JPH10101774A - Water-based epoxide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-based epoxide resin composition which can give coating films excellent in water resistance and acid resistance and is useful for coating materials, adhesives and binders by mixing a polyepoxide with a specified polyamine derivative. SOLUTION: This composition essentially consists of a polyepoxide having at least 1.5 glycidyl groups on the average per molecule and a polyamine derivative prepared by reacting polyamine containing a Mannich base obtained by reacting a phenolic compound with a carbonyl compound and a polyamine having at least two amino groups which are prim. and/or sec. amino groups with a diepoxide having an aromatic or alicyclic structure in the molecule and having two glycidyl groups and a diepoxide being a diglycidyl ether of polyoxyethylene glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous epoxide resin composition, and more particularly to an epoxide resin composition useful as a paint, an adhesive and a binder.

[0002]

2. Description of the Related Art Polyepoxide compounds have a peculiar property of strong reactivity derived from epoxy groups, so that they can be used in a wide variety of fields, especially as paints, adhesives and binders. The application has a great track record. In application, adhesion and bonding as these application fields, dilution with an organic solvent is often performed in order to improve workability. The organic solvent employed in this situation can hardly be an essential component, and has a convenient use of being naturally or forcibly evaporated after curing as an epoxide resin. The use of this solvent is not desirable due to problems such as resources, energy, air pollution, water pollution, fire hazard and human health hazards, and it is desired to switch to a method that does not use this organic solvent or to another. ing. Many attempts have been made to improve this demand. One approach to this solution is to use water as a diluent.
This water is almost inexhaustible in nature, harmless to the human body, has no danger of fire, and can be said to be an excellent natural resource that does not cause environmental destruction.

One of the methods using water is to disperse an epoxide resin or a curing agent substance in water using a surfactant. The surfactant used in this method remains in the cured resin, resulting in deterioration of water resistance when a desired cured product is obtained. Also, as one method,
There is a method in which an amine compound used as a curing agent substance is neutralized with an acidic substance and dispersed in water. In this case, the initial curing is inferior, and depending on the kind of the acidic substance, it remains in the cured product and becomes a factor of deteriorating the water resistance.

[0004] Published Patent Publications Nos. 36-16669 and 44
-32317 and 46-38915 describe an aqueous epoxide resin using a polyaminoamide synthesized from a polymerized fatty acid. However, the curing agent for epoxide resin produced by this method or the aqueous epoxide composition using the same can be used after being diluted with water according to the purpose. However, there is a disadvantage that it cannot be good.

JP-A-54-56700 describes a method in which a reaction product of a polyepoxide compound and a polyalkylene polyether polyol and a reaction product of a polyamine are used as a curing agent. In this case, since the reaction product of the polyepoxide and the polyalkylene polyether polyol to be reacted with the polyamine has a large molecular weight, the epoxy resin composition cures slowly.

JP-A-56-34767 discloses a method in which a reaction product of a diepoxide and a polyamine is neutralized with an acidic substance to make it water-soluble, and this is used as a curing agent. In this case, as described above, the acidic substance remains in the cured product, and the cured product has poor water resistance.

Japanese Patent Laid-Open Publication No. 4-335020 describes a method in which a reaction product of a polyalkylene polyether polyol and a diisocyanate is reacted with a polyamine as a curing agent. Also in this case, the reaction product of the polyalkylene polyether polyol and the diisocyanate has a large molecular weight, so that the curability of the epoxy resin composition is inferior.

As described above, there is no complete epoxide resin-related technology using water as a diluent, and much effort has been made at present.

The present inventors have disclosed in Japanese Patent Laid-Open Publication No. 7-484.
34, a polyamine adduct formed by a combination of a hydrophobic diepoxide and a hydrophilic diepoxide, or a product obtained by reacting a polyamine with a substance selected from hydrophobic diepoxide, hydrophilic diepoxide and monoepoxide or acrylonitrile is diluted with water. It is also possible to dilute these with various polyepoxides in the same manner with water, and the coating film obtained by curing this aqueous polyepoxide resin composition at room temperature is smooth, surface gloss, adhesion, and water resistance. It is excellent. However, since the acid resistance is still insufficient, there has been a situation where the use has to be limited to applications where acid resistance is not required.

[0010]

An object of the present invention is to improve the disadvantages of the polyepoxide resin composition described in Japanese Patent Application Laid-Open No. Hei 7-48434.

[0011]

The present invention provides a polyepoxide curing agent prepared by reacting a hydrophobic diepoxide and a hydrophilic diepoxide with a polyamine containing a Mannich base obtained by reacting a phenol compound, a carbonyl compound and a polyamine. A polyamine derivative, or a polyamine containing a Mannich base obtained by reacting a phenol compound and a carbonyl compound with a polyamine, by reacting a hydrophobic diepoxide, a hydrophilic diepoxide, a monoepoxide and acrylonitrile alone or a mixture thereof. An aqueous epoxide resin composition comprising the produced polyamine derivative as an essential component. By using the aqueous polyepoxide resin composition of the present invention, a cured coating film which is smooth and excellent in surface gloss, adhesion, water resistance, acid resistance and alkali resistance can be obtained.

That is, the present invention relates to a polyepoxide (A) having an average of 1.5 or more glycidyl groups in a molecule, a phenol compound (a) and a carbonyl compound (b), and a first or / and a second compound in a molecule. A polyamine containing a Mannich base obtained by reacting a polyamine (c) having at least two amino groups as diamino groups is added to a diepoxide having an aromatic or aliphatic cyclic structure and two glycidyl groups in the molecule ( d) and a polyamine derivative (B) prepared by reacting a diepoxide (e) which is a diglycidyl ether of polyoxyethylene glycol, wherein an aqueous epoxide containing the polyepoxide (A) and the polyamine derivative (B) as essential components Resin composition, polyepoxide (A) having an average of 1.5 or more glycidyl groups in the molecule, To a polyamine containing a Mannich base obtained by reacting a phenolic compound (a), a carbonyl compound (b) and a polyamine (c) having at least two amino groups as primary and / or secondary amino groups in the molecule. ,
Diepoxide (d) having an aromatic or aliphatic cyclic structure in the molecule and having two glycidyl groups, diepoxide (e) which is a diglycidyl ether of polyoxyethylene glycol, monoepoxide and acrylonitrile alone or these The polyamine derivative (C) produced by reacting the mixture (f) of the formula (1) contains the polyepoxide (A) and the polyamine derivative (C) as essential components, provided that the polyamine containing the Mannich base is a phenol compound (a ) As primary and / or secondary amino groups in the molecule in the range from 0.5 mol to 2.0 mol of carbonyl compound (b) and from 0.5 mol to 5.0 mol per mol. It is obtained by reacting a polyamine (c) having at least two amino groups, and comprises a diepoxide (d) and a diepoxide. The equivalent ratio to the poxide (e) is 0.1.
It relates to an aqueous epoxide resin composition which is in the range from 95: 0.05 to 0.4: 0.6.

The average molecular weight in the molecule used in the present invention is 1.5.
The polyepoxide compound (A) having two or more glycidyl groups has a glycidyl group represented by the formula (1), (2) or (3) in the molecule.

[0014]

Embedded image

Examples of these polyepoxides include catechol, resorcinol, hydroquinone, bis (hydroxyphenyl) alkane, phenol and alkylphenol novolak, phenol and alkylphenol resol, dioxynaphthalene, naphthalene and alkylnaphthalene novolak, naphthalene and alkyl. Glycidyl ethers of polyhydric phenols such as resol of naphthalene, novolak of phenol and naphthalene, resol of cresol and naphthalene, triglycidyl ether ester of hydroxybenzoic acid, diglycidyl ester of isophthalic acid, terephthalic acid, dicarboxyalkane, and polymerized fatty acid , Benzylamine, glycidylated alkylbenzylamine, triglycidyl aminophenol Product, tetraglycidyl product of diamines, phenols and anilines, cresol and aniline, cresols and alkyl anilines, glycidylated such cresol and alkyl anilines, dihydroxy cyclohexane, bis (hydroxycyclohexyl)
Methane, bis (hydroxycyclohexyl) propane,
Bis (hydroxycyclohexyl) butane, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol,
Diglycidyl ethers of dihydric alcohols such as polypropylene glycol, and polyglycidyl ethers of polyhydric alcohols such as trimethylolpropane, glycerin and pentaerythritol, and a reaction product of polyoxyalkylene glycol and diisocyanate, and a terminal isocyanate compound and bisphenol A or a reaction product with bisphenol F diglycidyl ether can be cited.

Of these, diglycidyl ethers of biphenylalkanes such as bisphenol A, bisphenol F and bisphenol AD are particularly preferred.

The phenol compound (a) which is a raw material of the polyamine derivatives (B) and (C) used in the present invention
(Hereinafter, it may be simply referred to as “a component”) is a phenol compound having an unsubstituted reactive position in at least one aromatic nucleus.

Examples of these phenolic compounds include:
Phenol, naphthol and ortho, meta, para cresol, tertiary butyl phenol, octyl phenol, nonyl phenol, xylenol, alkyl phenol compound such as ethyl phenol, halogen substituted phenol compound such as chlorophenol, nitro substituted phenol compound such as nitro phenol, such as anisole Alkoxy-substituted phenol compounds, resorcinol, hydroquinone, bis- (4-hydroxyphenyl) ether, bis- (4-hydroxyphenyl)
Ketone, bis- (4-hydroxyphenyl) sulfone,
Bis- (4-hydroxyphenyl) methane, bis- (4
-Hydroxyphenyl) propane and the like.

Among them, alkylphenol compounds such as phenol, naphthol and ortho, meta, para cresol, tert-butylphenol, octylphenol, nonylphenol, xylenol and ethylphenol are particularly preferred.

The carbonyl compound (b) which is a raw material of the polyamine derivatives (B) and (C) used in the present invention
Examples of the “component b” may include aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, and butyraldehyde, aromatic aldehydes such as benzaldehyde, and aliphatic ketones such as acetone.

Of these, formaldehyde and paraformaldehyde are particularly preferred.

The polyamine (c) having at least two amino groups as primary and / or secondary amino groups in the molecule which is the raw material of the polyamine derivatives (B) and (C) used in the present invention (hereinafter simply referred to as "polyamine derivative (B)") (may be referred to as component c)
Are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
-Or 1,3-diaminopropane, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, hexamethylenediamine, trimethylhexamethylenediamine, polyoxypropylenediamine, N-aminoethylpiperazine, bis (aminoethyl) piperazine, bis (Aminopropyl) piperazine,
Bis (aminopropyl) ethylenediamine, 1,2- or 1,3-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, metaxylylenediamine, paraxylylenediamine, bis (aminocyclohexyl) methane, bis (amino (Cyclohexyl) propane, bis (aminocyclohexyl) butane, isophoronediamine, and the like. These may be used alone or as a mixture.

A diepoxide (d) having an aromatic or aliphatic cyclic structure in its molecule and having two glycidyl groups (hereinafter simply referred to as "d component") as a raw material of the polyamine derivatives (B) and (C) used in the present invention. May be stated)
Diepoxides selected from glycidyl ethers of dihydric alcohols or phenols, examples of which are catechols, resorcinols, hydroquinones, bis (hydroxyphenyl) alkanes, dioxynaphthalenes, dihydroxyanthracenes, dihydroxyalkylnaphthalenes and the like. Or diglycidyl ethers synthesized from divalent alcohols such as dihydroxycyclohexane, bis (hydroxycyclohexyl) methane, bis (hydroxycyclohexyl) propane and bis (hydroxycyclohexyl) butane. it can.

What is referred to as diepoxide (e), which is a diglycidyl ether of polyoxyethylene glycol, which is a raw material of the polyamine derivatives (B) and (C) used in the present invention (hereinafter sometimes simply referred to as component e). It is synthesized by reacting a glycol having a molecular weight of 200 to 2,000, which is usually synthesized by polymerization of ethylene oxide, with epihalohydrin.

The monoamine or acrylonitrile, which is a raw material of the polyamine derivative (C) used in the present invention, alone or a mixture thereof (f) is
C18 such as glycidol, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, lauryl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, etc. Alkyl glycidyl ether, phenyl glycidyl ether up to 8 carbon atoms
Phenyl glycidyl ether, cyclohexyl glycidyl ether having up to 8 alkyl side chains, cyclohexyl glycidyl ether having an alkyl group having up to 8 carbon atoms, and acrylonitrile. These can be used either alone or as a mixture thereof.

The composition of the polyamine containing a Mannich base in the polyamine derivatives (B) and (C) used in the present invention is such that the ratio of the carbonyl compound (b) is 0.1 to 1 mol of the phenol compound (a). It is in the range from 5 moles to 2.0 moles, preferably in the range from 0.7 moles to 1.5 moles. The ratio of the polyamine (c) having at least two amino groups as primary and / or secondary amino groups in the molecule is from 0.5 mol to 5.0 mol per 1 mol of the phenol compound (a). Range, preferably 1.
It is in the range of 0 to 3.0 moles.

In this case, if the ratio of the carbonyl compound (b) to 1 mol of the phenol compound (a) is less than 0.5 mol, the polyamine derivative obtained thereby has a reduced Mannich base component and is excellent when formed into a coating film. If it does not show acid resistance, and if it is more than 2.0 mol, it will have a high viscosity and it will be difficult to discharge it from the reactor, resulting in poor practicality. If the ratio of the polyamine (c) to 1 mol of the phenol compound (a) is less than 0.5 mol, the polyamine derivative obtained therefrom has a high viscosity and is difficult to discharge from the reactor, resulting in poor practicality. On the other hand, if it is more than 5.0 moles, the amount of the Mannich base component is so small that the resulting coating film does not show good acid resistance.

In the polyamine derivative (B) used in the present invention, an adduct of a polyamine containing a Mannich base and an epoxide has an aromatic or aliphatic cyclic structure in the molecule with respect to the polyamine containing a Mannich base. Diepoxide (d) having two glycidyl groups and diepoxide (e) which is a diglycidyl ether of polyoxyethylene glycol having two glycidyl groups in the molecule
Is an amount such that the active hydrogen equivalent of the polyamine derivative (B) is in the range of 90 to 190, preferably 120 to 160. The equivalent ratio of diepoxide (d) to diepoxide (e) (d): (e)
Is in the range of 0.95: 0.05 to 0.4: 0.6,
Preferably it is in the range from 0.9: 0.1 to 0.6: 0.4.

In this case, when the active hydrogen equivalent of the polyamine derivative (B) is less than 90, amine brushing occurs (the film becomes cloudy before coating and drying = fogging) when the active hydrogen equivalent of the polyamine derivative (B) is less than 90; In this case, water resistance and acid resistance are lacking. The equivalent ratio (d) of diepoxide (d) to diepoxide (e):
When the amount of the component (e) is smaller than that of the case where (e) is 0.95: 0.05, the polyamine derivative obtained thereby has the following effects:
Does not show good dilutability with water, and (d): (e)
If the amount of the component (e) is larger than in the case of 0.4: 0.6, the cured product will have poor acid resistance.

In the polyamine derivative (C) used in the present invention, an adduct of a polyamine containing a Mannich base and an epoxide has an aromatic or aliphatic cyclic structure in the molecule with respect to the polyamine containing a Mannich base. Diepoxide (d) having two glycidyl groups and diepoxide (e) which is a diglycidyl ether of polyoxyethylene glycol having two glycidyl groups in the molecule
And the total equivalent weight of a mixture selected from monoepoxide and acrylonitrile or a mixture thereof (f) is such that the active hydrogen equivalent of the polyamine derivative (C) is in the range of 90 to 190, preferably in the range of 120 to 160. It is the amount that becomes. The equivalent ratio of diepoxide (d) to diepoxide (e) is in the range of 0.95: 0.05 to 0.4: 0.6, preferably 0.9: 0.1 to 0.6: 0.6. 4
In the range. In addition, the ratio of monoepoxide and acrylonitrile alone or a mixture thereof (f) to 1 mol of polyamine (c) is in the range of 0.01 mol to 1.2 mol.

In this case, when the active hydrogen equivalent of the polyamine derivative (C) is less than 90, amine brushing occurs when the coating is formed, and when it is more than 190, the coating lacks water resistance and acid resistance when the coating is formed. turn into. Also, the equivalent ratio (d) :( e) of diepoxide (d) to diepoxide (e) is (e) as compared with the case of 0.95: 0.05.
If the amount of the components is small, the polyamine derivative obtained therefrom does not show good dilutability with water, and 0.4:
When the amount of the component (e) is larger than that in the case of 0.6, the coating film becomes poor in acid resistance. Polyamine (c) 1
If the amount of the monoepoxide or acrylonitrile alone or a mixture of these mixtures (f) is more than 1.2 moles per mole, the resulting coating film lacks water resistance and acid resistance.

The polyamine derivatives (B) and (C) used in the aqueous epoxide resin composition of the present invention contain at least one of a phenol compound (a) and a carbonyl compound (b) as a primary and / or secondary amino group in the molecule. After reacting a polyamine (c) having two amino groups by a conventional method,
An epoxide compound or a mixture of an epoxide compound and acrylonitrile is added to the reaction product, and the reaction product is further reacted.

The reaction of the phenolic compound (a) with the carbonyl compound (b) and the polyamine (c) is carried out by reacting the phenolic compound (a) with the carbonyl compound (b) and then adding the polyamine (c). Any of a two-stage method and a one-stage method in which a carbonyl compound (b) is added to a mixture of a phenol compound (a) and a polyamine (c) to react them may be used. The reaction between the obtained reaction product and the epoxide compound or the mixture of the epoxide compound and acrylonitrile is performed in a temperature range from 60 ° C. to 150 ° C. In this case, the treatment is performed while dropping to avoid sudden heat generation. Usually, the dropwise addition is carried out at 100 ° C. or lower, and after the completion of the dropwise addition, the mixture is heated to a temperature of 100 ° C. or higher for a predetermined time in order to complete the reaction. The polyamine derivatives (B) and (C) may be used after being diluted with a certain amount of water for easy handling.

The epoxide resin composition of the present invention is obtained by mixing a polyepoxide (A) having an average of 1.5 or more glycidyl groups in a molecule with the above-described polyamine derivative (B) or (C). Made. These mixing ratios are mixed on a stoichiometric basis. That is, the active hydrogen equivalent 1 of the polyamine derivative is based on the epoxide equivalent 1 of the epoxide compound. However, there may be some changes. That is, this is not limited to the case where a method of use that emphasizes some of the curability as a composition and various properties as a cured product is used. Therefore, the active hydrogen equivalent of the polyamine derivative is practically in the range of 0.6 to 1.2 with respect to the epoxide equivalent of 1 of the epoxide compound.

In addition to the essential components of the epoxide compound and the polyamine derivative, other components commonly used can be added to the composition of the present invention. That is, a surfactant,
Reactive diluents, non-reactive diluents, extenders, pigments, extenders, plasticizers, solvents, fluidity improvers, surface condition improvers, flame retardants and the like.

[0036]

EXAMPLES Next, the present invention will be described in detail with reference to the synthesis examples and examples of the curing agent, but this patent is not limited to the materials and quantitative ranges shown in the examples.

The raw materials used here are represented by the following symbols, respectively, and the content components are as follows. PHOH: Phenol (Mitsui Petrochemical Co., Ltd.) NPHOH: Nonylphenol (Yokkaichi Gosei Co., Ltd.) HCHO: 37% Formalin (Mitsui Toatsu Co., Ltd.) MXDA: Meta-xylylenediamine (Mitsubishi Gas Chemical Co., Ltd.) DETA: Diethylenetriamine (Tosoh Co., Ltd.) Product) TETA: Triethylenetetramine (product of Tosoh Corporation) DGEBPA: Araldite GY-, a diglycidyl ether of bisphenol A having an epoxide equivalent of about 190
260 (a product of Ciba Geigy) DGEPOE-A: Denacol Ex-830, a diglycidyl ether of polyoxyethylene glycol having an epoxide equivalent of about 260 (a product of Nagase Kasei Co., Ltd.) DGEPOE-B: a dioxyethylene glycol having an epoxide equivalent of about 382 Denacol Ex-841, a glycidyl ether (a product of Nagase Kasei Co., Ltd.) DGEPOE-C: Denacol Ex-861, a diglycidyl ether of polyoxyethylene glycol having an epoxide equivalent of about 587 (a product of Nagase Kasei Co., Ltd.) EPGA: an epoxide equivalent of about 310 Epogose A, a monoglycidyl ether of C12,13 alcohol (Yokkaichi Gosei Co., Ltd.) BGE: butyl glycidyl ether AN: acrylonitrile

In the component units in the synthetic recipe, e represents an equivalent, m represents a mole, and g represents a weight in gram. The viscosity is a value measured by a rotational viscometer at 23 ° C. AHE represents the active hydrogen equivalent of the synthesized polyamine derivative, and was calculated.

Synthesis Example 1 of Polyamine Derivatives PHOH (0.1%) was placed in a flask equipped with a heating device, a thermometer, a stirring device, a nitrogen inflow device, a reflux cooling device, and a dropping device.
(5 mol), 110 g of NPHOH (0.5 mol), 64.9 g of 37% formalin (0.8 mol) and 2.5 g of triethylamine were charged. The mixture was heated to 80 ° C. with stirring while flowing nitrogen, and reacted at 80 ° C. for 1.5 hours. After that, it was cooled down to 50 ° C, and DETA was charged into the dropping device.
(1 mol) 103g of the contents was 7
The solution was added dropwise while maintaining the temperature at 0 ° C or lower. After the dropwise addition, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 0.5 hour. Thereafter, 53.2 g of DGEBPA (0.28 eq.) And DGEPOE-B (0.11 eq.) Charged in a cooled dropping device at 80 ° C.
A mixture of 0.0 g and 41 g of DGEPOE-C (0.07 equivalent) was added dropwise in small portions. The temperature was gradually increased and reached approximately 100 ° C. at the end of the dropping, after which it was heated to 120 ° C. and kept at this temperature for 2 hours. The polyamine derivative obtained by cooling is designated as H-1. This polyamine derivative (H
The aqueous solution having a resin content of 40% in -1) was transparent and had a viscosity of 17.0 Pa · s. The results are shown in Table 1 together with the ratio of the raw material components.

Synthesis Examples of Polyamine Derivatives 2 to 8 Polyamines and other components having different types and ratios within the scope of the claims were synthesized according to the method of Synthesis Example 1 of the above-described polyamine derivative. These polyamine derivatives were designated as H-2 to H-8, and the raw material component ratios and properties are shown in Table 1.

Polyamine Derivative Comparative Synthesis Examples 1 and 2, polyamines and other components having different types and ratios outside the scope of the claims were synthesized in accordance with the method of the above-described polyamine derivative synthesis example 1, and the properties thereof were used as raw materials. The results are shown in Table 1 together with the component ratio. Comparative Example 1 (H-9)
The ratio of the component to the e component is (d) :( e) = 10: 23 (0.
4: 0.92) and the amount of the e component is larger than when 0.4: 0.6, and Comparative Example 2 (H-10)
Is an example in which the component b is lower than 0.5 mole per mole of the component a.

Polyamine Derivative Comparative Synthesis Example 3 A polyamine derivative based on the polyepoxide resin composition described in Japanese Patent Laid-Open Publication No. Hei 7-48434, which does not have the component a and the component b of the present invention, was synthesized.

In a flask equipped with a heating device, a thermometer, a stirring device, a nitrogen inflow device, a reflux cooling device, and a dropping device, M
136 g of XDA (1 mol) were charged. The DG charged to the dropping device was heated to 80 ° C. and stirred while introducing nitrogen.
114 g of EBPA (0.6 equivalent), DGEPOE-B
(0.40 eq.) Of 235 g was added dropwise in small portions. The temperature was gradually increased and reached approximately 100 ° C. at the end of the dropping, after which it was heated to 120 ° C. and kept at this temperature for 2 hours. The polyamine derivative obtained by cooling was H-11
And The polyamine derivative (H-11) has a resin content of 4
The 0% aqueous solution was transparent and had a viscosity of 3.2 Pa · s. The results are shown in Table 1.

Examples 1 to 8 and Comparative Examples 1 to 3 Polyamine derivatives (H-1) to (H-8) synthesized according to Synthetic Examples 1 to 8 and polyamine derivatives Comparative Examples 1 to 3 were synthesized. Polyamine derivatives (H-9) to (H-11) and polyepoxide DGEBP
A was mixed according to the composition shown in Table 2 and diluted with distilled water in such an amount that the resin content became 50%. All the mixing ratios in this case were implemented by weight. This composition was applied to a mild steel plate using a bar coater # 75 and the relative humidity was 50 ° C at 23 ° C.
% For 7 days. The dry film thickness of these coatings was approximately 50 μm. Using these coating films, tests for water resistance and acid resistance were performed. In the water resistance test, the test piece was immersed in tap water, kept at a room temperature of 23 ° C., and the state of the coating film after 7 days was observed. In the acid resistance test, the test piece was immersed in a 5% sulfuric acid aqueous solution, kept at a room temperature of 23 ° C., and the surface state of the coating film was observed after 1 day, 3 days, and 7 days. The evaluation of the surface condition of the coating film was evaluated as follows: E: no abnormalities G: slight swelling F: partial swelling P: large swelling Table 2 shows the mixing ratio of the epoxy compound and the curing agent as the composition and the results of the water resistance and the acid resistance in these tests.

[0045]

As shown in the examples, the coating materials in which the polyepoxide and the polyamine derivative shown in the synthesis examples are mixed can give a coating film having excellent water resistance and acid resistance. This paint is disclosed in Japanese Patent Laid-Open Publication No. Hei 7-48434.
It is clear that the acid resistance is particularly excellent as compared with the polyepoxide resin composition described in (1).

[Table 1]

[0046]

[Table 2]

Continuing from the front page (72) Inventor Ritaro Nagabuchi 253-2, Ikeda-ku, Takemazawa, Miyoshi-cho, Iruma-gun, Saitama Prefecture Inside the Technical Research Laboratory, Fuji Chemical Industry Co., Ltd. (72) Inventor Yasuo Chiba, Takemazawa, Miyoshi-cho, Iruma-gun, Saitama 253-2, Ijikubo, Fuji Chemical Industry Co., Ltd.

Claims (3)

[Claims] 1. An aqueous epoxide resin composition containing a polyepoxide (A) and a polyamine derivative (B) as essential components, wherein the polyepoxide (A) has an average of 1.5 or more glycidyl groups in the molecule. Wherein the polyamine derivative (B) is a phenol compound (a)
And a carbonyl compound (b) and a polyamine (c) having at least two amino groups as primary and / or secondary amino groups in the molecule, the polyamine containing a Mannich base, (D) having an aliphatic or aliphatic cyclic structure and having two glycidyl groups, and a diepoxide (e) which is a diglycidyl ether of polyoxyethylene glycol. The polyamine containing the Mannich base Is a carbonyl compound (b) in the range of 0.5 mol to 2.0 mol per 1 mol of the phenol compound (a), and 0.5 mol to 5.0 mol.
A polyamine (c) having at least two amino groups as primary and / or secondary amino groups in the molecule in the range of 0 mol
And in addition of the Mannich base-containing polyamine and the diepoxides (d) and (e), an aromatic or aliphatic cyclic structure in the molecule with respect to the Mannich base-containing polyamine. The total equivalent weight of the diepoxide (d) having two glycidyl groups and the diepoxide (e) which is the diglycidyl ether of polyoxyethylene glycol having two glycidyl groups in the molecule is the active hydrogen equivalent of the polyamine derivative (B). 90 to 1
90, in which case the equivalent ratio of diepoxide (d) to diepoxide (e) is 0.95: 0.
An aqueous epoxide resin composition ranging from 0.05 to 0.4: 0.6. 2. An aqueous epoxide resin composition containing a polyepoxide (A) and a polyamine derivative (C) as essential components, wherein the polyepoxide (A) has an average of 1.5 or more glycidyl groups in the molecule. The polyamine derivative (C) is a phenol compound (a)
With a carbonyl compound (b) and a polyamine (c) having at least two amino groups as primary and / or secondary amino groups in the molecule, and a polyamine containing a Mannich base, Alternatively, a diepoxide (d) having an aliphatic cyclic structure and two glycidyl groups, a diepoxide (e) which is a diglycidyl ether of polyoxyethylene glycol, and a single or a mixture thereof (f) selected from monoepoxides and acrylonitrile Wherein the polyamine containing the Mannich base is in the range of 0.5 to 2.0 moles of the carbonyl compound (b) with respect to 1 mole of the phenol compound (a); 5 to 5.
A polyamine (c) having at least two amino groups as primary and / or secondary amino groups in the molecule in the range of 0 mol
In addition of the Mannich base-containing polyamine and the diepoxides (d) and (e), an aromatic or aliphatic cyclic structure is formed in the molecule with respect to the Mannich base-containing polyamine. Or a mixture thereof selected from diepoxide (d) having two glycidyl groups and diepoxide (e) which is a diglycidyl ether of polyoxyethylene glycol having two glycidyl groups in the molecule, monoepoxide and acrylonitrile The total equivalent of (f) is such that the active hydrogen equivalent of the polyamine derivative (C) is in the range of 90 to 190, and in this case, the equivalent ratio of diepoxide (d) to diepoxide (e) is 0.95: In the range of 0.05 to 0.4: 0.6, together with monoepoxide and 1 mole of polyamine (c) An aqueous epoxide resin composition wherein the proportion of a single or a mixture thereof (f) selected from acrylonitrile and acrylonitrile is in the range of 0.01 mol to 1.2 mol. 3. An epoxy equivalent (e), which is a polyoxyethylene glycol diglycidyl ether having two glycidyl groups in the molecule, having an epoxy equivalent of 200 to 20.
The aqueous epoxide resin composition according to claim 1 or 2, which is in the range of 00.