WO2010035641A1 - Composition de revêtement aqueux - Google Patents

Composition de revêtement aqueux Download PDF

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Publication number
WO2010035641A1
WO2010035641A1 PCT/JP2009/065807 JP2009065807W WO2010035641A1 WO 2010035641 A1 WO2010035641 A1 WO 2010035641A1 JP 2009065807 W JP2009065807 W JP 2009065807W WO 2010035641 A1 WO2010035641 A1 WO 2010035641A1
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WO
WIPO (PCT)
Prior art keywords
compound
water
coating composition
polyamine resin
resin
Prior art date
Application number
PCT/JP2009/065807
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English (en)
Japanese (ja)
Inventor
克彦 庄
宗夫 今村
崇宏 雲林院
Original Assignee
日本ペイント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ペイント株式会社 filed Critical 日本ペイント株式会社
Priority to CN200980138524.4A priority Critical patent/CN102165027B/zh
Priority to JP2010530809A priority patent/JP5421921B2/ja
Priority to KR1020117008902A priority patent/KR101474056B1/ko
Publication of WO2010035641A1 publication Critical patent/WO2010035641A1/fr

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate

Definitions

  • the present invention relates to a water-based coating composition.
  • Patent Document 1 a two-component water-based paint composition containing an epoxy resin and a polyamine compound can be cited.
  • Such an aqueous coating composition exhibits sufficient curability at a temperature of room temperature or higher and can form a normal coating film.
  • it is inferior in curability at low temperatures (for example, around 5 ° C.)
  • low-temperature areas for example, outdoors in winter
  • 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 having excellent low-temperature curability.
  • the aqueous coating composition of the present invention comprises a water-soluble or water-dispersible polyamine resin (A) having one or more primary amine groups and / or secondary amine groups in the molecule, and one or more in the molecule. And a compound (B) having a (meth) acryloyl group, the amine equivalent of the polyamine resin (A) is 100 to 3000, and the viscosity of the compound (B) at 25 ° C. is 3000 mPa ⁇ s or less.
  • the aqueous coating composition is a two-component aqueous coating composition
  • the main coating liquid contains the polyamine resin (A)
  • the curing agent contains the compound (B).
  • the polyamine resin (A) is an acrylic polyamine resin or an epoxy polyamine resin.
  • the molecular weight of the compound (B) is 150 or more and 2000 or less.
  • the compound (B) is a water-soluble compound
  • the polyamine resin (A) is a water-dispersed resin
  • the compound (B) is a self-emulsifying compound.
  • the compound (B) is emulsified or dispersed by the polyamine resin (A).
  • the compound (B) is a mixture of a water-soluble compound and a water-insoluble compound.
  • the compound (B) is an emulsion.
  • the curing agent further contains an emulsifier.
  • the aqueous coating composition of the present invention comprises a water-soluble or water-dispersible polyamine resin (A) having one or more primary amine groups and / or secondary amine groups in the molecule, and one or more in the molecule.
  • the compound (B) having a (meth) acryloyl group excellent low temperature curability is exhibited. That is, when the polyamine resin (A) and the compound (B) are used, they exhibit high reactivity with each other and the reaction proceeds even at low temperatures, so that an aqueous coating composition having excellent curability at low temperatures can be obtained. Can do.
  • the product obtained by the reaction of the polyamine resin (A) and the compound (B) can have a structure in which the polyamine resin (A) is crosslinked by the compound (B), the coating performance is improved. An excellent aqueous coating composition can be obtained.
  • the aqueous coating composition of the present invention comprises a water-soluble or water-dispersed polyamine resin (A) having one or more primary amine groups and / or secondary amine groups in the molecule, and a molecule. It contains a compound (B) having one or more (meth) acryloyl groups therein, and is cured by a reaction between the polyamine resin (A) and the compound (B) to obtain a coating film.
  • A water-soluble or water-dispersed polyamine resin having one or more primary amine groups and / or secondary amine groups in the molecule, and a molecule. It contains a compound (B) having one or more (meth) acryloyl groups therein, and is cured by a reaction between the polyamine resin (A) and the compound (B) to obtain a coating film.
  • the aqueous coating composition of the present invention is preferably a two-component aqueous coating composition comprising a main component coating liquid and a curing agent, and the main component coating liquid contains the polyamine resin (A), and the curing agent is the above compound. (B) is included.
  • the polyamine resin (A) and the compound (B) as a two-component aqueous coating composition, a combination of the polyamine resin (A) and the compound (B) that exhibits high reactivity with each other is selected. Therefore, an aqueous coating composition having excellent low temperature curability can be obtained.
  • the content of the polyamine resin (A) as a solid content is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, based on the total solid content of the aqueous coating composition.
  • the content of the compound (B) is preferably 2 to 40% by weight, more preferably 5 to 30% by weight, based on the total solid content of the aqueous coating composition.
  • the ratio of the number of amine groups of the polyamine resin (A) to the number of (meth) acryloyl groups of the compound (B) is preferably 1: 0.5 to 1: 1. 5, more preferably 1: 0.75 to 1: 1.25, and particularly preferably 1: 0.9 to 1: 1.1.
  • “the number of amine groups” means that when the polyamine resin (A) has a primary amine group in its molecule (including cases where it has a primary amine group and a secondary amine group). It means the number of one amine group (that is, does not include the number of secondary amine groups), and when it has only the secondary amine group in the molecule, it means the number of secondary amine groups.
  • the water-based coating composition of the present invention may contain a pigment, a solvent, an additive and the like as necessary.
  • the pigment include titanium oxide, yellow iron oxide, red iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, azo red, quinacridone red, benzimidazolone yellow, and the like; calcium carbonate, barium sulfate, kaolin, clay, Examples include extender pigments such as talc.
  • the solvent examples 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, Solvesso 100, Aromatic solvents such as Solvesso 150 and Solvesso 200; Hydrocarbon solvents such as mineral spirits; 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (CS-12), 2,2,4 -Ester solvents such as trimethyl-1,3-pentanediol diisobutyrate (CS-16), diethyl adipate, diisobutyl adipate It is.
  • the additive include a dispersant, a viscosity adjusting agent, a curing catalyst, a surface adjusting agent, an antifoaming
  • the polyamine resin (A) used in the aqueous coating composition of the present invention may be any resin as long as it has one or more primary amine groups and / or secondary amine groups and is a water-soluble or water-dispersible resin.
  • a suitable resin can be employed. Examples of such resins include aliphatic polyamine resins, aromatic polyamine resins, and alicyclic polyamine resins.
  • the amount of amine groups contained in the polyamine resin (A) is 100 to 3000 as an amine equivalent, more preferably 500 to 2000, and particularly preferably 800 to 1500.
  • the polyamine resin (A) has water solubility or water dispersibility, and a coating film having excellent low-temperature curability can be obtained.
  • the polyamine resin (A) has a primary amine
  • the amine equivalent is indicated by the molecular weight of the resin solids per primary amine group, and when the polyamine resin (A) does not have a primary amine group, It is indicated by the molecular weight of the resin solid content per secondary amine group.
  • the amine equivalent of polyamine resin (A) can be calculated
  • any appropriate molecular weight can be adopted as the molecular weight (number average) of the polyamine resin (A) depending on the desired film properties.
  • it is 500 to 20000 in terms of standard polystyrene using gel permeation chromatography (GPC), and more preferably 1000 to 3000.
  • GPC gel permeation chromatography
  • the molecular weight of the polyamine resin (A) is in such a range, the polyamine resin (A) and the compound (B) can be easily mixed, and thus can be reacted efficiently.
  • the molecular weight of a polyamine resin (A) is such a range, the coating film which is excellent in corrosion resistance, water resistance, and adhesiveness can be obtained.
  • any suitable glass transition temperature can be adopted as the glass transition temperature of the polyamine resin (A) depending on the desired physical properties of the coating film.
  • it is ⁇ 50 to 100 ° C., more preferably 0 to 50 ° C.
  • an aqueous solution obtained by neutralizing an amine group with an acid can be used as the polyamine resin (A).
  • the type of acid and the neutralization rate (neutralization rate with respect to the amine group of the polyamine resin before being made water-based) can be arbitrarily selected depending on the desired state of the polyamine resin (A) (water-soluble to aqueous dispersion)
  • the type of acid and the neutralization rate can be employed.
  • Examples of the acid include acetic acid, formic acid, lactic acid, and phosphoric acid.
  • the neutralization rate (neutralization rate with respect to the amine group of the polyamine resin before being made water-based) is preferably 10 to 70%, and more preferably 15 to 50%.
  • the polyamine resin (A) is preferably an epoxy polyamine resin obtained by amine-modifying an epoxy resin or an acrylic polyamine resin obtained by amine-modifying an acrylic resin, and more preferably an epoxy polyamine resin.
  • an epoxy-based polyamine resin can provide an aqueous coating composition with better anticorrosion performance. That is, by using the epoxy-based polyamine resin as the polyamine resin (A) and the compound (B), a coating exhibiting excellent anticorrosion performance equal to or better than that of a conventional epoxy resin coating composition comprising an epoxy resin-polyamine compound.
  • An aqueous coating composition capable of forming a film even at a low temperature can be obtained.
  • the epoxy polyamine resin and acrylic polyamine resin can be obtained by any suitable modification method.
  • the modification method include a method of adding a primary amine group-containing polyamine to an epoxy resin or an acrylic resin, and a method of adding a ketiminated amine group-containing compound to an epoxy resin or an acrylic resin.
  • the polyamine resin (A) thus obtained has one or more primary amine groups and / or secondary amine groups and secondary hydroxyl groups in the molecule.
  • the polyamine resin is a compound having 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 primary amine group, secondary amine group and / or hydroxyl group of the polyamine resin (A). It may be a resin obtained by reacting. By including a polyamine resin reacted with such a functional group as a part of the polyamine resin to be used, the physical properties of the obtained coating film can be adjusted.
  • the method of adding the first amine group-containing polyamine to the epoxy resin or acrylic resin means that the first amine group of the first amine group-containing polyamine and the reactive group (for example, epoxy group) of the epoxy resin or acrylic resin.
  • a second amine group is formed by reaction, and as a result, the epoxy polyamine resin or the acrylic polyamine resin having the second amine group is produced.
  • the method of adding the ketiminated amine group-containing compound to an epoxy resin or an acrylic resin means that the ketimine group is hydrolyzed after reacting the ketiminated amine group-containing compound with an epoxy resin or an acrylic resin.
  • the first amine group is formed, and as a result, the epoxy polyamine resin or the acrylic polyamine resin having the first amine group is produced.
  • a secondary amine such as diethanolamine, methylethanolamine, or diethylamine may coexist.
  • 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 2000, more preferably 400 to 1500. If the epoxy equivalent of an epoxy resin is such a range, the coating film which is excellent in water resistance, corrosion resistance, and adhesiveness can be obtained.
  • the above-mentioned epoxy resin can be chain-extended using the reaction between an active hydrogen-containing compound capable of reacting with an epoxy group and the epoxy group to increase the molecular weight or be modified.
  • active hydrogen-containing compound include bifunctional compounds such as dimer acid, diamine, and polyether polyol.
  • the epoxy resin may be used by adding a fatty acid to reduce the number of epoxy groups before reducing the amine, thereby reducing the number of amine-modified sites and reducing the reactivity.
  • any appropriate resin can be used as the acrylic resin.
  • An acrylic resin obtained by copolymerizing a monomer composition containing a radical polymerizable monomer having an epoxy group and / or a glycidyl group is preferable.
  • the radical polymerizable monomer having an epoxy group and / or glycidyl group include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, and 3,4-epoxycyclohexyl. Examples include methyl methacrylate.
  • first amine group-containing polyamine examples include diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine. These may be used alone or in combination.
  • the above-mentioned ketiminated amine group-containing compound can be obtained by reacting a first amine group-containing compound with a ketone.
  • the primary amine group-containing compound include primary amine 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.
  • 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.
  • the molecular weight of the compound (B) is within such a range, the polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing apparatus, and the coating composition has excellent dispersibility. You can get things. As a result, the 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 3000 mPa ⁇ s or less, preferably 50 mPa ⁇ s or more and 3000 mPa ⁇ s or less, more preferably 50 mPa ⁇ s or more and 2200 mPa ⁇ s or less, and particularly preferably 50 mPa ⁇ s. ⁇ S to 1100 mPa ⁇ s. If the viscosity of the compound (B) is in such a range, the polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing device, and the coating composition has excellent dispersibility. Can be obtained. As a result, the 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 polymerizable unsaturated monocarboxylic acid ester compounds of polyhydric alcohols (for example, 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-butane Diol diacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol diacrylate, pentaerythritol diacryl
  • the compound (B) needs to be easily mixed with the polyamine resin (A) (both can react).
  • the polyamine resin (A) and the compound (B) are used in a non-uniform state as long as they can be easily mixed (both can react).
  • the compound (B) and the polyamine resin (A) are used in different phase states. In such a state, the rapid progress of the reaction between the polyamine resin (A) and the compound (B) can be suppressed, and the reactivity can be appropriately adjusted.
  • the coating composition is used as a two-pack type coating, an aqueous coating composition having excellent handleability can be obtained.
  • the compound (B) is a water-soluble compound and the polyamine resin (A) is a water-dispersible resin
  • the compound (B) is self-emulsifying, and the compound ( A case where B) can be emulsified or dispersed by the polyamine resin (A) is mentioned.
  • 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. After settling, it can be judged as “water-insoluble” if precipitation occurs, “water-soluble” if there is no precipitate and clear, and “self-emulsifying” if there is no precipitation and turbidity.
  • 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 self-emulsifying compound (B) include polyethylene glycol # 400 diacrylate (EO 9 mol), polyethylene glycol # 600 diacrylate (EO 14 mol), polyethylene glycol # 1000 diacrylate (EO 23 mol), and 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 polyamine resin (A) include polyethylene glycol # 200 glycol diacrylate (EO 4 mol), ethoxylated bisphenol A diacrylate (EO 3 mol), and ethoxylated bisphenol A diacrylate (EO 4 mol).
  • the compound (B) is preferably used as a mixture of a water-soluble compound and a water-insoluble compound.
  • the water-insoluble compound can be easily introduced into the reaction system by the water-soluble compound.
  • the coating material obtained is excellent in low-temperature curability.
  • the water-soluble compound having one or more (meth) acryloyl groups in the molecule include the above-mentioned water-soluble compound (B).
  • the water-insoluble compound having one or more (meth) acryloyl groups in the molecule 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 compound (B) may be diluted with an organic solvent before the polyamine resin (A) and the compound (B) are mixed.
  • the organic solvent include ethylene glycol monobutyether (BC) and diethylene glycol monobutyl ether (BDG).
  • the compound (B) is an emulsion. That is, before mixing the polyamine resin (A) and the compound (B), an emulsifier may be mixed with the compound (B), and the compound (B) is emulsified or dispersed by a dispersant, an emulsifier or an aqueous resin. May be.
  • the aqueous coating composition of the present invention is a two-component aqueous coating composition
  • the curing agent may further contain an emulsifier.
  • the polyamine resin (A) and the compound (B) can be efficiently reacted with each other. Moreover, if these processes are performed, a compound (B) can be handled as a non-dangerous substance.
  • emulsifier a nonionic emulsifier, an anionic emulsifier, etc. are used, for example.
  • the 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.
  • the compound (B) may be dispersed in a dispersion of a resin different from the polyamine resin (A) before mixing the polyamine resin (A) and the compound (B).
  • the resin dispersion include an acrylic resin emulsion and dispersion, a urethane resin emulsion and dispersion, and the like.
  • the water-based coating composition of the present invention can be applied to any appropriate article to be coated. Typically, it is the surface of iron.
  • Examples of the coating method of the aqueous coating composition of the present invention include brush coating, air spray, airless spray, roller coating, and the like.
  • the coating amount of the aqueous coating composition of the present invention can be set to any appropriate coating amount depending on the application. Generally, it is preferably 10 to 300 g / m 2 .
  • 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. That is, the aqueous coating composition of the present invention may be used as a room temperature curable coating composition or a heat curable coating composition. In the case of natural drying, the drying time is preferably 24 hours or longer, more preferably 1 week or longer.
  • a test piece was obtained by applying the paint obtained in the example to a sandblast plate with a brush so as to be 200 g / m 2 and drying at 20 ° C. for 7 days.
  • test piece was subjected to a cyclic corrosion test defined in JIS K 5600 7-7, and the coating state after 120 cycles was confirmed based on the following criteria.
  • Ratio of rust area generated in coating film on surface of test piece A Less than 0.05% B: 0.05% or more and less than 0.1% B: 0.1% or more and less than 0.3% %more than
  • Example 1 118 parts of dipropylene glycol n-butyl ether (DPnB) was added to 2960 parts of the emulsion I obtained in Production Example 2 as a polyamine resin (A) while stirring with a disper, and then the compound (B ), 392 parts of ethoxylated trimethylolpropane triacrylate (EO 20 mol) (trade name “AT-20E” manufactured by Shin-Nakamura Chemical Co., Ltd.) was added and stirred for 10 minutes to obtain a clear paint. The obtained paint was applied to a glass plate with a 6 mil applicator in an environment of 25 ° C. and 5 ° C., and dried for 24 hours in the same environment as that used for coating to obtain a coating film. Then, the coating film state and curability of the obtained coating film were evaluated. The results are shown in Table 2.
  • Example 2 to 10 Except having replaced the compound (B) with 392 parts of ethoxylated trimethylolpropane triacrylate (EO 20 mol) in the same manner as in Example 1 except that the compound (B) shown in Table 1 was used in the content shown in Table 2, A coating film was obtained. Then, the coating film state and curability of the obtained coating film were evaluated. The results are shown in Table 2.
  • Example 11 A coating film was obtained in the same manner as in Example 10 except that the emulsion I obtained in Production Example 4 was used instead of the emulsion I in the polyamine resin (A). Then, the coating film state and curability of the obtained coating film were evaluated. The results are shown in Table 2.
  • Example 12 159 parts of ion-exchanged water and 16 parts of New Coal 740 (manufactured by Nippon Emulsifier Co., Ltd., nonionic emulsifier) were stirred with a disper and dissolved uniformly to prepare an aqueous emulsifier solution. Thereafter, 143 parts of ethoxylated trimethylolpropane triacrylate (EO 3 mol) as compound (B) was added, and the mixture was stirred and dispersed roughly for 10 minutes with a disper. Further, the mixture was dispersed with an ultrasonic homogenizer until the average particle size became 350 nm to obtain an emulsion of the compound (B).
  • New Coal 740 manufactured by Nippon Emulsifier Co., Ltd., nonionic emulsifier
  • Example 13 100 parts of tap water, 34 parts of DISPERBYK-190 (pig dispersant manufactured by Big Chemie), 2 parts of BYK-019 (antifoaming agent produced by Big Chemie), 170 parts of calcium carbonate, 185 parts of titanium oxide, 2 parts of calcium-based anticorrosive pigment
  • the pigment dispersion composition consisting of was dispersed with a disper for 30 minutes.
  • 450 parts of the emulsion I obtained in Production Example 2 as polyamine resin (A), 18 parts of DPnB, and 10 parts of Adecanol UH-420 (Adeka Co., Ltd. associative thickener) were added and mixed to obtain a base coating liquid.
  • Example 14 Instead of 41 parts of propoxylated bisphenol A diacrylate (PO 4 mol), 33 parts of ethoxylated glycerin triacrylate (EO 9 mol) (trade name “A-GLY-9E”, compound (B) No. 6) manufactured by Shin-Nakamura Chemical Co., Ltd.) A coating film was obtained in the same manner as in Example 13 except that it was used. Then, the coating film state of the obtained coating film, sclerosis
  • Example 15 A coating film was obtained in the same manner as in Example 13 except that 450 parts of emulsion II obtained in Production Example 4 was used in place of 450 parts of emulsion I obtained in Production Example 2 as the polyamine resin (A). Then, the coating film state of the obtained coating film, sclerosis
  • Example 1 A coating film was obtained in the same manner as in Example 1 except that the compound (B) was not used. Then, the coating film state and curability of the obtained coating film were evaluated. The results are shown in Table 4.
  • Example 2 In the same manner as in Example 1, except that 2100 parts of urethane acrylate having a molecular weight of 4200, a viscosity of 30,000 mPa ⁇ s, and a functional group number of 2 (UA-W2 manufactured by Shin-Nakamura Chemical Co., Ltd.) was used in place of the compound (B). A coating film was obtained. Then, the coating film state and curability of the obtained coating film were evaluated. The results are shown in Table 4.
  • Example 3 A coating film was obtained in the same manner as in Example 1 except that 94 parts of dipentaerythritol hexaacrylate having a molecular weight of 562, a viscosity of 6600 mPa ⁇ s, and a functional group number of 6 was used instead of the compound (B). Then, the coating film state and curability of the obtained coating film were evaluated. The results are shown in Table 4.
  • Example 4 The same as Example 1 except that 255 parts of a bisphenol type epoxy resin (Lipoxy VR-77 manufactured by Showa Polymer Co., Ltd.) having a molecular weight of 510, a viscosity of 100,000 mPa ⁇ s, and an acryloyl group number of 2 was used in place of the compound (B). Thus, a coating film was obtained. Then, the coating film state and curability of the obtained coating film were evaluated. The results are shown in Table 4.
  • a bisphenol type epoxy resin Lipoxy VR-77 manufactured by Showa Polymer Co., Ltd.
  • the water-based paint composition of the present invention can be suitably used as a rust preventive, sealer, primer, etc. for bridges, exteriors of buildings, floors, building materials, etc. as construction paints and heavy duty anti-corrosion paints.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de revêtement aqueux ayant une excellente capacité de durcissement à faible température. La composition de revêtement aqueux contient une résine polyamine (A) soluble dans l'eau ou dispersée dans l'eau ayant un ou plusieurs groupes amine primaire et/ou groupes amine secondaire dans chaque molécule, et un composé (B) ayant un ou plusieurs groupes (méth)acryloyle dans chaque molécule. La résine polyamide (A) a un poids équivalent amine allant de 100 à 3 000, et le composé (B) a une viscosité à 25°C inférieure ou égale à 3 000 mPa.s.
PCT/JP2009/065807 2008-09-29 2009-09-10 Composition de revêtement aqueux WO2010035641A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011118791A1 (fr) * 2010-03-26 2011-09-29 日本ペイント株式会社 Procédé pour la formation d'un film de revêtement
JP2012241088A (ja) * 2011-05-18 2012-12-10 Mitsubishi Rayon Co Ltd 活性エネルギー線硬化性含水被覆塗料
EP2727968A1 (fr) * 2012-11-06 2014-05-07 ALLNEX AUSTRIA GmbH Amine primaire multifonctionnel, procédure de préparation, et utilisation
US9440911B2 (en) 2011-05-05 2016-09-13 Allnex Austria Gmbh Multifunctional primary amine, process for its preparation, and use thereof
KR20180063724A (ko) * 2016-12-02 2018-06-12 자암건설(주) 콘크리트의 중성화, 염해 방지를 위한 친환경 수용성 도료조성물 및 이를 이용한 시공방법
US10536494B2 (en) 2012-05-04 2020-01-14 Electronic Arts Inc. Establishing a social application layer

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CN102702811A (zh) * 2012-06-01 2012-10-03 安徽省金盾涂料有限责任公司 水性涂料组合物
JP6106209B2 (ja) * 2015-05-26 2017-03-29 日本ペイント株式会社 自然乾燥型水性塗料組成物
BR112017019321B1 (pt) * 2016-02-12 2022-05-03 Nippon Paint Marine Coatings Co., Ltd Composição de tinta anticorrosiva, filme de revestimento, e navio ou estrutura offshore
CN106002091B (zh) * 2016-06-03 2017-12-01 南京钢铁股份有限公司 一种压平机垫铁的制作方法
CN105969169A (zh) * 2016-06-30 2016-09-28 广州中海环保科技有限公司 一种天然环保涂料

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US3975251A (en) * 1975-03-19 1976-08-17 Scm Corporation Cathodic electrocoating process
JPS5531889A (en) * 1978-08-28 1980-03-06 Ppg Industries Inc Hardenable resin composition
JPH03152168A (ja) * 1989-11-07 1991-06-28 Shikoku Kaken Kogyo Co Ltd 水性樹脂分散液

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011118791A1 (fr) * 2010-03-26 2011-09-29 日本ペイント株式会社 Procédé pour la formation d'un film de revêtement
JP5612667B2 (ja) * 2010-03-26 2014-10-22 日本ペイント株式会社 塗膜形成方法
US9440911B2 (en) 2011-05-05 2016-09-13 Allnex Austria Gmbh Multifunctional primary amine, process for its preparation, and use thereof
US10023547B2 (en) 2011-05-05 2018-07-17 Allnex Austria Gmbh Multifunctional primary amine, process for its preparation, and use thereof
JP2012241088A (ja) * 2011-05-18 2012-12-10 Mitsubishi Rayon Co Ltd 活性エネルギー線硬化性含水被覆塗料
US10536494B2 (en) 2012-05-04 2020-01-14 Electronic Arts Inc. Establishing a social application layer
EP2727968A1 (fr) * 2012-11-06 2014-05-07 ALLNEX AUSTRIA GmbH Amine primaire multifonctionnel, procédure de préparation, et utilisation
WO2014072308A3 (fr) * 2012-11-06 2014-08-07 Allnex Austria Gmbh Dispersions aqueuses d'une amine primaire multifonctionnelle, procédé pour leur préparation et leur utilisation
US9914800B2 (en) 2012-11-06 2018-03-13 Allnex Austria Gmbh Aqueous dispersions of a multifunctional primary amine, process for its preparation, and use therof
KR20180063724A (ko) * 2016-12-02 2018-06-12 자암건설(주) 콘크리트의 중성화, 염해 방지를 위한 친환경 수용성 도료조성물 및 이를 이용한 시공방법
KR101870910B1 (ko) 2016-12-02 2018-06-26 자암건설(주) 콘크리트의 중성화, 염해 방지를 위한 친환경 수용성 도료조성물 및 이를 이용한 시공방법

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MY153920A (en) 2015-04-15
JP5421921B2 (ja) 2014-02-19
KR101474056B1 (ko) 2014-12-17
KR20110071094A (ko) 2011-06-28
CN102165027A (zh) 2011-08-24
CN102165027B (zh) 2015-06-17
JPWO2010035641A1 (ja) 2012-02-23

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