JP3238753B2 - Aqueous dispersion of vinyl polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of a vinyl polymer, and more particularly, to an aqueous dispersion of a vinyl polymer which is extremely stable and uniformly dispersed by a water-soluble epoxy compound having a quaternary ammonium salt group. The present invention relates to an aqueous dispersion of a vinyl polymer, which is particularly suitable for an inner paint for food and beverage cans, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a carboxyl group-containing epoxy resin is prepared as an aqueous dispersion suitable for a paint for the inner surface of a can, and an aqueous solution or dispersion obtained by neutralizing a carboxyl group in the epoxy resin with an amine is used. Although it has been proposed to obtain a vinyl-based monomer by radical polymerization, a coating film obtained therefrom still has a large amount of polar groups remaining, and thus has a drawback that the coating film has a high affinity for water and has poor water resistance. Also, when using a high molecular weight epoxy resin, for example, an epoxy resin having a molecular weight larger than Epicoat 1007 (manufactured by Ciel Kagaku Kagaku KK, average molecular weight of about 2,900), it is difficult to produce a stable dispersion of a vinyl polymer. .

Further, the applicant of the present invention has previously proposed that a vinyl monomer is polymerized in an aqueous medium in the presence of a water-soluble acrylic polymer having at least one quaternary ammonium base in one molecule. A stable aqueous dispersion of the resulting vinyl polymer was proposed (see Japanese Patent Publication No. 60-43873). However, since the above-mentioned aqueous dispersion is composed of a quaternary salt-containing acrylic resin in both the core portion of the dispersed polymer particles and the skin portion which is a dispersion stabilizer, it is particularly suitable for food and beverage products. When used as a paint for the inner surface of a can, there is a problem that the flavor property is deteriorated and the adhesion is deteriorated due to the quaternary salt-containing acrylic resin.

Furthermore, the present applicant has obtained an aqueous dispersion of a vinyl polymer having extremely excellent stability by polymerizing a vinyl monomer in an aqueous medium in the presence of an epoxy resin having a quaternary ammonium base. (See Japanese Patent Application Laid-Open No. 62-223211). A coating film formed using this aqueous dispersion has a quaternary ammonium base or acid present therein which is usually separated from the polymer by heating to a temperature of 100 ° C. or higher to form an amine and an acid and volatilize. Alternatively, the acid reacts with the epoxy group to form an ester, so that the polarity of the coating film is low and the water resistance and the salt spray resistance are excellent. In addition, the obtained aqueous dispersion of the vinyl polymer is free from the problem of flavor by incorporating an acrylic resin in the internal measurement of the dispersed particles, and at the same time, the external measurement of the dispersed particles, that is, the dispersion stabilizer portion. Since it is an epoxy resin, it has the characteristic that the adhesion to metal substrates can be greatly improved.

[0005]

SUMMARY OF THE INVENTION Japanese Patent Application Laid-Open No. 62-22 / 1987
The invention of No. 3211 forms an excellent coating film, while the epoxy resin used has a relatively high molecular weight of 1,000 to 5,000 and is used for forming a quaternary ammonium base. Since an aliphatic organic acid having 5 or less carbon atoms is used as an anion to be produced, there is a problem that the surface activity is low and a large amount of expensive epoxy resin must be used.

[0006]

Means for Solving the Problems Accordingly, the present inventors have:
As a result of repeated studies for solving this problem, they have found that the problem can be solved by using a fatty acid having 6 to 40 carbon atoms as an anion, and have completed the present invention.

The present invention provides: “1. A vinyl polymer represented by the formula

Embedded image In the formula, R ₁ , R ₂ and R ₃ each independently represent an organic group, or R ₁ , R ₂ and R ₃ together form a nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded. and, Y ^- number average molecular weight 70 having at least 0.1 or an average is an anion consisting of fatty roots 6 to 40 carbon atoms, in the quaternary ammonium salt shown in a molecule
An aqueous dispersion of a vinyl polymer in which a water-soluble epoxy compound of up to 5,000 is dispersed in an aqueous medium using a dispersant. 2. The epoxy compound according to claim 1, wherein the epoxy compound is one or more selected from polyglycidyl ether of polyphenol, polyglycidyl ether of phenolic novolak resin and polyglycidyl ether of polyhydric alcohol, butylene oxide, styrene oxide and polyethylene oxide. Aqueous dispersion of vinyl polymer. 3. 3. The aqueous dispersion of a vinyl polymer according to item 1 or 2, wherein the tertiary amine forming the quaternary ammonium base is one or more selected from alkylamines, alcoholamines and morpholine. . 4. The vinyl polymer according to any one of items 1 to 3, wherein one or two or more selected from aminoplasts such as melamine formaldehyde resins, urea-formaldehyde resins, and phenol formaldehyde resins and blocked isocyanates are added as a crosslinking agent. The combined aqueous dispersion. 5. formula

Embedded image In the formula, R ₁ , R ₂ and R ₃ each independently represent an organic group, or R ₁ , R ₂ and R ₃ together form a nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded. and, Y ^- number average molecular weight having at least 0.1 or an average is an anion consisting of fatty roots 6 to 40 carbon atoms, in the quaternary ammonium salt shown in one molecule 70～5,0
A method for producing an aqueous dispersion of a vinyl polymer, comprising polymerizing a vinyl monomer in an aqueous medium in the presence of a water-soluble epoxy compound of No. 00. 6. The vinyl-based monomer has an epoxy resin to vinyl-based monomer percentage (weight) of 0.5 / 99.5 to 80/20.
The method for producing an aqueous dispersion of a vinyl polymer according to claim 5, wherein the polymerization is carried out in the presence of a water-soluble epoxy compound. About.

[0008]

According to the present invention, the vinyl polymer has the formula (1)

[0009]

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In the formula, R ₁ , R ₂ and R ₃ each independently represent an organic group, or R ₁ , R ₂ and R ₃ together form a nitrogen-containing complex together with the nitrogen atom to which they are bonded. forms a ring, Y ^- is 70 number average molecular weight having at least 0.1 or an average is an anion consisting of fatty roots 6 to 40 carbon atoms, in the quaternary ammonium salt shown in a molecule Provided is an aqueous dispersion of a vinyl polymer in which 5,000 water-solubilized epoxy compounds are dispersed in an aqueous medium using a dispersant.

Further, according to the present invention, the number average molecular weight of the quaternary ammonium base represented by the above formula (1) is at least 0.1 in one molecule and the number average molecular weight is 70 to 5,000.
A method for producing an aqueous dispersion of a vinyl polymer, comprising polymerizing a vinyl monomer in an aqueous medium in the presence of a water-solubilized epoxy compound.

A feature of the present invention is that a specific water-solubilized epoxy resin having a quaternary ammonium base is used instead of the dispersion stabilizer used in the conventional emulsion polymerization of vinyl monomers. is there. In the above formula (1), the “organic group” represented by R ₁ , R ₂ and R ₃ is any group as long as it does not substantially hinder the ionization of the ammonium base and does not participate in the polymerization reaction described below. In general, it may be substituted with a hydrocarbon group containing a hetero atom such as an oxygen atom in the form of a hydroxyl group or an alkoxy group.
Not more than 10, more preferably not more than 10 hydrocarbon groups. Examples of such a hydrocarbon group include an alkyl group, a cycloalkyl group, an aliphatic group such as an aryl group and an aralkyl group, an alicyclic or aromatic hydrocarbon group,
The alkyl group may be linear or branched, and preferably has 8 or less carbon atoms, and is preferably a lower alkyl group. For example, methyl, ethyl, n- or iso-propyl, n- , Iso-, sec- or tert-butyl, pentyl, heptyl, octyl and the like, and the cycloalkyl group has 5 carbon atoms.
Preferred are cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl groups and the like, and the aryl group includes phenyl, toluyl, xylyl group and the like, and the aralkyl group is preferably benzyl group. It is.

In the preferred specific examples of the above-mentioned hydrocarbon group containing a hetero atom such as an oxygen atom in the form of a hydroxyl group or an alkoxy group, the hydroxyalkyl group is particularly preferably a hydroxy lower alkyl group, such as hydroxymethyl or hydroxymethyl. Ethyl, hydroxybutyl, hydroxypentyl, hydroxyheptyl, hydroxyoctyl and the like;
As the alkoxyalkyl group, a lower alkoxy lower alkyl group is particularly preferred. For example, methoxymethyl, methoxyethyl, ethoxymethyl, n-propoxyethyl, iso
-Propoxymethyl, n-butoxymethyl, iso-butoxyethyl, tert-butoxyethyl and the like. When R ₁ , R ₂ and R ₃ are taken together to form a nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded, the heterocyclic ring is preferably a pyridine ring or a lower alkyl group, A pyridine ring mono-substituted with a methyl group is exemplified.

Here, the term "lower" means that the number of carbon atoms is six.
Means less than or equal to 4, especially less than or equal to 4. On the other hand, the anion Y ⁻
Is an anion composed of a fatty acid root having 6 to 40 carbon atoms. Examples of the anion-forming fatty acid include caproic acid (C ₅ H ₁₁ COOH) and capric acid (C ₉
H ₁₉ COOH), lauric acid (C ₁₁ H ₂₃ COO)
H), stearic acid (C17H35COOH), behenic acid (C21H43COOH), melissic acid _{(C 29} H
Saturated fatty acids such as ₅₉ COOH); oleic acid (C ₁₇
H ₃₃ COOH), linoleic acid (C ₁₇ H ₃₁ COO)
H) unsaturated fatty acids such as linolenic acid (C ₁₇ H ₂₉ COOH), stearic acid (C ₁₇ H ₃₁ COOH);
Dibasic acids such as sebacic acid; polyvalent fatty acids such as so-called dimer acid obtained by thermally polymerizing unsaturated fatty acids such as linoleic acid; and the like. These fatty acids can be used alone or as a mixture (for example, lanolin fatty acids). When the fatty acid has 6 or less carbon atoms, there is a disadvantage that the surface activity is low, and when it is 60 or more, the surface activity is undesirably reduced. Preferred fatty acids are those having 10 to 25 carbon atoms on average.

Representative examples of the quaternary ammonium base represented by the above formula (1) are as follows.

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The quaternary ammonium base can be present in an amount required to make the epoxy compound to which this group binds water-soluble, and the number can be changed according to the type and molecular weight of the base resin. In general, it is desirable that at least 0.1, preferably 0.5 to 1.5, be present on average in one molecule of the polymer. 0.
If it is less than 1, the epoxy compound cannot be made water-soluble.

As used herein, the term "water-soluble" used for an epoxy compound refers not only to a case where the compound forms a true solution in water, but also to a case where the compound is in a colloidal or micellar form in water. It refers to "water-soluble" in a broad sense, including the case where it is stably finely dispersed in a form. The water-soluble epoxy compound having the above ammonium base, for example,
The following reaction formula

[0018]

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In accordance with the above, an epoxy compound, a tertiary amine and an acid are allowed to coexist and the temperature is 50 to 130 ° C., preferably 60 to 130 ° C.
It can be easily produced by reacting at 0 ° C. for about 1 to 10 hours. In addition, the third for the epoxy compound
When the amount of the secondary amine and the acid is large, the reaction product tends to be in the form of a solution and the surface activity is reduced. On the other hand, when the amount is small, the reaction product tends to be in a dispersed state and the system becomes unstable. In the above reaction formula, P represents a base portion of the epoxy compound, m and n are each an integer of 1 or more, provided that m ≧ n, and R ₁ , R ₂ , R ₃ and Y are as defined above. It is on the street. The epoxy compound used in the above reaction is an epoxy group

[0020]

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A substance having an average of at least one in one molecule,
Generally at least 70, preferably 70-5,000,
More preferably, those having a number average molecular weight in the range of 350 to 1,400 are suitable. Number average molecular weight of 70
In the following, there are many defects in practical use, which is unsuitable. When it is more than 5,000, the surface activity is too low, so that the object is not achieved, which is not preferable. As such epoxy compounds, those known per se can be used, and include, for example, polyglycidyl ethers of polyphenols which can be produced by reacting polyphenols with epichlorohydrin in the presence of an alkali.

Examples of polyphenols usable herein include bis (4-hydroxyphenyl) -2,2
-Propane, 4,4'-dihydroxybenzophenone,
Bis (4-hydroxyphenyl) -1.1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane,
Bis (4-hydroxy-tert-butyl-phenyl)
-2,2-propane, bis (2-hydroxynaphthyl)
Methane, 1,5-dihydroxynaphthalene and the like can be mentioned. Other usable epoxy compounds include polyglycidyl ethers of phenolic novolak resins and polyglycidyl ethers of polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, etc.), butylene oxide, styrene oxide, polyethylene oxide, glycidyl. Esters and the like.

Among the above-mentioned epoxy compounds, bisphenol type epoxy resins having a number average molecular weight of about 350 or more are most suitable from the viewpoint of excellent coating film properties. As a commercially available product, for example, Epicoat 82 (trade name, manufactured by Ciel Chemical Co., Ltd.)
8, 1001, 1004, 1009, and the like. In the present invention, the unmodified aromatic epoxy resin as described above is further heat-treated in the presence of a modifier for an epoxy group, and is used after being modified into an aromatic epoxy resin having a high molecular weight and a low softening point. The coated film has the advantage that the amount of water extraction and the physical properties of the coated film are small and the adhesion to the substrate surface is further improved. Examples of the denaturing agent include adipic acid, sebacic acid, and dimer acid, but it is preferable to use dimer acid for the purpose of improving adhesion.

Specific examples of the tertiary amine used in the above reaction include alkylamines such as trimethylamine, triethylamine and tributylamine, 2-dimethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol and dimethylamine. Alcohol amines such as aminomethylpropanol, morpholine and the like are used. The vinyl-based monomer subjected to polymerization in an aqueous medium in the presence of the water-soluble epoxy compound thus obtained includes a vinyl-based monomer which has been conventionally polymerizable by solution polymerization,
Representative examples are as follows. (Meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, n-decyl (meth)
Acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; cyclohexyl (meth) acrylate; benzyl (meth) acrylate , Phenethyl (meth) acrylate; (meth) acrylamide, N-methylol (meth)
Acrylamide, N-methoxy (meth) acrylamide, N-butoxy (meth) acrylamide, Ni-propoxy (meth) acrylamide; (meth) acrylonitrile; styrene, α-methylstyrene, vinyltoluene, divinylbenzene and the like. Each of these monomers may be used alone, or two or more of them may be used in combination.

On the other hand, the aqueous medium used in the polymerization reaction of the present invention may be water or a mixture of water and a water-miscible inert organic solvent (the mixing ratio is 100/5 to 100/50 by weight of water).
And water-miscible inert organic solvents that can be used include, for example, alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl isobutyl ketone; ethylene glycol monomethyl Glycol ethers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and diethylene glycol monobutyl ether are exemplified. The aqueous dispersion in the present invention is obtained by radical polymerization of a vinyl monomer in the presence of a water-soluble epoxy compound, and the mixing ratio (weight) of the epoxy resin to the vinyl monomer is 0.5 / 99.5 to 80 /. 20 range, preferably 5
/ 95 to 30/70.

When the proportion of the epoxy compound is 0.5% or less, the system becomes unstable during radical polymerization of a vinyl monomer, and the storage stability of the obtained aqueous dispersion is poor.
When the ratio of the epoxy compound is 80% or more, the epoxy compound is economically disadvantageous because of its high price. The polymerization reaction between the epoxy compound and the vinyl monomer can be performed by a usual method. For example, a method in which a mixture of the vinyl monomer and the polymerization catalyst is dropped and polymerized in a solution in which an epoxy compound is dissolved; a method in which an epoxy resin and a vinyl monomer are mixed, and then a polymerization catalyst is added and polymerized; . As the polymerization catalyst that can be used, ammonium persulfate, potassium persulfate, sodium bisulfite, benzoyl peroxide, perbutyl octate, t-butyl hydroperoxide, azobisisobutyronitrile, azobisvaleronitrile, 2,2
2'-azobis (2-aminopropane) hydrochloride and the like.
Generally, it can be used in a ratio of 0.5 to 10 parts by weight with respect to 00 parts by weight. The main polymerization reaction may proceed at a relatively low temperature such as room temperature in some cases, but it is preferable to complete the polymerization at 60 to 100 ° C. for about 1 to 10 hours. The aqueous dispersion thus obtained is extremely stable even with a small amount of the epoxy resin acting as a surfactant, and changes in sedimentation, separation, thickening, etc. even after several months in a storage test at a temperature of 30 ° C. Does not occur.

In this aqueous dispersion, since the dispersion polymer has a hydroxyl group, a crosslinking agent such as aminoplast or block isocyanate such as melamine formaldehyde resin, urea-formaldehyde resin, and phenol formaldehyde resin is added. A high degree of water resistance and boiling resistance can be obtained. Examples of the use of the aqueous dispersion obtained by the present invention include a metal clear coating, a coloring coating, and a water-based ink. Particularly, when the aqueous dispersion is used for the inner surface of a can, it has good adhesion to a metal substrate and good workability. It is. Also, by dispersing the polymer particles in the same manner as the acrylic component,
It has the characteristic that good flavor can be obtained because an acrylic component having a poor flavor can be confined.

[0028]

The present invention will be further described with reference to the following examples. In the following Examples, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

Production of Water-Soluble Epoxy Resin Production Example 1 A four-necked flask was charged with 300 parts of purified lanolin fatty acid SKLIRO (manufactured by Croda Japan KK) and 150 parts of epoxy resin Epicoat 828 (manufactured by Ciel Chemical Co., Ltd.) and heated to about 100 ° C. After melting by heating, 35 parts of dimethylaminoethanol was added from the addition funnel in 5 minutes, and the mixture was kept at 100 ° C. for 2 hours. After confirming that the heat generation had completely stopped, 35 parts of dimethylaminoethanol was further added.
To neutralize the remaining fatty acids, then add 4 parts deionized water.
80 parts were added to prepare a paste-like water-soluble epoxy resin solution (A-1) having a nonvolatile content of 50%.

Production Example 2 The procedure of Production Example 1 was repeated except that 220 parts of linoleic acid were added in place of the purified lanolin fatty acid.
By adding 0 parts, a paste-like epoxy resin solution (A-2) having a nonvolatile content of 50% was produced.

Production Example 3 The same procedure as in Production Example 1 was repeated except that 560 parts of dimer acid was added in place of the purified lanolin fatty acid.
By adding 0 parts, a paste-like epoxy resin solution (A-3) having a nonvolatile content of 50% was produced.

Production Example 4 In place of the purified lanolin resin acid of Production Example 1, 105 parts of heptanoic acid and instead of Epicoat 828, Epicoat 10
04, 900 parts were added and the same.
Five parts were added to produce a paste-like epoxy resin solution (A-4) having a nonvolatile content of 50%.

Production Example 5 Acetic acid 48 was used instead of the purified lanolin fatty acid of Production Example 1.
Parts, except that 900 parts of Epicoat 1004 was added instead of Epicoat 828, and finally 980 parts of water was added to produce a paste-like water-soluble epoxy resin solution (A-5) having a nonvolatile content of 50%. .

Production Example 6 In place of the purified lanolin fatty acid of Production Example 1, 72 parts of lactic acid was added, and instead of Epikote 828, Epikote 100 was added.
9 except that 2400 parts were added.
By adding 0 parts, a paste-like epoxy resin solution (A-6) having a nonvolatile content of 50% was produced.

Example 1 Formulation (1) 40 parts of a water-soluble epoxy resin solution (A-1) (2) 360 parts of deionized water (3) 50 parts of styrene (4) 45 parts of n-butyl acrylate (5) Divinylbenzene 5 parts (6) 70% tert-butyl hydroperoxide 0.3 parts (7) Deionized water 100 parts (8) 50% ammonium bisulphide 0.45 parts In a four-necked flask (1) and (2) It was placed, _{N 2} and gas replacement, stirred well stirrer under a stream of _{N 2,} (3),
(4), (5) and (6) were added, and the mixture was stirred well and emulsified, and then kept at 70 ° C. in a hot water bath. Separately, in the flask (7)
A solution obtained by weighing and dissolving (8) was dropped from a dropping funnel over about 2 hours to carry out polymerization, and then kept at the same temperature for about 2 hours. As a result, the nonvolatile content was 20% and the particle size was 0.15 μm.
(B-1) was obtained. The obtained emulsion was mixed with a solvent, a thickener and a crosslinked resin as described below to form a coating. (1) 120% emulsion 120 parts (2) Butyl cellosolve 5 parts (3) Butanol 5 parts (4) Cymel 370 (Melamine resin manufactured by Mitsui Toatsu Co., Ltd.) 3 parts (5) 28% acrylol ASE-60 (Rohm & Haas (Thickener manufactured by Co., Ltd.) 3 parts (6) Ammonia 136 parts (1) was weighed in a stainless beaker, and (2), (3), (4), and (5) were sequentially added thereto with stirring. After uniform mixing, (6) was gradually added to adjust the pH to 8, and the non-volatile content was 20% and the viscosity was 230 cps (25 cps).
C).

Examples 2 to 4 In the same manner as in Example 1, the epoxy resin solution (A-2)
After obtaining an emulsion using (A-3) and (A-4), a water-based paint 2, 3
And 4 were obtained.

Comparative Examples 1 and 2 Emulsions were obtained using the epoxy resin solutions (A-5) and (A-6) in the same manner as in Example 1 and then mixed with a solvent, a thickener and a crosslinking agent. Water-based paints 5 and 6 were obtained. Table 1
Table 2 shows the main properties of the obtained water-based paints, and Table 2 shows the properties of the coatings.

[0038]

[Table 1]

[0039]

[Table 2]

[Test Method] Adhesion: Eleven cuts each in the vertical and horizontal directions were cut into a 1.5 mm width using a knife on the coating surface. 2
The cellophane adhesive tape with a width of 4 mm was adhered closely, and the adhesiveness of the gobang when strongly peeled was observed. ◎: No peeling at all ○: Slight peeling Δ: Significant peeling ×: Marked peeling

Hot water resistance: After immersion in boiling water for 30 minutes,
The coating film was visually and visually evaluated and peeled off with a cellophane adhesive tape. Workability: Using a special goby fold type Dupont impact tester, place the folded sample at the bottom and weigh 1 with a flat contact surface.
The length of a crack in the coating film at the bent portion when a Kg iron weight was dropped from a height of 50 cm was measured. 0 to 10 mm ◎ mark 10 to 15 mm ○ mark 15 to 25 mm △ mark 25 mm or more... Solvent extraction amount: An extraction test was performed for 3 hours with neflux of methyl ethyl ketone. Gel remainder 98% or more ◎ 95% or more ○ 92% or more △ 90% or more ×

Corrosion resistance: Various test cans were hot-packed with 10% pine juice at 98 ° C. and wound tightly. After storage at 37 ° C. for 6 months, an open can test was conducted to observe the state of internal corrosion. ：: No corrosion ○: Slight corrosion is observed △: Corrosion is remarkable

Storage property: The condition after storing the 20% aqueous dispersion at 30 ° C. for 2 months was visually observed. ◎: No abnormality was observed at all △: Particle size was slightly increased but no sedimentation was observed ×: Sediment was slightly observed Flavorability: Tap water was treated with activated carbon in a two-piece aluminum can coated to a dry film thickness of 20μ Filled with 250 ml of water, tightly wound and sterilized at 100 ° C. for 30 minutes.
After storing for 3 months at ℃, a flavor test was conducted. ◎: No change ○: Slight change ×: Notable change

[0044]

The aqueous dispersion obtained by the present invention maintains an extremely stable state even when the amount of the epoxy resin on which the surfactant acts is small, and the acrylic component having a poor flavor is dispersed inside the dispersed particles. Since it can be confined in a can, it shows excellent flavor properties even when used as a paint for the inner surface of a can.

Continuation of the front page (56) References JP-A-62-223211 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 2/28

Claims (6)

(57) [Claims] 1. A vinyl polymer represented by the formula: In the formula, R ₁ , R ₂ and R ₃ each independently represent an organic group, or R ₁ , R ₂ and R ₃ together form a nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded. and, Y ^- number average molecular weight having at least 0.1 or an average is an anion consisting of fatty roots 6 to 40 carbon atoms, in the quaternary ammonium salt shown in one molecule 70～5,0
An aqueous dispersion of a vinyl polymer in which the water-soluble epoxy compound of No. 00 is dispersed in an aqueous medium using a dispersant. 2. The epoxy compound is at least one selected from polyglycidyl ether of polyphenol, polyglycidyl ether of phenolic novolak resin and polyglycidyl ether of polyhydric alcohol, butylene oxide, styrene oxide, and polyethylene oxide. An aqueous dispersion of the vinyl polymer according to claim 1. 3. A tertiary ammonium salt forming a quaternary ammonium base.
Secondary amines are alkylamines, alcoholamines,
3. The aqueous dispersion of a vinyl polymer according to claim 1, which is one or more selected from morpholine. 4. The method according to claim 1, wherein one or more selected from aminoplasts such as melamine formaldehyde resin, urea-formaldehyde resin, phenol formaldehyde resin and the like and blocked isocyanates are added as a crosslinking agent. Aqueous dispersion of a vinyl polymer. 5. A compound of the formula In the formula, R ₁ , R ₂ and R ₃ each independently represent an organic group, or R ₁ , R ₂ and R ₃ together form a nitrogen-containing heterocyclic ring together with the nitrogen atom to which they are bonded. and, Y ^- number average molecular weight having at least 0.1 or an average is an anion consisting of fatty roots 6 to 40 carbon atoms, in the quaternary ammonium salt shown in one molecule 70～5,0
A method for producing an aqueous dispersion of a vinyl polymer, comprising polymerizing a vinyl monomer in an aqueous medium in the presence of a water-soluble epoxy compound of No. 00. 6. A vinyl monomer having an epoxy resin to vinyl monomer percentage ratio (weight) of 0.5 / 99.5 to 8%.
The method for producing a vinyl polymer aqueous dispersion according to claim 5, wherein the polymerization is carried out in the presence of a 0/20 water-soluble epoxy compound.