JP2002371164A - Aqueous emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous emulsion composition excellent in solvent resistance, water resistance and stability with time. SOLUTION: This aqueous emulsion comprises (A) a vinyl alcohol polymer containing 1-20 mole % <=4C α-olefin unit in the molecule and having >=90 mole % degree of saponification as a dispersant and a polymer containing 0.1-10 pts.wt. monomer unit having an N-alkylolamide group to 100 pts.wt. vinyl ester polymer as a dispersoid and (B) an aluminum compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous emulsion composition, and more particularly, to an aqueous emulsion composition having excellent solvent resistance, water resistance and shelf stability.

[0002]

2. Description of the Related Art Conventionally, polyvinyl alcohol (hereinafter referred to as P
VA) is widely used as a protective colloid for emulsion polymerization of ethylenically unsaturated monomers, particularly vinyl ester monomers represented by vinyl acetate, and is used as a protective colloid. Vinyl ester aqueous emulsion obtained by emulsion polymerization is used for various adhesives for paper, woodworking and plastics, various binders for impregnated paper and non-woven products, admixtures, jointing materials, paints, paper processing And widely used in fields such as fiber processing. By adjusting the degree of saponification of the PVA-based polymer, such an aqueous emulsion generally has a low viscosity, exhibits a viscosity close to a Newtonian flow, and has a relatively good water resistance. And has a relatively low temperature dependence of the emulsion viscosity, so that it has been used in various applications. However, some of the aqueous emulsions lack fluidity (high-speed coating properties), have poor water resistance, have a large temperature dependence of emulsion viscosity, and have a marked increase in emulsion viscosity at low temperatures. Has disadvantages. In order to improve this drawback, a vinyl alcohol polymer containing an ethylene unit has been proposed, and the water resistance and the low-temperature storage stability have been greatly improved.

However, since these conventional vinyl ester polymers have insufficient solvent resistance, the surface of a laminated material obtained by using an application requiring solvent resistance, for example, using an emulsion as an adhesive, can be treated with an organic solvent. In the case of applying with a solvent-based paint, there is a disadvantage that the adhesive performance of the emulsion is reduced due to the organic solvent. Further, an aluminum compound is blended with an aqueous emulsion containing a polymer composed of a monomer unit having a carboxyl group such as a vinyl acetate monomer and (meth) acrylic acid as a dispersoid using ethylene-modified PVA as a dispersant. An aqueous emulsion composition is also known (Japanese Patent Application Laid-Open No. 2001-72820), but this composition is not sufficient in terms of the solvent resistance of the film.

[0004]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an aqueous emulsion composition having excellent solvent resistance, water resistance and shelf stability (viscosity stability). The purpose is to do so.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to develop an aqueous emulsion composition having the above-mentioned preferable properties.
It contains 1 to 20 mol% of olefin units and has a saponification degree of 90.
Mol% or more of a vinyl alcohol polymer as a dispersant,
With respect to 100 parts by weight of the vinyl ester monomer unit, N-
Alkylamide group-containing monomer unit 0.1-1
The present inventors have found that an aqueous emulsion composition comprising an aqueous emulsion (A) containing a polymer containing 0 parts by weight as a dispersoid and an aluminum compound (B) satisfies the object, and completed the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION An α-olefin unit having 4 or less carbon atoms in a molecule used as a dispersant for the aqueous emulsion (A) used in the aqueous emulsion composition of the present invention has one to one.
A vinyl alcohol polymer containing 20 mol% and having a degree of saponification of 90 mol% or more can be obtained by saponifying a copolymer of a vinyl ester and an α-olefin having 4 or less carbon atoms. Here, the α-olefin unit having 4 or less carbon atoms includes ethylene, propylene, butylene, and isobutylene units, and ethylene units are preferable.

Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate and vinyl pivalate. Vinyl acetate is economically preferable.

The content of the α-olefin unit having 4 or less carbon atoms must be 1 to 20 mol%,
Preferably it is 2 to 15%, more preferably 3 to 10%. When the content of α-olefin units having 4 or less carbon atoms is 1
When the amount is less than mol%, an aqueous emulsion satisfying simultaneously the solvent resistance, the water resistance and the storage stability cannot be obtained.
If it exceeds 0 mol%, the water solubility will decrease, and there is a concern that a stable aqueous emulsion cannot be obtained.

[0009] Further, the molecule used for the dispersant contains 1 to 20 mol% of α-olefin units having 4 or less carbon atoms,
The vinyl alcohol polymer having a saponification degree of 90 mol% or more may be a copolymer of an ethylenically unsaturated monomer copolymerizable within a range not to impair the effects of the present invention. Such ethylenically unsaturated monomers include, for example, acrylic acid, methacrylic acid, fumaric acid, (anhydride) maleic acid,
Itaconic acid, acrylonitrile, methacrylonitrile,
Acrylamide, methacrylamide, trimethyl- (3
-Acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, Examples include vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, sodium allyl sulfonate, and the like. Further, in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid, a vinyl ester-based monomer such as vinyl acetate is converted to an α having 4 or less carbon atoms.
-A terminal modified product obtained by copolymerizing with an olefin and saponifying it can also be used.

The vinyl alcohol polymer having 1 to 20 mol% of α-olefin units in the molecule used as a dispersant for the aqueous emulsion of the present invention and having a saponification degree of 90 mol% or more has a saponification degree of 90 mol% or more. And more preferably at least 92 mol%, further preferably at least 93 mol%. If the saponification degree is less than 90 mol%, an aqueous emulsion composition having excellent solvent resistance and water resistance cannot be obtained. In order to more suitably achieve the object of the present invention, the polymerization degree of the vinyl alcohol-based polymer should be 1
The range is preferably from 00 to 8000, and more preferably from 300 to 3000.

The vinyl ester monomer constituting the dispersoid in the aqueous emulsion constituting the aqueous emulsion composition of the present invention includes vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate and vinyl versatate. However, vinyl acetate is preferably used.

In the present invention, it is essential to use a monomer containing an N-alkylolamide group. Examples of the monomer containing an N-alkylolamide group include N-methylolacrylamide, N-ethanolacrylamide, N-propanolacrylamide, N-
Methylol methacrylamide, N-methylol methacrylamide, N-propanol methacrylamide and the like are mentioned, and usually N-methylol acrylamide and N-methylol methacrylamide are preferably used. The number of carbons in the alkylol is preferably from 1 to 5.

In the present invention, the monomer unit containing an N-alkylolamide group is a vinyl ester monomer 1
It is important that the content is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.25 to 3 parts by weight with respect to 00 parts by weight. When the content of the monomer unit is less than 0.1 part by weight, water resistance and solvent resistance are insufficient, and when it exceeds 10 parts by weight, polymerization stability may be reduced.

The method of adding a monomer containing an N-alkylolamide group during the emulsion polymerization is not particularly limited, but a monomer containing an N-alkylolamide group may be added to a vinyl ester monomer. At the same time, or a method in which both are uniformly mixed and added at the early stage and / or late stage of the polymerization. The aqueous emulsion constituting the aqueous emulsion composition of the present invention is the above-mentioned α having 4 or less carbon atoms.
An aqueous solution of a vinyl alcohol polymer having an olefin unit (hereinafter sometimes abbreviated as α-olefin-modified PVA) is used as a dispersant, and a conventionally known polymerization initiator (eg, hydrogen peroxide, ammonium persulfate, peroxide) is used. In the presence of potassium sulfate or the like), the above-mentioned vinyl ester-based monomer and a monomer containing an N-alkylolamide group are added temporarily or continuously, followed by emulsion polymerization. An emulsion polymerization method in which a vinyl ester monomer and a monomer containing an N-alkylolamide group are emulsified in advance using an aqueous solution of an α-olefin-modified PVA, and the emulsion is continuously added to the polymerization reaction system. Can also be adopted. In the emulsion polymerization, other copolymerizable ethylenically unsaturated monomers can be used as long as the effects of the present invention are not impaired. Such ethylenically unsaturated monomers include ethylene, propylene, olefins such as isobutylene,
Halogenated olefins such as vinyl chloride, vinyl fluoride, vinylidene chloride, and vinylidene fluoride; acrylics such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and 2-hydroxyethyl acrylate Methacrylates such as acid esters, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and the like And acrylamide, methacrylamide, N, N-dimethylacrylamide, acrylamide-2-methylpropanesulfonic acid and its sodium salt. Riruamido monomer, styrene, alpha
Styrene-based monomers such as -methylstyrene, p-styrenesulfonic acid and its sodium and potassium salts, and other N-vinylpyrrolidone and the like, and butadiene, isoprene, and diene-based monomers such as chloroprene. They may be used alone or in combination of two or more. The amount of the α-olefin-modified PVA is not particularly limited, but is a polymer (dispersoid) of a vinyl ester monomer and a monomer containing an N-alkylolamide group.
It is preferably in the range of 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight. The amount used is 1
If the amount is less than 30 parts by weight or more than 30 parts by weight, the polymerization stability may be lowered or the water resistance may be lowered. As the aqueous emulsion used in the present invention, the aqueous emulsion obtained by the above method can be used as it is, but if necessary, various known emulsions may be added and used as long as the effects of the present invention are not impaired. Can be.
As the dispersant in the aqueous emulsion used in the present invention, α-olefin-modified PVA is used,
If necessary, a conventionally known anionic, nonionic or cationic surfactant, a PVA-based polymer, hydroxyethylcellulose or the like can be used in combination.

The aluminum compound (B) used in the present invention is not particularly limited, but a water-soluble aluminum compound is preferably used, and specifically, aluminum chloride, aluminum nitrate and its hydrate, aluminum sulfate (sulfate) Band) is preferably used. Among them, aluminum chloride and aluminum nitrate are more preferably used.

In the aqueous emulsion composition of the present invention, the amount of the aluminum compound (B) to be added to the aqueous emulsion is 0.01 to 5 parts by weight based on 100 parts by weight (solid content) of the aqueous emulsion (A). Preferably 0.02 to 3 parts by weight, more preferably 0.03 to 3 parts by weight.
More preferably, it is 2.5 parts by weight. When the compounding ratio of the aluminum compound (B) is less than 0.01 part by weight, water resistance and solvent resistance are reduced, and when it is more than 5 parts by weight, the viscosity stability of the aqueous emulsion composition may be reduced.

The aqueous emulsion composition of the present invention may contain various organic solvents such as toluene, perchrene, dichlorobenzene and trichlorobenzene in order to adjust the drying property, setting property, viscosity, film forming property and the like, if necessary. , Starch, modified starch, oxidized starch, sodium alginate,
Water-soluble polymers such as carboxymethylcellulose, methylcellulose, maleic anhydride / isobutene copolymer, maleic anhydride / styrene copolymer, maleic anhydride / methylvinyl ether copolymer, urea / formalin resin, urea / melamine / formalin resin , Thermosetting resins such as phenol / formalin resins, and fillers such as clay, kaolin, talc, calcium carbonate, and wood flour;
It may also contain a bulking agent such as flour, a pigment such as titanium oxide, or various additives such as a plasticizer, an antifoaming agent, an antifreezing agent, a preservative, and a rust inhibitor. Examples of the plasticizer include dibutyl phthalate, ethylene glycol monophenyl ether, and texanol. The aqueous emulsion composition of the present invention is excellent in solvent resistance, and takes advantage of its characteristics of excellent water resistance and shelf stability, and is used for adhesives required for solvent resistance, for example, by using an emulsion as an adhesive. Adhesive applications such as applying the surface of the obtained laminated wood with an organic solvent-based paint, other woodworking adhesives,
It is used in various applications such as paper processing adhesives, paints, and fiber treatment agents. In the present invention, the “solvent” having solvent resistance includes organic solvents such as acetone, toluene, ethanol, methanol, isopropanol, normal propanol, methyl acetate, and ethyl acetate.

[0018]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples, “parts” and “%” mean on a weight basis unless otherwise specified.

Production Example 1 of Aqueous Emulsion A 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was charged with 300 ion-exchanged water.
g, PVA-1 (polymerization degree: 1000, saponification degree: 99 mol%, ethylene modification amount: 7 mol%), and sodium acetate (0.5 g) were charged and stirred at 95 ° C. for 2 hours to completely dissolve. Next, the PVA aqueous solution was cooled and replaced with nitrogen.
After the temperature was raised to 60 ° C. while stirring at 0 rpm, 26 g of vinyl acetate and N-methylol were added while continuously dropping 15 g of a 20% aqueous solution of sodium tartrate and 30 g of 5% aqueous hydrogen peroxide over 2.5 hours. Acrylamide 0.
26 g was charged and polymerization was started. 30 minutes after the start of the polymerization, completion of the initial polymerization was confirmed. Next, 234 g of vinyl acetate and 2.34 g of N-methylolacrylamide were continuously added over 2 hours to complete the polymerization, and a polyvinyl acetate emulsion having a solid concentration of 48.5% (to 100 parts by weight of vinyl acetate unit). On the other hand, N-methylolacrylamide (containing 1 part by weight) was obtained. This emulsion 100
10 parts of dibutyl phthalate was added to and mixed with part by weight (solid content) (Em-1).

Production Example 2 of Aqueous Emulsion A 300 ml ion-exchanged water was placed in a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet.
PVA-2 (degree of polymerization 1700, degree of saponification 95 mol%, ethylene modification amount 5 mol%) 26 g, sodium acetate 0.5
g was stirred at 95 ° C. for 2 hours and completely dissolved. Next, the PVA aqueous solution was cooled and replaced with nitrogen.
After the temperature was raised to 60 ° C. while stirring with
15% aqueous solution and 30 g of 5% hydrogen peroxide solution in 2.5 g
While continuously dropping over time, 26 g of vinyl acetate and 0.26 g of N-methylolacrylamide were charged to initiate polymerization. 30 minutes after the start of the polymerization, completion of the initial polymerization was confirmed. Next, 234 g of vinyl acetate and 2.34 g of N-methylolacrylamide were continuously added over 2 hours to complete the polymerization, and a polyvinyl acetate emulsion having a solid content concentration of 48.5% (to 100 parts by weight of vinyl acetate unit). On the other hand, N-methylol acrylamide contained 1 part by weight)
was gotten. 100 parts by weight of this emulsion (solid content)
Was mixed with 10 parts of dibutyl phthalate (E
m-2).

Production Example 3 of Aqueous Emulsion Instead of using PVA-1 used in Production Example 1 of Aqueous Emulsion, PVA-3 (PVA-117 manufactured by Kuraray;
An aqueous emulsion (Em-3) was obtained in the same manner as in Production Example 2 of the aqueous emulsion except that the degree of polymerization was 1700 and the degree of saponification was 98.5 mol%.

Aqueous Emulsion Production Example 4 An aqueous emulsion (Em-4) was obtained in the same manner as in Aqueous Emulsion Production Example 1 except that N-methylolacrylamide was not used.

Aqueous Emulsion Production Example 5 An aqueous emulsion (Em-5) was obtained in the same manner as in the aqueous emulsion production example 1 except that N-methylol methacrylamide was used instead of N-methylol acrylamide. Was.

Example 1 "Em-1" 10 obtained in Production Example 1 of an aqueous emulsion
An aqueous emulsion composition was prepared by mixing 1 part by weight of aluminum nitrate nonahydrate with respect to 0 parts by weight (solid content). Water resistance of the film of the obtained aqueous emulsion composition,
Solvent resistance and storage stability (viscosity stability) were evaluated in the following manner. Table 1 shows the results.

(Evaluation of Emulsion) (1) Water Resistance of Film The obtained aqueous emulsion was prepared at 20 ° C. and 65% RH under P
It was cast on ET and dried for 7 days to obtain a dry film of 500 μm. When this film was punched into a circular shape having a diameter of 2.5 cm, and it was immersed in boiling water as a sample for 4 hours,
The water absorption and elution rate of the film were determined. Dissolution rate (%): {1- (weight of dried film after immersion / weight of dried film before immersion)} × 100 Water absorption (%): 吸 (weight of absorbed water of film after immersion / weight of dried film before immersion) Weight) -1｝ × 100 * Absolute dry weight of film before immersion; Film weight (water content) before immersion-
(Coating weight before dipping (water content) x coating water content (%) / 10
0) * Moisture content of film: The film (sample different from the sample immersed in water at 20 ° C) is completely dried at 105 ° C for 4 hours, and the water content of the film is determined in advance. * Weight of absolutely dried film after immersion: Weight of absolutely dried film after immersion at 105 ° C for 4 hours. Water absorption weight of the film after immersion: After the film after immersion was pulled out of water, the water on the film was wiped off with gauze and weighed. (2) Solvent resistance The obtained aqueous emulsion was subjected to P
It was cast on ET and dried for 7 days to obtain a dry film of 500 μm. This film was punched out into a circular shape having a diameter of 2.5 cm, and the sample was immersed in acetone for 24 hours to determine the absorption rate and elution rate of the film. Dissolution rate (%): {1- (absolute dry weight of film after immersion / absolute dry weight of film before immersion)} × 100 Liquid absorption rate (%): ｛(weight of absorbed liquid after immersion / film before immersion) Absolute dry weight) -1 x 100 * Absolute dry weight of film before immersion; Film weight before immersion (water content)-
(Coating weight before immersion (water content) x film water content (%) / 10
0) * Coating water content: The coating (sample different from the sample immersed in water at 20 ° C) is completely dried at 105 ° C for 4 hours, and the water content of the coating is determined in advance. * Weight of absolutely dried film after immersion: Weight of absolutely dried film after immersion at 105 ° C for 4 hours. Absorbent weight of film after immersion: After immersing the film from acetone, the acetone on the film was wiped off with gauze and weighed. (3) Viscosity stability 30 minutes when the emulsion was left at 5 ° C. and 50 ° C.
The change in viscosity after a day was observed.

Example 2 A test was performed in the same manner as in Example 1 except that 0.5 part by weight of aluminum chloride was used instead of 1 part by weight of aluminum nitrate 9-hydrate. The results are shown in Table 1.

Example 3 Example 1 was repeated except that 1 part by weight of aluminum nitrate 9 hydrate was used instead of 1 part by weight of aluminum nitrate.
The test was performed in the same manner as described above. The results are shown in Table 1.

Example 4 A test was conducted in the same manner as in Example 1 except that 1 part by weight of aluminum nitrate 9 hydrate was used instead of 1 part by weight of aluminum nitrate. The results are shown in Table 1.

Comparative Example 1 A test was performed in the same manner as in Example 1 except that the aluminum nitrate nonahydrate used in Example 1 was not used. The results are shown in Table 1.

Example 5 The procedure of Example 1 was repeated, except that “Em-2” obtained in Aqueous Emulsion Production Example 2 was used instead of “Em-1” obtained in Aqueous Emulsion Production Example 1. The test was performed in the same manner. The results are shown in Table 1.

Comparative Example 2 Example 1 was repeated except that “Em-3” obtained in Aqueous Emulsion Production Example 3 was used instead of “Em-1” obtained in Aqueous Emulsion Production Example 1. The test was performed in the same manner. The results are shown in Table 1.

Comparative Example 3 The procedure of Example 1 was repeated except that “Em-4” obtained in Aqueous Emulsion Production Example 4 was used instead of “Em-1” obtained in Aqueous Emulsion Production Example 1. The test was performed in the same manner. The results are shown in Table 1.

Example 6 Example 1 was repeated except that "Em-5" obtained in Aqueous Emulsion Production Example 5 was used in place of "Em-1" obtained in Aqueous Emulsion Production Example 1. The test was performed in the same manner. The results are shown in Table 1.

Comparative Example 4 A 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was charged with 100 parts of ion-exchanged water.
Parts, acetoacetyl group-modified PVA (polymerization degree 1030, saponification degree 98.5 mol%, acetoacetyl group modification amount 5.0
Mol%) of vinyl alcohol-based polymer (5 parts).
Dissolved completely at ° C. Next, this PVA aqueous solution is cooled,
After replacing with nitrogen, vinyl acetate 1 was stirred at 140 rpm.
After charging 0 parts and heating to 60 ° C., polymerization was started in the presence of a hydrogen peroxide / tartaric acid redox initiator system. After 15 minutes from the start of the polymerization, 90 parts of vinyl acetate were continuously added over 3 hours to complete the polymerization. Solids concentration 55
% Polyvinyl acetate emulsion was obtained. To 100 parts by weight (solid content) of this emulsion, 5 parts of phenoxyethanol was added and mixed (Em-6). An aqueous emulsion composition was prepared by blending 5 parts by weight (2 parts by weight of solid content) of a 40% aqueous glyoxal solution with 100 parts by weight of the obtained “Em-6”. The film water resistance, solvent resistance and viscosity stability of the obtained aqueous emulsion composition were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5 A 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was charged with ion-exchanged water 260.
g, 37 g of PVA-1 (polymerization degree 1000, saponification degree 99.0 mol%, ethylene modification amount 7.0 mol%) 9
The mixture was stirred at 5 ° C for 2 hours to completely dissolve. Next, this PV
The aqueous solution A was cooled, replaced with nitrogen, charged with 37 g of vinyl acetate and 3.7 g of acrylic acid while stirring at 200 rpm, heated to 60 ° C., and then polymerized in the presence of a hydrogen peroxide / tartaric acid redox initiator system. Started. Initiation of polymerization 1
After 5 minutes, 333 g of vinyl acetate was continuously added over 3 hours to complete the polymerization. Solids concentration 48.3%
Was obtained (containing 1 part by weight of acrylic acid with respect to 100 parts by weight of vinyl acetate). To 100 parts by weight (solid content) of this emulsion, 5 parts of dibutyl phthalate was added and mixed (Em-7). For 100 parts by weight (solid content) of the obtained “Em-7”,
An aqueous emulsion composition was prepared by mixing 0.5 parts by weight of aluminum chloride. Example 1 shows the film water resistance, solvent resistance and viscosity stability of the obtained aqueous emulsion composition.
The evaluation was performed in the same manner as described above. The results are shown in Table 1.

[0036]

[Table 1]

[0037]

The aqueous emulsion composition of the present invention is excellent in solvent resistance, water resistance and shelf stability, and is used for woodworking adhesive, plywood adhesive, paper processing agent, paint,
It is widely and suitably used as a fiber processing agent.

Claims (4)

[Claims] 1. A vinyl ester-based monomer unit containing 1 to 20 mol% of an α-olefin unit having 4 or less carbon atoms in a molecule thereof and a vinyl alcohol-based polymer having a saponification degree of 90 mol% or more as a dispersant. Aqueous emulsion (A) in which a polymer containing 0.1 to 10 parts by weight of a monomer unit having an N-alkylolamide group is used as a dispersoid with respect to 100 parts by weight.
And an aqueous emulsion composition comprising an aluminum compound (B). 2. The aqueous emulsion composition according to claim 1, wherein the α-olefin unit having 4 or less carbon atoms is an ethylene unit. 3. The method according to claim 1, wherein the aluminum compound (B) is contained in an amount of 0.1 part by weight (solid content) based on 100 parts by weight of the aqueous emulsion (A).
3. The aqueous emulsion composition according to claim 1, wherein the aqueous emulsion composition contains from 0.01 to 5 parts by weight. 4. The aluminum compound (B) is at least one compound selected from aluminum chloride, aluminum nitrate and aluminum sulfate.
An aqueous emulsion composition according to any one of the above.