JP7367162B2 - Water-based coating material - Google Patents

Description

The present invention relates to a novel aqueous coating.

In recent years, in the field of coatings for architectural and civil engineering structures, there has been a shift from solvent-based materials using organic solvents to water-based materials using water as a solvent. This is done to reduce health hazards for painting workers and residents, as well as to reduce atmospheric pollution, and various studies are being conducted to make water-based coatings for metals as well. There is.

As a coating material for such metals, for example, an aqueous coating material using an epoxy resin as a resin component and blending various antirust pigments with the resin component has been proposed. However, such water-based coating materials have problems in that they dry more slowly than solvent-based coating materials and have poor rust prevention properties. In particular, one-component water-based coating materials may require drying at high temperatures in order to obtain sufficient rust prevention properties.

In view of these problems, as an aqueous coating material that can be dried at room temperature, for example, Patent Document 1 discloses an aqueous coating material that contains a binder resin containing an acrylic modified epoxy resin and an anti-rust pigment. It is stated that drying at room temperature is possible by blending a specific compound.

Japanese Patent Application Publication No. 2015-151511

However, by simply blending a specific pigment as in Patent Document 1, sufficient coating film strength may not be obtained, resulting in insufficient adhesion, rust prevention, etc.

The present invention was made in view of these problems, and by including a specific powder component in a specific weight ratio in an aqueous coating material containing a film-forming component and a powder component, coating film strength, adhesion, It has been discovered that a water-based coating material with excellent rust prevention properties can be obtained, and the present invention has been completed.

That is, the present invention has the following features.
1. An aqueous coating material comprising a film-forming component and a powder component,
The film-forming component includes a resin component and a curing accelerator,
The resin component includes an aqueous epoxy resin emulsion, the aqueous epoxy resin emulsion includes an aqueous dispersion of a vinyl-modified epoxy ester resin,
The curing accelerator includes a metal dryer and one or more selected from a crosslinking agent and a silane compound,
The above powder component includes an anti-corrosion pigment, calcium carbonate, and a coloring pigment,
The colored pigment includes titanium oxide and red iron oxide pigment,
Containing 50 to 300 parts by weight of the powder component per 100 parts by weight of the resin component,
An aqueous coating material characterized in that the powder component contains 30 to 90% by weight of the calcium carbonate.
2. 1. It is a one-component curing water-based coating material. The water-based coating material described in .
3. 1. The crosslinking agent is characterized in that it contains a compound having a carbodiimide group. or 2. The water-based coating material described in .
4. 1. The silane compound includes an alkyl alkoxysilane compound. or 2. The water-based coating material described in .

The aqueous coating material of the present invention is excellent in coating strength, adhesion, rust prevention, etc.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated.

The present invention is an aqueous coating material containing a film-forming component and a powder component, wherein the film-forming component contains an aqueous epoxy resin emulsion as a resin component, and the powder component contains a rust-preventing pigment and calcium carbonate. It is characterized by containing.

The film-forming component (A) (hereinafter also referred to as "component (A)") used in the present invention is a water-based epoxy resin emulsion (A1- 1).

The aqueous epoxy resin emulsion (A1-1) is an aqueous dispersion of an epoxy resin in which the epoxy resin is dispersed and emulsified in an aqueous medium. The epoxy resin may be one that can be dispersed in an aqueous medium, and may be either a solid epoxy resin and/or a liquid epoxy resin, for example, one or more epoxy groups in the molecule, preferably A resin containing two or more can be used. Examples of such epoxy resins (a1) include bisphenol epoxy resins, alicyclic epoxy resins, phenol novolac epoxy resins, polyethylene glycol epoxy resins, and epoxidized polybutadiene resins. In the present invention, bisphenol type epoxy resins are preferred, and for example, one or more types selected from bisphenol A type epoxy resins, bisphenol AD type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, etc. are suitable.

Further, the aqueous epoxy resin emulsion (A1-1) preferably contains, as the epoxy resin, an epoxy ester resin in which the epoxy group of the above epoxy resin is esterified with an organic acid, and more preferably a vinyl-modified epoxy ester resin in which the epoxy group is esterified with an organic acid. Preferably, it contains an epoxy ester resin. Thereby, coating film strength, adhesion, rust prevention, etc. can be sufficiently exhibited.

The epoxy ester resin can be produced by subjecting the epoxy resin and an organic acid to an esterification reaction by heating (50 to 250° C.) in the presence of an esterification catalyst if necessary.

The organic acids mentioned above are not particularly limited, but include, for example, tung oil fatty acids, linseed oil fatty acids, dehydrated castor oil fatty acids, castor oil fatty acids, fish oil fatty acids, safflower oil fatty acids, soybean oil fatty acids, rice bran oil fatty acids, sesame oil fatty acids, and poppy oil fatty acids. Drying oil fatty acids or semi-drying fatty acids such as fatty acids, eno oil fatty acids, hempseed oil fatty acids, grape kernel oil fatty acids, corn oil fatty acids, tall oil fatty acids, sunflower oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids, rubber seed oil fatty acids, hygienic acid fatty acids, etc. Non-drying oil fatty acids such as oil fatty acids, coconut oil fatty acids, hydrogenated coconut oil fatty acids, palm oil fatty acids, olive oil fatty acids, or purified products of these fatty acids, such as oleic acid, linoleic acid, linoleic acid, eleostearic acid, ricinoleic acid, etc. Examples include unsaturated fatty acids such as octylic acid, lauric acid, and stearic acid. These can be used alone or in combination of two or more. Generally, drying oil fatty acids refer to unsaturated fatty acids with an iodine value of 130 or more, and semi-drying oil fatty acids refer to unsaturated fatty acids with an iodine value of 100 or more and less than 130. On the other hand, non-drying oil fatty acids usually refer to fatty acids having an iodine value of less than 100.

In the present invention, it is preferable to use the above-mentioned drying oil fatty acids or semi-drying oil fatty acids as the organic acid, and among them, tung oil fatty acids, linseed oil fatty acids, dehydrated castor oil fatty acids, fish oil fatty acids, and safflower oil fatty acids with an iodine value of 100 to 200. It is preferable to use one or more selected from , soybean oil fatty acids, rice bran oil fatty acids, and the like.

As the esterification catalyst, for example, dimethylbenzylamine, triethylamine, etc. can be used.

The vinyl-modified epoxy ester resin has polyvinyl groups bonded to at least some unsaturated groups of the epoxy ester resin, and the vinyl groups are bonded to at least some of the unsaturated groups of the epoxy ester resin using a radical polymerization initiator in the presence of the epoxy ester resin. It can be produced by radical polymerizing the containing compound. Note that the vinyl group-containing compound is a compound also called a monomer, and is a general term for compounds having a polymerizable unsaturated double bond.

The vinyl group-containing compound is not particularly limited as long as it is one or more monomers copolymerizable with the unsaturated group of the epoxy ester resin, but examples include (meth)acrylic acid alkyl ester, aromatic monomer, acid It is preferable that a group-containing monomer or the like is included.

Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and t-butyl (meth)acrylate. Acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, Examples include octadecyl (meth)acrylate and cyclohexyl (meth)acrylate. These can be used alone or in combination of two or more.
In the present invention, acrylic acid alkyl ester and methacrylic acid alkyl ester are collectively referred to as (meth)acrylic acid alkyl ester.

Aromatic monomers are compounds having an aromatic ring and a polymerizable unsaturated double bond, and specific examples thereof include styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorstyrene, vinylanisole, and vinyl. Examples include naphthalene, divinylbenzene, phenyl (meth)acrylate, benzyl (meth)acrylate, and the like. These can be used alone or in combination of two or more.

Examples of acid group-containing monomers include carboxyl group-containing monomers such as (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, and salicylic acid. These can be used alone or in combination of two or more.

Furthermore, other vinyl group-containing compounds can also be used within a range that does not impede the effects of the present invention. Examples of such vinyl group-containing compounds include,
Nitrile group-containing monomers such as (meth)acrylonitrile, vinylidene cyanide, α-cyanoethyl (meth)acrylate;
Maleic acid amide, (meth)acrylamide, N-monoalkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, 2-(dimethylamino)ethyl (methacrylate), N-[3-(dimethylamino)propyl] Amide group-containing monomers such as (meth)acrylamide and vinylamide;
Carbonyl group-containing monomers such as acrolein, diacetone (meth)acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone;
Aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth)acrylate, amino-n-butyl (meth)acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, N-methylaminoethyl (meth)acrylate, N -Amino group-containing monomer such as t-butylaminoethyl (meth)acrylate;
Glycidyl (meth)acrylate, diglycidyl fumarate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, ε-caprolactone modified glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, ) Epoxy group-containing monomers such as acrylates;

Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether; ε-caprolactone-modified hydroxyl-containing monomers obtained by adding ε-caprolactone to these hydroxyl-containing monomers;
Isocyanate group-containing monomers such as 2-isocyanatopropene, 2-isocyanatoethyl vinyl ether, 2-isocyanatoethyl (meth)acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate;
Vinylidene halide monomers such as vinylidene fluoride;
Monomers having active methylene groups such as vinyl acetoacetate and 2-acetoacetoxyethyl (meth)acrylate;
Monomers having a silyl group such as vinyltrimethoxysilane and 3-(meth)acryloyloxypropyltrimethoxysilane;
Examples include polyoxyalkylene ether (meth)acrylates such as polyoxyethylene ether glycol mono(meth)acrylate, polyoxypropylene ether glycol mono(meth)acrylate, and polyoxybutylene ether glycol (meth)acrylate.

Examples of the radical polymerization initiator include peroxide compounds such as benzoyl peroxide, dichlorobenzoyl peroxide, di-t-butyl peroxide, t-butyl peroxy 2-ethylhexanoate, azobisisobutylnitrile, and dimethyl Examples include azo compounds such as azobutyrate.

The solid acid value of the vinyl-modified epoxy ester resin is preferably 100 mgKOH/g or less (more preferably 1 to 50 mgKOH/g, still more preferably 2 to 40 mgKOH/g, particularly preferably 7 to 30 mgKOH/g). . When such a range is satisfied, an aqueous coating material with improved initial drying properties, water resistance, etc., and excellent coating film strength and rust prevention properties can be obtained. In the present invention, "α to β" is synonymous with "not less than α and not more than β". Note that the acid value is a value expressed by the number of mg of potassium hydroxide equivalent to the acid group contained in 1 g of solid content.

For example, a basic compound can be used to disperse the vinyl-modified epoxy ester resin (a3) in an aqueous medium. Examples of such basic compounds include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, 2-dimethylaminoethanol, ammonia, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. oxide, tetra-n-butylammonium hydroxide, trimethylbenzylammonium hydroxide, and the like. These basic compounds can also be used in the form of an aqueous solution such as aqueous ammonia. In addition, the basic compound is a coating material that does not volatilize and remain in the coating film when the aqueous coating material containing the vinyl-modified epoxy ester resin (a3) forms a coating film, and has excellent water resistance and corrosion resistance. Volatile basic compounds and their aqueous solutions, such as aqueous ammonia, triethylamine, and 2-dimethylaminoethanol, are preferred because they can form a film.

In addition, when dispersing the above-mentioned epoxy resin in an aqueous medium, an emulsifier or the like can be used as necessary. Note that the aqueous medium is a medium that mainly contains water, and if necessary, a water-soluble solvent such as a lower alcohol, a polyhydric alcohol, an ether compound, an ester compound, or an alkylene oxide-containing compound may be mixed. good.

As the emulsifier, for example, anionic surfactants and nonionic surfactants can be used alone or in combination.
Examples of anionic surfactants include sulfonic acid alkali metal salts such as sodium dodecylbenzenesulfonate, sodium laurylnaphthalenesulfonate, and sodium stearyl diphenyl ether disulfonate; sodium lauryl sulfate, polyoxyethylene sodium lauryl ether sulfate, polyoxyethylene Examples include alkali metal salts of sulfuric esters such as sodium octylphenyl ether sulfate.
Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, oxyethylene/oxypropylene block copolymer, and the like.

The average particle diameter of the resin particles of the aqueous epoxy resin emulsion (A-1) of the present invention is not particularly limited, but is preferably 500 nm or less (more preferably 5 to 300 nm, still more preferably 10 to 200 nm). Note that the average particle diameter referred to herein is a value measured by a dynamic light scattering method.

In addition to the aqueous epoxy resin emulsion (A1-1), the component (A1) of the present invention may contain another resin component (A1-2) (hereinafter also referred to as "component (A1-2)"). can. Component (A-2) is not particularly limited, but includes, for example, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, acrylic resin, urethane resin, acrylic silicone resin, fluorine resin, etc. Examples include complex systems. These can be used alone or in combination of two or more. As the embodiment of component (A-2), one or more selected from water-soluble resins and resin emulsions is suitable.

In the present invention, it is preferable that the aqueous epoxy resin emulsion (A1-1) is contained in the component (A1) in an amount of 60% by weight or more (more preferably 80% by weight or more, still more preferably 90% by weight or more). Note that an embodiment using only the above water-based epoxy resin emulsion (A1-1) is also suitable.

It is preferable that the component (A) of the present invention further contains a curing accelerator (A2). Examples of the curing accelerator include a metal dryer (A2-1), a crosslinking agent (A2-2), and a silane compound (A2-3). These can be used alone or in combination of two or more.

Examples of the metal dryer (A2-1) (hereinafter also simply referred to as "component (A2-1)") include cobalt, manganese, vanadium, cerium, iron, tin, zirconium, bismuth, aluminum, strontium, and zinc. , barium, copper, calcium, lead, nickel, and other metal-containing organic metal compounds (eg, octylate, naphthenate, etc.), etc. can be used. Specifically, for example, cobalt octylate, cobalt naphthenate, manganese octylate, manganese naphthenate, iron octylate, iron naphthenate, tin octylate, tin naphthenate, zirconium octylate, zirconium naphthenate, zinc octylate. , zinc naphthenate, barium octylate, barium naphthenate, copper octylate, copper naphthenate, calcium octylate, calcium naphthenate, and the like. These can be used alone or in combination of two or more.

The above component (A2-1) is preferably 0.01 to 10 parts by weight (more preferably 0.05 to 5 parts by weight) in terms of total metal amount, based on 100 parts by weight of the solid content of the above component (A1). include. In such a case, the gel fraction of the component (A) forming film can be increased, and the effects of the present invention can be fully exhibited.

The crosslinking agent (A2-2) (hereinafter also simply referred to as "component (A2-2)") may be one or more selected from, for example, a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group, a hydrazide group, etc. A compound containing a reactive functional group can be used. In the present invention, as component (A2-2), preferably a compound having one or more reactive functional groups selected from a carbodiimide group, an epoxy group, an aziridine group, and an oxazoline group (more preferably a compound having a carbodiimide group) is used. include. In this case, the effects of the present invention can be further enhanced.

Examples of crosslinking agents containing carbodiimide groups include JP-A No. 10-60272, JP-A 10-316930, JP-A 11-60667, JP-A 2016-196612, JP-A 2016-196613, and JP-A No. 2016-196613. Examples include those described in JP-A No. 2018-104605, JP-A No. 2019-038960, and the like.
Examples of crosslinking agents containing epoxy groups include polyethylene glycol diglycidyl ether, polyhydroxyalkane polyglycidyl ether, diglycerol polyglycidyl ether, and sorbitol polyglycidyl ether.

As a crosslinking agent containing an aziridine group, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate], 1,6-hexamethylene diethylene urea, diphenylmethane-bis-4,4'-N,N '-diethylene urea and the like.

As a crosslinking agent containing an oxazoline group, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, etc. Examples include resins in which a polymerizable oxazoline compound is copolymerized with a monomer that can be copolymerized with the compound.

Examples of the crosslinking agent containing a hydrazide group include malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, and the like.

The component (A2-2) is preferably contained in an amount of 0.01 to 20 parts by weight (more preferably 0.05 to 10 parts by weight) based on 100 parts by weight of the solid content of the component (A1). In such a case, the gel fraction of the component (A) forming film can be increased, and the effects of the present invention can be fully exhibited.

The silane compound (A2-3) (hereinafter also simply referred to as "component (A2-3)") is not particularly limited as long as it is a compound having an alkoxysilyl group, a silanol group, etc. For example, a vinyl group-containing silane Coupling agents, epoxy group-containing silane coupling agents, amino group-containing silane coupling agents, methacrylic group-containing silane coupling agents, chloropropyl group-containing silane coupling agents, mercapto group-containing silane coupling agents, and alkyl alkoxysilane compounds One or more types selected from the following can be used.

Examples of the vinyl group-containing silane coupling agent include vinyl group-containing silane coupling agents such as vinyltrichlorosilane, vinyltrimethoxysilane, and vinyltriethoxysilane.

Examples of the silane coupling agent containing an epoxy group (glycidyl group) include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, and β-glycidoxyethyltriethoxysilane. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethyl Methoxysilane, γ-glycidoxypropyl(ethyl)dimethoxysilane, β-3,4-epoxycyclohexylethyltrimethoxysilane, β-3,4-epoxycyclohexylethyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane , 8-glycidoxyoctylmethyldimethoxysilane, 8-glycidoxyoctylmethyldiethoxysilane and the like.

Examples of amino group-containing silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyl. Diethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)-γ-aminopropyltriethoxy Silane, N-β(aminoethyl)-γ-aminopropylmethyldiethoxysilane, N-β(aminoethyl)-γ-aminopropyltriisopropoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- Phenyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-β(aminoethyl)-8-aminooctyltrimethoxysilane, γ-triethoxysilyl-N-(1, Examples include 3-dimethyl-butylidene)probylamine.

Examples of methacrylic group-containing silane coupling agents include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, and the like. Can be mentioned.

Examples of the chloropropyl group-containing silane coupling agent include γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldichlorosilane, and γ-chloropropylmethyldimethoxysilane.

Examples of the mercapto group-containing silane coupling agent include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and 11-mercaptoundecyl. Examples include trimethoxysilane, S-(octanoyl)mercaptopropyltriethoxysilane, and the like.

As the alkylalkoxysilane compound, alkylalkoxysilane, hydrolyzed condensates thereof, etc. can be used. Examples of such alkyl alkoxysilane compounds include tetraethoxysilane, tetramethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetrat-butoxysilane, and tetraphenoxysilane. Tetrafunctional alkoxysilanes such as silane;

Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Propyltripropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxy Trifunctional alkyl alkoxysilanes such as silane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltributoxysilane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldibutoxysilane Difunctional alkyl alkoxysilanes such as ethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dimethoxymethylphenylsilane, methylphenyldiethoxysilane;
etc.

In the present invention, it is preferable that the component (A2-3) contains an alkyl alkoxysilane compound. Furthermore, in the present invention, it is preferable to include one containing a phenyl group. Examples of such component (A2-3) include phenyltrimethoxysilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenyltributoxysilane, diphenyldibutoxysilane, and the like. It will be done. When these are used, the strength of the formed film is increased, and the rust prevention properties are further improved. Furthermore, it can exhibit excellent effects in improving adhesion and adhesion to the substrate.

The component (A2-3) is preferably contained in an amount of 0.01 to 20 parts by weight (more preferably 0.05 to 10 parts by weight) based on 100 parts by weight of the solid content of the component (A1). In such a case, the gel fraction of the component (A) forming film can be increased, and the effects of the present invention can be fully exhibited.

Component (A) of the present invention contains the above-mentioned (A1) component as an essential component, and preferably contains the above-mentioned (A2) component in addition to the above-mentioned (A1) component. -1), the above-mentioned (A2-2) component, and the above-mentioned (A2-3) component.

In the present invention, the component (A) preferably has a gel fraction of the formed film of 10% or more (more preferably 12% or more, still more preferably 15% or more). Further, the upper limit thereof is not particularly limited, but is practically preferably 80% or less (more preferably 50% or less, still more preferably 30% or less). When the film formed from the film-forming component (A) satisfies this range, the coating strength, adhesion, etc. of the aqueous coating material of the present invention are improved, and the rust prevention properties can be further improved.

In the present invention, the gel fraction is determined by coating the film-forming component (A) on a polyester film so that the film thickness after drying is 0.15 mm, and drying at 23°C for 24 hours to form a film. After using a test piece as a test piece and immersing it in acetone for 24 hours, it is calculated using the following formula.
Gel fraction (%) = (Coating weight after immersion/Coating weight before immersion) x 100

Powder component (B) of the present invention (hereinafter also simply referred to as "component (B)") includes rust preventive pigment (B1) (hereinafter also simply referred to as "component (B1)"), calcium carbonate (B2 ) (hereinafter also simply referred to as "component (B2)"), and a coloring pigment (B3) (hereinafter also simply referred to as "component (B3)").

The rust preventive pigment (B1) is not particularly limited, but includes, for example, basic rust preventive pigments such as lead-based rust preventive pigments, boric acid-based rust preventive pigments, and complex oxide-based rust preventive pigments; chromic acid-based rust preventive pigments. Passive film-forming rust preventive pigments such as phosphoric acid rust preventive pigments, molybdate rust preventive pigments, tungstic acid rust preventive pigments, organometallic salt rust preventive pigments; metallic rust preventive pigments, phosphide rust preventive pigments Pigments, reducing rust-preventive pigments such as phosphorous acid/hypophosphorous acid-based rust preventive pigments; scale-like pigments such as mica-like iron oxide and leafing-type aluminum; and the like.
These can be used alone or in combination of two or more.

In the present invention, one type selected from phosphoric acid-based rust-preventing pigments, molybdic acid-based rust-preventing pigments, tungstic acid-based rust-preventing pigments, organometallic salt-based rust-preventing pigments, and phosphorous acid/hypophosphorous acid-based rust preventive pigments is used. It is preferable to include the above (preferably two or more types).
Examples of phosphoric acid-based rust preventive pigments include phosphoric acid compounds such as zinc phosphate, iron phosphate, aluminum phosphate, calcium phosphate, barium phosphate, and magnesium phosphate; zinc polyphosphate, iron polyphosphate, aluminum polyphosphate, etc. Examples include polyphosphoric acid compounds such as silicon phosphate, titanium phosphate, etc., and organic modified products and/or hydrates thereof.
Examples of molybdate-based rust preventive pigments include molybdate compounds such as zinc molybdate, aluminum molybdate, calcium molybdate, and barium molybdate; zinc phosphomolybdate, calcium phosphomolybdate, aluminum phosphomolybdate, and phosphomolybdate. Examples include phosphomolybdic acid compounds such as aluminum zinc; and organic modified products and/or hydrates thereof.
Examples of the tungstic acid-based antirust pigment include tungstic acid compounds such as zinc tungstate, aluminum tungstate, calcium tungstate, and barium tungstate; and organic modified products and/or hydrates thereof.
Examples of organic metal salt-based rust preventive pigments include zinc salts of organic nitro compounds, zinc salts of zinc butanoate, and the like.
Examples of phosphorous acid/hypophosphorous acid-based rust preventive pigments include lead phosphite, zinc phosphite, magnesium phosphite, manganese phosphite, iron hypophosphite, calcium hypophosphite, etc. .

The average particle diameter of component (B1) of the present invention is preferably 0.5 μm to 30 μm (more preferably 1 μm to 25 μm, still more preferably 1.5 μm to 20 μm). Note that the average particle diameter can be measured with a particle diameter distribution measuring device using a laser diffraction/scattering method.

The calcium carbonate (B2) is not particularly limited, and known ones such as heavy calcium carbonate and light calcium carbonate can be used. The average particle diameter of component (B2) of the present invention is preferably 0.5 μm to 100 μm (more preferably 1 μm to 80 μm, still more preferably 1.5 μm to 50 μm, particularly preferably 2 μm to 20 μm). In such a case, excellent rust prevention properties can be exhibited. Furthermore, the finish quality of the formed film can be improved. Note that the average particle diameter can be measured in the same manner as for component (B1) above.

It is characterized by containing titanium oxide and red iron oxide pigment (red iron oxide) as the coloring pigment (B3). In the present invention, the weight ratio of titanium oxide and red iron oxide pigment is preferably 10:90 to 90:10 (more preferably 20:80 to 80:20, still more preferably 25:75 to 70:30). . In such a range, excellent rust prevention properties can be obtained. It is also suitable for hiding properties, drying properties, etc.

Furthermore, other coloring pigments can be included within a range that does not impede the effects of the present invention. For example, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, cobalt black, copper manganese iron black, molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide. , titanium yellow, fast yellow, benzimidazolone yellow, cobalt green, phthalocyanine green, ultramarine, navy blue, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine violet, aluminum pigment, pearl pigment, etc. can do.

In the present invention, the content of component (B) is 50 to 300 parts by weight (preferably 80 to 280 parts by weight, more preferably 135 to 250 parts by weight) based on 100 parts by weight of the solid content of the resin component (A1). ). By satisfying such a range, the strength of the coating film can be improved and excellent rust prevention properties can be exhibited. Furthermore, various physical properties (eg, cracking resistance, shrinkage resistance, adhesion, etc.) of the formed film can be improved.

The content of component (B1) is preferably 1 to 100 parts by weight (more preferably 2 to 50 parts by weight) based on 100 parts by weight of the solid content of component (A1). In such a case, excellent rust prevention properties can be exhibited.
The content of component (B2) is preferably 50 to 280 parts by weight (more preferably 70 to 250 parts by weight) based on 100 parts by weight of the solid content of component (A1). In such a case, excellent effects can be exhibited in terms of coating film strength and adhesion (peeling strength).
The content of component (B3) is preferably 1 to 250 parts by weight (more preferably 10 to 200 parts by weight) based on 100 parts by weight of the solid content of component (A1).

Furthermore, in the present invention, the component (B2) contains 30 to 90% by weight (preferably 35 to 90% by weight, more preferably 40 to 88% by weight, even more preferably 50 to 86% by weight) of component (B). It is characterized by containing. By satisfying such a range, the strength of the coating film (peeling strength) and adhesion are further increased, and excellent rust prevention properties can be exhibited. The component (B) preferably contains the component (B1) in an amount of 0.5 to 20% by weight (more preferably 1 to 15% by weight). In such a case, the above effects can be fully exhibited. Component (B) preferably contains the component (B3) in an amount of 0.5 to 50% by weight (more preferably 1 to 30% by weight). In such a case, the above effects can be fully exhibited.

In the present invention, it is preferable that the component (B) includes an extender pigment (B4) and the like in addition to the component (B1), the component (B2), and the component (B3).

As the extender pigment, extender pigments other than the above component (B2) can be used, such as anhydrite, white carbon, talc, kaolin, clay, china clay, china clay, diatomaceous earth, barite powder, barium sulfate, precipitated barium sulfate, Examples include silica sand, silica powder, quartz powder, mica, resin beads, glass beads, hollow balloons, etc., and one or more of these can be used.
The content of the extender pigment (B4) is preferably 100 parts by weight or less (more preferably 1 to 100 parts by weight, still more preferably 2 to 80 parts by weight) based on 100 parts by weight of the solid content of the component (A1). be.

In addition to the above-mentioned components, the aqueous coating material of the present invention may include other components such as water, a dispersion medium such as a solvent, an aggregate, a film-forming aid, a plasticizer, an antifreeze agent, a preservative, and a fungicide. , antibacterial agent, antifoaming agent, pigment dispersant, thickener, anti-settling agent, aligning agent, leveling agent, surface conditioner, wetting agent, pH adjuster, fibers, matting agent, ultraviolet absorber, antioxidant , light stabilizers, adsorbents, catalysts, etc. can be mixed. By using such components in appropriate combinations, various types of covering materials can be designed.

The aqueous coating material of the present invention can be manufactured by uniformly mixing the above-mentioned components (A) and (B), and other components as necessary, by a conventional method, and is preferably a one-component curing material. It is a water-based coating material for molds.

The coating film formed by the aqueous coating material of the present invention has an oxygen permeability coefficient of preferably 50×10 ⁻¹² cc·cm/cm 2·sec·cmHg or less (more preferably 45×10 −12 cc·cm/cm ² ·sec·cmHg or less ^{) 12} cc·cm/cm ² ·sec·cmHg or less). In the case of such a range, even more excellent rust prevention properties can be exhibited.
The oxygen permeability coefficient was determined by applying a water-based coating material to a release paper to a dry film thickness of 0.15 mm, drying it at 23°C for 24 hours, and peeling off the coating film. The oxygen permeability was measured by gas chromatography according to test method JIS K 7126. The gas permeability measuring device used was "GTR-10XACT" manufactured by GTR Tech Co., Ltd., and the gas chromatograph used was "GC/TCD G2700" manufactured by Yanaco Technical Science Co., Ltd.

The water-based coating material of the present invention can be used as a material for coating metal members such as buildings and civil engineering structures. Sites where such metal members are used include, for example, walls, columns, floors, beams, roofs, stairs, and the like. In addition, as a coating method for the aqueous coating material of the present invention, brush coating, trowel coating, roller coating, spray coating, electrostatic coating, roll coater, curtain flow coater, dipping coating, electrodeposition coating, etc. can be used. A roller or a brush is suitable from the viewpoint of painting workability, adhesion, etc. The coating amount is not particularly limited, but is preferably 0.05 kg/m ² to 0.5 kg/m ² . The number of coats of the aqueous coating material may be appropriately set depending on the condition of the base, but is preferably 1 to 2 times. The drying time of the aqueous coating material is preferably from 1 hour to 1 week. The drying temperature is preferably -10°C or higher and 50°C or lower, more preferably -5°C or higher and 40°C or lower. The aqueous coating material of the present invention is preferably a room temperature curing type.

After applying the aqueous coating material of the present invention, various top coating materials can be applied. The top coating material is not particularly limited as long as it is generally used for painting buildings and civil engineering structures, and the binding materials include, for example, acrylic resin, polyurethane resin, epoxy resin, and fluorine resin. Examples include organic binders such as resins, alkyd resins, and polyester resins; inorganic binders such as silicone resins, alkoxysilanes, colloidal silica, and silicate; and organic-inorganic composite binders such as acrylic silicone resins.

Specific top coating materials include, for example, weather-resistant top coat paints for construction (JIS K5658:2010), weather-resistant paints for steel structures (JIS K5659:2008), glossy synthetic resin emulsion paints (JIS K5660:2008), Architectural fire protection paint (JIS K5661:1970), synthetic resin emulsion paint (JIS K5663:2008), road marking paint (JIS K5665:2011), multicolored pattern paint (JIS K5667:2003), synthetic resin emulsion pattern paint (JIS K5663:2008), K5668:2010), acrylic resin non-aqueous dispersion paint (JIS K5670:2008), lead and chromium-free anti-rust paint (JIS K5674:2008), high solar reflectance paint for roofs (JIS K5675:2011), for buildings Examples include floor paints (JIS K5970:2008), architectural coating waterproofing materials (JIS A6021:2011), architectural finishing coating materials (JIS A6909:2014), and the like. Particularly suitable as the top coating material of the present invention are weather-resistant top coatings for architecture and weather-resistant coatings for structures.

The coating method for the top coat material is not particularly limited and can be applied by any known method, for example, various methods such as brush coating, spray coating, roller coating, roll coater, flow coater, etc. can be used. That is, each top coat material may be coated based on the usual process with the optimum coating specifications for each top coat material.

Examples are shown below to clarify the features of the present invention.

(Production of water-based coating materials 1 to 17)
Aqueous coating materials 1 to 17 were produced by mixing component (A), component (B), and additives in accordance with the formulations shown in Table 1 in a conventional manner.
The following materials were used as raw materials.

(A) Resin component (A1) Aqueous epoxy resin emulsion (A1-1) Vinyl modified epoxy ester resin (acrylic modified bisphenol A type epoxy ester resin) [solid content: 40% by weight, acid value: 10 mgKOH/g, medium: water ]
(A1-2) Vinyl modified epoxy ester resin (acrylic styrene modified bisphenol A type epoxy ester resin) [solid content: 40% by weight, acid value: 6.5 mgKOH/g, medium: water]
(A2) Curing accelerator (A2-1) Metal dryer (metal soap)
(A2-1-1) Co-based metal dryer [Metal content: 4% by weight]
(A2-1-2) Zr-based metal dryer [metal content: 12% by weight]
(A2-2) Crosslinking agent (A2-2-1) Polycarbodiimide [solid content: 40% by weight, medium: water]
(A2-3) Silane compound (A2-3-1) Phenyltrimethoxysilane (A2-3-2) Dimethoxymethylphenylsilane

(B) Powder component (B1) Antirust pigment (B1-1) Phosphormolybdic acid compound [average particle size: 3.0 μm]
(B1-2) Zinc salt of organic nitro compound [average particle size: 3.8 μm]
(B2) Calcium carbonate (B2-1) Calcium carbonate [average particle size: 3.3 μm]
(B2-2) Calcium carbonate [average particle size: 21 μm]
(B2-3) Calcium carbonate [average particle size: 1.2 μm]
(B3) Colored pigment (B3-1) Titanium oxide (B3-2) Red iron oxide pigment (red iron oxide)
(B4) Talc/additives: antifoaming agents, thickeners, pigment dispersants, film forming aids, etc.

(Examples 1 to 15, Comparative Examples 1 to 5)
The following evaluations were performed on the obtained aqueous coating materials 1 to 20. The results are shown in Table 1.

<Coating film strength (peeling strength)>
One longitudinal end (10 mm) of a steel plate (150 x 70 x 0.8 mm) was covered with release paper, and a water-based coating material was applied at a coating amount of 120 g/m ² under standard conditions (temperature 23°C, Test specimen 1 was obtained by curing at a relative humidity of 50% for 7 days. Next, the coating film formed on the release paper was pulled in the longitudinal direction, and the coating film formed on the steel plate that did not peel off was designated as "a", and the coating film that was easily peeled off was designated as "d"4. Evaluation was performed in stages (a>b>c>d).

<Rust prevention test>
Test specimen 2 was obtained by applying water-based coating material to a steel plate (150 x 70 x 0.8 mm) at a coating amount of 120 g/m ² and curing it under standard conditions (temperature 23°C, relative humidity 50%) for 7 days. And so. The obtained test specimen 2 was subjected to a salt spray resistance test and evaluated after 50 hours and 100 hours. The results are shown in Table 2. Rust prevention 1 in the table indicates the evaluation after 50 hours, and rust prevention 2 indicates the evaluation after 100 hours. This evaluation was conducted on a four-level scale (a > b > c > d), with "a" indicating no rust formation and "d" indicating significant rust formation. .

In Examples 1 to 15 (aqueous coating materials 1 to 15), films with good coating strength, adhesion, and rust prevention properties could be obtained. In particular, Examples 7, 8, and 14 (aqueous coating materials 7, 8, and 14) were able to exhibit excellent rust prevention properties.

Next, the following evaluations were performed on water-based coating materials 7, 8, and 14.
A water-based coating material was applied to a steel plate (150 x 70 x 0.8 mm) at a coating amount of 120 g/ ^m2 , and after curing for 1 day under standard conditions (temperature 23°C, relative humidity 50%), it was applied as a weatherproof material for construction. Test specimen 3 was prepared by applying a topcoat paint (urethane resin paint) at a coating amount of 100 g/m ² and curing it under standard conditions (temperature 23° C., relative humidity 50%) for 7 days. The finished state of the obtained test specimen 3 was confirmed. As a result, water-based coating materials 7 and 8 had an excellent glossy finish. In comparison, water-based coating material 14 had a slightly less glossy finish.

Claims (4)

An aqueous coating material comprising a film-forming component and a powder component,
The film-forming component includes a resin component and a curing accelerator,
The resin component includes an aqueous epoxy resin emulsion, the aqueous epoxy resin emulsion includes an aqueous dispersion of a vinyl-modified epoxy ester resin,
The curing accelerator includes a metal dryer and one or more selected from a crosslinking agent and a silane compound,
The above powder component includes an anti-corrosion pigment, calcium carbonate, and a coloring pigment,
The colored pigment includes titanium oxide and red iron oxide pigment,
Containing 50 to 300 parts by weight of the powder component per 100 parts by weight of the resin component,
An aqueous coating material characterized in that the powder component contains 30 to 90% by weight of the calcium carbonate. The aqueous coating material according to claim 1 , which is a one-component curing type aqueous coating material. 3. The aqueous coating material according to claim 1, wherein the crosslinking agent contains a compound having a carbodiimide group. The aqueous coating material according to claim 1 or 2, wherein the silane compound includes an alkyl alkoxysilane compound.