JP3024006B2 - Aqueous epoxy resin curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous epoxy resin curable composition.

[0002]

2. Description of the Related Art In recent years,
It is a well-known fact that the use regulations of solvents are becoming stricter year by year due to the danger of fire due to the use of solvents, the problem of pollution due to air pollution, the effect on human bodies, and the increase in cost of solvents. However, a coating method using an aqueous epoxy resin to remove this adverse effect is in the limelight, for example, in the case of an epoxy resin emulsion,
In general, the emulsification method using surfactants is mainly used,
Depending on the type and amount of activator used, the physical properties of the cured product tend to be significantly reduced.

In particular, water resistance, adhesion, mechanical properties, etc. are inferior to those of solvent-based or non-solvent-based cured products. Usually, the production of these emulsions requires a high-speed rotation using a homomixer. The cost and labor are large because of complete equipment or production, and the stability of the emulsion,
In terms of storage stability, there are many emulsion separation phenomena depending on the selection of the emulsifier and the setting of the production conditions, so that there is also a defect in the long-term stability. Further, when such an emulsion is left outdoors in the winter, there are adverse effects such as long-lasting and crystallization, and it cannot always be said that physical properties and work efficiency are sufficient.

Japanese Patent Publication No. 40688/1986 discloses an aqueous epoxy resin curing agent obtained by reacting a polyether polyol with an epoxy compound and further reacting the same with an amine. Not yet sufficient in terms of power and viscosity.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to improve these drawbacks, and as a result, obtained by reacting a polyalkylene polyether polyol compound with a lactone 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 between the epoxy functional group-containing reactive nonionic surfactant and various polyamines in a known manner in a polyamine excess. However, this self-emulsifying hardener can easily emulsify an epoxy compound in the presence of any water, and at the time of emulsification, does not require high-speed rotation with a homomixer and can be sufficiently uniformly emulsified only by a simple stirring operation. In addition, the ratio of water to be added is smaller than that of the conventional emulsion system, which is usually within the range where 20 to 60% of the solid content can be emulsified. It has been found that the amount of water to be added can be arbitrarily adjusted, and the present invention has been completed.

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 a molecule, and (II) an average molecular weight of 200 to 45.
00 polyalkylene polyether polyol compound (II
-1-1), a lactone (II-1-2) and an epoxy compound (II-1-3) having at least more than 0.1 hydroxyl group and adjacent epoxy group in the molecule by a Lewis acid catalyst As a lactone (II-) with respect to 1.0 mol of the polyalkylene polyether polyol compound (II-1-1).
1-2) 0.1 to 5 mol, 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 mol is converted to an aliphatic polyamine (II-2-1) or an alicyclic polyamine (II -2-1), aromatic polyamines (II-2-1)
) And heterocyclic polyamines (II-2-1) or one or more polyamines (II-2-
1) and a self-emulsifying type active organic amine curing agent obtained by reacting with an excess of polyamine, and the aqueous epoxy resin curable composition of the present invention further comprises (I) An epoxy resin having an average of more than one adjacent epoxy group in it, and (II) an average molecular weight of 200
To 4500 polyalkylene polyether polyol compounds (II-1-1), lactones (II-1-2), and epoxy compounds having at least 0.1 hydroxyl groups and adjacent epoxy groups in the molecule (II- 1-3) with a Lewis acid as a catalyst, 0.1 to 5 mol of a lactone (II-1-2) per 1.0 mol of a polyalkylene polyether polyol compound (II-1-1), and an 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 mol,
Aliphatic polyamines (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)
1) and a self-emulsifying active organic amine curing agent (II-2) obtained by reacting with excess polyamine, and further reacting with acrylonitrile (II-3) to obtain a cyanoethylated self-emulsifying active organic amine curing agent obtained. It is characterized by consisting of.

The epoxy resin (I) having an average of more than one adjacent epoxy group in the molecule used in the present invention is represented by the following formula:

[0008]

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(Where Z is a hydrogen atom, a methyl group, an ethyl group) and an epoxy resin (I-I) having on average more than one substituted or unsubstituted glycidyl ether group represented by the following formula:
1), formula

[0010]

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(Where Z is a hydrogen atom, a methyl group, an ethyl group) and an epoxy resin having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule (I-
2), equation

[0012]

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(Where Z is a hydrogen atom, a methyl group or an ethyl group) An epoxy resin (I-3) having an average of more than one N-substituted substituted or unsubstituted 1,2-epoxypropyl group represented by the following formula: ) Etc. are included.

An epoxy resin (I-I) having more than one substituted or unsubstituted glycidyl ether group in the molecule
1) are an epoxy resin obtained by glycidyl etherification of a phenolic hydroxyl group and an epoxy resin obtained by glycidyl etherification of an alcoholic hydroxyl group. Preferred examples of the epoxy resin (I-1) include 1 Polyglycidyl ether of polyhydric phenol having one or more aromatic nuclei (I-1-
1) Polyglycidyl ether of an alcoholic polyhydroxyl compound derived from an addition reaction between a polyhydric phenol having one or more aromatic nuclei and an alkylene oxide having 2 to 4 carbon atoms (I-1- 2) Or polyglycidyl ether (I-1-3) of an aliphatic polyhydroxyl compound containing no nucleus.

Thus, polyglycidyl ether (I-1)
-1) means, for example, that a polyhydric phenol (a) having at least one aromatic nucleus and epihalohydrin (b) are reacted in a conventional manner in the presence of a basic catalyst such as sodium hydroxide or a reaction amount of a basic compound. Amount of an epoxy resin containing a polyglycidyl ether as a main reaction product or a polyhydric phenol (a) having at least one aromatic nucleus and epihalohydrin (b) as a main reaction product obtained by the reaction of a basic catalyst such as triethylamine And an epoxy resin obtained by reacting a polyhydrin ether obtained by a conventional reaction in the presence of a compound with a basic compound such as sodium hydroxide.

Similarly, polyglycidyl ether (I-1-)
2) Alternatively, polyglycidyl ether (I-1-3) refers to, for example, polyhydroxyl derived by an addition reaction of a polyhydric phenol having at least one aromatic nucleus with an alkylene oxide having 2 to 4 carbon atoms. Compound (c)
Or a polyhalohydrin ether and sodium hydroxide obtained by reacting an aliphatic polyhydroxyl compound (d) containing no nucleus with epihalohydrin (b) by a conventional method in the presence of an acidic catalyst such as boron trifluoride. An epoxy resin containing, as a main reaction product, polyglycidyl ether obtained by reacting with a basic compound such as

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

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

Examples of polynuclear polyhydric phenol (a-2) include compounds represented by the general formula (a-2-1)

[0020]

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[In the formula, Ar is an aromatic divalent hydrocarbon such as a naphthylene group and a phenylene group, and a phenylene group is preferable for the purpose of the present invention. Y ′ and Y ₁ may be the same or different and include a methyl group, an n-propyl group, an n-butyl group, an n-
Alkyl groups such as hexyl, n-octyl, preferably up to 4 carbon atoms, or halogens, i.e. chlorine, bromine, iodine or fluorine, or methoxy, methoxymethyl, ethoxy And alkoxy groups such as ethoxyethyl, n-butoxy and amyloxy, preferably up to 4 carbon atoms. When a substituent other than a hydroxyl group is present in either or both of the aromatic divalent hydrocarbon groups, these substituents may be the same or different. m
And z are integers having a value from 0 (zero) to the maximum value corresponding to the number of hydrogen atoms of the aromatic ring (Ar) that can be substituted by the substituent, and can be the same or different values. R ₁ is, for example, -CO-, -O-, -S-, -SO-, -SO ₂ -,-(S) _n- (n is 2
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, isopropylidene group,
Amylidene group, isoamylidene group, 1-phenylethylidene group, ω- (dicyclopentadienyl halide) alkylidene group, or cycloaliphatic group such as 1,4-cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene A den group, a halogenated alkylene group, a halogenated alkylidene group, or a halogenated cycloaliphatic group, or an alkoxy- and aryloxy-substituted alkylidene group or an alkoxy- and aryloxy-substituted alkylene Groups or alkoxy- and aryloxy-substituted cyclic aliphatic groups such as methoxymethylene, ethoxymethylene, ethoxyethylene, 2-ethoxytrimethylene, 3-ethoxypentamethylene, 1,4- (2-methoxy Cyclohexane) group, pheno Siethylene group, 2-phenoxytrimethylene group, 1,3- (2-phenoxycyclohexane) group, or arylalkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1,7-diphenylpentamethylene group, 2-phenyl Decamethylene group,
Alternatively, an aromatic group such as a phenylene group or a naphthylene group, or a halogenated aromatic group such as a 1,4- (2-chlorophenylene) group or 1,4- (2-fluorophenylene)
Or an alkoxy or aryloxy-substituted aromatic group such as a 1,4- (2-methoxyphenylene) group,
4- (2-ethoxyphenylene) group, 1,4- (2-n-
A propoxyphenylene) group, a 1,4- (2-phenoxyphenylene) group, or an alkyl-substituted aromatic group such as a 1,4- (2-methylphenylene) group or a 1,4- (2-ethylphenylene) group; 1,4- (2-n-propylphenylene) group, 1,4- (2-n-butylphenylene) group,
4- (2-n-dodecylphenylene) group, formula

[0022]

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

[0024]

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Wherein R ″ is a divalent group such as a divalent hydrocarbon group such as a hydrogen atom or a hydrocarbon group which may be substituted with a hydroxyl group or an epoxy group, or R ₁ is, for example, formula

[0026]

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The ring may be fused to one of the Ar groups as in the case of the compound represented by the formula, or R ₁ is a polyethoxy group, a polypropoxy group, a polythioethoxy group,
It can be a polyalkoxy group such as a polybutoxy group or a polyphenylethoxy group, or R ₁ is a group containing a silicon atom such as a polydimethylsiloxy group, a polydiphenylsiloxy group, or a polymethylphenylsiloxy group. Or R ₁ is an aromatic ring, a tertiary amino group ether bond, a carbonyl group or two or more alkylene groups or alkylidene groups separated by a sulfur-containing bond such as sulfur or sulfoxide. Can be. And a polynuclear dihydric phenol represented by the formula:

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

[0029]

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(Wherein Y ′ and Y ₁ have the same meanings as above, m and z are values from 0 to 4, and R ₁ is preferably from 1 to
Alkylene or alkylidene group having 3 carbon atoms or formula

[0031]

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A saturated group represented by the formula: Q is 0 or 1)
Is a polynuclear dihydric phenol represented by

Examples of such dihydric phenols include bisphenol A, which is commonly referred to as bisphenol A, 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) ethane, 1,1-
Bis (4-hydroxy-2-chlorophenyl) 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-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl)
Pentane, 2,2-bis (4-hydroxyphenyl) heptane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (hydroxyphenyl) alkanes such as 2-bis (4-hydroxyphenyl) -1,2-bis (phenyl) propane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, or 4,4 '-Dihydroxybiphenyl, 4,4'-dihydroxyoctachlorobiphenyl, 2,2'
-Dihydroxybiphenyl, dihydroxybiphenyl such as 2,4'-dihydroxybiphenyl, or bis- (4
-Hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone, chloro-2,4-dihydroxydiphenylsulfone, 5-chloro-4,4'-dihydroxydiphenylsulfone, 3'-chloro-4,4'-dihydroxydiphenyl Di (hydroxyphenyl) sulfone such as sulfone, or bis (4-hydroxyphenyl) ether,
4,3 ′-(or 4,2′- or 2,2′-dihydroxydiphenyl) ether, 4,4′-dihydroxy-2,6-dimethyldiphenylether, bis (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-bromophenyl) ether, bis (4-
(Hydroxynaphthyl) ether, bis (4-hydroxy-3-chloronaphthyl) ether, bis (2-hydroxybiphenyl) ether, 4,4′-dihydroxy-2,6-
Di (hydroxyphenyl) ethers such as dimethoxy-diphenylether, 4,4'-dihydroxy-2,5-diethoxydiphenylether, and 1,1-bis (4-hydroxyphenyl) -2-phenylethane; 1,
3,3-trimethyl-1- (4-hydroxyphenyl)-
6-Hydroxyindane, 2,4-bis (p-hydroxyphenyl) -4-methylpentane are also suitable.

Still another preferred group of the polynuclear dihydric phenols is a compound represented by the general formula (a-2-1-2)

[0035]

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Wherein R ₃ is a methyl or ethyl group, R ₂ is an alkylidene group or other alkylene group having 1 to 9 carbon atoms, and p is 0 to 4, for example, 1,4- Bis (4-hydroxybenzyl) benzene, 1,4-bis (4-hydroxybenzyl) tetramethylbenzene,
4-bis (4-hydroxybenzyl) tetraethylbenzene, 1,4-bis (p-hydroxycumyl) benzene,
1,3-bis (p-hydroxycumyl) benzene and the like.

Other polynuclear polyphenols (a-2) include, for example, 1,1,2,2-tetrakis (4-
Hydroxyphenyl) ethane, initial condensates of phenols and carbonyl compounds (eg, initial condensates of phenolic resins, condensation products of phenol and acrolein, condensation products of phenol and glyoxal, condensation of phenol and pentanediallyl Reaction product, condensation reaction product of resorcinol and acetone, xylene-phenol-formalin precondensate), condensation product of phenols and polychloromethylated aromatic compound (example: condensation formation of phenol with bischloromethylxylene) Material).

Thus, here, the polyhydroxyl compound
(c) is an ether obtained by reacting the above-mentioned polyhydric phenol (a) having at least one aromatic nucleus with an alkylene oxide in the presence of a catalyst which promotes the reaction between an OH group and an epoxy group. -ROH (where R is an alkylene group derived from an alkylene oxide) or (and)-(RO) _n H
(Where R is an alkylene group derived from an alkylene oxide and one polyoxyalkylene chain may contain a different alkylene group; n is an integer of 2 or more indicating the number of polymerization of the oxyalkylene group) Is a compound having In this case, the ratio of the polyhydric phenol (a) to the alkylene oxide is set to 1: 1 (mole: mol) or more, and preferably, the ratio of the alkylene oxide to the OH group of the polyhydric phenol (a) is 1 : 1 to 10, preferably 1 to 3 (equivalent: equivalent).

The alkylene oxides include, for example, ethylene oxide, propylene oxide, butylene oxide and the like, and those which form a side chain when these react with the polyhydric phenol (a) to form an ether bond are particularly preferred. Such compounds include propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide, and propylene oxide is particularly preferable.

A particularly preferred group of such polyhydroxyl compounds (c) is represented by the general formula (c-1)

[0041]

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(Wherein Y ′, Y ₁ , m, z and R ₁ are the above-mentioned (a-2-1)
-1) It is the same as that of the formula, wherein R ₂ is an alkylene group having 2 to 4 carbon atoms, and n ₁ and n ₂ are values of 1 to 3).

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

[0044]

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(Wherein R ₂ , R ₃ and p are the same as those in the formula (a-2-1-2), R is an alkylene group having 2 to 4 carbon atoms, n ₁ and n ₂ are 1 to 3) Which is a value of ３3).

Other polyhydroxyl compounds containing a nucleus
(c) includes an alicyclic polyol obtained by hydrogenating an aromatic nucleus of a polyhydric phenol (a).

Examples of the aliphatic polyhydroxyl compound (d) containing no nucleus include polyvalent compounds such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, glycerin and pentaerythritol. Polyhydric polyhydroxy compounds, polyether polyols and the like obtained by adding alkylene oxide to alcohols and these polyhydric alcohols or other active hydrogen-containing compounds (for example, compounds having groups such as amino group, carboxyl group, thiohydroxyl group) And polyhydroxyl compounds.

The epihalohydrin (b) is represented by the general formula (1)

[0049]

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Wherein Z is a hydrogen atom, a methyl group, an ethyl group, and X ′ is a halogen atom. 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.

Examples of the acidic catalyst for promoting the reaction between the epihalohydrin (b) and the polyhydroxyl compound (c) or the polyhydroxyl compound (d) include boron trifluoride, stannic chloride, zinc chloride and ferric chloride. Or a derivative thereof (eg, boron trifluoride-ether complex compound) or a mixture thereof, or the like.

Similarly, basic catalysts for promoting the reaction of epihalohydrin (b) with polyhydric phenol (a) include alkali metal hydroxides (eg, sodium hydroxide) and alkali metal alcoholates (eg, sodium ethoxide). Tertiary amine compounds (e.g., triethylamine, triethanolamine), quaternary ammonium compounds (e.g., tetramethylammonium bromide) or mixtures thereof, so that the glycidyl ether Or a basic compound which forms a glycidyl ether by closing a halohydrin ether formed as a result of the reaction by a dehydrohalogenation reaction, such as an alkali metal hydroxide (eg, sodium hydroxide) or aluminate Alkali metal salts (eg, sodium aluminate) If is often used.

However, these catalysts or basic compounds can be used as such or as a solution of an appropriate inorganic or organic solvent.

Further, an epoxy resin having an average of one or more substituted or unsubstituted glycidyl ester groups in the molecule (I-I
2) includes aliphatic or aromatic polycarboxylic acids (for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endmethylenetetrahydro Phthalic acid, methylendmethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
In addition to dimer fatty acids, trimellitic acid, trimesic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, and halogen-substituted compounds thereof, also include terminal carboxyl polyester oligomers obtained from these polycarboxylic acids and polyhydric alcohols Glycidyl methacrylate synthesized from epihalohydrin (b) represented by the general formula (1) and methacrylic acid, and an epoxy resin obtained by polymerizing glycidyl methacrylate synthesized from methacrylic acid.

Examples of the epoxy resin (I-3) having an average of one or more N-substituted substituted or unsubstituted 1,2-epoxypropyl groups in a molecule include aromatic amines (for example, aniline or nucleus). An epoxy resin obtained from an aniline having an alkali substituent) and an epihalohydrin (b) represented by the above general formula (1), an initial condensate of an aromatic amine with an aldehyde (for example, an aniline-formaldehyde precondensate, an aniline-phenol) -Formaldehyde precondensate) and epihalohydrin (b).

Other epoxy resins include epoxidized oils (eg, epoxidized linseed oil, epoxidized soybean oil,
Epoxidized safflower oil, epoxidized tung oil, epoxidized eno oil, epoxidized dehydrated castor oil, epoxidized euticica oil, epoxidized tall oil, etc. epoxidized fatty acids, epoxidized cyclic olefin compounds (for example, vinylcyclohexenedioxide, 1-methyl-1,2-epoxyethyl) -3,4-epoxy-4-methylcyclohexane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexyl Methyl-3,4-epoxy-
6-methylcyclohexanecarboxylate, bis (3,4
-Epoxy-6-methylcyclohexylmethyl) adipate, dicyclopentaenedioxide, dipentenedionoxide, tetrahydroindene dioxide, or a ring of these as previously shown as R ₁ in general formula (a-2-1) Araldite CY-175
Epoxidized conjugated diene polymer (eg, epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, epoxidized acrylonitrile-styrene copolymer), and unsaturated bonds. Epoxy products of polymers containing (eg, epoxidized products of polypropylene, epoxidized products of polyisobutene), polyglycidyl ethers of polysiloxane, and epoxy resins containing a heterocyclic ring include epoxy resins having an epoxy group bonded to an oxazolidinone ring via a carbon atom. Resin, diglycidyl ether of furan, diglycidyl ether of dioxane, diglycidyl ether of spirobi (m-dioxane), polyepoxy compound obtained from imidazoline in which polyunsaturated alkenyl group is substituted at position 2, triglycidin Isocyanurate and the like.
Other conventionally known epoxy resins such as various epoxy resins described in "Production and Application of Epoxy Resin" (edited by Hiroshi Kakiuchi) are used.

Further, an emulsified epoxy resin is also preferably used as the epoxy resin used in the present invention. The emulsified epoxy resin is a homomixer obtained by adding a polyoxyethylene alkylphenol ether-based nonionic surfactant and a polyoxyethylene polyoxypropylene block polyether to the above epoxy resin, preferably a bisphenol A epoxy resin or a bisphenol F epoxy resin. Alternatively, the emulsion can be easily emulsified by a known method using a homogenizer.

The average molecular weight of the polyalkylene polyether polyol compound (II-1-1) required to form the self-emulsifying type active organic amine curing agent of the present invention is from 200 to 45.
When the average molecular weight is more than 4500, the film-forming properties are insufficient, and when the average molecular weight is less than 200, the adhesiveness is unfavorably reduced. As the polyalkylene polyether polyol compound (II-1-1), for example, a compound represented by the general formula R ₄ [(OR ₅ ) _n OH] _p (2) (where R ₄ is a polyhydric alcohol residue, (OR ₅ ) _n Is carbon number 2
A polyoxyalkylene chain comprising an oxyalkylene group having from 4 to 4 alkylene groups, and n is a number indicating the degree of polymerization of the oxyalkylene group and a number corresponding to an average molecular weight of 200 to 4500. p is preferably a number from 2 to 4).

Preferred examples of the polyhydric alcohol corresponding to R ₄ in the general formula (2) include, for example, aliphatic dihydric alcohols (eg, ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentyl glycol) ), Trihydric alcohols (eg, 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, trimethylolpropane, etc.), tetrahydric alcohols (eg: erythritol, pentaerythritol,
1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentanetetrol, 1,3,4,5-
Hexane tetrol, etc.), pentahydric alcohols (eg, adnit, arabbit, xylit, etc.), hexahydric alcohols (eg, sorbitol, mannitol, idit, etc.).

The polyhydric alcohol is preferably a dihydric to tetrahydric alcohol, and particularly preferably ethylene glycol, propylene glycol, glycerin and the like.

The polyether polyol represented by the above general formula (2) is obtained by adding an alkylene oxide having preferably 2 to 4 carbon atoms to such a polyhydric alcohol by a conventional method so as to have a desired molecular weight. It can be manufactured by letting go.

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

The polyalkylene polyether polyol compound (II-1-1) may have a primary or secondary hydroxyl group and is preferably prepared from an alkylene oxide having 2 to 6 carbon atoms. Polyethers such as polyethylene ether glycol, polypropylene ether glycol and polybutylene ether glycol. The polyalkylene polyether polyol compound (II-1-1) used in the present invention is the above-mentioned 1
Species or mixtures of two or more can also be used.

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

The polyalkylene polyether polyol compound (II-1-1) of the present invention and the lactone (II-1-1)
Epoxy compounds having at least more than 0.1 hydroxyl groups and adjacent epoxy groups in the molecule, which react with (2)
Examples of 1-3) include the aforementioned epoxy compounds, and polyphenol glycidyl ethers are particularly preferable. For example, a reaction product comprising epichlorohydrin represented by the following formula and bisphenol A

[0066]

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Or an analog based on bisphenol F represented by the following formula:

[0068]

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Where r is not greater than 2, especially 0.1 to 1
Is preferred. Those having an epoxy equivalent of 160 to 600 are preferred. Further, one or a mixture of two or more of the above-mentioned epoxy compound (II-1-3) and the above-mentioned epoxy compound (I) can also be used.

The polyalkylene polyether polyol compound (II-1-1) of the present invention and a lactone (II-1-1)
2) and an epoxy compound having at least more than 0.1 hydroxyl group and adjacent epoxy group in the molecule (II-1-3)
The reaction ratio with the polyalkylene polyether polyol compound (II-1-1) 1.0 mol lactones (II-1-2) 0.1 to 5 mol Epoxy compound (II-1-3) 1.2 to 10 mol The reaction method includes (1) a polyalkylene polyether polyol compound (II
-1-1) and a lactone (II-1-2), and the resulting polyalkylene polyetherester product is
In the presence of a Lewis acid, excess epoxy compound (II-1-
Or (2) a polyalkylene polyether polyol compound (II)
-1-1), a lactone (II-1-2), and an excess of the epoxy compound (II-1-3) are prepared and reacted simultaneously in the presence of a Lewis acid.

The method (2) includes a case where the following reaction occurs between an epoxy group and a lactone, as disclosed in Japanese Patent Publication No. 3-6924.

[0072]

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The above reaction is carried out in an excess amount of the epoxy compound (II-
Using 1-3) in a solvent or without solvent, as a catalyst, BF
₃ Using a Lewis acid such as OC ₂ H ₅ , SnCl ₄ , TiCl ₄ , FeCl _3, etc., at a reaction temperature of 0 to 70 ° C., or at a temperature of 20 to 180 ° C. in the presence of a BF ₃ -amine complex salt. Reaction under The amine complex, BF ₃ - - preferably BF ₃ benzylamine, BF ₃ - monoethylamine, BF ₃ - triethylamine, BF ₃ - propylamine, BF ₃ - aniline, BF ₃
-Dimethylaniline and the like. Reaction time is 30 minutes ~
In 10 hours, the amount of catalyst is 0.1-5% by weight, preferably 0.1-2% by weight, based on the reaction mixture. The BF ₃ -amine complex salt remaining in the formed resin is obtained by adding an active substance having a base, for example, calcium oxide, calcium hydroxide, barium oxide, etc. in excess to the BF ₃ -amine complex salt, neutralizing, deactivating, and filtering. Can be removed.

The polyamines (II-2) used in the present invention
Examples of -1) include the following.

Aliphatic Polyamines Ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, hexamethylenediamine, 1,2-propylenediamine, 1,2-propylenediamine
3-propylenediamine, 2,2,4- (2,4,4-) trimethylhexamethylenediamine, polypropylene-polyamine, dipropylenetriamine, or polyoxypropylenepolyamines (Difamine manufactured by Mitsui Texaco Co., Ltd.)
D-230, D-400, T-403, D-2000).

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 meta-xylylenediamine, para-xylylenediamine heterocyclic polyamines

[0078]

Embedded image

Further, modified amines obtained by amidating, Mannich-forming, or epoxy-adducting the above-mentioned polyamines by a known method are also preferably used. Further, one or a mixture of two or more of the above-mentioned polyamines can also be used.

The reaction method for obtaining the self-emulsifying active organic amine curing agent (II-2) by reacting the epoxy group-containing compound (II-1) with the polyamines (II-2-1) is as follows. The reaction is preferably carried out at 40 to 150 ° C., preferably 60 to 110 ° C., for a reaction time of 1 to 10 hours, preferably about 3 to 5 hours. The reaction is preferably carried out in an equivalent ratio of amine to epoxy group. More preferably, the amino group / epoxy equivalent ratio is 1.8 to 5.0.

Further, water can be mixed in advance with the curing agent (II-2). The mixing ratio of the self-emulsifying active organic amine curing agent / water is 10 to 100/90 to 0 (weight ratio), preferably 50 to 100/50 to 0.

The preferred compounding ratio of the composition of the present invention is epoxy resin (I) / self-emulsifying active organic amine curing agent (II
-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 in order to further improve workability, curability and physical properties.

The cyanoethylated self-emulsifying active organic amine curing agent of the present invention comprises the self-emulsifying active organic amine curing agent (II-2) and acrylonitrile (II-3). Acrylonitrile = 100 /
3 to 30 (weight ratio), preferably 100/5 to 16 (weight ratio)
And obtained by reacting. After reacting the self-emulsifying active organic amine curing agent by the above-mentioned reaction method, the reaction method is 20 to 80.
Acrylonitrile is added or dropped at 30 ° C., preferably 30 to 70 ° C., and more preferably at 30 to 70 ° C. for 1 hour to 5 hours.
Manufactured by an aging reaction.

The reaction with acrylonitrile may be carried out beforehand with a polyamine (II-2-1), or a mixture of a 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 components, the compositions according to the invention may also contain reactive diluents, non-reactive diluents and extenders, fillers and / or reinforcing agents, pigments, solvents, plasticizers, leveling agents. ,
It may contain conventional modifiers such as thixotropic agents, flame retardants, release agents and the like. Suitable diluents, extenders, reinforcing agents, fillers and pigments that may be used in the compositions of the present invention include monoglycidyl ether, DOP
, DBP, xylene resin, benzyl alcohol, tetrahydrofurfuryl alcohol, bitumens such as allolyzer, coal tar, bitumen, textile fiber, cellulose, glass fiber, synthetic fiber, asbestos fiber, boron fiber, carbon fiber,
Cellulose, polyethylene powder, clay, sand, rock, quartz powder, mineral silicates such as mica, asbestos powder, crushed shale, kaolin, aluminum hydroxide, powdered chalk, gypsum, antimony trioxide, bentonite, silica airgel, lithopone , Barite, titanium dioxide, talc, calcium carbonate, carbon black, graphite, oxide pigments such as iron oxide, and metal powders such as aluminum powder or iron powder.

Suitable solvents for modifying the curable composition of the present invention include, for example, toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone,
There are diacetone, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether.

Suitable plasticizers for modifying the curable compositions according to the invention include, for example, dibutyl, dioctyl and dinonyl esters of phthalic acid, tricresyl phosphate, trixylenyl phosphate and polypropylene glycol.

When the curable composition of the present invention is to be used especially for surface protection, leveling agents which may be added include, for example, silicone, acetylbutylcellulose, polyvinyl acetate, wax, stearate and the like. There is.

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

A water-based dispersion comprising an epoxy resin (I), a curing agent (II), a filler, a pigment and the like can be produced by any known method. The resulting dispersion is applied in any suitable manner, e.g. brushing, roller,
It can be applied to a substrate by a method such as spraying, spatula coating, press coating, doctor blade coating, electrodeposition coating, dip coating and 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 by examples and comparative examples, but these do not limit the present invention.

[0094]Production example of epoxy group-containing compound  Production Example-1 Glass three-necked fruss equipped with thermometer, stirrer, and cooling pipe
2,000g of polyethylene glycol with a molecular weight of 2000 and ε
-Add 228 g of caprolactone and react at 80 ° C for 2 hours.
After that, boron trifluoride monoethylamine complex salt (Hashimoto Kasei
6.7 g and EP-4100 (Asahi Denka Kogyo Co., Ltd.)
, WPE = 190), and react at 140 ° C for 4 hours.
Thus, an epoxy group-containing compound (A) having a WPE of 480 was obtained.

Production Example 2 In a glass three-necked flask equipped with a thermometer, a stirrer, and a condenser, 1000 g of polyethylene glycol having a molecular weight of 1,000 and ε were added.
After adding 228 g of caprolactone and reacting at 80 ° C. for 2 hours, 6.7 g of boron trifluoride monoethylamine complex and EP
−4100 3040 g, and react at 140 ° C. for 4 hours.
An epoxy group-containing compound (B) having PE = 385 was obtained.

Production Example-3 In a glass three-necked flask equipped with a thermometer, a stirrer, and a condenser, 2,000 g of polyethylene glycol having a molecular weight of 2,000 and ε were added.
After adding 114 g of caprolactone and reacting at 80 ° C. for 2 hours, 6.7 g of boron trifluoride monoethylamine complex salt and EP
−4100 3040 g, and react at 140 ° C. for 4 hours.
An epoxy group-containing compound (C) having a PE of 465 was obtained.

Production Example-4 In a glass three-necked flask equipped with a thermometer, a stirrer, and a cooling tube, 4000 g of polyethylene glycol having a molecular weight of 4000 and ε were added.
After adding 228 g of caprolactone and reacting at 80 ° C. for 3 hours, 6.7 g of boron trifluoride monoethylamine complex salt and EP
−4100 3040 g, and react at 140 ° C. for 4 hours.
An epoxy group-containing compound (D) having a PE of 640 was obtained.

Production Example-5 A glass three-necked flask equipped with a thermometer, a stirrer, and a cooling tube was charged with 2000 g of polyethylene glycol having a molecular weight of 2,000 and ε.
After adding 570 g of caprolactone and reacting at 80 ° C. for 3 hours, 6.7 g of boron trifluoride monoethylamine complex salt and EP
−4100 3040 g, and react at 140 ° C. for 4 hours.
An epoxy group-containing compound (E) having PE = 515 was obtained.

Production Example-6 A glass three-necked flask equipped with a thermometer, a stirrer, and a condenser was charged with 2000 g of polyethylene glycol having a molecular weight of 2,000 and ε.
After adding 228 g of caprolactone and reacting at 80 ° C. for 2 hours, 6.7 g of boron trifluoride monoethylamine complex and EP
-4100 1900 g, and react at 140 ° C for 4 hours.
An epoxy group-containing compound (F) having a PE of 700 was obtained.

Production Example-7 A glass three-necked flask equipped with a thermometer, a stirrer, and a condenser was charged with 2000 g of polyethylene glycol having a molecular weight of 2,000 and ε.
-Add 228 g of caprolactone and 3040 g of EP-4100,
After reacting at 80 ° C. for 2 hours, 6.7 g of boron trifluoride monoethylamine complex salt was added, and reacted at 140 ° C. for 4 hours to obtain W
An epoxy group-containing compound (G) having a PE of 480 was obtained.

Production Example-8 285 g of ε-caprolactone and 1000 ml of methylene chloride were placed in a three-neck glass flask equipped with a thermometer, a stirrer, and a condenser.
And 0.7 ml of triethylamine, and add EP to the dropping funnel.
380 g of -4100 and 750 ml of methylene chloride were added. After cooling the four-necked flask to 10 ° C. with ice water, 1.5 ml of BF ₃ OC ₂ H ₅ was added, and the EP-4100 solution was stirred for 4 hours while maintaining the temperature at 10 ° C.
After dropwise addition over a period of time, the mixture was reacted at 10 ° C. for 5 hours.

To the reaction mixture, 3 ml of triethylamine was added to deactivate the catalyst.
After adding 1500 ml of an aqueous NaOH solution and stirring for 30 minutes, the mixture was separated into an aqueous alkali solution layer and an organic layer.

The organic layer was washed with 500 ml of water, separated by centrifugation twice, and then dehydrated with magnesium sulfate. Further, 0.2 g of tri (n-octyl) amine was added, and the mixture was distilled under reduced pressure to obtain an epoxy group-containing compound of WPE = 490.
(H) was obtained.

[0104]Production example of self-emulsifying active organic amine curing agent  Production Example-9 Glass three-necked flask equipped with thermometer, stirrer, and cooling pipe
In the co, 140g of metaxylylenediamine and epoxy group
Add 210 g of compound (A) and 10 g of EP-4100, and add
After reacting for 90 hours, add 90 g of water and add an active hydrogen equivalent of 125
The active organic amine curing agent (1) was obtained.

Production Example-10 In a glass three-necked flask equipped with a thermometer, a stirrer, and a condenser, 140 g of metaxylylenediamine, 210 g of the epoxy group-containing compound (B), and 10 g of EP-4100 were added. 90 ℃, 2
After reacting for 90 hours, 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-11 140 g of meta-xylylenediamine, 210 g of the epoxy group-containing compound (C) and 10 g of EP-4100 were added to a three-neck glass flask equipped with a thermometer, a stirrer and a condenser. 90 ℃, 2
After reacting for 90 hours, 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-12 140 g of metaxylylenediamine, 210 g of an epoxy group-containing compound (D) and 10 g of EP-4100 were added to a three-neck glass flask equipped with a thermometer, a stirrer, and a condenser. 90 ℃, 3
After reacting for 90 hours, 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-13 140 g of meta-xylylenediamine, 210 g of the epoxy group-containing compound (E) and 10 g of EP-4100 were added to a three-neck glass flask equipped with a thermometer, a stirrer, and a condenser. 90 ℃, 2
After reacting for 90 hours, 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 A glass three-necked flask equipped with a thermometer, a stirrer, and a condenser was charged with 140 g of metaxylylenediamine, 210 g of the epoxy group-containing compound (F), and 10 g of EP-4100. 90 ℃, 2
After reacting for 90 hours, 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-15 140 g of meta-xylylenediamine, 210 g of an epoxy group-containing compound (G) and 10 g of EP-4100 were added to a three-neck glass flask equipped with a thermometer, a stirrer, and a condenser. 90 ℃, 2
After reacting for 90 hours, 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, a stirrer, and a condenser, 140 g of metaxylylenediamine, 1 part of the epoxy group-containing compound (H) and one part of the epoxy group-containing compound (A) were placed. 210 g of the 1: 1 mixture and 10010 g of EP-4100 were added and reacted 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 A glass three-necked flask equipped with a thermometer, stirrer, and cooling tube was charged with 80 g of metaxylylenediamine and Jeffamine D-
230 (manufactured by Jefferson Chemical Co., USA) and mix well until uniform, then add epoxy group-containing compound.
(F) 210 g and 10 g of EP-4100 were added and 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 Self-emulsification with an active hydrogen equivalent of 153 was carried out in the same manner as in Production Example-14 except that 140 g of isophoronediamine was used instead of 140 g of metaxylylenediamine. A type active organic amine curing agent (10) was obtained.

Preparation Example-19 In Preparation Example-14, instead of 140 g of meta-xylylenediamine,
Using 140 g of 1,3-bisaminoethylcyclohexane, all other conditions were the same as in Preparation Example-14, and a self-emulsifying active organic amine curing agent having an active hydrogen equivalent of 125 was used.
(11) was obtained.

Production Example-20 100 g of metaxylylenediamine and 60 g of PACM (manufactured by Anchor Chemical Co., UK) were added to a three-neck glass flask equipped with a thermometer, a stirrer, and a condenser, and the mixture was thoroughly stirred until uniform. , Epoxy group-containing compound (F) 210 g and EP-4100
10 g, and reacted at 90 ° C. for 2 hours. 95 g of water was added, and a self-emulsifying active organic amine curing agent (1) having an active hydrogen equivalent of 127 was added.
2) was obtained.

Production Example-21 In a glass three-necked flask equipped with a thermometer, a stirrer, and a condenser, 140 g of metaxylylenediamine, 175 g of the epoxy group-containing compound (F), and 45 g of EP-4100 were added. ° C, 2
After reacting for 90 hours, 90 g of water was added to obtain a self-emulsifying active organic amine curing agent (13) having an active hydrogen equivalent of 124.

[0117]Cyanoethylated self-emulsifying active organic amine
Production example of hardener  Production Example-22 Three-neck glass glass with thermometer, stirrer and cooling tube
Add 450 g of self-emulsifying active organic amine curing agent (1) to
And 25 g of acrylonitrile was added dropwise at 60 ° C or lower.
Thereafter, the reaction was carried out at 60 ° C. for 2 hours to obtain cyano having an active hydrogen equivalent
An ethylated self-emulsifying type active organic amine curing agent (1) was obtained.

Production Example-23 Self-emulsifying active organic amine curing agent (1) 450 in Production Example-22
Instead of g, a self-emulsifying active organic amine curing agent (5) 4
The reaction was carried out in the same manner as in Production Example 22 except that 50 g was used, and a cyanoethylated self-emulsifying active organic amine curing agent (2) having an active hydrogen equivalent of 146 was obtained.

Production Example-24 Production Example-22 was repeated except that 25 g of acrylonitrile was used instead of 25 g of acrylonitrile, and all other conditions were the same as those in Production Example-22.
The reaction was carried out in the same manner as in Example 22 to obtain a cyanoethylated self-emulsifying active organic amine curing agent (3) having an active hydrogen equivalent of 188.

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

Comparative Examples 1-4 Epicoat # 828 or EM-1-60 and ACR Hardener H-23-
50W (self-emulsifying polyamide curing agent manufactured by AC R Co., Ltd., solid content: 50%, amine value 140 mgKOH / g) or Adeka Hardener EH-220 (Asahi Denka Kogyo Co., Ltd., aliphatic polyamine curing agent, solid content: 100%, amine value: 350mgKOH /
g) or WPE obtained in Production Example 1 using 912 g of ε-caprolactone instead of 228 g of ε-caprolactone.
= Self-emulsifying active organic amine curing agent (A) having an active hydrogen equivalent of 122 obtained by reacting with an epoxy group-containing compound of 542 under the same conditions as in Production Example 9 or the molecular weight of Production Example 1
Molecular weight instead of 2000g of polyethylene glycol 2000g
6000 polyethylene glycol obtained using 6000 g
Production Example 9 Using Epoxy Group-Containing Compound with WPE = 845
A self-emulsifying active organic amine curing agent (B) with an active hydrogen equivalent of 118, obtained by reacting under the same conditions as above, and water were mixed in the formulation shown in Table 2 and cured, and the physical properties of the coating film were compared. The test was performed. Table 2 shows the results.

[0122]

[Table 1]

[0123]

[Table 2]

<Evaluation method> ・ Emulsifying property ○: good emulsification, ○ △: time required for emulsification, ×: no emulsification ・ Coating state ○: good coating / gloss, △: semi-gloss, △ ×: Semi-gloss / soft, ×: No film formation ・ Adhesiveness (after 7 days of curing) 100/100: Cross-cut and not peeled, 80/100: Cross-cut and 20% peel, 50/100: Cross-cut 50% peeling, ×: No film formation ・ Water resistance (7 days after immersion in water) ○: No change, △: Film formation becomes cloudy, ×: Dissolve ・ Bending test (7 days after curing) Centering on 3mm rod Surface when bent 180 °

[0125]

The epoxy resin (I) and the curing agent (I)
The emulsifying merit of the aqueous epoxy resin curable composition of the present invention which contains I) and is emulsified and cured by adding water is disclosed in Japanese Patent Application Laid-Open Nos. 50-98960 and 53-31517. Compared to imidazoline ring-containing compounds with emulsifying properties, it is characterized by excellent leveling and film forming properties of the coating film, transparent cured film, and excellent surface gloss, hardness, adhesion, water resistance and chemical resistance. .

[0126]

Continuation of front page (56) References JP-A-1-204923 (JP, A) JP-A-1-132615 (JP, A) JP-A-63-189420 (JP, A) JP-A-54-56700 (JP) JP-A-63-168425 (JP, A) JP-A-57-125211 (JP, A) JP-B-61-40688 (JP, B2) JP-B-44-11554 (JP, B1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 59/40-59/66 C09D 163/00-163/10

Claims (2)

(57) [Claims] (1) an epoxy resin having an average of more than one adjacent epoxy group in a molecule, and (II) an average molecular weight.
200 to 4500 polyalkylene polyether polyol compounds (II-1-1), lactones (II-1-2),
An epoxy compound (II-1-3) having at least more than 0.1 hydroxyl groups and adjacent epoxy groups in a molecule is converted into 1.0 mole of a polyalkylene polyether polyol compound (II-1-1) using Lewis acid as a catalyst. 0.1 to 5 mol of lactone (II-1-2) and epoxy compound (II-
1-3) Epoxy group-containing compound (II-1) obtained by reacting at a reaction ratio of 1.2 to 10 mol in a solvent or without a solvent
With aliphatic polyamines (II-2-1), alicyclic polyamines (II-2-1), and aromatic polyamines (II-
2-1) and heterocyclic polyamines (II-2-1)
), One or more polyamines (II
-2-1) and an aqueous epoxy resin curable composition comprising a self-emulsifying active organic amine curing agent obtained by reacting with excess polyamine. 2. An epoxy resin having an average of more than one adjacent epoxy group in the molecule, and (II) an average molecular weight.
200 to 4500 polyalkylene polyether polyol compounds (II-1-1), lactones (II-1-2),
An epoxy compound (II-1-3) having at least more than 0.1 hydroxyl groups and adjacent epoxy groups in a molecule is converted into 1.0 mole of a polyalkylene polyether polyol compound (II-1-1) using Lewis acid as a catalyst. 0.1 to 5 mol of lactone (II-1-2) and epoxy compound (II-
1-3) Epoxy group-containing compound (II-1) obtained by reacting at a reaction ratio of 1.2 to 10 mol in a solvent or without a solvent
With aliphatic polyamines (II-2-1), alicyclic polyamines (II-2-1), and aromatic polyamines (II-
2-1) and heterocyclic polyamines (II-2-1)
), One or more polyamines (II
-2-1) and 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) to obtain a cyanoethylated self-emulsifying active organic compound. An aqueous epoxy resin curable composition comprising an amine curing agent.