JPS5949213A - Aqueous coating resin composition - Google Patents

Abstract

PURPOSE:To obtain titled composition with excellent properties including dispersion stability and adhesivity, by radical polymerization of a specific monomer mixture in the presence of a vinyl chloride vinyl acetate copolymer, etc. CONSTITUTION:(A) At least one sort of substance selected from a vinyl chloride vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, and modified copolymer from vinyl chloride and vinyl acetate (e.g., saponified product), and (B) if required, an epoxy resin are dissolved in an organic solvent (e.g., ethylene glycol monobutyl ether). With the rsulting solution, a radical polymerization in the presence of an initiator, of a monomer mixture comprising acrylic acid and other ethylenic unsaturated compounds [e.g. ethyl (meth) acrylate] is carried out followed by dispersing in the system a basic compound (e.g., ammonia), thus obtaining the objective composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous coating J1 resin composition having excellent dispersion stability and the like, which is composed of a combination of different tumor resins.

More specifically, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic acid copolymer, and/or modified products of vinyl chloride-vinyl acetate copolymer in water V1-medium. By using a water-dispersible or water-soluble acrylic resin in 'r) ii+, it is possible to provide an aqueous coating composition that is superior to that of the gods.

Conventionally, coating materials such as paints, printing inks, and adhesives1
In this case, instead of coatings using organic solvents, coatings using aqueous media such as water and water-alcohol have been considered.
In terms of work environment, pollution, etc., it is considered as a desirable coating material by 3%.

One use of coating agents is coating metal plates and ＼, especially for coating the inner surfaces of metal cans. The inner surface coating is coated with eboxo-funol resin.Secondly, it is coated with vinyl chloride-vinyl acetate copolymer, which satisfies the physical properties required for an inner surface coating.In this field of coating materials, vinyl chloride-vinyl acetate copolymer is also coated. There has been no attempt to use an aqueous coating agent in place of the vinyl acetate copolymer solvent bath solution. Few aqueous coatings are available that offer physical properties that are better or comparable to those of polymeric coatings.

The resin that is used as a coating agent and has been considered is acrylic (liquid resin), and in fact, the water content of acrylic resin is Paints, printing inks, adhesives y,
Adhesion with QsaIL profiteering, storage stability:, Peel 11Qσ
) G, strength is good, but there is a drawback that depending on the use of the coating material, the problem of flavor defects is likely to occur.

In addition, modified versions of vinyl chloride-vinyl acetate copolymer or vinyl pentide-Δ-acid copolymer are also being considered as resins for water-based coatings, but low molecular weight resins It is difficult to disperse in water, or to make the dark fat of polymer 11 water dispersible, it is necessary to
;If you don't use a large amount of a surfactant, you won't get 4C's.
The use of low-molecular-weight surfactants can result in poor coatings (Q).
lIIj It has drawbacks such as a decrease in aqueous properties and a tendency to form a hygienist's surface layer depending on the use. Therefore, it is generally said that aqueous dispersions of vinyl chloride-vinyl acetate copolymers are superior.

In this way, the actual situation is that aqueous dispersions using a single resin have the disadvantage that it is difficult to satisfy the required physical properties, and only those with poor fractional stability can be prepared. In addition, in order to take advantage of the water-soluble properties of each resin,
Some attempts have been made to mix two or more types of water biodegradants, but there is a difference between anionic type and radio/hydrogen type.
Due to this difference in the stabilized pH, phenomena such as coagulation and precipitation of the resin were likely to occur.

The purpose of the present invention is to produce vinyl chloride-vinegar/dry vinyl copolymer, G
Modified vinyl chloride-vinyl acetate-maleic copolymer and vinyl chloride-vinyl acetate copolymer (hereinafter referred to as
It provides a stable aqueous dispersion of (using salt-vinyl acetate resin as an expression including the three) and also provides a stable aqueous dispersion without using a low molecular weight surfactant. It is something to do. In addition to the advantages of the salt-vinyl acetate resin, it also improves the drawbacks of the salt-vinyl acetate diencephalon, such as its adhesion to profiteering. Another object of the present invention is to improve the drawbacks of acrylic resin alone, which tend to cause problems such as poor flavor when using the aqueous molecule R& form.

Examples of the salt-vinyl acetate-based resin according to the present invention include vinyl chloride-vinyl acetate copolymer (A-11, vinyl chloride-vinyl acetate-maleinom Ji:polymer (, ni-2), vinyl chloride-vinyl acetate copolymer It is a modified product (8-3) of the combination. Vinyl chloride-vinyl acetate copolymer (As A-11, a copolymer having a vinyl acetate content of about 3 to 30% by weight is used. Vinyl chloride-vinyl acetate copolymer is used) Vinyl acetate-maleinoic acid 112 complex (
8-2) The three component glue 1-1 ratio is 70 to 95/3
~30/0.1~・54 presentation rl is used for one history. In addition, maleic acid means maleic acid and/or maleic anhydride. Also,
Vinyl chloride-vinegar 1! Vinyl co-4 (modified form of union (A-
Examples of 3) include saponified vinyl chloride-vinyl acetate copolymers of (A-1). It is of course possible to use a modified product other than saponification, which does not deteriorate the physical properties of the resin (A-1).

As the salt-vinyl acetate resin mentioned above, various commercially available resins can be used. For example, Vinylite-■Y T,i
H, V M CH, V A G H, V
M CC, V YNS (U.S. Union Carbide Company), MP It, -TS N%TA,, T2
H1T5.1"M, ■1SH (all from Shinji Kagaku Kogyo), Detsukabinyl #1000A, t#1000A-'
l", #1O00Q, #1000C, #10001.S
#1000LT3, #1 (+00 L e H
%Itl 0001i T 3, MHEloo, MM
90 (above, ?I℃ Kagaku Kogyo Co., Ltd.), Zeo 7-400
X-150M L.

400X-110A, 1031up8J, +35J, 1
Examples include 35J (hereinafter referred to as Nippon Zeon Co., Ltd.).

In order to disperse these 7 tons of salt-vinyl acetate resin into an aqueous medium,
It is usually used dissolved in an organic solvent that dissolves salt-vinyl acetate resin. Examples of this organic solvent include methyl acetate, ethyl acetate, isopropyl acetate, isopropyl acetate, acid ff1
Esters such as n-butyl, acetone, methyl ethyl ketone, methyl isobutyl ketone, esters, methyl cellosolve, ethyl cellosolve, cellosolves from Bufour cellosolve are preferable, and only a few poor solvents are used. It is also possible to mix in toluene and kill/nao. Furthermore, the salt-vinyl acetate resin may not only be dispersed in an aqueous medium but also in other forms.

Monomer 67 used in the present invention, i9 snout (C) is '7
It consists of acrylic acid and/or methacrylic acid and other ethylenically unsaturated 11-carbon carriers, and contains acrylic acid and/or methacrylic acid in an amount of 5 to 90% by weight of the total molymer, J
) preferably Iυ~80 weight saving, more preferably 15~
70 oki, 'nj% use.

Other unsaturated (1i compounds) copolymerized with acrylic acid and/or methacrylic acid include alkyl esters of acrylic acid or methacrylic acid, such as (
Methyl acrylate, ethyl (meth)acrylate,
Isopropyl (meth)acrylate, (meth)acrylic (
VR n-butyl, isobutyl (meth)acrylate, (meth)acrylic m n-amyl, inoamyl (meth)acrylate, n-hexyl (meth)acrylate 2-ethylhexyl (meth)acrylate, (meth)acrylic acid 11 −
Groups such as octyl<〒, hydroxyl group, etc. include methaneacrylic acid alkyl ester acrylamide, styrene, methylstyrene, vinyltoluene, or ethylenic carbonic acids other than acrylic acid or methacrylic acid. These ethylenically unsaturated compounds account for 10 to 95% by weight, preferably 20 to 9% by weight of the total polymerization components.
It is used in an amount of about 0% by weight.

The epoxy resin (B) is blended as necessary, and those used have a number average molecular weight of 1, O O
O ~5 0, O O o degree ffi no resinte;jFr
Epoxy resins obtained from bisphenol A and epichlorohydrin are representative resins.

For example, shrimp: ff-to 10011 1002, 1004
, 1007, 1009, (Yukaken L Eboxy Co., Ltd.)
List 7L. In addition, other epoxy resins can also be used, and furthermore, bisphenol A/epicchlorine type epoxy resins may be used.

The blending ratio of the monomer mixture tc) and the epoxy resin (B) varies depending on the amount of carboxyl group, but 1
/l O to l/0 (solid content weight ratio), preferably 115 to I/Ii degrees.

The blending ratio of the salt vinyl acetate resin and the pre-he enomer mixture (C') is 9515 to 01/999, preferably 90/10 to 5/95, based on the solid content weight ratio.

Note that if the blending ratio of the monomer mixture (Cl) is too low, the stability as a permanent dispersion will be poor.

The method for producing the aqueous breaking fat composition of the present invention includes 1
For example, salt vinyl acetate resin and epoxy resin 1 if necessary.
For example, a 7-mer mixture consisting of ethylene glycol monobutyl ether (methacrylic acid) and other ethylene unsaturated compounds may be used, as well as radical initiators such as anbisiso7'tyronitrile or fat Ja oxide. After the solution containing the agent is added dropwise to react, a base-opening compound such as ammonia or amine and water are added dropwise and dispersed. After dispersion, the M solvent is usually removed by stirring under reduced pressure, but it may not be necessary to remove it depending on the use of the aqueous coating material. As another production example, a salt vinyl acetate resin is dissolved in a solvent, and a solution containing zero initiator is added dropwise to the above-mentioned 7-mer mixture to react, and then EBOKI 7 resin is added and reacted to produce a basic compound. Alternatively, water may be added dropwise and dispersed.

Although the above is a typical dispersion method, it is not limited to this 2'L method.

Examples of the basic compounds used in the present invention include ammonia and amines, and examples of amines include alkyl amines such as triethylamine and butylamine, 2-dimethylamine ethanol, jetanolamine, etc. , alcohol amines such as triethanolamine, aminomethylglopanol, and dimethylaminomethylglopanol, morpholine, ethylenediamine, and diethylenetriamine π11.

The water content and medium used in the present invention are at least 10
At least % by weight is water. Of course, water alone may be used, but it is also possible to use a mixture of water, hydrophilic P, and an organic solvent. cellosolve, ethyl cellonorb, globil cellosolve, butyl cellosolve blue-hyrosolves, methyl cellosolve ace F-1-blue ether esters,
Other materials such as dioxane, dimethylformamide, diacetone dercol, etc. can be used.

The 404 fat composition for aqueous coating of the present invention may further contain fillers such as Gosaijun f1 and Inorganic Face 1'1 Tatami, and other resins may also be used in accordance with the present invention. It is possible to add 111- to the extent that it does not hinder the effectiveness of the Sung Dynasty.

The aqueous coating resin composition of the present invention has good dispersion stability and provides the advantages of salt-vinyl acetate resins as an aqueous dispersion.

Although the reason for the good dispersion stability is not necessarily clear, it is due to entanglement with the molecules of hydrophilic acrylic resin, despite the fact that salt-vinyl acetate resin has poor hydrophilicity, or It is thought that System 1 alcoholic acid contributes as a dispersion and stabilizes it in water.

The aqueous coating resin composition of the present invention can be used directly on metal plates such as tin plates, aluminum plates, treated steel plates, etc.
Alternatively, after applying a pace coat, or to a formed metal plate with or without a base coat, coating, spray painting, dip painting, roll painting, etc.
It can be coated by means such as gravure coating or electrolayer coating.

The aqueous coating resin composition of the present invention can be used as a coating agent for metal plates, a coating agent for the inner surface of metal cans, other reusable coatings, printing inks, adhesives, fiber processing agents, or water-based coatings thereof. Can be used.

Below are production examples and examples! The present invention will be described with reference to FIG. In the example, "part" and "%" are ilj fil, fte1
; Weight not indicated.

Example 1 (1) Styrene/91ζ Shiku 2) Acrylic ethyl
Part 1 (3) Methacrylic acid
20 parts (4) benzoyl peroxide
Part 2 (5) Epoxy resin Ebiko 1-1009 (manufactured by Yuka Zoel Epokin Co., Ltd.) 70 liters (6) Ethylene glycol monobutyl ether
7 o0 part (7) Vinyl chloride-n'"vinyl acid cojP split vinylite V Y )-I H (manufactured by Union Carbide Co., Ltd.) 210 sounds]! (8) / Clohexanone 40
0 parts (9) 2-dimethylamine ethanol
16.5iB(]0) Ion exchange water
70 copies (1'
1) Ion exchange water
Into 4 1" flasks purged with 700 parts nitrogen (
8) Prepare f+'fL while preparing (7). Next, prepare (5) and (6) 1211 ``cmate''
f1η11'1'cNoru. 'After dissolving in the ashigane (1)
, (2), (3), and (4) were added dropwise over 1 hour, and the reaction was continued for another 2 hours. Next, set the temperature to 70'G7
After lowering the temperature, (9) and (10) were added dropwise, followed by (1) and cooled. After cooling, the mixture was stirred under reduced pressure, the solvent was removed, and ion-exchanged water was added to adjust the solid content to 20% to obtain a milky white emulsion.

Example 2 (1) Steel/
18 parts (,2) ethyl acrylate
Part 2 (3) Methacrylic acid
40 copies (4)
benzoyl peroxide
4 parts (5) EBOKI/Resin Epicoat 1009 (manufactured by Yuka Shell Epoxy Co., Ltd.) 140 parts (6 ethylene glycol monobutyl)
140 parts (7) Vinyl chloride-vinyl acetate copolymer Vinylite VY)H (manufactured by Union Carbide)
Part 21 Part (8) Cyclohexanone
40.0 parts (9) 2-dimethylaminoethanol 33 parts (10)
ion exchange water
70 parts (11) Ion exchange water
4th flask j with 1018 parts nitrogen substitution
Add (7) while stirring. Next, add (5) and (6) and warm to 20"c. After completely melting, add (1), (2), (:3n, (4)
) was added dropwise over 1 hour, and the reaction was continued for another 2 hours. Next, after lowering the temperature by 7°C (9),
(10) was added dropwise, and then (11) was added dropwise to the mixture and cooled.

After cooling, the mixture was stirred under reduced pressure, the solvent was removed, and ion-exchanged water was added to adjust the solid content to 20% to obtain a milky white emulsion.

Example 3 (1) Steel/
Part 6 (2) Afrylmyethyl
Part 6 (3) Methacrylic acid
18 parts (4) Benzoyl peroxide 2
Part (5) Eboki 4f1M Eboki ~ Tol 009 (
70 parts (6) Ethylene glycol monobutyl ether
70 parts (vinyl chloride-vinyl acetate copolymer vinylyl) VYHI ((manufactured by Union Carbide Co., Ltd. 1
210 parts (8) cyclohexanone
400 parts (9) 2-dimethylaminoethanol 14.9RB (10)
Ion exchange water 7
0 parts (11) Ion exchange water
Charge (7) into a four-bottle flask purged with 700 parts of nitrogen while stirring.

Next, add (5) and (6) and raise the temperature to 120°C.

After completely dissolving (1), (2), (3), (4)
The mixture was added dropwise over time and the reaction was continued for an additional 2 hours. Next, after lowering the temperature to 70°C, (9) and (10) were added dropwise, and then (11) was added dropwise to cool the mixture. After cooling, stirring was continued under reduced pressure, the solvent was removed, and ion-exchanged water was added to adjust the solid content to 20%, resulting in a milky white emulsion (↑
Ta.

Example 4 (11 styrene
Part 6 (2) Ethyl acrylate
Part 6 (3) Methacrylic acid
18 parts (4) Be/diyl peroxide 2
Part (5n ebogishi tree) J't1 Ebiko 4-t1 old) 7
(Oilization) [L; Manufactured by Bokizo 71] 70 parts L61 Ethylene dalicol monobutyl ether 7-L
70 parts (71 vinyl chloride-vinyl acetate A
Co-IF combined vinylite VYHH (Union Carbide J-IJ'41 210 MB (8) Cyclohexanone 400 parts (9) 2
-dimethylaminoethanol 3
Part 3 (January ion exchange water
70 parts (11)'1 oni/replacement water
1018 parts Nitrogen-substituted 2% 4 "" plus: 1 (81) was added while stirring (7
). Next, prepare (5) and (6) to 120%
: Wait fl I'Af+. After completely dissolving (1
)% (2), (3), and (4) were added dropwise over 1 hour,
Continue anti-Ls for another 2 hours. Then increase the temperature to 70'
C. Add 1 drop of barley (9 tons, (1υ), and then add (
1]) was added dropwise and cooled. After cooling, the mixture was stirred under reduced pressure, the bath agent was removed, and ion-exchanged water was added to adjust the solid content to 20% to obtain a milky white emalun.

Example 5 (1) Styrene
61τ6(2) Ethyl acrylate
6 parts (3) methacrylic acid 18 parts (
4) Benzoyl peroxide
Part 2 (5) Epoxy resin Ebiko) 1009
(Manufactured by Yuka L Evokin Co., Ltd.) 70 parts (6) Ethylene glycol monobutyrylether
7 parts (7) Vinyl chloride-vinyl acetate-maleic acid copolymer Vinyrite VMCH (manufactured by Union Carbide) 210 parts (8) Cyclohexanone
400 parts (9) 2-dimethyl-rminoethanol 33 parts (
10) Ion exchange water
70 parts (11) Ion exchange water
(8) was charged into a 7 ton round flask which had been purged with 1018 parts of nitrogen, and (7) was added thereto with stirring.

Next, add (5) and (6) and raise the temperature to 120°C.

After completely dissolving (1), (2), (3), (4)
The mixture was added dropwise over time and the reaction was continued for an additional 2 hours. Next, after lowering the temperature to 70°C, (9), (10) 8i lower, S') Ic (l + 1': i fill lower L T: Cooled. After cooling, stirring was continued while reducing the pressure.
The solvent was removed and ion-exchanged water was added to adjust the solids content to 20%, resulting in a milky white emulsion.

Example 6 (11 styrene
Part 6 (2) Ethyl acrylate
Part 6 (3) Methacrylic acid
Part 18 (4)
benzoyl peroxide
Part 2 (5) Epoxy resin Epicoat +00! l(
Oil [manufactured by Reel Ebokino Co., Ltd.] 70 parts (6) Ethylene coolicol monobutyl ether
70 parts (7) Vinyl chloride-vinyl acetate-vinyl roof' alcohol copolymer @Vinylye 1 VAoH (manufactured by Unio/Carpai 1 Co., Ltd. 1 210 parts (8) Cyclohexanono 4 'O0 parts (9)
) 2-dimethylaminoethanol
33 parts (10) Ion exchange water
70 parts (IIH, d-/exchanged water
1018 parts Nitrogen purged to 3% Into a fourth flask, charge (8) and add (7) (J) while stirring. Next, charge (5) and (6) and raise the temperature to 120°C. Completely dissolve. After (1), (2
), (3], and (4) were added dropwise over 1 hour, and the reaction was continued for an additional 2 hours.Next, after lowering the temperature to 70°C, (
9) and (10) were added dropwise, and then (11) was added dropwise and cooled. After cooling, stirring was continued under reduced pressure, the solvent was removed, and ion-exchanged water was added to adjust the solid content to 20% to obtain a milky white emulsion.

Example 7 (1) Styrene
18 parts (2) Ethyl acrylate
Part 2 (3) Methacrylic acid
40 parts (4) Benzoyl peroxide
4 Go 1 ((5) Vinyl chloride - Vinyl acetate Kyodo Toki Vinyrite vYHI-1 (manufactured by Union Carbide Co., Ltd. 1
210 parts (6) Cyclo＼Canon
400 parts (7) 2-dimethylaminoethanol 33.0+911 (8
) Ion exchange water
70 parts (9) Ion exchange water
70 parts nitrogen 16 exchanged 21. Add (6)"x into a 4-glass flask, add (5) while stirring, and raise the temperature to 120"C. Completely dissolved r&
(+1, (2+, (31,
9.7 (After lowering the temperature to 1"C, add (7) and (8), and then (9) to cool the mixture. The solvent was removed and ion-exchanged water was added to 11% to adjust the solids content to 20% to obtain a milky white emulsion (4).

Example 8 (1) Styrene
9 parts (2) Ethyl acrylate
1 part (3) 20 parts methacrylic acid (
4) Benzoyl peroxide
2 parts (5) Epoxy resin Epicoat 1 (1
70 parts (61 ethylene glycol monobutyl ester)
7% (7) Vinyl chloride-vinyl acetate co-iF
, L, F vinylite V Y HH (union carbide JI crack 1 210 parts (8) cyclohexanone
400 copies (9) 2-
Dimethylaminoethanol 16
5 parts (10) Ion exchange water
Into a fourth flask that had been purged with 770 parts of nitrogen, (8) was charged and (7) was added while stirring. After raising the temperature to 12 ()℃ and completely melting, (] ), (
2), (3), and (41) were added dropwise over 1 hour, and the reaction was continued for another 2 hours. Into this solution, (5) and (61) were added to another four flasks and completely dissolved. Mix the ingredients, stir thoroughly, and then heat to 60℃.(9)
was added dropwise and reacted for 30 minutes, and then (10) was added dropwise with stirring and cooled. The mixture was stirred while reducing the pressure in the oven to remove the dissolved material, and ion-exchanged water was added to adjust the solid content to 20% to obtain a milky white emulsion.

Example 9 (1) Steel/
Part 6 (2) Ethyl acrylate
Part 6 (3) Methacrylic acid
, Part 18 (4)
benzoyl peroxide
Part 2 (5) Evokin Resin Epicoat 1009 (Yuka/manufactured by L-Evokin Co., Ltd.) 70f! (6) Ethylene glycol monobutyl gothyl
70 parts (7) Vinyl tetrachloride-vinyl acetate 1[
(Combined vinyl light VYHI-1 (Unio/Carbide d
) 210 parts (8) Nochlohexanone
400 parts (9) 2-) Methylaminoethanol 149 parts (10) Ion exchange water 77
Charge (8) into a 4-piece D flask that has been purged with 0 parts nitrogen and charge (7) with stirring. After raising the temperature to 120°C and completely dissolving, (1), (21, (3), (4)
) was added dropwise over 1 hour, and the reaction was continued for an additional 2 hours. Add another four flasks (5) and (6) to this solution and completely dissolve them, stir thoroughly and heat to 60°C. Next, (9) was added dropwise and reacted for 30 minutes (101 was added dropwise while stirring and cooled. While reducing the pressure (1' was continued with stirring), the solvent was removed, and ion-exchanged water was added to the The solid content was adjusted to 20% and a milky white emulsion was obtained.

Comparative example (i) Styrene 6
0 parts (2) ethyl acrylate
60 parts (3) methacrylic acid
180 parts (4) Benzoyl peroxide
Part 72 (5) Lobetanol
420 parts (6) Butyl acetate
420 parts (7) Ion exchange water
2.10 parts (8) 2-dimethylamine ethanol 74.5 parts (9) Ion exchange water
Charge (5) and (61) into a four-bottle flask that has been purged with 600 parts of nitrogen, and raise the temperature to 110"C. Next, add (1), (2), (3), and (4) over 2 hours. Then, the temperature was lowered to 80°C, and (7) and (8) were added dropwise over 30 minutes, and then (9) was added dropwise to obtain an aqueous dispersion. .

Test results of the aqueous dispersions obtained in the Examples and Comparative Examples are shown below.

(Results measured using No. 4 Ford force at 1125°C.

(2) After storage at 50°C for 1 month, check for presence of gel or precipitate.

(3) After painting the tin plate with A20 bar coater, 18
After baking at 0°C for 5 minutes, use a knife to make 100 cuts in the shape of base lines at 1 mm intervals on the coating film.T1 Apply cellophane tape and do not peel it off. All peeled off at this time is O/1
00, 100/100 indicates no peeling at all.

(4) Is the aluminum Δ plate coated under the coating conditions shown in (3) above in purified water? After soaking and boiling at 100°C for 1 hour, changes in taste and odor were examined.

A rating of 1 indicates good quality, and a 3-level evaluation is performed from 1 to 3.

patent applicant Toyo Ink Rizo Co., Ltd.

Claims (1)

[Claims] 1. Vinyl chloride-vinyl acetate copolymer has the form (A-1), vinyl chloride = Mli! and nirumarein awakened copolymer (A-
2), and a modified vinyl chloride=Of vinyl copolymer (A-3) 21. A monomer mixture (by radical polymerization of C1) consisting of acrylic acid or methacrylic acid and another ethylenically unsaturated compound in the presence of at least one type of epoxy resin and, if necessary, an epoxy resin (3). An aqueous coating resin composition characterized by: 2. A monomer mixture (
After radical polymerization of C), epoxy resin (
1. The aqueous coating resin composition according to claim 1, which is obtained by pressing B). 11 - ・ ゛ ・ - and - 12 Old mouth blind complex string ## = F3, (A-1, (A-2), 13 Yohi (A-3) The aqueous coating resin composition according to claim 1 or 2, comprising at least 1 elongation and the monomer mixture (C) in a ratio of 90/10 to 5/95.