JP5088599B2 - Aqueous resin composition - Google Patents

Description

The present invention has good storage stability of varnish, does not generate odor during processing, and is excellent in adhesion, corrosion resistance, etc. of the obtained processed product, and suitable for paints, adhesives, fiber sizing agents, concrete primers, etc. The present invention relates to an aqueous resin composition that can be used.

  Epoxy resin compositions are generally used in various fields such as paints, adhesives, laminates, and electrical / electronic parts because they are generally excellent in the mechanical properties, corrosion resistance, adhesion and the like of the cured products obtained. Epoxy resins are often diluted in organic solvents and used as compositions. However, due to recent environmental problems, the amount of organic solvents discharged from the compositions is reduced without impairing the above-mentioned high performance of epoxy resins. Is desired.

In order to solve the above-mentioned problems, a method for solving the problem has been performed by using an aqueous resin composition in which the solvent is mainly water. As the aqueous resin , for example, an epoxy resin obtained by reacting with a polyoxyalkylamine is used. Proposals include those in which a carboxyl group is introduced into a phosphoric acid-modified epoxy resin and then neutralized with an amine, and the epoxy resin and alkanolamine are reacted to introduce a carboxyl group into the side chain and then neutralized with an amine. ing.

  In the method of making these epoxy resins water-based, polyoxyalkylamine, which is a hydrophilic part, is introduced into the resin skeleton, so that a balance between obtaining a continuous epoxy resin skeleton and making it water-based is balanced. It is difficult to maintain and often adversely affects the performance of the resulting cured product, such as a decrease in water resistance of the coating film when used as a paint.

  In addition, when a carboxyl group is introduced into an epoxy resin and neutralized with amines, the amines used for neutralization do not react with the resin, so it is easy to store during varnishing or during heat processing. There are problems such as volatilization and odor generation, and corrosion of the heating furnace used during processing.

JP-A-10-183055 (pages 3-4) JP 7-157711 A (pages 2 to 4) JP 2000-053745 (pages 3 to 4)

In view of the above situation, the object of the present invention is to introduce a phosphoric acid, a polyoxyalkylamine skeleton, and to make it water-based without using an amine as a neutralizing agent. It is desirable to provide an aqueous resin composition that can be suitably used for, for example, an anticorrosion property and adhesion property of a coating film.

As a result of intensive studies to solve the above problems, the present inventor has obtained an aqueous resin containing a compound (A) and water (B) obtained by reacting an active hydrogen-containing compound (a1) with an epoxy resin (a2). The present inventors have found that the composition is effective as a method for solving the above-mentioned problems, and have completed the present invention.

That is, the present invention is an aqueous resin composition containing a compound (A) obtained by reacting an active hydrogen-containing compound (a1) with an epoxy resin (a2) and water (B), and comprising the epoxy resin (a2) Is obtained by reacting an active hydrogen-containing compound (x1) having a quaternary onium group with an epihalohydrin (x2), which provides an aqueous resin composition.

According to the present invention, the introduction of phosphoric acid, a polyoxyalkylamine skeleton, and the use of a neutralizing agent without using an amine is possible, and it can be suitably used for paints, adhesives, fiber sizing agents, concrete primers, and the like. It is possible to provide an aqueous resin composition that is excellent in anticorrosion and adhesion of the coating film.

  Hereinafter, the present invention will be described in detail.

  The compound (A) used in the present invention is a compound obtained by reacting an active hydrogen-containing compound (a1) with an epoxy resin (a2), and is active against 1 equivalent of an epoxy group in the epoxy resin (a2). It is a compound obtained by reacting active hydrogen groups in the hydrogen-containing compound (a1) at a ratio of 0.80 to 2.50.

The structure of the active hydrogen-containing compound (a1) used in the present invention is not particularly limited as long as it can react with the epoxy group present in the epoxy resin (a2). Examples thereof include compounds, alcoholic hydroxyl group-containing compounds, carboxyl group-containing compounds, amino group-containing compounds. Among these, the reactivity with the epoxy group in the epoxy resin (a2), the anticorrosive property of the coating film when the aqueous resin composition obtained from the resulting compound (A) is used for coatings, phenolic properties. It is preferable to use a hydroxyl group-containing compound or an amino group-containing compound.

  Although it does not specifically limit as said phenolic hydroxyl group containing compound, It is preferable that it is a compound which has a 2 or more phenolic hydroxyl group in 1 molecule, for example, as bisphenol, bis (4-hydroxy Phenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (bisphenol C), 1,1- Bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), bis (4-hydroxyphenyl) sulfone (bisphenol S), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), diphenolic acid , And substituent-containing products thereof. The Le, phenol novolak resin, cresol novolak resin, p-tert-butylphenol novolak resin, nonylphenol novolak resin, Zizi Black pentadiene phenol resin and t- butyl catechol, hydroquinone, resorcinol, and their substituent-containing products and the like. For the purpose of adjusting the molecular weight of the resulting epoxy resin (a2), monohydric phenols can be used in combination, for example, phenol, p-ethylphenol, o-cresol, m-cresol, p-cresol. P-tert-butylphenol, s-butylphenol, p-octylphenol, nonylphenol, xylenol and the like. These phenolic hydroxyl group-containing compounds may be used alone or in combination of two or more.

  Examples of the alcoholic hydroxyl group-containing compound include aliphatic alcohols such as butanol, monohydric alcohols such as aliphatic alcohols having 11 to 12 carbon atoms, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6 -Polyhydric alcohols such as hexanediol, glycerin, erythritol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and trimethylolpropane may be used, and these may be used alone or in combination of two or more. .

  Examples of the carboxyl group-containing compound include aliphatic carboxyl group-containing compounds such as adipic acid and long-chain synthetic dibasic acids, aromatic carboxyl group-containing compounds such as phthalic acid and terephthalic acid, and aromatic rings in various stages. Cyclic carboxyl group-containing compounds such as tetrahydrophthalic acid and hexahydrophthalic acid hydrogenated, polymerized fatty acid carboxyl group-containing compounds such as dimer acid, neodecanoic acid and neononanoic acid, etc., can be used. Also, two or more types may be used in combination.

  Examples of the amino group-containing compound include diaminodiphenylmethane and its substituent-containing compounds, aromatic amines such as aniline, toluidine, and diaminodiphenylsulfone, aliphatic amines such as metaxylenediamine and 1,3-bisaminomethylcyclohexane, Examples include aminophenols such as p-aminophenol, m-aminophenol, and p-aminocresol, and these may be used alone or in combination of two or more.

  In addition, the phenolic hydroxyl group-containing compound, alcoholic hydroxyl group-containing compound, carboxyl group-containing compound, amino group-containing compound and the like may be used singly, or different types of compounds may be used in combination.

  The epoxy resin (a2) used in the present invention is obtained by reacting an active hydrogen-containing compound (x1) having a quaternary onium group with an epihalohydrin (x2), and is an epoxy that can react with the active hydrogen-containing compound (a1). It is a compound containing at least one group in the molecular structure.

  The active hydrogen-containing compound (x1) having a quaternary onium group may be any compound as long as a compound having an epoxy group can be obtained by a reaction of a quaternary onium group and an epihalohydrin (x2) in the structure. Examples thereof include a phenolic hydroxyl group-containing compound having a quaternary onium group, an alcoholic hydroxyl group-containing compound having a quaternary onium group, a carboxyl group-containing compound having a quaternary onium group, and an amino group-containing compound having a quaternary onium group. Among these, a phenolic hydroxyl group-containing compound having a quaternary onium group from the viewpoint that the resulting compound can be easily made water-based, has excellent curability of the epoxy resin composition, and has excellent mechanical properties of the resulting cured product. Is preferably used.

  The phenolic hydroxyl group-containing compound having a quaternary onium group is not particularly limited as long as it has a quaternary onium group and a phenolic hydroxyl group in the molecule at the same time. A compound obtained by reaction with a compound having an onium group is preferred. The phenolic hydroxyl group-containing compound is preferably a compound having two or more phenolic hydroxyl groups in one molecule. Examples of bisphenols include bis (4-hydroxyphenyl) methane (bisphenol F), 2,2- Bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (bisphenol C), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z) Bis (4-hydroxyphenyl) sulfone (bisphenol S), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), diphenolic acid, and their substituent-containing products. Polyphenols include phenol novolac resins, Resole novolac resin, p-tert-butylphenol novolak resin, nonylphenol novolak resin, Zizi Black pentadiene phenol resin, t- butyl catechol, hydroquinone, resorcinol and substituent-containing products and the like. For the purpose of adjusting the molecular weight of the resulting epoxy resin (a2), monohydric phenols can be used in combination, for example, phenol, p-ethylphenol, o-cresol, m-cresol, p-cresol. , P-tertiarybutylphenol, s-butylphenol, p-octylphenol, nonylphenol, xylenol, orthohydroxybenzoic acid, metahydroxybenzoic acid, parahydroxybenzoic acid and the like. These phenolic hydroxyl group-containing compounds may be used alone or in combination of two or more.

  The alcoholic hydroxyl group-containing compound having a quaternary onium group is not particularly limited as long as it has a quaternary onium group and an alcoholic hydroxyl group in the molecule at the same time. A compound obtained by reaction with a compound having an onium group is preferred. Examples of the alcoholic hydroxyl group-containing compound include aliphatic alcohols such as butanol, monohydric alcohols such as aliphatic alcohols having 11 to 12 carbon atoms, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6 -Polyhydric alcohols such as hexanediol, glycerin, erythritol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and trimethylolpropane may be used, and these may be used alone or in combination of two or more. .

  The carboxyl group-containing compound having a quaternary onium group is not particularly limited as long as it has both a quaternary onium group and a carboxyl group in the molecule. The compound obtained by reaction with the compound which has is preferable. Examples of the carboxyl group-containing compound include aliphatic carboxyl group-containing compounds such as adipic acid and long-chain synthetic dibasic acids, aromatic carboxyl group-containing compounds such as phthalic acid and terephthalic acid, and aromatic rings in various stages. Cyclic carboxyl group-containing compounds such as tetrahydrophthalic acid and hexahydrophthalic acid hydrogenated, polymerized fatty acid carboxyl group-containing compounds such as dimer acid, neodecanoic acid and neononanoic acid, etc., can be used. Also, two or more types may be used in combination.

  The amino group-containing compound having a quaternary onium group is not particularly limited as long as it has both a quaternary onium group and an amino group in the molecule, but the amino group-containing compound and the quaternary onium group are not limited. A compound obtained by reaction with a compound having an amino group-containing compound is preferable. Examples of the amino group-containing compound include diaminodiphenylmethane and its substituent-containing compounds, aromatic amines such as aniline, toluidine, and diaminodiphenylsulfone, metaxylenediamine, and 1,3- Examples include aliphatic amines such as bisaminomethylcyclohexane, and aminophenols such as p-aminophenol, m-aminophenol, and p-aminocresol. These may be used alone or in combination of two or more. Also good.

  In addition, the phenolic hydroxyl group-containing compound, alcoholic hydroxyl group-containing compound, carboxyl group-containing compound, amino group-containing compound and the like may be used singly, or different types of compounds may be used in combination.

  The reaction of the phenolic hydroxyl group-containing compound, alcoholic hydroxyl group-containing compound, carboxyl group-containing compound, amino group-containing compound and compound having a quaternary onium group is carried out at room temperature or in the absence of a catalyst or in the presence of a catalyst, It can be done under heating.

  Among the phenolic hydroxyl group-containing compounds, alcoholic hydroxyl group-containing compounds, carboxyl group-containing compounds, and amino group-containing compounds, it is preferable to use a phenolic hydroxyl group-containing compound, and the reactivity with epihalohydrin (x2) and epoxy resin ( The following general formula (1) having a phenolic hydroxyl group and a carboxyl group in the molecule at the same time because of easy molecular weight adjustment of a2)

〔式（１）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５は同一でも異なっても良い、水素原子又は炭素数１〜４のアルキル基であり、Ｙは単結合又は炭素数１〜４のアルキレン鎖である。
〕
で示される化合物（ｙ１）や、オルソヒドロキシ安息香酸、メタヒドロキシ安息香酸、パラヒドロキシ安息香酸が好ましい。

[In Formula (1), R1, R2, R3, R4, R5 may be the same or different, and are a hydrogen atom or a C1-C4 alkyl group, and Y is a single bond or a C1-C4 alkylene. Is a chain.
]
The compound (y1) shown by these, orthohydroxybenzoic acid, metahydroxybenzoic acid, and parahydroxybenzoic acid are preferable.

  The general formula (1) is preferably a compound in which R1, R2, R3, and R4 are the same or different linear alkyl groups having 1 to 4 carbon atoms from the viewpoint of easy availability, R2, R3 and R4 are preferably hydrogen atoms, R5 is a methyl group, and Y is preferably an ethylene chain.

  As the compound having a quaternary onium group, for example, a compound represented by the following general formula (2) or an acrylic monomer having a quaternary onium salt can be used. (Wherein R6 is a hydrogen atom or a methyl group, Q is a nitrogen atom or a phosphorus atom, X is a chlorine atom, a bromine atom or an iodine atom, and R7, R8 and R9 are an alkyl group or an aryl group, respectively. Yes, these may be the same or different.)

  In the general formula (2), it is preferable to use a compound in which R7, R8, and R9 are the same or different linear alkyl groups having 1 to 4 carbon atoms from the viewpoint of easy availability, and R6 is hydrogen. SY-GTA80 [trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., NV = 80% aqueous solution, epoxy equivalent (solid content) in which atoms, Q are nitrogen atoms, R7, R8, R9 are methyl groups, and X is a chlorine atom : 151 g / eq] is most preferable.

Examples of the acrylic monomer having a quaternary onium salt include DMAEA-Q (manufactured by Kojin Co., Ltd., N, N-dimethylaminoethyl acrylate-methyl chloride salt, 79% aqueous solution) and DMAPAA-Q (Kokou Co., Ltd.). (Manufactured, N, N-dimethylaminopropylacrylamide-methyl chloride salt, 75% aqueous solution).

Among these, as the quaternary onium salt, the use of the quaternary onium salt-containing epoxy compound (y2) represented by the general formula (2) makes it possible to react with (y1) and obtain the quaternary onium salt. It is preferable in the reactivity of the containing active hydrogen compound (x1) and epihalohydrin.

Further, the active hydrogen-containing compound (x1) is a compound obtained by copolymerizing an acrylic monomer such as acrylic acid, methacrylic acid or 2-hydroxyethyl acrylate and an acrylic monomer having a quaternary onium salt, or an acrylic monomer polymerization. A compound in which a compound represented by the following general formula (2) is introduced into the active hydrogen group in the product by reaction can be used. Wherein R6 is a hydrogen atom or a methyl group, Q is a nitrogen atom or a phosphorus atom, X is a chlorine atom, a bromine atom or an iodine atom, and R7, R8 and R9 are an alkyl group or an aryl group, respectively. Yes, these may be the same or different.)

  The active hydrogen-containing compound (x1) may be the same as or different from the active hydrogen-containing compound (a1).

  The epihalohydrin (x2) used in the present invention is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like, and it is preferable to use epichlorohydrin because it is easily industrially available.

  Next, the manufacturing method of the epoxy resin (a2) used by this invention is explained in full detail. The production method is not limited at all except that the active hydrogen-containing compound (x1) having the quaternary onium salt and epihalohydrin (x2) are used as raw materials, but can be industrially implemented. Thus, for example, when a phenolic hydroxyl group-containing compound having a quaternary onium salt is used, a dissolved mixture of the phenolic hydroxyl group-containing compound having a quaternary onium salt and an epihalohydrin (x2) such as sodium hydroxide or potassium hydroxide is used. A method of reacting at 20 to 120 ° C. for 1 to 10 hours while adding or adding an alkali metal hydroxide is preferable. The addition amount of epihalohydrin (x2) is usually in the range of 0.3 to 20 equivalents relative to 1 equivalent of active hydrogen (hydroxyl group) in the phenolic hydroxyl group-containing compound having a quaternary onium salt, preferably The range is 0.6 to 4.0 equivalents.

  An aqueous solution of the alkali metal hydroxide may be used. In that case, the alkali metal hydroxide can be produced by supplying the aqueous solution of the alkali metal hydroxide into the reaction system all at once, intermittently or continuously. .

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride is added to a dissolved mixture of a phenolic hydroxyl group-containing compound having a quaternary onium group and epihalohydrin (x2) as a catalyst, Add a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the phenol obtained by reacting at 150 ° C. for 1 to 5 hours, and react again at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate A method of (ring closure) may be used.

  Furthermore, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide, etc. are used in order to facilitate the reaction. It is preferable to carry out the reaction by adding. The amount of the solvent used is usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the amount of epihalohydrin (x2). Moreover, when using an aprotic polar solvent, it is 5 to 100 weight% normally with respect to the quantity of epihalohydrin (x2), Preferably it is 10 to 60 weight%.

  Epihalohydrin (x2), other added solvents, and the like are removed after washing the reaction product of these epoxidation reactions with or without washing with water at 110 to 250 ° C. and a pressure of 10 mmHg or less. Thereafter, the crude compound is dissolved again in a solvent such as toluene and methyl isobutyl ketone, the formed salt is removed by filtration and the like, and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under reduced pressure by heating to an epoxy resin ( a2) can be obtained.

  In the type in which epichlorohydrin (x2) is used in the reaction, the reaction product of the epoxidation reaction is washed with water and then removed by dehydration filtration, and a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure. Thus, the epoxy resin (a2) can be obtained.

  Further, if necessary, the crude compound obtained after recovering the epihalohydrin (x2), the additive solvent, etc. is dissolved again in a solvent such as toluene, methyl isobutyl ketone, Ring closure can be ensured by adding an aqueous solution of an alkali metal hydroxide such as sodium oxide or potassium hydroxide to cause further reaction. In this case, the usage-amount of an alkali metal hydroxide is 0.5-10 mol normally with respect to 1 mol of hydrolyzable chlorine which remains in a crude compound, Preferably it is 1.2-5.0 mol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by weight based on the crude compound. Thereafter, the produced salt is removed by washing with water, dehydrating filtration, and the like, and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under reduced pressure by heating to obtain the epoxy resin (a2).

  Next, the case where an alcoholic hydroxyl group-containing compound having a quaternary onium group is used as the active hydrogen-containing compound (x1) will be described in detail. When using an alcoholic hydroxyl group-containing compound, there are roughly two methods. In the first method, a Lewis acid such as boron trifluoride ether complex is added to alcohols having a quaternary onium group, and epihalohydrin (x2) is added dropwise to react with the chlorohydrin adduct obtained after the reaction. Furthermore, the method of making ring-closing reaction at 20-120 degreeC for 1 to 10 hours, adding alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, is mentioned. At this time, a reaction solvent such as toluene can be used if necessary.

  In the second method, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or ethyl is dissolved in a mixture of an alcoholic hydroxyl group-containing compound having a quaternary onium group and epihalohydrin (x2). Add or add alkali metal hydroxides such as sodium hydroxide and potassium hydroxide using quaternary phosphonium salts such as triphenylphosphonium bromide, tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide as catalysts. However, the method of making it react at 20-120 degreeC for 1 to 10 hours is mentioned.

  An aqueous solution of the alkali metal hydroxide may be used. In that case, the alkali metal hydroxide can be produced by supplying the aqueous solution of the alkali metal hydroxide into the reaction system all at once, intermittently or continuously. .

  Epihalohydrin (x2), other added solvents, and the like are removed after washing the reaction product of these epoxidation reactions with or without washing with water at 110 to 250 ° C. and a pressure of 10 mmHg or less. Thereafter, the crude compound is dissolved again in a solvent such as toluene and methyl isobutyl ketone, the formed salt is removed by filtration and the like, and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under reduced pressure by heating to an epoxy resin ( a2) can be obtained.

In order to further reduce the hydrolyzable halogen, a re-ring closure reaction / purification is carried out in the same manner as when using the phenolic hydroxyl group-containing compound having a quaternary onium group as described above. Also good.

  When the carboxyl group-containing compound having a quaternary onium group is used as the active hydrogen-containing compound (x1), sodium hydroxide, a dissolved mixture of the carboxyl group-containing compound having a quaternary onium group and a large excess of epihalohydrin (x2), The method of making it react at 20-120 degreeC for 1 to 10 hours, adding alkali metal hydroxides, such as potassium hydroxide, is added. If necessary, a quaternary ammonium salt or the like may be used as a catalyst. The addition amount of epihalohydrin (x2) is usually in the range of 5.0 to 20 equivalents with respect to 1 equivalent of active hydrogen (carboxyl group) in carboxyl group-containing compounds having a quaternary onium group. preferable.

  An aqueous solution of the alkali metal hydroxide may be used. In that case, the alkali metal hydroxide can be produced by supplying the aqueous solution of the alkali metal hydroxide into the reaction system all at once, intermittently or continuously. .

  Furthermore, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide, etc. are used in order to facilitate the reaction. It is preferable to carry out the reaction by adding. The amount of the solvent used is usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-60 weight%.

  After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Thereafter, the crude compound is dissolved again in a solvent such as toluene and methyl isobutyl ketone, the formed salt is removed by filtration and the like, and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under reduced pressure by heating to an epoxy resin ( a2) can be obtained.

Further, in order to obtain a compound having less hydrolyzable halogen, if necessary, the re-ring closure reaction / purification may be carried out by the same method as in the case of using the above-mentioned phenolic hydroxyl group-containing compound .

  Next, an amino group-containing compound having a quaternary onium group is used as the active hydrogen-containing compound (x1). In this case, an excess amount of epihalohydrin (x2) and water or an alcohol as a cosolvent are used. The amino group-containing compound having a quaternary onium group is gradually charged into the dissolved mixture to form 1,2 chlorohydrin, and then an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added, Or the method of making it react at 20-90 degreeC for 1 to 10 hours, adding is preferable.

  An aqueous solution of the alkali metal hydroxide may be used. In that case, the alkali metal hydroxide can be produced by supplying the aqueous solution of the alkali metal hydroxide into the reaction system all at once, intermittently or continuously. .

  After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Thereafter, the crude compound is dissolved again in a solvent such as toluene and methyl isobutyl ketone, the formed salt is removed by filtration and the like, and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under reduced pressure by heating to an epoxy resin ( a2) can be obtained.

Further, in order to obtain a compound having less hydrolyzable halogen, if necessary, the re-ring closure reaction / purification may be carried out by the same method as in the case of using the above-mentioned phenolic hydroxyl group-containing compound .

  Moreover, in the range which does not impair the effect of this invention, it is also possible to use together epoxy resins other than the above-mentioned epoxy resin (a2) as needed.

  Other epoxy resins that can be used in combination are not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol Novolac type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol Aralkyl epoxy resin, naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic carbonization Containing formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins.

In addition to the method described above, the epoxy resin (a2) may be one obtained by once synthesizing an epoxy resin and further extending the molecular weight with an active hydrogen-containing compound .

  As a method of polyaddition reaction between the active hydrogen-containing compound (a1) and the epoxy resin (a2), for example, in the presence of a catalyst such as an acid, a base, a metal salt, or a metal oxide or without a catalyst, The method performed in presence of a solvent is mentioned. The reaction temperature at this time is preferably 50 to 160 ° C., particularly preferably 60 to 140 ° C. The solvent is not particularly limited as long as the active hydrogen-containing compound (a1) and the epoxy resin (a2) as raw materials can be uniformly dissolved. For example, carbonization such as toluene, xylene, cyclohexane, decalin, etc. Hydrogens, ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, ethoxyethyl propionate, 3-methoxybutyl acetate, methoxypropyl acetate, cellosolve acetate, esters, methanol, ethanol, isopropanol, n- Alcohols such as butanol and isobutanol, cellosolves such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, isobutyl cellosolve, tert-butyl cellosolve, monoglyme, diglyme, triglyme, etc. , Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol mono tert-butyl ether, among these, alcohols and cellosolves Glymes and propylene glycol monoalkyl ethers are preferred.

  As the reaction ratio of the active hydrogen-containing compound (a1) and the epoxy resin (a2), the active hydrogen group in the active hydrogenation-containing compound is 0.80 to 1 equivalent of the epoxy group in the epoxy resin (a2). Preferably it is at 2.5. If it is less than 0.80, the mechanical properties of the coating film may be lowered, and if it is more than 2.5, the liquid resistance of the coating film may be lowered. More preferably, it is 0.90-2.2.

  The compound (A) obtained by the reaction may be used as it is, or may be subjected to a purification step such as removal of a solvent as necessary.

The water (B) used in the present invention is used for uniformly dissolving or dispersing the compound (A), and deionized water is preferable. Water (B) is added at the time of the reaction of the active hydrogen-containing compound (a1) and the epoxy resin (a2) [reaction to obtain the compound (A)] or after completion of the reaction, and is stirred and mixed uniformly. It can be set as an aqueous resin composition. Preferably after compound (A) synthesis.

As the aqueous resin composition of the present invention, a hydrophilic auxiliary can be used as necessary. Examples of hydrophilic auxiliaries include lower alcohols such as methanol, ethanol and isopropanol, and cellosolves such as methyl solosolv, ethyl cellosolve, n-propyl cellosolve, isopropyl cellosolve, butyl cellosolve, isobutyl cellosolve, and tert-butyl cellosolve. , Glymes such as monoglyme, diglyme and triglyme, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol mono n-butyl ether, polypropylene glycol monoisobutyl ether, polypropylene glycol mono-tert-butyl ether Is mentioned.

  Among these, it is preferable to use isopropanol, propyl cellosolve, butyl cellosolve, isobutyl cellosolve, tert-butyl cellosolve, diglyme, propylene glycol monomethyl ether from the viewpoint of good solubility in the epoxy resin (a2) and the compound (A). . These auxiliary agents can be added during the reaction of the active hydrogen-containing compound (a1) and the epoxy resin (a2) or after the completion of the reaction.

In addition, as the aqueous resin composition of the present invention, other polyester-based aqueous resins, acrylic-based aqueous resins, and the like may be used in combination within the range not impairing the characteristics of the present invention.

Furthermore, the aqueous resin composition of the present invention can be used in combination with a curing agent (C) in order to improve the performance of the obtained workpiece, for example, the adhesion to the substrate and the corrosion resistance.

  The curing agent (C) is not particularly limited as long as it is a compound that can undergo a curing reaction with the hydroxyl group in the compound (A). An amino resin, an isocyanate compound, and a phenol resin are preferably used from the viewpoint of excellent membrane performance.

  Examples of the amino resins include melamine resins derived from melamine and aldehyde compounds, guanamine resins derived from aldehyde compounds such as benzoguanamine and acetoguanamine, and urea resins derived from aldehyde compounds such as urea and thiourea. Can be mentioned. These can be used alone or in combination of two or more.

  Further, as the amino resin, those in which amino components such as melamine and urea are co-condensed, and those in which methylol groups in the resin are substituted with alcohols such as methanol, propanol, isopropanol, butanol and isobutanol may be used. it can.

The amino resin is used in a solid content in the amino resin with respect to 100 parts by weight of the resin solid content of the compound obtained by the reaction of the active hydrogen-containing compound (a1) and the epoxy resin (a2) in the aqueous resin composition. Is preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight.

  Although it does not specifically limit as said isocyanate compound, For example, aromatic isocyanates, such as phenylene diisocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate, metaxylylene diisocyanate, as diisocyanate, for example. Aliphatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated metaxylylene diisocyanate, norbornene Alicyclic diisocyanates such as diisocyanates S and the like, and solvent-free, can be used those which are diluted in a solvent.

  Examples of the polyisocyanate other than the diisocyanate include polymethylene polyphenyl isocyanate, dimethyltriphenylmethane tetraisocyanate, triphenylmethane triisocyanate, and tris (isocyanatophenyl) -triphosphate.

  Furthermore, as the isocyanate compound, it is also possible to use those subjected to various modification reactions for the purpose of reducing the vapor pressure, adjusting the viscosity, the number of functional groups, the reactivity, and imparting special physical properties using the above isocyanate. it can. Examples of these are urethane prepolymers that are reaction products with alcohols, allophanate-modified isocyanates obtained by addition reaction of isocyanate groups, biuret-modified isocyanates, uretdione-modified isocyanates, isocyanurate-modified isocyanates, Examples thereof include a carbodiimide-modified product, an uretonimine-modified product, an acylurea diisocyanate product, and the like utilizing an isocyanate group condensation reaction.

  Examples of the urethane prepolymers include diols composed of dimers of unsaturated alcohols such as ethylene glycol, polyethylene glycol, polypropylene glycol, and oleyl alcohol, trimethylolpropane, glycerin, 1,2,6-hexanetriol, Examples thereof include compounds having an isocyanate group at the terminal, obtained by reacting a polyol such as polyester polyol with the isocyanate compound.

  These isocyanate compounds may be used alone or as a mixture of two or more.

Although it does not restrict | limit especially as said isocyanate compound and a usage rate, From the point which is excellent in the said performance of the hardened | cured material obtained, the active hydrogen containing compound (a1) and epoxy resin (a2) in an aqueous resin composition are included. The solid content in the isocyanate compound is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, based on 100 parts by weight of the resin solid content of the compound obtained by the reaction.

  The phenol resin is not particularly limited as long as it is a compound in which a phenol and an aldehyde compound are subjected to a condensation reaction in the presence of a catalyst, and can be used alone or in combination of two or more.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, nonylphenol, and xylenol. Monohydric phenols, bisphenols such as bisphenol A, bisphenol F, tetramethylbisphenol F, bisphenol AD, bisphenol Z, naphthalenediols such as 1,5-dioxynaphthalene, 1,6-dioxynaphthalene, biphenols, Examples thereof include tetramethylbiphenol, and these can be used alone or in combination of two or more.

  As the catalyst, a basic catalyst or an acid catalyst can be used. Examples of the basic catalyst include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, amines, ammonia and the like, and a resol-type condensate is obtained. Examples of the acid catalyst include hydrochloric acid, phosphoric acid, oxalic acid, and the like, and a novolac type condensate is obtained.

The proportion of the phenol resin used is not particularly limited, but the phenol resin is used with respect to 100 parts by weight of the resin solid content of the compound obtained by the reaction of the active hydrogen-containing compound (a1) and the epoxy resin (a2) of the aqueous resin composition. The solid content is preferably 1 to 40 parts by weight, and more preferably 2 to 30 parts by weight.

In addition, the aqueous resin composition of the present invention may contain various additives such as repellency inhibitors, anti-sagging agents, spreading agents, antifoaming agents, curing accelerators, ultraviolet absorbers, and light stabilizers as necessary. You may mix | blend.

Although it does not restrict | limit especially as a use of the aqueous resin composition of this invention, For example, it can use suitably as a coating material, an adhesive agent, a fiber sizing agent, a concrete primer, etc.

When the aqueous resin composition of the present invention is used for coating applications, it is preferable to incorporate various fillers such as rust preventive pigments, colored pigments, extender pigments, various additives, and the like as necessary. Examples of the anticorrosion pigment include zinc powder, aluminum phosphomolybdate, zinc phosphate, aluminum phosphate, barium chromate, aluminum chromate, graphite and other scaly pigments, and the coloring pigment includes carbon black, oxidation pigment, etc. Examples thereof include titanium, zinc sulfide, and bengara. Examples of extender pigments include barium sulfate, calcium carbonate, talc, and kaolin. The blending amount of these fillers is 10 to 70 parts by weight with respect to a total of 100 parts by weight of the compound (A), water (B) and the curing agent (C) blended as necessary. It is preferable from the viewpoints of film performance and painting workability.

The coating method when the aqueous resin composition of the present invention is used for coating is not particularly limited, and can be performed by roll coating, spraying, brushing, spatula, bar coater, dip coating, or electrodeposition coating. As the processing method, room temperature drying to heat curing can be performed. In the case of heating, a coating film can be obtained by reacting at 50 to 250 ° C., preferably 60 to 230 ° C. for 2 to 30 minutes, preferably 5 to 20 minutes.

In addition, when using the aqueous resin composition of the present invention as an adhesive, it is not particularly limited, and can be performed by matching the adhesive surface of the substrate after application to the substrate with spray, brush, spatula, The bonding portion can form a strong adhesive layer by fixing the surrounding area or pressure bonding. Steel plates, concrete, mortar, wood, resin sheets, resin films are suitable as the base material, and various surface treatments such as physical treatment such as polishing, electrical treatment such as corona treatment, and chemical treatment such as chemical conversion treatment are performed as necessary. More preferably, it is applied after application.

In addition, when the aqueous resin composition of the present invention is used as a fiber sizing agent, it can be carried out without any particular limitation. For example, after applying to a fiber immediately after spinning using a roller coater and winding it as a fiber strand And a method of drying. The fiber to be used is not particularly limited. For example, inorganic fibers such as glass fiber, ceramic fiber, asbestos fiber, carbon fiber, and stainless steel fiber, natural fibers such as cotton and hemp, synthetic fibers such as polyester, polyamide, and urethane. Examples of the shape of the base material include short fibers, long fibers, yarns, mats, and sheets. The amount used as the fiber sizing agent is preferably 0.1 to 2% by weight as the resin solid content with respect to the fiber.

Moreover, when using the aqueous resin composition of this invention as a concrete primer, it is not specifically limited, It can carry out with a roll, a spray, a brush, a spatula, and a scissors.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.

Synthesis Example 1 (Synthesis of x1)
A diphenolic acid (hydroxyl equivalent 143 g / eq, carboxyl equivalent 286 g / eq, Otsuka Chemical Co., Ltd.) was added to a four-necked flask equipped with a thermometer, stirring device, dropping funnel, cooling pipe, nitrogen gas introduction pipe, and separation cock at the bottom. Co., Ltd.) 286 parts, SY-GTA80 (glycidyl group-containing quaternary onium salt-80% aqueous solution, Sakamoto Yakuhin Kogyo Co., Ltd.) 227 parts and isopropyl alcohol 120 parts, heated to 50 ° C. and stirred uniformly It was set as the solution. Furthermore, by making it react at the same temperature for 4 hours, the phenolic active hydrogen containing compound (x1-1) which has a quaternary onium group was obtained.

Synthesis example 2
Into the flask (x1-1) obtained in Synthesis Example 1, 370 parts of epichlorohydrin was charged and dissolved while heating to 40 ° C. with stirring. Thereafter, 8 parts of a 49% aqueous sodium hydroxide solution were added and reacted for 4 hours while purging with nitrogen gas. Subsequently, it heated to 50 degreeC and 100 parts of 49-% sodium hydroxide aqueous solution was dripped over 5 hours. Thereafter, 157 parts of water was added to dissolve the produced salt, and then the saturated saline was discarded from the lower separation cock. Unreacted epichlorohydrin was distilled off under atmospheric pressure to a flask temperature of 130 ° C., and then the salt remaining in the reaction solution was filtered off. From the filtrate, an unreacted epichlorohydrin was further distilled off under reduced pressure at a flask temperature of 130 ° C. to obtain an epoxy resin (a2-1) having an epoxy equivalent of 403 g / eq.

Synthesis example 3
In the flask (x1-1) obtained in Synthesis Example 1, 228 parts of bisphenol A and 1480 parts of epichlorohydrin were charged and dissolved while heating to 40 ° C. with stirring. Thereafter, 33 parts of a 49% aqueous sodium hydroxide solution was added and reacted for 4 hours while purging with nitrogen gas. Subsequently, it heated to 50 degreeC and 400 parts of 49% sodium hydroxide aqueous solution was dripped over 5 hours. Then, after adding 564 parts of water and dissolving the produced | generated salt, the saturated salt solution was discarded from the cock for lower liquid separation. Unreacted epichlorohydrin was distilled off under atmospheric pressure to a flask temperature of 130 ° C., and then the salt remaining in the reaction solution was filtered off. From the filtrate, unreacted epichlorohydrin was further distilled off at a flask temperature of 130 ° C. under reduced pressure, and then 99 parts of propyl cellosolve was added and homogenized by stirring to obtain an epoxy having a non-volatile content of 90% and an epoxy equivalent of 277 g / eq. Resin (a2-2) was obtained.

Synthesis example 4
In the flask (x1-1) obtained in Synthesis Example 1, 456 parts of bisphenol A and 2220 parts of epichlorohydrin were charged and dissolved while heating to 40 ° C. with stirring. Thereafter, 58.8 parts of a 49% aqueous sodium hydroxide solution were added and reacted for 4 hours while purging with nitrogen gas. Subsequently, it heated to 50 degreeC and 705 parts of 49% sodium hydroxide aqueous solution was dripped over 5 hours. Thereafter, 800 parts of water was added to dissolve the produced salt, and then the saturated saline was discarded from the lower separation cock. Unreacted epichlorohydrin was distilled off under atmospheric pressure to a flask temperature of 130 ° C., and then the salt remaining in the reaction solution was filtered off. From the filtrate, unreacted epichlorohydrin was further distilled off at a flask temperature of 130 ° C. under reduced pressure, and then 134 parts of propyl cellosolve was added and homogenized with stirring to obtain a non-volatile content of 90% and an epoxy equivalent of 298 g / eq. An epoxy resin (a2-3) was obtained.

Synthesis example 5
A flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube was charged with 300 parts of the epoxy resin (a2-1) obtained in Synthesis Example 2 and 82 parts of butyl cellosolve, and the mixture was heated to 50 ° C. and homogenized with stirring. Next, 27.2 parts of monoethanolamine (alkanolamine, active hydrogen equivalent 30.5 g / eq, manufactured by Nippon Shokubai Co., Ltd.) was added (the active hydrogen / epoxy group equivalent ratio at this time was 1.20. And stirred at 130 ° C. for 4 hours. Furthermore, compound (A-1) was obtained by adding 40 parts of butyl cellosolve and stirring and homogenizing. In (A-1), 486 parts of ion-exchanged water was added in portions, and the mixture was stirred and homogenized to obtain a white liquid aqueous resin composition (E-1) having a nonvolatile content of 35%.

Synthesis Example 6
A flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube was charged with 300 parts of the epoxy resin (a2-2) obtained in Synthesis Example 3 and 76 parts of butyl cellosolve, and the temperature was raised to 50 ° C. and the mixture was stirred and homogenized. Next, 35.6 parts of monoethanolamine was added (the active hydrogen / epoxy group equivalent ratio at this time was 1.20), and the mixture was stirred at 130 ° C. for 4 hours. Furthermore, compound (A-2) was obtained by adding 25 parts of butyl cellosolve and stirring and homogenizing. In (A-2), 436 parts of ion-exchanged water was added in portions, and the mixture was stirred and homogenized to obtain a white liquid aqueous resin composition (E-2) having a nonvolatile content of 35%.

Synthesis example 7
A flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube was charged with 300 parts of the epoxy resin (a2-2) obtained in Synthesis Example 3, 102.6 parts of bisphenol A, and 124 parts of butyl cellosolve, and the temperature was raised to 80 ° C. Stirring was homogenized. The mixture was further heated to 140 ° C. and stirred for 7 hours to obtain an epoxy resin having an epoxy equivalent of 5100 g / eq. Next, 7.7 parts of diethanolamine (alkanolamine, active hydrogen equivalent 105 g / eq, manufactured by Mitsui Chemicals, Inc.) was added (the equivalent ratio of active hydrogen / epoxy group at this time was 1.00) and the same temperature. For 6 hours. Further, 51 parts of butyl cellosolve was added and the mixture was stirred and homogenized to obtain compound (A-3). In (A-3), 622 parts of ion-exchanged water was added in portions, and the mixture was stirred and homogenized to obtain a white liquid aqueous resin composition (E-3) having a nonvolatile content of 35%.

Synthesis Example 8
A flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube was charged with 300 parts of the epoxy resin (a2-3) obtained in Synthesis Example 4, 73 parts of bisphenol A, and 60 parts of butyl cellosolve. Made it. The mixture was further heated to 140 ° C. and stirred for 4 hours to obtain an epoxy resin having an epoxy equivalent of 1350 g / eq. Next, 15.5 parts of monoethanolamine was added (the active hydrogen / epoxy group equivalent ratio at this time was 2.00), and the mixture was stirred at the same temperature for 6 hours. Further, 84 parts of butyl cellosolve was added and the mixture was stirred and homogenized to obtain compound (A-4). In (A-4), 492 parts of ion-exchanged water was added in portions, and the mixture was stirred and homogenized to obtain a white liquid aqueous resin composition (E-4) having a nonvolatile content of 35%.

Synthesis Example 9
A flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube was charged with 300 parts of the epoxy resin (a2-2) obtained in Synthesis Example 3 and 33.3 parts of bisphenol A, and the temperature was raised to 140 ° C. and stirred for 2 hours. An epoxy resin having an epoxy equivalent of 460 g / eq was obtained. Furthermore, 117 parts of bisphenol A (the equivalent ratio of active hydrogen / epoxy group at this time is 1.40) and 106 parts of butyl cellosolve were added, and after heating to 160 ° C. and stirring for 5 hours, 109 parts of butyl cellosolve were added. The compound (A-5) was obtained by stirring and homogenizing. In (A-5), 708 parts of ion-exchanged water was added in portions, and the mixture was stirred and homogenized to obtain a light brown liquid aqueous resin composition (E-5) having a nonvolatile content of 30%.

Synthesis Example 10
A flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube was charged with 300 parts of the epoxy resin (a2-1) obtained in Synthesis Example 2 and 15 parts of bisphenol A, heated to 140 ° C. and stirred for 2 hours to obtain an epoxy equivalent. An epoxy resin of 550 g / eq was obtained. Further, 52.4 parts of monoethanolamine (the active hydrogen / epoxy group equivalent ratio at this time is 3.00) and 35 parts of butyl cellosolve were charged, heated to 160 ° C. and stirred for 5 hours, and then butyl cellosolve 104 The compound (A-6) was obtained by adding a part and stirring uniform. In (A-6), 708 parts of ion-exchanged water was added in portions, and the mixture was stirred and homogenized to obtain a light brown liquid aqueous resin composition (E-6) having a nonvolatile content of 30%.

Synthesis Example 11
EPICLON 1055 (Bisphenol A type solid epoxy resin, epoxy equivalent 475 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.) is attached to a four-necked flask equipped with a thermometer, stirring device, dropping funnel, cooling tube, and nitrogen gas introduction tube. ) 300 parts and 135 parts of butyl cellosolve were charged, heated to 100 ° C. and stirred and homogenized, then 4 parts of monoethanolamine, Jeffamine M-1000 (polyoxyalkylene compound, manufactured by PTI Japan Ltd.) 101 The portions were sequentially charged while paying attention to heat generation, and the reaction was carried out at 130 ° C. until the solution viscosity was saturated to obtain compound (A-7). 360 parts of ion-exchanged water was added to (A-7) and the mixture was stirred and homogenized to obtain a white translucent liquid aqueous resin composition (E-7) having a nonvolatile content of 45%.

Synthesis Example 12
EPICLON 2055 (Bisphenol A type solid epoxy resin, epoxy equivalent 625 g / eq, manufactured by Dainippon Ink & Chemicals, Inc.) ) 300 parts and 180 parts of diglyme were charged, heated to 70 ° C. and homogenized with stirring, 21 parts of monoethanolamine was added, and the mixture was reacted at 100 ° C. for 7 hours. After cooling to 70 ° C., 59 parts of succinic anhydride was added, the temperature was raised to 95 ° C. and reacted for 1 hour. Next, the reaction solution is cooled to 60 ° C., 35 parts of 29% ammonia water is added, and after stirring and homogenizing, 527 parts of ion-exchanged water is added, and stirring is homogenized to form a pale yellow translucent liquid having a nonvolatile content of 33%. Aqueous resin composition (E-8) was obtained.

Table 1 shows the property values of the aqueous resin compositions (E-1) to (E-8) obtained in Synthesis Examples 5 to 12 and changes in the appearance during storage in a dryer at 40 ° C. In Table 1, varnish storage stability was measured by weighing 90 g of the aqueous resin composition into a 100 ml mayonnaise bottle and storing it in a dryer at 40 ° C., and visually observing the appearance after 3 months.
○: No precipitation or separation. X: Separation or aggregate generation.
Moreover, the mayonnaise bottle 3 months after the stability test was opened, and a sensory test was performed for odor.
○: No odor. X: Odor is present.

Footnotes in Table 1 NV (%): non-volatile content in aqueous resin composition

Test Examples 1-14 and Comparative Test Examples 1-9
Next, using the obtained aqueous resin composition, water-based paints were prepared with the blending ratios shown in Tables 2 to 4, and the dried film was formed with a bar coater on a cold-rolled steel sheet that had been surface-treated with # 400 sandpaper. After coating so as to have a thickness of 20 μm, the physical properties of the coating film were evaluated. The lacquer coating properties shown in Table 2 are test results after baking at 100 ° C. for 20 minutes, and the coating properties shown in Tables 3 and 4 are test results after baking at 160 ° C. for 20 minutes. Each test method and evaluation criteria are as follows. The PWC in the paint is 50%.

Weight drop resistance: In accordance with JIS K-5600-5-3 (1999), a DuPont type was used with a striker of 1/2 inch and a load of 500 g.
◯: No crack or the like at 50 cm. X: Generation | occurrence | production of a crack etc. is recognized by 50 cm.

Adhesion test: According to JIS K-5600-5-6 (1999), cuts were made at intervals of 1 mm, and the state of the coating film was visually observed after peeling off after applying the tape.
○: No peeling. X: Peeling is seen.

Liquid resistance (water immersion method): In accordance with JIS K-5600-2 (1999), the occurrence of swelling on the coating surface immersed at 40 ° C. for 1 week was observed.
◯: No swelling occurs. X: Swelling occurred.

Medium-resistant salt sprayability: Performed according to JIS K-5600-7-1 (1999). The presence or absence of blisters in the flat part after the 300 hr test was confirmed.
◯: No swelling occurs. X: Swelling occurred.

Footnotes in Table 2 Paint NV: Paint non-volatile content%
K-White: Anti-corrosion pigment manufactured by Teika Co., Ltd. CR-97: Titanium oxide Type CR-97 manufactured by Ishihara Sangyo Co., Ltd.
NS-100: Nitto Powder Co., Ltd. Calcium carbonate SN deformer 777: Sannopco Corporation antifoam agent BYK-341: Big Chemie company additive

Footnotes in Table 3 S-695: Water-soluble methyl etherified melamine resin “Watersol S-695” manufactured by Dainippon Ink and Chemicals, Inc., 65% nonvolatile content
Curing catalyst: Dainippon Ink & Chemicals, Inc. Becamine P-198

Footnote DNW-500 in Table 4: Water-soluble isocyanate “Bernock DNW-500” manufactured by Dainippon Ink & Chemicals, Inc. 80% non-volatile content, NCO content 13.5%

Claims (10)

An aqueous resin composition containing a compound (A) obtained by reacting an active hydrogen-containing compound (a1) with an epoxy resin (a2) and water (B), wherein the epoxy resin (a2) is a quaternary onium group An aqueous resin composition characterized by being obtained by reacting an active hydrogen-containing compound (x1) with an epihalohydrin (x2). The active hydrogen-containing compound (x1) having a quaternary onium group is a compound obtained by reacting a compound (y1) having both phenolic and carboxyl active hydrogens with a quaternary onium salt-containing epoxy compound (y2). The aqueous resin composition according to claim 1. The compound (y1) having both the phenolic and carboxyl active hydrogens is represented by the following general formula (1)

[In Formula (1) , R1, R2, R3, R4, R5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y is a single bond or an alkylene chain having 1 to 4 carbon atoms. is there. ]
The aqueous resin composition of Claim 2 which is a compound shown by these. The quaternary onium salt-containing epoxy compound (y2) is represented by the following general formula (2)

(Wherein R6 is a hydrogen atom or a methyl group, Q is a nitrogen atom or a phosphorus atom, X is a chlorine atom, a bromine atom or an iodine atom, and R7, R8 and R9 are each independently an alkyl group or an aryl group. Represents a group.)
The aqueous resin composition of Claim 2 or 3 which is a compound represented by these. The aqueous resin composition according to claim 4, wherein R7, R8 and R9 in the general formula (2) are each independently a linear alkyl group having 1 to 4 carbon atoms. The aqueous resin composition according to any one of claims 1 to 5, wherein the active hydrogen-containing compound (x1) having a quaternary onium group is an active hydrogen-containing compound having a quaternary ammonium group. The compound (A) is reacted by using 0.80 to 2.50 times equivalent of active hydrogen in the active hydrogen-containing compound (a1) to 1 equivalent of epoxy group in the epoxy resin (a2) The aqueous resin composition according to any one of claims 1 to 6, wherein The aqueous resin composition according to any one of claims 1 to 7, wherein the active hydrogen-containing compound (a1) is an amino active hydrogen-containing compound or a phenolic hydroxyl group-containing compound. The aqueous resin composition according to any one of claims 1 to 8, further comprising a curing agent (C). The aqueous resin composition according to claim 9, wherein the curing agent (C) is a compound selected from at least one of an amine compound and an isocyanate compound.