WO2013140893A1

WO2013140893A1 - Aqueous resin composition and cured article

Info

Publication number: WO2013140893A1
Application number: PCT/JP2013/053244
Authority: WO
Inventors: 朋和髭白
Original assignee: Dic株式会社
Priority date: 2012-03-22
Filing date: 2013-02-12
Publication date: 2013-09-26
Also published as: JPWO2013140893A1; JP5360337B1; TW201348327A

Abstract

The present invention solves the problem of providing an aqueous resin composition making it possible to form a coating film having excellent water resistance and solvent resistance. The present invention pertains to an aqueous resin composition characterized in that a vinyl ester resin (a1) obtained by reacting together at least one species of epoxy resin (a1-1) selected from the group consisting of novolac-type epoxy resins and bisphenol-type epoxy resins, and a polymerizable unsaturated monomer (a1-2) having an acid group is dispersed in an aqueous vehicle (B) by a polymer (a2) having a hydrophilic group.

Description

Aqueous resin composition and cured product

The present invention relates to an aqueous resin composition that can be used in various applications including coating agents and adhesives.

The coating agent is generally required to be able to form a coating film with excellent durability capable of preventing the deterioration of the substrate surface. In particular, in recent years, coating agents that can form a coating film with excellent solvent resistance at a level that can prevent deterioration of the substrate due to adhesion of, for example, cleaning agents and magic pens, as well as water resistance, have been received from the industry. It has been demanded.

The coating agent having the above-mentioned characteristics is often used as a coating agent for protecting the surface of a metal substrate that easily generates rust or corrosion due to contact with water or the like. The coating material for surface protection of the metal substrate is required to form a coating film having a level of water resistance capable of preventing corrosion of the metal substrate and a high level of solvent resistance. Especially for solvent resistance, in the steel industry where the surface of the coating formed on the surface of a metal substrate is frequently cleaned using an alkaline cleaning agent, the coating is peeled off or dissolved by the influence of the cleaning agent. This is an important characteristic for preventing deterioration of the metal substrate.

Examples of the coating agent capable of forming a coating film excellent in water resistance and solvent resistance include 99 parts by weight of a polyester resin having a weight average molecular weight of 6,000 or more and an acid value of 8 mgKOH / g to 80 mgKOH / g. Resin aqueous solution containing 60 parts by mass and 1 part by mass to 40 parts by mass of an epoxy resin having a solubility in water of 5% by mass or less at 25 ° C. A coating agent made of a dispersion is known (for example, see Patent Document 1).

With the coating agent, it is possible to form a coating film having a certain degree of good water resistance and solvent resistance. However, the coating film obtained by using the coating agent does not reach the water resistance and solvent resistance required in the steel industry, so when water or a cleaning agent comes into contact with the coating film, In some cases, peeling or dissolution of the film was caused, and deterioration of the metal base material was caused.

By the way, as a method of forming a coating film excellent in water resistance and solvent resistance using a coating agent, after coating the coating agent on the surface of the base material, by heating at a temperature of about 150 ° C. A method of forming a cross-linked structure on the surface is known.

However, when the substrate is a substrate that is likely to cause deformation or discoloration due to the influence of heat, it cannot be heated at the above temperature to form a crosslinked structure in the coating film, resulting in water resistance or solvent resistance. In some cases, it was not possible to form a coating film excellent in properties.

JP 2004-107568 A

The problem to be solved by the present invention is to provide an aqueous resin composition capable of forming a coating film excellent in water resistance and solvent resistance.

Further, the problem to be solved by the present invention is to provide an aqueous resin composition capable of forming a coating film excellent in water resistance and solvent resistance even when heated at a relatively low temperature of about 100 ° C. That is.

As a result of studies to solve the above problems, the present inventors have found that an aqueous vinyl ester resin derived from a specific epoxy resin is dispersed in an aqueous medium (B) with a polymer having a hydrophilic group such as an anionic group. It has been found that the above-mentioned problems can be solved by using a resin composition.

That is, the present invention relates to at least one epoxy resin (a1-1) selected from the group consisting of a novolac type epoxy resin and a bisphenol type epoxy resin, a monomer having an acid group and polymerizable unsaturation (a1-2). And a vinyl ester resin (a1) obtained by reacting with a polymer (a2) is dispersed in an aqueous medium (B) by a polymer (a2) having a hydrophilic group. .

The present invention also relates to a cured product obtained by Michael addition reaction of the vinyl ester resin (a1) and the polyamine contained in the aqueous resin composition.

Since the aqueous resin composition of the present invention can form a coating film having excellent water resistance and solvent resistance even when heated at a relatively low temperature, it can be used in various applications including, for example, coating agents and adhesives. Can be used.

Specifically, the aqueous resin composition is used for various film anchor coating agents, can inner or outer surface coating agents, steel plate coatings, rust preventive coatings, pre-coated metal coatings, steel plate adhesives, resin sheets or films. It can be used in various applications including adhesives, film coating agents, ink binders, carbon fiber and glass fiber fiber treatment agents, and paper coating agents.

The aqueous resin composition of the present invention comprises at least one epoxy resin (a1-1) selected from the group consisting of novolak type epoxy resins and bisphenol type epoxy resins, and a monomer having an acid group and a polymerizable unsaturated group The vinyl ester resin (a1) obtained by reacting with (a1-2) is dispersed in the aqueous medium (B) by the polymer (a2) having a hydrophilic group.

The vinyl ester resin (a1) and the polymer (a2) used in the present invention do not exist in a state where they form resin particles independently and are dispersed in the aqueous medium (B). The ester resin (a1) is present in a state dispersed in the aqueous medium (B) by the polymer (a2). Specifically, a part or all of the vinyl ester resin (a1) is present in the polymer (a2) particles to form composite resin particles (A).

The composite resin particles (A) are preferably core-shell type composite resin particles in which the vinyl ester resin (a1) forms a core portion and the polymer (a2) forms a shell portion.

As the composite resin particle (A), it is preferable to use the composite resin particle (A) that does not substantially form a crosslinked structure in the state dispersed in the aqueous medium (B).

Here, “substantially does not form a crosslinked structure” means that the inside of the composite resin particle (A), specifically, between the polymers (a2) constituting the shell portion and the core portion is constituted. No cross-linked structure is formed between the vinyl ester resin (a1) or between the polymer (a2) and the vinyl ester resin (a1), or the water dispersion stability of the aqueous resin composition of the present invention, etc. The state which formed the fine crosslinked structure of the grade which does not inhibit this is pointed out. The cross-linking density inside the composite resin particle (A) achieves both excellent water dispersion stability (storage stability) and excellent film-forming property of the aqueous resin composition of the present invention, and excellent water resistance and resistance. In forming a coating film having solvent properties, it is preferably as low as possible, and more preferably a crosslinked structure is not formed.

The vinyl ester resin (a1) and the polymer (a2) include a mass ratio [vinyl ester resin (a1) / polymer (a2)] in the range of 70/30 to 20/80. It is preferable for forming a coating film excellent in water resistance and solvent resistance while giving good water dispersion stability, more preferably in the range of 70/30 to 30/70, and more preferably 70/30 to More preferably, it is contained in the range of 50/50.

Even when the vinyl ester resin (a1) and the polymer (a2) form the composite resin particle (A), the vinyl ester resin (a1) and the polymer constituting the composite resin particle (A) are also included. The mass ratio [vinyl ester resin (a1) / polymer (a2)] to (a2) is also preferably in the range of 70/30 to 20/80, and in the range of 70/30 to 30/70. More preferably, the range is from 70/30 to 50/50.

First, the vinyl ester resin (a1) contained in the aqueous resin composition of the present invention will be described in detail.

Examples of the vinyl ester resin (a1) include one or more epoxy resins (a1-1) selected from the group consisting of novolak type epoxy resins and bisphenol type epoxy resins, and a single monomer having an acid group and a polymerizable unsaturated group. What is obtained by reacting the body (a1-2) is used.

The vinyl ester resin (a1) has a polymerizable unsaturated group derived from the monomer (a1-2). The polymerizable unsaturated group may be present in a cured product such as a formed coating film, but a part thereof is cross-linked by using a thermal polymerization initiator or a photopolymerization initiator in combination. Also good. Moreover, the said polymerizable unsaturated group may react with crosslinking agents (C), such as polyamine mentioned later, and may form a crosslinked structure.

The polymerizable unsaturated group is preferably present in the vinyl ester resin (a1) in the range of 200 g / eq to 2,000 g / eq in order to form a cured product having excellent water resistance and solvent resistance.

One or more epoxy resins (a1-1) selected from the group consisting of the novolak-type epoxy resin and bisphenol-type epoxy resin that can be used in producing the vinyl ester resin (a1) include, for example, a cresol novolak-type epoxy Resin, novolac type epoxy resin such as phenol novolac type epoxy resin; bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin Resin can be used.

Among these, it is preferable to use a novolac type epoxy resin having a large number of epoxy groups that can react with the acid group of the monomer (a1-2), and a cresol novolak type epoxy resin or a phenol novolak type epoxy resin is used. It is more preferable to form a cured product having even more excellent water resistance and solvent resistance.

The epoxy resin (a1-1) has an epoxy equivalent of 100 g / eq to 2,000 g / eq for further improving the cured density of the cured product and further improving the water resistance and solvent resistance of the cured product. The upper limit is more preferably 1,000 g / eq or less, and further preferably 500 g / eq or less.

Of the epoxy groups of the epoxy resin (a1-1), 80 mol% to 100 mol% of the epoxy groups are consumed by reacting with the acid groups of the monomer (a1-2). It is preferable to further improve the cured density of the cured product and further improve the water resistance and solvent resistance of the cured product, and all of the epoxy groups of the monomer (a1-2) More preferably it is consumed by reacting with acid groups.

In addition, the monomer (a1-2) used in the production of the vinyl ester resin (a1) reacts with the epoxy group of the epoxy resin (a1-1) to convert the polymerizable unsaturated group into the vinyl ester resin ( It can be given to a1).

As the monomer (a1-2), one having an acid group capable of reacting with the epoxy group and a polymerizable unsaturated group can be used.

Examples of the monomer (a1-2) include acrylic acid, methacrylic acid, itaconic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2,2,2, -trisacryloyloxymethyl. Ethylphthalic acid or the like can be used. Among them, it is preferable to use acrylic acid because it can easily undergo a crosslinking reaction even at a relatively low temperature, and acrylic acid is used in an amount of 50% by mass or more based on the total amount of the monomer (a1-2). More preferably.

The reaction between the epoxy resin (a1-1) and the monomer (a1-2) is preferably performed at 60 ° C. to 150 ° C., more preferably 80 ° C. to 120 ° C.

It is preferable to use a polymerization inhibitor when reacting the epoxy resin (a1-1) and the monomer (a1-2). The addition amount of the polymerization inhibitor is preferably in the range of 500 ppm to 5000 ppm with respect to the total mass of the epoxy resin (a1-1) and the monomer (a1-2).

Examples of the polymerization inhibitor include 2,6-bis (tert-butyl) -4-methylphenol, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), p-tert-butylcatechol, nitrobenzene, nitrobenzoic acid, o -Dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrophenol, trinitrobenzene and the like can be used alone or in combination of two or more.

When reacting the epoxy resin (a1-1) and the monomer (a1-2), a reaction catalyst can be used. The amount of the reaction catalyst used is preferably 0.1% by mass to 5% by mass with respect to the solid content of the epoxy resin (a1-1).

As the reaction catalyst, for example, an amine catalyst, an imidazole catalyst, a phosphorus catalyst, a boron catalyst, a phosphorus-boron catalyst, or the like can be used. Specifically, alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine; 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea 3-substituted 4-phenyl-1,1-dimethylureas such as 3- (4-chlorophenyl) -1,1-dimethylurea; 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline Imidazolines such as 2-aminopyridine; amine imides such as N, N-dimethyl-N- (2-hydroxy-3-allyloxypropyl) amine-N′-lactoimide; ethylphosphine, propylphosphine, butyl Phosphine, phenylphosphine, trimethylphos Organophosphorus catalysts such as fin, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine-triphenylborane complex, tetraphenylphosphonium tetraphenylborate, 1,8-diazabicyclo [5,4 , 0] undecene-7,1,4-diazabicyclo [2,2,2] octane and the like can be used alone or in combination of two or more.

The vinyl ester resin (a1) obtained by the above method has a range of 500 to 5,000 in order to further increase the cured density of the resulting cured product and to give further excellent water resistance and solvent resistance. It is preferable to use those having a weight average molecular weight of

Further, the vinyl ester resin (a1) is preferably more hydrophobic than the polymer (a2) in forming the composite resin particle (A) in the polymer (a2) particles described later. The hydrophobic property refers to a property that is difficult to dissolve in water.

Next, the polymer (a2) used in the present invention will be described.

The polymer (a2) has a hydrophilic group, and is used for stably dispersing the vinyl ester resin (a1) in the aqueous medium (B).

As the hydrophilic group, an anionic group, a cationic group, or a nonionic group can be used.

As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, or the like can be used. Among these, the use of a carboxylate group or sulfonate group, part or all of which is neutralized with a basic compound, enables the vinyl ester resin (a1) to be stably dispersed in the aqueous medium (B). preferable.

Examples of basic compounds that can be used for neutralizing the carboxyl group and sulfonic acid group include organic amines such as ammonia, triethylamine, pyridine, and morpholine, alkanolamines such as monoethanolamine, sodium, potassium, lithium, and calcium. The contained metal base compound can be used.

When a carboxylate group or a sulfonate group is used as the anionic group, the vinyl ester resin may be present in the range of 0.1 mol / kg to 1.5 mol / kg with respect to the whole polymer (a2). It is preferable for stably dispersing (a1) in the aqueous medium (B).

As the cationic group, for example, a tertiary amino group, an acid neutralizing group of a tertiary amino group, or a quaternized group can be used.

Examples of the acid that can be used for neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid; organic acids such as sulfonic acid and methanesulfonic acid. Sulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid can be used.

Examples of the quaternizing agent that can be used for quaternizing a part or all of the tertiary amino group include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; methyl chloride, ethyl chloride, benzyl Alkyl halides such as chloride; alkyl such as methyl methanesulfonate and methyl paratoluenesulfonate; ethylene oxide; epoxy compounds such as propylene oxide and epichlorohydrin can be used.

In addition, as the nonionic group, for example, a polyoxyethylene group, a poly (oxyethylene-oxypropylene) group, a polyoxyethylene-polyoxypropylene group, or the like can be used.

As the polymer (a2) having a hydrophilic group, specifically, a resin capable of introducing a hydrophilic group, such as a polyurethane resin, a polyester resin, or an acrylic resin, can be used. Among them, it is easy to introduce a hydrophilic group and to use one or more selected from the group consisting of urethane resin, polyester resin and acrylic resin, and it has excellent compatibility with the vinyl ester resin (a1). The resin (A) is preferable because it is easy to form.

As the urethane resin, for example, a resin produced by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender can be used.

As the polyol, for example, polyester polyol, polycarbonate polyol, polyether polyol, polyolefin polyol and the like can be used alone or in combination of two or more. Among these, the use of polyester polyol and polycarbonate polyol can improve the substrate adhesion of the aqueous resin composition of the present invention and improve the compatibility with the vinyl ester resin (a-1). It is preferable because good coating film properties such as solvent properties can be maintained.

Examples of the polyester polyol include those obtained by esterifying low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, and copolyesters thereof. Etc. can be used.

Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butanediol having a molecular weight of about 50 to 300. An aliphatic polyol such as cyclohexane dimethanol, a polyol having an aliphatic cyclic structure, a bisphenol compound such as bisphenol A, and a polyol having an aromatic structure such as an alkylene oxide adduct thereof can be used.

Examples of the polycarboxylic acid that can be used in the production of the polyester polyol include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and the like Aromatic polycarboxylic acids of the above; their anhydrides or esterifications can be used.

As the polyester polyol, those having a number average molecular weight in the range of 500 to 4,000 are preferably used. Also, as the polycarbonate polyol usable for the polyol, for example, it is obtained by reacting a carbonate and a polyol. And those obtained by reacting phosgene and bisphenol A can be used.

As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

Examples of the polyol that can react with the carbonate ester include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5. A relatively low molecular weight diol having a molecular weight of 50 to 2,000, such as pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol; polyethylene glycol, polypropylene glycol, polyhexamethylene adipate, etc. Polyester polyol or the like can be used.

The polycarbonate polyol preferably has a number average molecular weight in the range of 500 to 4,000.

Examples of the polyether polyol that can be used for the polyol include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.

Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, glycerin, and triglyceride. Methylolethane, trimethylolpropane and the like can be used.

As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like can be used.

Examples of the polyolefin polyol that can be used for the polyol include polyethylene polyol, polypropylene polyol, polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, and hydrogenated (hydrogenated) polyisoprene polyol.

As the polyol, from the viewpoint of imparting good water dispersion stability to the urethane resin, in addition to those described above, a polyol having a hydrophilic group can be used in combination.

As the polyol having a hydrophilic group, for example, a polyol having an anionic group other than the aforementioned polyol, a polyol having a cationic group, and a polyol having a nonionic group can be used. Among these, it is preferable to use a polyol having an anionic group or a polyol having a cationic group, and it is more preferable to use a polyol having an anionic group.

As the polyol having an anionic group, for example, a polyol having a carboxyl group or a polyol having a sulfonic acid group can be used.

As the polyol having a carboxyl group, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like can be used. Preference is given to using methylolpropionic acid. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group, and various polycarboxylic acids react can also be used.

Examples of the polyol having a sulfonic acid group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof, and the aromatic structure. The polyester polyol obtained by making it react with the low molecular weight polyol illustrated as what can be used for manufacture of a polyester polyol can be used.

As the polyol having a cationic group, for example, a polyol having a tertiary amino group can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies per molecule, a secondary amine, Polyols obtained by reacting can be used.

As the polyol having a nonionic group, polyalkylene glycol having a structural unit derived from ethylene oxide can be used.

The polyol having a hydrophilic group is preferably used in the range of 0.3% by mass to 10% by mass with respect to the total amount of polyol used for the production of the urethane resin.

Further, as the polyol, in addition to the above-described polyol, other polyols can be used as necessary.

Examples of the other polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Polyol having a relatively low molecular weight such as 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol, etc. can be used.

Examples of the polyisocyanate that can react with the polyol include aromatics such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate. Polyisocyanate; aliphatic polyisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate; polyisocyanate having an aliphatic cyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. Can Kill.

The urethane resin is produced by reacting the polyol and the polyisocyanate, for example, in the absence of a solvent or in the presence of an organic solvent, and then when there is a hydrophilic group in the urethane resin, A product obtained by neutralizing a part or all of the hydrophilic group as necessary can be produced by mixing with an aqueous medium (B) to make it aqueous and reacting with a chain extender as necessary. it can.

The reaction between the polyol and the polyisocyanate is preferably performed, for example, when the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol is in the range of 0.8 to 2.5, preferably 0.9 to It is more preferable to carry out in the range of 1.5.

Moreover, as the acrylic resin that can be used for the polymer (a2), an acrylic resin having the hydrophilic group can be used.

As the acrylic resin, those having a weight average molecular weight in the range of 5,000 to 1,000,000 are preferably used. In order to improve production efficiency, the weight in the range of 5,000 to 500,000 is used. It is more preferable to use one having an average molecular weight.

As the acrylic resin, conventionally known (meth) acrylic monomers and those obtained by polymerizing a mixture thereof can be used.

Examples of the (meth) acrylic monomer that can be used for producing an acrylic resin that can be used for the polymer (a2) include (meth) acrylic monomers such as (meth) acrylic acid alkyl ester and (meth) acrylic acid. Etc. can be used. Of these, the use of (meth) acrylic acid alkyl ester is preferable because the compatibility with the vinyl ester resin (a1) is improved and good coating properties such as solvent resistance can be imparted.

Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and tert (meth) acrylic acid. -Butyl, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, (meth) Stearyl acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like can be used. Among them, it is preferable to use (meth) acrylic acid alkyl ester having an alkyl group having 1 to 6 carbon atoms. The “(meth) acrylic acid” refers to one or both of acrylic acid and methacrylic acid.

The (meth) acrylic acid alkyl ester is preferably used in a range of 25% by mass to 80% by mass with respect to the total mass of monomers used for the production of the vinyl polymer (B), and 30% by mass. It is more preferable that the content be in the range of from 80% by mass to 80% by mass because compatibility with the vinyl ester resin (a1) is improved and good coating properties such as solvent resistance can be maintained.

Further, as the (meth) acrylic acid alkyl ester, specifically, a (meth) acrylic acid alkyl ester capable of forming a homopolymer in the range of −50 ° C. to 0 ° C. and a range of 50 ° C. to 120 ° C. A (meth) acrylic acid alkyl ester capable of forming a homopolymer can be used in combination. In such a case, [(meth) acrylic acid alkyl ester capable of forming a homopolymer in the range of −50 ° C. to 0 ° C./(meth)acrylic acid alkyl ester capable of forming a homopolymer in the range of 50 ° C. to 120 ° C. ) Is preferably used in the range of 100/0 to 25/75 in order to further improve the film forming property of the aqueous resin composition.

As the (meth) acrylic acid alkyl ester capable of forming a homopolymer in the range of −50 ° C. to 0 ° C., for example, n-butyl (meth) acrylate can be used, and the range of 50 ° C. to 120 ° C. As the (meth) acrylic acid alkyl ester capable of forming a homopolymer of, for example, methyl (meth) acrylate can be used.

Moreover, as a monomer which can be used at the time of manufacturing the acrylic resin, from the viewpoint of imparting an anionic group as a hydrophilic group to the acrylic resin, for example, a single monomer having a carboxyl group such as acrylic acid or methacrylic acid The body can be used. The acrylic acid, methacrylic acid and the like are preferably used in the range of 0.5% by mass to 30% by mass with respect to the total amount of monomers used for producing the acrylic resin.

Examples of the monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate from the viewpoint of imparting a cationic group as a hydrophilic group to the acrylic resin. ) Monomers having a tertiary amino group such as acrylamide can be used. The monomer having a tertiary amino group is preferably used in the range of 0.5% by mass to 30% by mass with respect to the total amount of monomers used in producing the acrylic resin.

In addition, as the monomer, from the viewpoint of imparting a nonionic group as a hydrophilic group to the acrylic resin, for example, a monomer having a polyoxyethylene structure in a side chain such as methoxypolyethylene glycol (meth) acrylate Can be used. The monomer containing the polyoxyethylene structure is preferably used in the range of 5% by mass to 70% by mass with respect to the total amount of monomers used for producing the acrylic resin.

In addition to the monomers described above, monomers that can be used for producing the acrylic resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) Acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2, (meth) acrylic acid 3,3-pentafluoropropyl, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, ( (Meth) acrylamide, N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) acryl Amides, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, styrene and α- Methyl styrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether, (meth) acrylonitrile, vinyl toluene, vinyl anisole, α-halostyrene , Vinyl naphthalene, divinyl styrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinyl chloride Lidon, (meth) acrylic acid, β-carboxyethyl (meth) acrylate, 2- (meth) acryloylpropionic acid, crotonic acid, itaconic acid half ester, maleic acid half ester, β- (meth) acryloyloxyethyl hydrogen succin Nate, isoprene, butadiene and the like can be used. Further, as the vinyl monomer having a carboxyl group, Aronix M-5300 (manufactured by Toagosei Co., Ltd., ω-carboxy-polycaprolactone monoacrylate) or the like can be used.

Further, as the polyester resin usable for the polymer (a2), the polyester resin having the hydrophilic group can be used.

As the polyester resin, it is preferable to use a polyester resin having a sulfonate group as the anionic group, and using an aromatic polyester resin having the sulfonate group is excellent in water resistance and solvent resistance. It is more preferable when forming a coating film.

As the polyester resin, those having a weight average molecular weight of 5,000 to 30,000 are preferably used, and more preferably in the range of 5,000 to 15,000. If the weight average molecular weight is within the above-mentioned range, it is possible to impart good coating workability and film-forming property with an appropriate viscosity without impairing excellent water resistance, solvent resistance and storage stability. Become.

The polyester resin preferably has a glass transition temperature of 30 ° C. to 100 ° C. If the polyester resin (a1) has the glass transition temperature, it imparts good coating workability and film-forming property with an appropriate viscosity without impairing excellent water resistance, solvent resistance and storage stability. Is possible.

As the polyester resin, those obtained by reacting polyol and polycarboxylic acid can be used.

In addition, as the sulfonate group possessed by the polyester resin, a compound having a sulfonate group such as a polyol having a sulfonate group or a polycarboxylic acid having a sulfonate group is used as part of the polyol or polycarboxylic acid. By this, it can be introduced into the polyester resin.

In addition, the compound having a sulfonate group that can be used in producing the polyester resin is 3% by mass to 30% by mass with respect to the total mass of the polyol and the polycarboxylic acid used in producing the polyester resin. % Is preferably used in order to impart good water dispersibility.

Examples of polyols that can be used in producing the polyester resin include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 2-methyl-1,3-propanediol. 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, diethylene glycol, triethylene glycol Aliphatic polyols such as ethylene glycol and dipropylene glycol; polyols having an aliphatic cyclic structure such as 1,4-cyclohexanedimethanol can be used. Moreover, as said polyol, the polyol which has 3 or more of hydroxyl groups, such as glycerol, a trimethylol ethane, a trimethylol propane, a pentaerythritol, can also be used, for example.

As the polyol that can be used in the production of the polyester resin, a polyol having a sulfonate group as a compound having a sulfonate group in a part or all of the polyol can be used. For example, 2-butene-1,4- A polyol having a sulfonate group obtained by sulfonating a polyol having an unsaturated group such as a diol can be used.

Examples of the polycarboxylic acid capable of reacting with a polyol that can be used in producing the polyester resin include aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid; oxalic acid , Succinic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic acid, Aliphatic polycarboxylic acids such as dimer acids; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid and its anhydride, tetrahydrophthalic acid and It has an aliphatic cyclic structure such as its anhydride. That polycarboxylic acid can be used. Among these, from the viewpoint of imparting further excellent water resistance and solvent resistance, it is preferable to use an aromatic polycarboxylic acid, and it is more preferable to use terephthalic acid or isophthalic acid.

In addition to the above-mentioned polycarboxylic acids that can be used for producing the polyester resin, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, anhydrous base Three or more carboxyls such as nzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), 1,2,3,4-butanetetracarboxylic acid Those having a group can be used.

As the polycarboxylic acid that can be used when the polyester resin is produced, a polycarboxylic acid having a sulfonate group in part or all thereof can be used. Examples include 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid dimethyl, and the like It is preferable to use the esterified product.

Among these, 5-sodium sulfoisophthalic acid and its esterified products are more preferably used from the viewpoint of imparting excellent water resistance and solvent resistance without impairing storage stability over a long period of time. More preferably, dimethyl acid is used.

The composite resin particles (A) formed by the vinyl ester resin (a1) and the polymer (a2), for example, produce a polymer (a2) such as the urethane resin, acrylic resin, or polyester resin, It can be produced by mixing the polymer (a2), the vinyl ester resin (a1) and the aqueous medium (B).

When the urethane resin is used as the polymer (a2), the urethane resin reacts the polyol, the polyisocyanate, and, if necessary, the chain extender at 40 ° C. to 120 ° C. in the absence of solvent or in the solvent. Can be manufactured.

When the acrylic resin is used as the polymer (a2), the acrylic resin is a vinyl monomer containing the (meth) acrylic monomer, a polymerization initiator is added, and the conditions are 30 ° C. to 120 ° C. It can be produced by radical polymerization with

When the polyester resin is used as the polymer (a2), the polyester resin is produced by subjecting the polyol and the polycarboxylic acid to an esterification reaction in a conventionally known method under no solvent or in an organic solvent. can do.

Specifically, in the esterification reaction, the polyol and the polycarboxylic acid are preferably heated to 180 ° C. to 300 ° C. in an inert gas atmosphere in the presence or absence of a catalyst to perform esterification or It can be carried out by a method of transesterification followed by polycondensation under reduced pressure.

The polymer (a2) is prepared by previously dissolving or dispersing the composite resin particles in the aqueous medium (B) or an organic solvent in order to form the composite resin particles (A) with the vinyl ester resin (a1). It is preferable.

Next, the polymer (a2) composition dissolved or dispersed in the aqueous medium (B) or the organic solvent obtained by the above method and the vinyl ester resin (a1) are mixed and stirred. Thus, an aqueous resin composition containing the composite resin particles (A) in which a part or all of the vinyl ester resin (a1) is contained in the polymer (a2) particles and the aqueous medium (B). Obtainable.

When the organic resin is contained in the aqueous resin composition obtained by the above method, the organic solvent may be removed by a distillation method or the like from the viewpoint of reducing the environmental load. Thereby, the aqueous resin composition in which the composite resin particles (A) are dispersed in the aqueous medium (B) can be obtained.

The aqueous resin composition preferably has a non-volatile content in the range of 10% by mass to 90% by mass, and preferably 30% by mass to 70% by mass from the viewpoint of maintaining coating workability and long-term storage stability. More preferably, it is the range.

Among them, the vinyl ester resin (a1) and the polymer (a2) are preferably used in the range of 5% by mass to 85% by mass with respect to the total amount of the aqueous resin composition, and 20% by mass to 65%. It is more preferable to use in the range of mass%.

Also, examples of the aqueous medium (B) used in the present invention include water, organic solvents miscible with water, and mixtures thereof. Examples of organic solvents miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

The aqueous medium (B) is preferably contained in an amount of 10% by mass to 90% by mass, and more preferably in the range of 30% by mass to 70% by mass with respect to the total amount of the aqueous resin composition.

In the aqueous resin composition of the present invention, if necessary, a film-forming aid, a curing agent, a polymerization initiator, a curing catalyst, a plasticizer, an antistatic agent, a wax, a light stabilizer, a flow regulator, a dye, and a leveling Additives, rheology control agents, ultraviolet absorbers, antioxidants, photocatalytic compounds, additives such as inorganic pigments, organic pigments, extender pigments, other resins such as polyester resins, urethane resins, acrylic resins, etc. it can. When the additive is water-insoluble, it can be used when the polymer (a2) is dissolved or dispersed in the aqueous medium (B) or the organic solvent, thereby stably dispersing the additive in the solvent. It becomes possible to do.

As the film forming aid, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, butyl cellosolve, polypropylene glycol monomethyl ether, butyl cellosolve and the like can be used. Of these, the use of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone is preferable for producing films and coating films that are required to have higher transparency.

As the curing agent, it is preferable to use a water-soluble or water-dispersible one. Specific examples include aliphatic amines, amines having a cyclic structure, aliphatic aromatic amines, polyoxyalkylene polyamines and other polyamines, and polythiol compounds.

Aliphatic amines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, bis- (3-aminopropyl) Methylamine, N, N-bis- (3-aminopropyl) ethylenediamine, hexamethylenediamine, 2-methyl-1,5-pentanediamine, 1,3-diaminopentane, terminal aminated polypropylene glycol, etc. may be used. it can.

Examples of amines having a cyclic structure (eg, cycloalkyl ring, benzene ring, heterocyclic ring) include piperazine, N-aminoethylpiperazine, piperazine such as 1,4-bis- (3-aminopropyl) piperazine, 1,3 -Bisaminomethylcyclohexane, isophoronediamine, 1-cyclohexylamino-3-aminopropane, 1,4-diaminocyclohexane, 2,4-diamino-cyclohexane, N, N'-diethyl-1,4-diaminocyclohexane, 3, An alicyclic polyamine such as 3′-dimethyl-4,4′-diaminocyclohexylmethane, and an araliphatic amine such as metaxylylenediamine and paraxylylenediamine can be used.

Examples of the polythiol compound include methanedithiol, 1,2-dimercaptoethane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,4-dimercaptobutane. 1,6-dimercaptohexane, bis (2-mercaptoethyl) sulfide, and the like can be used.

The curing agent is an equivalent ratio of the polymerizable unsaturated group of the vinyl ester resin (a1) to the active hydrogen atom of the amino group of the curing agent [polymerizable unsaturated group / amino group of the curing agent. The active hydrogen atom] is preferably used in the range of 100/80 to 100/300 in order to form a cured product such as a coating film having excellent water resistance and solvent resistance by the Michael addition reaction.

Further, as the polymerization initiator, those capable of generating radicals by light or heat and initiating the reaction of the polymerizable unsaturated group can be used. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl. ] -2-Hydroxy-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1-bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide-bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide or the like can be used.

Examples of the thermal polymerization initiator include peroxides and azo compounds, such as benzoyl peroxide, tert-butyl-peroxybenzoate, and azobisisobutyronitrile.

In the present invention, an emulsifier or the like may be used from the viewpoint of improving the dispersion stability of the composite resin particles (A). However, the emulsifier or the like generally reduces the water resistance of a cured product such as a coating film. Tend to cause.

On the other hand, the aqueous resin composition of the present invention has sufficient storage stability without using the emulsifier and the like, and can form a cured product such as a coating film excellent in water resistance, etc. The amount of the emulsifier used is preferably 5% by mass or less, and more preferably 0% by mass with respect to the total amount of the aqueous resin composition.

Since the aqueous resin composition of the present invention as described above can form a cured product such as a coating film excellent in water resistance and solvent resistance, for example, a coating agent such as a top coat agent or a primer coat agent, an adhesive, or a film In particular, it can be used as a coating agent.

Examples of the substrate on which the coating agent and the adhesive can be applied include a metal substrate, a plastic substrate, a glass substrate, paper, a wood substrate, and a fibrous substrate.

As the metal substrate, for example, a plated steel plate such as a galvanized steel plate or an aluminum-zinc alloy steel plate; an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate, a substrate having a metal vapor deposition surface on the surface, or the like is used. be able to.

As the plastic base material, polycarbonate base materials, polyester base materials, acrylonitrile-butadiene-styrene base materials, poly base materials, which are generally used in plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, OA equipment, etc. An acrylic base material, polystyrene base material, polyurethane base material, epoxy resin base material, polyvinyl chloride base material, polyamide base material and the like can be used.

The various base materials described above may be coated in advance, but since the coating agent of the present invention has excellent adhesion to a plastic substrate or the like, surface treatment such as coating is performed in advance. Excellent adhesion to non-base materials.

The coating agent of the present invention can be suitably used as a primer for the plastic substrate. The base materials may be plate-shaped, spherical, film-shaped, and sheet-shaped, respectively.

The coating agent of the present invention can form a coating film on its surface by, for example, applying it directly to the surface of the substrate, and then drying and curing.

Examples of the method for applying the coating agent on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.

The drying and curing may be carried out by curing at room temperature for about 1 day to 10 days. From the viewpoint of rapidly curing, the method is performed at a temperature of 100 ° C. to 150 ° C. for 1 to A method of heating for about 600 seconds is preferable. Further, when using a plastic substrate that is easily deformed or discolored at a relatively high temperature, it is preferable to perform the curing at a relatively low temperature of about 70 ° C. to 100 ° C.

The film thickness of the coating film formed using the coating agent or adhesive of the present invention can be appropriately adjusted according to the use of the substrate, etc., but is usually preferably about 0.01 μm to 20 μm. .

Since the coated material in which the coating film is formed by the coating agent can achieve both excellent water resistance and solvent resistance, for example, heat exchangers such as air conditioners and refrigerators, antifouling properties and antifogging properties are required. Can be used for home appliances and displays that use optical members such as antireflection films, optical filters, optical lenses, spectacle lenses, mirrors, automotive interior materials and exterior materials, building materials such as wall materials and roofing materials, etc. It is.

Furthermore, as a primer coating agent used for the purpose of modifying the surface of a plastic film such as polyester resin, polypropylene resin, polyamide resin, etc. and providing an easy adhesion layer, for example, aluminum vapor deposited plastic film for food packaging, optical use For film applications, optical members such as liquid crystal displays and flat displays can be used for highly functional films such as prism lens films and antiglare films.

Synthesis Example 1 (Synthesis of polyester polyol (X))
While introducing nitrogen gas into a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 830 parts by mass (5 mol) of isophthalic acid, 730 parts by mass (5 mol) of adipic acid, 1026 of 1,4-butanediol 1026 The polyester polyol (X) (hydroxyl equivalent: 1000 g / wt) was charged by adding 15 parts by mass (11.4 mol) and 0.5 parts by mass of dibutyltin oxide and performing a polycondensation reaction at 230 ° C. for 15 hours until the acid value became 1 or less. eq) was obtained.

Synthesis Example 2 (Synthesis of polyol (Y) having tertiary amino group)
In a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 590 parts by mass of DENACOL EX-211 (manufactured by Nagase Chemtech, neopentyl glycol diglycidyl ether, epoxy equivalent = 138 g / eq) Was added, and the atmosphere in the flask was replaced with nitrogen.

Next, after heating using an oil bath until the temperature in the flask reached 35 ° C., 312.7 parts by mass of diethylamine was added dropwise over 30 minutes using a dropping device. Reacted for hours.

After completion of the reaction, using an infrared spectrophotometer (FT / IR-460Plus, manufactured by JASCO Corporation), it was confirmed that the absorption peak near 842 cm-1 due to the epoxy group of the reaction product had disappeared. Thus, a polyol (Y) having a tertiary amino group (amine equivalent 211 g / eq, hydroxyl equivalent 211 g / eq) was obtained.

Production Example 1 (Synthesis of vinyl ester resin composition (I-1))
In a reaction vessel, EPICLON N-673 (manufactured by DIC Corporation, cresol novolac type epoxy resin, solid content epoxy equivalent 209 g / eq, nonvolatile content 100% by mass) 1040 parts by mass, acrylic acid 369.3 parts by mass, methoquinone 2.2 parts by mass And 5.2 parts by mass of triphenylphosphine were added and reacted at a reaction temperature of 115 ° C. until the acid value was 1.5 or less.

Next, after the reaction product was cooled to 80 ° C. or less, 472.2 parts by mass of methyl ethyl ketone was charged and mixed uniformly to prepare a vinyl ester resin composition (I-1) having a nonvolatile content of 75% by mass.

Production Example 2 (Synthesis of vinyl ester resin composition (I-2))
EPICLON N-673 (manufactured by DIC Corporation, cresol novolac type epoxy resin, solid content epoxy equivalent 209 g / eq, nonvolatile content 100% by mass) EPICLON N-740 (manufactured by DIC Corporation, phenol novolak type epoxy resin, solid (Epoxy equivalent 180 g / eq, nonvolatile content 100% by mass) 1040 parts by mass, acrylic acid 369.2 parts by mass instead of acrylic acid 428.8 parts by mass, methyl ethyl ketone 472.2 parts by mass methyl ethyl ketone 492.1 parts by mass A vinyl ester resin composition (I-2) having a nonvolatile content of 75% by mass was prepared in the same manner as in Production Example 1 except that was used.

Production Example 3 (Synthesis of vinyl ester resin composition (I-3))
EPICLON 850S (made by DIC Corporation, bisphenol A type epoxy resin, solid content epoxy) instead of EPICLON N-673 (made by DIC Corporation, cresol novolac type epoxy resin, solid content epoxy equivalent 209 g / eq, nonvolatile content 100 mass%) Equivalent 188 g / eq, non-volatile content 100% by mass) 1040 parts by mass, 410.6 parts by mass of acrylic acid instead of 369.3 parts by mass of acrylic acid, and 486 parts by mass of methyl ethyl ketone instead of 472.2 parts by mass of methyl ethyl ketone A vinyl ester resin composition (I-3) having a nonvolatile content of 75% by mass was prepared in the same manner as in Production Example 1 except for the above.

Production Example 4 (Synthesis of vinyl ester resin composition (I-4))
Except for using 221.6 parts by weight of acrylic acid and 176.5 parts by weight of methacrylic acid instead of 369.3 parts by weight of acrylic acid, and using 481.8 parts by weight of methyl ethyl ketone instead of 472.2 parts by weight of methyl ethyl ketone. A vinyl ester resin composition (I-4) having a nonvolatile content of 75% by mass was prepared in the same manner as in Production Example 1.

Production Example 5 (Synthesis of vinyl ester resin composition (I-5))
Instead of EPICLON N-673 (manufactured by DIC Corporation, cresol novolac type epoxy resin, solid content epoxy equivalent = 209 g / eq, nonvolatile content = 100% by mass), DENACOL EX-614B (manufactured by Nagase Chemtech Co., Ltd., sorbitol polyglycidyl) Ether, solid content epoxy equivalent = 171 g / eq, non-volatile content 100% by mass) 1040 parts by mass, acrylic acid 451.4 parts by mass instead of acrylic acid 369.3 parts by mass, methyl ethyl ketone 4799 parts by mass instead of methyl ethyl ketone 499 A vinyl ester resin composition (I-5) having a nonvolatile content of 75% by mass was prepared in the same manner as in Production Example 1, except that .6 parts by mass was used.

Production Example 6 (Synthesis of vinyl ester resin composition (I-6))
1889 parts by mass of vinyl ester resin composition (I-1) obtained by the same method as in Production Example 1 and 544.9 parts by mass of LATEMUL E-118B (manufactured by Kao Corporation, sodium polyoxyethylene alkyl ether sulfate, And 26% by mass of non-volatile content) were uniformly mixed. Next, 2288.6 parts by mass of ion-exchanged water is added over 1 hour, and methyl ethyl ketone is removed at 30 to 50 ° C. under reduced pressure, whereby the non-volatile content of 50% by mass in which the vinyl ester resin is dispersed in the ion-exchanged water. A vinyl ester resin composition (I-6) was obtained.

EPICLON N-673 (manufactured by DIC Corporation, cresol novolac type epoxy resin, solid content epoxy equivalent 209 g / eq, nonvolatile content 100% by mass)
EPICLON N-740 (manufactured by DIC Corporation, phenol novolac type epoxy resin, solid content epoxy equivalent 180 g / eq, nonvolatile content 100% by mass)
EPICLON 850S (manufactured by DIC Corporation, bisphenol A type epoxy resin, solid content epoxy equivalent 188 g / eq, nonvolatile content 100% by mass)
・ DENACOL EX-614B (manufactured by Nagase Chemtech Co., Ltd., sorbitol polyglycidyl ether, solid content epoxy equivalent 171 g / eq, nonvolatile content 100% by mass)
・ LATEMUL E-118B (manufactured by Kao Corporation, sodium polyoxyethylene alkyl ether sulfate, nonvolatile content: 26% by mass)
Production Example 7 (Preparation of Urethane Resin Composition (II-1) Having Anionic Group)
633.6 parts by mass of the polyester polyol (X) obtained in Synthesis Example 1 was supplied to a reaction vessel and dehydrated by heating at 100 ° C. under reduced pressure.

Next, after adjusting the temperature in the reaction vessel to 80 ° C., 139.1 parts by mass of methyl ethyl ketone and 418.4 parts by mass of N-methyl-2-pyrrolidone were supplied and stirred uniformly.

Next, 50 parts by mass of 2,2-dimethylolpropionic acid is added to the reaction vessel, and 153.3 parts by mass of isophorone diisocyanate and 0.4 parts by mass of stannous octylate are added and reacted at 80 ° C. for 12 hours. It was.

After confirming that the mass ratio of the isocyanate group (isocyanate value) to the total mass of the raw materials used for the production of the urethane resin was 0.1 mass% or less, 3 parts by mass of n-butanol was added, and the reaction was continued for 2 hours. Then, the resultant was cooled to 50 ° C. to obtain a urethane resin composition (II-1) having an anionic group.

Production Example 8 (Preparation of urethane resin composition (II-2) having an anionic group)
Manufactured except that polycarbonate polyol (hydroxyl equivalent: 1000 g / eq) obtained by reacting 1,6-hexanediol, 1,4-butanediol and dimethyl carbonate was used instead of the polyester polyol (X). A urethane resin composition (II-2) having an anionic group was obtained in the same manner as in Example 7.

Production Example 9 (Preparation of urethane resin composition (II-3) having a cationic group)
In a reaction vessel, 531.6 parts by mass of the polyester polyol (X) was supplied to the reaction vessel and dehydrated by heating under reduced pressure.

Next, after adjusting the temperature in the reaction vessel to 80 ° C., 30.6 parts by mass of 1,4-butanediol, 204.1 parts by mass of methyl ethyl ketone, and 311.2 parts by mass of N-methyl-2-pyrrolidone were supplied. Stir to be uniform.

Next, 15.6 parts by mass of the polyol (Y) having a tertiary amino group obtained in Synthesis Example 2 was added, 145.7 parts by mass of isophorone diisocyanate, and 0.4 parts by mass of stannous octylate were added. The reaction was carried out at 20 ° C. for 12 hours.

Next, 54.5 parts by mass of polyethylene glycol monomethyl ether (hydroxyl value 28.05) was added, and the reaction was continued for 4 hours. After confirming that the mass ratio of isocyanate groups (isocyanate value) to the total mass of the raw materials used for the production of the urethane resin was 0.1 mass% or less, 3 parts by mass of n-butanol was added, and further 2 hours After the reaction, the polyurethane resin composition (II-3) having a cationic group was obtained by cooling to 50 ° C.

Production Example 10 (Preparation of acrylic resin composition (II-4) having a polyoxyethylene structure)
M-90G (manufactured by Shin-Nakamura Chemical Co., Ltd., methoxypolyethylene glycol methacrylate, 9 moles of added ethylene oxide) 250 parts by mass, methyl methacrylate 200 parts by mass, cyclohexyl methacrylate 50 parts by mass, methyl ethyl ketone 300 parts by mass, N A mixture containing 200 parts by weight of methyl-2-pyrrolidone and 25 parts by weight of azoisobutyronitrile was prepared.

-25% by mass of the mixture was charged in a reaction vessel and heated to 80 ° C.

Next, the remaining 75 mass% of the mixture was added dropwise over 3 hours with stirring in a nitrogen atmosphere. At this time, the temperature in the reaction vessel was kept at 80 ° C.

After completion of the dropwise addition, 5 parts by mass of azoisobutyronitrile was added, and the mixture was further reacted at 80 ° C. for 5 hours to obtain an acrylic resin composition (II-4) having a polyoxyethylene structure having a nonvolatile content of 50% by mass. .

Production Example 11 (Preparation of polyester resin composition having an anionic group (II-5))
In a reaction vessel prepared at 180 ° C., 558 parts by mass of ethylene glycol (8.99 mol), 478 parts by mass of diethylene glycol (4.50 mol), 896 parts by mass of terephthalic acid (5.39 mol), 478 parts by mass of isophthalic acid ( 2.88 mol), 0.5 part by mass of butylhydroxytin oxide was charged, the temperature was raised to 240 ° C. over 4 hours, and then reacted at 240 ° C. to trap about 260 parts by mass of distillate.

After adjusting the inside of the reaction vessel to 180 ° C., 213 parts by mass (0.72 mol) of dimethyl 5-sodium sulfoisophthalate and 0.5 parts by mass of tetraisopropyl titanate were added, and the temperature was raised to 260 ° C. Polyester resin composition having an anionic group having a non-volatile content of 100 mass% by polycondensation reaction for 1 hour under reduced pressure of 0 mm, further mixing with 200 mass parts of N-methyl-2-pyrrolidone and slowly stirring The product (II-5) was obtained.

“Polyester polyol (X)” in Table 2 represents the polyester polyol obtained in Synthesis Example 1. “Polycarbonate polyol” represents a polycarbonate polyol (hydroxyl equivalent: 1000 g / eq) obtained by reacting 1,6-hexanediol, 1,4-butanediol and dimethyl carbonate. “Polyol (Y)” represents the polyol obtained in Synthesis Example 2.

“M-90G” in Table 3 represents methoxypolyethylene glycol methacrylate (additional mole number of ethylene oxide: 9 mol) manufactured by Shin-Nakamura Chemical Co., Ltd.

Example 1
After supplying 1397.8 parts by mass of the urethane resin composition (II-1) having an anionic group obtained in Production Example 7 to the reaction vessel, the vinyl ester resin composition (I-1) obtained in Production Example 1 was used. 1115.7 parts by mass and 37.7 parts by mass of triethylamine were supplied, and 1915 parts by mass of ion-exchanged water were slowly supplied to mix them.

Next, an aqueous resin composition (III-1) having a nonvolatile content of 45% by mass was prepared by heating under reduced pressure at a temperature of 30 ° C. to 50 ° C. to remove methyl ethyl ketone in the reaction vessel.

Example 2
After supplying 1397.8 parts by mass of the urethane resin composition (II-1) having an anionic group to a reaction vessel, 2603.6 parts by mass of the vinyl ester resin composition (I-1), and 37. 7 parts by mass, and 3933.7 parts by mass of ion-exchanged water were slowly supplied to mix them.

Next, heating was performed at a temperature of 30 ° C. to 50 ° C. under reduced pressure to remove methyl ethyl ketone in the reaction vessel, thereby preparing an aqueous resin composition (III-2) having a nonvolatile content of 50% by mass.

Example 3
After supplying 1397.8 parts by mass of the urethane resin composition (II-1) having an anionic group to a reaction vessel, 3347.5 parts by mass of the vinyl ester resin composition (I-1), and 37. 7 parts by mass and 4026 parts by mass of ion-exchanged water were slowly supplied to mix them.

Next, heating was performed at a temperature of 30 ° C. to 50 ° C. under reduced pressure to remove methyl ethyl ketone in the reaction vessel, thereby preparing an aqueous resin composition (III-3) having a nonvolatile content of 50% by mass.

Example 4
After supplying 1397.8 parts by mass of the urethane resin composition (II-1) having an anionic group to a reaction vessel, 600.8 parts by mass of the vinyl ester resin composition (I-1), and 37. 7 parts by mass, and 4258.6 parts by mass of ion-exchanged water were slowly supplied to mix them.

Next, an aqueous resin composition (III-4) having a nonvolatile content of 30% by mass was prepared by heating under reduced pressure at a temperature of 30 ° C. to 50 ° C. to remove methyl ethyl ketone in the reaction vessel.

Example 5
After supplying 1397.8 parts by mass of the urethane resin composition (II-1) having an anionic group to a reaction vessel, 371.9 parts by mass of the vinyl ester resin composition (I-1) and 37. 7 parts by mass, and 4758.9 parts by mass of ion-exchanged water were slowly supplied to mix them.

Next, an aqueous resin composition (III-5) having a nonvolatile content of 25% by mass was prepared by heating under reduced pressure at a temperature of 30 ° C. to 50 ° C. to remove methyl ethyl ketone in the reaction vessel.

Example 6
A non-volatile content of 50 mass by the same method as in Example 2 except that instead of the vinyl ester resin composition (I-1), the vinyl ester resin composition (I-2) obtained in Production Example 2 was used. % Aqueous resin composition (III-6) was prepared.

Example 7
A non-volatile content of 50 mass by the same method as in Example 2 except that instead of the vinyl ester resin composition (I-1), the vinyl ester resin composition (I-3) obtained in Production Example 3 was used. % Aqueous resin composition (III-7) was prepared.

Example 8
A non-volatile content of 50 mass by the same method as in Example 2 except that instead of the vinyl ester resin composition (I-1), the vinyl ester resin composition (I-4) obtained in Production Example 4 was used. % Aqueous resin composition (III-8) was prepared.

Example 9
After supplying 1397.8 parts by mass of the urethane resin composition (II-2) having an anionic group obtained in Production Example 8 to the reaction vessel, 2603.6 parts by mass of the vinyl ester resin composition (I-1) Then, 37.7 parts by mass of triethylamine was supplied, and 3933.7 parts by mass of ion-exchanged water was slowly supplied to mix them.

Next, an aqueous resin composition (III-9) having a nonvolatile content of 50% by mass was prepared by heating under reduced pressure at a temperature of 30 ° C. to 50 ° C. to remove methyl ethyl ketone in the reaction vessel.

Example 10
After supplying 1296.6 parts by mass of the polyurethane resin composition (II-3) having a cationic group obtained in Production Example 9 to the reaction vessel, 2420.3 parts by mass of the vinyl ester resin composition (I-1) And 8.1 parts by mass of 89% by mass orthophosphoric acid, and 5523 parts by mass of ion-exchanged water were slowly supplied to mix them.

Next, heating was performed at a temperature of 30 ° C. to 50 ° C. under reduced pressure to remove methyl ethyl ketone in the reaction vessel, thereby preparing an aqueous resin composition (III-10) having a nonvolatile content of 40% by mass.

Example 11
After supplying 1000 parts by mass of the acrylic resin composition (II-4) having a polyoxyethylene structure obtained in Production Example 10 to a reaction vessel, 1555.5 parts by mass of the vinyl ester resin composition (I-1) Then, 2595 parts by mass of ion-exchanged water were supplied and mixed.

Next, an aqueous resin composition (III-11) having a nonvolatile content of 50% by mass was prepared by heating at a temperature of 30 ° C. to 50 ° C. under reduced pressure to remove methyl ethyl ketone in the reaction vessel.

Example 12
After supplying 400 parts by mass of the polyester resin composition (II-5) obtained in Production Example 11 to the reaction vessel, supply 266.7 parts by mass of the vinyl ester resin composition (I-1) until uniform. Stir.

Next, 1000 parts by mass of ion-exchanged water is supplied over 1 hour, heated at a temperature of 30 ° C. to 50 ° C., and methyl ethyl ketone in the reaction vessel is removed, whereby an aqueous resin composition having a nonvolatile content of 45% by mass ( III-12) was obtained.

Comparative Example 1
A non-volatile content of 50% by mass was obtained in the same manner as in Example 2 except that the vinyl ester resin composition (I-5) obtained in Production Example 5 was used instead of the vinyl ester resin composition (I-1). Aqueous resin composition (III′-1) was prepared.

Comparative Example 2
After mixing 697.3 parts by mass of the urethane resin composition (II-1) having an anionic group and 18.8 parts by mass of triethylamine, 2092 parts by mass of ion-exchanged water was slowly supplied, and then Production Example 6 1948.2 parts by mass of the vinyl ester resin composition (I-6) obtained in 1 above was supplied and stirred.

Next, an aqueous resin composition (III′-2) having a nonvolatile content of 50% by mass was prepared by heating under reduced pressure at a temperature of 30 ° C. to 50 ° C. to remove methyl ethyl ketone in the reaction vessel.

Comparative Example 3
After mixing 1397.8 parts by mass of the urethane resin composition having an anionic group (II-1) and 37.7 parts by mass of triethylamine, 4184 parts by mass of ion-exchanged water was slowly supplied, An aqueous resin composition (III′-3) having a nonvolatile content of 20% by mass was prepared by heating at 30 ° C. to 50 ° C. to remove methyl ethyl ketone in the reaction vessel.

Example 13
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-1) and 11.9 parts by mass of a 20% by mass ethylenediamine aqueous solution.

The aqueous resin composition containing this curing agent was applied on a film made of polyethylene terephthalate so that the thickness of the cured coating film was 5 μm, and dried at 100 ° C. for 5 minutes to obtain a cured coating film.

Example 14
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-1) and 34.0 parts by mass of a 10% by mass piperazine aqueous solution.

Example 15
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-2) and 18.5 parts by mass of a 20% by mass aqueous ethylenediamine solution.
The aqueous resin composition containing this curing agent was applied onto a film made of polyethylene terephthalate so that the thickness of the cured coating film was 5 μm, and dried at 100 ° C. for 5 minutes to obtain a cured coating film.

Example 16
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-3) and 19.8 parts by mass of a 20% by mass ethylenediamine aqueous solution.

Example 17
By mixing 100 parts by mass of the aqueous resin composition (III-4) and 5.5 parts by mass of a 20% by mass ethylenediamine aqueous solution, an aqueous resin composition containing a curing agent was obtained.

Example 18
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-5) with 3.3 parts by mass of a 20% by mass ethylenediamine aqueous solution.

Example 19
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-6) with 20.6 parts by mass of a 20% by mass ethylenediamine aqueous solution.

Example 20
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-7) and 20.0 parts by mass of a 20% by mass ethylenediamine aqueous solution.

Example 21
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-8) and 18.1 parts by mass of a 20% by mass aqueous ethylenediamine solution.

Example 22
By mixing 100 parts by mass of the aqueous resin composition (III-9) and 18.5 parts by mass of a 20% by mass ethylenediamine aqueous solution, an aqueous resin composition containing a curing agent was obtained.

Example 23
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-10) and 14.8 parts by mass of a 20% by mass aqueous ethylenediamine solution.

Example 24
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III-11) and 18.5 parts by mass of a 20% by mass aqueous ethylenediamine solution.

Example 25
An aqueous resin composition containing a curing agent was obtained by mixing 11.9 parts by mass of a 20% by mass aqueous ethylenediamine solution with respect to 100 parts by mass of the aqueous resin composition (III-12).

Example 26
In addition to 1397.8 parts by mass of the urethane resin composition (II-1) obtained in Production Example 7, 1115.7 parts by mass of the vinyl ester resin composition (I-1) obtained in Production Example 1 and 37.7 parts by mass of triethylamine. And 25.1 parts by mass of Irganox 184 (BASF photopolymerization initiator) were added, and 1915 parts by mass of ion-exchanged water were slowly added. Subsequently, methyl ethyl ketone was removed at 30 ° C. to 50 ° C. under reduced pressure to prepare an aqueous resin composition (III-13) having a nonvolatile content of 45% by mass.

The aqueous resin composition (III-13) was applied onto a film made of polyethylene terephthalate so that the thickness of the cured coating film was 5 μm, and dried at 100 ° C. for 5 minutes. The coated surface was irradiated with ultraviolet rays at an irradiation intensity of 500 mJ / cm ² using a high-pressure mercury lamp as a light source to obtain a cured coating film.

Comparative Example 4
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III′-1) and 21.3 parts by mass of a 20% by mass ethylenediamine aqueous solution.

Comparative Example 5
An aqueous resin composition containing a curing agent was obtained by mixing 100 parts by mass of the aqueous resin composition (III′-2) and 16.8 parts by mass of a 20% by mass aqueous ethylenediamine solution.

Comparative Example 6
Cured by mixing 100 parts by mass of the aqueous resin composition (III′-3) and 5.0 parts by mass of BECKAMINE J-101 (Melamine-based curing agent, non-volatile content = 80% by mass, manufactured by DIC Corporation). An aqueous resin composition containing an agent was obtained.

Comparative Example 7
100 parts by mass of the aqueous resin composition (III′-3) and DENACOL EX-614B (manufactured by Nagase Chemtech Co., Ltd., sorbitol polyglycidyl ether, solid content epoxy equivalent = 171 g / eq, nonvolatile content = 100% by mass) 1 An aqueous resin composition containing a curing agent was obtained by mixing 6 parts by mass.

Comparative Example 8
100 parts by mass of the aqueous resin composition (III′-3) and 4.0 parts by mass of AQUANATE 210 (manufactured by Nippon Polyurethane Industry Co., Ltd., NCO group content = 16.5% by weight, nonvolatile content = 100% by mass) Was mixed to obtain an aqueous resin composition containing a curing agent.

Comparative Example 9
EPOCROSS WS-700 (manufactured by Nippon Shokubai Co., Ltd., oxazoline number (solid content) = 220 g / eq, nonvolatile content = 25% by mass) 7.8 with respect to 100 parts by mass of the aqueous resin composition (III′-3) An aqueous resin composition containing a curing agent was obtained by mixing with parts by mass.

[Evaluation method of solvent resistance 1]
Using a cotton swab soaked with 100% by mass of ethanol, the surface of the cured coating film obtained above was rubbed 30 times at a pressure of about 0.3 kg. The surface of the cured coating film after rubbing was visually observed and evaluated according to the following evaluation criteria.

◎: There was no change in the coating surface before and after rubbing.

○: Slight whitening and scratches could be confirmed on the surface of the coating film before and after rubbing, but sufficient transparency was maintained and the level was not problematic in practice.

Δ: Clear whitening and scratches could be confirmed on the coating surface before and after rubbing, and a clear decrease in transparency could be confirmed.

X: The surface of the coating film was dissolved, and the surface of the film made of polyethylene terephthalate was confirmed.

[Evaluation method of solvent resistance 2]
The marking pen black, red, and blue pen tips specified in JIS S 6037 are pressed against the surface of the cured coating obtained as described above, and approximately every second in a direction perpendicular to the wide side of the pen tip. The film was moved at a speed of 150 mm, and three lines having a line width of about 2 cm were drawn on the surface of the coating film so as to be in contact with each other, thereby filling an area of about 36 cm ^{2 on} the surface of the coating film.

After coating, the surface of the coating film left for 18 hours in a room temperature environment is wiped with a clean gauze dipped in a mixed solvent containing petroleum benzine and ethanol at a mass ratio of 1: 1, and the coating surface The ink of the marking pen adhered to the surface was wiped off. Next, the surface of the coating film was lightly wiped with a clean dry gauze and allowed to stand for 1 hour at room temperature.

The surface of the cured coating film after standing was visually observed under diffuse daylight, and the color and gloss of the cured coating film and the presence or absence of swelling were visually evaluated as compared with the cured coating film before the test.

◎: No change in color and gloss such as fading of color and reduction in gloss was observed.

○: The above-mentioned color and gloss were slightly changed, but the level was not problematic for practical use.

(Triangle | delta): The said color and the change of gloss were recognized in about the half range of the range of about 4 cm < ² > of a cured coating film.

X: The change of the color and gloss was recognized remarkably, and there was a problem in practical use.

[Evaluation method of water resistance 1]
The cured coating films obtained in the examples and comparative examples were immersed in water at 40 ° C. for 24 hours, and then the surface of the cured coating film was visually observed and evaluated according to the following evaluation criteria.

A: There was no change in the surface of the cured coating film before and after immersion.

◯: Slight whitening and scratches were confirmed on the surface of the cured coating film before and after immersion, but sufficient transparency was maintained and it was at a level with no practical problems.

Δ: Clear whitening and scratches were confirmed on the surface of the cured coating film before and after immersion, and a clear decrease in transparency was confirmed.

X: Clear whitening and scratches were confirmed on the surface of the cured coating film before and after immersion, and a significant decrease in transparency was confirmed.

The abbreviations in Table 8 are as follows.

・ BECKAMINE J-101 (Melamine-based curing agent by DIC Corporation, non-volatile content: 80% by mass)
・ DENACOL EX-614B (manufactured by Nagase Chemtech Co., Ltd., sorbitol polyglycidyl ether, solid content epoxy equivalent 171 g / eq, nonvolatile content 100% by mass)
-AQUANATE 210 (manufactured by Nippon Polyurethane Industry Co., Ltd., NCO group content 16.5% by mass, nonvolatile content 100% by mass)
EPOCROSS WS-700 (manufactured by Nippon Shokubai Co., Ltd., oxazoline number (solid content) 220 g / eq, nonvolatile content 25% by mass)
Any of the aqueous resin compositions obtained in Examples 13 to 16 could form a coating film having excellent solvent resistance and water resistance.

In addition, the aqueous resin compositions obtained in Examples 17 and 18 in which the mass ratio of the vinyl ester resin (a1) and the polymer (a2) was changed are also coating films having good solvent resistance and water resistance. Could be formed.

In addition, the aqueous resin composition described in Example 19 obtained using a phenol novolac resin as an epoxy resin could form a coating film having excellent solvent resistance and water resistance. The aqueous resin composition described in Example 20 obtained using a bisphenol A type epoxy resin as an epoxy resin can form a coating film having good solvent resistance and excellent water resistance. It was.

In addition, the aqueous resin composition described in Example 21 containing a vinyl ester resin obtained by using a combination of acrylic acid and methacrylic acid forms a coating film with a certain degree of good solvent resistance and water resistance. I was able to.

Further, with the aqueous resin composition described in Examples 22 to 25 in which the composition of the polymer (a2) was changed, a coating film having excellent solvent resistance and water resistance could be formed.

With the aqueous resin composition described in Example 26 using a photopolymerization initiator, a coating film having good solvent resistance and excellent water resistance could be formed.

On the other hand, in the aqueous resin composition described in Comparative Example 4 obtained by using sorbitol polyglycidyl ether instead of the novolak type epoxy resin and bisphenol type epoxy resin, it was possible to form a coating film having a certain degree of good water resistance. However, a coating film having excellent solvent resistance could not be formed.

Further, by using LATEMUL E-118B (manufactured by Kao Corporation, sodium polyoxyethylene alkyl ether sulfate), the epoxy resin (a1-1) and the polymer (a2) are independent from each other in the aqueous medium (B). In the aqueous resin composition described in Comparative Example 5 dispersed in this manner, it was not possible to form a coating film particularly excellent in water resistance.

Further, the aqueous resin compositions described in Comparative Examples 6 to 9 obtained without using the epoxy resin (a1-1) cannot form a coating film having good solvent resistance and water resistance. It was.

Claims

One or more epoxy resins (a1-1) selected from the group consisting of novolak-type epoxy resins and bisphenol-type epoxy resins are reacted with a monomer (a1-2) having an acid group and a polymerizable unsaturated group. An aqueous resin composition, wherein the vinyl ester resin (a1) obtained in this manner is dispersed in an aqueous medium (B) with a polymer (a2) having a hydrophilic group.
2. The aqueous resin composition according to claim 1, wherein the polymer (a2) is one or more selected from the group consisting of a urethane resin, a polyester resin, and an acrylic resin.
The aqueous resin composition according to claim 1, wherein a part or all of the vinyl ester resin (a1) is present in the polymer (a2) particles to form composite resin particles (A).
The aqueous solution according to claim 1, wherein the mass ratio [vinyl ester resin (a1) / polymer (a2)] of the vinyl ester resin (a1) and the polymer (a2) is in the range of 70/30 to 20/80. Resin composition.
Furthermore, the aqueous resin composition of Claim 1 which contains a polyamine as a crosslinking agent (C).
A cured product obtained by Michael addition reaction of the vinyl ester resin (a1) and the polyamine by heating the aqueous resin composition according to claim 5 at 70 ° C to 150 ° C.