl ethyl ketone, acetone, and methyl isobutyl ketone.
  • the epoxy-based polyamine resin may be further modified by reacting a compound having a functional group that reacts with an amino group in accordance with desired film properties.
  • the functional group that reacts with an amino group include an epoxy group, a (meth) acryloyl group, an isocyanate group, and an acid anhydride group.
  • the amount of amino groups contained in the epoxy polyamine resin may be any appropriate amount of amino groups depending on the properties of the desired aqueous coating composition or the physical properties of the coating film.
  • the amount of the amino group is preferably 100 to 3000, more preferably 500 to 2000, and particularly preferably 800 to 2000 as the equivalent of the amino group.
  • the epoxy-based polyamine resin is water-based, and the water-based epoxy-based polyamine resin (A) can be obtained. If the said water-based epoxy-type polyamine resin (A) is used, the coating film which is excellent in low-temperature curability can be obtained. If the equivalent of the amino group of the epoxy-based polyamine resin is less than 100, the resulting coating film may have low water resistance.
  • the epoxy-based polyamine resin when it exceeds 3000, the epoxy-based polyamine resin does not disperse in water but causes phase separation, and the coating composition may not be water-based.
  • “equivalent of amino group” means that the epoxy-based polyamine resin has a first amino group (including the case where the epoxy-based polyamine resin has a first amino group and a second amino group), When the epoxy-based polyamine resin does not have the first amino group, the molecular weight of the resin solid per one second amino group is indicated by the molecular weight of the resin solid per one amino group.
  • the amino group equivalent of the epoxy-based polyamine resin can be determined from the amount of the raw material blended.
  • the aqueous epoxy polyamine resin (A) can also be obtained, for example, by making the amino group of the epoxy polyamine resin (that is, the amine-modified epoxy resin) neutralized with an acid.
  • the type of acid and the neutralization rate (neutralization rate with respect to the amino group of the epoxy-based polyamine resin before making it aqueous) depend on the desired state of the aqueous epoxy-based polyamine resin (A) (water-soluble to water-dispersed type). Any suitable acid type and neutralization rate may be employed. Examples of the acid include acetic acid, formic acid, lactic acid, and phosphoric acid.
  • the neutralization rate (neutralization rate with respect to amino groups of the epoxy-based polyamine resin before making it aqueous) is preferably 10% to 100%, more preferably 10% to 70%, and particularly preferably 15% to 50%. %. If the neutralization rate is less than 10%, the resin does not disperse in water and phase separation may occur, and the coating composition may not be water-based. Moreover, if the neutralization rate is adjusted to 70% or less, a water-dispersed aqueous epoxy polyamine resin (A) can be obtained.
  • any appropriate molecular weight can be adopted as the molecular weight (number average) of the water-based epoxy polyamine resin (A) depending on the properties of the desired water-based coating composition or the physical properties of the coating film. Preferably, it is 500 to 20000 in terms of standard polystyrene using gel permeation chromatography (GPC), and more preferably 1000 to 10,000. If the molecular weight of the aqueous epoxy polyamine resin (A) is in such a range, the aqueous epoxy polyamine resin (A) and the above compound (B) can be easily mixed, so that they can be reacted efficiently. Can do. Moreover, if the molecular weight of water-based epoxy-type polyamine resin (A) is such a range, the coating film which is excellent in corrosion resistance, water resistance, and adhesiveness can be obtained.
  • GPC gel permeation chromatography
  • the aqueous coating composition of the present invention may contain two or more of the above-mentioned aqueous epoxy polyamine resins (A).
  • the aqueous coating composition of the present invention is preferably an aqueous epoxy polyamine resin (A) obtained by amine modification of the epoxy resin (a1) having an epoxy equivalent of 400 to 1500 as the aqueous epoxy polyamine resin (A).
  • the mass ratio a1 / a2 of the epoxy resin (a1) having an epoxy equivalent of 400 to 1500 and the epoxy resin (a2) having an epoxy equivalent of 2000 to 3200 is preferably 8/2 to 2/8, More preferably, it is 7/3 to 3/7. If it is such a range, the water-based coating composition which can form the coating film excellent in initial rainfall resistance and water-resistant adhesiveness can be obtained.
  • the characteristics of the aqueous coating composition or the physical properties of the coating film can be controlled by the molecular weight and amino group amount of the aqueous epoxy polyamine resin (A).
  • Compound (B) The compound (B) used in the aqueous coating composition of the present invention has one or more (meth) acryloyl groups in the molecule.
  • the molecular weight of the compound (B) is preferably 150 or more and 2000 or less, more preferably 200 or more and 1700 or less, and particularly preferably 250 or more and 1300 or less. If the molecular weight of the compound (B) is in such a range, the aqueous epoxy polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing device, and have excellent dispersibility. Water-based coating composition can be obtained. As a result, the aqueous epoxy polyamine resin (A) and the compound (B) can be efficiently reacted with each other, and an aqueous coating composition having excellent curability can be obtained. The molecular weight of the compound (B) can be calculated from the chemical formula.
  • the number of (meth) acryloyl groups possessed by the compound (B) is 1 or more, preferably 2 to 4.
  • the number of (meth) acryloyl groups possessed by the compound (B) can be determined according to the desired physical properties of the coating film.
  • the viscosity of the compound (B) at 25 ° C. is preferably 3000 mPa ⁇ s or less, more preferably 50 mPa ⁇ s to 3000 mPa ⁇ s, particularly preferably 50 mPa ⁇ s to 2200 mPa ⁇ s, and most preferably 50 mPa ⁇ s to 1100 mPa ⁇ s. If the viscosity of the compound (B) is in such a range, the aqueous epoxy polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing apparatus, and the dispersibility is excellent. An aqueous coating composition can be obtained. As a result, the aqueous epoxy polyamine resin (A) and the compound (B) can be efficiently reacted with each other, and an aqueous coating composition having excellent curability can be obtained.
  • Examples of the compound (B) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1, 3 -Butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, neopentyl Glycol diacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol Dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate, pen
  • Examples thereof include adducts of an ethylenically unsaturated monomer and a carboxyl group-containing ethylenically unsaturated monomer; and polymerizable unsaturated monocarboxylic amide compounds of polyvalent amines such as ethylenediamine diacrylate. These compounds may be used alone or in combination.
  • the compound (B) can be easily mixed with the aqueous epoxy polyamine resin (A) (both can react). More preferably, the water-based epoxy polyamine resin (A) and the compound (B) are used in a non-uniform state within a range where they can be easily mixed (both can react). Particularly preferably, the compound (B) and the aqueous epoxy polyamine resin (A) are used in mutually different phase states. If it is such a state, the progress of the rapid reaction of water-based epoxy-type polyamine resin (A) and a compound (B) can be suppressed, and reactivity can be adjusted moderately.
  • the water-based epoxy polyamine resin (A) and the compound (B) are in a non-uniform state, the water-based paint composition before coating is difficult to come in contact with both of these components. The reaction does not proceed easily, and the storage and coating properties are good.
  • the dispersion medium for example, water
  • the aqueous epoxy polyamine resin (A) and the compound (B) are easily brought into contact with each other, and the curing reaction proceeds even at a low temperature. Can be formed.
  • the compound (B) when the compound (B) is a water-soluble compound and the aqueous epoxy polyamine resin (A) is a water-dispersed resin, the compound (B) has a self-emulsifying property or is water-dispersed with a dispersant. And the case where the compound (B) is emulsified or dispersed by the aqueous epoxy polyamine resin (A). It should be noted that whether the compound (B) is “water-insoluble”, “water-soluble” or “self-emulsifying” is determined by adding 5 g of compound (B) to 100 g of water at room temperature. The state after stirring (for example, 3 minutes) and leaving still (for example, after 5 minutes) can be visually observed.
  • the compound (B) when the compound (B) is modified with polyethylene oxide, it can be made water-soluble or self-emulsifiable compound by increasing the number of moles of ethylene oxide added to increase hydrophilicity.
  • water-soluble compound (B) examples include ethoxylated bisphenol A diacrylate (EO 30 mol), ethoxylated trimethylolpropane triacrylate (EO 20 mol), ethoxylated trimethylolpropane triacrylate (EO 30 mol), and ethoxylated pentaerythritol tetra.
  • examples include acrylate (EO 35 mol), ethoxylated glycerin triacrylate (EO 20 mol), and ethoxylated bisphenol A dimethacrylate (EO 30 mol). These may be used alone or in combination. In the present specification, for example, “EO 30 mol” represents that 30 ethylene oxides are contained in the molecule.
  • Examples of the compound (B) having the self-emulsifying property or capable of being dispersed in water with a dispersant include polyethylene glycol # 400 diacrylate (EO 9 mol), polyethylene glycol # 600 diacrylate (EO 14 mol), polyethylene glycol # 1000.
  • Examples include diacrylate (EO 23 mol), ethoxylated bisphenol A diacrylate (EO 10 mol), ethoxylated bisphenol A diacrylate (EO 20 mol), ethoxylated glycerin triacrylate (EO 9 mol), polyethylene glycol # 1000 dimethacrylate (EO 23 mol), and the like. These may be used alone or in combination.
  • Examples of the compound (B) that can be emulsified or dispersed by the aqueous epoxy polyamine resin (A) include polyethylene glycol # 200 glycol diacrylate (EO 4 mol), ethoxylated bisphenol A diacrylate (EO 3 mol), and ethoxylated bisphenol A diester.
  • the compound (B) can be used as a mixture of a plurality of types of compounds (B).
  • the physical property control of a water-based coating composition and the coating film obtained can be performed by combining and using the compound (B) from which a characteristic differs.
  • the curability can be controlled by mixing the compound (B) having two (meth) acryloyl groups and the compound (B) having three (meth) acryloyl groups. If a mixture of the water-soluble compound (B) and the water-insoluble compound (B) is used, the water-insoluble compound (B) is easily introduced into the reaction system by the water-soluble compound (B). be able to. Moreover, the coating material obtained is excellent in low-temperature curability.
  • water-insoluble compound (B) examples include compounds that are not completely water-soluble, such as propoxylated bisphenol A diacrylate (PO4 mol).
  • the mixing ratio (water-soluble / water-insoluble) of the water-soluble compound (B) and the water-insoluble compound (B) is preferably 1/9 to 9/1, more preferably 2/8 to 8 / 2.
  • the aqueous coating composition of the present invention contains an alkoxysilane compound (C). If the alkoxysilane compound (C) is included, a coating film having excellent adhesion to the substrate can be obtained.
  • the coating film formed by the aqueous coating composition of the present invention is excellent in adhesion to a substrate even when formed at a low temperature. Thus, the coating film formed with the aqueous coating composition of the present invention having excellent adhesion to the substrate exhibits excellent corrosion resistance.
  • the alkoxysilane compound (C) has a functional group showing reactivity or affinity for organic substances and a functional group showing reactivity or affinity for inorganic substances. Therefore, the aqueous coating composition of the present invention can improve the adhesion between the formed coating film (organic substance) and the substrate (inorganic substance) by including the alkoxysilane compound (C).
  • the functional group showing reactivity or affinity for organic substances include a vinyl group, an epoxy group, a methacryl group, an amino group, a mercapto group, and the like.
  • the functional group showing reactivity or affinity for inorganic substances is preferably a hydrolyzable functional group, and examples thereof include a methoxysilane group, an ethoxysilane group, and a propoxysilane group.
  • the alkoxysilane compound (C) may be partially hydrolyzed and / or hydrolyzed and dehydrated, and specific examples thereof include ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -glycidoxypropyltriethoxy.
  • ⁇ -glycidoxyalkyltrialkoxysilane such as silane and ⁇ -glycidoxypropoxytrimethoxysilane; ⁇ -aminopropyltrialkoxysilane such as ⁇ -aminopropyltriethoxysilane and ⁇ -aminopropyltripropoxysilane; N— N-phenyl- ⁇ -aminoalkyltrialkoxysilane such as phenyl- ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltripropoxysilane, etc. .
  • aqueous coating composition of the present invention can be applied to inner and outer plate portions of ships and underwater structures in seawater or fresh water. Concretely, deck and hatch combing, upper part, outer part, engine room, living area, inside and outside parts of a ship such as car hold; seawater or freshwater underwater structures such as piping materials to be coated ( Substrate).
  • the material of the base material include metal materials such as iron-based, zinc-based, and aluminum-based materials.
  • any appropriate method can be adopted as a method for applying the aqueous coating composition of the present invention.
  • the coating method include airless coating, air spray, brush coating, trowel coating, and roller coating. Of these, airless coating is preferred. If coating is performed by airless coating, a thick coating can be obtained. Further, a coating film may be formed by coating a plurality of times (for example, 2 to 3 times). If it is applied several times, a thick coating can be formed with good appearance.
  • the thickness of the coating film when applying the aqueous coating composition of the present invention is a dry coating film, preferably 50 ⁇ m to 250 ⁇ m, and more preferably 50 ⁇ m to 200 ⁇ m.
  • a dry coating film preferably 50 ⁇ m to 250 ⁇ m, and more preferably 50 ⁇ m to 200 ⁇ m.
  • any appropriate drying method may be employed as a method for drying the aqueous coating composition of the present invention. Natural drying or heat drying is preferred. In the case of natural drying, the drying time is preferably 24 hours or longer, more preferably 1 week or longer.
  • a top coating layer may be formed on the coating film by further applying a top coating composition.
  • a multilayer coating film forming method can be provided. If an overcoat layer is formed, a coating film having improved anticorrosion properties and appearance can be obtained.
  • top coat any appropriate paint can be adopted as the top coat.
  • the top coat include epoxy / amine-based paints, two-component urethane curable paints, one-component urethane curable paints, and paints containing a carbodiimide curing agent.
  • the top coat may be solvent-based or water-based. Preferably, it is aqueous. If the top coat is water-based, the environmental load can be reduced during the formation of the coating film.
  • the thickness of the top coat layer can be set to any appropriate thickness depending on the type of paint and the purpose of painting. Typically, the film thickness of the dried coating film is 10 ⁇ m to 300 ⁇ m.
  • An intermediate coating layer may be formed between the coating film formed from the aqueous coating composition and the top coating layer.
  • the intermediate coating layer can be formed by applying an intermediate coating on the coating film formed from the aqueous coating composition. If an intermediate coating layer is formed, a coating film with further improved anticorrosion properties can be obtained.
  • any appropriate paint can be adopted as the intermediate paint.
  • the intermediate coating include epoxy / amine-based paints, two-component urethane curable paints, and one-component urethane curable paints.
  • the intermediate coating material may be solvent-based or water-based. Preferably, it is aqueous. If the intermediate coating is water-based, the environmental load can be reduced when forming the coating film.
  • the thickness of the intermediate coating layer can be set to any appropriate thickness depending on the type of paint and the purpose of painting. Typically, the dry coating film thickness is 10 ⁇ m to 50 ⁇ m.
  • an undercoat layer Before forming the coating film with the aqueous coating composition, an undercoat layer may be formed by applying an undercoat paint on the substrate. If an undercoat layer is formed, a coating film with improved anticorrosion properties can be obtained.
  • the undercoat paint can be any appropriate paint.
  • the undercoat paint include organic or inorganic zinc rich paint.
  • the undercoat paint may be solvent-based or water-based. Preferably, it is aqueous. If the undercoat paint is water-based, the environmental load can be reduced during the formation of the coating film.
  • the thickness of the undercoat layer can be set to any appropriate thickness depending on the type of paint and the purpose of painting. Typically, the film thickness of the dried coating film is 20 ⁇ m to 300 ⁇ m.
  • the above-mentioned top coat, intermediate coat and undercoat may contain pigments, additives and the like.
  • the pigment and additive include the pigment and additive described in the above section A.
  • the number, type, and amount of pigments and additives to be added can be appropriately selected depending on the purpose.
  • any appropriate method can be adopted as a coating method and a drying method for the top coating material, intermediate coating material, and under coating material, depending on the type of the coating material used.
  • Examples of the coating method and the drying method for the top coating material, intermediate coating material, and undercoating coating material include the same methods as the coating method and the drying method for the aqueous coating composition described above.
  • a ketimine compound of aminoethylethanolamine (73 mass% MIBK solution) was added and reacted at 117 ° C. for 1 hour. Then, it diluted with MIBK until it became non-volatile content 75%, and the epoxy-type polyamine resin of 1184 equivalent of an amino group was obtained. Acetic acid was added thereto to achieve a neutralization rate of 35.0% (neutralization rate relative to the amino group of the resin), and diluted by adding ion-exchanged water.
  • ion-exchanged water 27 parts of ion-exchanged water and 188 parts of neodecanoic acid glycidyl ester (trade name “Cardura E10-P” manufactured by Hexion Specialty Chemicals) were charged and reacted at 100 ° C. for 2 hours. Then, it diluted with MIBK until it became non-volatile content 75%, and the epoxy-type polyamine resin of the equivalent 810 of an amino group was obtained. Acetic acid was added thereto to achieve a neutralization rate of 20.0% (neutralization rate with respect to the amino group of the resin), and ion-exchanged water was added for dilution.
  • DBP dipropylene glycol monobutyl ether
  • an epoxy polyamine resin having an amino group equivalent of 2050 was diluted with MIBK until the non-volatile content became 75% to obtain an epoxy polyamine resin having an amino group equivalent of 2050.
  • Acetic acid was added thereto to achieve a neutralization rate of 40.0% (neutralization rate with respect to the amino group of the resin), and ion-exchanged water was added for dilution. Thereafter, the mixture of MIBK and water was removed under reduced pressure until the solid content became 40% by mass, to prepare an epoxy polyamine resin.
  • the epoxy polyamine resin was phase-separated in water without being made aqueous.
  • Example 1 Manufacture of main component paint liquid
  • talc made by Fuji Talc Kogyo, trade name “Talc SP42”, specific gravity: 2.7 g / cm 3
  • calcium carbonate made by Maruo Calcium Co., trade name “N heavy coal”, Specific gravity: 2.7 g / cm 3
  • titanium oxide manufactured by DuPont, trade name “TI-PUR R706”, specific gravity: 4.3 g / cm 3
  • 172 parts rust preventive pigment (manufactured by Toho Pigment)
  • a pigment dispersion paste was produced by adding 32 parts (man
  • Example 2 to 22 An aqueous coating composition was obtained in the same manner as in Example 1 except that the types and amounts of the main coating liquid I, the curing agent I and the alkoxysilane compound (C) were as shown in Table 2 or Table 3.
  • the main coating liquids II to VIII were obtained in the same manner as in Example 1 except that the aqueous epoxy polyamine resin (A) shown in Table 4 was used instead of the aqueous epoxy polyamine resin (A) I.
  • Curing agents II to IX were obtained according to the production method of the curing agent of Example 1 according to the compound (B), blending ratio and mixing method shown in Table 5, and obtained curing agents II to IX containing compound (B). .
  • a nonionic emulsifier manufactured by Nippon Emulsifier Co., Ltd., trade name “New Coal 740” was used.
  • Table 5 shows the viscosity at 25 ° C., the molecular weight, the number of functional groups, the acryloyl group equivalent and the properties (self-emulsifying property, water-insoluble property, water-soluble property) of the compound (B) used in each example.
  • the characteristics of the compound (B) are as follows. At room temperature, 5 g of the compound (B) was added to 100 g of water, stirred for 3 minutes and allowed to stand.
  • the aqueous coating composition obtained above was evaluated by the following method. The results are shown in Tables 2 and 3. (Low temperature curability) The aqueous coating composition obtained above was applied to a 20 cm ⁇ 30 cm grit blast steel plate using an applicator so that the film thickness of the dried coating film was 100 ⁇ m, and then an atmosphere having a relative humidity of 50% at 5 ° C. A test plate on which a coating film was formed was obtained by allowing it to stand for 16 hours. With respect to the obtained coating film, a worker weighing 65 kg visually evaluated the state of the coating film after stepping on the coating film surface from the top with the heel of safety shoes for 30 seconds based on the following evaluation criteria. .
  • a test plate was obtained in the same manner as in the evaluation of the low temperature curability.
  • the pencil hardness of the coating film formed on the test plate was measured according to JISK5600-5-4. (Initial rainfall resistance)
  • the aqueous coating composition obtained above was applied to a polished steel plate with a brush at a coating amount of 200 g / m 2 and then dried in an environment of 5 ° C. for 24 hours to obtain a test plate.
  • the test plate was immersed in water at 5 ° C., pulled up after 24 hours, and allowed to stand at 5 ° C. for 24 hours.
  • an oil-based paint manufactured by Nippon Paint Marine Co., Ltd., trade name “CR Marine Finish”
  • solvent-based urethane paint manufactured by Nippon Paint Marine Co., Ltd., trade name “Polyuremite Rack M”
  • solvent-based epoxy Paint made by Nippon Paint Marine Co., Ltd., trade name “Epoxy Finish M”
  • water-based epoxy paint made by Nihon Paint Marine Co., Ltd., trade name “Odemarine PF”
  • water-based urethane paint made by Nippon Paint Co., Ltd., trade name “Audeuretop”
  • the aqueous coating composition of the present invention is excellent in low-temperature curability by containing the aqueous epoxy polyamine resin (A) and the compound (B). Further, as apparent from a comparison between Examples 1 to 21 and Comparative Example 1, the water-based coating composition of the present invention contains an alkoxysilane compound (C), thereby providing a coating film with more excellent anticorrosion properties. Can be formed.
  • the composition can form a coating film that is remarkably excellent in initial rainfall resistance.
  • the aqueous coating composition of the present invention can be suitably applied as an anticorrosive coating to inner and outer plate portions of ships and underwater structures in seawater or fresh water. Specifically, it is suitably used for decks, hatch combing, upper frame parts, outer fence parts, engine rooms, residential areas, inner and outer parts of ships such as car hold; seawater or freshwater underwater structures such as piping materials, etc. obtain.

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Abstract

La présente invention concerne une composition de revêtement aqueuse présentant une excellente aptitude au durcissement à basses températures et pouvant former un film de revêtement avec une excellente adhésion à un substrat. La composition de revêtement aqueuse comporte (A) une résine polyamine époxyde aqueuse comprenant un ou des groupe(s) amine(s) primaire(s) ou secondaire(s) dans la molécule, (B) un composé comprenant un ou des groupe(s) (méth)acryloyle dans la molécule, et (C) un composé alcoxysilane, le rapport équivalent de (méth)acryloyle du composé (B) à l'amine de la résine (A) [(méth)acryloyle/amine] est compris entre 0,7 et 2,5, et la teneur du composé alcoxysilane (C) est comprise entre 0,2 et 5% en poids par rapport à la matière solide de la composition de revêtement aqueuse.
PCT/JP2011/057408 2010-03-26 2011-03-25 Composition de revêtement aqueuse et procédé pour la formation d'un film de revêtement WO2011118792A1 (fr)

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SG2012071205A SG184263A1 (en) 2010-03-26 2011-03-25 Water-based coating composition and process for formation of coating film
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CN201180010254.6A CN102770499B (zh) 2010-03-26 2011-03-25 水性涂料组合物及涂膜形成方法
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KR101867252B1 (ko) * 2016-02-12 2018-06-12 닛뽄 페인트 마린 가부시키가이샤 방식 도료 조성물 및 건조 도막의 형성 방법
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KR20130018239A (ko) 2013-02-20
CN102770499A (zh) 2012-11-07
JPWO2011118792A1 (ja) 2013-07-04
JP5543581B2 (ja) 2014-07-09
KR101656912B1 (ko) 2016-09-12
CN102770499B (zh) 2015-05-13
SG184263A1 (en) 2012-11-29
MY156470A (en) 2016-02-26

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