JPH07268064A - Water-base resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain a water-base resin compsn. which is excellent in stability of a water-base fluid, forms a coating film of which the surface is smooth without causing bubbling, and gives a cured coating film excellent in the resistances to hot water, corrosion, and solvent, processibility, and flavor characteristics. CONSTITUTION:A monomer mixture comprising an ethylenically unsatd. aliph. carboxylic acid and an unsatd. monomer copolymerizable therewith and having an acid value of 100-500 is grafted onto an arom. epoxy resin and/or a phenoxy resin to give a carboxylated graft epoxy resin. The graft epoxy resin is mixed with an arom. epoxy resin or a mixture thereof with a phenoxy resin, and the resulting mixture is partially bonded to a carboxylated acrylic resin having an acid value of 100-500 to give a composite resin. The objective water-base resin compsn. is obtd. by dispersing or dissolving the composite resin in water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin composition and a method for producing the same, and more particularly to metal cans, particularly food cans, which are excellent in stability of aqueous liquid, defoaming property, coatability and processability of coating film. TECHNICAL FIELD The present invention relates to an aqueous epoxy resin composition suitable for coating the inner surface of a beverage can and a method for producing the same.

[0002]

2. Description of the Related Art A coating material for a metal can is required to sufficiently withstand various conditions received from processing, distribution or contents of the metal can. In addition, it is important to deal with various problems related to hygiene of work environment and disaster prevention such as fire explosion, and it is particularly necessary to satisfy food hygiene requirements for beverage cans and edible cans. Therefore, in recent years, water-based paints have been widely used.

Under such circumstances, the aqueous epoxy resin composition is particularly noted because it is easy to handle, and various compositions and manufacturing methods have been proposed. For example, JP-A-53-
No. 1228, a catalyst such as benzoyl peroxide is used to graft-polymerize an acrylic monomer containing a carboxyl group-containing monomer on the main chain of an epoxy resin,
A production method in which the obtained graft resin is dispersed in water containing a basic compound such as ammonia and amine. JP 58-1
Japanese Patent Publication No. 98513 discloses a production method in which a macromer obtained by reacting an epoxy resin with methacrylic acid is copolymerized with another polymerizable monomer, and a basic compound is dispersed in water. JP-A-56-43362 discloses a method for producing a water-dispersible resin composition in which an epoxy resin and a polymer containing a carxyl group are partially reacted in an aqueous organic solvent. JP-A-56-10924
In JP-A-3, an aqueous resin dispersion obtained by dispersing an epoxy resin / acrylic resin partial reaction product having an excess of carboxyl groups in an aqueous medium in the presence of an amine. Japanese Patent Laid-Open No. 61-26876
In the publication, a high acid value acrylic resin-modified epoxy resin aqueous dispersion composition containing a specific phenol resin. JP-A-60-215015 discloses an acrylic resin-modified epoxy resin aqueous dispersion prepared by precondensing a phenol resin.

However, these conventional water-based epoxy resin compositions are generally poor in dispersion stability and defoaming property, inferior in processability, corrosion resistance, solvent resistance, and flavor property, and are used for coating. There is a problem that the coated surface is not smooth, or cracking occurs due to bumping of water and an organic solvent.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve such problems and is excellent in stability and defoaming property, has good smoothness of the coated surface, does not cause cracking, and cures the same. It is intended to provide an aqueous resin composition having a coating film excellent in hot water resistance, processability, solvent resistance, and flavor, and a method for producing the same.

[0006]

The present invention provides an aromatic epoxy resin and / or a phenoxy resin (A) having an acid value of an ethylenically unsaturated aliphatic carboxylic acid and an unsaturated monomer copolymerizable therewith. A mixture of a carboxylic acid-modified grafted epoxy resin (C) obtained by graft-polymerizing a monomer mixture (B) of 100 to 500 and an aromatic epoxy resin (D) contains a carboxyl group having an acid value of 100 to 500. It is an aqueous resin composition in which a composite resin (F) in which an acrylic resin (E) is partially bonded is dispersed or dissolved in water.

The aqueous resin composition of the present invention is manufactured through the following steps. Aromatic epoxy resin and / or phenoxy resin (A)
Is graft-polymerized with an ethylenically unsaturated aliphatic carboxylic acid and a monomer mixture (B) having an acid value of 100 to 500 consisting of a copolymerizable unsaturated monomer with the carboxylic acid-modified grafted epoxy resin. (C) is obtained, and the carboxylic acid-modified grafted epoxy resin (C) is mixed with the aromatic epoxy resin (D), and then the mixture is mixed with a carboxyl group-containing acrylic resin (E) having an acid value of 100 to 500. To obtain a composite resin (F), and the composite resin (F) is dispersed or dissolved in water.

The aromatic epoxy resin (D) may be a mixture of an aromatic epoxy resin and a phenoxy resin. Furthermore, the composition of the present invention may further be mixed with a phenol resin and / or an amino resin (G), and these phenol resin and / or amino resin (G) are aromatic epoxy resin and / or phenoxy resin (A). ), A grafted epoxy resin (C), an aromatic epoxy resin or a mixture thereof and a phenoxy resin, (D) and an acrylic resin (E) may be pre-condensed.

The present invention will be described in detail below. The aromatic epoxy resins (A) and (D) used in the present invention have a condensation unit of bisphenol A, F, B or a halogen substitution product thereof with epihalohydrin or β-methylepihalohydrin of 40% or more, preferably 60%. It is the following epoxy resin containing the above and having at least one oxirane ring at the end and having a number average molecular weight of 1,000 to 8,000, and can be produced by the following method. A mixture of these aromatic epoxy resins may be used.

1. 1. An epoxy resin obtained by reacting bisphenol A, F, B or a halogen-substituted product thereof with epihalohydrin or β-methylepihalohydrin. The epoxy resin of the above 1 and bisphenol A, F,
2. Epoxy resin obtained by reaction with B or a halogen-substituted product thereof. 3. A modified epoxy resin obtained by reacting the epoxy resin of 1 or 2 with a dibasic acid such as (anhydrous) phthalic acid, (anhydrous) maleic acid or adipic acid. 4. A modified epoxy resin obtained by reacting the epoxy resin of 1 or 2 with a monobasic acid such as acetic acid, butyric acid, benzoic acid, castor oil fatty acid, soybean oil fatty acid, tall oil fatty acid. Modified epoxy resin obtained by reaction of the epoxy resin of 1 or 2 with a polyester polyol obtained from a (polyhydric) alcohol and a (poly) basic acid

Here, as an example of the polyhydric alcohol,
1,6-hexanediol, trimethylolpropane, etc. are mentioned. Examples of polybasic acids include dibasic acids such as (anhydrous) phthalic acid, (anhydrous) maleic acid, and adipic acid; trimellitic anhydride, and pyromellitic dianhydride. If the condensation unit of bisphenol A, F, B or a halogen substitution product thereof and epihalohydrin is 40% or less, the corrosion resistance is not sufficient. The number average molecular weight is 1,000.
If it is less than 8,000, the processability and adhesion of the cured coating film will be deteriorated. On the other hand, if it exceeds 8,000, it tends to gel during the reaction with the acrylic resin (E), and the viscosity of the coating composition is increased, resulting in stability of the coating composition. Tends to decrease. From the viewpoint of these characteristics, 3,000 to 7,500 is more preferable.

The phenoxy resins (A) and (D) used in the present invention have a higher molecular weight than the above epoxy resins (A) and (D) and have a number average molecular weight of 8,000 to 5.
It is 50,000. Union Carbide P
KHC, PKHH, PKHJ and YP-made by Tohto Kasei Co.
50, YP-50S, etc. can be used.

The ethylenically unsaturated aliphatic carboxylic acid to be reacted with the aromatic epoxy resin and / or the phenoxy resin (A) in the present invention includes α, β-ethylene such as acrylic acid, methacrylic acid, maleic acid and itaconic acid. Unsaturated carboxylic acid, and as the unsaturated monomer copolymerizable therewith, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Methacrylic acid n-
Α, β such as butyl and 2-ethylhexyl methacrylate
-Alkyl esters of ethylenically unsaturated aliphatic carboxylic acids; 2-hydroxyethyl acrylate, 2-acrylic acid
Α, β-ethylenically unsaturated aliphatic carboxylic acid having a hydroxyl group such as hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide , Acrylamide derivatives such as diacetone acrylamide; glycidyl esters of α, β-ethylenically unsaturated aliphatic carboxylic acids such as glycidyl acrylate and glycidyl methacrylate; vinyl esters of saturated aliphatic carboxylic acids such as vinyl acetate and vinyl propionate Styrene-based monomers such as styrene, α-methylstyrene and vinyltoluene. The acid value of the monomer mixture (B) is 1
0 to 500, more preferably 200 to 400
Is. When the acid value is less than 100, the dispersion stability is lowered or the gloss when formed into a coating film is lowered, and when the acid value is more than 500, the workability and water resistance of the coating film are deteriorated.

To obtain the carboxylic acid-modified grafted epoxy resin (C), the above-mentioned monomer mixture (B) is added to the aromatic epoxy resin and / or phenoxy resin (A), azobisisobutyronitrile, t- It can be carried out by heating to 80 to 130 ° C. in the presence of a free radical generator such as butyl peroxybenzoate, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide. In order to enhance the grafting efficiency of the carboxylic acid-modified grafted epoxy resin (C), the free radical generator is contained in an amount of 4% by weight or more, preferably 6 to 15% by weight, more preferably 6 to 15% by weight, based on the monomer mixture (B). Is 7-1
It is desirable to use in the range of 2% by weight.

The solid content weight ratio of both the mixture (D) of the aromatic epoxy resin and the phenoxy resin is 40 to 100 /.
60 to 0 is preferable, and if the weight ratio of the phenoxy resin exceeds 60, the dispersibility decreases. Acrylic resin (E) is
It is obtained by copolymerizing the same monomer as the monomer mixture (B). The copolymerization is carried out in the presence of a free radical generator such as azobisisobutyronitrile, t-butylperoxybenzoate, benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide,
It can be performed by heating to 80 to 130 ° C. The acrylic resin (E) has an acid value of 100 to 500, preferably 20.
It is preferably adjusted to 0 to 320. Acid value is 100
When it is less than the above range, the water solubility or water dispersibility of the composite resin (F) obtained after the reaction with the grafted epoxy resin (C) and / or the aromatic epoxy resin or the mixture thereof (D) with the phenoxy resin is poor. Further, when the acid value exceeds 500, coating film characteristics (particularly hot water resistance) are deteriorated. In addition, the product tends to gel during the reaction. The number average molecular weight of the acrylic resin (E) is 3,000 to 12,000 and 4,000 to 1
1,000 is more preferable. Number average molecular weight of 3,000
If it is less than 1, the water resistance of the coating film, processability and solvent resistance are poor, and 1
When it exceeds 2,000, the viscosity of the final product becomes high, which is not preferable.

Aromatic epoxy resin and / or phenoxy resin (A): monomer mixture (B) constituting the composite resin (F) has a solid content weight ratio of 10 to 95: 5 to 90, preferably 30 to 90. : 10 to 70, more preferably 50 to 8
It is 5:15 to 50, and when the use ratio of the aromatic epoxy resin and / or the phenoxy resin (A) exceeds 95, the solvent resistance and the flavor property of the coating film are poor, and when it is less than 10, the viscosity of the aqueous resin composition is low. Tends to be high. If the use ratio of the monomer mixture (B) exceeds 90, the solvent resistance and flavor of the coating film are poor, and if it is less than 5, the dispersibility of the aqueous resin composition is poor. Carboxylic acid modified grafted epoxy resin (C = A
+ B): Aromatic epoxy resin or a mixture thereof and a phenoxy resin (D): acrylic resin (E), the solid content weight ratio is 10 to 80:10 to 80: 5 to 70, preferably 30 to 70:20. To 60:10 to 50, and more preferably 40 to 60:30 to 50:10 to 30, and an aromatic epoxy resin or a mixture thereof (D) with a phenoxy resin.
If the use ratio exceeds 80, the dispersibility of the aqueous resin composition is poor, and if it is less than 10, the solvent resistance and flavor of the coating film are poor. If the usage ratio of the acrylic resin (E) exceeds 70,
The viscosity of the aqueous resin composition tends to increase, and if it is less than 5, the solvent resistance and flavor of the coating film are poor.

A mixture of a carboxylic acid-modified grafted epoxy resin (C) and an aromatic epoxy resin or a mixture thereof (D) with an acrylic resin (E).
Can be partially bound by using no catalyst or a base such as amine as a catalyst. When performing without catalyst,
It can be carried out by keeping the temperature in an organic solvent at 100 to 150 ° C. for 1 to 20 hours. When using a base such as an amine as a catalyst, the reaction can be carried out by keeping the temperature at 50 to 100 ° C. for 10 minutes to 3 hours in an organic solvent or an aqueous solvent prepared by adding water to the organic solvent. The solid acid value of the obtained composite resin (F) is 15 to 50.

The phenolic resin (G) used in the present invention is a resol obtained by reacting phenol, phenol having an alkyl substituent having 1 to 12 carbon atoms or bisphenol A, F, B or the like with formaldehyde with an alkali catalyst. Type phenolic resin or a novolac type phenolic resin obtained by reacting an acid catalyst. Further, as the amino resin (G), a melamine resin such as a partially or completely methylated melamine resin, a partially or completely butylated melamine resin; a partially or fully methylated benzoguanamine resin, a partially or completely methylated butylated benzoguanamine resin or the like benzoguanamine resin A urea resin such as a partially or fully methylated urea resin. The phenol resin and / or amino resin (G) in the present invention can be added before the composite resin (F) is dispersed or dissolved in water, or can be added after the dispersion or dissolution in water.

Phenolic resin and / or amino resin (G), aromatic epoxy resin and / or phenoxy resin (A), carboxylic acid modified grafted epoxy resin (C), aromatic epoxy resin or phenoxy resin (D) And the precondensation with at least one selected from the acrylic resin (E) is preferably 50 in a hydrophilic solvent.
It can be performed by reacting at 10 to 150 ° C. for 10 minutes to 3 hours. The amount of phenol resin and / or amino resin (G) in the final aqueous resin composition is 1 to 40% by weight, preferably 1 to 20% by weight, more preferably 2 to 40% by weight based on the solid content of the aqueous resin composition. It is 10% by weight, and if it is less than 1% by weight, the contribution to the curing rate of the coating film is insufficient, and if it exceeds 40% by weight, physical properties such as processability and flavor property of the coating film tend to be deteriorated.

In the present invention, in order to produce an aqueous resin composition, 40% to 130% of the acid groups of the composite resin (F) are used.
It may be dispersed or dissolved in an aqueous medium to which ammonia or amine necessary for neutralizing the is added. Examples of the amine include monopropylamine, monobutylamine, diethylamine, dibutylamine, triethylamine, tributylamine, monoethanolamine, ethylaminomonoethanol, dimethylaminoethanol, 2-amino-2-methyl-1-propanol, cyclohexylamine, Primary, secondary or tertiary amines such as morpholine, piperidine can be used. If the neutralization rate is less than 40%, the water dispersibility or water solubility tends to be poor.
If it exceeds%, the viscosity becomes too high.

In the production of the aqueous resin composition of the present invention,
Aromatic epoxy resin and / or phenoxy resin (A),
Dissolving a carboxylic acid-modified grafted epoxy resin (C), an aromatic epoxy resin or a phenoxy resin (D), an acrylic resin (E), a composite resin (F), a phenol resin and / or an amino resin (G). An organic solvent that can be used can be used. Usually, examples of the solvent that can be used include alcohols such as isopropanol, methanol, ethanol, 2-ethylhexanol and cyclohexanol; methyl cellosolve, ethyl cellosolve,
Ether alcohols such as butyl cellosolve; glycols such as ethylene glycol and diethylene glycol;
Diglycols such as methyl carbitol, ethyl carbitol and butyl carbitol; ketones such as methyl ethyl ketone, isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; other diacetone alcohol, 3-methoxy-3- Methylbutane-1-
All can be used. However, it is preferable that the amount of these organic solvents is as small as possible within a range that does not hinder the handling work. If necessary, the solvent may be removed from the aqueous resin composition under normal pressure or reduced pressure. The final organic solvent content of the aqueous resin composition is preferably 20% by weight or less.

Further, a catalyst such as an inorganic acid such as hydrochloric acid or phosphoric acid, an organic acid such as paratoluenesulfonic acid or the like may be added to the aqueous resin composition of the present invention. The amount used is preferably 1 part by weight or less based on 100 parts by weight of the solid content of the aqueous resin composition. The aqueous resin composition of the present invention is a pigment depending on the purpose,
A rust preventive agent, other water-soluble resin, an additive, etc. may be blended to be used as a water-based coating composition such as a rust-preventive primer or rust-preventive paint, or a water-based printing ink.

The aqueous resin composition of the present invention is a plated steel plate obtained by plating a metal such as a steel plate, an aluminum plate or a steel plate with a single or multiple metals such as zinc, tin, chromium, nickel and aluminum, or these. It is useful for coating the surface of which is chemically or electrolytically treated with chromic acid, phosphoric acid or the like, and further to a substrate such as paper or wood. As the coating method, spray coating, roll coater coating,
Known methods such as electrodeposition coating, dip coating and brush coating can be adopted. As the curing conditions, it is possible to dry at room temperature, but
Forced drying in the temperature range of 0 to 350 ° C. for 10 seconds to 30 minutes is preferable.

[0024]

The present invention will be specifically described with reference to the following examples.

Synthesis Example 1. Synthesis of acrylic resin (E) A flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet is charged with 35 parts by weight of butyl cellosolve and 20 parts by weight of n-butanol, and heated to 130 ° C. At the same temperature, a monomer mixture liquid consisting of 28 parts by weight of styrene, 26 parts by weight of 2-hydroxyethyl acrylate, 46 parts by weight of methacrylic acid and 0.6 part by weight of t-butylperoxybenzoate was added to the flask over 3 hours. Was gradually added dropwise. Then, 5 parts by weight of butyl cellosolve and 23 parts by weight of n-butanol were added dropwise over 20 minutes and then kept warm for 2 hours to obtain an acrylic resin solution having a solid content of 55%, a solid acid value of 300, and a number average molecular weight of 9,700. It was

Synthesis Example 2. Synthesis of Acrylic Resin (E) Except that 32 parts by weight of styrene, 30 parts by weight of ethyl acrylate, 38 parts by weight of methacrylic acid and 0.6 part by weight of t-butylperoxybenzoate were used as the monomer mixture liquid (B). Was synthesized in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution having a solid content of 55%, a solid content acid value of 250, and a number average molecular weight of 9,500.

Synthesis Example 3. Synthesis of acrylic resin (E) As a monomer mixture, 10.0 parts by weight of styrene, 28.5 parts by weight of ethyl acrylate, 61.5 parts by weight of methacrylic acid and 0.6 part by weight of t-butylperoxybenzoate. Except that the same procedure as in Synthesis Example 1 was conducted except that the solid content was 5
An acrylic resin solution having a solid content of 5%, an acid value of 400, and a number average molecular weight of 10,500 was obtained.

Synthesis Example 4. Synthesis of acrylic resin (E) As a monomer mixture, 42.4 parts by weight of styrene, 42.3 parts by weight of ethyl acrylate, 15.3 parts by weight of methacrylic acid and 0.6 part by weight of t-butylperoxybenzoate. Except that the same procedure as in Synthesis Example 1 was conducted except that the solid content was 5
An acrylic resin solution having a solid content of 5%, an acid value of 100, and a number average molecular weight of 7,500 was obtained.

Synthesis Example 5. Synthesis of aromatic epoxy resin (A) In a flask equipped with a stirrer, a reflux condenser, a thermometer, an inert gas inlet, 500 parts by weight of Epicoat 1007 (epoxy resin manufactured by Shell Chemical Co., Ltd.), 7.6 parts by weight of adipic acid. Department,
1 part by weight of tri (n-butyl) amine and 338 parts by weight of cellosolve acetate were charged and reacted at 120 ° C. for 5 hours to obtain an epoxy resin solution having a solid content of 60% and a solid acid value of 0.2.

Synthesis Example 6. Synthesis of Phenolic Resin (G) 94 parts by weight of carboxylic acid, 37% formalin 28 in a flask equipped with a stirrer, reflux condenser, thermometer, and inert gas inlet.
0 parts by weight and 48 parts by weight of a 25% aqueous sodium hydroxide solution were charged and reacted at 50 ° C. for 2 hours. This was neutralized with hydrochloric acid and then extracted with a mixed solvent of ethyl acetate / n-butanol = 1/1 to obtain a resol type phenol resin solution having a solid content of 80%.

Synthesis Example 7. Synthesis of Phenolic Resin (G) The same formulation as in Synthesis Example 6 was used, the same reaction was performed, 80 parts by weight of allyl chloride was added, and the mixture was reacted at the same temperature for 1 hour, treated in the same manner as in Synthesis Example 6, and solidified. An allylated resol type phenolic resin solution having a content of 80% was obtained.

Synthesis Example 8.9.10.11.12.13.
Synthesis of acrylic resin (E) An acrylic resin solution was obtained in the same manner as in Synthesis Example 1, except that the composition of the monomer mixture (B) was as shown in Table 1. The solid acid value and the number average molecular weight of each are also shown in Table 1.

[0033]

[Table 1]

Synthesis Example 14.15.16.17. Synthesis of acrylic resin (E) An acrylic resin solution was obtained in the same manner as in Synthesis Example 1 except that the amount of t-butylperoxybenzoate shown in Table 2 was used. The number average molecular weight of each is also shown in Table 2.

[0035]

[Table 2]

Example 1. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin manufactured by Toto Kasei Co., Ltd.) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide. The monomer mixed solution (B) consisting of 10 parts was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, 5 parts by weight of butyl cellosolve, n-butanol 23
A mixed solution of 1 part by weight and 0.7 part by weight of benzoyl peroxide was added dropwise over 20 minutes and the temperature was kept for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). Then, 135 parts by weight of Epicoat 1010 (D) (Aromatic epoxy resin manufactured by Shell Chemical Co., Ltd.) was added to the flask and dissolved, and then the acrylic resin (E) solution 128 obtained in Synthesis Example 1 was added.
Add a mixed solution of 40 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water, and add 1 part at 80 to 85 ° C.
The mixture was stirred for reaction to obtain a composite resin (F). The solid acid value of this composite resin was 31. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 15
It was 00 cps (B-type viscometer 6 rpm). This is applied to one side and both sides of a 0.30 mm thick aluminum plate with a bar coater so that the dry coating amount is 120 mg / dm ² .
Both were baked at 250 ° C. for 30 seconds. The stability of the aqueous resin composition, the surface of the coating film on one-sided coated plate, the workability, the corrosion resistance, the retort resistance, and the MEK extraction rate were evaluated, and the flavor property on the two-sided coated plate was evaluated by the following test methods. The results are shown in Table 3.

Stability of Aqueous Resin Composition: Diluted with 10 times amount of deionized water and allowed to stand at 25 ° C. for 24 hours, and then it was observed whether or not there was sedimentation. ◯: No sedimentation Δ: Slight sedimentation X: Significant sedimentation Coating film test method Waki: The appearance of wrinkles was visually observed. ○: No cracking △: Slight cracking ×: Significant cracking Machining resistance: Two aluminum plates of the same thickness were used as test pieces.
Insert the sheets and tighten with a vise. The degree of cracking of the processed portion was judged with a 50 times magnifying glass. ○: No cracks △: Some cracks ×: Significant cracks

Corrosion resistance: A test piece whose back surface was sealed with a polyester tape was immersed in boiling 3% saline for 1 hour to determine the degree of corrosion of the coated surface. ○: No corrosion △: Slight corrosion ×: Significant corrosion Retort resistance: Ion-exchanged water was put into the autoclave, the test piece was dipped and treated at 125 ° C for 30 minutes to judge the degree of whitening of the coating film. did. ○: No whitening △: Slight whitening ×: Significant whitening

MEK extraction rate: The test piece was immersed in boiling methyl ethyl ketone for 1 hour, and the weight loss of the coating film was measured. When the MEK extraction rate was 30% or more, the degree of crosslinking was insufficient. Flavorability: A 10 cm × 10 cm test piece was placed in a clean pressure-resistant glass bottle, 200 ml of ion-exchanged distilled water was added, and sterilization treatment was performed at 100 ° C. for 30 minutes, and then 5
The content solution stored at 0 ° C. for 6 months was compared with the content solution prepared in the same manner without the test piece. ○: There is no difference △: There is a slight difference ×: There is a considerable difference

[0040]

[Table 3]

Example 2. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 22 parts by weight of butyl cellosolve, 56 parts by weight of n-butanol and 50 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 18.6 parts by weight of styrene, 14.3 parts by weight of ethyl acrylate, 1 part of acrylic acid
A monomer mixed solution (B) composed of 7.2 parts by weight and 3.8 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.64 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was maintained for another 2 hours to carry out carboxylic acid-modified grafting. An epoxy resin (C) was obtained. Thereafter, 350 parts by weight of Epicoat 1010 (D) (epoxy resin described above) was added into the flask and dissolved, and then 91 parts by weight of the acrylic resin solution (E) obtained in Synthesis Example 1, 30 parts by weight of dimethylethanolamine, and desorption. A mixed solution of 40 parts by weight of deionized water was added, and the mixture was stirred and reacted at 80 to 85 ° C for 1 hour to obtain a composite resin (F). The acid value of the solid content of this resin was 20.
Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 2500 cps (B type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.

Example 3. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 155 parts by weight of butyl cellosolve, 388 parts by weight of n-butanol and 400 Phenototo YP-50 (A) (phenoxy resin described above) were added.
Part by weight was charged and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 15.2 parts by weight of styrene, 14.3 parts by weight of ethyl acrylate, 20.6 parts by weight of methacrylic acid and 3.8 parts by weight of benzoyl peroxide were added. The monomer mixed solution (B) consisting of 10 parts was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.63 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was kept for 2 hours for grafting with carboxylic acid modification. An epoxy resin (C) was obtained. Then, 50 parts by weight of Epicoat 1010 (D) (epoxy resin) was added to the flask and dissolved, then 91 parts by weight of the acrylic resin solution (E) obtained in Synthesis Example 1, 30 parts by weight of dimethylethanolamine, and A mixed solution of 40 parts by weight of deionized water was added, and the mixture was stirred and reacted at 80 to 85 ° C for 1 hour to obtain a composite resin (F). The acid value of the solid content of this resin was 25.
Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 1100 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.

Example 4. Phenothote YP-50 (A)
Epoxy resin (A) of Synthesis Example 5 instead of 203 parts by weight
The procedure of Example 1 was repeated, except that 338 parts by weight of the solution and 154 parts by weight of the acrylic resin (E) solution of Synthesis Example 2 were used instead of 128 parts by weight of the acrylic resin solution (E) of Synthesis Example 1. An aqueous resin composition having a solid content of 35% and a viscosity of 2100 cps (B type viscometer 6 rpm) was obtained. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.

Example 5. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and 203 parts by weight of Phenothote YP-50S (A) (phenoxy resin manufactured by Toto Kasei Co., Ltd.) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide. The monomer mixed solution (B) consisting of 10 parts was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, 5 parts by weight of butyl cellosolve, n-butanol 23
A mixed solution of 1 part by weight and 0.7 part by weight of benzoyl peroxide was added dropwise over 20 minutes and the temperature was kept for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). After that, Epicoat 1007 (D) (epoxy resin described above) 1
After adding 35 parts by weight into the flask and dissolving, 50 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 4, 3 parts by weight of dimethylethanolamine, and 21 parts by weight of deionized water were added. Then, the mixture was stirred at 80 to 85 ° C. for 1 hour for reaction. Furthermore, 84 parts by weight of the acrylic resin (E) solution previously obtained in Synthesis Example 3 and dimethylethanolamine 37
A mixed solution of 20 parts by weight of deionized water and 20 parts by weight of deionized water is prepared,
The whole amount was added. Then, it stirred at 80-85 degreeC for 1 hour, and was made to react, and the composite resin (F) was obtained. The solid acid value of this resin was 36. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 800 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.

Example 6. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, 100 parts by weight of Phenothote YP-50S (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). ) 100 parts by weight were charged and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide. The monomer mixed solution (B) consisting of 10 parts was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, 5 parts by weight of butyl cellosolve, n-butanol 23
A mixed solution of 1 part by weight and 0.7 part by weight of benzoyl peroxide was added dropwise over 20 minutes and the temperature was kept for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). Then, Epicoat 1010 (D) (epoxy resin described above) 1
35 parts by weight and 10 parts by weight of Phenothote YP-50 (D) (phenoxy resin described above) were added to the flask and dissolved, and then 128 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 1 and dimethylethanolamine. A mixture of 36 parts by weight and 40 parts by weight of deionized water was added. Then 80-8
The mixture was stirred at 5 ° C. for 1 hour and reacted to obtain a composite resin (F).
The solid acid value of this resin was 18. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes,
A white aqueous dispersion was obtained. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 1600 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the test results of coating film physical properties.
Shown in.

Example 7. To 500 parts by weight of the aqueous resin composition obtained in Example 1, 15 parts by weight of the phenol resin (G) of Synthesis Example 6 was gradually added while stirring with a disper to obtain an aqueous resin composition containing a phenol resin. This is Example 1
A coating film was prepared by the same method as described above, and the physical properties of the coating film were tested. The test results are shown in Table 3.

Example 8. To 500 parts by weight of the aqueous resin composition obtained in Example 2, 10 parts by weight of the phenol resin of Synthesis Example 7 and Cymel 303 were stirred with a disper.
(G) (Mitsui Cyanamide Co., Ltd., melamine resin) 5 parts by weight was gradually added to obtain an aqueous resin composition containing a phenol resin and a melamine resin. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the test results
Shown in.

Example 9. To 500 parts by weight of the aqueous resin composition obtained in Example 3, 10 parts by weight of Cymel 303 (G) (previously described melamine resin) was gradually added while stirring with a disper to obtain an aqueous resin composition containing a melamine resin. It was A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.

Example 10. 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, PKH in a flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet.
H (A) (Phenoxy resin manufactured by Union Carbide)
122 parts by weight and 81 parts by weight of Epicoat 1010 (A) (epoxy resin) were charged, heated to 130 ° C. and completely dissolved, and then cooled to 120 ° C., and 15 parts by weight of the phenolic resin (G) of Synthesis Example 6. Was charged and stirred for 2 hours at the same temperature. By the molecular weight measurement by GPC, it was confirmed that the phenol resin was precondensed with the phenoxy resin and / or the epoxy resin. The temperature was further lowered to 100 ° C., and 16.6 parts by weight of styrene and 15.7 of ethyl acrylate were added.
Part by weight, monomer mixture solution (B) consisting of 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide
Was gradually added dropwise to the flask over 3 hours. 3 at the same temperature
After keeping the temperature for 0 minutes, a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was kept for 2 hours, and the carboxylic acid-modified grafted epoxy resin ( C) was obtained. Then, 135 parts by weight of Epicoat 1010 (D) (epoxy resin described above) was added into the flask and dissolved, and then 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1, 36 parts by weight of dimethylethanolamine and deionized. A mixture of 40 parts by weight of water was added. Then, it stirred at 80-85 degreeC for 1 hour, and was made to react, and the composite resin (F) was obtained. The acid value of the solid content of this resin was 20. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 1800 cps
(B type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.

Example 11. 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and Phenothote YP-50 (A) (phenoxy resin described above) were placed in a flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet.
3 parts by weight were charged and heated. After the temperature was raised to 130 ° C and it was completely dissolved, the temperature was lowered to 100 ° C.
The monomer mixed solution (B) consisting of 1 part by weight, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After keeping the same temperature for 30 minutes, 2 parts by weight of a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of butanol and 0.7 parts by weight of benzoyl peroxide was added.
The mixture was added dropwise over 0 minutes and kept warm for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). Meanwhile, another stirrer,
In a flask equipped with a reflux condenser, a thermometer, and an inert gas inlet, 50 parts by weight of methyl ethyl ketone and 4 parts of n-butanol.
Charge 0 parts by weight and 135 parts by weight of Epototo YD-20H (D) (Epoxy resin manufactured by Tohto Kasei Co., Ltd.), and 130 ° C.
The temperature was raised to 120 ° C. and the temperature was lowered to 120 ° C.
15 parts by weight of the phenol resin (G) was added and stirred at the same temperature for 2 hours. By the molecular weight measurement by GPC, it was confirmed that the phenol resin was precondensed with the epoxy resin. The total amount of this, 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1, and dimethylethanolamine 3
A mixture of 6 parts by weight and 40 parts by weight of deionized water was added to the flask. Then, it stirred at 80-85 degreeC for 1 hour, and was made to react, and composite resin (F) was obtained. The acid value of the solid content of this resin was 32. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion.
The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 1400 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.

Example 12 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and PK in a flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet.
203 parts by weight of HH (A) (phenoxy resin described above) were charged and heated. After heating up to 130 ℃ and completely dissolving, 10
The temperature was lowered to 0 ° C., and a monomer mixed solution (B) containing 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide was added. Was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was further maintained for 2 hours for grafting with carboxylic acid. An epoxy resin (C) was obtained. After that, Epototo YD-20
Charge 135 parts by weight of H (D) (epoxy resin),
The temperature is raised to 130 ° C. and completely dissolved. On the other hand, 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1 and Cymel 303 (G) (the above-mentioned melamine resin) were placed in a flask equipped with another stirrer, a reflux condenser, a thermometer, and an inert gas inlet. ) 1
Add 0 parts by weight and stir at 100 ° C. for 1 hour. It was confirmed by the molecular weight measurement by GPC that the melamine resin (G) was precondensed with the acrylic resin (E).
The total amount of this and 1 part by weight of dimethylethanolamine were added. Then, it stirred at 100 degreeC for 1 hour, and was made to react, and the composite resin (F) was obtained. The solid acid value of this resin was 31. Then, a mixed solution of 950 parts by weight of deionized water and 35 parts by weight of dimethylethanolamine was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. At this time, the viscosity was 870 cps (B type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.

Example 13. A flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, and 203 parts by weight of Epicoat 1010 (A) (epoxy resin). After the temperature was raised to ℃ and completely dissolved, 100
The temperature was lowered to ℃, and a monomer mixture solution (B) consisting of 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide was added. It was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, butyl cellosolve 5
By weight, a mixed solution of 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the mixture was kept warm for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). After that, Epototo YD-20
135 parts by weight of H (D) (epoxy resin) was added to the flask and dissolved, and then 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1 was added. Then, at 130 ℃ 2
The mixture was stirred and reacted for 0 hour to obtain a composite resin (F). The acid value of the solid content of this resin was 24. Then, a mixed solution of 36 parts by weight of dimethylethanolamine and 990 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 800 cps (B
Type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.

Example 14 A flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet was charged with 11 parts by weight of butyl cellosolve, 28 parts by weight of n-butanol, and 25 parts by weight of Phenothote YP-50 (A) (phenoxy resin). Charged and heated. After the temperature was raised to 130 ° C and completely dissolved, the temperature was lowered to 100 ° C, and 7.5 parts by weight of styrene, 7 parts by weight of ethyl acrylate and 10.5 of methacrylic acid were added.
The monomer mixed solution (B) consisting of 1 part by weight and 1.9 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.32 part by weight of benzoyl peroxide was added dropwise over 20 minutes, and the mixture was further maintained for 2 hours and grafted with carboxylic acid. An epoxy resin (C) was obtained. Then Epicote 10
After adding 350 parts by weight of 10 (epoxy resin) to the flask and dissolving, 182 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 1, 38 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water were added. Add the mixture, 80-8
The mixture was stirred at 5 ° C. for 1 hour and reacted to obtain a composite resin (F). The acid value of the solid content of this resin was 27. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 9
It was 50 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested.
The test results are shown in Table 3.

Example 15. In a flask equipped with a stirrer, a reflux condenser, a thermometer, and an inert gas inlet, 155 parts by weight of butyl cellosolve, 390 parts by weight of n-butanol and Phenothote YP-50 (A) (phenoxy resin described above) 3
50 parts by weight were charged and heated. After the temperature was raised to 130 ° C and completely dissolved, the temperature was lowered to 100 ° C.
The monomer mixed solution (B) consisting of 1 part by weight and 7.6 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 1.3 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was kept for 2 hours for grafting with carboxylic acid. An epoxy resin (C) was obtained. After that, Epicote 101
25 parts by weight of 0 (epoxy resin described above) was added to the flask and dissolved, and then the acrylic resin (E) solution 4 obtained in Synthesis Example 1
A mixed liquid of 5 parts by weight, 35 parts by weight of dimethylethanolamine and 23.5 parts by weight of deionized water was added to 80-85.
The mixture was stirred at 0 ° C. for 1 hour and reacted to obtain a composite resin (F). The solid content acid value of this resin was 49. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 95
It was 0 cps (B-type viscometer 6 rpm). This is Example 1
A coating film was prepared by the same method as described above, and the physical properties of the coating film were tested. The test results are shown in Table 3.

Comparative Example 1. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 150 parts by weight of butyl cellosolve, 375 parts by weight of n-butanol, 135 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). ) 203 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C., to which 25.5 parts by weight of styrene, 24.1 parts by weight of ethyl acrylate, 34.9 parts by weight of methacrylic acid and A monomer mixed solution (B) consisting of 6.5 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After incubating at the same temperature for 30 minutes, a mixed solution consisting of 7.9 parts by weight of butyl cellosolve, 36.1 parts by weight of n-butanol and 1.1 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the mixture was heated for an additional 2 hours, and then heated for 2 hours. An acid-modified grafted epoxy resin (C) was obtained. A mixed solution of 23.5 parts by weight of dimethylaminoethanol and 950 parts by weight of deionized water was gradually added dropwise thereto over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time was 600 cps (B-type viscometer 6 rpm). A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. The test results are shown in Table 3.

Comparative Example 2. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, 200 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). )
150 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C.
A monomer mixed solution (B) consisting of 1.3 parts by weight and 7.6 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After keeping the same temperature for 30 minutes, 2 parts by weight of a mixed solution of 9 parts by weight of butyl cellosolve, 42 parts by weight of n-butanol and 1.3 parts by weight of benzoyl peroxide was added.
The mixture was added dropwise over 0 minutes and kept warm for 2 hours to obtain an acrylic grafted epoxy resin (C). Then, a mixed solution of 45.5 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 1, 35 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water was added, and the mixture was stirred at 80 to 85 ° C. for 1 hour. The reaction was carried out to obtain a composite resin (F). The acid value of the solid content of this resin was 40. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes to obtain a white aqueous dispersion. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is 1100 cps (B type viscometer 6 rpm
)Met. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 3 shows the stability of the aqueous resin composition and the results of the coating film physical property test.

Comparative Example 3. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 150 parts by weight of butyl cellosolve, 375 parts by weight of n-butanol, 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). ) 135 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C., to which 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and A monomer mixed solution (B) consisting of 4.2 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After being kept at the same temperature for 30 minutes, a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and the temperature was kept for 2 hours, and the acrylic grafted epoxy resin was added. (C) was obtained. Then, a mixed solution of 128 parts by weight of the acrylic resin (E) solution obtained in Synthesis Example 1, 36 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water was added, and the mixture was stirred at 80 to 85 ° C. for 1 hour to react. A composite resin (F) was obtained. The acid value of the solid content of this resin was 32. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes, but a stable aqueous dispersion could not be obtained.

Comparative Example 4. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol and PKHH
(A) 203 parts by weight of the above-mentioned phenoxy resin were charged,
After heating up to 130 ℃ and completely dissolving, cool down to 100 ℃,
A mixed solution of 96 parts by weight of the acrylic resin (E) obtained in Synthesis Example 3, 22 parts by weight of dimethylethanolamine and 40 parts by weight of deionized water was added. Then, the mixture was stirred at 80 to 85 ° C. for 3 hours for reaction. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes, but a stable aqueous dispersion could not be obtained.

Comparative Example 5. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). )
135 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C., 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1 and dimethylethanolamine 21.
A mixture of parts by weight and 40 parts by weight of deionized water was added. Then, it stirred at 80-85 degreeC for 3 hours, and was made to react, and the composite resin (F) was obtained. The acid value of this resin was 23. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes, but a stable aqueous dispersion could not be obtained.

Comparative Example 6. Stirrer, reflux condenser, thermometer,
In a flask equipped with an inert gas inlet, 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol, 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and Epicoat 1010 (A) (epoxy resin described above). )
135 parts by weight were charged, the temperature was raised to 130 ° C. and completely dissolved, and then the temperature was lowered to 100 ° C., 128 parts by weight of the acrylic resin (E) obtained in Synthesis Example 1 and dimethylethanolamine 21.
A mixture of parts by weight and 40 parts by weight of deionized water was added. Then, the mixture was stirred at 80 to 85 ° C. for 1 hour for reaction. Thereafter, a monomer mixed solution (B) consisting of 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate, 22.7 parts by weight of methacrylic acid and 4.2 parts by weight of benzoyl peroxide was added thereto over 3 hours. Slowly dropped into the flask. After incubating at the same temperature for 30 minutes, 5 parts by weight of butyl cellosolve,
A mixed solution of 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added dropwise over 20 minutes, and further 2
I kept it warm for an hour. Although 950 parts by weight of deionized water was gradually added dropwise thereto over 1 hour and 30 minutes, a stable aqueous dispersion could not be obtained.

Comparative Example 7. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol and 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate and 2 parts of methacrylic acid were added.
A monomer mixed solution (B) consisting of 2.7 parts by weight and 4.2 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After being kept at the same temperature for 30 minutes, 2 parts by weight of a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added.
The mixture was added dropwise over 0 minutes and kept warm for 2 hours to obtain a carboxylic acid-modified grafted epoxy resin (C). Then, 135 parts by weight of Phenototo YP-50 (D) (phenoxy resin described above) was added to the flask and dissolved, and then 128 parts by weight of the acrylic resin solution (E) obtained in Synthesis Example 1 and 21 parts by weight of dimethylethanolamine. And 40 parts by weight of deionized water was added. Then, the mixture was stirred at 80 to 85 ° C. for 1 hour for reaction. Then, 950 parts by weight of deionized water was gradually added dropwise over 1 hour and 30 minutes, but a stable aqueous dispersion could not be obtained.

Comparative Example 8. Stirrer, reflux condenser, thermometer,
A flask equipped with an inert gas inlet was charged with 90 parts by weight of butyl cellosolve, 225 parts by weight of n-butanol and 203 parts by weight of Phenothote YP-50 (A) (phenoxy resin described above) and heated. After the temperature was raised to 130 ° C. and completely dissolved, the temperature was lowered to 100 ° C., and 16.6 parts by weight of styrene, 15.7 parts by weight of ethyl acrylate and 2 parts of methacrylic acid were added.
A monomer mixed solution (B) consisting of 2.7 parts by weight and 1.9 parts by weight of benzoyl peroxide was gradually added dropwise to the flask over 3 hours. After being kept at the same temperature for 30 minutes, 2 parts by weight of a mixed solution of 5 parts by weight of butyl cellosolve, 23 parts by weight of n-butanol and 0.7 parts by weight of benzoyl peroxide was added.
The mixture was added dropwise over 0 minutes and kept warm for 2 hours. Thereafter, 135 parts by weight of Epicoat 1010 (D) (epoxy resin) was added to the flask, and after dissolution, 128 parts by weight of the acrylic resin solution (E) obtained in Synthesis Example 1, 21 parts by weight of dimethylethanolamine, and A mixture of 40 parts by weight of deionized water was added. Then, it stirred at 80-85 degreeC for 1 hour, and was made to react, and the composite resin (F) was obtained. The acid value of the solid content of this resin was 21. Then, 950 parts by weight of deionized water is used for 1 hour 30
Although the solution was gradually added dropwise over a period of time, a stable aqueous dispersion could not be obtained.

Example 16.17.18.19.20. And comparative example 9.10. A white aqueous dispersion was obtained in the same manner as in Example 1 except that the monomer mixture (B) had the composition shown in Table 4. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is shown in Table 4. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 4 shows the stability of the aqueous resin composition and the test results of coating film physical properties.

[0064]

[Table 4]

Example 21.22.23.24.25.2
6. And Comparative Example 11. A white aqueous dispersion was obtained in the same manner as in Example 1 except that the amount of benzoyl peroxide added dropwise together with the monomer mixture (B) was changed to the amount shown in Table 5. The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is shown in Table 5. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 5 shows the stability of the aqueous resin composition and the test results of the coating film physical properties.

[0066]

[Table 5]

Example 27.28.29.30. And comparative example 12.13. A white water dispersion was obtained in the same manner as in Example 1 except that the acrylic resin (E) solution shown in Table 6 was used as the acrylic resin (E). The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is shown in Table 6. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 6 shows the stability of the aqueous resin composition and the results of the coating film physical property test.

[0068]

[Table 6]

Example 31.2.32.33.34. A white aqueous dispersion was obtained in the same manner as in Example 1 except that the acrylic resin (E) solution shown in Table 2 was used as the acrylic resin (E). The excess solvent was distilled off under reduced pressure so that the solid content was 35%. The viscosity at this time is shown in Table 7. A coating film was prepared from this by the same method as in Example 1, and the physical properties of the coating film were tested. Table 7 shows the stability and coating film physical property test of the aqueous resin composition.

[0070]

[Table 7]

[0071]

EFFECT OF THE INVENTION The aqueous resin composition of the present invention is excellent in stability, the surface of the coating film is smooth without cracking, and the cured coating film has hot water resistance, processability, corrosion resistance, solvent resistance, and flavor. It has excellent properties.

Claims (8)

[Claims] 1. An acid value of 100 to 50 comprising an ethylenically unsaturated aliphatic carboxylic acid and an unsaturated monomer copolymerizable therewith in an aromatic epoxy resin and / or phenoxy resin (A).
A carboxyl group-containing acrylic resin having an acid value of 100 to 500 is added to a mixture of a carboxylic acid-modified grafted epoxy resin (C) obtained by graft-polymerizing a monomer mixture (B) of 0 and an aromatic epoxy resin (D). A water-based resin composition in which a composite resin (F) in which (E) is partially bound is dispersed or dissolved in water. 2. The aqueous resin composition according to claim 1, wherein the aromatic epoxy resin (D) is a mixture of an aromatic epoxy resin and a phenoxy resin. 3. The aqueous resin / fat composition according to claim 1, further comprising a phenol resin and / or an amino resin (G). 4. The phenol resin and / or amino resin (G) is an aromatic epoxy resin and / or a phenoxy resin (A), a grafted epoxy resin (C), an aromatic epoxy resin (D) and an acrylic resin ( The aqueous resin composition according to claim 3, which is pre-condensed with at least one selected from E). 5. An aromatic epoxy resin and / or phenoxy resin (A) having an acid value of 100 to 100, which is composed of an ethylenically unsaturated aliphatic carboxylic acid and an unsaturated monomer copolymerizable therewith.
Graft-polymerize 500 monomer mixture (B) to obtain carboxylic acid-modified grafted epoxy resin (C), and mix this carboxylic acid-modified grafted epoxy resin (C) with aromatic epoxy resin (D). Next, the mixture is reacted with a carboxyl group-containing acrylic resin (E) having an acid value of 100 to 500 to obtain a composite resin (F), and the composite resin (F) is dispersed or dissolved in water. And a method for producing an aqueous resin composition. 6. The method for producing an aqueous resin composition according to claim 5, wherein the aromatic epoxy resin (D) is a mixture of an aromatic epoxy resin and a phenoxy resin. 7. The method for producing an aqueous resin composition according to claim 5, wherein the phenol resin and / or amino resin (G) is added before or after the composite resin (F) is dispersed or dissolved in water. 8. A phenol resin and / or an amino resin (G) is an aromatic epoxy resin and / or a phenoxy resin (A), a grafted epoxy resin (C), an aromatic epoxy resin (D) and an acrylic resin ( The method for producing an aqueous resin composition according to claim 7, which is pre-condensed with at least one selected from E).