JPH04351628A - Water-base curable epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which is excellent in leveling and film- forming properties and gives a transparent cured coating film excellent in surface gloss, hardness, adhesive properties, water resistance, and chemical resistance. CONSTITUTION:The title compsn. comprises an epoxy resin having, on an average, at least one vicinal epoxy group in the molecule and a self-emulsifying active org. amine curative which is prepd. by reacting an epoxy compd. obtd. by reacting 1.0mol of a polyalkylene polyether polyol having an average mol.wt. of 200-4,500 with 0.1-5mol of a lactone and 0.1-10mol of an epoxy compd. having at least 0.1 hydroxyl group and vicinal epoxy group in the molecule in the presence of a Lewis acid catalyst in the presence or absence of a solvent with an excess amt. of a polyamine selected from the group consisting of an aliph. polyamine, an alicyclic polyamine, an arom. polyamine, and a heterocyclic polyamine.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to aqueous epoxy resin curable compositions.

0002

[Prior art and problems to be solved by the invention] In recent years,
It is a well-known fact that regulations on the use of solvents are becoming stricter year by year due to the risk of fire caused by the use of solvents, the problem of pollution caused by air pollution, the effects on the human body, and the increase in the cost of solvents. However, a coating method using water-based epoxy resin that eliminates this problem is attracting attention, but for example, in the case of epoxy resin emulsion,
Generally, emulsification using surfactants is the main method;
Depending on the type and amount of activator used, the physical properties of the cured product tend to deteriorate significantly.

[0003] In particular, water resistance, adhesion, mechanical properties, etc. are inferior to those of solvent-based or non-solvent-based cured products, and the preparation of these emulsions usually requires the use of a homomixer and high-speed rotation. It takes a lot of money and labor to fully equip equipment or manufacturing, and the stability of the emulsion
In terms of storage stability, the emulsion often separates depending on the selection of the emulsifier and the setting of the manufacturing conditions, so there are also deficiencies in terms of long-term stability. Furthermore, if such an emulsion is left outdoors during the winter, it may suffer from problems such as permanent setting and crystallization, and its physical properties and working efficiency are not necessarily satisfactory.

[0004] Furthermore, Japanese Patent Publication No. 61-40688 discloses an aqueous epoxy resin curing agent made by reacting a polyether polyol with an epoxy compound, which is further reacted with an amine, but this is an emulsifying agent. It is still insufficient in terms of strength and viscosity.

[0005]

[Means for Solving the Problems] In order to improve these drawbacks, the present inventors have made extensive studies and have developed a product obtained by reacting a polyalkylene polyether polyol compound, lactones, and an epoxy compound having a hydroxyl group. A self-emulsifying active organic amine curing agent having surface activity in the molecule is provided by conducting an adduct reaction with a reactive nonionic surfactant containing an epoxy functional group and various polyamines in a known manner with an excess of polyamine. However, this self-emulsifying curing agent can easily emulsify the epoxy compound in the presence of any water, and can emulsify sufficiently uniformly with a simple stirring operation without requiring high-speed rotation with a homomixer. Furthermore, we have found that the proportion of water added can be adjusted arbitrarily in the composition of the present invention, whereas in conventional emulsion systems, the solid content is usually within the range of 20 to 60%. , we have completed the present invention.

The aqueous epoxy resin curable composition of the present invention comprises (I) an epoxy resin having an average of more than one adjacent epoxy group in the molecule, and (II) an average molecular weight of 200.
~4500 polyalkylene polyether polyol compound (II-1-1) and lactones (II-1-2)
and an epoxy compound having at least 0.1 hydroxyl group and adjacent epoxy group in the molecule (II-1-3
) and 0.1 to 5 mol of lactones (II-1-2) and epoxy compound (II) per 1.0 mol of polyalkylene polyether polyol compound (II-1-1) using a Lewis acid as a catalyst. -1-3) Epoxy group-containing compound (II-1) obtained by reacting in a solvent or without solvent at a reaction ratio of 1.2 to 10 moles, aliphatic polyamines (II-2-1■) , alicyclic polyamines (II-
2-1■), one or more polyamines (II-2-1) selected from aromatic polyamines (II-2-1■), and heterocyclic polyamines (II-2-1■)
The aqueous epoxy resin curable composition of the present invention is characterized by comprising a self-emulsifying active organic amine curing agent obtained by reacting with an excess of polyamine. an epoxy resin having an average of more than one vicinal epoxy group, and (II) an average molecular weight of 200
~4500 polyalkylene polyether polyol compound (II-1-1) and lactones (II-1-2
) and an epoxy compound (II-1-
3) and 0.1 to 5 mol of lactones (II-1-2) and epoxy compound ( II-1-3) An epoxy group-containing compound (II-1) obtained by reacting in a solvent or without a solvent at a reaction ratio of 1.2 to 10 moles is mixed with an aliphatic polyamine (II-2-1). ), alicyclic polyamines (II
-2-1■), aromatic polyamines (II-2-1■)
and one or more polyamines (II-2-1) selected from heterocyclic polyamines (II-2-1■)
) and a cyanoethylated self-emulsifying active organic amine curing agent obtained by reacting a self-emulsifying active organic amine curing agent (II-2) obtained by reacting with an excess of polyamine, and further reacting with acrylonitrile (II-3). It is characterized by:

[0007] The epoxy resin used in the present invention has an average of more than one adjacent epoxy group in the molecule (
I) is the formula

[0008]

[Chemical formula 1]

(where Z is a hydrogen atom, methyl group, or ethyl group) Epoxy resin (I
-1), formula

0010

[Case 2]

(where Z is a hydrogen atom, a methyl group, or an ethyl group) Epoxy resin (I
-2), formula

0012

[Chemical formula 3]

(where Z is a hydrogen atom, methyl group, or ethyl group) Substituted or unsubstituted 1,2-
Epoxy resins (I-3) having an average of more than one epoxypropyl group in the molecule are included.

Epoxy resin having more than one substituted or unsubstituted glycidyl ether group in the molecule (I-1
) are epoxy resins obtained by glycidyl etherification of phenolic hydroxyl groups and epoxy resins obtained by glycidyl etherification of alcoholic hydroxyl groups, and preferred examples of such epoxy resins (I-1) include one or polyglycidyl ether of polyhydric phenol having two or more aromatic nuclei (I-1-1)
, a polyglycidyl ether (I-1-2) of an alcoholic polyhydroxyl compound derived by the addition reaction of a polyhydric phenol having one or more aromatic nuclei and an alkylene oxide having 2 to 4 carbon atoms. Alternatively, polyglycidyl ether (I-1-3) of an aliphatic polyhydroxyl compound containing no nucleus may be mentioned.

[0015] Polyglycidyl ether (I-1
-1) means, for example, that a polyhydric phenol (a) having at least one aromatic nucleus and an epihalohydrin (b) are mixed in a conventional manner in the presence of a basic catalyst such as sodium hydroxide or a reaction amount of a basic compound. An epoxy resin containing polyglycidyl ether as the main reaction product, such as obtained by reacting a polyhydric phenol (a) having at least one aromatic nucleus, and an epihalohydrin (b) in a catalytic amount of a basic catalyst such as triethylamine. It is an epoxy resin obtained by reacting a polyhydrin ether obtained by a conventional method in the presence of a basic compound such as sodium hydroxide.

Similar polyglycidyl ether (I-1-2
) or polyglycidyl ether (I-1-3),
For example, a polyhydroxyl compound (c) derived by an addition reaction between a polyhydric phenol having at least one aromatic nucleus and an alkylene oxide having 2 to 4 carbon atoms.
or an aliphatic polyhydroxyl compound (d) that does not contain a nucleus.
and epihalohydrin (b) by a conventional method in the presence of a catalytic amount of an acidic catalyst such as boron trifluoride. It is an epoxy resin containing polyglycidyl ether as the main reaction product.

Here, the polyhydric phenol (a) having at least one aromatic nucleus includes mononuclear polyhydric phenol (a-1) having one aromatic nucleus and two or more aromatic nuclei. There is a polynuclear polyhydric phenol (a-2) that has

Examples of such mononuclear polyhydric phenol (a-1) include resorcinol, hydroquinone, pyrocatechol, phloroglucinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxy Examples include naphthalene.

Further, as an example of the polynuclear polyhydric phenol (a-2), general formula (a-2-1)

[0020]

[C4]

[In the formula, Ar is an aromatic divalent hydrocarbon such as a naphthylene group or a phenylene group, with a phenylene group being preferred for the purposes of the present invention. Y' and Y1 may be the same or different and are alkyl groups, preferably having up to 4 carbon atoms, such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl. an alkyl group or a halogen atom, i.e., a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, or an alkoxy group such as a methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy group, preferably up to 4 It is an alkoxy group with 5 carbon atoms. When a substituent other than a hydroxyl group is present on either or both of the above-mentioned aromatic divalent hydrocarbon groups, these substituents may be the same or different. m and z are aromatic rings (A
r) is an integer having a value from 0 (zero) to a maximum value corresponding to the number of hydrogen atoms, and can be the same or different values. R1 is, for example, -CO-, -O-, -S-,
-SO-, -SO2-, -(S)n -(n is 2
-6 integer) or an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a 2-ethylhexamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, or an alkylidene group For example, ethylidene group, propylidene group, isopropylidene group, isobutylidene group,
Amylidene group, isoamylidene group, 1-phenylethylidene group, ω-(halogenated dicyclopentadienyl)alkylidene group, or cycloaliphatic group such as 1,4-cyclohexylene group, 1,3-cyclohexylene group, cyclohexylene group Dene group, or halogenated alkylene group, or halogenated alkylidene group, or halogenated cycloaliphatic group, or alkoxy- and aryloxy-substituted alkylidene group, or alkoxy- and aryloxy-substituted alkylene group; or alkoxy- and aryloxy-substituted cycloaliphatic groups such as methoxymethylene, ethoxymethylene, ethoxyethylene, 2-ethoxytrimethylene, 3-ethoxypentamethylene, 1,4-(2-methoxy cyclohexane) group, phenoxyethylene group, 2
-phenoxytrimethylene group, 1,3-(2-phenoxycyclohexane) group, or arylalkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1,7-diphenylpentamethylene group, 2-phenyldecamethylene group, or an aromatic group such as a phenylene group, a naphthylene group, or a halogenated aromatic group such as a 1,4-(2-chlorophenylene) group, a 1,4-
(2-fluorophenylene) group, or alkoxy- and aryloxy-substituted aromatic groups such as 1,4-(
2-methoxyphenylene) group, 1,4-(2-ethoxyphenylene) group, 1,4-(2-n-propoxyphenylene) group, 1,4-(2-phenoxyphenylene) group, or alkyl-substituted Aromatic groups such as 1,4
-(2-methylphenylene) group, 1,4-(2-ethylphenylene) group, 1,4-(2-n-propylphenylene) group, 1,4-(2-n-butylphenylene) group, 1 , 4-(2-n-dodecylphenylene) group,
formula

[0022]

[C5]

A group represented by (R' is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms),

[0024]

[C6]

(wherein R'' is a hydrogen atom or a hydrocarbon group optionally substituted with a hydroxyl group or an epoxy group), or R1 is a divalent group such as

[0026]

[C7]

Alternatively, R1 can be a ring fused to one Ar group as in the case of the compound represented by It can also be a polyalkoxy group, such as a phenylethoxy group, or R1 can be, for example, a polydimethylsiloxy group, a polydiphenylsiloxy group,
It can be a group containing a silicon atom, such as a polymethylphenylsiloxy group, or R1 may be separated by an aromatic ring, a tertiary amino group, an ether linkage, a carbonyl group, or a sulfur-containing linkage, such as a sulfur or sulfoxide group. It can also be two or more alkylene or alkylidene groups. ] There is a polynuclear dihydric phenol represented by

Particularly preferred among such polynuclear dihydric phenols is one represented by the general formula (a-2-1-1)

[0029]

[Chemical formula 8]

(In the formula, Y' and Y1 have the same meanings as above, m and z have values of 0 to 4, and R1 preferably represents an alkylene group or alkylidene group having 1 to 3 carbon atoms, or formula

[0031]

[Chemical formula 9]

It is a polynuclear dihydric phenol represented by a saturated group represented by the following formula (Q is 0 or 1).

Examples of such dihydric phenols include 2,2-bis-(4-
hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane, bis(2-hydroxyphenyl)
Methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)methane, -hydroxyphenyl)ethane, 1,1-bis(4-hydroxy-2-
Chlorphenyl)ethane, 1,1-bis(3,5-
dimethyl-4-hydroxyphenyl)ethane, 1,3-
Bis(3-methyl-4-hydroxyphenyl)propane, 2,2'-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(
3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(2-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxynaphthyl)propane, 2,2-bis(4-hydroxy phenyl)pentane, 3,3-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)heptane, bis(4-hydroxyphenyl)
Methane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis(4-hydroxyphenyl)
bis(hydroxyphenyl)alkanes such as -1,2-bis(phenyl)propane, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, or
, 4'-dihydroxybiphenyl, 4,4'-dihydroxyoctachlorobiphenyl, 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, or bis-(4-hydroxyphenyl)sulfone, 2 , 4'-dihydroxydiphenylsulfone, chloro-2,4-dihydroxydiphenylsulfone, 5-chloro-4,4'-dihydroxydiphenylsulfone, 3'-chloro-4,4'-dihydroxydiphenylsulfone. phenyl) sulfone, or bis(4-hydroxyphenyl) ether, 4,3'-(or 4,2'- or 2,2'-dihydroxydiphenyl) ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether ,Screw(
4-hydroxy-3-isobutylphenyl) ether,
Bis(4-hydroxy-3-isopropylphenyl) ether, bis(4-hydroxy-3-chlorophenyl)
Ether, bis(4-hydroxy-3-fluorophenyl) ether, bis(4-hydroxy-3-bromphenyl) ether, bis(4-hydroxynaphthyl) ether, bis(4-hydroxy-3-chlornaphthyl) ether , bis(2-hydroxybiphenyl)ether,
4,4'-dihydroxy-2,6-dimethoxy-diphenyl ether, 4,4'-dihydroxy-2,5-
Includes di(hydroxyphenyl) ethers such as diethoxydiphenyl ether, and also 1,1-bis(4-
hydroxyphenyl)-2-phenylethane, 1,3,
3-trimethyl-1-(4-hydroxyphenyl)-
Also suitable are 6-hydroxyindan, 2,4-bis(p-hydroxyphenyl)-4-methylpentane.

Furthermore, another group of preferable polynuclear dihydric phenols is represented by the general formula (a-2-1-2).

[0035]

[Chemical formula 10]

(Here, R3 is a methyl or ethyl group, R2
is an alkylidene group or other alkylene group having 1 to 9 carbon atoms, p is 0 to 4), for example, 1,
4-bis(4-hydroxybenzyl)benzene, 1,
4-bis(4-hydroxybenzyl)tetramethylbenzene, 1,4-bis(4-hydroxybenzyl)tetraethylbenzene, 1,4-bis(p-hydroxycumyl)benzene, 1,3-bis(p-hydroxy cumyl) benzene, etc.

Other polynuclear polyhydric phenols (a-2) include, for example, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, and initial condensates of phenols and carbonyl compounds. (Example: phenolic resin initial condensate, condensation reaction product of phenol and acrolein, condensation reaction product of phenol and glyoxal, condensation reaction product of phenol and pentanediallyl, condensation reaction product of resorcinol and acetone, xylene-
(phenol-formalin initial condensate), condensation products of phenols and polychloromethylated aromatic compounds (e.g. condensation products of phenol and bischloromethylxylene)
etc. can be mentioned.

[0038] Here, the polyhydroxyl compound (c) refers to the above-mentioned polyhydric phenol (a) having at least one aromatic nucleus and alkylene oxide.
-ROH (where R is an alkylene group derived from an alkylene oxide) bonded to the phenol residue through an ether bond obtained by reacting the H group and the epoxy group in the presence of a catalyst that promotes the reaction, or (
and)-(RO)n H (where R is an alkylene group derived from alkylene oxide, and one polyoxyalkylene chain may contain different alkylene groups. n is 2 or 2 indicating the number of polymerized oxyalkylene groups) It is a compound having an atomic group (an integer of 2 or more). in this case,
The ratio of the polyhydric phenol (a) to the alkylene oxide is 1:1 (mol: mol) or more, but preferably the ratio of the alkylene oxide to the OH groups of the polyhydric phenol (a) is 1:1 to 1:1. 10, preferably 1
: 1 to 3 (equivalent: equivalent).

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., but those which form a side chain when reacting with the polyhydric phenol (a) to form an ether bond are particularly preferred. , such as propylene oxide, 1,2-butylene oxide, 2,
3-Butylene oxide is preferred, with propylene oxide being particularly preferred.

A particularly preferred group of such polyhydroxyl compounds (c) are those of the general formula (c-1).

[0041]

[Chemical formula 11]

(In the formula, Y', Y1, m, z and R1 are the same as those in the above formula (a-2-1-1), R is an alkylene group having 2 to 4 carbon atoms, n1 and n2 is 1-3
It is a polyhydroxyl compound represented by

Furthermore, another group of preferred polyhydroxyl compounds is represented by the general formula (c-2).

[
0044

[Chemical formula 12]

(In the formula, R2, R3 and p are the above (a-2-
1-2), where R is an alkylene group having 2 to 4 carbon atoms, and n1 and n2 have values of 1 to 3.

Other polyhydroxyl compounds containing a nucleus (
Examples of c) include alicyclic polyols obtained by hydrogenating the aromatic nucleus of polyhydric phenol (a).

[0047] Examples of the aliphatic polyhydroxyl compound (d) which does not contain a nucleus include polyhydric compounds such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, glycerin, and pentaerythritol. Polyhydric polyhydroxy compounds, polyether polyols, etc. in which alkylene oxide is added to alcohols and these polyhydric alcohols or other active hydrogen-containing compounds (for example, compounds with groups such as amino groups, carboxyl groups, and thiohydroxyl groups). Examples include polyhydroxyl compounds.

[0048] Also, the epihalohydrin (b)
is the general formula (1)

[0049]

[Chemical formula 13]

(where Z is a hydrogen atom, methyl group, or ethyl group, and X' is a halogen atom), and examples of such epihalohydrin (b) include:
For example, epichlorohydrin, epibromohydrin, 1,
2-Epoxy-2-methyl-3-chloropropane, 1
, 2-epoxy-2-ethyl-3-chloropropane, and the like.

[0051] Examples of the acidic catalyst that promotes the reaction between the epihalohydrin (b) and the polyhydroxyl compound (c) or polyhydroxyl compound (d) include boron trifluoride, stannic chloride, zinc chloride, and ferric chloride. Lewis acids such as, derivatives exhibiting these activities (eg, boron trifluoride-ether complex compounds), or mixtures thereof can be used.

[0052] Similarly, as a basic catalyst for promoting the reaction between epihalohydrin (b) and polyhydric phenol (a), an alkali metal hydroxide (eg, sodium hydroxide) can be used.
, alkali metal alcoholates (e.g. sodium ethylate), tertiary amine compounds (e.g. triethylamine, triethanolamine), quaternary ammonium compounds (e.g. tetramethylammonium bromide) or mixtures thereof can be used; Therefore, the basic compound that generates glycidyl ether simultaneously with such a reaction, or that generates glycidyl ether by ring-closing the halohydrin ether generated as a result of the reaction by dehydrohalogenation reaction, is an alkali metal hydroxide ( Examples: sodium hydroxide), alkali metal aluminates (e.g., sodium aluminate), etc. are conveniently used.

Of course, these catalysts and basic compounds can be used as they are or as a solution in an appropriate inorganic or/and organic solvent.

[0054] Epoxy resins (I-2
) include aliphatic polycarboxylic acids or aromatic polycarboxylic acids (e.g. phthalic acid, isophthalic acid, terephthalic acid,
Tetrahydrophthalic acid, methyltetrahydrophthalic acid,
hexahydrophthalic acid, methylhexahydrophthalic acid,
Endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid,
Itaconic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimer fatty acid, trimellitic acid, trimesic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, halogen substitution of these In addition to these compounds, there are also polyglycidyl esters of carboxyl-terminated polyester oligomers obtained from these polyhydric carboxylic acids and polyhydric alcohols, such as epihalohydrin (b) represented by the general formula (1) and the like. Also included are epoxy resins obtained by polymerizing glycidyl methacrylate synthesized from methacrylic acid.

[0055] Also, substituted or unsubstituted 1,2- of N-substituted
Examples of epoxy resins (I-3) having more than one epoxypropyl group in the molecule include aromatic amines (
For example, epoxy resins obtained from aniline or aniline having an alkali substituent in the nucleus) and epihalohydrin (b) represented by the above general formula (1), initial condensates of aromatic amines and aldehydes (for example, aniline-formaldehyde initial condensation Examples include epoxy resins obtained from aniline-phenol-formaldehyde initial condensate) and epihalohydrin (b).

Other epoxy resins include epoxidized oils (for example, epoxidized linseed oil, epoxidized soybean oil,
Epoxidized safflower oil, epoxidized tung oil, epoxidized eno oil, epoxidized dehydrated castor oil, epoxidized oiticica oil, epoxidized tall oil, etc.), epoxidized fatty acids, epoxidized cyclic olefin compounds (e.g. vinyl cyclohexene dioxide, 1-( 1-Methyl-1,2-epoxyethyl)-3,4-epoxy-4-methylcyclohexane, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexane carboxylate,
3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, dicyclopentaene dioxide, dipentene dioxide , tetrahydroindene dioxide, or a compound in which these rings are bonded with a group as shown above as R1 in the general formula (a-2-1), and other Araldite CY-175
(Ciba product name), etc.), epoxidized products of conjugated diene polymers (e.g., epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, epoxidized acrylonitrile-styrene copolymer), Examples of epoxidized polymers (e.g., epoxidized polypropylene, epoxidized polyisobutene), polyglycidyl ethers of polysiloxane, and epoxy resins containing heterocycles include epoxy resins in which an epoxy group is bonded to an oxazolidinone ring via a carbon atom. resin, diglycidyl etherified product of furan, diglycidyl etherified product of dioxane, diglycidyl etherified product of spirobi(m-dioxane), polyepoxy compound obtained from imidazoline substituted with a polyunsaturated alkenyl group at the 2-position, Examples include glycidyl isocyanurate. In addition, conventionally known epoxy resins such as the various epoxy resins described in "Manufacture and Application of Epoxy Resins" (edited by Hiroshi Kakiuchi) may be used.

[0057] Also, emulsified epoxy resins are preferably used as the epoxy resins used in the present invention. The emulsified epoxy resin is prepared by adding a polyoxyethylene alkylphenol ether type nonionic surfactant and polyoxyethylene polyoxypropylene block polyethers to the above-mentioned epoxy resin, preferably bisphenol A type epoxy resin or bisphenol F type epoxy resin, and then adding a polyoxyethylene alkylphenol ether type nonionic surfactant and polyoxyethylene polyoxypropylene block polyethers to the above-mentioned epoxy resin, preferably bisphenol A type epoxy resin or bisphenol F type epoxy resin. Alternatively, it can be easily emulsified by a known method using a homogenizer.

The average molecular weight of the polyalkylene polyether polyol compound (II-1-1) necessary for forming the self-emulsifying active organic amine curing agent of the present invention is 200.
-4,500; if the average molecular weight exceeds 4,500, film-forming properties will be insufficient, and if it is less than 200, adhesiveness will deteriorate, which is undesirable. As the polyalkylene polyether polyol compound (II-1-1), for example, general formula R4[(OR5)n OH]p
(2) (where R4 is a polyhydric alcohol residue, (
OR5) n is a polyoxyalkylene chain consisting of an oxyalkylene group having an alkylene group having 2 to 4 carbon atoms, n is a number indicating the degree of polymerization of the oxyalkylene group, and is a number corresponding to an average molecular weight of 200 to 4500. be. There are polyether polyols represented by p (preferably a number from 2 to 4).

Preferred examples of the polyhydric alcohol corresponding to R4 in the above general formula (2) include aliphatic dihydric alcohols (eg, ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentyl glycol). , trihydric alcohols (e.g. glycene, trioxyisobutane, 1,2,3-butanetriol, 1
,2,3-pentanetriol,2-methyl-1,2
,3-propanetriol,2-methyl-2,3,4
-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol,
2,3,4-hexanetriol, 4-propyl-3
, 4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylol propane, etc.), tetrahydric alcohols (e.g. erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentantetrol), Troll, 1, 3, 4
.

[0060] Preferred as the polyhydric alcohol are dihydric to tetrahydric alcohols, with ethylene glycol, propylene glycol, glycerin and the like being particularly preferred.

[0061] The polyether polyol represented by the above general formula (2) can be obtained by adding an alkylene oxide preferably having 2 to 4 carbon atoms to the polyhydric alcohol by a conventional method to obtain a desired molecular weight. It can be manufactured by letting it dry.

As the alkylene oxide having 2 to 4 carbon atoms, it is suitable to use, for example, ethylene oxide, propylene oxide, butylene oxide, and hetero- or block copolymers of these oxides, especially ethylene oxide. .

The polyalkylene polyether polyol compound (II-1-1) may have primary or secondary hydroxyl groups and is preferably produced from an alkylene oxide having 2 to 6 carbon atoms. polyethers such as polyethylene ether glycol, polypropylene ether glycol and polybutylene ether glycol. As the polyalkylene polyether polyol compound (II-1-1) used in the present invention, one type or a mixture of two or more of the above types can also be used.

Lactones (II-1) used in the present invention
Examples of -2) include γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

Polyalkylene polyether polyol compound (II-1-1) and lactones (II-1-1) of the present invention
The epoxy compound (II-1-3) having at least more than 0.1 hydroxyl group and adjacent epoxy group in the molecule that reacts with 1-2) includes the above-mentioned epoxy compounds, but especially polyphenols. Glycidyl ethers are preferred. For example, a reaction product consisting of epichlorohydrin and bisphenol A represented by the following formula:

[0066]

[Chemical formula 14]

Alternatively, analogues based on bisphenol F represented by the following formula:

[0068]

[Chemical formula 15]

and r is not greater than 2, especially 0.1
-1 is preferred. Epoxy equivalent is 160~
600 is preferred. Furthermore, one or a mixture of two or more of the above epoxy compound (II-1-3) and the above epoxy compound (I) can also be used.

[0070] The polyalkylene polyether polyol compound (II-1-1) of the present invention and lactones (II-1-1)
1-2) and an epoxy compound having at least 0.1 hydroxyl groups and adjacent epoxy groups in the molecule (II-
1-3) is the reaction ratio with polyalkylene polyether polyol compound (II-
1-1) 1.0 molar lactones (II-1-
2)
0.1 to 5 mol epoxy compound (II-1-3)
The reaction method is (1) reacting the polyalkylene polyether polyol compound (II-1-1) with the lactones (II-1-2), and the resulting polyalkylene polyether The ester product and excess epoxy compound (
(II-1-3), or (2) a method of reacting a polyalkylene polyether polyol compound (II-1-1) with a lactone (II-1-2) and an excess of an epoxy compound (II-1-3). ) and react simultaneously in the presence of a Lewis acid.

In the case of method (2), Japanese Patent Publication No. 3-69
This also includes cases where the following reaction occurs between an epoxy group and a lactone, as disclosed in Publication No. 24.

[0072]

[Chemical formula 16]

The above reaction is carried out using excess epoxy compound (II
-1-3) as a catalyst in a solvent or without a solvent,
BF3OC2H5, SnCl4, TiCl4, F
Using a Lewis acid such as eCl3, the reaction temperature is 0 to 7.
The reaction is carried out at 0°C or at a temperature of 20-180°C in the presence of a BF3-amine complex. Preferred BF3-amine complex salts include BF3-benzylamine, BF3-monoethylamine, BF3-triethylamine, BF3-propylamine, BF3
-aniline, BF3-dimethylaniline, etc. The reaction time is 30 minutes to 10 hours, and the amount of catalyst is 0.1 to 5% by weight, preferably 0.1 to 2% by weight based on the reaction mixture.
Weight%. The BF3-amine complex remaining in the resulting resin contains active substances with bases, such as calcium oxide,
It can be removed by adding calcium hydroxide, barium oxide, etc. in excess to the BF3-amine complex salt, neutralizing it, inactivating it, and filtering it.

Polyamines (II-
Examples of 2-1) include those shown in (1) to (2) below.

■ Aliphatic polyamines ethylenediamine, diethylenetriamine, triethylenetetramine,
Dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, hexamethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 2,2,4-(2,4,4-)trimethylhexamethylenediamine, Polypropylene-polyamine, dipropylene triamine, or polyoxypropylene polyamines (Dipharmin D-230, D-400, T-403, D manufactured by Mitsui Texaco Co., Ltd.)
-2000, etc.).

■ Alicyclic polyamines N-aminoethylpiperazine, piperazines, 1,3-bisaminocyclohexylamine (1,3-BAC), isophoronediamine, 1-cyclohexylamino-3-aminopropane, 1,4 -Diaminocyclohexane, di(aminocyclohexyl)methane, 1,3-di-(aminocyclohexyl)propane, 2,4-diamino-cyclohexane, N,N'-diethyl-1,4-diaminocyclohexane, 3,3'- Dimethyl-4,4'-diaminocyclohexylmethane.

■ Aromatic polyamines metaxylylene diamine, paraxylylene diamine ■ Heterocyclic polyamines

[0078]

[Chemical formula 17]

Modified amines obtained by converting the above-mentioned polyamines into amidation, Mannich formation, or epoxy adduct formation by known methods are also preferably used. Moreover, one kind or a mixture of two or more kinds of the above-mentioned polyamines can also be used.

The above epoxy group-containing compound (II-1)
and polyamines (II-2-1) to obtain the self-emulsifying active organic amine curing agent (II-2), the reaction temperature is 40 to 150 °C, preferably 60 to 11 °C.
It is preferable to carry out the reaction at 0° C. for about 1 to 10 hours, preferably about 3 to 5 hours. The reaction is preferably carried out in an equivalent ratio of excess amine to epoxy group. More preferably, the amino group/epoxy equivalent ratio is 1.8 to 5.0.

Furthermore, water may be mixed in advance with this curing agent (II-2). The mixing ratio is self-emulsifying active organic amine curing agent/water = 10-100/90-0 (weight ratio), preferably 50-100/50-0.

The preferred blending ratio of the composition of the present invention is epoxy resin (I)/self-emulsifying active organic amine curing agent (I).
I-2)=90-10/10-90 (weight ratio).

As the self-emulsifying active organic amine curing agent of the present invention, a cyanoethylated self-emulsifying active organic amine curing agent can be used to improve workability, curing properties, and physical properties.

The cyanoethylated self-emulsifying active organic amine curing agent of the present invention combines the above self-emulsifying active organic amine curing agent (II-2) and acrylonitrile (II-3) into a self-emulsifying active organic amine curing agent/ Acrylonitrile = 1
00/3 to 30 (weight ratio), preferably 100/5
-16 (weight ratio). The reaction method is to react a self-emulsifying active organic amine curing agent by the above reaction method, and then add or drop acrylonitrile at 20 to 80°C, preferably 30 to 70°C, and react more preferably at 30 to 70°C. It is produced by aging and reacting for 1 to 5 hours.

[0085] In addition, the reaction with acrylonitrile may be carried out by reacting with polyamines (II-2-1) in advance, or by a mixture of the self-emulsifying active organic amine curing agent (II-2) and water. may be reacted with acrylonitrile by the above reaction method.

In addition to these essential ingredients, the compositions according to the invention contain reactive diluents, non-reactive diluents and fillers, fillers and/or reinforcing agents, pigments, solvents, plasticizers, leveling agents. ,
It may also contain conventional modifiers such as thixotropic agents, flame retardants, mold release agents, etc. Suitable diluents, extenders, reinforcing agents, fillers and pigments that may be used in the compositions of the invention include monoglycidyl ethers, DO
P, DBP, xylene resin, benzyl alcohol,
Tetrahydrofurfuryl alcohol, allolizer, coal tar, bituminous materials such as bitumen, textile fibers, cellulose, glass fibers, synthetic fibers, asbestos fibers, boron fibers, carbon fibers, cellulose, polyethylene powder, clay, sand, rock, quartz powder , mineral silicates such as mica, asbestos powder, ground shale, kaolin, aluminum hydroxide, powdered chalk, gypsum, antimony trioxide, bentonite,
Silica airgel, lithopone, barite, titanium dioxide,
Examples include talc, calcium carbonate, carbon black, graphite, oxide pigments such as iron oxide, and metal powders such as aluminum powder or iron powder.

Solvents suitable for modifying the curable compositions of the invention include, for example, toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone,
These include diacetone, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether.

Plasticizers suitable for modifying the curable compositions of the invention include, for example, dibutyl-, dioctyl- and dinonyl esters of phthalic acid, tricresyl phosphate, tricylenyl phosphate and polypropylene glycols.

When the curable composition of the present invention is to be used particularly for surface protection, leveling agents that may be added include, for example, silicone, acetyl butylcellulose, polyvinyl acetate, wax, stearate, etc. There is.

The curable composition of the present invention can be produced by a conventional method using a known mixing device (stirrer, kneader, roller, etc.).

The water-based dispersion comprising the epoxy resin (I), curing agent (II), filler, pigment, etc. can be produced using any known method. The resulting dispersion can be applied to a substrate by any suitable method, such as brush coating, roller coating, spray coating, spatula coating, press coating, doctor blade coating, electrodeposition coating, dip coating, or the like.

The dispersion according to the present invention can be used as an undercoat, a filler, a sealing material, a protective coating, a coating material, a sealing material, a mortar, and a coating material.

[0093]

[Examples] Hereinafter, the effects of the present invention will be specifically shown in Examples and Comparative Examples, but these are not intended to limit the present invention.

Production Example of Epoxy Group-Containing Compound Production Example-1 Polyethylene glycol 200 with a molecular weight of 2000 was placed in a glass three-necked flask equipped with a thermometer, a stirrer, and a cooling tube.
Add 0g and 228g of ε-caprolactone at 80°C.
After reacting for 2 hours, 6.7 g of boron trifluoride monoethylamine complex salt (manufactured by Hashimoto Kasei Kogyo Co., Ltd.) and EP-41 were added.
00 (manufactured by Asahi Denka Kogyo Co., Ltd., WPE = 190) 304
0g and reacted at 140°C for 4 hours to form
=480 epoxy group-containing compound (A) was obtained.

Production Example-2 Polyethylene glycol 100 with a molecular weight of 1000 was placed in a three-necked glass flask equipped with a thermometer, stirrer, and cooling tube.
Add 0g and 228g of ε-caprolactone at 80°C.
After reacting for 2 hours, 6.7 g of boron trifluoride monoethylamine complex salt and 3040 g of EP-4100 were added and reacted at 140°C for 4 hours to give WPE=385.
An epoxy group-containing compound (B) was obtained.

Production Example-3 Polyethylene glycol 200 with a molecular weight of 2000 was placed in a glass three-necked flask equipped with a thermometer, stirrer, and cooling tube.
Add 0g and 114g of ε-caprolactone at 80°C.
After reacting for 2 hours, 6.7 g of boron trifluoride monoethylamine complex salt and 3040 g of EP-4100 were added and reacted at 140°C for 4 hours to give WPE=465.
An epoxy group-containing compound (C) was obtained.

Production Example-4 Polyethylene glycol 400 with a molecular weight of 4000 was placed in a three-necked glass flask equipped with a thermometer, stirrer, and cooling tube.
Add 0g and 228g of ε-caprolactone at 80°C.
After reacting for 3 hours, 6.7 g of boron trifluoride monoethylamine complex salt and 3040 g of EP-4100 were added and reacted at 140°C for 4 hours to obtain WPE=640.
An epoxy group-containing compound (D) was obtained.

Production Example-5 Polyethylene glycol 200 with a molecular weight of 2000 was placed in a three-necked glass flask equipped with a thermometer, stirrer, and cooling tube.
Add 0g and 570g of ε-caprolactone at 80°C.
After reacting for 3 hours, 6.7 g of boron trifluoride monoethylamine complex salt and 3040 g of EP-4100 were added and reacted at 140°C for 4 hours to give WPE=515.
An epoxy group-containing compound (E) was obtained.

Production Example-6 Polyethylene glycol 200 with a molecular weight of 2000 was placed in a three-necked glass flask equipped with a thermometer, stirrer, and cooling tube.
Add 0g and 228g of ε-caprolactone at 80°C.
After reacting for 2 hours, 6.7 g of boron trifluoride monoethylamine complex salt and 1900 g of EP-4100 were added and reacted at 140°C for 4 hours to obtain WPE=700.
An epoxy group-containing compound (F) was obtained.

Production Example-7 Polyethylene glycol 200 with a molecular weight of 2000 was placed in a glass three-necked flask equipped with a thermometer, a stirrer, and a cooling tube.
0g and ε-caprolactone 228g and EP-4100
After adding 3,040 g of the mixture and reacting at 80°C for 2 hours, 6.7 g of boron trifluoride monoethylamine complex salt was added and reacting at 140°C for 4 hours. WPE = 480
An epoxy group-containing compound (G) was obtained.

Production Example-8 In a three-necked glass flask equipped with a thermometer, stirrer, and cooling tube, 285 g of ε-caprolactone and 1 part of methylene chloride were added.
000 ml and triethylamine 0.7 ml,
380 g of EP-4100 and 750 ml of methylene chloride were added to the dropping funnel. After cooling the four-necked flask to 10°C with ice water, 1.5 ml of BF3OC2H5 was added, and EP-4100 was added while stirring while maintaining the temperature at 10°C.
The solution was added dropwise over 4 hours, and then reacted at 10°C for 5 hours.

After adding 3 ml of triethylamine to this reaction solution to deactivate the catalyst, 1500 ml of a 10% NaOH aqueous solution was added while cooling to 10° C. with ice water, and after stirring for 30 minutes, the alkali aqueous solution layer and the organic layer were separated. .

[0103] This organic layer was washed with 500 ml of water,
After separation by centrifugation twice, it was dehydrated with magnesium sulfate. Furthermore, tri(n-octyl)amine 0.2
After adding g, an epoxy group-containing compound (H) having a WPE of 490 was obtained by distillation under reduced pressure.

Production example of self-emulsifying active organic amine curing agent Production example-9 In a glass three-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 140 g of metaxylylene diamine and 210 g of epoxy group-containing compound (A) were added. g and EP-4100 1
0 g was added, and the mixture was reacted at 90° C. for 2 hours, and 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (1) having an active hydrogen equivalent of 125.

Production Example-10 In a glass three-necked flask equipped with a thermometer, stirrer, and cooling tube, 140 g of meta-xylylene diamine, 210 g of epoxy group-containing compound (B), and 1 EP-4100 were added.
0 g was added, and the mixture was reacted at 90° C. for 2 hours, and 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (2) having an active hydrogen equivalent of 129.

Production Example-11 In a glass three-neck flask equipped with a thermometer, stirrer, and cooling tube, 140 g of metaxylylene diamine, 210 g of epoxy group-containing compound (C), and 1 EP-4100 were added.
0 g was added, and the mixture was reacted at 90° C. for 2 hours, and 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (3) having an active hydrogen equivalent of 126.

Production Example-12 In a glass three-necked flask equipped with a thermometer, stirrer, and cooling tube, 140 g of meta-xylylene diamine, 210 g of epoxy group-containing compound (D), and 1 EP-4100 were added.
0 g was added, and the mixture was reacted at 90° C. for 3 hours, and 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (4) having an active hydrogen equivalent of 121.

Production Example-13 In a glass three-necked flask equipped with a thermometer, stirrer, and cooling tube, 140 g of meta-xylylene diamine, 210 g of epoxy group-containing compound (E), and 1 EP-4100 were added.
0 g was added, and the mixture was reacted at 90° C. for 2 hours, and 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (5) having an active hydrogen equivalent of 121.

Production Example-14 In a glass three-neck flask equipped with a thermometer, stirrer, and cooling tube, 140 g of metaxylylene diamine, 210 g of epoxy group-containing compound (F), and 1 EP-4100 were added.
0 g was added, and the mixture was reacted at 90° C. for 2 hours, and 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (6) having an active hydrogen equivalent of 120.

Production Example-15 In a glass three-necked flask equipped with a thermometer, stirrer, and cooling tube, 140 g of metaxylylene diamine, 210 g of epoxy group-containing compound (G), and 1 EP-4100 were added.
0 g was added, and the mixture was reacted at 90° C. for 2 hours, and 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (7) having an active hydrogen equivalent of 125.

Production Example-16 In a glass three-necked flask equipped with a thermometer, stirrer, and cooling tube, 140 g of meta-xylylene diamine, epoxy group-containing compound (H), and epoxy group-containing compound (A) were placed.
210 g of a one-to-one mixture of EP-410010
After reaction at 90° C. for 3 hours, 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (8) having an active hydrogen equivalent of 124.

Production Example-17 In a three-necked glass flask equipped with a thermometer, stirrer, and cooling tube, 80 g of meta-xylylene diamine and 80 g of Jeffamine D-230 (manufactured by Jefferson Chemical Company, USA) were added.
After stirring well until homogeneous, 210 g of epoxy group-containing compound (F) and 1 g of EP-4100 were added.
0 g was added, and the mixture was reacted at 90° C. for 2 hours, and 95 g of water was added to obtain a self-emulsifying active organic amine curing agent (9) having an active hydrogen equivalent of 147.

Production Example-18 Using 140 g of isophorone diamine instead of 140 g of meta-xylylene diamine in Production Example-14, and keeping all other conditions the same as Production Example-14, the reaction was carried out to form a self-emulsification with an active hydrogen equivalent of 153. Type active organic amine curing agent (10)
I got it.

Production Example-19 In Production Example-14, 140 g of 1,3-bisaminoethylcyclohexane was used instead of 140 g of metaxylylene diamine.
A self-emulsifying active organic amine curing agent (11) having an active hydrogen equivalent of 125 was obtained by using 0 g and all other conditions being the same as in Production Example 14.

Production Example 20 In a three-necked glass flask equipped with a thermometer, stirrer, and cooling tube, 100 g of metaxylylenediamine and PACM (
(manufactured by Anchor Chemical Co., Ltd.) in the UK, and stirred well until homogeneous, then epoxy group-containing compound (F) 2
Add 10 g and 10 g of EP-4100, and make 90
℃, react for 2 hours, add 95 g of water and make active hydrogen equivalent 12
A self-emulsifying active organic amine curing agent (12) of No. 7 was obtained.

Production Example-21 In a glass three-necked flask equipped with a thermometer, stirrer, and cooling tube, 140 g of metaxylylene diamine, 175 g of epoxy group-containing compound (F), and EP-4100 4 were added.
5 g was added thereto, and the mixture was reacted at 90° C. for 2 hours, and 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (13) having an active hydrogen equivalent of 124.

Production example of cyanoethylated self-emulsifying active organic amine curing agent Production example-22 In a glass three-necked flask equipped with a thermometer, stirrer, and cooling tube, self-emulsifying active organic amine curing agent (1) 450
25 g of acrylonitrile was added dropwise at 60° C. or below, and after the dropwise addition, the reaction was carried out at 60° C. for 2 hours to obtain a cyanoethylated self-emulsifying active organic amine curing agent (1) having an active hydrogen equivalent of 152.

Production Example-23 Self-emulsifying active organic amine curing agent (1) in Production Example-22
Instead of 450 g, 450 g of self-emulsifying active organic amine curing agent (5) was used, and all other conditions were the same as in Production Example 22.
A cyanoethylated self-emulsifying active organic amine curing agent (2) of No. 6 was obtained.

Production Example-24 In Production Example-22, 50 g of acrylonitrile was used instead of 25 g of acrylonitrile, and all other conditions were the same as in Production Example-22.
No. 8 cyanoethylated self-emulsifying active organic amine curing agent (
3) Obtained.

Examples 1 to 19 Epicoat #828 or EM-1-60 (epoxy emulsion manufactured by ACR Co., Ltd., solid content 60%, W
PE=320) and a self-emulsifying active organic amine curing agent (
1) - (13) or cyanoethylated self-emulsifying active organic amine curing agent (1) - (3) and water were mixed and cured in the formulation shown in Table 1 or Table 2, and the physical properties of the coating film were evaluated. Tested. The results are shown in Tables 1 and 2.

Comparative Examples 1 to 4 Epicote #828 or EM-1-60 and ACR
Hardener H-23-50W (ACR Co., Ltd.)
self-emulsifying polyamide curing agent, solid content: 50%, amine value 140mgKOH/g) or Adeka Hardener EH
-220 (Asahi Denka Kogyo Co., Ltd. aliphatic polyamine curing agent, solid content: 100%, amine value: 350mgKOH/
g), or 228 g of ε-caprolactone in Production Example-1
A self-emulsifying active organic amine with an active hydrogen equivalent of 122 obtained by reacting under the same conditions as in Production Example-9 using an epoxy group-containing compound with WPE = 542 obtained by using 912 g of ε-caprolactone instead of ε-caprolactone. Hardening agent (A)
Or WPE obtained by using 6000 g of polyethylene glycol with a molecular weight of 6000 instead of 2000 g of polyethylene glycol with a molecular weight of 2000 in Production Example-1 =
A self-emulsifying active organic amine curing agent (B) with an active hydrogen equivalent of 118 obtained by reacting the epoxy group-containing compound No. 845 under the same conditions as in Production Example-9 and water are shown in Table 2.
The compositions shown in the following were mixed and cured, and a comparative test was conducted on the physical properties of the coating film. The results are shown in Table 2.

[0122]

[Table 1]

[0123]

[Table 2]

<Evaluation method> Emulsifying property ○: Good emulsification, ○△: Emulsification takes time, ×
: No emulsification, coating condition ○: Good coating, glossy, △: Semi-gloss, △×: Semi-gloss/soft, ×: No film formation, adhesion (7 days after curing) 100/100: Cross cut No peeling, 80/
100: Cross cut and 20% peeling, 50/100
: 50% peeled off after cross cutting, ×: No film formation, water resistance (after 7 days of water immersion) ○: No change, △: Film formation becomes cloudy, ×: Dissolved, bending test (after 7 days of curing) 3mm Surface condition when bent 180° around the rod

[0125]

[Effect of the invention] The above epoxy resin (I) and curing agent (I)
The merits of the aqueous epoxy resin curable composition of the present invention, which contains I) and is emulsified and cured by adding water, are those of the conventional JP-A-50-98960 and JP-B-Sho 53-3.
Compared to the self-emulsifying imidazoline ring-containing compound disclosed in Publication No. 1517, it has superior coating film leveling and film-forming properties, a transparent cured film, and superior surface gloss, hardness, adhesion, water resistance, and chemical resistance. This is a characteristic.

[0126]

Claims (2)

[Claims] 1. (I) an epoxy resin having an average of more than one adjacent epoxy group in the molecule; and (II) a polyalkylene polyether polyol compound (II-1-1) having an average molecular weight of 200 to 4,500; Lactones (II
-1-2) and an epoxy compound (I
I-1-3) and a Lewis acid as a catalyst, polyalkylene polyether polyol compound (II-1-1) 1
．． Lactones (II-1-2) 0.1 per mol
~5 mol, epoxy compound (II-1-3) 1.2
Epoxy group-containing compound (II-1) obtained by reacting in a solvent or without solvent at a reaction ratio of ~10 moles, aliphatic polyamines (II-2-1), alicyclic polyamines (II -2-1■), aromatic polyamines (II-2
-1■) and heterocyclic polyamines (II-2-1■
) one or more polyamines selected from (II
-2-1) and a self-emulsifying active organic amine curing agent obtained by reacting with an excess of polyamine. 2. (I) an epoxy resin having an average of more than one adjacent epoxy group in the molecule; and (II) a polyalkylene polyether polyol compound (II-1-1) having an average molecular weight of 200 to 4,500; Lactones (II
-1-2) and an epoxy compound (I
I-1-3) and a Lewis acid as a catalyst, polyalkylene polyether polyol compound (II-1-1) 1
．． Lactones (II-1-2) 0.1 per mol
~5 mol, epoxy compound (II-1-3) 1.2
Epoxy group-containing compound (II-1) obtained by reacting in a solvent or without solvent at a reaction ratio of ~10 moles, aliphatic polyamines (II-2-1), alicyclic polyamines (II -2-1■), aromatic polyamines (II-2
-1■) and heterocyclic polyamines (II-2-1■
) one or more polyamines selected from (II
-2-1) and a self-emulsifying active organic amine curing agent (II-2) obtained by reacting with an excess of polyamine, and a cyanoethylated self-emulsifying active organic amine curing agent obtained by further reacting with acrylonitrile (II-3). An aqueous epoxy resin curable composition comprising an amine curing agent.