JP2007277392A - Aqueous epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous epoxy resin composition which exhibits good water dispersibility and film formability and can give coating films excellent in an anti-corrosion property. <P>SOLUTION: This aqueous epoxy resin composition comprising an epoxy resin (A) and an amine-based curing agent (B) is characterized in that the amine-based curing agent (B) comprises a compound obtained by reacting a polyamine compound (b1) with a monovalent glycidyl compound (b2) which comprises a compound (b3) represented by the general formula (1) and having a quaternary amine portion and a glycidyl group reacting with an amino group in the polyamine compound (b1). <P>COPYRIGHT: (C)2008,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)

  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 with excellent anticorrosion properties.

  As a result of intensive studies to solve the above problems, the present inventors have excellent water dispersibility and film-forming properties by using a curing agent obtained by reacting a polyamine compound and a monoepoxy compound as an amine curing agent. The inventors have found that a cured coating film having good anticorrosion properties can be obtained, and have completed the present invention.

  That is, the present invention is an aqueous epoxy resin composition containing an epoxy resin (A) and an amine curing agent (B), and the amine curing agent (B) is a polyamine compound (b1) and a monovalent glycidyl compound. An aqueous epoxy resin composition characterized by being a compound obtained by reacting with (b2) is provided.

  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 is not particularly limited by its structure. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, biscresol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, p-tert-butylphenol Examples of the epoxy resin include polyvalent epoxy resins such as novolac type epoxy resin, nonylphenol novolac type epoxy resin, and t-butylcatechol type epoxy resin. Further, monovalent epoxy resins include aliphatic alcohols such as butanol, and carbon numbers of 11 to 12. Aliphatic alcohol, phenol, p-ethylphenol, o-cresol, m-cresol, p-cresol, p-tertiarybutylphenol, s-butylphenol, nonylphenol, xyl Examples include condensates of monohydric phenols such as diols and epihalohydrins, condensates of monovalent carboxylic acids such as neodecanoic acid and epihalohydrins, etc. Examples of glycidylamine include polycondensates of diaminodiphenylmethane and epihalohydrins, Examples of the aliphatic epoxy resin include polyglycidyl ethers of vegetable oils such as soybean oil and castor oil. Examples of the polyvalent alkylene glycol type epoxy resin include ethylene glycol, propylene glycol, 1,4-butanediol, 1, 6-hexanediol, glycerin, erythritol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, condensate of trimethylolpropane and epihalohydrin, and the like, and further described in JP-A-2005-239928 Aqueous epoxy resin, and the like. These may be used in one kind, or may be used in combination of two or more.

  Even if the epoxy resin is liquefied or reduced in viscosity by adding an organic solvent, a non-reactive diluent or the like as necessary, it is preliminarily used with a surfactant such as a polyoxyethylene alkylphenyl ether compound. An emulsified emulsified epoxy resin 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 a compound obtained by reacting the polyamine compound (b1) with the monovalent glycidyl compound (b2). 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 (b1) is not particularly limited, and aliphatic polyamines, aromatic polyamines, heterocyclic polyamines and the like, epoxy adducts thereof, Mannich modified products, and polyamide modified products may be 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 m-xylylenediamine, norbornadiamine, bis (aminomethyl) cyclohexane, and isophoronediamine are preferable from the viewpoint of excellent mechanical properties of the resulting cured product. It is preferable to use tetraethylenepentamine, diethylenetriamine, triethylenetetramine or a modified product thereof.

  Further, in order to improve the anticorrosion performance of the cured product, those subjected to various modifications described above are preferable, and the modified product is not particularly limited, but a mono- or polyepoxy compound is reacted with an amino group. Examples thereof include an epoxy adduct obtained, a Mannich modified product obtained by reacting phenols and formaldehyde, and a polyamide obtained by reacting a carboxylic acid such as dimer acid.

  The monovalent glycidyl compound (b2) used in the present invention has a glycidyl group capable of reacting with an amino group in the polyamine compound (b1) and a quaternary amine moiety and is represented by the following general formula (1) A compound (b4) having a glycidyl group and a hydroxyl group capable of reacting with (b3) and an amino group in the polyamine compound (b1).

  The monovalent glycidyl compound (b3) having a quaternary amine moiety used in the present invention comprises a monovalent glycidyl group capable of reacting with an amino group in the polyamine compound (b1) and a quaternary amine moiety in the molecule. Any compound can be used without particular limitation.

Examples of the monovalent glycidyl compound (b3) having a quaternary amine moiety include compounds represented by the following general formula (1). Wherein R is a hydrogen atom or a methyl group, Q is a nitrogen atom or a phosphorus atom, X is a chlorine atom, bromine atom or iodine atom, and R ₁ , R ₂ and R ₃ are each independently an alkyl group or Represents an aryl group.)

  Among these, R1, R2, and R3 in the general formula (1) are excellent in compatibility with the amine-based curing agent obtained by the reaction with the polyamine compound (b1) and water and easily available. It is preferable to use compounds each having the same or different linear alkyl group having 1 to 4 carbon atoms, wherein R is a hydrogen atom, Q is a nitrogen atom, R1, R2, and R3 are methyl groups, and X is chlorine. SY-GTA80 [trade name, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., NV = 80% aqueous solution, epoxy equivalent (solid content): 151 g / eq] is most preferable.

  The monovalent glycidyl compound (b4) having the above hydroxyl group is not particularly limited as long as it is a compound having a monovalent glycidyl group and a hydroxyl group capable of reacting with active hydrogen in the above polyamine compound (b1). Can be used for

  Among these, regardless of whether the β-position of the glycidyl group is unsubstituted or alkyl-substituted, it is possible to use a compound in which a hydroxyl group and a C1-C4 glycol end are introduced into a carbon atom adjacent to a monovalent glycidyl group. The amine-based curing agent (B) is preferably compatible with water, and particularly preferably a hydroxyl group.

  The reaction of the polyamine compound (b1) and the monovalent glycidyl compound (b2) can be carried out in the absence of a solvent or in an appropriate solvent. Examples of usable solvents include the compound (b1) and the monovalent glyceryl compound (b2). It is not particularly limited as long as it uniformly dissolves the glycidyl compound (b2) and is inactive. For example, water, methanol, ethanol, isopropanol, n-butanol, isobutanol and other alcohols, toluene, Hydrocarbons such as xylene, cyclohexane, 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, buty Cellosolves such as cellosolve, isobutylcellosolve, tert-butylcellosolve, 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 A tert-butyl ether etc. are mentioned, It can use also as 1 type, or 2 or more types of mixed solvents. 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 (b1) and the monovalent glycidyl compound (b2) is not particularly limited, but the water dispersibility when an aqueous epoxy resin composition is obtained and the resulting cured coating. From the point which is excellent in balance with the anticorrosive property of a film | membrane, the epoxy group in monovalent glycidyl compound (b2) is 0.02-0.40 with respect to 1 equivalent of active hydrogen of the amino group in a polyamine compound (b1). It is preferable to use it so that it may become equivalent, and it is preferable to use it so that it may become 0.05-0.35 equivalent especially. Although it does not specifically limit as reaction conditions in this reaction, Usually, 50-130 degreeC, Preferably it is 70-120 degreeC, It can carry out by stirring for 1 to 6 hours, Preferably it is 2 to 4 hours. .

  The ratio of the monovalent glycidyl compound (b3) having the quaternary amine moiety and the monovalent glycidyl compound (b4) having a hydroxyl group is quaternary amine to 1 equivalent of active hydrogen of the amino group of the polyamine compound (b1). If the total amount of the epoxy group in the monovalent glycidyl compound (b4) having a hydroxyl group and the epoxy group in the monovalent glycidyl compound (b4) having a hydroxyl group is 0.05 to 0.40 equivalent, there is no particular limitation. In the reaction with (b1), a monovalent glycidyl compound (b3) having a quaternary amine moiety and a monovalent glycidyl compound (b4) having a hydroxyl group may be mixed in advance. It may be added separately.

  In addition, a monovalent glycidyl compound other than the monovalent glycidyl compound (b3) having a quaternary amine moiety and the monovalent glycidyl compound (b4) having a hydroxyl group may be used as long as the characteristics of the present invention are not impaired. it can. For example, a monovalent glycidyl ether having a C1-C18 alkyl group introduced therein, a glycidyl ester, a monovalent glycidyl ether of an alkyl-substituted phenol compound having 1 to 5 positions C1-C9 of an aromatic ring, or a monovalent glycidyl. Examples thereof include acrylic acid derivatives having a group and methacrylic acid derivatives having a monovalent glycidyl group, and two or more of these can be used in combination.

  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 solvent removal as necessary. Two or more amine curing agents (B) may be used in combination in the aqueous epoxy resin composition of the present invention.

  The aqueous epoxy resin composition of the present invention is not limited in any way other than the use of the above-described epoxy resin (A) and 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 various amine compounds, amide compounds, and acid anhydride compounds can be used as long as they can undergo a curing reaction with the epoxy group in the epoxy resin. Any curing agent such as a phenol 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. And polyamide resins synthesized from ethylenediamine, and acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl Examples include tetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Examples of phenolic compounds include phenol novolac resins, cresol novolac resins, Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (commonly known as zylock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol Condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group) ), Polyphenol compounds such as aminotriazine-modified phenol resins (polyphenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.) and These modified products are mentioned.

  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 1.5 equivalents with respect to a total of 1 equivalent of 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 the additive into the aqueous epoxy resin composition of the present invention is not particularly limited. For example, the filler and the additive are sufficiently kneaded using an apparatus such as a mixing mixer or a ball mill. A uniformly dispersed pigment paste is prepared in advance, and this and an emulsified epoxy resin are further kneaded and dispersed using the above apparatus, and then adjusted to a desired concentration using water, and an amine curing agent Can be obtained by mixing.

  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.

<Synthesis example of epoxy emulsion>
Synthesis example 1
EPICLON 1055 (Dainippon Ink & Chemicals, BPA type solid epoxy resin)
500 g was dissolved in 47.5 g of benzyl alcohol and 47.5 g of methoxypropanol at 100 ° C. 25 g of Newcol 780 (60) (manufactured by Nippon Emulsifier Co., Ltd.) was added to this resin solution 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 emulsion (A-1) had an epoxy equivalent (solution value) of 926 g / eq and a viscosity (25 ° C.) of 2350 mPa · S.

Synthesis example 2
A four-necked flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet was charged with 187 g of metaxylenediamine and 120.0 g of propyl cellosolve and heated to 40 ° C., and EPICLON 850 (manufactured by Dainippon Ink and Chemicals, BPA Type liquid epoxy resin, epoxy equivalent of 188 g / eq) was charged in four portions at 258 g and stirred at 90 ° C. for 3 hours. Thereafter, 50.9 g of glycidol was gradually added while being careful of heat generation, and stirred at 100 ° C. for 2 hours. Next, 129.8 g of SY-GTA80 (manufactured by Sakamoto Pharmaceutical Co., Ltd., NV = 80% aqueous solution) was gradually charged while paying attention to heat generation, and stirred at 110 ° C. for 2 hours. Next, 253.7 g of water was added and dissolved uniformly to obtain an amine curing agent (B-1) having a solid content of 60%.

Synthesis example 3
A four-necked flask equipped with a thermometer, stirrer, condenser, and nitrogen inlet was charged with 147.3 g of metaxylenediamine, 46.0 g of isophoronediamine, and 120.0 g of propylcellosolve, and the temperature was raised to 40 ° C., and EPICLON 850 was added. 283.6 g was charged in four portions and stirred at 90 ° C. for 3 hours. Thereafter, 50.1 g of glycidol was gradually added while paying attention to heat generation and stirred at 100 ° C. for 2 hours. Next, 127.7 g of SY-GTA80 was gradually charged while paying attention to heat generation, and stirred at 110 ° C. for 2 hours. Next, 254.0 g of water was added and dissolved uniformly to obtain an amine curing agent (B-2) having a solid content of 60%.

Synthesis example 4
A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet was charged with 146.6 g of triethyltetramine and 120.0 g of propyl cellosolve, heated to 40 ° C., and 283.6 g of EPICLON 850 was divided into four parts. , And stirred at 90 ° C. for 3 hours. Thereafter, 55.8 g of glycidyl was gradually added while paying attention to heat generation and stirred at 100 ° C. for 2 hours. Next, 142.4 g of SY-GTA80 was gradually charged while paying attention to heat generation, and stirred at 110 ° C. for 2 hours. Next, 251.5 g of water was added and dissolved uniformly to obtain an amine curing agent (B-3) 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 186.1 g of metaxylenediamine and 120.0 g of propyl cellosolve, and the temperature was raised to 40 ° C., and BPF liquid epoxy resin EPICLON 830 (large NIPPON CHEMICAL INDUSTRIES, BPF type liquid epoxy resin, epoxy equivalent 170 g / eq) was charged into 116.3 g in four portions and stirred at 90 ° C. for 3 hours. Furthermore, 143.7 g of EPICLON HP-820 (manufactured by Dainippon Ink and Chemicals, t-butylcatechol type epoxy resin, epoxy equivalent 210 g / eq) was charged in four portions and stirred at 90 ° C. for 3 hours. Thereafter, 50.6 g of glycidyl was gradually added while paying attention to heat generation, and stirred at 100 ° C. for 2 hours. Next, 238.4 g of SY-GTA80 was gradually charged while paying attention to heat generation, and stirred at 110 ° C. for 2 hours. Next, after adding 232.2 g of water, the mixture was uniformly dissolved to obtain an amine curing agent (B-4) 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 171.8 g of metaxylenediamine and 120.0 g of propyl cellosolve and heated to 40 ° C., and EPICLON 850 was divided into 237.5 g in four portions. The mixture was stirred and stirred at 90 ° C for 3 hours. Thereafter, 238.4 g of SY-GTA80 was gradually added while being careful of heat generation, and stirred at 110 ° C. for 2 hours. Next, after adding 232.2 g of water, the mixture was uniformly dissolved to obtain an amine curing agent (B-5) having a solid content of 60%.

Synthesis example 7
A four-necked flask equipped with a thermometer, a stirrer, a condenser tube, and a nitrogen inlet was charged with 205.0 g of metaxylenediamine and 120.0 g of propyl cellosolve and heated to 40 ° C., and EPICLON 850 was divided into 283.4 g in four portions. The mixture was stirred and stirred at 90 ° C for 3 hours. Thereafter, 111.6 g of glycidol was gradually added while paying attention to heat generation and stirred at 100 ° C. for 2 hours. Next, 280.0 g of water was added and then uniformly dissolved to obtain an amine curing agent (B-6) having a solid content of 60%.

Synthesis example 8
A four-necked flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet was charged with 148.6 g of metaxylenediamine and 120.0 g of propyl cellosolve and heated to 40 ° C., and EPICLON 850 was divided into 205.5 g in four portions. The mixture was stirred and stirred at 90 ° C for 3 hours. Thereafter, 80.9 g of glycidol was gradually added while paying attention to heat generation and stirred at 100 ° C. for 2 hours. Next, after 238.7 g of water was added, the mixture was uniformly dissolved to obtain an amine curing agent (B-7) having a solid content of 60%.

Synthesis Example 9
Bisphenol A propylene having 488.1 g of polypropylene glycol diamine compound (H2N- (C3H60) 3-C3H6-NH2) and epoxy equivalent of 315 in a four-necked flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen inlet 311 g of diglycidyl ether of oxide 5 mol adduct was charged in four portions and stirred at 80 ° C. for 2 hours. Next, 200 g of water was added and sufficiently stirred to obtain an amine curing agent (B-8) having a solid content of 80%.

Examples 1-4 and Comparative Examples 1-4
The components shown in Table 1 were blended with the emulsions and amine curing agents obtained in Synthesis Examples 1 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 subjected to sandpaper # 240 surface treatment) as a bar coater. Was applied to a dry film thickness of 60 μm and dried at 25 ° C. for 7 days to prepare a test piece.

  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. Also,
The test piece was immersed in a chemical solution of 5% aqueous sodium hydroxide and 5% hydrochloric acid at 25 ° C. for 7 days.
○: No abnormality, no rust △: Dandruff, no rust ×: Significant blister, rust

  Titanium oxide in Table 1 is manufactured by CR-97 Ishihara Sangyo Co., Ltd., talc is talc No. 1 manufactured by Takehara Chemical Industry Co., Ltd., and calcium carbonate is manufactured by Brilliant 1500 Shiraishi Kogyo Co., Ltd.

Claims (8)

An aqueous epoxy resin composition containing an epoxy resin (A) and an amine curing agent (B), wherein the amine curing agent (B) comprises a polyamine compound (b1) and a monovalent glycidyl compound (b2). An aqueous epoxy resin composition, which is a compound obtained by reaction. The amine-based curing agent (B) has an epoxy group in the monovalent glycidyl compound (b2) in an amount of 0.02 to 0.40 equivalent to 1 equivalent of active hydrogen of the amino group in the polyamine compound (b1). The aqueous epoxy resin composition according to claim 1, wherein the aqueous epoxy resin composition is reacted by being used. 3. The monovalent glycidyl compound (b2) contains a monovalent monoglycidyl compound (b3) having a quaternary amine moiety and a monovalent glycidyl compound (b4) having a hydroxyl group. An aqueous epoxy resin composition. The monoglycidyl compound (b3) having a quaternary amine moiety is represented by the following general formula (1)

Wherein 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 independently an alkyl group or Represents an aryl group.)
The aqueous epoxy resin composition according to claim 3, which is a compound represented by the formula: The aqueous epoxy resin composition according to any one of claims 1 to 4, wherein the monovalent glycidyl compound (b4) having a hydroxyl group is glycidol. The aqueous epoxy resin composition according to any one of claims 1 to 5, wherein the polyamine compound (b1) is a chain aliphatic polyamine compound. The aqueous epoxy resin composition according to any one of claims 1 to 6, wherein the polyamine compound (b1) is an epoxy adduct other than the monovalent glycidyl compound (b2). The aqueous epoxy resin composition according to claim 1, wherein the epoxy resin (A) is an epoxy resin emulsion.