JP2021001314A - Aqueous coating material - Google Patents

Abstract

To provide an aqueous coating material having excellent coat strength, adhesion, rust-prevention properties or the like.SOLUTION: An aqueous coating material contains a coat formation component and a powder component. The coat formation component contains an aqueous epoxy resin emulsion as a resin component, and a coat to be formed has a gel fraction of 10% or more. The powder component contains an antirust pigment, and calcium carbonate. Relative to the resin component 100 pts.wt., the content of the powder component is 50-300 pts.wt. In the powder component, the content of the calcium carbonate is 30-90 wt.%.SELECTED DRAWING: None

Description

The present invention relates to a novel aqueous coating material.

In recent years, in the field of coatings for buildings and civil engineering structures, there is a shift from solvent-type materials using organic solvents as solvents to water-based materials using water as a solvent. This is done for the purpose of reducing the health hazards of painters and residents and for reducing air pollution, and various studies have been conducted on the water-based coating materials for metals. There is.

As such a coating material for metals, for example, an aqueous coating material in which an epoxy resin is used as a resin component and various rust preventive pigments are mixed with the resin component has been proposed. However, such a water-based coating material has a problem that it dries slowly and is inferior in rust prevention property as compared with a solvent-based coating material. In particular, a one-component water-based coating material may need to be dried at a high temperature in order to obtain sufficient rust prevention properties.

From such a problem, as an aqueous coating material that can be dried at room temperature, for example, Patent Document 1 discloses a binder resin containing an acrylic-modified epoxy resin and an aqueous coating material containing a rust preventive pigment. It is described that it is possible to dry at room temperature by blending a specific compound.

JP-A-2015-151511

However, just by blending a specific pigment as in Patent Document 1, sufficient coating film strength cannot be obtained, and there are cases where the adhesiveness, rust prevention, etc. are insufficient.

The present invention has been made in view of such a problem, and in an aqueous coating material containing a film-forming component and a powder component, a film-forming component having a gel fraction of 10% or more of the formed film, and a specific powder. It has been found that a water-based coating material having excellent coating strength, adhesion, rust prevention, etc. can be obtained by containing the components in a specific weight ratio, and the present invention has been completed.

That is, the present invention has the following features.
1. 1. A water-based coating material containing a film-forming component and a powder component.
The film-forming component contains an aqueous epoxy resin emulsion as a resin component, and the gel content of the formed film is 10% or more.
The powder component contains a rust preventive pigment and calcium carbonate.
50 to 300 parts by weight of the powder component is contained with respect to 100 parts by weight of the resin component.
An aqueous coating material containing 30 to 90% by weight of the calcium carbonate in the powder component.
2. 2. The aqueous epoxy resin emulsion is characterized by containing an aqueous dispersion of an epoxy ester resin. Aqueous coating material according to.
3. 3. The film-forming component is characterized by containing a curing accelerator. Or 2. Aqueous coating material according to.
4. 1. It is a one-component curing type water-based coating material. ~ 3. The water-based coating material according to any one of.

The water-based coating material of the present invention is excellent in coating film strength, adhesion, rust prevention and the like.

Hereinafter, modes for carrying out the present invention will be described.

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

The film-forming component (A) (hereinafter, also referred to as “(A) component”) used in the present invention is an aqueous epoxy resin emulsion (A1-) as a resin component (A1) (hereinafter, also referred to as “(A1) component”). It is characterized by containing 1) and having a gel fraction of 10% or more (preferably 12% or more, more preferably 15% or more) of the forming film. The upper limit 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 such a range, the coating film strength, adhesion and the like of the water-based coating material of the present invention are improved, and excellent rust prevention can be exhibited.

In the present invention, the gel fraction is such that the film-forming component (A) is applied onto a polyester film so that the film thickness after drying is 0.15 mm, and dried at 23 ° C. for 24 hours to form a film. The test piece is used as a test piece, immersed in acetone for 24 hours, and then calculated by the following formula.
Gel fraction (%) = (coating weight after immersion / coating weight before immersion) x 100

The aqueous epoxy resin emulsion (A1-1) is an aqueous dispersion of an epoxy resin obtained by dispersing and emulsifying an epoxy resin in an aqueous medium. The epoxy resin may be any of solid epoxy resin and / or liquid epoxy resin as long as it can be dispersed in an aqueous medium. For example, one or more epoxy groups are contained in the molecule, preferably one or more. A resin containing two or more can be used. Examples of such an epoxy resin include a bisphenol type epoxy resin, an alicyclic epoxy resin, a phenol novolac type epoxy resin, a polyethylene glycol type epoxy resin, an epoxidized polybutadiene resin and the like. In the present invention, a bisphenol type epoxy resin is preferable, and for example, one or more selected from bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and the like are suitable.

Further, the aqueous epoxy resin emulsion (A1-1) preferably contains an epoxy ester resin in which the epoxy group of the epoxy resin is esterified with an organic acid as the epoxy resin, and further, vinyl modification of the epoxy ester resin by vinyl modification. It is preferable to contain an epoxy ester resin. As a result, the coating film strength, adhesion, rust prevention, etc. can be sufficiently exhibited.

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

The organic acid is not particularly limited, but for example, tung oil fatty acid, flaxseed oil fatty acid, dehydrated castor oil fatty acid, castor oil fatty acid, fish oil fatty acid, saflower oil fatty acid, soybean oil fatty acid, rice bran oil fatty acid, sesame oil fatty acid, poppy oil. Dry oil fatty acids such as fatty acids, eno oil fatty acids, hemp oil fatty acids, grape kernel oil fatty acids, corn oil fatty acids, tall oil fatty acids, sunflower oil fatty acids, cotton seed oil fatty acids, walnut oil fatty acids, rubber seed oil fatty acids, hygiene 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 oleic acid, linoleic acid, linoleic acid, eleostiaic acid, ricinolic acid, etc. Saturated fatty acids such as unsaturated fatty acids, octyl acid, lauric acid, and stearic acid. These can be used alone or in combination of two or more. Usually, the drying oil fatty acid means an unsaturated fatty acid having an iodine value of 130 or more, and the semi-drying oil fatty acid means an unsaturated fatty acid having an iodine value of 100 or more and less than 130. On the other hand, the non-drying oil fatty acid usually refers to a fatty acid having an iodine value of less than 100.

In the present invention, it is preferable to use the above-mentioned dry oil fatty acid or semi-drying oil fatty acid as the organic acid, and among them, tung oil fatty acid, flaxseed oil fatty acid, dehydrated castor oil fatty acid, fish oil fatty acid, and saflower oil fatty acid having an iodine value of 100 to 200. , Soybean oil fatty acid, rice bran oil fatty acid and the like are preferably used.

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

The vinyl-modified epoxy ester resin is formed by bonding a polyvinyl group to at least a part of unsaturated groups of the epoxy ester resin, and in the presence of the epoxy ester resin, a vinyl group is used by using a radical polymerization initiator. It can be produced by radical polymerization of the contained compound. The vinyl group-containing compound is 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 selected from the monomers copolymerizable with the unsaturated group of the epoxy ester resin. For example, (meth) acrylic acid alkyl ester, aromatic monomer, and acid. It is preferable to contain a group-containing monomer and the like.

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

The aromatic monomer is a compound having a polymerizable unsaturated double bond with an aromatic ring, and specific examples thereof include styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, and vinyl. Examples thereof include naphthalene, divinylbenzene, phenyl (meth) acrylate, and benzyl (meth) acrylate. These can be used alone or in combination of two or more.

Examples of the acid group-containing monomer 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 be used as long as the effects of the present invention are not impaired. As such a vinyl group-containing compound, for example,
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, and 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 monomers such as -t-butylaminoethyl (meth) acrylate;
Glycidyl (meth) acrylate, diglycidyl fumarate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxyvinylcyclohexane, allylglycidyl ether, ε-caprolactone-modified glycidyl (meth) acrylate, β-methylglycidyl (meth) ) Epoxy group-containing monomer such as acrylate;

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, and 6-hydroxyhexyl vinyl ether; Ε caprolactone-modified hydroxyl group-containing monomer obtained by adding ε caprolactone to these hydroxyl group-containing monomers;
Isocyanate group-containing monomers such as 2-isocyanate propene, 2-isocyanate ethyl vinyl ether, 2-isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate;
Halogenated vinylidene-based monomers such as vinylidene fluoride;
Monomers having an active methylene group such as vinyl acetoacetate and 2-acetoacetoxyethyl (meth) acrylate;
Monomers having a silyl group such as vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane;
Examples thereof 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-butylperoxy2 ethylhexanoate, azobisisobutylnitrile, and dimethyl. Examples thereof include azo compounds such as azobutyrate.

The solid content 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, the initial drying property, water resistance and the like are enhanced, and a water-based coating material having excellent coating film strength and rust prevention can be obtained. In the present invention, "α to β" is synonymous with "α or more and β or less". The acid value is a value represented by the number of mg of potassium hydroxide equimolar to the acid group contained in 1 g of solid content.

For dispersing the vinyl-modified epoxy ester resin in an aqueous medium, for example, a basic compound or the like can be used. Examples of such basic compounds include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, 2-aminoethanol, 2-dimethylaminoethanol, ammonia, sodium hydroxide, potassium hydroxide, and tetramethylammonium hydro. Examples thereof include oxides, tetra-n-butylammonium hydroxides, and trimethylbenzylammonium hydroxides. These basic compounds can also be used as an aqueous solution such as aqueous ammonia. Further, as the basic compound, the aqueous coating material containing the vinyl-modified epoxy ester resin volatilizes when forming the coating film and does not remain in the coating film to form a coating film having excellent water resistance and corrosion resistance. A volatile basic compound or an aqueous solution thereof, for example, aqueous ammonia, triethylamine, 2-dimethylaminoethanol or the like is preferable.

When the epoxy resin is dispersed in an aqueous medium, an emulsifier or the like can be used if necessary. The aqueous medium is a medium mainly containing water, and if necessary, even if a water-soluble solvent such as a lower alcohol, a polyhydric alcohol, an ether compound, an ester compound, or an alkylene oxide-containing compound is mixed. Good.

As the emulsifier, for example, an anionic surfactant and a nonionic surfactant can be used alone or in combination, respectively.
Examples of the anionic surfactant include alkali metal sulfonic acid salts such as sodium dodecylbenzene sulfonate, sodium laurylnaphthalene sulfonate, and sodium stearyldiphenyl ether disulfonate; sodium lauryl sulfate, polyoxyethylene sodium lauryl ether sulfate, and polyoxyethylene. Examples thereof include sulfate ester alkali metal salts such as octylphenyl ether sodium 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 size of the resin particles of the aqueous epoxy resin emulsion (A1-1) 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). The average particle size referred to here is a value measured by a dynamic light scattering method.

The component (A1) of the present invention may contain another resin component (A1-2) (hereinafter, also referred to as "(A1-2) component") in addition to the aqueous epoxy resin emulsion (A1-1). it can. The component (A-2) is not particularly limited, but is, for example, vinyl acetate resin, polyester resin, alkyd resin, vinyl chloride resin, acrylic resin, urethane resin, acrylic silicon resin, fluororesin, or the like, or any of these. A complex system or the like can be mentioned. These can be used alone or in combination of two or more. As the aspect of the component (A-2), one or more selected from a water-soluble resin and a resin emulsion is preferable.

In the present invention, it is preferable that the component (A1) contains 60% by weight or more (more preferably 80% by weight or more, still more preferably 90% by weight or more) of the aqueous epoxy resin emulsion (A1-1). In addition, the aspect of only the above-mentioned aqueous 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 cross-linking agent (A2-2), a silane compound (A2-3), and the like. 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 “(A2-1) component”) include cobalt, manganese, barium, cerium, iron, tin, zirconium, bismuth, aluminum, strontium, and zinc. , Organic metal compounds containing metals such as barium, copper, calcium, lead and nickel (for example, octylate, naphthenate and the like) and the like 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 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 with respect to 100 parts by weight of the solid content of the component (A1). Including. In such a case, the gel fraction of the component-forming film (A) can stably satisfy the above range, and the effect of the present invention can be fully exhibited.

The cross-linking agent (A2-2) (hereinafter, also simply referred to as “(A2-2) component”) is one or more selected from, for example, a carbodiimide group, an epoxy group, an aziridine group, an oxazoline group, a hydrazide group and the like. Those containing a compound having a reactive functional group of can be used. In the present invention, as the component (A2-2), a compound having one or more reactive functional groups preferably 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. Including. In this case, the effect of the present invention can be further enhanced.

Examples of the cross-linking agent containing a carbodiimide group include JP-A-10-60272, JP-A-10-316930, JP-A-11-60667, JP-A-2016-196612, JP-A-2016-196613, and Japanese Patent Publication No. Examples thereof include those described in Kai 2018-104605, Japanese Patent Application Laid-Open No. 2019-038960, and the like.
Examples of the cross-linking agent containing an epoxy group include polyethylene glycol diglycidyl ether, polyhydroxyalkane polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like.

As a cross-linking agent containing an aziridine group, 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylenediethyleneurea, diphenylmethane-bis-4,4'-N, N '-Diethylene urea and the like can be mentioned.

Examples of the cross-linking agent containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline and the like. Examples thereof include a resin obtained by copolymerizing a polymerizable oxazoline compound with a monomer copolymerizable with the compound.

Examples of the cross-linking agent containing a hydrazide group include malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleate dihydrazide and the like.

The component (A2-2) preferably contains 0.01 to 20 parts by weight (more preferably 0.05 to 10 parts by weight) with respect to 100 parts by weight of the solid content of the component (A1). In such a case, the gel fraction of the component-forming film (A) can stably satisfy the above range, and the effect of the present invention can be fully exhibited.

The silane compound (A2-3) (hereinafter, also simply referred to as “(A2-3) component”) is not particularly limited as long as it is a compound having an alkoxysilyl group, a silanol group, or the like, and for example, a vinyl group-containing silane. Coupling agent, epoxy group-containing silane coupling agent, amino group-containing silane coupling agent, methacryl group-containing silane coupling agent, chloropropyl group-containing silane coupling agent, mercapto group-containing silane coupling agent, and alkylalkoxysilane compound. One or more selected from the above can be used.

Examples of the vinyl group-containing silane coupling agent include vinyl group-containing silane coupling agents such as vinyl trichlorosilane, vinyl trimethoxysilane, and vinyl triethoxysilane.

Examples of the epoxy group (glycidyl group) -containing silane coupling agent include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, and β-glycidoxyethyltriethoxy. 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 the amino group-containing silane coupling agent 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, 3-Dimethyl-butylidene) Proviramine and the like can be mentioned.

Examples of the methacryl group-containing silane coupling agent include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane. 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 thereof include trimethoxysilane and S- (octanoyl) mercaptopropyltriethoxysilane.

As the alkylalkoxysilane compound, alkylalkoxysilane, a hydrolyzed condensate thereof, or the like can be used. Examples of such alkylalkoxysilane compounds include tetraethoxysilane, tetramethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetrat-butoxysilane, and tetraphenoxy. 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 alkylalkoxysilanes such as silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldi Bifunctional alkylalkoxysilanes such as ethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dimethoxymethylphenylsilane, methylphenyldiethoxysilane;
And so on.

In the present invention, it is preferable to contain an alkylalkoxysilane compound as the component (A2-3). Further, in the present invention, it is preferable to include one containing a phenyl group. Examples of such (A2-3) components include phenyltrimethoxysilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenyltributoxysilane, diphenyldibutoxysilane and the like. Be done. When these are used, the strength of the formed film is increased, and the rust preventive property is further improved. Furthermore, it is possible to exert an excellent effect in improving the adhesion to the substrate and the adhesion.

The component (A2-3) preferably contains 0.01 to 20 parts by weight (more preferably 0.05 to 10 parts by weight) with respect to 100 parts by weight of the solid content of the component (A1). In such a case, the gel fraction of the component-forming film (A) can stably satisfy the above range, and the effect of the present invention can be fully exhibited.

The component (A) of the present invention contains the component (A1) as an essential component, preferably contains the component (A2) in addition to the component (A1), and the component (A2) is preferably described above (A2). -1) It contains at least one or more (more preferably two or more, still more preferably three or more) selected from the component (A2-2) and the component (A2-3).

The powder component (B) of the present invention (hereinafter, also simply referred to as “(B) component”) is a rust preventive pigment (B1) (hereinafter, also simply referred to as “(B1) component”), and calcium carbonate ( It is characterized by containing B2) (hereinafter, also simply referred to as “(B2) component”).

The rust preventive pigment (B1) is not particularly limited, and is, for example, a basic rust preventive pigment such as a lead-based rust preventive pigment, a boric acid-based rust preventive pigment, and a composite oxide-based rust preventive pigment; a chromium acid-based rust preventive pigment. , Phosphoric acid type rust preventive pigment, molybdic acid type rust preventive pigment, tungonic acid type rust preventive pigment, organic metal salt type rust preventive pigment, etc. Reducing rust preventive pigments such as pigments and phosphite / hypophosphoric acid rust preventive pigments; scaly pigments such as mica-like iron oxide and leafing type aluminum can be mentioned.
These can be used alone or in combination of two or more.

In the present invention, one selected from phosphoric acid-based rust preventive pigments, molybdic acid-based rust preventive pigments, tungsten acid-based rust preventive pigments, organic metal salt-based rust preventive pigments, and phosphorous acid / hypophosphoric acid-based rust preventive pigments. It is preferable to include the above (preferably two or more types).
Examples of the phosphoric acid-based rust preventive pigment 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 and the like. Polyphosphoric acid compounds; silicon phosphate, titanium phosphate and the like; and organic modified products and / or hydrates thereof and the like.
Examples of molybdic acid-based rust preventive pigments include molybdic compounds such as zinc molybdate, aluminum molybdenate, calcium molybdate, and barium molybate; zinc molybdate, calcium phosphate, aluminum phosphate, and phosphomolybdic acid. Phosphomolybdate compounds such as aluminum zinc; and organic modified products and / or hydrates thereof and the like can be mentioned.
Examples of the tungstic acid-based rust preventive pigment include tungstic acid compounds such as zinc tungstic acid, aluminum tungstic acid, calcium tungstic acid, and barium tungstic acid; and organic modified products and / or hydrates thereof.
Examples of the organic metal salt-based rust preventive pigment include a zinc salt of an organic nitro compound and a zinc salt of zinc butate.
Examples of the phosphorous acid / hypophosphoric acid-based rust preventive pigment include lead phosphite, zinc phosphite, magnesium phosphite, manganese phosphite, iron hypophosphite, calcium hypophosphite and the like. ..

The average particle size of the 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). The average particle size can be measured by a particle size distribution measuring device by a laser diffraction / scattering method.

The calcium carbonate (B2) is not particularly limited, and known calcium carbonate such as heavy calcium carbonate and slight calcium carbonate can be used. The average particle size of the component (B2) of the present invention is preferably 0.5 μm to 100 μm (more preferably 1 μm to 80 μm, further preferably 1.5 μm to 50 μm, and particularly preferably 2 μm to 20 μm). In such a case, excellent rust prevention can be exhibited. Furthermore, the finishability of the formed film can be improved. The average particle size can be measured by the same method as for the component (B1).

In the present invention, the content of the component (B) is 50 to 300 parts by weight (preferably 80 to 280 parts by weight, more preferably 135 to 250 parts by weight) with respect to 100 parts by weight of the solid content of the resin component (A1). ). By satisfying such a range, the strength of the coating film is improved and excellent rust prevention can be exhibited. Further, various physical characteristics (for example, crack resistance, shrinkage resistance, adhesion, etc.) of the formed film can be improved.
The content of the component (B1) is preferably 1 to 100 parts by weight (more preferably 2 to 50 parts by weight) with respect to 100 parts by weight of the solid content of the component (A1). In such a case, excellent rust prevention can be exhibited.
The content of the component (B2) is preferably 50 to 280 parts by weight (more preferably 70 to 250 parts by weight) with respect to 100 parts by weight of the solid content of the component (A1). In such a case, excellent effects can be exhibited in coating film strength and adhesion (peeling strength).

Further, in the present invention, the component (B2) is contained in the component (B) in an amount of 30 to 90% by weight (preferably 35 to 90% by weight, more preferably 40 to 88% by weight, still more preferably 50 to 86% by weight). It is characterized by including. By satisfying such a range, the coating film strength (peeling strength) and the adhesiveness are further enhanced, and excellent rust prevention can be exhibited. In addition, the component (B1) 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 effect can be fully exerted.

In the present invention, it is preferable that the component (B) contains a coloring pigment (B3), an extender pigment (B4), and the like in addition to the component (B1) and the component (B2).
Examples of the coloring pigment (B3) include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, cobalt black, copper manganese iron black, red iron oxide, molybdate orange, permanent red, and permanent carmine. , Anthraquinone Red, Perylene Red, Kinacridon Red, Yellow Iron Oxide, Titanium Yellow, First Yellow, Benzimidazolone Yellow, Cobalt Green, Phthalocyanine Green, Ultramarine, Navy Blue, Cobalt Blue, Phthalocyanine Blue, Kinacridone Violet, Dioxazine Violet, Aluminum Pigment , Pearl pigment and the like, or two or more kinds can be used.
The content of the coloring pigment (B3) is preferably 250 parts by weight or less (more preferably 1 to 250 parts by weight, still more preferably 10 to 200 parts by weight) with respect to 100 parts by weight of the solid content of the component (A1). is there.

As the extender pigment (B4), extender pigments other than the above component (B2) can be used, for example, cold water stone, white carbon, talc, kaolin, clay, porcelain clay, China clay, diatomaceous earth, barite powder, barium sulfate, sedimentation property. Examples thereof include barium sulfate, silica sand, silica stone powder, quartz powder, mica, resin beads, glass beads, hollow balloons and the like, 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) with respect to 100 parts by weight of the solid content of the component (A1). is there.

In addition to the above components, the water-based coating material of the present invention includes, for example, dispersion media such as water and solvents, aggregates, film-forming aids, plasticizers, antifreeze agents, preservatives, and fungicides. , Antibacterial agents, antifoaming agents, pigment dispersants, thickeners, antisettling agents, alignment agents, leveling agents, surface conditioners, wetting agents, pH adjusters, fibers, matting agents, UV absorbers, antioxidants , Light stabilizers, adsorbents, catalysts and the like can be mixed. By using such components in appropriate combinations, various forms of covering materials can be designed.

The aqueous coating material of the present invention can be produced by uniformly mixing these other components in addition to the above components (A) and (B), if necessary, by a conventional method, and is preferably one-component curing. A type of water-based coating material.

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). In such a range, even better rust prevention can be exhibited.
The oxygen permeability coefficient is a test piece obtained by applying a water-based coating material to a release paper so that the dry film thickness is 0.15 mm and drying at 23 ° C. for 24 hours to peel off the coating film. The oxygen permeability was measured by a gas chromatograph method according to the test method JIS K 7126. The gas transmittance 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 a metal member such as a building or a civil engineering structure. Examples of parts where such metal members are used include walls, columns, floors, beams, roofs, stairs, and the like. Further, as the coating method of the water-based coating material of the present invention, brush coating, iron coating, roller coating, spray coating, electrostatic coating, roll coater, curtain flow coater, dipping coating, electrodeposition coating and the like can be used. Rollers or brushes are suitable in terms of coating workability, coating property, and the like. The smeared amount is not particularly limited, preferably ^{0.05kg / m 2 ~0.5kg / m 2} . The number of times the water-based coating material is applied may be appropriately set depending on the condition of the base, but is preferably 1 to 2 times. The drying time of the water-based coating material is preferably 1 hour or more and 1 week or less. The drying temperature may be preferably −10 ° C. or higher and 50 ° C. or lower, more preferably −5 ° C. or higher and 40 ° C. or lower. The water-based coating material of the present invention is preferable as a room temperature curing type.

After applying the water-based coating material of the present invention, various topcoat materials can be applied. The topcoat material is not particularly limited as long as it is generally used for painting buildings and civil engineering structures, and the binder thereof is, for example, acrylic resin, polyurethane resin, epoxy resin, and fluororesin. Examples thereof include organic binders such as resins, alkyd resins and polyester resins, inorganic binders such as silicone resins, epoxysilanes, colloidal silicas and silicates, and organic-inorganic composite binders such as acrylic silicone resins.

Specific topcoat materials include, for example, weather-resistant topcoat paints for construction (JIS K5658: 2010), weather-resistant paints for steel structures (JIS K5659: 2008), glossy synthetic resin emulsion paints (JIS K5660: 2008), and the like. Fireproof paint for construction (JIS K5661: 1970), synthetic resin emulsion paint (JIS K5663: 2008), road surface marking paint (JIS K5665: 2011), multicolored pattern paint (JIS K5667: 2003), synthetic resin emulsion pattern paint (JIS) K5668: 2010), acrylic resin-based non-aqueous dispersion paint (JIS K5670: 2008), lead / chrome-free rust preventive paint (JIS K5674: 2008), high solar reflectance paint for roofs (JIS K5675: 2011), for buildings Examples thereof include floor paints (JIS K5970: 2008), building coating waterproofing materials (JIS A6021: 2011), building finishing coatings (JIS A6909: 2014), and the like. In particular, as the topcoat material of the present invention, a weatherproof topcoat for construction and a weatherproof paint for structures are suitable.

The coating method of the topcoat material is not particularly limited and can be coated by a known method, but for example, it can be coated by various methods such as brush coating, spray coating, roller coating, roll coater, and flow coater. That is, each topcoat material may be coated based on a normal process with the optimum coating specifications for each topcoat material.

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

(Manufacturing of water-based coating materials 1 to 17)
In accordance with the formulation shown in Table 1, the components (A), (B), and additives were mixed by a conventional method to produce aqueous coating materials 1 to 17.
The following raw materials were used.

(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) Rust preventive pigment (B1-1) Phosphomolybic 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) Titanium 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 carried out on the obtained water-based coating materials 1 to 20. The results are shown in Table 1.

<Coating film strength (peeling strength)>
One end (10 mm) of the steel sheet (150 × 70 × 0.8 mm) in the longitudinal direction is covered with a paper pattern, and the water-based coating material is applied at a coating amount of 120 g / m ² in a standard state (temperature 23 ° C., Specimen 1 was cured at a relative humidity of 50% for 7 days. Next, the coating film is pulled in the longitudinal direction from the coating film portion formed on the release paper, and the coating film formed on the steel plate is referred to as "a" and the easily peeled coating film is referred to as "d" 4 Evaluation was performed in stages (a>b>c> d).

<Rust prevention test>
Specimen ² is a steel sheet (150 x 70 x 0.8 mm) coated with a water-based coating material at a coating rate of 120 g / m ² and cured under standard conditions (temperature 23 ° C., relative humidity 50%) for 7 days. And said. The obtained test body 2 was subjected to a salt spray resistance test and evaluated after 50 hours and 100 hours. The results are shown in Table 2. In the table, the rust preventive property 1 indicates the evaluation after 50 hours, and the rust preventive property 2 indicates the evaluation after 100 hours. In addition, this evaluation was carried out in four stages (a>b>c> d) in which the one in which no rust was observed was designated as "a" and the one in which rust was significantly generated was designated as "d". ..

In Examples 1 to 15 (water-based coating materials 1 to 15), a forming film having good coating film strength, adhesion, and rust prevention was obtained. In particular, in Examples 5 to 8 and 14 (water-based coating materials 5 to 8 and 14), excellent rust prevention properties could be exhibited.

Next, the following evaluations were carried out for the water-based coating materials 5 to 8 and 14.
A water-based coating material is applied to a steel plate (150 x 70 x 0.8 mm) at a coating amount of 120 g / m ² , and after curing under standard conditions (temperature 23 ° C., relative humidity 50%) for 1 day, weather resistance for construction The test piece 3 was prepared by applying a weathering topcoat paint (urethane resin-based 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 body 3 was confirmed. As a result, the water-based coating materials 5 to 8 had an excellent glossy finish. Compared with this, the water-based coating material 14 had a slightly low gloss finish.

Claims (4)

A water-based coating material containing a film-forming component and a powder component.
The film-forming component contains an aqueous epoxy resin emulsion as a resin component, and the gel content of the formed film is 10% or more.
The powder component contains a rust preventive pigment and calcium carbonate.
50 to 300 parts by weight of the powder component is contained with respect to 100 parts by weight of the resin component.
An aqueous coating material containing 30 to 90% by weight of the calcium carbonate in the powder component. The aqueous coating material according to claim 1, wherein the aqueous epoxy resin emulsion contains an aqueous dispersion of an epoxy ester resin. The aqueous coating material according to claim 1 or 2, wherein the film-forming component contains a curing accelerator. The water-based coating material according to any one of claims 1 to 3, wherein the water-based coating material is a one-component curing type.