KR101474056B1 - Aqueous coating composition - Google Patents

Abstract

And to provide a waterborne coating composition excellent in low temperature curability.
(A) a water-soluble or water-dispersible polyamine resin having at least one first amine group and / or a second amine group in the molecule and a compound (B) having at least one (meth) acryloyl group in the molecule, The amine equivalent of the polyamine resin (A) is 100 to 3000, and the viscosity of the compound (B) at 25 占 폚 is 3000 mPa 占 퐏 or less.

Description

AQUEOUS COATING COMPOSITION [0001]

The present invention relates to an aqueous coating composition.

Recently, from the viewpoint of environmental protection, it is socially demanded to change from a solvent-based paint to an aqueous paint. As such an aqueous coating material, there can be mentioned, for example, a two-pack type aqueous coating composition containing an epoxy resin and a polyamine compound (Patent Document 1). Such an aqueous coating composition exhibits sufficient curability at a temperature of room temperature or higher, and can form a normal coating film. However, since the curability is low at a low temperature (for example, around 5 캜), there is a problem that it is difficult to exhibit an original sufficient coating film performance when used in a low-temperature paper (for example, outdoors in synchronism).

Patent Document 1: Japanese Laid-Open Publication No. 11-166153

The present invention has been made to solve the above-mentioned conventional problems, and an object thereof is to provide a water-based coating composition excellent in low temperature curability.

The water-based coating composition of the present invention comprises a water-soluble or water-dispersible polyamine resin (A) having at least one primary amine group and / or a secondary amine group in the molecule and at least one (B), the amine equivalent of the polyamine resin (A) is 100 to 3000, and the viscosity of the compound (B) at 25 占 폚 is 3000 mPa 占 퐏 or less.

In a preferred embodiment, the water-base coating composition is a two-component aqueous coating composition, the base coating solution contains the polyamine resin (A), and the curing agent includes the compound (B).

In a preferred embodiment, the polyamine resin (A) is an acrylic polyamine resin or an epoxy polyamine resin.

In a preferred embodiment, the compound (B) has a molecular weight of 150 or more and 2000 or less.

In a preferred embodiment, the compound (B) is a water-soluble compound and the polyamine resin (A) is an aqueous dispersion resin.

In a preferred embodiment, the compound (B) is a self-emulsifiable compound.

In a preferred embodiment, the compound (B) is emulsified or dispersed by the polyamine resin (A).

In a preferred embodiment, the compound (B) is a mixture of a water-soluble compound and a water-insoluble compound.

In a preferred embodiment, the compound (B) is an emulsion.

In a preferred embodiment, the curing agent further comprises an emulsifier.

The water-based coating composition of the present invention comprises a water-soluble or water-dispersible polyamine resin (A) having at least one primary amine group and / or a secondary amine group in the molecule and at least one By including the compound (B), 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 a low temperature, so that a waterborne coating composition excellent in curability at low temperatures can be obtained. 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) A composition can be obtained.

A. Overview of aqueous coating compositions

The water-based coating composition of the present invention comprises a water-soluble or water-dispersible polyamine resin (A) having at least one primary amine group and / or a secondary amine group in the molecule and at least one (B), and is cured by the reaction of the polyamine resin (A) and the compound (B) to obtain a coating film.

The water-base coating composition of the present invention is preferably a two-component aqueous coating composition comprising a main coating solution and a curing agent, wherein the main coating solution contains the above-mentioned polyamine resin (A) . By using the polyamine resin (A) and the compound (B) as a two-pack type water-based coating composition, it is possible to select a combination in which both of the polyamine resin (A) and the compound (B) exhibit high reactivity, An excellent water-based coating composition can be obtained.

The content of the polyamine resin (A) as solid content is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, based on the total solids content of the aqueous coating composition.

The content of the compound (B) is preferably from 2 to 40% by weight, and more preferably from 5 to 30% by weight, based on the total solids content of the aqueous coating composition.

The ratio of the number of amine groups of the polyamine resin (A) to the number of the (meth) acryloyl groups of the compound (B) (amine group: acryloyl group) is preferably from 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. In the present specification, the "number of amine groups" means that when the polyamine resin (A) has a primary amine group (including primary amine groups and secondary amine groups) in the molecule, the primary amine group (That is, the number of the second amine groups is not included), and when the molecule has only the second amine group, it means the number of the second amine group.

The water-base coating composition of the present invention may optionally contain a pigment, a solvent, an additive and the like. Examples of the pigment include color pigments such as titanium oxide, yellow iron oxide, red iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, azo red, quinacridone red and benzimidazolone yellow; And extender pigments such as calcium carbonate, barium sulfate, kaolin, clay and talc. Examples of the solvent include 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 and the like Glycol solvents; Aromatic solvents such as xylene, Solvesso 100, Solvesso 150, and Solvesso 200; Hydrocarbon solvents such as mineral spirits; 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (CS-12), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (CS- And ester solvents such as adipate and diisobutyl adipate. Examples of the additives include a dispersant, a viscosity adjusting agent, a curing catalyst, a surface conditioner, a defoaming agent, a plasticizer, a film forming aid, an ultraviolet absorber and an antioxidant.

B. Polyamine resin (A)

The polyamine resin (A) used in the water-base coating composition of the present invention may be any suitable resin as long as it has at least one primary amine group and / or secondary amine group and is a water-soluble or water-dispersible resin. Examples of such a resin include an aliphatic polyamine resin, an aromatic polyamine resin, and an alicyclic polyamine resin.

The amine group of the polyamine resin (A) has an amine equivalent of 100 to 3000, more preferably 500 to 2000, and particularly preferably 800 to 1500. When the amine equivalent of the polyamine resin (A) is in this range, the polyamine resin (A) has a water-soluble or water-dispersible property, and a coating film excellent in low-temperature curability can be obtained. When the polyamine resin (A) has a primary amine, the amine equivalent is represented by the molecular weight of the resin solid component per primary amine group. When the polyamine resin (A) has no primary amine group, the secondary amine group In terms of the molecular weight of the resin solid content per one part of the resin. The amine equivalent of the polyamine resin (A) can be determined from the blending amount of the raw material.

The molecular weight (number average) of the polyamine resin (A) may be any suitable molecular weight, depending on the desired coating film properties. It is preferably 500 to 20000, more preferably 1000 to 3000 in terms of standard polystyrene using gel permeation chromatography (GPC). When the molecular weight of the polyamine resin (A) is within this range, the polyamine resin (A) and the compound (B) can be easily mixed and thus the reaction can be efficiently performed. When the molecular weight of the polyamine resin (A) is within this range, a coating film excellent in anticorrosion, water resistance, and adhesion can be obtained.

The glass transition temperature of the polyamine resin (A) may be any suitable glass transition temperature depending on the desired coating film properties. It is preferably -50 to 100 占 폚, more preferably 0 to 50 占 폚.

The polyamine resin (A) can be obtained by converting an amine group into an acid by neutralization with an acid. The kind of the acid and the degree of neutralization (neutralization rate relative to the amine group of the polyamine resin before the water treatment) are arbitrarily selected depending on the state of the desired polyamine resin (A) (water-soluble to water-dispersible) . Examples of the acid include acetic acid, formic acid, lactic acid, and phosphoric acid. The neutralization ratio (neutralization ratio with respect to the amine group of the polyamine resin before water conversion) is preferably 10 to 70%, and more preferably 15 to 50%.

The polyamine resin (A) is preferably an epoxy-based polyamine resin obtained by amine-modifying an epoxy resin or an acrylic-based polyamine resin obtained by amine-modifying an acrylic resin, and among these, an epoxy-based polyamine resin. This is because, if the epoxy-based polyamine resin is used, a water-based coating composition having excellent performance performance can be obtained. That is, by using the epoxy-based polyamine resin as the polyamine resin (A) and the above-mentioned compound (B), it is possible to obtain a coating film having excellent performance equivalent to that of a conventional epoxy resin coating composition comprising an epoxy resin- A water-based coating composition can be obtained.

The epoxy-based polyamine resin and the acrylic-based polyamine resin can be obtained by any suitable method of denaturation. Examples of the modification method include a method of adding a first amine group-containing polyamine to an epoxy resin or an acrylic resin, and a method of adding a ketimine-containing amine group-containing compound to an epoxy resin or an acrylic resin. The polyamine resin (A) thus obtained has at least one first amine group and / or a second amine group and a secondary hydroxyl group in the molecule. The polyamine resin is obtained by reacting a compound having a functional group such as an epoxy group, an acid anhydride group, an acid halide group or an isocyanate group on a first amine group, a second amine group and / or a hydroxyl group of the polyamine resin (A) Resin. As a part of the polyamine resin to be used, the physical properties of the obtained coating film can be adjusted by containing a polyamine resin reacted with such a functional group.

The method of adding the first amine group-containing polyamine to an epoxy resin or an acrylic resin, that is, reacting a first amine group of the first amine group-containing polyamine with a reactor (for example, an epoxy group) of an epoxy resin or an acrylic resin 2 amine group, and as a result, the epoxy-based polyamine resin having a second amine group or the acrylic polyamine resin is produced.

The method of adding the ketimine-containing amine group-containing compound to an epoxy resin or an acrylic resin, that is, reacting the ketiminated amine group-containing compound with an epoxy resin or an acrylic resin and then hydrolyzing the ketimine group, Group, and as a result, the epoxy-based polyamine resin having the first amine group or the acrylic-based polyamine resin is produced. When the ketimine-containing amine group-containing compound is reacted with an epoxy resin or an acrylic resin, a secondary amine such as diethanolamine, methylethanolamine or diethylamine may be co-existed.

As the epoxy resin, any suitable one can be used. A bisphenol A type epoxy resin or a bisphenol F type epoxy resin is preferable, and a bisphenol A type epoxy resin is particularly preferable.

The epoxy equivalent of the epoxy resin can be determined according to desired physical properties of the coating film. Preferably from 180 to 2000, more preferably from 400 to 1500. When the epoxy equivalent of the epoxy resin is within this range, a coating film excellent in water resistance, anticorrosion property and adhesion property can be obtained.

The epoxy resin can be chain-extended by using a reaction between an active hydrogen-containing compound capable of reacting with an epoxy group and an epoxy group, thereby increasing or decreasing the molecular weight of the epoxy resin. Examples of the active hydrogen-containing compound include bifunctional compounds such as dimer acid, diamine, and polyether polyol.

Depending on the application, the epoxy resin may be modified by reducing the number of epoxy groups by adding a fatty acid to reduce amine-denatured sites and reactivity before amine-denaturation.

Any suitable resin may be used for the acrylic resin. Preferably an acrylic resin obtained by copolymerizing a monomer composition comprising a radically polymerizable monomer having an epoxy group and / or a glycidyl group. Examples of the radical polymerizable monomer having an epoxy group and / or a glycidyl group include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and the like.

Examples of the first amine group-containing polyamine include diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, and the like. These may be used alone or in combination.

The ketimine-containing amine group-containing compound can be obtained by reacting a first amine group-containing compound with a ketone. Examples of the first amine group-containing compound include primary amine group-containing polyamines such as diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine; Aminoethylethanolamine, methylaminopropylamine, ethylaminoethylamine, and the like. These may be used alone or in combination. Examples of the ketone include methyl ethyl ketone, acetone, methyl isobutyl ketone, and the like.

C. Compound (B)

The compound (B) used in the aqueous coating composition of the present invention has at least one (meth) acryloyl group 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. When the molecular weight of the compound (B) is within this range, the polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing apparatus, and a coating composition excellent in dispersibility can be obtained. As a result, the polyamine resin (A) and the compound (B) can be efficiently reacted with each other, and a waterborne coating composition excellent in curability can be obtained. The molecular weight of the compound (B) can be calculated from the formula.

The number of (meth) acryloyl groups of the compound (B) is 1 or more, and preferably 2 to 4. The number of (meth) acryloyl groups possessed by the compound (B) can be determined according to desired coating film properties.

The viscosity of the compound (B) at 25 占 폚 is not more than 3000 mPa 占 퐏, preferably not less than 50 mPa 占 퐏 and not more than 3000 mPa 占 퐏, more preferably not less than 50 mPa 占 퐏 and not more than 2200 mPa 占 퐏, And is not less than 50 mPa 占 퐏 and not more than 1100 mPa 占 퐏. When the viscosity of the compound (B) is within this range, the polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing apparatus, and a coating composition excellent in dispersibility can be obtained. As a result, the polyamine resin (A) and the compound (B) can be efficiently reacted with each other, and a waterborne coating composition excellent in curability can be obtained.

Examples of the compound (B) include polymerizable unsaturated monocarboxylic acid ester compounds of polyhydric alcohols (e.g., 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 , Trimethylol propane 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, penta Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol acroxydimethacrylate, 1, 2-butanediol dimethacrylate, pentaerythritol tetramethacrylate, 1,1-tris hydroxymethyl ethane diacrylate, 1,1,1-tris hydroxymethyl ethane dimethacrylate, 1,1,1-tris hydroxymethyl ethane triacrylate, 1,1,1- 1,1,1-trishydroxymethylpropane diacrylate, 1,1,1-trishydroxymethylpropane dimethacrylate, etc.), an epoxy group-containing ethylenically unsaturated monomer and an epoxy group-containing ethylenically unsaturated monomer, (For example, glycidyl acrylate, glycidyl methacrylate, and acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, A reaction product of lactic acid, etc.), and a polymerizable unsaturated monocarboxylic acid amide compound (e.g., ethylenediamine diacrylate) of a polyhydric amine. These may be used alone or in combination.

The compound (B) needs to be readily miscible with the polyamine resin (A) (both can react) as described above. Preferably, the polyamine resin (A) and the compound (B) are used in a non-uniform state within a range where they can be mixed easily (both can react). More preferably, the compound (B) and the polyamine resin (A) are used in different phase states from each other. In such a state, the progress of the rapid reaction of the polyamine resin (A) and the compound (B) can be inhibited and the reactivity can be appropriately adjusted. For example, in the case of using the aqueous coating composition of the present invention as a two- , A waterborne coating composition having excellent handling properties can be obtained. Preferred examples of such a state include a case where the compound (B) is a water-soluble compound, the polyamine resin (A) is a water-dispersible resin, the compound (B) And may be emulsified or dispersed. Whether the compound (B) is "water-insoluble", "water-soluble" or "self-emulsifiable" is determined by adding 5 g of the compound (B) to 100 g of water at room temperature, (For example, three minutes), and after leaving the state (for example, after five minutes), the state can be visually observed. When the precipitate is formed, it is judged that it is "non-water-soluble". If there is no precipitate, if it is transparent, it is "water-soluble."

When the compound (B) is modified with, for example, polyethylene oxide, the number of moles of the ethylene oxide is increased so that the compound (B) can be made into a water-soluble or self-emulsifying compound with increased hydrophilicity.

Examples of the water-soluble compound (B) include ethoxylated bisphenol A diacrylate (EO 30 mol), ethoxylated trimethylolpropane triacrylate (EO 20 mol), ethoxylated trimethylolpropane triacrylate (EO 30 mol) Ethoxylated pentaerythritol tetraacrylate (EO 35 mol), ethoxylated glycerin triacrylate (EO 20 mol), ethoxylated bisphenol A dimethacrylate (EO 30 mol), and the like. These may be used alone or in combination. In this specification, for example, the notation "EO 30 mol" indicates that 30 molecules of ethylene oxide are contained in the molecule.

Examples of the self-emulsifiable compound (B) include polyethylene glycol # 400 diacrylate (EO 9 mol), polyethylene glycol # 600 diacrylate (EO 14 mol), polyethylene glycol # 1000 diacrylate (EO 23 mol), ethoxylated bisphenol A diacrylate (EO 10 mol), ethoxylated bisphenol A diacrylate (EO 20 mol), ethoxylated glycerin triacrylate (EO 9 mol) and polyethylene glycol # 1000 dimethacrylate (EO 23 mol). These may be used alone or in combination.

Examples of the compound (B) which 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), ethoxylated bisphenol A diacrylate (EO 4 mol), propoxylated bisphenol A diacrylate (PO 3 mol), 1,10-decanediol diacrylate, tricyclodecane dimethanol diacrylate, ethoxylated 2-methyl- Diol diacrylate (EO2mol), neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate (PO2mol), tripropylene glycol diacrylate (PO3mol), polypropylene glycol # 400 diacrylate (PO7mol), polypropylene glycol # 700 diacrylate (PO12mol), ethoxylated trimethylolpropane triacrylate (EO3mol), ethoxylated trimethylolpropane tri (EO 9 mol), trimethylol propane triacrylate, propoxylated trimethylol propane triacrylate (PO 3 mol), pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate (EO 4 mol), ditrimethol (PO4mol), propoxylated bisphenol A diacrylate (PO4mol), ethylene glycol dimethacrylate (EO1mol), diethylene glycol dimethacrylate (EO2mol), diethylene glycol dimethacrylate ), Triethylene glycol dimethacrylate (EO 3 mol), tetraethylene glycol dimethacrylate (EO 4 mol), polyethylene glycol # 400 dimethacrylate (EO 9 mol), polyethylene glycol # 600 dimethacrylate (EO 14 mol) 3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, ethoxylated bisphenol A (EO2.6 mol), ethoxylated bisphenol A dimethacrylate (EO4 mol), ethoxylated bisphenol A dimethacrylate (EO6 mol), ethoxylated bisphenol A dimethacrylate (EO 10 mol), ethoxylated bisphenol A (PO 12mol, EO 6mol), glycerin dimethacrylate, tripropylene glycol dimethacrylate (PO 3mol), dimethylacrylate dimethacrylate (EO 17mol), neopentyl glycol dimethacrylate, ethoxylated polypropylene glycol # 700 dimethacrylate Polypropylene glycol # 400 dimethacrylate (PO7mol), trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane trimethacrylate (EO9mol), and the like. These may be used alone or in combination.

The compound (B) is preferably used as a mixture of a water-soluble compound and a water-insoluble compound in combination. As described above, when a mixture of a water-soluble compound and a water-insoluble compound is used, the water-insoluble compound can easily introduce a water-insoluble compound into the reaction system. The obtained coating material is excellent in low-temperature curing property. As the water-soluble compound having at least one (meth) acryloyl group in the molecule, for example, the above-mentioned water-soluble compound (B) can be mentioned. Examples of the water-insoluble compound having at least one (meth) acryloyl group in the molecule include compounds which are not fully water-soluble such as propoxylated bisphenol A diacrylate (PO4mol). 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, and more preferably 2/8 to 8/2.

In one embodiment, before mixing the polyamine resin (A) and the compound (B), the compound (B) may be diluted with an organic solvent. Examples of the organic solvent include ethylene glycol monobutyl ether (BC), diethylene glycol monobutyl ether (BDG), and the like. When the compound (B) is previously diluted with an organic solvent, the polyamine resin (A) and the compound (B) can be mixed without using a special mixing apparatus, and a coating composition excellent in dispersibility can be obtained. As a result, the polyamine resin (A) and the compound (B) can be efficiently reacted with each other.

In another embodiment, the compound (B) is an emulsion. That is, an emulsifier may be mixed with the compound (B) before mixing the polyamine resin (A) and the compound (B), or the compound (B) may be emulsified or dispersed by a dispersant, emulsifier or an aqueous resin. When the water-base coating composition of the present invention is a two-component aqueous coating composition, an emulsifier may be further contained in the curing agent. By carrying out these treatments, the polyamine resin (A) and the compound (B) can be mixed without using a special mixing apparatus, and a coating composition excellent in dispersibility can be obtained. As a result, the polyamine resin (A) and the compound (B) can be efficiently reacted with each other. When these treatments are carried out, the compound (B) can be treated as a non-hazardous substance. As the emulsifier, for example, a nonionic emulsifier, an anionic emulsifier and the like are used. Examples of 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. Examples of the anionic emulsifier include dodecylbenzenesulfonic acid salt, dialkylsuccinate sulfonic acid salt, polyoxyethylene alkyl ether sulfuric acid ester salt, polyoxyethylene styrenated phenyl ether sulfuric acid ester salt, alkyl diphenyl ether disulfonic acid salt, etc. . Examples of the dispersing agent include sodium polyacrylate salts and ammonium salts of half ester of styrene maleic acid copolymer. Examples of the aqueous resin include a sodium salt of a polyacrylic ester.

In another embodiment, the compound (B) may be dispersed in a dispersion of the resin different from the polyamine resin (A) before the polyamine resin (A) and the compound (B) are mixed. Examples of the dispersion medium of the resin include emulsion and dispersion of an acrylic resin, emulsion and dispersion of a urethane resin, and the like. When the compound (B) is dispersed in the dispersion of the resin in advance, the polyamine resin (A) and the compound (B) can be mixed without using a special mixing apparatus and a coating composition excellent in dispersibility can be obtained have. As a result, the polyamine resin (A) and the compound (B) can be efficiently reacted with each other.

D. Painting Method

The water-base coating composition of the present invention can be applied to any appropriate substrate (substrate). Typically, it is the surface of iron.

Examples of the coating method of the water-base coating composition of the present invention include brushing, air spraying, airless spraying, roller coating, and the like.

The coating amount of the water-base coating composition of the present invention may be set at an appropriate appropriate amount depending on the application. Generally, it is preferably 10 to 300 g / m ² .

As the drying method of the water-base coating composition of the present invention, any appropriate drying method may be employed. Preferably, it is natural drying or heat drying. That is, the aqueous coating composition of the present invention may be used as a room temperature curing type coating composition or as a heat curing type coating composition. In the case of natural drying, the drying time is preferably at least 24 hours, more preferably at least one week.

<Examples>

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Unless otherwise specified, parts and% in the examples are by weight. The evaluation items in the examples are as follows.

(Coating film state)

The coatings obtained in Examples and Comparative Examples were painted and dried (24 hours) at 25 캜, and the glass plate was visually evaluated for coating film gloss such as luster, transparency and blistering of the coating film.

Gloss ○: High gloss

?: Semi gloss degree

X: non-glossy

Transparency ○: No or almost no turbidity

?: Somewhat turbid

X: large turbidity

Coating film abnormality: No, or almost no blister, no lump

△: A little blister with lumps

X: Blister with cluster on the whole surface

(Hardenability)

The coatings obtained in Examples and Comparative Examples were coated on a glass plate at 25 ° C and at 5 ° C and dried (24 hours) to obtain a coating film. The coating films were then coated with methyl ethyl ketone (MEK ), And the number of reciprocations until the glass substrate was exposed was measured. The notation &quot; 200 &quot; in the table means that the glass substrate was not exposed even after 200 reciprocations. In addition, the number of reciprocations until the exposure is 100 times or more passes.

(Anti-corrosive)

The paint obtained in the examples was applied to the sandblast plate by a sol to be 200 g / m ² and dried at 20 캜 for 7 days to obtain a test piece. The test piece was subjected to a cycle corrosion test according to JIS K 5600 7-7, and the state of the coated film after 120 cycles was confirmed based on the following criteria.

The ratio of the rust area generated on the coating film to the surface of the test piece

◎: Less than 0.05%

○: 0.05% or more and less than 0.1%

?: 0.1% or more and less than 0.3%

×: 0.3% or more

[Preparation Example 1] Production of polyamine resin (epoxy-based polyamine resin)

In a reaction vessel equipped with a stirrer, a condenser, a nitrogen introduction tube and a thermometer, 702 parts of an epoxy resin having an epoxy equivalent of 188 synthesized with bisphenol A and epichlorohydrin, 269 parts of bisphenol A, 108 parts of dimer acid, Hereinafter referred to as &quot; MIBK &quot;), and the mixture was allowed to react at 117 ° C in the presence of 1 part of benzyldimethylamine until the epoxy equivalent was 1270. Then, 255 parts of a ketimine compound of aminoethylethanolamine (73 mass% of MIBK solution) was added, and the mixture was reacted at 117 DEG C for 1 hour. Thereafter, the mixture was diluted with MIBK until the nonvolatile content became 75% to obtain an epoxy-based polyamine resin having a number average molecular weight of 2400 and an amine equivalent of 1184.

[Production Example 2] Emulsion of epoxy-based polyamine resin

Acetic acid was added to the epoxy-based polyamine resin obtained in Preparation Example 1 so as to obtain a neutralization ratio of 20.0% (neutralization rate relative to the amine group of the resin), and ion-exchanged water was added to dilute the epoxy-based polyamine resin. Thereafter, the mixture of MIBK and water was removed under reduced pressure until the solid content became 40% by mass to prepare Emulsion I.

[Production Example 3] Production of polyamine resin (acrylic polyamine resin)

In a reaction vessel equipped with a stirrer, a condenser, a nitrogen introduction tube, a thermometer and a dropping funnel, 670 parts of MIBK was added and the temperature was raised to 110 占 폚. In the reaction tank, a solution comprising 540 parts of styrene, 400 parts of n-butyl acrylate, 140 parts of glycidyl methacrylate, 100 parts of MIBK and 20 parts of t-butyl peroctoate was added dropwise to the reaction vessel over 3 hours . After the completion of the dropwise addition, the temperature was maintained at 110 캜 over 30 minutes, and then a solution composed of 2 parts of t-butyl peroctoate and 50 parts of MIBK was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was continued at 110 캜 for further 1 hour to obtain an acrylic resin varnish having a nonvolatile content of 60% containing an epoxy group. To 1920 parts of the obtained varnish, 255 parts of a ketimine compound of aminoethylethanolamine (73 mass% of MIBK solution) was added and the mixture was reacted at 117 DEG C for 1 hour to obtain an acrylic polyamine resin having a number average molecular weight of 10,000 and an amine equivalent of 1184.

[Production Example 4] Acrylic polyamine resin emulsion

To the acrylic polyamine resin obtained in Preparation Example 3, acetic acid was added to make a neutralization ratio of 20.0% (neutralization rate relative to the amine group of the resin), and ion exchange water was added to dilute the acrylic polyamine resin. Thereafter, the mixture of MIBK and water was removed under reduced pressure until the solid content became 40 mass%, and Emulsion II was prepared.

[Production Example 5] Production of polyamine resin (epoxy-based polyamine resin)

742 parts of an epoxy resin having an epoxy equivalent of 188 synthesized from bisphenol A and epichlorohydrin, 336 parts of bisphenol A and 190 parts of MIBK were placed in a reaction vessel equipped with a stirrer, a condenser, a nitrogen introduction pipe and a thermometer, and 1 part of benzyldimethylamine And reacted at 117 DEG C until an epoxy equivalent of 1270 was obtained. Thereafter, 350 parts of a ketimine compound of diethylenetriamine (73 mass% of MIBK solution) was added and the mixture was reacted at 117 DEG C for 1 hour. Thereafter, 27 parts of ion-exchanged water and 188 parts of glycidyl neodecanoate (Kajura E10-P) were added, and the mixture was reacted at 100 DEG C for 2 hours. Thereafter, the mixture was diluted with MIBK until a nonvolatile content of 75% was obtained. Thus, an epoxy-based polyamine resin having a number average molecular weight of 2600 and an amine equivalent of 947 was obtained.

[Production Example 6] Emulsion of epoxy-based polyamine resin

Acetic acid was added to the epoxy-based polyamine resin obtained in Preparation Example 5 to make the neutralization ratio 20.0% (neutralization ratio with respect to the cationic group of the resin), and ion-exchanged water was added to dilute the epoxy-based polyamine resin. Thereafter, the mixture of MIBK and water was removed under reduced pressure until the solid content became 40% by mass to prepare Emulsion III.

[Example 1]

11860 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 disperser, And 392 parts of shhytrimethylolpropane triacrylate (EO 20 mol) (trade name "AT-20E", manufactured by Shin-Nakamura Chemical Co., Ltd.) were added and stirred for 10 minutes to obtain a clear paint. The obtained paint was applied to a glass plate with an applicator of 6 mil under the environment of 25 占 폚 and 5 占 폚 and dried for 24 hours under the same conditions as during coating to obtain a coated film. Thereafter, the coating film condition and curability of the obtained coating film were evaluated. The results are shown in Table 2.

[Examples 2 to 10]

A coating film was obtained in the same manner as in Example 1 except that the compound (B) was used in an amount shown in Table 2 instead of 392 parts of ethoxylated trimethylolpropane triacrylate (E020 mol) . Thereafter, the coating film condition 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 polyamine resin (A) was replaced with Emulsion II obtained in Production Example 4 instead of Emulsion I. Thereafter, the coating film condition 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 Nyukol 740 (nonionic emulsifier manufactured by Nippon Emulsifier) were stirred with a disper and dissolved uniformly to prepare an emulsifier aqueous solution. Thereafter, 143 parts of ethoxylated trimethylolpropane triacrylate (EO3mol) as the compound (B) was added and stirred for 10 minutes by a disperser to be roughly dispersed. And further dispersed with an ultrasonic homogenizer until the average particle diameter became 350 nm to obtain an emulsion of the compound (B).

To 2367 parts of the emulsion III obtained in Production Example 6 as the polyamine resin (A), 118 parts of dipropylene glycol n-butyl ether (DPnB) was added while stirring with a disperser. Further, ) (The content of the compound (B): 143 parts) was added and stirred for 10 minutes to obtain a clear paint. As for the obtained paint, a coating film was obtained in the same manner as in Example 1. Thereafter, the coating film condition and curability of the obtained coating film were evaluated. The results are shown in Table 2.

[Example 13]

A pigment dispersion composition consisting of 100 parts of tap water, 34 parts of DISPERBYK-190 (pigment dispersant manufactured by BICKEMI Co.), 2 parts of BYK-019 (antifoaming agent manufactured by Big Chemie), 170 parts of calcium carbonate, 185 parts of titanium oxide and 2 parts of calcium- , And dispersed in a disper for 30 minutes. Then, 450 parts of Emulsion I, 18 parts of DPnB and 10 parts of adecanol UH-420 (associative thickener of Adeka Corporation) obtained in Production Example 2 as a polyamine resin (A) were added and mixed to prepare a main coating solution. Further, 41 parts of propoxylated bisphenol A diacrylate (PO4mol) as a compound (B) was dissolved in 41 parts of DPnB as the compound (B), and the mixture was stirred for 10 minutes to obtain an enamel paint. The obtained paint was applied to a glass plate with an applicator of 6 mil under the environment of 25 占 폚 and 5 占 폚 and dried for 24 hours under the same conditions as during coating to obtain a coated film. Thereafter, the coating film condition, curability and corrosion resistance of the obtained coating film were evaluated. The results are shown in Table 3.

[Example 14]

33 parts of ethoxylated glycerin triacrylate (EO9mol) (trade name: A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd., compound (B) No. 6) was used in place of 41 parts of propoxylated bisphenol A diacrylate (PO4mol) , A coating film was obtained in the same manner as in Example 13. Thereafter, the coating film condition, curability and corrosion resistance of the obtained coating film were evaluated. The results are shown in Table 3.

[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 instead of 480 parts of Emulsion I obtained in Production Example 2 as the polyamine resin (A). Thereafter, the coating film condition, curability and corrosion resistance of the obtained coating film were evaluated. The results are shown in Table 3.

450 parts of the emulsion III obtained in Production Example 6 was used in place of the 450 parts of the emulsion I obtained in Production Example 2 as the polyamine resin (A), and 41 parts of propoxylated bisphenol A diacrylate (PO4mol) as the compound (B) A coating film was obtained in the same manner as in Example 13, except that 61 parts of ethoxylated trimethylolpropane triacrylate (E03 mol) emulsion prepared in Example 12 was used instead of 41 parts of the emulsion. Thereafter, the coating film condition, curability and corrosion resistance of the obtained coating film were evaluated. The results are shown in Table 3.

[Comparative Example 1]

A coating film was obtained in the same manner as in Example 1 except that the compound (B) was not used. Thereafter, the coating film condition and curability of the obtained coating film were evaluated. The results are shown in Table 4.

[Comparative Example 2]

A coating film was obtained 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, and a functional group number of 2 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of the compound (B) Thereafter, the coating film condition and curability of the obtained coating film were evaluated. The results are shown in Table 4.

[Comparative Example 3]

A coating film was obtained in the same manner as in Example 1 except that the compound (B) was replaced by 94 parts of dipentaerythritol hexaacrylate having a molecular weight of 562, a viscosity of 6600 mPa s and a functional group of 6. Thereafter, the coating film condition and curability of the obtained coating film were evaluated. The results are shown in Table 4.

[Comparative Example 4]

Except that 255 parts of a bisphenol type epoxy resin having a molecular weight of 510, a viscosity of 100,000 mPa · s and an acryloyl group number of 2 (manufactured by Showa High Polymer Co., Ltd., Lipoxy VR-77) was used in place of the compound (B) Thereby obtaining a coated film. Thereafter, the coating film condition and curability of the obtained coating film were evaluated. The results are shown in Table 4.

[Comparative Example 5]

1,000 parts of ADEKA RESIN EM-101-50 (aqueous epoxy resin emulsion, Adeka Co., Ltd., epoxy equivalents: 1000, 50% of solid content) and 50 parts of DPnB were mixed to prepare a main coating solution.

Next, 200 parts of Sanmade WH-900 (a modified aliphatic polyamine manufactured by Air Products, nonvolatile content 60% amine value 220) as a curing agent was added to the coating composition for the target, and the mixture was mixed by dispersing. The obtained paint was applied to a glass plate with an applicator of 6 mil under the environment of 25 占 폚 and 5 占 폚 and dried for 24 hours under the same conditions as during coating to obtain a coated film. The curability of the obtained coating film was evaluated, and the curability at 25 ° C was good (MEK> 200 times). At 5 ° C, it was not cured at all (easily melted in MEK).

As is apparent from Tables 2 and 3, the water-base coating composition of the present invention can obtain sufficient curability at low temperature, which was not obtained in the conventional water-based paint (Comparative Example 5).

As is clear from the results of Examples 13, 14, and 16 (Table 3), when an epoxy-based polyamine resin is used as the polyamine resin, a water-based coating composition capable of obtaining a coating film exhibiting excellent anticorrosive property in addition to low- .

The water-based coating composition of the present invention can be suitably used as a construction paint, a heavy corrosion protection paint, a rust preventive such as a bridge, a building exterior, a flooring, a building material, a sealer, a primer and the like.

Claims (10)

(A) an aqueous dispersion type polyamine resin having at least one first amine group and / or a second amine group in the molecule,
(B) having at least one (meth) acryloyl group in the molecule,
Wherein the water-base coating composition is a two-component aqueous coating composition, the base coating solution contains the polyamine resin (A), the curing agent comprises the compound (B)
The amine equivalent of the polyamine resin (A) is 100 to 3000,
The neutralization ratio of the polyamine resin (A) is 10 to 70%
Wherein the viscosity of the compound (B) at 25 占 폚 is 3000 mPa 占 퐏 or less. The waterborne coating composition according to claim 1, wherein the polyamine resin (A) is an acrylic polyamine resin or an epoxy polyamine resin. The aqueous coating composition according to claim 1 or 2, wherein the compound (B) has a molecular weight of 150 or more and 2000 or less. The waterborne coating composition according to claim 1 or 2, wherein the compound (B) is a water-soluble compound and the polyamine resin (A) is a water-dispersible resin. The aqueous coating composition according to claim 1 or 2, wherein the compound (B) is a self-emulsifiable compound. The aqueous coating composition according to claim 1 or 2, wherein the compound (B) is emulsified or dispersed by the polyamine resin (A). The aqueous coating composition according to claim 1 or 2, wherein the compound (B) is a mixture of a water-soluble compound and a water-insoluble compound. The aqueous coating composition according to claim 1 or 2, wherein the compound (B) is an emulsion. The aqueous coating composition according to claim 1 or 2, wherein the curing agent further comprises an emulsifier. delete