JPH06145593A - Water-base coating composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which is used for coating the interior surface of a can, requiring esp. high processibility and corrosion resistance, and is applied to a metallic material directly or to an undercoating layer and baked. CONSTITUTION:The compsn. at least contains 5-40wt.% epoxy resin, 25-80wt.% phenoxy resin, 7-30wt.% carboxylated acrylic resin, and 2-30wt.% resole phenol resin, and is prepd. by modifying the epoxy resin and the phenoxy resin with the carboxylated acrylic resin and dispersing the resulting modified resins and the resole phenol resin in water using ammonia or an amine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous coating composition. More specifically, directly on the metal material or on the base paint,
Particularly, an aqueous coating composition applied to the inner surface of a metal can which requires high workability and corrosion resistance.

[0002]

2. Description of the Related Art Conventionally, metal cans have usually been provided with a thin synthetic resin protective coating in order to prevent metal materials such as tin plate, tin-free steel and aluminum from directly contacting the contents and corroding.

Epoxy-based paints such as epoxy / phenol, epoxy / amino, and epoxy / acryl are usually used as the inner surface paint because of their excellent adhesion, anticorrosiveness and flavor. However, since the above-mentioned paint is based on a thermosetting resin, it has a drawback of poor workability. Therefore, vinyl chloride resin-based organosol paints have been used for the types and applications of which processability is particularly required, although they are based on thermoplastic resins and have the drawback of having many extracted components and poor flavor.

On the other hand, in recent years, epoxy / acrylic water-based paints have begun to be used in view of work hygiene / environmental measures or safety (dangerous substances). What has been disclosed so far is an aqueous coating obtained by esterifying an epoxy resin with an acrylic resin containing a carboxyl group, neutralizing it with a base and dispersing it in water (JP-B-59-37026), containing a carboxyl group. A water-based paint prepared by grafting a polymerizable monomer mixture onto an epoxy resin using a free radical generator and dispersing it in water in the same manner as described above (Japanese Patent Publication No. Sho 63-17869), and an epoxy resin having an acroyl group to acrylic acid. Alternatively, an aqueous paint obtained by copolymerizing with an ethylenic monomer containing methacrylic acid and dispersing in water by the same method as described above (Japanese Patent Publication No. 62-721
No. 3 bulletin) etc. These are self-emulsifying epoxy resin-based water-based paints in which the resin itself exhibits dispersibility,
It contained no surfactant for dispersion in water and was excellent in chemical performance and water resistance.

[0005]

However, the above self-emulsifying type epoxy resin-based water-based coating composition needs to contain at least 10% or more of an acrylic resin as an emulsifying component, which lowers processability and has few reaction points and crosslink density. The corrosion resistance was inferior because of low. The problems to be solved by the present invention are various problems of conventional vinyl chloride resin-based organosol paints, and self-emulsifying epoxy resin-based water-based paints, and particularly, workability, and an aqueous paint composition excellent in corrosion resistance. To provide.

[0006]

The present invention, in order to solve the above problems, an epoxy resin and a phenoxy resin modified with a carboxyl group-containing acrylic polymer,
Provided is an aqueous coating composition in which a resol-type phenol resin is aqueously dispersed using ammonia or amine.

The epoxy resin used in the present invention includes bisphenol A type epoxy resin and bisphenol F.
Examples of the epoxy resins include epoxy resins having 1.1 to 2.0 epoxy groups in one molecule. Among these epoxy resins, a bisphenol A type epoxy resin having a number average molecular weight of 1500 to 7,000 or a bisphenol F type epoxy resin is preferable. Commercially available products include "Epicote 1004", "Epicote 1007", "Epicote 1009" manufactured by Shell Chemical Co., Ltd., and "YDF2004" manufactured by Toto Kasei Co., Ltd.
And the like. One or more of the above epoxy resins can be selected and used. Epoxy resin is 5
If it is less than 5% by weight, the adhesion to the metal substrate is poor, and if it exceeds 40% by weight, the workability is poor and it is preferably 5 to 40% by weight.

The phenoxy resin used in the present invention is
It is a resin having a resin skeleton similar to that of the bisphenol A type epoxy resin, having 0.5 or less epoxy groups in one molecule, and having a number average molecular weight of 9,000 or more, which is an extremely high molecular weight. A commercially available product is Phenoxy PKHH manufactured by Union Carbide Chem. If the phenoxy resin is less than 25% by weight, the workability is poor, and if it exceeds 80% by weight, the adhesion to the metal substrate is poor, and 25-80% by weight is preferable.

As a method for modifying the epoxy resin and the phenoxy resin with a carboxyl group-containing acrylic polymer in the present invention, the above-mentioned publications (JP-B-59-37026, JP-B-63-17869, JP-B-62-7213) are mentioned. The method described in Japanese Patent Laid-Open Publication No. 2004-242242 can be applied correspondingly, and specifically, the following method is preferable.

(1) Epoxy resin and phenoxy resin
A method of esterifying with a separately prepared carboxyl group-containing acrylic polymer; the carboxyl group-containing acrylic polymer is a carboxyl group-containing vinyl monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid. Vinyl monomers copolymerizable with one kind or two or more kinds, for example, styrene-based monomers such as styrene, vinyltoluene, 2-methylstyrene, t-butylstyrene, chlorostyrene; methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, n-2 ethylhexyl acrylate, n acrylate -Acrylic ester monomers such as octyl, decyl acrylate, dodecyl acrylate; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, Methacrylic acid ester-based monomers such as n-hexyl methacrylate, n-2 ethylhexyl methacrylate, n-octyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate; 2-acrylic acid acrylate Hydroxyl group-containing monomers such as roxyethyl, hydroxypropyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate; N- such as N-methylol (meth) acrylamide and N-butoxymethyl (meth) acrylamide. It is obtained by copolymerizing one or two or more of substituted (meth) acrylic monomers. The carboxyl group-containing acrylic polymer,
The composition ratio and type are not particularly limited, but the carboxyl group-containing vinyl monomer is 5% by weight or more, especially 30%.
Methacrylic acid is used in an amount of up to 80% by weight, and copolymerizable vinyl monomers are used in an amount of 95% by weight or less.
00 is preferable. The esterification reaction is basically a reaction of a carboxyl group with an epoxy group and / or a hydroxyl group in the acrylic polymer, and an amine-based esterification catalyst can be used. Examples of the amine-based esterification catalyst include dimethylethanolamine, dimethylbenzylamine, ethanolamine, diethanolamine and morpholine.

(2) Epoxy resin and phenoxy resin,
A method of grafting a copolymerizable vinyl monomer mixture containing a carboxyl group-containing vinyl monomer with a free radical generator; the vinyl monomer mixture is a carboxyl group-containing vinyl monomer alone or in a mixture with another vinyl monomer, Specific examples include those described in (1) above. The composition ratio and type of the vinyl monomer mixture are not particularly limited, but the carboxyl group-containing vinyl monomer is 5% by weight or more, particularly 30 to 100%.
Methacrylic acid is preferably used in an amount of 95% by weight, and copolymerizable vinyl monomers are preferably used in an amount of 95% by weight or less.

(3) Epoxy resin and phenoxy resin,
By reacting acrylic acid and / or methacrylic acid
A method of introducing a (meth) acryloyl group and then copolymerizing a vinyl monomer mixture containing acrylic acid and / or methacrylic acid in the group; Reaction of epoxy resin and phenoxy resin with acrylic acid and / or methacrylic acid The ratio is preferably in the range of 1 / 0.1 to 1 / 1.5 (molar ratio). Specific examples of the vinyl monomer mixture include those shown in (1) above, and the composition ratio and type are not particularly limited.
Methacrylic acid at more than 5% by weight, especially 30-80% by weight,
Copolymerizable vinyl monomer is 95% by weight or less, especially 20 to
Styrene and ethyl acrylate are preferred at 70% by weight.

The carboxyl group-containing vinyl monomer and copolymerizable vinyl monomer and the epoxy resin and the phenoxy resin are preferably in the range of 8/92 to 50/50 (weight ratio), and the epoxy resin and the phenoxy resin are less than 50% by weight. Then, the adhesion to the base material, the corrosion resistance, the workability, etc. are deteriorated. On the other hand, if it exceeds 92% by weight, it becomes difficult to make it aqueous. More preferably, the above ratio is 10/90 to 30/70 (weight ratio)%.

The acrylic polymer-modified epoxy resin and phenoxy resin shown in the above (1) to (3) are mainly those in which a carboxyl group-containing acrylic polymer is bonded,
In some solutions, some unbonded carboxyl group-containing acrylic polymers coexist.

Examples of the vinyl monomer polymerization catalyst used for modifying the acrylic polymer described in (1) to (3) above and the catalyst for grafting a carboxyl group-containing vinyl monomer onto an epoxy resin and a phenoxy resin include organic peroxides. An oxide, a persulfate, an azobis compound, and a redox system in which these are combined with a reducing agent can be used. Specifically, benzoyl peroxide, perbutyl octate, t-butyl hydroperoxide, azobisisobutyronitrile, azobisvaleronitrile, 2,2
^, -Azobis (2-aminopropane) hydrochloride and the like are mentioned, and benzoyl peroxide is particularly preferable as a free radical generator as a graft catalyst. These are generally less than 100 parts by weight of the reaction components.
It can be used in a proportion of 5 to 20 parts by weight.

The acrylic polymer of (1) above and (1) to (3)
The acrylic polymer reaction shown in is preferably carried out in an organic solvent system, and the organic solvent used is a monomer such as a vinyl monomer and a copolymer thereof, an epoxy resin and a phenoxy resin, and the like. A solvent that is easy to mix is preferred,
Examples thereof include alcohol-based, glycol-based, diglycol-based, acetate-based solvents and the like. Specifically, n
-Propanol, isopropal, n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, amyl alcohol, methylamyl alcohol, ethylene glycol, diethylene glycol, 1,3-butylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, methyl propylene glycol, methyl propylene diglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3 -M · The butyl acetate, ethylene glycol monobutyl ether acetate, 3-methyl-3
-Methoxybutyl acetate and the like can be mentioned.
Other solvents can be used, but until the production of water-based paint,
Alternatively, those which can be removed under reduced pressure later are preferable.

The ammonia or amine used in the present invention is used for neutralizing the carboxyl group of the carboxyl group-containing acrylic polymer shown in the above (1) to (3). Examples of the amine include trimethylamine, triethylamine, There are alkylamines such as butylamine, alcohol amines such as dimethylaminoethanol, diethanolamine and aminomethylpropanol, and volatile amines such as morpholine.

The resol type phenol resin used in the present invention is a resin obtained by condensing an arbitrary phenol component and formaldehyde in the presence of a basic catalyst.
Further, as the phenol component constituting the resol type phenol resin, o-cresol, p-cresol, p-te
rt-butylphenol, p-ethylphenol, 2,3
-Bifunctional phenols such as xylenol, 2,5-xylenol, p-tert-aminophenol, p-nonylphenol, p-phenylphenol, p-cyclohexylphenol, carboxylic acid, m-cresol, m-ethylphenol, 3, Trifunctional phenols such as 5-xylenol and m-methoxyphenol, monofunctional phenols such as 2,4-xylenol and 2,6-xylenol,
Bisphenol A: Bifunctional phenols such as bisphenol B and bisphenol F may be used alone or in combination of two or more. As the basic catalyst, for example, ammonia, amine, hydroxide of alkaline earth metal, oxide of alkali metal, oxide of alkaline earth metal and the like can be used. If the resol type phenolic resin is less than 2% by weight, the crosslink density is low and the corrosion resistance is inferior.
On the other hand, if it exceeds the range, on the contrary, the crosslinking density becomes too high and the workability is deteriorated, so 2 to 30% by weight is preferable.

It is possible to add a solvent, a surfactant or a defoaming agent for improving the coating property to the water-based coating composition of the present invention, if necessary. It is also possible to add a wax, which is a lubricant, to the water-based coating composition of the present invention after forming a coating film to prevent scratches on the coating film during processing and transportation.

Although it is possible to add an amino resin as a curing agent to the water-based coating composition of the present invention, addition of a large amount undesirably increases the crosslink density and reduces the processability. Addition of 5% by weight or less is preferable.

As a base material to be applied, a metal plate of a treated or untreated one such as an aluminum plate, a steel plate, a zinc steel plate, a tin plate, etc. is suitable, and an epoxy-based or vinyl-based undercoat is used. Even on the primer,
It may be directly on the metal material. As a coating method, various methods known in this field, such as roll coater coating, spray coating, dip coating, and electrodeposition coating, can be applied, and among them, roll coater coating and spray coating are preferable.
The drying and curing conditions are preferably 150 to 230 ° C. for 1 to 30 minutes or 240 to 300 ° C. for 15 to 60 seconds.

[0022]

The aqueous coating composition of the present invention comprises (A) an epoxy resin 5 to 40% by weight (B) a phenoxy resin 25 to 80% by weight (C) a carboxyl group-containing acrylic polymer 7 to 30% by weight (D) resole Type phenol resin 2 to 30% by weight At least, the epoxy resin and phenoxy resin obtained from the above (A) to (D) modified with a carboxyl group-containing acrylic polymer (a), and a resol type phenol resin are used. Concerning the aqueous dispersion using ammonia or amine, the processability is imparted by including the phenoxy resin skeleton which is a linear high molecular weight resin, and the epoxy resin skeleton and the resol type phenol resin are included to form the base material. It is possible to improve the adhesiveness and increase the crosslink density after curing to impart corrosion resistance.

[0023]

EXAMPLES Next, the present invention will be described more specifically by way of examples. In the examples, "parts" and "%" indicate "parts by weight" and "% by weight", respectively.

Production Example 1 Production of epoxy resin and phenoxy resin solution (A) Epicoat 1004 (produced by Yuka Shell Epoxy Co., Ltd.) 120.0 parts Phenoxy PKHH (produced by Union Cabide Chem.) 480.0 parts Ethylene glycol monoethyl ether 400.0 Part 4 is charged into a 4-necked flask and charged under a nitrogen stream to 100.
It was heated to ℃ and completely dissolved to obtain a 60% epoxy resin and phenoxy resin solution (A).

Production Example 2 Production of Epoxy Resin and Phenoxy Resin Solution (B) Epicoat 1004 (manufactured by Yuka Shell Epoxy Co., Ltd.) 240.0 parts Phenoxy PKHH (manufactured by Union Cabide Chem.) 360.0 parts Ethylene glycol monoethyl ether 400.0 A 60% epoxy resin and phenoxy resin solution (B) was obtained in the same manner as in Part (1).

Production Example 3 Production of Acrylic Polymer Containing Carboxyl Group (C) Styrene 210.0 parts Ethyl acrylate 210.0 parts Methacrylic acid 180.0 parts Benzoyl peroxide 20.0 parts n-Butanol 380.0 parts 4 neck flask was charged under a nitrogen stream. The mixture solution was heated to 100 ° C. at 100 ° C. and added dropwise at 100 ° C. for 3 hours and kept at the same temperature for 2 hours to obtain a 60% carboxyl group-containing acrylic polymer solution (C).

Production Example 4 Production of Resol-type Phenolic Resin Solution (D) Bisphenol A 485.1 parts Formalin 40% n-butanol solution 478.7 parts 25% Ammonia water 36.2 parts 4 to 4 flasks were charged with and under a nitrogen stream.
After reacting at 5 ° C for 5 hours, xylene / n-butanol / cyclohexanone = 1/1/1 was added to dilute and further dehydrated to obtain 35% resol type phenol resin solution (D).

Production Example 5 Production of Resol-type Phenolic Resin Solution (E) p-Cresol 417.7 parts Formalin 40% n-butanol solution 580.1 parts Magnesium hydroxide 2.2 parts Reaction was carried out for 2.5 hours in the same manner as in (5). After that, neutralize with phosphoric acid, add a large amount of water such as xylene / n-butanol / cyclohexanone = 1/1/1 and let stand for 5 hours to separate and remove the aqueous layer containing the produced salt, and further azeotropic dehydration. Then 35%
To obtain a resol type phenol resin solution (E).

Example 1 Epoxy resin and phenoxy resin solution (A) 271.0 parts Carboxyl group-containing acrylic polymer (C) 83.1 parts Dimethylaminoethanol 15.5 parts Resol type phenol resin solution (D) 107.2 parts Ion-exchanged water 523.2 parts 4 parts After charging ~ in a necked flask and adding under stirring under a nitrogen stream to neutralize equimolar moles of the contained carboxyl groups, the internal temperature was raised to 80 ° C and stirred at this temperature for 30 minutes. After that, it was cooled to room temperature. The reduction rate of oxirane% was 70%, and the viscosity was increased as compared with that before cooking. After cooking, the mixture was added with stirring, and the mixture was added little by little to obtain an aqueous dispersion having a solid content of 25%.

Examples 2 to 4 Epoxy resin and phenoxy resin solutions (A) and (B) and a carboxyl group-containing acrylic polymer solution (C) having the composition shown in Table 1 were cooked in the same manner as in Example 1. Then, the resol type phenol resin solution (D), (E) and ion-exchanged water were added to obtain an aqueous dispersion having a solid content of 25%.

Table 1

[Table 1]

Example 5 Epoxy resin and phenoxy resin solution (A) 270.8 parts n-butanol 70.0 parts Styrene 17.5 parts Ethyl acrylate 17.5 parts Methacrylic acid 15.0 parts Benzoyl peroxide 3.5 parts Resol type phenol resin solution (D) 107.1 parts Dimethyl Aminoethanol 15.5 parts Ion-exchanged water 483.1 parts To a 4-necked flask was charged with, the internal temperature was raised to 110 ° C., and while stirring under a nitrogen stream, the mixed solution of was added dropwise over 2 hours and cooled to room temperature. After adding ~, a small amount was added little by little to obtain an aqueous dispersion having a solid content of 25%.

Examples 6-8

In the same manner as in Example 1, the epoxy resin and phenoxy resin solutions (A) and (B) having the formulations shown in Table 2 were prepared.
35 parts of styrene, 35 parts of ethyl acrylate, 30 parts of methacrylic acid, and 7 parts of benzoyl peroxide are added dropwise to the vinyl monomer mixture, and the resol type phenol resin solutions (D), (E) and dimethylaminoethanol are added. Then
Further, ion-exchanged water was added little by little to obtain an aqueous dispersion having a solid content of 25%.

Table 2

[Table 2]

Example 9 (1) Epoxy resin and phenoxy resin solution (A) 270.8 parts (2) Methacrylic acid 1.5 parts (3) Sodium hydroxide 0.03 parts (4) n-Butanol 70.0 parts (5) Styrene 17.5 parts ( 6) Ethyl acrylate 17.5 parts (7) Methacrylic acid 13.5 parts (8) Benzoyl peroxide 1.0 part (9) Resol type phenolic resin solution (D) 107.1 parts (10) Dimethylaminoethanol 13.9 parts (11) Deionized water 487.2 Part (1) to (3) are charged in a 4-necked flask and the internal temperature is 120 to
Raise the temperature to 130 ℃, proceed the reaction under nitrogen flow, cool when the acid value becomes 0.5 or less, add (4) at 90 ℃, keep it at 90 ℃ and stir (5 ) To (8) was added dropwise over 2 hours and cooled to room temperature. continue
(9) to (10) were added, and (11) was added little by little with stirring to obtain an aqueous dispersion having a solid content of 25%.

Examples 10 to 12 Epoxy resins and phenoxy resin solutions (A) and (B), methacrylic acid and sodium hydroxide were added in the formulations shown in Table 3 in the same manner as in Example 1 to react them. Styrene 35 parts, ethyl acrylate 35 parts, methacrylic acid 27
Part, benzoyl peroxide 2 parts vinyl monomer mixed solution was added dropwise, and then resol type phenol resin solution
(D), (E) and dimethylaminoethanol were added, and ion-exchanged water was added little by little while stirring to obtain an aqueous dispersion having a solid content of 25%.

Table 3

[Table 3]

Comparative Production Example 1 Production of Epoxy Resin Solution (F) Epicoat 1007 (manufactured by Yuka Shell Epoxy Co., Ltd.) 600.0 parts Ethylene glycol monoethyl ether 400.0 parts A 4-necked flask was charged with and under a nitrogen stream. 100
Heat to ℃, completely dissolve 60% epoxy resin solution (F)
Got

Comparative Production Example 2 Production of Epoxy Resin Solution (G) Epicoat 1009 (manufactured by Yuka Shell Epoxy Co., Ltd.) 600.0 parts Ethylene glycol monoethyl ether 400.0 parts A 4-necked flask was charged with and under a nitrogen stream. 100
60% epoxy resin solution (G)
Got

Comparative Example 1 An aqueous dispersion having a solid content of 25% was prepared in the same manner as in Example 1 except that the epoxy resin and phenoxy resin solution (A) in Example 1 was changed to the epoxy resin solution (F). Got

Comparative Example 2 An aqueous dispersion having a solid content of 25% was prepared in the same manner as in Example 5, except that the epoxy resin solution (A) in Example 5 was replaced with the epoxy resin solution (G). Got

Comparative Example 3 An aqueous dispersion having a solid content of 25% was prepared in the same manner as in Example 9 except that the epoxy resin and phenoxy resin solution (A) in Example 9 was changed to the epoxy resin solution (G). Got

Comparative Example 4 Resol-type phenol resin solution in Example 9 above
Ion-exchanged water was adjusted in the same manner as in Example 9 except that (D) was excluded to obtain an aqueous dispersion having a solid content of 25%.

Comparative Examples 5 to 8 All were carried out in the same manner as in Example 1 except that the composition in Example 1 was changed to the composition shown in Table 4, and the solid content was 25%.
A water dispersion of

Table 4

[Table 4]

[0047]

[Preparation of paint] The organic solvent contained in the water dispersions obtained in the above Examples and Comparative Examples was removed under reduced pressure so that the content of the solid content was 25% and the content was 15% of the paint. I adjusted it.

Performance test The storage stability test results of the aqueous coating compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 10 were applied to a tin plate with a bar coater so as to have a thickness of 10 μm, and the temperature was 200 ° C. Tables 5 and 6 show the results of evaluation of various physical properties by baking for 5 minutes to prepare a test panel.

The various test methods in Table 5 are as follows. (1) Storage stability of paint: Stored in a thermostat at 50 ° C, and periodically evaluated the appearance and properties. Good storage stability ・ ・ ・ ・ ○ Abnormalities such as gelation, sedimentation, and separation occurred during storage ・ ・ ・ ・ ×

(2) Adhesion: Using a knife on the surface of the coating film, make 11 cuts in each of the vertical and horizontal directions with a width of about 1.5 mm in the scoring. The number of unpeeled parts of the crevices when strongly peeled with a cellophane adhesive tape having a width of 24 mm adhered is shown in the molecule.

(3) Water resistance: Treated in water at 125 ° C. for 40 minutes to judge the surface condition of the coating film.

(4) Workability: Using a special goby folding type DuPont impact tester, a folded sample is placed at the bottom and a contact weight of 1 kg of iron weight is dropped from a height of 50 cm. The length of the crack in the coating film at the bent portion caused when the test piece was exposed was measured. 0 ~ 10mm ・ ・ ・ ・ ○ 10-20mm ・ ・ ・ ・ △ 20mm or more ・ ・ ・ ・ X

[0053]

(5) Corrosion resistance: using a knife on the coated surface ×
The test piece with the notch is marked with 125% in 1% saline solution.
The treatment is performed at 40 ° C. for 40 minutes, and the degree of corrosion in the vicinity of the mark X is judged. No abnormality ・ ・ ・ ・ ○ Mark slightly corroded ・ ・ ・ ・ △ mark Marked corrosion ・ ・ ・ ・ × mark

Table 5

[Table 5]

Table 6

[Table 6]

[Figure 6]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 171/10 PLQ 9167-4J // C09D 5/00 PSG 6904-4J (72) Inventor Tetsuhisa Nakamura Toyo Inki Manufacturing Co., Ltd., 2-3-13 Kyobashi, Chuo-ku, Tokyo

Claims (1)

[Claims] 1. (A) Epoxy resin 5-40 wt% (B) Phenoxy resin 25-80 wt% (C) Carboxyl group-containing acrylic polymer 7-30 wt% (D) Resol-type phenol resin 2-30 wt% % At least one obtained from (A) to (D) above, which is obtained by modifying an epoxy resin and a phenoxy resin with a carboxyl group-containing acrylic polymer (a), and a resol-type phenol resin which is aqueous with ammonia or amine. An aqueous coating composition characterized by being dispersed.