JPH08245751A - Vinyl-modified amine adduct epoxy resin - Google Patents

Abstract

PURPOSE: To obtain the subject resin suitable as a cathodic electrodeposition coating capable of forming a film excellent in weather, corrosion resistances, etc. CONSTITUTION: This water-soluble or water-dispersible vinyl-modified amine adduct epoxy resin is obtained by reacting a vinyl-modified epoxy resin prepared by copolymerizing (A) an epoxy prepolymer, containing isocyanate group and obtained by copolymerizing an epoxy prepolymer, containing double bonds and prepared by reacting (a) an epoxy resin having at least one epoxy group and at least one hydroxyl group in one molecule with (b) an unsaturated lsocyanate compound having average 0.8-1.2 polymerizable double bonds and average 0.8-1.2 isocyanate groups in one molecule with (B) a vinylic monomer or reacting the vinyl-modified epoxy resin obtained by reacting a vinyl prepolymer, containing isocyanate groups and prepared by copolymerizing (b) the unsaturated isocyanate compound having average 0.8-1.2 double bonds and average 0.8-1.2 isocyanate groups in one molecule with (B) the vinylic monomer with (a) the epoxy resin having at least one epoxy group and at least one hydroxyl group in one molecule with (C) an amino compound containing active hydrogen.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel water-soluble or water-dispersible vinyl-modified amine-added epoxy resin, which is water-soluble or water-dispersible and has excellent weather resistance and corrosion resistance. It can be preferably used for a cathodic electrodeposition coating composition capable of forming

[0002]

2. Description of the Related Art Conventionally, as a water-based resin dispersion for cathodic electrocoating, an amine-added epoxy resin obtained by a reaction between an epoxy resin and an amino compound containing active hydrogen is compounded with a blocked polyisocyanate compound as a curing agent. The composition is used. The coating film formed by using this composition has excellent corrosion resistance, but has a drawback that the weather resistance is not sufficient.

In order to improve the weather resistance, it has been attempted to modify the epoxy resin with a polyester resin, a polyether resin, an acrylic resin or the like. According to this, the weather resistance of the coating film is slightly improved. However, there is a problem that the anticorrosion property, which is an inherent property of the epoxy resin, is deteriorated.

In addition, the modification of the epoxy resin with the acrylic resin is not only difficult to sufficiently carry out the modification reaction due to the poor compatibility of these two components, and
There is a drawback that the viscosity of the obtained modified product becomes high.

The present inventors have conducted earnest studies for the purpose of developing an aqueous resin composition capable of forming a coating film having both excellent corrosion resistance and weather resistance. It has been found that the above object can be achieved by using a double bond-containing epoxy prepolymer that can be polymerized, and the present invention has been completed.

According to the present invention, therefore, (A) an epoxy resin (a) having at least one epoxy group and at least one hydroxyl group in one molecule,
Epoxy pre containing double bond obtained by reaction of unsaturated isocyanate compound (b) having an average of 0.8 to 1.2 double bonds and an average of 0.8 to 1.2 isocyanate groups in one molecule Provided is a water-soluble or water-dispersible vinyl-modified amine-added epoxy resin obtained by reacting a vinyl-modified epoxy resin obtained by copolymerization of a polymer (B) with a vinyl-based monomer and (C) an amino compound containing active hydrogen. To be done.

According to the invention, it is also possible to obtain an average of 0.
Isocyanate groups obtained by copolymerization of unsaturated isocyanate compound (b) having 8 to 1.2 double bonds and an average of 0.8 to 1.2 isocyanate groups with (B) vinyl monomer. Water-soluble water obtained by reacting a vinyl-modified epoxy resin (C) with an amino compound containing a vinyl prepolymer and an epoxy resin (a) having at least one epoxy group and at least one hydroxyl group in one molecule, and (C) A vinyl-modified amine-added epoxy resin that is water-soluble or water-dispersible is provided.

According to the present invention, there is further provided an aqueous resin composition containing a water-soluble product or water-dispersed product of the above vinyl-modified amine-added epoxy resin.

The vinyl-modified amine-added epoxy resin and aqueous resin composition of the present invention will be described in more detail below.

Double bond containing epoxy prepolymer
(A): The double bond-containing epoxy prepolymer (A) is
An epoxy group-containing compound obtained by reacting a hydroxyl group-containing epoxy resin (a) with a double bond-containing isocyanate compound (b).

As the hydroxyl group-containing epoxy resin (a), any epoxy resin can be used without particular limitation as long as it has at least one epoxy group and at least one hydroxyl group in one molecule. , For example,
Aromatic epoxy resin represented by bisphenol type epoxy resin, hydrogenated bisphenol type epoxy resin,
Examples thereof include cycloaliphatic epoxy resins such as EHPE3150 (manufactured by Daicel Chemical Industries Ltd.) and aliphatic epoxy resins such as polypropylene glycol diglycidyl ether. Among these, a bisphenol type epoxy resin is particularly preferable because it gives a coating film excellent in flexibility and corrosion resistance.

The bisphenol type epoxy resin is a compound having at least one, preferably at least two epoxy groups in one molecule, and in particular, a bisphenol obtained by a condensation reaction of a bisphenol compound and epihalohydrin. The diglycidyl ether of is preferable because it is easy to obtain a coating film having excellent flexibility and anticorrosion property. Such bisphenol type epoxy resin is generally 310 to 10,000.
It can have a number average molecular weight in the range of 0, especially 320 to 2,000 and an epoxy equivalent weight in the range of 155 to 5,000, especially 160 to 1,000.

Representative examples of the bisphenol-based compound that can be used for preparing the bisphenol type epoxy resin include bis (4-hydroxyphenyl) -2,2-propane and bis (4
-Hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) -methane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) ) -1,1-Isobutane, bis (4-hydroxy-3-t-butylphenyl) -2,
2-propane and the like can be mentioned.

Of the epoxy resins formed using such bisphenol compounds, the bisphenol A type diglycidyl ether represented by the following formula is particularly preferable in that it gives a coating film excellent in flexibility and anticorrosion. It is suitable.

[0015]

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As the bisphenol type epoxy resin, the one obtained by further etherifying the excess amount of the diglycidyl ether of bisphenol obtained by the condensation reaction of the bisphenol compound and epihalohydrin with the bisphenol compound is also preferable. Can be used for

On the other hand, the double bond-containing isocyanate compound (b) has an average of 0.8 to 1.2, preferably 0.9 to 1.1, polymerizable double bonds and an average of 0 to 1.2 in one molecule. .
Those having an isocyanate group of 8 to 1.2, preferably 0.9 to 1.1 are used, and for example, 2-methacryloyl-oxyethyl isocyanate (manufactured by Showa Denko KK), meta-isopropenyl-α, α. In addition to dimethylbenzyl isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd.) and the like, a polyisocyanate compound in which some of the isocyanate groups are blocked with a hydroxy group-containing vinyl monomer can be used.

The above-mentioned polyisocyanate compound is a compound having two or more, preferably two, isocyanate groups in one molecule, and those generally used in the production of polyurethane resins can be similarly used. Examples of such a polyisocyanate compound include aliphatic, alicyclic, aromatic, and araliphatic polyisocyanate compounds, and the following can be typically exemplified.

Hexamethylene diisocyanate (HMD
I), biuret compounds of HMDI, aliphatic polyisocyanate compounds of isocyanurate compounds of HMDI; isophorone diisocyanate (IPDI), IPD
Alicyclic polyisocyanate compounds such as I biuret compounds, IPDI isocyanurate compounds, hydrogenated xylylene diisocyanates, and hydrogenated 4,4'-diphenylmethane diisocyanates; fragrances such as tolylene diisocyanates and xylylene diisocyanates Group polyisocyanate compounds. These are either alone or 2
A combination of two or more species can be used.

Examples of the hydroxy group-containing vinyl monomer that can be used to block a part of the isocyanate groups of the polyisocyanate compound include (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. Mention may be made of hydroxyalkyl esters of acrylic acid.

The functional group ratio in the blocking reaction is
Usually, 0.8 to 1.2 equivalents, preferably 0.9 equivalents of hydroxy group-containing vinyl monomer to 1 mol of isocyanate compound.
It can be within the range of to 1.1 equivalents. When the hydroxy group-containing vinyl monomer is less than 0.8 equivalent to 1 mol of the isocyanate compound, the isocyanate group becomes excessive and the reaction between the double bond-containing isocyanate compound (b) and the hydroxyl group-containing epoxy compound (a) In the above, since the double bond-containing epoxy prepolymer (A) to be formed is likely to have a multidimensional structure and may have a high molecular weight, it is not preferable. If the hydroxy group-containing vinyl monomer exceeds 1.20 equivalents per 1 mol of the isocyanate compound,
A vinyl-modified amine-added epoxy resin produced by the reaction of the double bond-containing epoxy prepolymer (A) or the double bond-containing isocyanate compound (b) with the vinyl-based monomer (B) due to excess vinyl groups, or The vinyl-modified epoxy resin is not preferable because it may have a multidimensional structure and have a high molecular weight.

There is no particular restriction on the reaction between the hydroxyl group-containing epoxy compound (a) and the double bond-containing isocyanate compound (b) described above. For example, per one hydroxyl group of the compound (a), the isocyanate of the compound (b) can be used. The double bond-containing epoxy prepolymer (A) can be produced by reacting the groups at a ratio of 1 equivalent or less until substantially no unreacted isocyanate group is present.

In the above reaction, if necessary, a known catalyst for urethane synthesis, for example, a tertiary amine such as triethylamine, or an organometallic compound such as dibutyltin dilaurylate can be used.

In the double bond-containing epoxy prepolymer (A) thus obtained, the number of double bonds contained in one molecule is not particularly limited, but in general, it is 0.1 to 0.1 on average. It is preferably in the range of 1, and more preferably in the range of 0.2 to 0.6 on average.

The molecular weight of the double bond-containing epoxy prepolymer (A) thus obtained is also not particularly limited, but it is generally about 45 in terms of number average molecular weight.
It is desirable to have a molecular weight in the range of 0 to about 10,000, preferably 550 to 5,000, more preferably 1,000 to 3,000.

[0026]Vinyl monomer (B):Contains the above double bond
Vinyl that can be copolymerized with epoxy prepolymer (A)
The system monomer (B) has less polymerizable double bonds in one molecule.
Also a compound containing only one, preferably only one,
Especially the ones that are usually used in the production of acrylic resin
Suitable, specifically, for example, methyl (meth) acryloyl
Rate, ethyl (meth) acrylate, propyl (meth)
A) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, tert-butyl
(Meth) acrylate, 2-ethylhexyl (meth) a
Acrylate, cyclohexyl (meth) acrylate, n
-Octyl (meth) acrylate, lauryl (meth) acrylate
Acrylate, dodecyl (meth) acrylate, steari
Alkyl (meth) acrylic acid such as (meth) acrylate
Kill or cycloalkyl ester; methoxybutyl
(Meth) acrylate, methoxyethyl (meth) acry
Rate, ethoxybutyl (meth) acrylate, etc.
Ta) Alkoxyalkyl esters of acrylic acid; hydro
Xyethyl (meth) acrylate, hydroxypropyl
(Meth) acrylate, hydroxybutyl (meth) ac
Hydroxyalkyl (meth) acrylic acid such as relate
Ester; 2- (dimethylamino) ethyl (meth) ac
Tertiary amino group-containing amides of (meth) acrylic acid such as relate
Rualkyl ester; benzyl (meth) acrylate
Esters of aromatic alcohols and (meth) acrylic acid;
Lysidyl (meth) acrylate or (meth) acrylic acid
Hydroxyalkyl esters of capric acid and laurin
Acid, linoleic acid, oleic acid and other monocarboxylic acids
Ore generation: (meth) acrylic acid and "Curdra E-10"
Addition with a monoepoxy compound (made by Shell Chemical Co., Ltd.)
Products; styrene, α-methylstyrene, vinyltoluene,
p-chlorotoluene, p-tert-butylstyrene, etc.
Vinyl aromatic compounds may be mentioned. These are each
They can be used alone or in combination of two or more. Vinyl modified epoxy resin: According to one aspect of the invention,
The nil-modified epoxy resin is a double bond-containing epoxy resin as described above.
Copolymerization of poxyprepolymer (A) and vinyl monomer (B)
Obtained by polymerizing. The copolymerization is peroxy
Radical Polymerization Using Sid Initiator or Azo Initiator
Method, anionic polymerization method, cationic polymerization method, functional group transfer polymerization
It can be performed by a method such as a method.

Double bond-containing epoxy prepolymer (A)
The reaction ratio of the vinyl monomer (B) with the vinyl monomer (B) is not particularly limited, but generally (A) is 10 to 80% by weight, particularly 30 to 60% by weight based on the total weight of both. , (B) is 20 to 90% by weight, especially 40 to 70% by weight
The range of is preferable.

According to another aspect of the present invention,
The vinyl-modified epoxy resin is obtained by copolymerizing the above-mentioned double bond-containing isocyanate compound (b) with the vinyl-based monomer (B), and then obtaining the obtained isocyanate group-containing vinyl prepolymer as the above-mentioned hydroxyl group-containing epoxy resin (a). It can also be obtained by reacting with.

The copolymerization reaction of the above-mentioned double bond-containing isocyanate compound (b) with the vinyl-based monomer (B) can be carried out by the radical polymerization method using a peroxide-based initiator or an azo-based initiator, as in the above. It can be carried out by a method such as a polymerization method, a cationic polymerization method or a functional group transfer polymerization method.

The ratio of the double bond-containing isocyanate compound (b) and the vinyl monomer (B) in the above copolymerization reaction is not particularly limited, but is generally based on the total weight of both. , (B) is 2 to 10% by weight, particularly 3 to 7% by weight, (B) is 90 to 98% by weight, particularly 93 to
A range of 97% by weight is preferred.

Although the molecular weight of the isocyanate group-containing vinyl prepolymer obtained by this copolymerization is not particularly limited, it is generally about 700 to 50 in terms of number average molecular weight,
It can have a molecular weight in the range of 000, preferably 900 to 10,000, more preferably 900 to 5,000. The content of isocyanate groups in the prepolymer is also not particularly limited, but it is generally 0.2 to 16 on average per molecule, particularly 0.3 to 10.
It is preferable that 1.6 pieces are contained.

The obtained isocyanate group-containing prepolymer is then reacted with the hydroxyl group-containing epoxy resin (a) as described above to produce a vinyl-modified epoxy resin. The above reaction is carried out by using the compound (a)
Per 1 hydroxyl group of the isocyanate group-containing acrylic prepolymer at a ratio of 1 equivalent or less,
It can be carried out by reacting until substantially no unreacted isocyanate groups are present, whereby a vinyl-modified epoxy resin can be produced.

The molecular weight of the vinyl-modified epoxy resin obtained as described above is not particularly limited, but generally about 1,000 to about 50,000, particularly 1,20.
It preferably has a number average molecular weight in the range of 0 to 10,000. Further, the vinyl-modified epoxy resin is 1
Contain at least one, preferably two or more epoxy groups in the molecule, usually 155-5,000, especially 160
It can have an epoxy equivalent weight in the range of -1,000.

Active hydrogen-containing amino compound (C): The active hydrogen-containing amino compound (C) is an amino compound having active hydrogen capable of reacting with an epoxy group and is an aliphatic, alicyclic or araliphatic type compound. It includes primary or secondary amines or alkanolamines or modified products thereof, tertiary amine salts and the like. Examples of these amino compounds having active hydrogen include the following.

(1) Diethylenetriamine; an amine compound containing one secondary amino group and one or more primary amino groups such as hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine and the like, a ketone, (2) Diethylamine, diethanolamine, di-n- or a compound in which the primary amino group thereof is modified with ketimine, aldimine, oxazolidine or imidazoline by heating with aldehyde or carboxylic acid at a temperature of 100 to 230 ° C. secondary monoamines such as isopropanolamine, N-methylethanolamine, N-ethylethanolamine; and (3) Monoalkanolamines such as monoethanolamine and dialkyl (meth) acrylamides as Mic.
secondary amino group-containing compound obtained by addition by a hael addition reaction; (4) monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol,
A compound obtained by modifying the primary amine group of an alkanolamine such as 2-hydroxy-2 '-(aminopropoxy) ethyl ether into a ketimine; (5) dimethylethanolamine, triethylamine,
Salts of tertiary amines such as trimethylamine, triisopropylamine and methyldiethanol with organic acids such as acetic acid and lactic acid.

Of these, the compounds of the groups (1), (2) and (4) are preferable, and among them compounds such as diethanolamine and diethylenetriamine ketimine compounds are used after the secondary amino group reacts with the epoxy group. Those which themselves have an active hydrogen group or which can generate an active hydrogen by the hydrolysis of ketimine are particularly suitable because they have a crosslinkable functional group.

Vinyl-modified amine-added epoxy resin: The vinyl-modified amine-added epoxy resin of the present invention can be obtained by adding the active hydrogen-containing amino compound (C) to the vinyl-modified epoxy resin described above. The above-mentioned addition reaction can be carried out, for example, by adding the active hydrogen-containing amino compound (C) to the vinyl-modified epoxy resin solution and reacting it at a temperature of 30 to 160 ° C. for about 1 to 5 hours.

The reaction ratio of the active hydrogen-containing amino compound (C) to the vinyl-modified epoxy resin is such that the vinyl-modified amine-added epoxy resin produced has an amine value of generally 15 to 15.
It is preferably chosen to fall within the range of 100, in particular 15-60.

The vinyl-modified amine-added epoxy resin of the present invention is produced as described above, but as an alternative method, the double bond-containing epoxy prepolymer (A) of the active hydrogen-containing amino compound (C) is used. It is also possible to carry out the addition to the above prior to the copolymerization of the double bond-containing epoxy prepolymer (A) and the vinyl monomer (B). The reaction between the active hydrogen-containing amino compound (C) and the epoxy group of the double bond-containing epoxy prepolymer (A) is, for example, about 30
It can be carried out by reacting at a temperature of about 160 ° C. for about 1 to 5 hours.

The vinyl-modified amine-added epoxy resin formed is usually 1,000 to 50,000, and particularly 1,200.
It is desirable to have a number average molecular weight within the range of 10,000.

The vinyl-modified amine-added epoxy resin preferably contains a primary hydroxyl group, and although the primary hydroxyl group equivalent is not particularly limited, it is usually from 300 to
It is preferably in the range of 1000, particularly 450 to 650. The primary hydroxyl group provided by the active hydrogen-containing amino compound (C) and the like, and the secondary hydroxyl group present in the double bond-containing epoxy prepolymer (A) portion serve as a reactive functional group with the crosslinking agent. Acrylic-modified amine-added epoxy resins include, for example, tertiary amine salts, monocarboxylic acids, and 2
It is also possible to control the water dispersibility of the resin and improve the smoothness of the coating film by reacting it with a reaction reagent such as a primary sulfide salt, monophenol or monoalcohol.

Further, in the vinyl-modified amine-added epoxy resin, a blocked isocyanate group, β-hydroxycarbamic acid ester group, α, β-unsaturated carbonyl group, N
-Internal crosslinkability can also be improved by introducing a crosslinkable functional group such as a methylol group.

The reaction with the reaction reagent and the introduction of the crosslinkable functional group may be carried out before the addition of the active hydrogen-containing amino compound (C) to the vinyl-modified epoxy resin.

The acrylic modified amine-added epoxy resin obtained as described above can be used in combination with an external crosslinking agent. As the external cross-linking agent which can be used in combination, a compound having two or more cross-linkable functional groups in one molecule, for example, blocked polyisocyanate, polyamine β-hydroxycarbamic acid ester, malonic acid ester, malonic acid ester derivative, methylolation Examples thereof include melamine and methylolated urea. The compounding ratio (solid content ratio) of the vinyl-modified amine-added epoxy resin and these external cross-linking agents is not strictly limited, but is usually 100 / by weight.
It is preferably in the range of 0 to 60/40, particularly 85/15 to 60/40.

Aqueous resin composition: The above vinyl-modified amine-added epoxy resin is water-solubilized or water-dispersed by protonating an amino group in the resin with a water-soluble organic acid such as formic acid, acetic acid and lactic acid. be able to. The amount of the acid that can be used for the above-mentioned protonation (neutralization value) cannot be strictly defined depending on the type of the resin, etc., but is generally about 5 to about 40 KOHmg per 1 g of the resin solid content.
The number, especially within the range of 10 to 20 KOHmg is preferable in terms of electrodeposition characteristics.

The water-solubilized or water-dispersed product of the acrylic modified amine-added epoxy resin thus obtained can be made into an aqueous resin dispersion by dissolving or dispersing it in an aqueous medium. The concentration of the vinyl-modified amine-added epoxy resin in the dispersion liquid is not particularly limited and can be varied over a wide range depending on the application of the dispersion liquid and the like. Usually, the solid content concentration is 20 to 40% by weight,
Particularly, the range of 25 to 35% by weight is suitable.

The aqueous resin dispersion of the present invention is particularly suitable for use in a cathodic electrocoating composition. In this case, a pigment, a solvent, a curing catalyst, a surfactant and the like may be added if necessary. it can.

As the method and apparatus for carrying out electrodeposition coating on an article using the aqueous resin dispersion of the present invention, known methods and apparatus conventionally used in cathodic electrodeposition coating can be used. You can At this time, it is desirable to use the object to be coated as a cathode and the anode to use stainless steel or a carbon plate. The electrodeposition coating conditions that can be used are not particularly limited, but generally, bath temperature: 20 to 30 ° C.,
Voltage: 100-400V (preferably 200-300
V), current density: 0.01 to 3 A / dm ² , energization time: 1
The electrode area ratio (A / C): 2/1 to 1/2, the distance between the electrodes: 10 to 100 cm, and electrodeposition in a stirring state are desirable.

The coating film deposited on the cathode coating can be baked and cured at a temperature of about 140 ° C. to about 180 ° C. after cleaning.

[0050]

FUNCTION AND EFFECT Since the vinyl-modified amine-added epoxy resin of the present invention is modified with an acrylic resin by an acrylic resin by a specific method, it is used in a coating film formed by using the aqueous resin dispersion of the present invention. The compatibility between the vinyl-modified epoxy resin and the unmodified epoxy resin is excellent. Therefore, by using the aqueous resin dispersion of the present invention, it is possible to form a coating film having excellent weather resistance, corrosion resistance and appearance.

[0051]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples. In addition, "%" means "weight%" below.

Production Example 1 Production of double bond-containing isocyanate compound In a flask equipped with a stirrer, a thermometer, a dry air introduction tube and a reflux condenser, isophorone diisocyanate (manufactured by Daicel-Huls KK) 233.1 g, 2- 116.0 g of hydroxyl acrylate and 0.1 of hydroquinone.
07 g was added, and the isocyanate group concentration was 3.
The reaction was carried out while flowing dry air to 15 mmol / g to obtain a double bond-containing polyisocyanate compound.

Preparation of double bond containing epoxy prepolymer
A flask equipped with a stirrer, a thermometer, a nitrogen introducing tube, a dry air introducing tube, a nitrogen introducing tube and a reflux condenser was equipped with 760 g of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 228 g of bisphenol A and dimethylbenzylamine 13 0.5 g was added and reacted at 110 ° C. under a nitrogen atmosphere until the epoxy concentration became 1.9 mmol / g to obtain an epoxy resin (number average molecular weight 1002, epoxy equivalent 527).

To this epoxy resin was added 126.9 g of the double bond-containing isocyanate compound prepared in, and the reaction was carried out at 90 ° C. while blowing dry air until the isocyanate groups were exhausted. Then, it was diluted with ethylene glycol monobutyl ether to a solid content of 75%, and the double bond concentration was reduced to 0.5.
A viscous resin solution of a double bond-containing epoxy prepolymer having an epoxy equivalent of 594 at 322 mmol / g was obtained.

Preparation of vinyl-modified amine-added epoxy resin
Concrete stirrer, a thermometer, was charged with ethylene glycol monobutyl ether 25g nitrogen inlet tube and a flask fitted with a reflux condenser and allowed to warm to 120 ° C.. 66.7 g of the double bond-containing epoxy prepolymer solution described above, and Praxel FM-3X (O which is a double bond-containing polyester)
H equivalent: 472, double bond concentration: 2.12 mmol /
g, product diluted to 80% with xylene, manufactured by Daicel Chemical Industries, Ltd.) 20 g, 2-hydroxyethyl methacrylate 9 g, styrene 15 g, n-butyl acrylate 10 g, azobisisobutyronitrile (polymerization initiator)
10 g of the mixture are added dropwise over 3 hours to complete the polymerization. Thus, a vinyl-modified epoxy resin solution is obtained.

To this vinyl-modified epoxy resin solution, 8.84 g of diethanolamine was added, and the reaction was carried out at 90 ° C. until the epoxy groups disappeared. Thus the primary hydroxyl equivalent 4
A vinyl-modified amine-added epoxy resin (1) having an amine value of 31 and an amine value of 42.4 was obtained.

Production Example 2 Production of double bond-containing isocyanate compound Same as Production Example 1.

Preparation of Epoxy Prepolymer Containing Double Bond
It is the same as the manufacturing example 1.

Production of vinyl-modified amine-added epoxy resin
Concrete stirrer, a thermometer, was charged with ethylene glycol monobutyl ether 29g to a flask fitted with a nitrogen inlet tube and a reflux condenser and allowed to warm to 120 ° C.. Production example 1
66.7 g of the double bond-containing epoxy prepolymer solution obtained in step 2.
4 g, methyl methacrylate 6.4 g, n-butyl acrylate 17.6 g, 2-ethylhexyl methacrylate 1
2.6 g, azobisisobutyronitrile (polymerization initiator)
10 g of the mixture are added dropwise over 3 hours to complete the polymerization. Thus, a vinyl-modified epoxy resin solution is obtained.

To this vinyl-modified epoxy resin solution, 8.84 g of diethanolamine was added, and the reaction was carried out at 90 ° C. until the epoxy groups disappeared. Thus the primary hydroxyl equivalent 4
An acrylic modified amine-added epoxy resin (2) having an amine value of 31 and an amine value of 42.4 was obtained.

Production Example 3 Production of Isocyanate Group-Containing Vinyl Prepolymer 29 g of ethylene glycol monobutyl ether was placed in a flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a reflux condenser, and the temperature was raised to 120 ° C. Production example 1
Double bond-containing isocyanate compound prepared in 5.
5g, styrene 15.0g, n-butyl acrylate 2
3 g of a mixture of 5.0 g, methyl methacrylate 10.0 g, and azobisisobutyronitrile (polymerization initiator) 5.5 g
Add dropwise over time to complete the polymerization. Thus, an isocyanate group-containing vinyl prepolymer is obtained.

Production of Epoxy Resin A flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a reflux condenser was equipped with 700 g of bisphenol A diglycidyl ether having an epoxy equivalent of 190 and bisphenol A1.
92 g and dimethylbenzylamine (13.5 g) were added and reacted at 110 ° C. under a nitrogen atmosphere until the epoxy concentration became 2.1 mmol / g to obtain an epoxy resin (number average molecular weight 906, epoxy equivalent 477). This was diluted with ethylene glycol monobutyl ether to a solid content of 75% to obtain an epoxy resin solution. Production of vinyl-modified amine-added epoxy resin 90 g of isocyanate group-containing vinyl prepolymer obtained in a flask equipped with a stirrer, thermometer, nitrogen introducing tube and reflux condenser, 59.2 epoxy resin solution obtained
g, and 0.1 g of dibutyltin dilaurate are added, and the mixture is reacted at 90 ° C. under a nitrogen atmosphere until the isocyanate groups are exhausted. Then add 9.78 g of diethanolamine,
React at 90 ° C. until the epoxy groups are gone. Thus, a vinyl-modified amine-added epoxy resin (3) having a primary hydroxyl equivalent of 589 and an amine value of 47.6 was obtained.

Production Example 4 (for comparison) A reaction apparatus similar to that of Production Example 1 was charged with 700 g of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 192 g of bisphenol A and dimethylbenzylamine 13.
5 g was added and reacted at 110 ° C. until the epoxy group concentration became 2.44 mmol / g.

Obtained epoxy resin [number average molecular weight 10
25, epoxy equivalent 539], an acrylic compound having a carboxyl group at the terminal synthesized by a general radical polymerization method [monomer composition: 2-hydroxyethyl methacrylate / styrene / 2-ethylhexyl methacrylate / n-
Butyl methacrylate = 20/40/30/10
(%), Polymerization initiator: azobisvaleric acid, number average molecular weight (Mn): 7120, Mw / Mn = 11.8, resin acid value: 14.3] 2381 g, ethylene glycol monobutyl ether 599 g, and epoxy group concentration Is 0.4
The reaction is carried out at 110 ° C. until it reaches 26 mmol / g.

Next, the system was cooled, and when it reached 100 ° C., 121 g of diethanolamine was added, and the reaction was carried out at 100 ° C. until the epoxy groups disappeared, and the solid content was diluted to 75% with ethylene glycol monobutyl ether. An acrylic modified amine-added epoxy resin (4) having an amine value of 20.6 was obtained.

Examples and Comparative Examples Methyl ethyl ketoxime block isophorone diisocyanate was added to the resins obtained in the above Examples 1, 2, 3 and 4, and the ratio of the solid content of the acrylic modified amine-added epoxy resin to the solid content of the blocked isocyanate was adjusted. Is 75/2
It was blended so as to be 5. Furthermore, the solid content of the resin composition 1
For 00g, polypropylene glycol (Sanyo Kasei Co., Ltd., Sannix PP4000) 1g, formic acid 0.82
g, 1 g of lead acetate are added. Warm the system to 40 ° C,
While stirring, deionized water was gradually added and dispersed in water to obtain a stable emulsion having a resin solid content of 30%. 3 g of basic lead silicate, 13 g of titanium white, and 0.3 of carbon per 100 g of resin solids of the emulsion thus obtained.
g, 3 g of clay, 2 g of dibutyltin oxide and 1 g of a nonionic surfactant (trade name: Neugen 142B, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) were added, and the pigment was dispersed in a ball mill until the particle size became 10 μm or less, and then deionized. It was diluted with water to a resin solid content of 15%.

The four types of diluted coating materials obtained as described above were subjected to cationic electrodeposition coating on a non-treated steel sheet at a bath temperature of 28 ° C. and a voltage of 250 V for 3 minutes. 17 of these electrodeposition coated plates
The coated panel was obtained by baking at 0 ° C. for 20 minutes. Table 1 shows the test results of the coated panels obtained.

The test methods in Table 1 are as follows.

(* 1) Weather resistance Top clear (Magicalon 700
0, manufactured by Kansai Paint Co., Ltd.) to obtain a weather resistance test panel. About this test plate, a sunshine weather meter (test temperature: 63 ± 3 ° C., spray cycle: 12 out of 60 minutes)
Min, humidity: 50 ± 5%) 20 hours, 40 ° C. hot water dip 2 hours Repeat the test cycle. At the end of each cycle, a cross cut is put in the coated plate and a peeling test with cellophane tape is performed to evaluate the adhesion between the base and the clear. When the peeling of the clear hardly occurred, it was marked with ◯, and when the peeling occurred over a wide area around the cross cut, it was marked with x. The weather resistance was evaluated as the test time until it became x.

(* 2) Corrosion resistance (salt spray resistance) A cross cut was put in a coated plate and tested according to JIS Z2871, and after 480 hours, a peel test was performed on the cross cut portion with cellophane tape to measure the peel width.

[0071]

[Table 1]

Claims (3)

[Claims] 1. (A) An epoxy resin (a) having at least one epoxy group and at least one hydroxyl group in one molecule, and an average of 0.8 to 1.2 polymerizable resins in one molecule. By copolymerizing a double bond-containing epoxy prepolymer obtained by the reaction of an unsaturated isocyanate compound (b) having a heavy bond and an average of 0.8 to 1.2 isocyanate groups with (B) a vinyl monomer. A water-soluble or water-dispersible vinyl-modified amine-added epoxy resin obtained by reacting the resulting vinyl-modified epoxy resin with (C) an active hydrogen-containing amino compound. 2. An unsaturated isocyanate compound (b) and (B) vinyl system having an average of 0.8 to 1.2 double bonds and an average of 0.8 to 1.2 isocyanate groups in one molecule. An isocyanate group-containing vinyl prepolymer obtained by copolymerization with a monomer and a vinyl-modified epoxy resin obtained by reacting an epoxy resin (a) having at least one epoxy group and at least one hydroxyl group in one molecule. (C) A water-soluble or water-dispersible vinyl-modified amine-added epoxy resin obtained by the reaction of an active hydrogen-containing amino compound. 3. An aqueous resin composition comprising a water-solubilized or water-dispersed product of the vinyl-modified amine-added epoxy resin according to claim 1 or 2.