JPS60215015A - Aqueous resin dispersion - Google Patents

Abstract

PURPOSE:The titled dispersion excellent in storage stability, etc., and capable of forming an excellent film when used as a can interior coating, prepared by dispersing a composite resin composition comprising a specified acrylic resin, an aromatic epoxy resin and a phenolic resin. CONSTITUTION:An acrylic resin (A) of a weight-average MW of 3,000-80,000, obtained by copolymerizing a copolymerizable monomer mixture containing 12- 70wt% monobasic carboxylic acid monomer unit in the presence of a catalyst, is reacted with an aromatic epoxy resin (B) having, on the average, 1.1-2 epoxy groups in the molecule and a number-average MW >=900, and 2-40wt%, based on the total resin weight, phenolic resin (C) in a hydrophilic solvent to obtain a carboxyl group-excess composite resin composition in which component A is combined partially with component B, and component C is precondensed with component A and/or component B. This resin composition is dispersed in an aqueous medium in the presence of NH3 or an amine in such an amount that the pH of the final composition is 4-11 (provided that the ratio between the solids of components A and B is 2:1-1:6).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous resin dispersion, more particularly as a coating composition for baking on metals.

In particular, the present invention relates to an aqueous resin dispersion that can form an excellent film as a paint for the inner surface of a can.

Conventionally, it has been desired to shift paints for single cans and anticorrosion paints to water-based paints from the viewpoints of resource conservation, energy conservation, and environmental pollution. As with the solvent-based type, epoxy resin-based ones have been mainly studied in water-based systems, and various methods have been proposed for dispersing epoxy resins in water.

For example, as a method for dispersing an epoxy resin in water using a surfactant, two methods are known: a method using an anionic surfactant and a method using a nonionic surfactant. However, in the former case, the oxirane ring opens during the emulsification process and storage, resulting in a decrease in reactivity and poor performance of the formed coating, and also causes problems of thickening and gelation during storage. On the other hand, in the latter case, from the viewpoint of bidispersity and storage stability, the system contains a considerably large amount of surfactant, and this surfactant affects the chemical and mechanical properties of the coating film formed. tends to have a negative impact on

As a solution to this problem, various self-emulsifying epoxy resins have been proposed in which epoxy resins are modified with acrylic resins and segments with emulsifying power are introduced into the molecules.

For example, JP-A-53-1228 discloses a grafted polymer obtained by polymerizing a monomer mixture containing a carboxylic acid monomer using a free radical generator such as benzoyl peroxide in the presence of an epoxy resin. It has been shown that epoxy resins can be stably dispersed in aqueous media containing bases. Japanese Patent Publication No. 53-1496
No. 3 and JP-A-55-9433 disclose that a partial reactant containing an excess of carboxyl groups obtained by reacting an acrylic resin with a relatively high molecular weight aromatic epoxy resin is dissolved in an aqueous medium in the presence of ammonia or an amine. It has been shown that it can be stably dispersed in Japanese Patent Application Publication No. 55-3481,
In JP-A-55-3482, a carboxyl group-functional polymer is esterified with an epoxy resin in the presence of an amine esterification catalyst, and a compound substantially free of oxirane groups of the epoxy resin is self-emulsified in water with a base. A self-emulsifying epoxy ester copolymer is disclosed. JP-A-57-105418 and JP-A-58-198513 G.

A basic compound is obtained by polymerizing a monomer mixture containing acrylic acid or methacrylic acid and a low-molecular compound having an epoxy group and an acryloyl group in one molecule, which is obtained by partially reacting an aromatic epoxy resin and (meth)acrylic acid. Disclosed is an aqueous dispersion composition obtained by neutralization with. Since the self-emulsifying epoxy resin obtained by the above technique does not contain a surfactant in the coating material, a strong coating film can be obtained by itself. Water-soluble amino resins and phenolic resins are blended into these paints when faster curing speed is required. For example, an appropriate amount of water-soluble amino resin can improve the curing speed without reducing the physical properties of the formed coating.
Preferred coating hardness can sometimes be obtained by increasing the crosslinking density, especially when used as a coating for the inside of cans.

Low molecular weight compounds caused by the amine resin were eluted into the contents of the can during the heat sterilization process, posing a hygiene problem.

The present inventors have made extensive studies to overcome the above-mentioned problems, and as a result, have arrived at the present invention. That is, the present invention provides an acrylic resin (A) containing 12 to 70% by weight of monobasic carboxylic acid monomer units as an essential component, - having an average of 1.1 (II to 2.0 epoxy groups in the molecule) A carboxyl group-excess composite resin composition containing a resin bond of an aromatic epoxy resin (B) and a phenolic resin (C) is aqueous in the presence of ammonia or amine in an amount such that the final composition has a pH of 4 to 11. In an aqueous resin dispersion formed by dispersing in a medium, an acrylic resin (A
) and the aromatic epoxy resin (B) are at least partially combined, and the phenol resin (C) is combined with the acrylic resin (A
) and/or an aromatic epoxy resin (B).

The aqueous resin dispersion in the present invention is preferably.

- Acrylic resin (A) formed by copolymerizing a copolymerizable monomer mixture containing 12 to 70% by weight of basic carboxylic acid monomers - An aromatic resin having an average of 1.1 to 2.0 epoxy groups in the molecule It is obtained by chemically bonding a group-based epoxy resin (B) and a phenol resin (C).

Acrylic resin (A) is a monomer mixture consisting of monobasic carboxylic acid monomers such as acrylic acid and methacrylic acid and other copolymerizable monomers, such as 7zobisisobutyronitrile and benzoyl peroxide, in an organic solvent. 80°C to 1°C using a conventional radical polymerization initiator
It can be obtained by copolymerization at a temperature of 50°C.

Examples of the copolymerizable monomer include methyl acrylate, ethyl acrylate, and isopropyl acrylate.

n-butyl acrylate, isobutyl acrylate.

n-amyl acrylate, isoamyl acrylate.

Acrylic acid esters such as n-hexyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate.

Methacrylic acid esters such as 2-ethylhexyl methacrylate, decyl methacrylate, and dodecyl methacrylate, styrene, vinyltoluene, 2-methylstyrene, t
- Styrene threads such as butylstyrene and chlorstyrene, hydroxyethyl acrylate, and hydroxypropyl acrylate.

Hydroxy group-containing monomers such as hydroxyethyl methacrylate and hydroxypropyl methacrylate, N-methylol (meth)acrylamide, N-butoxymethyl (
It can be selected from one or more of N-substituted (meth)acrylic monomers such as meth)acrylamide, epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, and acrylonitrile.

The amount of monobasic carboxylic acid monomer used is 12 to 70% by weight based on the total amount of monomers.

If the amount used is less than 12% by weight, the dispersion stability of the resin in an aqueous medium, the adhesion of the painted film to metal and solvent resistance, and the flavor permeability when used for the inside of a can will all deteriorate. Therefore, it is not desirable; on the contrary,
If the amount used is more than 70% by weight, the viscosity of the reaction system becomes extremely high when polymerizing the acrylic resin (A), which not only makes manufacturing difficult, but also reduces the water resistance of the painted film and the inner surface of the can. If used, boiling resistance etc. will deteriorate.

The acrylic resin (A) preferably has a weight average molecular weight in the range of 3.000 to so, ooo.

When the weight average molecular weight is less than 3.000, the crosslinking density of the coating film increases, which impairs processability.

Also, 40.000. In particular, if it is larger than s o or o o o, gelation tends to occur during reaction with the aromatic epoxy resin (B).

Aromatic epoxy resin (B) is obtained by condensing bisphenol A and epihalohydrin in the presence of an alkali catalyst, and has an average of 1 to 2.0 epoxy groups per molecule, Those having a number average molecular weight of 300 or more, preferably 900 or more are used. A commercially available product is Epicoat 828. manufactured by Shell Chemical Co., Ltd. Epicoat) 1001° Epicoat 1004. Ebiko) 1007
．． Examples include Epicote 1009. Further, as an aromatic epoxy resin, dehydrated castor oil and soybean oil fatty acid are added to the epoxy group of the above-mentioned bisphenol A type epoxy resin.

It is also possible to use a modified epoxy resin in which a vegetable oil fatty acid such as coconut oil fatty acid or a modifier such as bisphenol A is reacted.

The phenol resin (C) is obtained by addition condensation of phenols and formaldehyde in the presence of a catalyst, and may be one in which the phenolic hydroxyl group or the alcoholic hydroxyl group is modified with a low molecular weight alcohol. The above catalysts include organic amines such as ammonia, ethylamine, butylamine, jetanolamine, etc., basic compounds such as sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and hydrochloric acid, phosphoric acid, sulfuric acid, and acetic acid. .

There are acidic compounds such as oxalic acid. As a phenol, p-
Bifunctional phenols such as cresol, 0-cresol, p-tertbutylphenol, p-ethylphenol, 2I 3-xylenol, 2,5-xylenol, 1m-cresol carbolic acid, rn-ethylphenol, 3.
Examples include trifunctional phenols such as 5-xylenol and m-methoxyphenol, and tetrafunctional phenols such as bisphenol and bisphenol B.

A particularly preferred phenol resin is a phenol resin (C) whose main component is a relatively low molecular weight phenol resin represented by the following formula.

(In the formula, R+ is a hydrogen atom or a carbon number of 1 to 12
an alkyl group, Rt+'P'a represents a hydrogen atom or a methylol group, and n represents an integer from 1 to 3. ) The above-mentioned relatively low molecular weight phenolic resin is obtained by addition condensation of formaldehyde to alkylphenol in the presence of an alkali catalyst, but it produces alkylphenol dialcohol in high yield at a relatively low temperature of about room temperature to 60°C. After that, a method of proceeding with condensation or other known synthetic means can be used. The reaction conditions for producing such a phenol resin can be freely selected within a range that satisfies the above requirements. Of course, there is no problem even if the phenol resin (C) having a specific n number is reacted under reaction conditions that allow a high yield to be obtained, further purified by a conventional method, and used substantially as a single substance. It is also possible to prepare two or more types of alkylphenols with different types of alkylphenols or with different n numbers, and use them by mixing them.

In the present invention, the acrylic resin-aromatic epoxy resin partial bond (D) contains -basic carboxylic acid monomer 1
An acrylic resin (A) obtained by copolymerizing a copolymerizable upper-layer mixture containing 2 to 70% by weight and an average of 1.
It can be produced by partially reacting with an aromatic epoxy resin (B) having 1 to 2.0 epoxy groups. To prepare the acrylic resin-aromatic epoxy resin partial reactant, in a hydrophilic organic solvent such as ethylene glycol monobutyl ether.

It is preferable to stir the mixture at 60° C. to 170° C. for about 10 minutes to 2 hours in the presence of ammonia or amine as described below. The reaction is controlled by measuring the oxirane percentage,
This can be checked by measuring the viscosity increase or by charting the molecular weight distribution by gel verminion chromatography (GPC).

In addition, when the reaction is carried out in a relatively high boiling point solvent such as hexyl cellosolve, butyl cellosolve, methyl cellosolve acetate, or ethyl cellosolve acetate at 120°C or higher, acrylic resin can be produced even without the coexistence of an esterification catalyst such as ammonia or amine. A partial reaction product of (A) and aromatic epoxy resin (B) can be obtained.

The reaction can also be controlled by measuring the % oxirane. As a method for measuring oxirane%.

A method in which a predetermined amount of tetraethylammonium bromide solution is added to a sample solvent solution, and titrated with standardized perchloric acid using crystal hiolesotho as an indicator. Is the application of the titration method due to the inhibitory effect of the coexisting excess carboxyl groups?

Since the end point of the titration is often unclear, proton N
Quantification by MR is convenient and preferred. In proton NMR, the methylene of the oxirane group is at 2.5 to 2.9 ppm, so we tracked the area of this peak during the 5 reactions and investigated other peaks that serve as standards, such as the proton of the benzene ring contained in the aromatic epoxy resin. The reduction rate of oxirane groups can be estimated by comparing the area of the peak. At this time, if a monomer having a benzene ring is used in the acrylic resin, the amount must be taken into account in the calculation. The reduction rate of oxirane groups in the reaction stage is 5 to 95%, more preferably 30 to 70%, based on the oxirane content of the aromatic epoxy resin as a raw material. If the reduction rate of oxirane groups is less than 5%, the acrylic resin-aromatic epoxy resin partial reaction product cannot be sufficiently self-emulsified in the aqueous medium and tends to separate during storage, and if it is greater than 95%, the acrylic resin-aromatic epoxy resin partial reaction product tends to separate during storage. The processability of the film tends to deteriorate. In particular, an aqueous resin obtained when the oxirane group content is in the range of 30 to 70% is excellent in coating suitability.

The acrylic resin-aromatic epoxy resin partial bond (D) in the present invention contains 12 to 70% by weight of a monobasic carboxylic acid monomer in the presence of the aromatic epoxy resin (B).
It can be obtained by polymerizing a copolymerizable monomer mixture containing the compound using a relatively large amount of an organic peroxide such as hensyl peroxide. In this case, an aromatic epoxy resin grafted with an acrylic resin is obtained.

In the present invention, the acrylic resin-aromatic epoxy resin partial bond (D> also represents the aromatic epoxy resin (B)
A copolymerizable monomer mixture containing 12 to 70% by weight of a monobasic carboxylic acid monomer and a compound having both an epoxy group and a double bond, which is obtained by reacting a basic carboxylic acid monomer with a basic carboxylic acid monomer in the presence of a base, is radically polymerized. It can be obtained by stopping the polymerization using an initiator.

The solid content ratio of the acrylic resin (A) and the aromatic epoxy resin (B) is selected from the range of 1:1 to 1:6.

In the present invention, the precondensate of the acrylic resin (A) or the aromatic epoxy resin and the phenol resin (C) is preferably reacted in a hydrophilic solvent at 50°C to 150°C for 10 minutes to 3 hours. It can be obtained by

In the present invention, the composite resin composition can be obtained using various methods. For example, (a) an aromatic epoxy resin-phenolic resin precondensate having an epoxy group and an acrylic resin (A) are reacted in the presence of ammonia or an amine. (b) The acrylic resin-aromatic epoxy resin partial bond (D) and the phenol resin (C) are reacted in a preliminary tank at 50° C. to 150° C. for 10 minutes to 3 hours. (c) A copolymerizable monomer mixture containing 12 to 70% by weight of a monobasic carboxylic acid heptamer in the presence of an aromatic epoxy resin-phenol resin precondensate, and an organic peroxide such as hensyl peroxide. Polymerization is carried out using a relatively large amount of.

(d) After reacting the aromatic epoxy resin (B) with a compound having both an epoxy group and a double bond, which is obtained by reacting a basic carboxylic acid monomer in the presence of a base, with the phenol resin (C). ,-12 basic carbonic acid monomers
A copolymerizable monomer mixture containing ~70% by weight is polymerized using a radical polymerization initiator. It is preferable that the reactions (a) to (ii) above be carried out in a hydrophilic solvent, and the amount of phenolic resin (C) in the composite resin composition is 2 to 40% by weight based on the total amount of resin, and 2% by weight. If it is less than %, the contribution to the curing speed of the coating film is insufficient,
Moreover, when the amount exceeds 40% by weight, physical properties such as processability of the coating film tend to deteriorate.

In the present invention, the aqueous resin composition may be prepared by adding ammonia or amine to the composite resin composition in an amount such that the final composition has a pH of 4 to 11 and dispersing it in an aqueous medium. When high boiling point solvents are used, it is preferable to remove these solvents in advance under reduced pressure.

The above amine is, for example, trimethylamine.

Alkylamines such as triethylamine and butylamine, alcohol amines such as 2-dimethylaminoethanol, jetanolamine, triethanolamine, and aminomethyl propane, morpholine, etc. are used. Also ethylenediamine.

Polyvalent amines such as diethylenetriamine can also be used.

In the present invention, the aqueous medium means water alone or a mixture with a hydrophilic organic solvent in which at least 10% by weight is water, and examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, isopropanol, n-propanol, -butanol, 5ec-butanol, tert-butanol,
Alkyl alcohols such as isobutanol, ether alcohols such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, methyl carpitol, ethyl carbitol, methyl cellosolve acef
-), ether esters such as ethyl cellosolve acetate, dioxane, dimethylformamide, dia-7ton alcohol, etc. are used.

Since the aqueous resin dispersion of the present invention uses a phenol resin that has been precondensed in advance, it has excellent curability, and the resulting coating film has excellent extraction properties. It also has extremely high adhesion to metals.

The aqueous resin dispersion according to the present invention can be used as a paint by adding a surfactant, an antifoaming agent, etc. to improve coating properties, if necessary.

Suitable substrates are metal plates such as untreated steel plates, treated steel plates, galvanized iron plates, and tin plates.As for the coating method, spray painting such as air spray, airless spray, and electrostatic spray is preferable. Dip coating, roll coater coating, electrodeposition coating, etc. are also possible. The baking conditions can be selected from a temperature range of 150°C to 230°C for 2 to 30 minutes per hour.

The aqueous resin dispersion of the present invention can be formulated with suitable rust preventive agents, pigments, fillers, etc., depending on the intended use, so that it can be used as a rust preventive primer, as a sealant, etc.
It can also be used in inks, anticorrosive paints, etc.

The present invention will be explained below using two examples. In addition.

In the examples, "parts" and "%" are "parts by weight" and "% by weight," respectively.
” is shown.

Example 1 [Preparation of phenolic resin solution] I) 136 parts of tert-butylphenol, 162 parts of a 37% formaldehyde aqueous solution, and 160 parts of a 25% aqueous sodium hydroxide solution were placed in a flask, reacted at 50°C for 3 hours, and then diluted with hydrochloric acid. and water was separated. After water separation,
250 parts of p-tert-butylphenol, 3.7 parts of 10% hydrochloric acid and 250 parts of water were added and stirred for about 30 minutes, at which point the second heat generation was completed.

Add 160 parts of 25% sodium hydroxide and 120 parts of 37% formaldehyde aqueous solution, react at 50°C for 3 hours, neutralize with hydrochloric acid, separate the aqueous layer, and wash with water.

Repeat water separation 3 times, n-butanol/xylene/=
It was dissolved in a 1/1 mixed solvent to obtain a 60% phenol resin solution. As a result of analysis using the obtained resin-1lzGPc, 91% of p-tert-butylphenol was methylolated as a trimer, and the rest were methylolated dimers, methylolated dimers, and methylolated tetramers. A small amount of methylol compound was contained.

[Adjustment of acrylic resin solution]

Styrene 300.0 parts Ethyl acrylate 210.0 Methacrylic acid 90.0 Ethylene glycol monobutyl ether 388.0 Hendiyl peroxide 12.0 The mixture Z of the above composition was placed in a tetrasol flask with nitrogen gas purged and heated to 80 to 90°C. Heat it up and gradually add the remaining amount over 2 hours while keeping it at that temperature.After adding 2 drops,
After further stirring at that temperature for 2 hours, it was cooled and the acid value was 93 (
Solid content (the same applies hereafter), solid content 59.7%, viscosity 41
A carboxyl group-containing resin solution was obtained.

[Adjustment of epoxy resin solution]

Epicoat 1007 500 parts Ethylene glycol monobutyl ether 333.3 Pour the entire amount into a tetra-Solo flask purged with nitrogen gas and gradually heat to raise the internal temperature to 100°C. Stir for 1 hour until completely melted, then cool to 80°C to reduce the solid content. A 60% epoxy resin solution was obtained.

[Adjustment of aqueous dispersion]

■ 50 parts of the above acrylic resin solution ■ 100 parts of the above epoxy resin solution ■ 30 parts of the above phenolic resin solution ■ 2-dimethylaminoethanol 4.8 ■ Ion exchange water 355.2 Charge ■, ■, and ■ into a four-solo flask, and while stirring. 10
The reaction was carried out at 0°C for 2 hours. GPC measurements before and after the reaction confirmed that a portion of the epoxy resin and phenol resin were bonded. The temperature of the liquid was lowered to 80°C, and (2) was added to the mixture, which was allowed to react for 30 minutes and then cooled.

The bond between the acrylic resin and the epoxy resin was confirmed by GPC measurements before and after the reaction. Further, (2) was gradually added without stirring to obtain a milky white dispersion with a solid content of 20% and a viscosity of 385 cps. The obtained dispersion was stored at 50°C for 3 months, but no abnormalities were observed.

Example 2 [Preparation of phenol resin solution] 136 parts of p-terketylphenol, 162 parts of 37% formaldehyde aqueous solution, and 80 parts of 25% sodium hydroxide aqueous solution were charged into a flask and reacted at 100°C for 2.5 hours. After neutralization with hydrochloric acid.

It was extracted with a mixed solvent of n-butanol/xylene=-1/1 to obtain a 60% phenol resin solution. As a result of GPC analysis, unreacted p-tertbutylphenol 8
%, p-, tert-butylphenol methylolated product was 16%, dimer to tetramer methylolated product was 21%, and pentamer or more methylolated product was 55%.

The acrylic resin solution and epoxy resin solution were prepared in the same manner as in Example 1. Also, the preparation of aqueous dispersion.

The same procedure as in Example 1 was carried out except that the above phenol resin solution was used as the phenol example solution. The resulting dispersion had a solids content of 20% and a viscosity of 412 cps.

Example 3 [Preparation of phenolic resin solution] 108 parts of p-cresol, 162 parts of a 37% formaldehyde aqueous solution, and 160 parts of a 25% aqueous sodium hydroxide solution were charged into a flask and reacted at 50°C for 2 hours, and then
The temperature was raised to 0°C, and the reaction was further carried out at 100°C for 1 hour, neutralized with hydrochloric acid, and extracted with a mixed solvent of n-butanol/xylene = 1/1 to obtain a 60% phenol resin solution. GPC
As a result of analysis at 50°C for 2 hours, more than 90% of the reaction product was a dimethylol compound of p-cresol, 9% of the final product was a methylol compound of p-cresol, and 36% was a dimer. methylolated product, 41% methylolated trimer, 9% methylolated tetramer, 5
% was a methylolated product of pentamer or more.

The acrylic resin solution and epoxy resin solution were mw! as in Example 1. did. Also, the preparation of aqueous dispersion.

The same procedure as in Example 1 was carried out except that the phenol resin solution was replaced with the above phenol resin solution. The resulting dispersion had a solids content of 20% and a viscosity of 450 CPS.

The obtained dispersion was stored at 50°C for 3 months, but no abnormalities were observed.

Comparative Example 1 An acrylic resin solution and an epoxy resin solution were prepared in the same manner as in Example 1.

[Adjustment of aqueous dispersion]

■ 50 parts of the above acrylic resin solution ■ 100 parts of the above epoxy resin solution ■ 2-dimethylaminoethanol 4.8 ■ Ion-exchanged water 295.2 Charge ■, ■, and ■ into a four-solo flask, raise the liquid temperature to 80°C, and do so for 30 minutes. The mixture was allowed to react and cooled. The reaction between the epoxy resin and acrylic resin was confirmed by GPC measurements before and after the reaction. When I gradually added ■ without further stirring, the solid content was 20.
%, a milky white dispersion with a viscosity of 362 cps was obtained. No abnormalities were observed in the obtained dispersion when it was stored at 50°C for 3 months.

Comparative Example 2 An acrylic resin solution and an epoxy resin solution were prepared in the same manner as in Example 1. Further, the phenol resin was prepared in the same manner as in Example 2.

[Adjustment of aqueous dispersion]

■ 50 parts of the above acrylic resin solution ■ 100 parts of the above epoxy resin solution ■ 2-dimethylaminoethanol 4.8 ■ 30 parts of the above phenol resin solution ■ Ion exchange water 355.2 Place ■ and ■ in a four-solo flask, stir, and then add ■. After the addition and neutralization, the mixture was cooled. GPC measurements before and after the reaction confirmed that the acrylic resin and epoxy resin were partially bonded. After cooling, 2 was added and stirred to make a homogeneous solution, and 2 was gradually added without stirring to obtain a milky white dispersion with a solid content of 20% and a viscosity of 405 cps. The obtained dispersion was stored at 50°C for 3 months, but no abnormalities were observed.

Comparative Example 3 An acrylic resin solution and an epoxy resin solution were prepared in the same manner as in Example 1. Also, the preparation of aqueous dispersion.

Cyful 325 (instead of 30 parts of phenolic resin solution)
Water-soluble amino resin manufactured by Mitsui Toatsu ■, solid content 80%) 22
．． The same procedure as in Comparative Example 1 and Example 2 was conducted except that 5 parts were used.

The resulting aqueous dispersion had a solids content of 20% and a viscosity of 385 cp.
It was s.

Examples 1-2. The aqueous dispersions obtained in Comparative Examples 1 to 3 were applied to a tin plate to a thickness of 8 to 10 μm, and baked and dried at 165° C. and 200° C. for 5 minutes each to prepare test panels. The results of various resistance tests are shown in Table I. In addition, the above water-based dispersion was applied by spraying to the inner surface of a 2-piece tin can with a content capacity of 250 m1, and baked at 165°C and 200°C for 5 minutes each to dry to create an inner-coated can and test its various resistances. did. The results are shown in Table H.

Tables 1 and 2 show that Examples 1, 2.3 and Comparative Example 2.3 containing rifenol resin or melamine resin exhibited superior performance to Comparative Example 1 in retort resistance, corrosion resistance, and saline storage tests. There is. However, in comparison with Comparative Examples 2 and 3, Examples 1 and 2.3 had extremely small amounts of potassium permanganate consumed and had excellent extraction characteristics, and also had excellent flavor retention.

The various test methods in Table I and Table ■ are as follows.

(11 Adhesion: Approximately 1.5 m using a knife on the coating surface
Make 11 cuts vertically and horizontally with a width of m. When a 24 mm cellophane adhesive tape is tightly applied and then strongly peeled off, the number of unpeeled goblin areas is expressed as a numerator.

(2) Retort resistance: After treatment in water at 125°C for 30 minutes.

The coating film is judged visually and by peeling off the cellophane adhesive tape.

(3) Workability: This occurs when a special fold-type DuPont impact tester is used, a sample folded in half is placed at the bottom, and an iron weight with a flat contact surface weighing I kg is dropped from a height of 50 cm. The length of the crack in the paint film at the bent part was measured.

0~101111...O mark 10-20 fins...△ mark 20 dragons or more... Indicated by an X mark.

(4) A test piece with an X mark made on the coating surface using a knife was treated in 1% saline at 125°C for 30 minutes.
Determine the degree of corrosion near the X mark.

Items with no abnormality...○○ Items with slight corrosion △ Items with significant corrosion ・
・・・・×(5) Potassium permanganate consumption: Fill the inside coated can with 250ml of ion-exchanged water and tighten once.
The samples were treated at 60°C for 30 minutes and at 100°C for 30 minutes, and measured according to the test method described in 1 Food Sanitation Act.

(6) Salt solution storage test: 25% of 1% salt solution in a can with internal coating
After filling 0ml and tightening once, pack the cardboard boxes (15 cans in a 30-can-sized box) and apply vibration with a vibrator for 5 hours to cause the two cans to collide with each other, then store at 25°C for 1 month. saved.

The above test cans were opened and the amount of iron eluted into the saline solution was measured by atomic absorption spectrometry. (n: early average of l 5) (7) Flavor retention: 250 m of ion-exchanged water in a can with internal coating
1 was filled and sealed, and after sterilization at 100°C for 30 minutes, the can was further stored at 50°C for 6 months, and a flavor test was conducted on the solution in the can.

No change at all...O There are some changes...Δ There was a significant change...indicated by ×.

Example 4 Adjustment of epoxy resin] Adjustments were made in the same manner as in Example 1.

[Adjustment of aqueous resin dispersion]

■The above epoxy resin solution 150 parts ■Butyl cellosolve 30 ■Methacrylic acid 3゜■Styrene 18 ■Ethyl acrylate 2 ■Benzoyl peroxide 3.5 ■Phenol resin solution of Example 3 3゜■2-dimethylaminoethanol 4.8■ Pour ion-exchanged water 560 ■ and ■ into four solo flasks and lower the liquid temperature to 1 while stirring.
Raise the temperature to 15°C. Next, a mixture of (1) and (2) was added dropwise over 1 hour, and the mixture was allowed to react at 115° C. for an additional 2 hours. After that, (2) was added and the mixture was allowed to react for 2 hours while stirring. After cooling, (2) was added, and then (2) was gradually added to obtain a stable aqueous dispersion.

Using the obtained aqueous resin dispersion, tests similar to those shown in Table I1 and Table ■ were conducted, and as a result, excellent properties were obtained in all items 6;

Procedural amendment (spontaneous) April 1985 Commissioner of the Japan Patent Office 1, Indication of case Patent application No. 70133 of 1988 2
, Title of the invention Aqueous resin dispersion 3, Relationship with the case of the person making the amendment The columns of the "Claims" and "Detailed Description of the Invention" in the patent applicant's specification, the content of the amendment as shown in the attached sheet. Content ■・The scope of the claims is amended as shown in the attached sheet.

2. Second line from the bottom of page 6 of the specification r　2. Correct OJ to "2.0 pieces".

3. Line 14 of page 7 of the specification r　2. Correct OJ to "2.0 pieces".

4. On page 11 of the specification, lines 6-5 from the bottom, "bisphenol" is corrected to "hisphenol A."

5. On page 12 of the specification, lines 11 to 10 from the bottom, "alkylphenol dialcohol" is corrected to "dimethylolated product of alkylphenol."

6. Specification, page 13, line 6 r　2. Correct OJ to "2.0 pieces".

7. Specification page 21, lines 2 to 4 [91% is methylolated dimer, the rest are methylolated monomer, methylolated dimer, and methylolated tetramer” Correct as shown below.

"91% of the products are dimethylolated trimers, and the rest are dimethylolated monomers, dimethylolated dimers, and dimethylolated tetramers" 8, Specification, page 23, No. 1
Lines 3 to 15 r p-tert butylphenol methylol compound 1
6%, methylolated products of dimers to tetramers, 55% methylolated products of pentamers or more" is corrected as follows.

16% of dimethylolated products of p-tert butylphenol, 55% of dimethylolated products of dimers to tetramers, and 55% of dimethylolated products of pentamers or more.9, Specification page 24, lines 13 to 16 "Methylolated products, 36% methylolated dimer,
"41% is methylolated trimer, 9% is methylolated tetramer, and 5% is methylolated pentamer or more" is corrected as follows.

"Dimethylolated product, 36% is dimethylolated product of dimer, 41% is dimethylolated product of trimer, 9% is dimethylolated product of tetramer, 5% is dimethylolated product of pentamer or more" 10, Specification No. Page 28, line 4 from the bottom r (4) Insert the following words between J and "on the coating surface."

"Corrosion resistance:" 11, page 31 of the specification, line 1, "Properties have been obtained."
Insert the following text between “Table I” on page 2.

[Example 5] [Preparation of phenolic resin solution] [460 parts of 11% sulfur/lium hydroxide aqueous solution was charged into a flask, and while stirring, 1 part of 92% rose formaldehyde was added.
After adding 28 parts little by little and melting, 1 part p-cresol
08 parts were charged and reacted at 50°C for 2 hours.

Subsequently, the reaction was carried out at 70° C. for 6 hours, and the slurry, which was neutralized with hydrochloric acid and washed with water, was extracted with n-butanol to obtain a 30% phenol resin solution. As a result of GPC analysis, 2% of p
- Dinotylolated cresol, 90% dimethylolated dimer, 5% dimethylolated trimer, 3
% was a dimethylol compound of tetramer or more.

[Preparation of aqueous dispersion]

■ Acrylic resin solution of Example 1 50 parts ■ Epoxy resin solution of Example 1 100 parts ■ 2-dimethylaminoethanol 4.8 parts ■ The above phenol resin solution 60 parts ■ Ion exchange water 325.2 parts ■, ■ , (2) were added, the temperature of the solution was raised to 80°C, and the reaction was allowed to proceed for 30 minutes. The reaction between the epoxy resin and acrylic resin was confirmed by GPC measurements before and after the reaction. moreover,
After adding (2) and reacting for 30 minutes at 80°C, (2) was gradually added to obtain a milky white dispersion with a solid content of 20% and a viscosity of 850 cps. The obtained dispersion was stored at 50°C for 3 months, but no foreign substances were observed.

Example 6 [Preparation of acrylic resin solution] ■ Methyl cellosolve acetate 1- 1000 parts ■ Styrene 180.6 parts ■ Ethyl acrylate 86 parts ■ Mekkryl UI! , 163 parts ■ Henjiyl peroxide 6.49 Reflux condenser, monomer tank, monomer flow rate regulator, temperature δ1. A four-north flask equipped with a stirrer was purged with nitrogen and charged with (2). The monomer tank contains the monomer mixture■
~■ and polymerization catalyst ■ are mixed together.

One-fourth of the mixture was added to the above flask, and the mixture was gradually heated and maintained at 105°C. 2 of the remaining mixed monomers
The mixture was added over a period of time, and after the completion of one drop, the mixture was stirred for an additional 2 hours and then cooled to room temperature. The resulting solution is.

The acrylic resin solution had a solid content of 30.1%, a viscosity of UV (Gardner bubble viscometer, 25°C), and an acid value of 247 mg KOII/g (in terms of solid content).

[Preparation of epoxy resin-acrylic resin partial reactant solution]

■Methyl cellosolve acetate 2,100 parts ■Epikote 1009 900 parts ■Above acrylic resin solution 1,000 parts Add a stirrer, a reflux condenser, and a thermometer to a four-wheeled flask.

After installing a solvent removal device and purging with nitrogen, ① and ③ were added, heated to 110'C, and continued stirring.

After completely dissolving the epoxy resin, add ■ and heat to 135°C.
The mixture was heated to a temperature of 100.degree. C., and stirring was continued for 8 hours while maintaining this temperature to obtain an epoxy resin-acrylic resin partial reaction product.

During this period, samples were taken out periodically to check their viscosity. At the end of the reaction, the solution had a solid content of 30.1% and a viscosity of UV. Thereafter, a portion of the solvent was removed under reduced pressure to obtain a solid content of 60%.

[Preparation of aqueous dispersion]

■The above epoxy resin-acrylic resin partial reactant solution 5
00 parts [Phase] Phenol resin solution of Example 5 100 parts■25
% Ammonia water 19.5 parts @ ion exchange water 1180.5 Department Charge ■ and @l in a solo flask, heat with stirring, react at 100°C for 3 hours, then cool, and cool to 50°C.
0 was added. After stirring for 30 minutes, slowly add @.
A yellowish, milky white dispersion with a solid content of 20% and a viscosity of 500 cps was prepared at 1:7. The obtained dispersion was stored at 50°C for 3 months, but no abnormalities were observed.

Example 7 [tIIil of epoxy acrylate l-441 fatty acid solution]
[manufactured] ■Epicor L 1009 646 parts ■Ethylene glycol monobutyl ether 349 parts 010% sulfur/lium hydroxide? g/& 1 part ■ Hydroquinone 0.02 &lS ■ Methacrylic v1 4 parts ■ and ■ were charged and stirred at 110° C. for 2 hours, and after confirming melting, the mixture was cooled. ■■ was added at 100°C, and after heating, ■ was added. Reacted at 130°C for 5 hours and the acid value was 0°3 mg K.
The process was terminated when the OII/g (in terms of solid content) was lowered, and the mixture was taken out after cooling. The number average molecular weight of the product is 38
00. The epoxy equivalent was 2750, and the number of epoxy groups per molecule was 1.38 on average.

Solid content 65%, viscosity at 50°C is 80,000 cps
Met.

[Preparation of aqueous dispersion]

■Methyl ethyl getone 40 parts ■Epoxy acrylate resin/8 parts above 158.5 parts ■Styrene 15.4 parts ■Ethyl acrylate 18 parts [Phase] Methacrylic acid 18 parts ■Ethylene glycol monobutyl ether 68.3 parts @Azobisiso Butyronitrile 0.5 parts 0 Azobis-
0.6 parts of isobutyronitrile ■ 57.3 parts of the phenol resin solution of Example 5 ■ 10 parts of methyl ethyl ketone [Phase] 70 parts of a 10% aqueous solution of dimethylaminoethanol 543.4 parts of O-ion-exchanged water ■ were charged into a flask. The mixture was heated and refluxed, and the mixed solutions from ■ to @ were added little by little over a period of 3 hours. After the addition was completed, the temperature was raised to 90°C, and 0 was added to continue the reaction.

When the solid content reached 55% or more after sampling, ① was added, and the reaction was continued for 2 hours at 90°C, and then the [phase] was added while cooling, and the [phase] was added at 60°C.

After 15 minutes, O was added little by little and the solid content was 20%.
, an aqueous dispersion with a viscosity of 15 cps was obtained.

Example 8 ■ Acrylic resin solution of Example 1 50 parts ■ Phenol resin solution of Example 5 60 parts ■ Epoxy resin solution of Example 1 100 parts 02 = -dimethylaminoethanol 48
Part ■ Ion exchange water 325.2 Put ■ and ■ into a solo flask and add 100 ml while stirring.
After reacting at ℃ for 2 hours, it was cooled to 80℃.
(2) was added and allowed to react for 30 minutes. Further, when stirring was added gradually, the solid content was 20% and the viscosity was 350.
A milky white dispersion of cps was obtained. This dispersion was stored at 50°C for 3 months, but no abnormalities were observed.

Example 9 ■ Epoxy resin solution of Example 1 100 parts ■ Phenol resin solution of Example 5 60 parts ■ Acrylic resin solution of Example 1 50 fjl- ■ 2-dimethylaminoethanol 48 parts ■ Ion exchange water 325.2 parts Put ■ and ■ into a solo flask and bring to 100 ml while stirring.
The reaction was carried out at ℃ for 2 hours. GPC measurements before and after the reaction confirmed that a portion of the epoxy resin and phenol resin were bonded. Lower the liquid temperature to 80℃.

(1) and (2) were added and reacted for 30 minutes, followed by cooling. G before and after reaction
The bond between the acrylic resin and the epoxy resin was confirmed by PC measurement. Further, (2) was gradually added without stirring to obtain a milky white dispersion with a solid content of 20% and a viscosity of 400 cps. The obtained dispersion was stored at 50°C for 3 months, but no abnormalities were observed.

Regarding the aqueous dispersions obtained in Examples 4 to 9, Example 1
A coating film test was conducted using the same procedure. This test result is shown in 2 tables■
and shown in Table IV. 12. The first item from the top in Table ■ on page 32 of the specification (closed ``potassium permanganate consumption'') is ``potassium permanganate consumption 1i''.
(ppm) Correct as J.

13. On page 32 of the specification, insert "Table ■" and "Table IVJ" between Table "■ and 1 Patent Applicant".

Claims: 1. An acrylic resin (A) containing 12 to 70% by weight of monobasic carboxylic acid monomer units as an essential component, - having an average of 1.1 to 2.0 epoxy groups in the molecule. Aromatic epoxy resin (B) and phenol resin (C
) is dispersed in an aqueous medium in the presence of ammonia or amine in an amount such that the final composition has a pH of 4 to 11. The acrylic resin (A) and the aromatic epoxy resin (B) are at least partially combined, and the phenolic resin (C) is precondensed with the acrylic resin (A) and/or the aromatic epoxy resin (B). The aqueous resin dispersion as described above.

2. The composite resin composition is a composite resin composition with an excess of carboxyl groups obtained by precondensing an acrylic resin-aromatic epoxy resin partial bond (one) and a phenol resin (C). Aqueous resin dispersion according to scope 1.

3. The acrylic resin-aromatic epoxy resin partial bond (D) is obtained by partially reacting the acrylic resin (A) and the aromatic epoxy resin (+3), resulting in an acrylic resin with excess carboxyl groups-aromatic The aqueous resin dispersion according to claim 2, which is a partial reactant of a group-based epoxy resin.

4. The composite resin composition is a composite with an excess of carboxyl groups, which is obtained by subjecting an aromatic epoxy resin (B) to a precondensate obtained by precondensing an acrylic resin (A) and a phenol resin (C). The aqueous resin dispersion according to claim 1, which is a resin composition.

5. The composite resin composition is a carboxyl compound obtained by partially reacting an acrylic resin (A) with a precondensate having an epoxy group obtained by precondensing an aromatic epoxy resin (B) and a phenol resin (C). The aqueous resin dispersion according to claim 1, which is a composite resin composition with an excess of groups.

6. Acrylic resin (A) and aromatic J: Boxy resin (
The aqueous resin limb body according to claims 2 to 5, wherein the solid content ratio with B) is 2:1 to 1:6.

7. 7. The aqueous resin dispersion according to claim 1, wherein the weight of the phenolic resin (C) is 2 to 40% by weight based on the total weight of the resin.

8. The weight average molecular weight of the acrylic resin (A) is 3000
80,000 to 80,000.

9. The aqueous resin dispersion according to claims 1 to 8, wherein the aromatic epoxy resin has a number average molecular weight of 900 or more.

Claims (1)

[Claims] 1.12 to 70% by weight of an acrylic resin (A) containing one unit of a monobasic carboxylic acid as an essential component, - an aromatic resin having an average of 1.1 to 2.0 epoxy groups in the molecule; based epoxy resin (B) and phenolic resin (C
) is dispersed in an aqueous medium in the presence of ammonia or amine in an amount such that the pI of the final composition is 4 to 11. , acrylic resin (A)
and the aromatic epoxy resin (B) are at least partially bonded, and the phenol resin (C) is bonded to the acrylic resin (A).
and/or the above aqueous resin dispersion, which is precondensed with an aromatic epoxy resin (B). 2. The claim that the composite resin composition is a composite resin composition with an excess of carboxyl groups, which is obtained by precondensing an acrylic resin-aromatic epoxy resin partial bond (D) and a phenol resin (C). The aqueous resin dispersion according to item 1. 3. Acrylic resin-aromatic epoxy resin partially bonded with acrylic resin-aromatic epoxy resin (D) is obtained by partially reacting acrylic resin (A) and aromatic epoxy resin (B). Acrylic resin with excess carboxyl groups-aromatic The aqueous resin dispersion according to claim 2, which is a partial reactant of a group-based epoxy resin. 4. The composite resin composition is a composite with an excess of carboxyl groups, which is obtained by partially reacting an aromatic epoxy resin (B) with a precondensate obtained by precondensing an acrylic resin (A) and a phenolic resin (C). The aqueous resin dispersion according to claim 1, which is a resin composition. 5. The composite resin composition is a carboxyl compound obtained by partially reacting an acrylic resin (A) with a precondensate having an epoxy group obtained by precondensing an aromatic epoxy resin (B) and a phenol resin (C). 2. The aqueous resin dispersion according to claim 1, which is a composite resin composition with a base layer. 6. Acrylic resin (A), aromatic resin, poxy resin (
The aqueous resin dispersion according to claims 2 to 5, wherein the solid content ratio with B) is 2:1 to 1:6. 7. The aqueous resin dispersion according to claims 1 to 6, wherein the weight of the phenolic resin (C) is 2 to 40% by weight based on the total weight of the resin. 8. The weight average molecular weight of the acrylic resin (A) is 3゛00
The aqueous resin dispersion according to claims 2 to 7, which has a molecular weight of 0 to 80,000. 9. The aqueous resin dispersion according to claims 1 to 8, wherein the aromatic epoxy resin has a number average molecular weight of 900 or more.