JP2019183159A - Aqueous coating material - Google Patents

Abstract

To provide an aqueous coating material exhibiting excellent adhesiveness to various substrates and coated films.SOLUTION: The aqueous coating material contains an aqueous resin (A) and a silane compound (B), and having pH of 4 to 11, and the silane compound (B) of 1 to 100 pts.wt. based on 100 pts.wt. of a resin solid component of the aqueous resin (A), in which the silane compound (B) contains an amino group-containing silane compound (M) and a silane compound (N) other than the amino group-containing silane compound, and a weight ratio is (M)/(N)>1.2.SELECTED DRAWING: None

Description

  The present invention relates to a novel aqueous coating material.

In coating on the interior and exterior wall surfaces and floor surfaces of buildings, various undercoat materials are selected and used in consideration of adhesion to the base material. Conventionally, such a primer is mainly a solvent-based one, but recently, a water-based primer is being adopted in consideration of the environment, safety, and the like. For example, Patent Document 1 describes an aqueous primer containing a self-emulsifying cationic aqueous dispersion having a hydroxyl group and an amino group and an epoxy group-containing organosilane.

However, the water-based primer may be inferior in adhesion as compared with the solvent-based primer. Particularly in recent years, exterior coating materials used for exterior wall surfaces have been provided with various coating films having functionality such as high weather resistance and contamination resistance. In such coating film refurbishment, it is difficult to obtain sufficient adhesion with a water-based primer, and solvent-based primer is often used at present.

JP 2002-256221 A

  This invention is made | formed in view of such a problem, and it aims at obtaining the water-based coating | covering material which can ensure sufficient adhesiveness with respect to a various base material and a coating film. .

  As a result of intensive studies on such problems, the inventors of the present invention include an aqueous resin (A) and a silane compound (B), the pH is in a specific range, and the silane compound (B) is an amino group-containing silane compound. An aqueous coating material containing (M) and (N) other than the amino group-containing silane compound at a specific weight ratio was found, and the present invention was completed.

That is, the present invention has the following characteristics.
1. Including aqueous resin (A) and silane compound (B), pH is 4-11,
1-100 parts by weight of the silane compound (B) is included with respect to 100 parts by weight of the resin solid content of the aqueous resin (A),
The silane compound (B) includes an amino group-containing silane compound (M) and (N) other than the amino group-containing silane compound, and the weight ratio thereof is (M) / (N)> 1.2. A characteristic water-based coating material.

  The aqueous coating material of the present invention exhibits excellent adhesion to various substrates and coating films.

  The aqueous coating material of the present invention includes an aqueous resin (A) and a silane compound (B), and has a pH of 4 to 11.

The aqueous resin (A) of the present invention (hereinafter also simply referred to as “component (A)”) is not particularly limited as long as it can be dissolved or dispersed in an aqueous medium, and a known resin can be used. Examples of such resin include vinyl acetate resin, vinyl chloride resin, acrylic resin, acrylic styrene resin, acrylic urethane resin, acrylic silicon resin, epoxy resin, fluororesin, and urethane resin. These can be used alone or in combination of two or more. In the present invention, one or more selected from acrylic resins, acrylic styrene resins, and epoxy resins are particularly suitable. Furthermore, as the component (A), a water-dispersible resin (resin emulsion) in which the resin component is dispersed in an aqueous medium is suitable, and in particular, one type selected from an acrylic resin emulsion, an acrylic styrene resin emulsion, and an epoxy resin emulsion. It is preferable to include the above. The aqueous medium is a medium mainly containing water, and if necessary, for example, a water-soluble solvent such as a lower alcohol, a polyhydric alcohol, an ether compound, an ester compound, an alkylene oxide-containing compound may be mixed. Good.

The acrylic resin (A1) of the component (A) (hereinafter also simply referred to as “component (A1)”) is one in which (meth) acrylic acid alkyl ester is the main component of the resin skeleton. In addition, the acrylic styrene resin (A2) (hereinafter also referred to simply as “(A2) component”), which is the component (A), has a (meth) acrylic acid alkyl ester and an aromatic monomer as main components of the resin skeleton. It is. 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. A monomer is a general term for compounds having a polymerizable unsaturated double bond.

 Specific examples of the (meth) acrylic acid alkyl ester in the components (A1) and (A2) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, 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, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

The aromatic monomer in the component (A2) is a compound having an aromatic ring and a polymerizable unsaturated double bond. Specific examples thereof include styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chloro. Examples include styrene, vinyl anisole, vinyl naphthalene, divinyl benzene, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These can be used alone or in combination of two or more. The component (A1) does not include these aromatic monomers.

Furthermore, it is preferable that the component (A1) and the component (A2) include an epoxy group-containing monomer in addition to the (meth) acrylic acid alkyl ester and / or the aromatic monomer. Thereby, the adhesiveness with respect to various base materials and a coating film can be improved. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, diglycidyl fumarate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxyvinylcyclohexane, allyl glycidyl ether, and ε-caprolactone-modified glycidyl (meta ) Acrylate, β-methylglycidyl (meth) acrylate, and the like. These can be used alone or in combination of two or more. The content of the epoxy group-containing monomer is preferably 0.5 to 50% by weight (more preferably 1 to 30% by weight) in all monomers constituting the component (A).

Furthermore, in the above components (A1) and (A2), other monomers copolymerizable with the above components can be used as long as the effects of the present invention are not impaired. As such a monomer, 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, vinyl butyl ketone;

Carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, salicylic acid;
Aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, N-methylaminoethyl (meth) acrylate, N An amino group-containing monomer such as t-butylaminoethyl (meth) acrylate;
Hydroxyl group-containing monomers such as hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate;
Vinylidene halide monomers such as vinylidene fluoride;
Examples thereof include ethylene, propylene, isoprene, butadiene, vinyl ether, vinyl ketone, and silicone macromer.

The component (A1) and the component (A2) can be produced by emulsion polymerization of a monomer group obtained by appropriately mixing the monomers. As the polymerization method, a known method may be employed, and soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, etc. may be employed in addition to ordinary emulsion polymerization. During the polymerization, an emulsifier, an initiator, a dispersant, a polymerization inhibitor, a polymerization inhibitor, a buffer, a chain transfer agent, and the like can be used.

As the emulsifier, various surfactants usable in emulsion polymerization can be used, and these may be reactive types (reactive surfactants) having a polymerizable unsaturated double bond. As the emulsifier, preferably, an anionic surfactant and a nonionic surfactant can be used alone or in combination.
Examples of anionic surfactants include sulfonic acid alkali metal salts such as sodium dodecylbenzene sulfonate, sodium lauryl naphthalene sulfonate, sodium stearyl diphenyl ether disulfonate; sodium lauryl sulfate, polyoxyethylene sodium lauryl ether sulfate, polyoxyethylene Examples thereof include sulfate ester alkali metal salts such as sodium octylphenyl ether sulfate.
Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and oxyethylene / oxypropylene block copolymer.
The blending amount of the emulsifier is preferably 0.1 to 15% by weight (more preferably 0.1 to 10% by weight, still more preferably 0) based on the resin solid content of the component (A1) and the component (A2). 0.5 to 5% by weight). In the present invention, “α to β” has the same meaning as “α to β”.

  The glass transition temperature (hereinafter simply referred to as “Tg”) of the component (A1) and the component (A2) can be adjusted by selecting the type of monomer, the mixing ratio, and the like. The glass transition temperature may be appropriately set in consideration of final required performance and the like, but is preferably about −50 to 80 ° C. (more preferably about −40 to 60 ° C.). The glass transition temperature can be obtained by the Fox calculation formula.

Although the average particle diameter of the said (A1) component and (A2) component is not specifically limited, Preferably it is 300 nm or less (more preferably 20-120 nm, More preferably, it is 30-100 nm). When the average particle size is within such a range, advantageous effects can be obtained in impregnation reinforcement, sealing properties, whitening resistance, and the like. The average particle diameter referred to here is a value measured by a dynamic light scattering method.

The epoxy resin (A3) (hereinafter also referred to simply as “component (A3)”) as the component (A) is not particularly limited as long as it can be dissolved or dispersed in an aqueous medium, and is a solid epoxy resin and / or liquid. Any type epoxy resin may be used. As such an epoxy resin, for example, a resin containing one or more, preferably two or more epoxy groups in the molecule can be used. For example, an aromatic epoxy resin, an aliphatic epoxy resin, an alicyclic epoxy resin, Polybutadiene resin having an epoxy group, polyurethane resin having an epoxy group, and the like can be given. In the present invention, aromatic epoxy resins are preferable, and examples thereof include bisphenol A type epoxy resins, bisphenol AD type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins and the like. One or more selected from bisphenol AD type epoxy resins and bisphenol F type epoxy resins are preferred. Further, the epoxy resin may be one having an increased molecular weight as required, a fatty acid-modified epoxy resin obtained by reacting a fatty acid, or an amine-added epoxy resin (amine) obtained by addition reaction of an amino group-containing compound. It may be obtained by making the modified epoxy resin) aqueous. These can be used alone or in combination of two or more. The solid epoxy resin is solid at normal temperature (23 ° C.), and the liquid epoxy resin is liquid at normal temperature (23 ° C.).

In this invention, the aspect which contains solid-type epoxy resin as an essential component as said (A3) component is preferable. As such an aspect, the aspect containing only a solid type epoxy resin, the aspect containing a solid type epoxy resin and a liquid type epoxy resin are mentioned. Thereby, the effect of this invention can fully be acquired. The mixing ratio (solid weight ratio) of the solid epoxy resin and the liquid epoxy resin is preferably 100: 0 to 5:95 (more preferably 90:10 to 10:90).

The method for preparing the epoxy resin aqueous dispersion (epoxy resin emulsion) is not particularly limited. For example, a solid epoxy resin and / or a liquid epoxy resin and, if necessary, an emulsifier are mixed to obtain a resin solution. And a method of emulsifying by mixing with an aqueous medium (including an emulsifier if necessary). In addition, it can also heat as needed at the time of said preparation. In the present invention, when a solid epoxy resin and a liquid epoxy resin are used in combination, it is preferable to adjust the respective aqueous dispersions of the solid epoxy resin and the liquid epoxy resin and then use them after mixing. The resin solid content of the epoxy resin aqueous dispersion is not particularly limited, but is preferably 10 to 80% by weight (more preferably 20 to 70% by weight).

  As said emulsifier, the same thing as said (A1) component and said (A2) component can be used. The amount of the emulsifier is preferably 0.1 to 15% by weight (more preferably 0.1 to 10% by weight, still more preferably 0.5 to 5% by weight) based on the resin solid content of the component (A3). Is within the range.

Although the average particle diameter of the epoxy resin aqueous dispersion of the component (A3) of the present invention is not particularly limited, it is preferably 100 to 1000 nm (more preferably 150 to 900 nm, still more preferably 200 to 800 nm). When the average particle diameter is within such a range, advantageous effects can be obtained in sealing properties, whiteness resistance, whitening resistance, and the like. The average particle diameter referred to here is a value measured by a dynamic light scattering method.

In the present invention, it is preferable that the component (A1), the component (A2), and the component (A3) are mixed and contained as the component (A). In this case, an embodiment including the component (A1) and / or the component (A2) and the component (A3) is preferable.
-Aspect containing the component (A1) and the component (A3),
-Aspect containing the component (A2) and the component (A3),
-The aspect containing said (A1) component and said (A2) component, and said (A3) component,
Etc. The mixing ratio in this case is preferably 1 to 80% by weight (more preferably 3 to 70% by weight) of the component (A1) and / or the component (A2) in the component (A) (weight solid content). The component (A3) is preferably 20 to 99% by weight (more preferably 30 to 97% by weight, still more preferably 40 to 95% by weight). In such a case, excellent adhesion to various substrates and coating films can be exhibited, and in particular, adhesion to existing coating films and top coating films can be enhanced.

  The silane compound (B) of the present invention (hereinafter also simply referred to as “(B) component”) is composed of an amino group-containing silane compound (M) (hereinafter also simply referred to as “(M) component”) and an amino group-containing silane. A silane compound (N) other than the compound (M) (hereinafter also simply referred to as “(N) component”).

  As the amino group-containing silane compound (M) of the present invention, a compound having an amino group and an alkoxysilyl group or a compound having an amino group and a cyclic siloxane can be used. These can be used alone or in combination of two or more.

Examples of the compound having an amino group and an alkoxysilyl group include an amino group-containing silane coupling agent, a hydrolyzed oligomer thereof, a polymer having an alkoxysilyl group and an amino group, and the like. Specifically, as an amino group-containing silane coupling agent, for example,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl)- γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ- Aminopropylmethyldiethoxysilane, N-β (aminoethyl) -γ-aminopropyltriisopropoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-anilinopropyltri Methoxysilane, γ-ureidopropi Trimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-β (aminoethyl) -8-aminooctyltrimethoxysilane, γ-triethoxysilyl -N- (1,3-dimethyl-butylidene) propylamine and the like.

As the hydrolysis oligomer of the amino group-containing silane coupling agent, those having an alkoxysilyl group and an amino group,
As such a component (M), it is also possible to use a component in which part or all of the alkoxysilyl group is in a silanol group state.

In particular, in the present invention, an amino group-containing silane coupling agent is suitable as the component (M). For example, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl)- One or more selected from γ-aminopropylmethyldimethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane are preferred. When these are used, the adhesion development property to a base material etc. improve.

  In the aqueous coating material of the present invention, the component (M) is preferably 1 to 75 parts by weight (more preferably 2 to 60 parts by weight, further preferably 4 to 50 parts by weight) based on the resin solid content of the component (A). Part) contained. In this case, the effect of the present invention can be sufficiently obtained.

  As the silane compound (N) other than the amino group-containing silane compound (M) of the present invention (hereinafter also simply referred to as “(N) component”), any compound having an alkoxysilyl group may be used. A glycidyl group-containing silane compound (N1), an alkylalkoxysilane compound (N2), or the like is preferable.

As the glycidyl group-containing silane compound (N1), a compound having a glycidyl group (epoxy group) and an alkoxysilyl group, a compound having a glycidyl group and a cyclic siloxane, or the like can be used. These can be used alone or in combination of two or more.

Examples of the compound having a glycidyl group (epoxy group) and an alkoxysilyl group include a glycidyl group-containing silane coupling agent and a hydrolyzed oligomer thereof. Specifically, as the glycidyl group-containing silane coupling agent, for example, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyl (ethyl) dimethoxysilane, β-3,4-epoxy Cyclohexylethyltrimethoxysilane, β-3,4-epoxycyclohexylethyltriethoxysilane,
Examples include 8-glycidoxyoctyltrimethoxysilane, 8-glycidoxyoctylmethyldimethoxysilane, and 8-glycidoxyoctylmethyldiethoxysilane.

The hydrolyzed oligomer of the glycidyl group-containing silane coupling agent has an alkoxysilyl group and a glycidyl group, and preferably has an alkoxy group amount of 10 to 80 wt% (more preferably 20 to 75 wt%) and an epoxy equivalent. Examples thereof include 200 to 950 (more preferably 300 to 900). As such (N1) component, those having two or more kinds of alkoxysilyl groups, or those in which a part or all of the alkoxysilyl groups are in a silanol group can be used.

  Examples of the compound having a glycidyl group and a cyclic siloxane include silicone oligomers having only a glycidyl group as a reactive functional group, and preferably those having an epoxy equivalent of 100 to 500 (more preferably 150 to 400).

In particular, in the present invention, a glycidyl group-containing silane coupling agent is suitable as the component (N1). For example, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β-glycidoxyethyltri Methoxysilane, β-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-3,4-epoxycyclohexylethyltrimethoxysilane, β-3, One or more selected from 4-epoxycyclohexylethyltriethoxysilane is preferable, and one or more selected from β-3,4-epoxycyclohexylethyltrimethoxysilane and β-3,4-epoxycyclohexylethyltriethoxysilane The aspect containing is more suitable. When these are used, the adhesion development and adhesion to the substrate are further improved. Furthermore, the stability and pot life of the aqueous coating material can be increased.

As the alkylalkoxysilane compound (N2) (hereinafter, also simply referred to as “(N2) component”), alkylalkoxysilane, a hydrolysis condensate thereof, and the like can be used. These can be used alone or in combination of two or more. By using such (N2) component, the adhesion to the substrate can be further enhanced.

Examples of such (N2) component include tetraethoxysilane, tetramethoxysilane, tetra n-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, and phenyltributoxysilane Down like;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldi Bifunctional alkylalkoxysilanes such as ethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dimethoxymethylphenylsilane, methylphenyldiethoxysilane;
Etc. These may be used alone or in combination of two or more.

In the present invention, it is preferable to include a trifunctional alkylalkoxysilane and / or a bifunctional alkylalkoxysilane as the (N2) component. Furthermore, it is preferable to include those containing a phenyl group. Examples of such (N2) component include phenyltrimethoxysilane, dimethoxymethylphenylsilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, phenyltributoxysilane, and diphenyldibutoxysilane. When these are used, the sclerosis | hardenability of a formation film increases, and adhesion development to a base material and a coating film and adhesiveness improve further. In particular, it is possible to exert excellent effects in improving adhesion development and adhesion to a substrate having an existing coating film.

  The aqueous coating material of the present invention preferably contains 1 to 25 parts by weight (more preferably 2 to 20 parts by weight) of the component (N) with respect to the resin solid content of the component (A). In this case, the effect of the present invention can be sufficiently obtained.

In the present invention, the component (B) is such that the weight ratio of the content of the component (M) to the component (N) is (M) / (N)> 1.2 (more preferably (M) / ( N) is 1.5 to 8, more preferably 1.8 to 7.5). If it is such a ratio, sufficient effect in adhesiveness can be acquired. Furthermore, the stability and pot life of the water-based coating material can be ensured.

The component (B) (total amount of the component (M) and the component (N)) is 1 to 100 parts by weight (preferably 5 to 100) with respect to 100 parts by weight of the resin solid content of the component (A). Parts by weight, more preferably 10 to 75 parts by weight). In such a range, the stability of the water-based coating material and the pot life can be ensured, and sufficient adhesion can be obtained.

Furthermore, the aqueous coating material of the present invention can contain a crosslinking agent (curing agent) having crosslinking reactivity with the component (A). In this case, the strength, water resistance, weather resistance, adhesion and the like of the coating can be increased. Such crosslinking reactivity includes, for example, hydroxyl group and isocyanate group, carbonyl group and hydrazide group, epoxy group and amino group, aldo group and semicarbazide group, keto group and semicarbazide group, alkoxyl group, carboxyl group and metal ion, carboxyl group It can be imparted by combining a reactive functional group such as a group and a carbodiimide group, a carboxyl group and an epoxy group, a carboxyl group and an aziridine group, a carboxyl group and an oxazoline group. These may be one type or two or more types. Among these, it is preferable to include a crosslinking agent that exhibits an amino group crosslinking reaction with an epoxy group.

Specifically, it is preferable to include an amino group-containing resin (C) (hereinafter also simply referred to as “component (C)”) as a crosslinking agent containing an amino group. The component (C) reacts with the component (A) (mainly the component (A3)) to enhance the curability of the film. As such a component (C), for example, a polyamine resin containing two or more amino groups in one molecule can be used. For example, an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, a heterocyclic amine, and these Examples thereof include modified polyamine resins obtained by modifying amino groups of polyamine resins. For the modification of the polyamine resin, a known method can be used, and examples thereof include amidation of an amino group, Mannich reaction between an amino group and a carbonyl compound, and addition reaction between an amino group and an epoxy group. As the component (C), aliphatic polyamides, alicyclic polyamides, aromatic polyamides, aliphatic polyamide amines, alicyclic polyamide amines, aromatic polyamide amines and the like can also be used. These can be used alone or in combination of two or more. Further, the aspect of the component (C) is not particularly limited, but is preferably dissolved or dispersed in an aqueous medium, and particularly preferably a water-dispersed resin.

  The mixing ratio of the component (C) is preferably 0.1 to 50 parts by weight (more preferably 1 to 30 parts by weight, still more preferably 1.5 to 20 parts by weight based on 100 parts by weight of the solid content of the component (A). Parts by weight). In such a case, adhesion development and adhesion to the substrate and the coating film are improved. Furthermore, the stability and pot life of the aqueous coating material can be increased.

The aspect of the aqueous coating material of the present invention is not particularly limited as long as it includes the component (A) and the component (B).
-(A) component, 1 component type containing (B) component,
-A two-component type comprising a main agent containing (A) component and a curing agent containing (B) component,
-A two-component type comprising a main component containing (A) component, (N) component, and a curing agent containing (M) component,
A two-component type comprising a main component containing (A) component and (M) component and a curing agent containing (N) component,
A three-component type comprising (A) component, (M) component, and (N) component,
Etc. In addition, when coexisting components that can react with each other, for example, a prescription such as masking or blocking can be employed. In this invention, it is preferable to set it as the 2 liquid type aqueous coating material which consists of the main ingredient containing the said (A) component and (N) component, and the hardening | curing agent containing (M) component.

Moreover, when a crosslinking agent (the above component (C) or the like) is included, it can be added to either the main agent side, the curing agent side, or both, but in the present invention, it is preferably added to the curing agent. Thereby, the stability of the aqueous coating material can be ensured, and the adhesion can be further improved.

Furthermore, the aqueous coating material of the present invention can be mixed with a catalyst (P) (hereinafter also simply referred to as “component (P)”). The component (P) is, for example, for promoting hydrolysis / condensation of alkoxysilyl groups in the aqueous coating material or reaction between glycidyl groups (epoxy groups) and amino groups. In particular, the adhesion to a substrate having an existing coating film can be further enhanced.

Examples of the component (P) include various aromatic carboxylic acids such as benzoic acid, salicylic acid, trihydroxybenzoic acid, phthalic acid, cinnamic acid, and benzenehexacarboxylic acid; trimethylamine, ethyldimethylamine, propyldimethylamine, N , N′-dimethylpiperazine, pyridine, picoline, 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), benzyldimethylamine, 2- (dimethylaminomethyl) phenol (DMP-10), 2, Tertiary amines such as 4,6-tris (dimethylaminomethyl) phenol (DMP-30), hydroxylamines such as hydroxylamine and phenoxyamine, imidazole, 1-methylimidazole, 2-methylimidazole, 4 (5) -Methylimidazole, 2-ethyl-4methyl Components (B) such as imidazoles such as imidazole, 2-ethylimidazole and 2-phenylimidazole, amines other than the component (M); phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak And phenols such as dicyclopentadiene cresol, and organometallic compounds such as tin octylate, dibutyltin dilaurate, dibutyltin diacetate, organotitanate, and sodium acetate. These can be used alone or in combination of two or more. Among these (P) components, organic tin compounds such as tin octylate, dibutyltin dilaurate, and dibutyltin diacetate are particularly preferably used.

  The mixing amount of the component (P) is 0.01 to 10 parts by weight (preferably 0.02 to 8 parts by weight) with respect to 100 parts by weight of the component (A) (solid content). In such a range, the effect of the present invention can be enhanced.

When the component (P) is included, it may be blended at the time of mixing each component. For example, it may be blended in advance in either the main agent or the curing agent, or may be blended at the time of mixing the main agent and the curing agent. In this invention, it is preferable to mix | blend previously with the main ingredient side.

In the aqueous coating material of the present invention, in addition to the above-described components, if necessary, a color pigment, an extender pigment, a rust preventive pigment, a pH adjuster, a plasticizer, an antiseptic agent, an antifungal agent, an antialgae agent, an antifoaming agent, Leveling agent, dispersant, anti-settling agent, anti-sagging agent, thickener (thixotropic regulator), film-forming aid, matting agent, curing accelerator, adhesion promoter, UV absorber, light stabilizer, etc. Can be mixed as long as the effects of the present invention are not inhibited.

The pH of the aqueous coating material of the present invention is 4 to 11 (more preferably 4.5 to 10.5). Thereby, sufficient effect in adhesion can be exhibited. Further, the stability and adhesion of the aqueous coating material can be further improved by adjusting to alkaline (preferably pH 8.5 or more) with a pH adjuster. In addition, when the aqueous coating material of this invention is the said 2 liquid type, the pH of a main ingredient should just satisfy | fill the above.

The aqueous coating material of the present invention preferably has a solid content of 5 to 60% by weight (more preferably 6 to 50% by weight, still more preferably 7 to 45% by weight). The solid content can be adjusted by mixing the aqueous medium. In such a range, the coating workability is excellent, and the adhesion to various base materials and coating films can be further improved.

  The water-based coating material of the present invention is suitably used as an undercoat material for coating on inner and outer wall surfaces and floor surfaces. For example, mortar, concrete, ceramic siding board, ceramic siding board, metal siding board, extrusion molding board, slate board, calcium silicate board, ALC board, metal, wood, glass, ceramics, synthetic resin, etc. Alternatively, it is suitably used as a primer for application to a substrate such as a wide variety of existing coating films formed on such a substrate (the surface of the substrate). In addition, as the shape of such a base (base material or existing coating film), smooth (flat), various uneven patterns (for example, stone tone, brick / tile tone, wood tone, border tone, painted wall tone, And the like having a spraying tone). Furthermore, the present invention can be applied to a base including a sealing joint.

In particular, the water-based coating material of the present invention is suitable as an undercoat material for repairing a base, and for example, can be suitably applied as an undercoat material for repairing a siding board provided with an existing coating film.

The existing coatings are various coatings that have already been applied on the above-mentioned base material by on-site coating or factory coating (line coating). For example, organic coatings, inorganic coatings, organic-inorganic composite coatings And at least one coating film selected from the above. In addition, as the existing coating film, a colored coating film (enamel-based coating film, printing coating film, etc.), a clear coating film, or a laminated coating film thereof can be mentioned, and various coating materials are applied and cured on a substrate. It is the formed coating film. Such a coating material may be any one of a room temperature drying type, a room temperature curing type, a bake curing type, an ultraviolet (UV) curing type, an electron beam curing type, and the like.

  Examples of such a binder for the coating material include organic binders such as acrylic resin, polyurethane resin, epoxy resin, fluororesin, alkyd resin, and polyester resin, or silicon resin, alkoxysilane, colloidal silica, silicate, and the like. Inorganic binders, and organic-inorganic composite binders such as acrylic silicon resin.

In the present invention, in particular, the existing coating film includes an inorganic coating film (a coating film including the inorganic binder), an organic-inorganic composite coating film (a coating film including the organic-inorganic composite binding material), a fluororesin coating film (the fluorine film). It is suitable when it is at least one selected from a coating film containing a resin, and the like, and can be suitably applied to these clear coating films. Such an existing coating film may contain a photocatalytic titanium oxide or the like.

Specific coating materials include, for example, a weather-resistant top coat for construction (JIS K5658: 2010), a weather-resistant paint for steel structures (JIS K5659: 2008), a glossy synthetic resin emulsion paint (JIS K5660: 2008), Fireproof paint for construction (JIS K5661: 1970), synthetic resin emulsion paint (JIS K5663: 2008), road marking paint (JIS K5665: 2011), multicolored paint (JIS K5667: 2003), synthetic resin emulsion paint (JIS) K5668: 2010), acrylic resin-based non-water-dispersed paint (JIS K5670: 2008), lead / chromium-free anticorrosive paint (JIS K5674: 2008), high solar reflectance paint for roofs (JIS K5675: 2011), for buildings Examples include floor paint (JIS K5970: 2008), architectural waterproofing coating material (JIS A6021: 2011), and finishing coating material for construction (JIS A6909: 2014).

In the coating of the aqueous coating material of the present invention, for example, various methods such as brush coating, roller coating, and spray coating can be employed. Moreover, when painting in a factory, it can also paint using a roll coater, a flow coater, etc. besides the above.

The coating amount of the aqueous coating material is preferably about 0.05 to 0.5 kg / m ² (more preferably 0.07 to 0.3 kg / m ² ). The number of application of the aqueous coating material may be appropriately set depending on the state of the base, but is preferably 1 to 2 times. The drying time of the aqueous coating material is preferably 1 hour or more and 1 week or less. The drying temperature is preferably −10 ° C. or more and 50 ° C. or less, more preferably −5 ° C. or more and 40 ° C. or less. The aqueous coating material of the present invention is preferable as a room temperature curing type.

  The coating film formed by the aqueous coating material of the present invention has excellent adhesion to a wide variety of top coating materials. The top coating material is not particularly limited as long as it is generally used for building coating. Examples of the binding material include acrylic resin, polyurethane resin, epoxy resin, fluororesin, and alkyd resin. And organic binders such as polyester resin, inorganic binders such as silicon resin, alkoxysilane, colloidal silica, and silicate, and organic-inorganic composite binders such as acrylic silicon resin. In particular, in the present invention, it is possible to sufficiently exhibit adhesion with a top coating material containing one or more selected from the organic binder and the organic-inorganic composite binder.

Specific examples of the top coat material include, for example, a weather-resistant top coat for construction (JIS K5658: 2010), a weather-resistant paint for steel structures (JIS K5659: 2008), a glossy synthetic resin emulsion paint (JIS K5660: 2008), Fireproof paint for construction (JIS K5661: 1970), synthetic resin emulsion paint (JIS K5663: 2008), road marking paint (JIS K5665: 2011), multicolored paint (JIS K5667: 2003), synthetic resin emulsion paint (JIS) K5668: 2010), acrylic resin-based non-water-dispersed paint (JIS K5670: 2008), lead / chromium-free anticorrosive paint (JIS K5674: 2008), high solar reflectance paint for roofs (JIS K5675: 2011), for buildings Floor paint ( JIS K5970: 2008), architectural coating waterproofing material (JIS A6021: 2011), architectural finishing coating material (JIS A6909: 2014), and the like.

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

Examples and comparative examples are shown below to clarify the features of the present invention.
(Production of aqueous coating materials 1 to 25)
In accordance with the formulation shown in Table 1, (A) component, (N) component, and additives are mixed by a conventional method, and a pH adjuster (ammonia water) is further mixed so that the pH shown in Table 1 is obtained. Prepared. A mixture of the (M) component and the (C) component was used as a curing agent.
In addition, the following were used as a raw material.

(A) Water-dispersible resin (A1-1) Acrylic resin emulsion [methyl methacrylate / cyclohexyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer, solid content: 50% by weight]
(A2-1) Acrylic styrene resin emulsion [styrene / n-butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid copolymer, solid content: 50% by weight]
(A2-2) Epoxy group-containing acrylic resin emulsion [styrene / 2-ethylhexyl acrylate / glycidyl methacrylate copolymer, solid content: 33 wt%, glycidyl methacrylate content: 9 wt%]
(A3-1) Aqueous epoxy resin [Bisphenol A type epoxy resin (solid type) aqueous dispersion, solid content 46 wt%]

(B) Silane compound [(M) amino group-containing silane compound, (N1) glycidyl group-containing silane compound, (N2) alkylalkoxysilane compound]
(M-1) N-β (aminoethyl) -γ-aminopropyltrimethoxysilane (M-2) N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane (N1-1) γ-glycidoxy Propyltrimethoxysilane (N1-2) γ-glycidoxypropylmethyldimethoxysilane (N1-3) β-3,4-epoxycyclohexylethyltrimethoxysilane (N2-1) phenyltrimethoxysilane (N2-2) dimethoxy Methylphenylsilane (C) amino group-containing resin [modified aliphatic polyamine aqueous dispersion, solid content 60 wt%]
(P) Catalyst [Organic tin compound dispersion, solid content: 10% by weight]
・ Additives: Antifoaming agents, thickeners, film-forming aids, etc.

(Examples 1-20, Comparative Examples 1-5)
<Pot life>
After mixing the main agent and curing agent at the mixing ratio shown in Table 1, the time until fluidity was lost was measured. The evaluation criteria are as follows. The results are shown in Table 1.
AA: 360 minutes or more A: 240 minutes or more and less than 360 minutes B: 120 minutes or more and less than 240 minutes C: 30 minutes or more and less than 120 minutes D: Less than 30 minutes

<Evaluation 1>
(Test specimen production 1)
An aqueous coating material obtained by mixing the main agent and the curing agent at a mixing ratio shown in Table 1 on a siding board on which an inorganic clear coating film was formed as an existing coating film was applied in an amount of 0.1 kg / m ² . It is applied immediately after mixing, dried in a standard state (temperature 23 ° C., relative humidity 50%) for 4 hours, and then an aqueous top coat (acrylic silicone resin emulsion paint) is applied in an amount of 0.1 kg / m ^2. Specimen [I] was applied so that it was dried in a 50 ° C. environment for 1 day.
The produced test specimen [I] was evaluated for adhesion by a cross-cut tape method according to JIS K 5600-5-6. The evaluation criteria are as follows.
A: Defect area is less than 5% A: Defect area is 5% or more and less than 10% B: Defect area is 10% or more and less than 25% C: Defect area is 25% or more and less than 50% D: Defect area Is over 50%

Next, the following specimens [II], [III], and [IV] were prepared, and the adhesion was evaluated in the same manner as the specimen [I].
(Test specimen production 2)
An aqueous coating material obtained by mixing the main agent and the curing agent at a mixing ratio shown in Table 1 on a siding board on which an inorganic clear coating film was formed as an existing coating film was applied in an amount of 0.1 kg / m ² . It is applied immediately after mixing, dried in a standard state (temperature 23 ° C., relative humidity 50%) for 4 hours, and then an aqueous top coat (acrylic silicone resin emulsion paint) is applied in an amount of 0.1 kg / m ^2. A test specimen [II] dried for 1 day and a test specimen [III] dried for 4 days and a specimen [IV] dried for 7 days in a standard state were prepared. The results are shown in Table 1.

The aqueous coating materials 1 to 7 and 12 to 20 (Examples 1 to 7 and 12 to 20) had excellent adhesion to the base material and the top coating material. Therefore, the following test bodies [V] were prepared for the aqueous coating materials 1 to 7 and 12 to 20, and the adhesion was evaluated in the same manner as the test body [I].
(Test specimen production 3)
An aqueous coating material obtained by mixing the main agent and the curing agent at a mixing ratio shown in Table 1 on a siding board on which an inorganic clear coating film was formed as an existing coating film was applied in an amount of 0.1 kg / m ² . So that it is applied immediately after mixing, dried in an environment of 50 ° C. for 7 days, and then an aqueous top coating material (acrylic silicone resin emulsion paint) is applied to a coating amount of 0.1 kg / m ² , A test specimen [V] dried for one day in a standard state was prepared. The results are shown in Table 1.
An aqueous coating material obtained by mixing the main agent and the curing agent at a mixing ratio shown in Table 1 on a siding board on which an inorganic clear coating film was formed as an existing coating film was applied in an amount of 0.1 kg / m ² . So that it is applied immediately after mixing, dried in an environment of 50 ° C. for 7 days, and then an aqueous top coating material (acrylic silicone resin emulsion paint) is applied to a coating amount of 0.1 kg / m ² , A test specimen [V] dried for one day in a standard state was prepared. The results are shown in Table 1.

Claims (1)

Including aqueous resin (A) and silane compound (B), pH is 4-11,
1-100 parts by weight of the silane compound (B) is included with respect to 100 parts by weight of the resin solid content of the aqueous resin (A),
The silane compound (B) includes an amino group-containing silane compound (M) and a silane compound (N) other than the amino group-containing silane compound,
An aqueous coating material characterized in that the weight ratio is (M) / (N)> 1.2.