JP2007182496A - Aqueous epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous epoxy resin composition exhibiting good dispersibility in water and film-forming properties, and providing a coated film having excellent anticorrosion property. <P>SOLUTION: The aqueous epoxy resin composition contains (A) an epoxy resin and (B) an amine-based curing agent. The amine-based curing agent (B) is a compound obtained by reacting (b-1) a polyamine compound with (b-2) an epoxy group-containing resin obtained by reacting (x1) a compound having active hydrogen, with (x2) an epihalohydrin and (x3) a quaternary onium salt-containing epoxy compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aqueous epoxy resin composition that exhibits good water dispersibility and film-forming properties and can provide a coating film with excellent anticorrosion properties.

  In general, epoxy resin compositions have excellent mechanical and electrical properties, and cured products with good adhesion, solvent resistance, water resistance, heat resistance, etc. can be obtained. Widely used in chemicals, paints, civil engineering and other applications.

  Especially for paint applications, solvent dilution types using various organic solvents were common, but in recent years, volatile organic compounds (VOC) have been used from the viewpoint of global environmental conservation including air pollution prevention and work environment improvement. ) Progress toward the implementation of total volume regulation. For this reason, the water-based epoxy resin composition which does not use an organic solvent attracts attention. The aqueous epoxy resin composition is advantageous in terms of working environment, handling workability, and the like, and the development of a curing agent used in the aqueous epoxy resin composition is being actively conducted.

  Conventionally, a modified polyamine obtained by adding an epoxy compound to a polyamine compound is known as a curing agent for an aqueous epoxy resin. However, such a modified polyamine can be dispersed in water when the addition rate of the epoxy compound is small. Although the solubility is relatively good, the resulting cured product has poor anticorrosion properties.On the other hand, increasing the addition rate has the problem that the anticorrosion properties are improved, but the dispersibility and solubility in water are insufficient. ing.

  As a means for improving the above problem, for example, a curing agent for an aqueous epoxy resin obtained by modifying a polyamine compound having an oxypropylene chain with a specific polyglycidyl ether compound having an oxypropylene chain has been proposed (for example, Patent Document 1). reference.). However, the cured coating film obtained using the aqueous epoxy resin curing agent proposed in Patent Document 1 still has a water resistance that is not at a practical level, and further improvements are required.

JP-A-9-227658 (pages 3-6)

  In view of the above circumstances, an object of the present invention is to provide an aqueous epoxy resin composition that exhibits good water dispersibility and film-forming properties and can provide a coating film having excellent corrosion resistance.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an epoxy group-containing resin obtained by reacting an active hydrogen-containing compound, an epihalohydrin, and a quaternary onium salt-containing epoxy compound as an amine-based curing agent. By using an epoxy adduct compound obtained by reacting with a polyamine compound, it was found that a cured coating film having excellent water dispersibility, film-forming property and good anticorrosion property was obtained, and the present invention was completed. It was.

  That is, the present invention is an aqueous epoxy resin composition containing an epoxy resin (A) and an amine-based curing agent (B), and the amine-based curing agent (B) is active with the polyamine compound (b-1). A compound obtained by reacting a compound (x1) having hydrogen, an epihalohydrin (x2) and an epoxy group-containing resin (b-2) obtained by reacting a quaternary onium salt-containing epoxy compound (x3). The present invention provides an aqueous epoxy resin composition.

  According to the present invention, it is possible to provide a curing agent for an aqueous epoxy resin that exhibits good water dispersibility when mixed with an epoxy resin, and the coating film obtained using the aqueous epoxy resin composition has anticorrosion properties, etc. Therefore, it can be suitably used for paints, adhesives, fiber sizing agents, concrete primers and the like.

Hereinafter, the present invention will be described in detail.
The epoxy resin (A) used in the present invention may be a compound having an epoxy group in the molecule, and the structure thereof is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, p-tert-butylphenol novolak type epoxy resin, nonylphenol novolak Type epoxy resins, polyvalent epoxy resins such as t-butylcatechol type epoxy resins, etc., and monovalent epoxy resins include aliphatic alcohols such as butanol, aliphatic alcohols having 11 to 12 carbon atoms, phenol, Monohydric phenols such as p-ethylphenol, o-cresol, m-cresol, p-cresol, p-tertiarybutylphenol, s-butylphenol, nonylphenol, xylenol and the like. A condensate with halohydrin, a condensate of monovalent carboxylic acid such as neodecanoic acid and epihalohydrin, and the like. Examples of glycidylamine include a condensate of diaminodiphenylmethane and epihalohydrin. And polyglycidyl ethers of vegetable oils such as soybean oil and castor oil, and polyvalent alkylene glycol type epoxy resins include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, erythritol , Polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, a condensate of trimethylolpropane and epihalohydrin, and further, an aqueous epoxy resin described in JP-A-2005-239928, and the like. These can be used in one kind, or may be used in combination of two or more.

  Even if the epoxy resin (A) is liquefied and reduced in viscosity by adding an organic solvent or a non-reactive diluent as necessary, a surfactant such as a polyoxyethylene alkylphenyl ether compound is used. An emulsified epoxy resin emulsified in advance may be used.

  Among these, it is preferable to use a bisphenol type epoxy resin or a t-butylcatechol type epoxy resin from the viewpoint of good curability of the aqueous epoxy resin composition and excellent corrosion resistance of the resulting cured coating film. It is preferable to use a bisphenol type epoxy resin.

  The amine curing agent (B) used in the present invention is an epoxy group-containing resin (x3) obtained by reacting an active hydrogen-containing compound (x1), an epihalohydrin (x2), and a quaternary onium salt-containing epoxy compound (x3). It is an epoxy adduct compound obtained by further reacting b-2) with the polyamine compound (b-1). By using such an amine-based curing agent (B), it is possible to combine the water dispersibility of the composition, which has been a problem with aqueous epoxy resin curing agents, and the corrosion resistance of the cured coating film. It is possible.

  The polyamine compound (b-1) is not particularly limited, and aliphatic polyamines, aromatic polyamines, heterocyclic polyamines, epoxy adducts thereof, Mannich modified products, polyamide modified products, and the like are used. Is possible. For example, methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1 , 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc., diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylene Decamine, trimethylhexamethylenediamine, etc., tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2′-aminoethylamino) propane, triethylene-bis (trime Len) hexamine, bis (3-aminoethyl) amine, bishexamethylenetriamine, etc., 1,4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexylamine, norbornadiamine Bis (aminomethyl) cyclohexane, diaminodicyclohexylmethane, isophoronediamine, mensendiamine, etc., bis (aminoalkyl) benzene, bis (aminoalkyl) naphthalene, bis (cyanoethyl) diethylenetriamine, o-xylylenediamine, m-xylylenediamine Amine, p-xylylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis (4-aminophenyl) propane, 4, '-Diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4'- Diaminobiphenyl, 2,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene, etc., N- Methylpiperazine, morpholine, 1,4-bis- (8-aminopropyl) -piperazine, piperazine-1,4-diazacycloheptane, 1- (2′-aminoethylpiperazine), 1- [2 ′-(2 "-Aminoethylamino) ethyl] piperazine, 1,11-diazacycloeicosane, 1,15-di" Azacyclooctacosane and the like can be mentioned, and they can be used alone or as a mixture of two or more.

  Among these, aliphatic polyamines are preferable from the viewpoint of excellent curability, and metaxylylenediamine, isophoronediamine, and triethylenetetramine are preferably used from the viewpoint of excellent mechanical properties of the resulting cured product.

  The epoxy group-containing resin (b-2) contains a quaternary onium salt as a raw material when a conventional method for obtaining an epoxy resin by reacting an active hydrogen-containing compound (x1) with an epihalohydrin (x2). An epoxy compound (x3) is used in combination.

  As the compound (x1) having active hydrogen, any compound having an epoxy group can be obtained by reaction with epihalohydrin (x2). For example, a phenolic hydroxyl group-containing compound, an alcoholic hydroxyl group-containing compound, a carboxyl group Examples thereof include a compound containing compound and an amino group-containing compound. Among these, it is preferable to use a compound having a phenolic hydroxyl group from the viewpoint that the resulting aqueous epoxy resin composition is excellent in curability and the cured product has good mechanical properties.

  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) and substitution thereof Group-containing bodies and the like. Nord novolak resin, cresol novolak resin, p-tert-butylphenol novolak resin, nonylphenol novolak resin, Zizi Black pentadiene phenol resin, t- butyl catechol, hydroquinone, resorcinol, and the like. Monovalent phenols can be used in combination for the purpose of adjusting the molecular weight of the resulting epoxy group-containing resin (b-2), for example, phenol, p-ethylphenol, o-cresol, m-cresol. , P-cresol, p-tertiarybutylphenol, s-butylphenol, 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 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.

  Examples of the quaternary onium salt-containing epoxy compound (x3) used in the present invention include epoxy group-containing vinyl monomers such as glycidyl acrylate, glycidyl methacrylate, and alicyclic monoepoxide having a vinyl group, and quaternary onium salts. A copolymer with a vinyl monomer having a quaternary onium salt such as an acrylic acid monomer having the following general formula (1)

（式中、Ｒは水素原子又はメチル基であり、Ｑは窒素原子又はリン原子であり、Ｘは塩素原子、臭素原子又はヨウ素原子であり、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれアルキル基又はアリール基であり、これらは同一でも異なっていても良い。）
で表される化合物が挙げられる。

(In the formula, R 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 R ₁ , R ₂ and R ₃ are each an alkyl group or An aryl group, which may be the same or different.)
The compound represented by these is mentioned.

  Examples of the alicyclic monoepoxide having a vinyl group include Celoxide 2000 (trade name: manufactured by Daicel Chemical Industries, Ltd.). Examples of the acrylic acid monomer having a quaternary onium salt include, for example, DMAEA-Q ( Kojin Co., Ltd., N, N-dimethylaminoethyl acrylate-methyl chloride salt, 79% aqueous solution) and DMAPAA-Q (Kojin Co., Ltd., N, N-dimethylaminopropylacrylamide-methyl chloride salt, 75% Aqueous solution) and the like.

  In addition, as the quaternary onium salt-containing epoxy compound (x3), a compound obtained by copolymerizing an epoxy group-containing vinyl monomer and an acrylic monomer having acrylamide or a tertiary amine and then quaternizing with an alkyl halide may be used. it can.

Among these, it is preferable to use the compound represented by the general formula (1) from the viewpoint of excellent curability of the obtained aqueous epoxy resin composition, and it is particularly easy to obtain the general formula (1). ), R ₁ , R ₂ and R ₃ are preferably the same or different, each having a linear alkyl group having 1 to 4 carbon atoms, wherein R is a hydrogen atom, Q is a nitrogen atom, R ₁ SY-GTA80 [trade name, Sakamoto Yakuhin Kogyo Co., Ltd., NV = 80% aqueous solution, epoxy equivalent (solid content): 151 g / eq], wherein R ₂ and R ₃ are methyl groups and X is a chlorine atom Most preferably, it is used.

The quaternary onium salt-containing epoxy compound (x3) is an addition reaction of an epoxy group to an active hydrogen in a compound (x1) having an active hydrogen, or a reaction between a compound (x1) having an active hydrogen and an epihalohydrin (x2). The epoxy group-containing resin (b-2) is incorporated into the molecule of the epoxy group-containing resin (b-2) by the addition reaction of the epoxy group to the hydroxyl group of the halohydrin produced by the above-mentioned method. It becomes a mixture. Since the halogen ion content in the epoxy group-containing resin (b-2) obtained using the quaternary onium salt-containing epoxy compound (x3) is at a level of several ppm, the quaternary incorporated in the molecule. The counter ion of the onium salt is OH ⁻ due to an alkali used as a catalyst described later. That the counter ion is OH ⁻ is also useful as an electronic material and has high industrial value.

  The manufacturing method of the said epoxy group containing resin (b-2) is explained in full detail. The production method is not limited at all except that the compound (x1) having an active hydrogen, epihalohydrin (x2), and quaternary onium salt-containing epoxy compound (x3) are used as raw materials. In the case of using a phenolic hydroxyl group-containing compound, for example, sodium hydroxide, A method of adding an alkali metal hydroxide such as potassium hydroxide or reacting at 20 to 120 ° C. for 1 to 10 hours while adding is preferable. The added amount of epihalohydrin (x2) is usually in the range of 0.3 to 20 equivalents, preferably 0.6 to 4.4, per 1 equivalent of active hydrogen (hydroxyl group) in the phenolic hydroxyl group-containing compound. The range is 0 equivalent. The amount of the quaternary onium salt-containing epoxy compound (x3) used is preferably in the range of 0.01 to 0.30 equivalents relative to 1 equivalent of active hydrogen (hydroxyl group) of the phenolic hydroxyl group-containing compound. Is in the range of 0.03 to 0.15 equivalent, and is preferably set as appropriate according to the epoxy equivalent of the target epoxy group-containing resin (A).

  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, trimethylbenzylammonium chloride, etc. is catalyzed in a dissolved mixture of a phenolic hydroxyl group-containing compound, epihalohydrin (x2) and a quaternary onium salt-containing epoxy compound (x3) Then, a solid or aqueous solution of an alkali metal hydroxide is added to the halohydrin etherified product of the phenol obtained by reacting at 50 to 150 ° C. for 1 to 5 hours, and again at 20 to 120 ° C. for 1 to 10 hours. A method of reacting and dehydrohalogenating (ring closure) may also 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 or methyl isobutyl ketone, and the resulting salt is removed by filtration, etc., and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to contain an epoxy group. Resin (b-2) 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, then the salt generated by dehydration filtration is removed, and further, toluene, methyl isobutyl ketone, etc. are heated under reduced pressure. Epoxy group-containing resin (b-2) can be obtained by distilling off the solvent.

  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, dehydration filtration, and the like, and further, a solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain an epoxy group-containing resin (b-2).

  Next, the case where the alcoholic hydroxyl group-containing compound is used as the compound (x1) having active hydrogen will be described in detail. When using an alcoholic hydroxyl group-containing compound, there are roughly two methods. In the first method, Lewis acid such as boron trifluoride ether complex was added to a dissolved mixture of alcohol and quaternary onium salt-containing epoxy compound (x3), and epihalohydrin (x2) was added dropwise to react. Examples include a method in which an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is further added to the halohydrin adduct obtained later, or a ring-closing reaction is performed at 20 to 120 ° C. for 1 to 10 hours while adding. At this time, a reaction solvent such as toluene can be used if necessary.

  In the second method, a quaternary compound such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride is dissolved in a dissolved mixture of an alcoholic hydroxyl group-containing compound, epihalohydrin (x2), and a quaternary onium salt-containing epoxy compound (x3). Add quaternary phosphonium salts such as ammonium salt, ethyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetra-n-butylphosphonium bromide, etc., and add alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Or a method of reacting at 20 to 120 ° C. for 1 to 10 hours while adding.

  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 or methyl isobutyl ketone, and the resulting salt is removed by filtration, etc., and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to contain an epoxy group. Resin (b-2) 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.

  When the carboxyl group-containing compound is an active hydrogen-containing compound (x1), it is hydroxylated into a dissolved mixture of the carboxyl group-containing compound, a large excess of epihalohydrin (x2), and a quaternary onium salt-containing epoxy compound (x3). The method of making it react at 20-120 degreeC for 1 to 10 hours, adding alkali metal hydroxides, such as sodium and potassium hydroxide, is added. If necessary, a quaternary ammonium salt or the like may be used as a catalyst. The added amount of epihalohydrin (x2) is usually in the range of 5.0 to 20 equivalents relative to 1 equivalent of active hydrogen (carboxyl group) in the carboxyl group-containing compounds. Moreover, it is preferable to use a quaternary onium salt containing epoxy compound (x3) in the range of 0.01-0.30 equivalent with respect to 1 equivalent of active hydrogen (carboxyl group) of a carboxyl group-containing compound.

  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 (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 or methyl isobutyl ketone, and the resulting salt is removed by filtration, etc., and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to contain an epoxy group. Resin (b-2) 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, the amino group-containing compound is used as the compound (x1) having active hydrogen. In this case, an excess amount of epihalohydrin (x2), quaternary onium salt-containing epoxy compound (x3), and The amino group-containing compound is gradually charged into a dissolved mixture of water and alcohols as a solvent to form 1,2 halohydrins, and then an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. Alternatively, a method of reacting at 20 to 90 ° C. for 1 to 10 hours while adding is preferable.

  The addition reaction between the amino group and the epihalohydrin (x2) proceeds even without a catalyst, and is accompanied by a rapid exotherm. If necessary, a part of the epihalohydrin (x2) is allowed to coexist with the quaternary onium salt-containing epoxy compound (x3). The remaining epihalohydrin (x2) may be charged after the amino group-containing compound is charged. The added amount of epihalohydrin (x2) is usually in the range of 1.5 to 20 equivalents per 1 equivalent of active hydrogen in the amino group-containing compounds. Moreover, it is preferable to use a quaternary onium salt containing epoxy compound (x3) in the range of 0.01-0.30 equivalent with respect to 1 equivalent of active hydrogens of an amino group containing compound.

  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 or methyl isobutyl ketone, and the resulting salt is removed by filtration, etc., and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to contain an epoxy group. Resin (b-2) 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.

  The amine-based curing agent (B) used in the present invention is a so-called epoxy adduct type curing agent obtained by reacting the polyamine compound (b-1) with the epoxy group-containing resin (b-2). However, when this reaction is performed, it is also possible to perform an adduct reaction using a conventionally known epoxy resin in combination with the epoxy group-containing resin (b-2) as long as the effects of the present invention are not impaired. .

  The reaction between the polyamine compound (b-1) and the above-described epoxy group-containing resin (b-2) can be carried out under conditions conventionally known as addition reactions. At this time, it can be carried out in the absence of a solvent or in an appropriate solvent, and as a usable solvent, the compound (b-1) and the epoxy group-containing resin (b-2) are further used in combination as necessary. It is not particularly limited as long as it uniformly dissolves other epoxy resins and is inactive. For example, water, methanol, ethanol, isopropanol, n-butanol, isobutanol and other alcohols, toluene, xylene , Hydrocarbons such as cyclohexane and decalin, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, ethoxyethyl propionate, 3-methoxybutyl acetate, methoxypropyl acetate, cellosolve acetate, methyl Cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, Cellosolves such as butyl cellosolve, tert-butyl cellosorb, glymes such as monoglyme, diglyme, triglyme, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, propylene glycol mono tert-butyl ether 1 type or 2 types or more of mixed solvents can be used. Among these, the solution of the reaction product obtained can be used as it is as the aqueous epoxy resin composition of the present invention, so that water alone or a mixed solvent of water and alcohols, cellosolves and glymes is used. It is preferable to use it.

  The reaction ratio between the polyamine compound (b-1) and the epoxy group-containing resin (b-2) is not particularly limited, but water dispersibility when obtained as an aqueous epoxy resin composition, and Epoxy group-containing resin (b-2) containing other epoxy resin with respect to 1 mol of active hydrogen of the amino group in polyamine compound (b-1) from the point which is excellent in the balance with the anticorrosion property of the cured coating film obtained It is preferable to use it so that the total amount of epoxy groups in it may be 0.02 to 0.30 mol, and it is particularly preferable to use it so as to be 0.05 to 0.20 mol. Although it does not specifically limit as reaction conditions in this reaction, Usually, 40-130 degreeC, Preferably it is 60-120 degreeC, It can carry out by stirring for 1 to 6 hours, Preferably it is 2 to 4 hours.

  The amine-based curing agent (B) 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, and may be further homogenized by adding water. good. Two or more amine curing agents (B) may be used in combination in the aqueous epoxy resin composition of the present invention.

  The amine-based curing agent (B) obtained by the above reaction exhibits water dispersibility by itself, but an organic acid such as acetic acid may be used as necessary to give better water dispersibility. The amino group may be neutralized by water dispersion.

  The aqueous epoxy resin composition of the present invention is not limited in any way other than using the epoxy resin (A) and the amine-based curing agent (B), and within the range not impairing the effects of the present invention. Epoxy resin curing agents, film-forming aids, other polyester aqueous resins, acrylic aqueous resins, etc., reactive diluents, non-reactive diluents, fillers, reinforcing agents, pigments, plasticizers, thixotropic agents, Additives such as anti-repellent agents, anti-sagging agents, spreading agents, antifoaming agents, curing accelerators, ultraviolet absorbers, and light stabilizers can be used in combination as appropriate.

The other curing agent is not particularly limited, and may be various amine compounds, amide compounds, phenolic compounds as long as they can be cured and reacted with the epoxy group in the epoxy resin (A). Any curing agent such as a compound can be used. Examples of amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like. Examples of amide compounds include dicyandiamide and linolenic acid. Polyamide resins synthesized from ethylenediamine and the like, and phenolic compounds include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resins, Phenol aralkyl resin (commonly known as zylock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak Fatty, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resin (phenol nuclei are linked by bismethylene groups) Polyhydric naphthol compounds), aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.), and modified products thereof.

  The blending amount of the epoxy resin (A) and the amine curing agent (B) in the aqueous epoxy resin composition of the present invention is not particularly limited, but from the point that the properties of the resulting cured product are good. The amount of active groups in the curing agent containing the amine curing agent (B) is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the total epoxy groups in the epoxy resin (A).

  Examples of the film-forming aid include lower alcohols such as methanol, ethanol and isopropanol, cellosolves such as methyl cellosolve, ethyl cellosolve, n-propyl cellosolve, isopropyl cellosolve, butyl cellosolve, isobutyl cellosolve, and tert-butyl cellosolve, Glymes such as monoglyme, diglyme and triglyme, propylene such as propylene glycol monomethyl ether, polypropylene glycol monoethyl ether, propylene glycol monopropyl ether, polypropylene glycol mono n-butyl ether, polypropylene glycol monoisobutyl ether, polypropylene glycol mono-tert-butyl ether Examples include glycol monoalkyl ethers and diacetone alcohol It is.

  Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts.

  The aqueous epoxy resin composition of the present invention can be obtained by emulsifying and / or dispersing in water together with the epoxy resin (A), the amine-based curing agent (B) and additives used as necessary. At this time, after emulsifying and / or dispersing the epoxy resin (A) and the amine-based curing agent (B), respectively, the two are mixed, and one is emulsified and / or dispersed while the other is added to emulsify and Either a method of dispersing and / or a method of emulsifying and / or dispersing both at the same time can be applied.

  The aqueous epoxy resin composition obtained as described above is coated by an appropriate method such as brush coating, roller, spray, spatula coating, press coating, doctor blade coating, electrodeposition coating, dip coating, or the like. It is used as an undercoating or intermediate coating, filler, sealing material, coating material, sealing material, mortar coating material, etc. by applying to materials, and is particularly useful as an anticorrosion coating for metals because of its excellent anticorrosion properties .

  Although it does not restrict | limit especially as a use of the water-based epoxy 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 epoxy 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 rust preventive pigment include zinc powder, aluminum phosphomolybdate, zinc phosphate, aluminum phosphate, barium chromate, aluminum chromate, and scaly pigments such as graphite. Color pigments include carbon black, oxidized Examples thereof include titanium, zinc sulfide, and bengara. Examples of extender pigments include barium sulfate, calcium carbonate, talc, and kaolin. As a compounding quantity of these fillers, it is 10-70 weight part with respect to a total of 100 weight part of an epoxy resin (A), an amine hardening | curing agent (B), and the other hardening | curing agent mix | blended as needed. Is preferable from the viewpoints of coating film performance, coating workability, and the like.

  The method of blending the filler and additive into the aqueous epoxy resin composition of the present invention is not particularly limited. For example, the filler and additive are sufficiently kneaded and uniformly dispersed using an apparatus such as a mixing mixer or a ball mill. Prepared in advance, kneaded and dispersed epoxy resin previously emulsified with the above-mentioned apparatus, prepared with water to a desired concentration, and mixed with an amine curing agent. Can be obtained.

  The coating method in the case of using the aqueous epoxy resin composition of the present invention for coating is not particularly limited, and may be performed by roll coating, spraying, brushing, spatula, bar coater, dip coating, electrodeposition coating method. 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 the aqueous epoxy resin composition of the present invention is used as an adhesive, it is not particularly limited, and can be performed by applying the sprayed, brushed, or spatula to the base material, and then matching the adhesive surface of the base material. In addition, the bonding portion can form a strong adhesive layer by fixing or pressing the periphery. 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.

  Further, when the aqueous epoxy resin composition of the present invention is used as a fiber sizing agent, it can be carried out without any particular limitation. For example, the fiber immediately after spinning is applied using a roller coater and wound as a fiber strand. Thereafter, a method of drying is mentioned. The fiber used is not particularly limited. For example, inorganic fibers such as glass fiber, ceramic fiber, asbestos fiber, carbon fiber, and stainless 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, sheets, and the like. 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 water-based epoxy 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.

<Example of epoxy resin emulsion synthesis>
Synthesis example 1
500 g of EPICLON 1055 (manufactured by Dainippon Ink and Chemicals, BPA type solid epoxy resin) was dissolved in 47.5 g of benzyl alcohol and 47.5 g of methoxypropanol at 100 ° C. To this resin solution, 40 g of Newcol 780 (60) (manufactured by Nippon Emulsifier Co., Ltd.) was added and dissolved sufficiently. After dissolution, the temperature was lowered, and water was added in portions while stirring at 50-60 ° C. at high speed to obtain an emulsion having a nonvolatile content of 55%. The obtained epoxy resin emulsion (A-1) had an epoxy equivalent (solution value) of 930 g / eq and a viscosity (25 ° C.) of 2350 mPa · s.

<Synthesis example of epoxy group-containing resin for adduct>
Synthesis example 2
A flask equipped with a thermometer and a stirrer was charged with 228 g (1.0 mol) of bisphenol A, 740 g (8.0 mol) of epichlorohydrin, 28.3 g (0.15 mol) of SY-GTA80, and 175 g of n-butanol. Dissolved. Thereafter, the temperature was raised to 65 ° C. while purging with nitrogen gas, and then 171.4 g (2.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under these conditions for 0.5 hour. Next, 250 g of water was added and mixed uniformly to remove the aqueous layer. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. Then, 50 g of toluene was added to the obtained crude resin and dissolved. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy group-containing resin (b-2-1). The epoxy equivalent of the epoxy group-containing resin (b-2-1) was 217 g / eq.

Synthesis example 3
A flask equipped with a thermometer and a stirrer was charged with 228 g (1.0 mol) of bisphenol A, 740 g (8.0 mol) of epichlorohydrin, 9.4 g (0.05 mol) of SY-GTA80, and 175 g of n-butanol. Dissolved. Thereafter, the temperature was raised to 65 ° C. while purging with nitrogen gas, and then 171.4 g (2.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under these conditions for 0.5 hour. Next, 250 g of water was added and mixed uniformly to remove the aqueous layer. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. Then, 50 g of toluene was added to the obtained crude resin and dissolved. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy group-containing resin (b-2-2). The epoxy equivalent of the epoxy group-containing resin (b-2-2) was 208 g / eq.

<Synthesis example of amine curing agent>
Synthesis example 4
A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet was charged with 146 g of triethylenetetramine and 214.1 g of propyl cellosolve, and the temperature was raised to 40 ° C., and EPICLON 520 (Dainippon Ink Chemical Industries, Ltd. , Alkylphenol glycidyl ether) was charged in 288.0 g in 4 portions while paying attention to heat generation, and stirred at 90 ° C. for 3 hours. Thereafter, 208.3 g of the epoxy group-containing resin (b-2-1) obtained in Synthesis Example 2 (0.2 mol with respect to 1 mol of active hydrogen of the amine adduct) was gradually charged while paying attention to heat generation, and 100 Stir for 2 hours at ° C. Next, after 214.1 g of water was charged, 16 g of acetic acid was added and dissolved uniformly to obtain an amine curing agent (B-1) having a solid content of 60%.

Synthesis example 5
A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet was charged with 146 g of triethylenetetramine and 210 g of propyl cellosolve, heated to 40 ° C., and the EPICLON 520 was divided into 259. 2 g was charged and stirred at 90 ° C. for 3 hours. Thereafter, 224.7 g of the epoxy group-containing resin (b-2-2) obtained in Synthesis Example 3 (0.22 mol with respect to 1 mol of active hydrogen of the amine adduct) was gradually charged while paying attention to heat generation. Stir for 2 hours at ° C. Next, after adding 210 g of water, 16 g of acetic acid was added and dissolved uniformly to obtain an amine curing agent (B-2) having a solid content of 60%.

Synthesis Example 6
A four-necked flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet was charged with 136 g of metaxylenediamine and 155.6 g of propyl cellosolve, heated to 40 ° C., and 192 g of EPICLON 520 divided into four parts while paying attention to heat generation. The mixture was stirred and stirred at 90 ° C. for 3 hours. Thereafter, 138.9 g of an epoxy group-containing resin (b-2-1) (0.2 mol with respect to 1 mol of active hydrogen of the amine adduct) was gradually charged while paying attention to heat generation, and stirred at 100 ° C. for 2 hours. Next, after charging 155.6 g of water, 19 g of acetic acid was added and dissolved uniformly to obtain an amine curing agent (B-3) having a solid content of 60%.

Synthesis example 7
A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet was charged with 170 g of isophoronediamine and 167 g of propyl cellosolve, heated to 40 ° C., and 192 g of EPICLON 520 was charged in four portions while paying attention to heat generation. The mixture was stirred at 90 ° C. for 3 hours. Thereafter, 138.9 g of an epoxy group-containing resin (b-2-1) (0.2 mol with respect to 1 mol of active hydrogen of the amine adduct) was gradually charged while paying attention to heat generation, and stirred at 100 ° C. for 2 hours. Next, after adding 167 g of water, 17 g of acetic acid was added and dissolved uniformly to obtain an amine curing agent (B-4) having a solid content of 60%.

Synthesis example 8
A four-necked flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet was charged with 146 g of triethylenetetramine and 204.8 g of propyl cellosolve, heated to 40 ° C., and EPICLON 520 was divided into four parts while paying attention to heat generation 288 g was charged and stirred at 90 ° C. for 3 hours. Thereafter, 180.5 g of EPICLON 850 (BPA type liquid epoxy resin, manufactured by Dainippon Ink & Chemicals, Inc.) (0.2 mol with respect to 1 mol of active hydrogen of amine adduct) was gradually charged while paying attention to heat generation. Stir for 2 hours at ° C. Next, after 204.8 g of water was charged, 20 g of acetic acid was added and dissolved uniformly to obtain an amine curing agent (B′-1) having a solid content of 60%.

Synthesis Example 9 <Synthesis of amine curing agent (B′-2), curing agent described in Patent Document 1>
Polypropylene glycol diamine compound (H ₂ N— (C ₃ H ₆₀ ) ₃ —C ₃ H ₆ —NH ₂ ) 124 g and epoxy equivalent in a four-necked flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet 79 g of diglycidyl ether of 315 bisphenol A propylene oxide 5 mol adduct was charged in four portions and stirred at 80 ° C. for 2 hours. Next, 51 g of water was added and sufficiently stirred to obtain an amine-based curing agent (B′-2) having a solid content of 80%.

Examples 1-4 and Comparative Examples 1-2
The components shown in Table 1 were blended in the emulsions and amine curing agents obtained in Synthesis Example 1 and Synthesis Examples 4 to 9 to prepare water-based paints. These aqueous paints were tested for pencil hardness, impact resistance (DuPont impact test), and corrosion resistance (salt spray, 5% sodium hydroxide immersion test, 5% hydrochloric acid immersion test). The results are shown in Table 2.

<Method for preparing specimen>
The adjusted water-based paint is applied to a cold hot-rolled steel sheet (JIS, G, 3141 SPCC.SB, 0.8 × 70 × 150 mm, sandpaper # 240 surface treated) with a bar coater to a dry film thickness of 60 μm. Then, the test piece was prepared by drying at 25 ° C. for 7 days.

  Each evaluation item test was performed according to the following method.

Pencil hardness It implemented based on JISK5400-6.14.

Impact resistance A DuPont impact test (300 g) was performed in accordance with JIS K5400-7.8.
○: No abnormality up to 50 cm Δ: No abnormality up to 45 cm x: No abnormality up to 40 cm

Corrosion resistance A salt spray test (300 hours) was conducted in accordance with JIS K5400-7.8. The test piece was immersed in a 5% aqueous solution of sodium hydroxide and 5% hydrochloric acid at 25 ° C. for 7 days.
○: No abnormality, no rust △: Dandruff, no rust ×: Significant blister, rust

Footnotes in Table 1 Titanium oxide: CR-97 Ishihara Sangyo Co., Ltd. Talc: Talc No. 1 Takehara Chemical Industry Co., Ltd. Calcium carbonate: Brilliant 1500 Shiraishi Kogyo Co., Ltd.

Claims (9)

An aqueous epoxy resin composition containing an epoxy resin (A) and an amine curing agent (B), the amine curing agent (B) comprising a polyamine compound (b-1) and a compound having active hydrogen ( It is a compound obtained by reacting x1), an epihalohydrin (x2), and an epoxy group-containing resin (b-2) obtained by reacting a quaternary onium salt-containing epoxy compound (x3). An aqueous epoxy resin composition. In the amine-based curing agent (B), the epoxy group in the epoxy group-containing resin (b-2) is 0.02 to 0.000 per 1 mol of active hydrogen of the amino group in the polyamine compound (b-1). The aqueous epoxy resin composition according to claim 1, wherein the aqueous epoxy resin composition is used by being reacted so as to be 30 mol. The aqueous epoxy resin composition according to claim 1, wherein the quaternary onium salt-containing epoxy compound (x3) is a quaternary ammonium salt-containing epoxy compound. The quaternary onium salt-containing epoxy compound (x3) is represented by the following general formula (1)

(In the formula, R 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 R ₁ , R ₂ and R ₃ are each an alkyl group or An aryl group, which may be the same or different.)
The aqueous epoxy resin composition according to claim 3, which is a compound represented by the formula: The aqueous epoxy resin composition according to claim 4, wherein R ₁ , R ₂ , and R _{3 in the} general formula (1) are the same or different linear alkyl groups having 1 to 4 carbon atoms. The epoxy group-containing resin (b-2) makes the quaternary onium salt-containing epoxy compound (x3) 0.01 to 0.30 equivalent to 1 equivalent of active hydrogen in the compound (x1) having active hydrogen. The aqueous epoxy resin composition according to claim 1, wherein the aqueous epoxy resin composition is reacted by being used. The aqueous epoxy resin composition according to claim 1, wherein the compound (x1) having active hydrogen is a compound having a phenolic hydroxyl group. The aqueous epoxy resin composition according to any one of claims 1 to 7, wherein the polyamine compound (b-1) is an aliphatic polyamine compound. The aqueous epoxy resin composition according to claim 8, wherein the epoxy resin (A) is a bisphenol type epoxy resin.