JP2002371165A - Aqueous emulsion composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous emulsion composition excellent in boiling water- resistant adhesiveness and solvent resistance and excellent in water resistance and viscosity stability with time. SOLUTION: This aqueous emulsion comprises (A) a vinyl alcohol polymer containing 1-15 mole % <=4C α-olefin unit in the molecule and having 90-99.5 mole % degree of saponification as a dispersant and a polymer containing 0.1-10 pts.wt. monomer unit having a carboxyl group and/or monomer unit having an N-alkylolamide group to 100 pts.wt. vinyl ester polymer as a dispersoid and (B) an aluminum compound and presents a film having >=60% gel content when the composition is made to be a film at 20 deg.C.

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 boiling water adhesion and solvent resistance, and further having excellent water resistance and storage stability, and a method for producing the same. .

[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. Such an aqueous emulsion generally has a low viscosity by adjusting the degree of saponification of the PVA-based polymer, has a viscosity close to a Newtonian flow, and has a relatively good water resistance. Since it has a high viscosity and relatively low temperature dependence of emulsion viscosity, it has been awarded for various uses. 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,
Even if it has an ethylene unit, the requirement cannot be completely satisfied in an application requiring strict water resistance, for example, an application in which a boiling water immersion test must be cleared, because of PVA. In addition, conventional vinyl ester-based polymer emulsions do not have sufficient solvent resistance, so applications requiring solvent resistance, such as applying the surface of a glued laminate obtained using the emulsion as an adhesive, with an organic solvent-based paint In such a case, there is a disadvantage that the adhesion 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. Although an aqueous emulsion composition is also known (Japanese Patent Application Laid-Open No. 2001-72820), this composition has good adhesion resistance to boiling water, but is still not sufficient, and furthermore has sufficient solvent resistance. is not.

[0004]

SUMMARY OF THE INVENTION Under such circumstances, the present invention is excellent in boiling water adhesion and solvent resistance,
An object of the present invention is to provide an aqueous emulsion composition having excellent water resistance and storage stability and a method for producing the same.

[0005]

An object of the present invention is to provide a vinyl alcohol-based polymer having an α-olefin unit having 4 or less carbon atoms in the molecule in an amount of 1 to 15 mol% and a saponification degree of 90 to 99.5 mol%. The coalescing agent is used as a dispersant, and a carboxyl group-containing monomer unit and / or an N-alkylolamide group-containing monomer unit is 0.1 to 10 parts by weight based on 100 parts by weight of a vinyl ester monomer unit An aqueous emulsion composition comprising an aqueous emulsion (A) having a polymer containing a part thereof as a dispersoid and an aluminum compound (B), and having a gel content of 6 when the composition is formed into a film at 20 ° C.
This is achieved by providing an aqueous emulsion composition that is at least 0%. In addition, the above-mentioned object is to carry out (1) an α-olefin unit having 4 or less carbon atoms in the molecule as a dispersant when the aqueous emulsion (A) is emulsion-polymerized.
% Of a vinyl alcohol-based polymer having a degree of saponification of 90 mol% to 99.5 mol%, and a vinyl ester monomer and a carboxyl group-containing monomer and / or an N-alkylolamide group. In the emulsion polymerization of the contained monomers, (2) at least one polymerization initiator selected from hydrogen peroxide, ammonium persulfate and potassium persulfate is used in a molar ratio of 0.001 to 0 relative to all monomers. .
(3) In the early stage of the polymerization, the vinyl ester monomer is used in an amount of 5 to 20% by weight based on the total amount of the vinyl ester monomer.
An aluminum compound is added to an aqueous emulsion (A) obtained by performing a polymerization operation in which the polymerization initiator is charged and the polymerization initiator is added in a molar ratio of 0.005 to 0.025 with respect to all monomers initially charged. This is achieved by providing a method of making an emulsion composition.

[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 15 mol% and having a degree of saponification of 90 mol% to 99.5 mol% can be obtained by saponifying a copolymer of a vinyl ester and an α-olefin having 4 or less carbon atoms. . Here, α having 4 or less carbon atoms
Examples of the olefin unit include ethylene, propylene, butylene, and isobutylene units, with ethylene units being preferred.

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

[0008] The content of α-olefin units having 4 or less carbon atoms must be 1 to 15 mol%,
Preferably 2 to 13 mol%, more preferably 3 to 10 mol%.
Mol%. When the content of the α-olefin unit having 4 or less carbon atoms is less than 1 mol%, an aqueous emulsion which simultaneously satisfies the boiling water resistance, solvent resistance, water resistance and storage stability cannot be obtained. If the amount exceeds mol%, the water solubility is reduced, and there is a concern that a stable aqueous emulsion cannot be obtained.

Further, the dispersant contains 1 to 15 mol% of an α-olefin unit having 4 or less carbon atoms in a molecule used for the dispersant,
The vinyl alcohol polymer having a saponification degree of 90 mol% to 99.5 mol% may be a copolymer of an ethylenically unsaturated monomer copolymerizable within a range not impairing 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-acrylamide -3-dimethylpropyl)
-Ammonium chloride, acrylamide-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, Examples thereof include sodium vinyl sulfonate and sodium allyl sulfonate. In addition, in the presence of thiol compounds such as thiolacetic acid and mercaptopropionic acid,
Vinyl ester monomers such as vinyl acetate are converted to
A terminal modified product obtained by copolymerizing with the following α-olefin and saponifying it can also be used.

The degree of saponification of a vinyl alcohol polymer containing 1 to 15 mol% of α-olefin units in the molecule and having a degree of saponification of 90 to 99.5 mol% is used as a dispersant for the aqueous emulsion of the present invention. , 90 mol% to 99.5
Mol%, more preferably 92 mol% to 98 mol%, even more preferably 93 mol% to 97 mol%.
Mol%. When the degree of saponification is less than 90 mol%,
An aqueous emulsion composition having excellent boiling water adhesion, solvent resistance and water resistance cannot be obtained, and the saponification degree is 99.
If it exceeds 5 mol%, an aqueous emulsion having excellent boiling water adhesion and solvent resistance cannot be obtained. In addition, the polymerization degree of the vinyl alcohol-based polymer is preferably in the range of 100 to 8000, and more preferably 300 to 3000, in order to more suitably achieve the object of the present invention.

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 a carboxyl group and / or a monomer containing an N-alkylolamide group as a monomer constituting the dispersoid. . Each of these monomers may be used alone, but the solvent resistance of the film is improved by using both the monomer containing a carboxyl group and the monomer containing an N-alkylolamide group in combination. It is preferable because it further improves. Examples of the monomer containing a carboxyl group include ethylenically unsaturated monomers containing a carboxyl group, for example, acrylic acid, methacrylic acid, itaconic acid, maleic anhydride and the like, and particularly acrylic acid and methacrylic acid. It is preferably used. Examples of the monomer containing an N-alkylolamide group include N-alkylol (meth) acrylamide, for example, N-methylolacrylamide, N-ethanolacrylamide, N-propanolacrylamide, N-methylolmethacrylamide, N-methylol Examples thereof include methacrylamide and N-propanol methacrylamide. 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 containing a carboxyl group and / or the monomer containing an N-alkylolamide group is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl ester monomer. It is important to use parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.25 to 5 parts by weight.
3 parts by weight. When the monomer unit containing a carboxyl group and / or the monomer containing an N-alkylolamide group (the total amount thereof when used in combination) is less than 0.1 part by weight, water-resistant and boiling-water-adhesive If the power is insufficient, and if it exceeds 10 parts by weight, the polymerization stability may decrease. The dispersoid may be copolymerized with an ethylenically unsaturated monomer or a diene-based monomer which can be copolymerized within a range not to impair the effects of the present invention. Such ethylenically unsaturated monomers include ethylene, propylene, olefins such as isobutylene, vinyl chloride, vinyl fluoride, vinylidene chloride, halogenated olefins such as vinylidene fluoride, methyl acrylate, ethyl acrylate, acrylic Acrylates such as butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2 methacrylic acid −
Methacrylic esters such as hydroxyethyl, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and quaternaries thereof, furthermore, acrylamide, methacrylamide, N, N-dimethylacrylamide, acrylamido-2-methylpropanesulfonic acid and Acrylamide monomers such as sodium salts thereof, styrene, α-methylstyrene, p-styrenesulfonic acid and its sodium, styrene monomers such as potassium salts, and other N-vinylpyrrolidone,
Diene monomers such as butadiene, isoprene, and chloroprene are exemplified, and these may be used alone or in combination of two or more.

In the present invention, when the aqueous emulsion composition is formed into a film at 20 ° C., it is essential that the gel content is 60% or more. Here, the gel component means that a circular film having a thickness of 500 μm and a diameter of 2.5 cm obtained by casting the emulsion on a substrate at 20 ° C. and 65% RH and drying for 7 days was subjected to acetone soxhlet extraction for 24 hours. And the insoluble matter (% by weight) when extracted in 5 liters of boiling water for 24 hours. When the gel content is less than 60%, the boiling water-resistant adhesive strength and the solvent resistance decrease. The gel content is preferably at least 65%, more preferably at least 70%. 20 ° C. of the present invention
An aqueous emulsion composition having a gel content of 60% or more when formed into a film by the following method is obtained, for example, by the following method. That is, (1) as a dispersant, a compound having 4 carbon atoms in the molecule.
A vinyl ester-based monomer containing a carboxyl group and a vinyl alcohol-based polymer containing 1 to 15 mol% of the following α-olefin unit and having a degree of saponification of 90 to 99.5 mol%: And / or an emulsion polymerization of a monomer containing an N-alkylolamide group,
(2) At least one polymerization initiator selected from hydrogen peroxide, ammonium persulfate and potassium persulfate is used in a molar ratio of 0.001 to 0.01 with respect to all monomers, and (3) at the beginning of polymerization, The vinyl ester monomer is charged in an amount of 5 to 20% by weight of the total amount of the vinyl ester monomer, and the polymerization initiator is used in a molar ratio of 0.005 to 0.025 with respect to the initially charged vinyl ester monomer. It is obtained by blending an aluminum compound with the aqueous emulsion (A) obtained by performing the polymerization operation to be added.

In producing the aqueous emulsion (A) used in the present invention, it is important to use at least one polymerization initiator selected from hydrogen peroxide, ammonium persulfate and potassium persulfate. Hydrogen oxide is preferred. In the present invention, the molar ratio is 0.00
It is also important to use 1 to 0.01 for emulsion polymerization,
Preferably it is 0.002-0.007, More preferably, it is 0.0025-0.005. Although the reason is not clear, by using the above-mentioned amount of the initiator, it is possible to obtain an aqueous emulsion having improved boiling water adhesion and solvent resistance and also excellent water resistance and shelf stability.

Further, the polymerization initiator is used in combination with a reducing agent,
It is sometimes used in redox systems. In that case, hydrogen peroxide is usually used together with tartaric acid, sodium tartrate, L-ascorbic acid, Rongalit and the like. Further, ammonium persulfate and potassium persulfate are used together with sodium hydrogen sulfite, sodium hydrogen carbonate and the like. The amount of the reducing agent to be used is not particularly limited either, but is usually 0.05 to 3 equivalents, preferably 0.1 to 2 equivalents, more preferably 0.3 to 1.5 equivalents, based on the polymerization initiator.

As a method of adding the polymerization initiator at the beginning of the polymerization, a method of adding the polymerization initiator all at once or a method of adding the polymerization initiator continuously is used, and the method of adding the polymerization initiator all at once is particularly preferable. That is, 5 to 20% of the total amount of the vinyl ester monomer is charged in the early stage of the polymerization, and the polymerization initiator is used in a molar ratio of 0.005 to 5% with respect to the initial charged monomers.
It is preferable to add 0.025 at a time, preferably 0.008 to 0.020, more preferably 0.08 to 0.020.
1 to 0.018. If the initial charge of the polymerization initiator is less than 0.005 in molar ratio to all monomers, there is a concern that an aqueous emulsion cannot be obtained stably. Also, when the initial charge of the polymerization initiator exceeds 0.025, there is a concern that an emulsion having excellent boiling water adhesion and solvent resistance, which is the object of the present invention, cannot be obtained. Further, by setting the initial charge amount of the vinyl ester monomer to 5 to 20% by weight, the emulsion intended for the present invention can be obtained. In the initial polymerization, a monomer and a polymerization initiator are added to an aqueous solution of a dispersant, and the polymerization temperature is 50 to 70 ° C, preferably 55 to 65 ° C.
C. and a polymerization time of 15 to 60 minutes, preferably 20 to 50 minutes. In the initial polymerization, it is preferable to add the monomers all at once. In the initial polymerization, the residual concentration of vinyl ester (% by weight based on the produced polymer) is 10% or less,
It ends when it is preferably 5% or less, more preferably 1% or less. After the initial polymerization, it enters into the late polymerization. In the latter stage polymerization, the polymerization initiator and the vinyl ester-based monomer may be added all at once (shot addition), or may be added continuously or intermittently. In the latter polymerization, the polymerization temperature is preferably 5 to 30 ° C. higher than the initial polymerization temperature.
A range from 5 to 100 ° C, preferably from 60 to 95 ° C, is suitable.

The method of adding the monomer containing a carboxyl group and / or the monomer containing an N-alkylolamide group is not particularly limited. At the same time, or a method in which both are uniformly mixed, and then added at the early stage and / or late stage of the polymerization is preferred.

The amount of the α-olefin-modified PVA used in the aqueous emulsion (A) of the present invention is not particularly limited, but may be a vinyl ester monomer unit and a carboxyl group-containing monomer unit and / or 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 of the polymer (dispersoid) composed of a monomer unit containing an N-alkylolamide group. α
When the amount of the olefin-modified PVA is less than 1 part by weight or more than 30 parts by weight, the polymerization stability may be reduced, or the adhesive strength to boiling water may be reduced. As the aqueous emulsion used in the present invention, the aqueous emulsion obtained by the above method can be used as it is, but various conventionally known emulsions can be used in combination as long as the effects of the present invention are not impaired. As the dispersant in the aqueous emulsion used in the present invention, the above-mentioned α-olefin-modified PVA is used. If necessary, a conventionally known anionic, nonionic or cationic surfactant or PVA-based surfactant may be used. A polymer, hydroxyethyl cellulose or the like can be used in combination.

Aluminum compound (B) used in the present invention
Although there is no particular limitation, a water-soluble aluminum compound is preferably used, and specifically, aluminum chloride, aluminum nitrate and its hydrate, aluminum sulfate (sulfate band) and the like are 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). And preferably 0.02 to 3 parts by weight, more preferably 0.03 to 2.5 parts by weight.
More preferably, it is part by weight. When the compounding ratio of the aluminum compound (B) is less than 0.01 part by weight, the boiling water-resistant adhesive strength, solvent resistance, and water resistance decrease, and when it exceeds 5 parts by weight, the viscosity stability of the aqueous emulsion composition. May decrease.

The aqueous emulsion composition of the present invention is required
Depending on the drying, setting, viscosity, film forming properties, etc.
To adjust, toluene, perchrene, dichloroben
Various organic solvents such as zen and trichlorobenzene, starch
Starch, denatured starch, oxidized starch, sodium alginate,
Carboxymethylcellulose, methylcellulose, anhydrous
Maleic acid / isobutene copolymer, maleic anhydride / s
Tylene copolymer, maleic anhydride / methyl vinyl ether
Water-soluble polymer such as urea copolymer and urea / formalin tree
Fat, urea / melamine / formalin resin, phenol / ho
Thermosetting resins such as rumarin resin, clay,
Fillers such as olin, talc, calcium carbonate, wood flour,
Fillers such as flour, pigments such as titanium oxide or
Plasticizer, defoamer, antifreeze, preservative, rust inhibitor
Any of various additives may be contained. Where plastic
Agents include dibutyl phthalate, ethylene glycol
Nophenyl ether, Texanol and the like.
Aqueous emulsion obtained by the method as described above
By adding an aluminum compound to (A), 2
Aqueous solution containing 60% or more of gel when the film is formed at 0 ° C.
A marion composition is obtained, and the gelation content is increased to 60% or more.
This gives the emulsion excellent boiling water adhesion and
Solvent resistance can be imparted. Also, according to the present invention
The resulting aqueous emulsion has a tensile shear adhesive strength of 3.
5N (Newton) / mm²It is more preferable to show the above
4N / mm ²It is best to show the above
It is like. Here, the tensile shear adhesive strength is Bri Briness.
Tissue Standard EN204 D4 Class S
area Number of condition
ng sequence 6
The boiling water resistance is shown. Aqueous emulsion of the present invention
The composition is excellent in boiling water adhesion, solvent resistance, and
Utilizing the characteristics of excellent aqueous stability and storage stability,
For adhesive applications, e.g. using emulsion as adhesive
And apply the surface of the glued laminated wood obtained with
Adhesives, woodworking adhesives, paper processing adhesives,
Effectively used in various applications such as paints and fiber treatment agents
You. In the present invention, "solvent" of solvent resistance,
Acetone, toluene, ethanol, methanol, isop
Lopanol, normal propanol, methyl acetate, acetic acid
Organic solvents such as ethyl are exemplified.

[0023]

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 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.
g, 19.5 g of PVA-1 (polymerization degree: 1700, saponification degree: 95 mol%, ethylene modification amount: 5 mol%), and 95
The mixture was stirred at 2 ° C. for 2 hours to completely dissolve. Next, this PVA
After cooling the aqueous solution and purging with nitrogen, the temperature was raised to 60 ° C. while stirring at 200 rpm, and then a 10% aqueous solution of tartaric acid 4.4.
g and 3 g of a 5% aqueous hydrogen peroxide solution (0.015 in terms of a molar ratio with respect to all monomers initially charged) were added, and then 26 g of vinyl acetate and 0.26 g of acrylic acid were charged to initiate polymerization. It was confirmed that the initial polymerization was completed 30 minutes after the start of the polymerization (the residual amount of vinyl acetate was less than 1%). 10% of tartaric acid
After adding 0.9 g of an aqueous solution and 3 g of 5% aqueous hydrogen peroxide in a shot, 234 g of vinyl acetate and 2.34 of acrylic acid were added.
g was added continuously over 2 hours and the polymerization temperature was increased to 80
The polymerization was completed by maintaining the temperature at ° C. to obtain a polyvinyl acetate emulsion having a solid content of 47.2% (containing 1 part by weight of acrylic acid per 100 parts by weight of vinyl acetate). To 100 parts by weight (solid content) of this emulsion, 5 parts of phenoxyethanol was added and mixed (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.
g of PVA-1 and 19.5 g of PVA-1 were stirred at 95 ° C. for 2 hours and completely dissolved. Next, the PVA aqueous solution was cooled, replaced with nitrogen, and then stirred at 200 rpm at 60 ° C.
After the temperature was raised, 4.4 g of a 10% aqueous solution of tartaric acid and 5
After adding 3 g of a 3% aqueous hydrogen peroxide solution (0.015 in molar ratio to all monomers initially charged), 26 g of vinyl acetate was added.
g and methacrylic acid 0.31 g were charged to initiate polymerization. It was confirmed that the initial polymerization was completed 30 minutes after the start of the polymerization (the residual amount of vinyl acetate was less than 1%). After adding 0.9 g of a 10% aqueous solution of tartaric acid and 3 g of 5% aqueous hydrogen peroxide in a shot, 234 g of vinyl acetate and 3.09 g of methacrylic acid were added.
Was continuously added over 2 hours, and the polymerization temperature was 80 ° C.
To complete the polymerization to obtain a polyvinyl acetate emulsion having a solid content of 47.3% (containing 1 part by weight of methacrylic acid with respect to 100 parts by weight of vinyl acetate). To 100 parts by weight (solid content) of this emulsion, 5 parts of phenoxyethanol was added and mixed (Em-2).

Production Example 3 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.
g of PVA-1 and 19.5 g of PVA-1 were stirred at 95 ° C. for 2 hours and completely dissolved. Next, the PVA aqueous solution was cooled, replaced with nitrogen, and then stirred at 200 rpm at 60 ° C.
After the temperature was raised, 4.4 g of a 10% aqueous solution of tartaric acid and 5
After adding 3 g of a 3% aqueous hydrogen peroxide solution (0.015 in molar ratio to all monomers initially charged), 26 g of vinyl acetate was added.
g was charged to initiate polymerization. It was confirmed that the initial polymerization was completed 30 minutes after the start of the polymerization (the residual amount of vinyl acetate was less than 1%).
After adding 0.9 g of a 10% aqueous solution of tartaric acid and 3 g of a 5% aqueous hydrogen peroxide solution, 234 g of vinyl acetate and N-
2.6 g of methylol acrylamide was continuously added over 2 hours to complete the polymerization while maintaining the polymerization temperature at 80 ° C., and a polyvinyl acetate emulsion having a solid content of 47.2% (based on 100 parts by weight of vinyl acetate) N-methylolacrylamide (containing 1 part by weight) was obtained. Five parts of phenoxyethanol was added to and mixed with 100 parts by weight (solid content) of this emulsion (Em-3).

Production Example 4 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.
g of PVA-1 and 19.5 g of PVA-1 were stirred at 95 ° C. for 2 hours and completely dissolved. Next, the PVA aqueous solution was cooled, replaced with nitrogen, and then stirred at 200 rpm at 60 ° C.
After the temperature was raised, 4.4 g of a 10% aqueous solution of tartaric acid and 5
After adding 3 g of a 3% aqueous hydrogen peroxide solution (0.015 in molar ratio to all monomers initially charged), 26 g of vinyl acetate was added.
g and acrylic acid 0.26 g were charged to initiate polymerization. It was confirmed that the initial polymerization was completed 30 minutes after the start of the polymerization (the residual amount of vinyl acetate was less than 1%). After adding 0.9 g of a 10% aqueous solution of tartaric acid and 3 g of a 5% aqueous hydrogen peroxide solution by shot, 234 g of vinyl acetate, 2.34 g of acrylic acid and 2.6 g of N-methylolacrylamide were continuously added over 2 hours. Was maintained at 80 ° C. to complete the polymerization, and a polyvinyl acetate emulsion having a solid content of 47.4% (1 part by weight of acrylic acid and 1 part by weight of N-methylolacrylamide per 100 parts by weight of vinyl acetate;
(Containing 2 parts by weight in total). 1 of this emulsion
Phenoxyethanol 5 per 100 parts by weight (solid content)
Was added and mixed (Em-4).

Aqueous Emulsion Production Example 5 Emulsion polymerization was carried out in the same manner as in Aqueous Emulsion Production Example 1 except that the acrylic acid used in Aqueous Emulsion Production Example 1 was not used. A system emulsion was obtained. 100 of this emulsion
5 parts by weight of phenoxyethanol was added to and mixed with part by weight (solid content) (Em-5).

Aqueous emulsion production example 6 The same as the aqueous emulsion production example 1 except that PVA-2 (polymerization degree 1700, saponification degree 95 mol%) was used instead of PVA-1 used in the aqueous emulsion production example 1. To obtain a polyvinyl acetate emulsion having a solid content of 47.2% (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 phenoxyethanol was added and mixed (Em-6).

Aqueous emulsion production example 7 Instead of using PVA-1 used in aqueous emulsion production example 1, PVA-3 (polymerization degree 1000, saponification degree 99.
Emulsion polymerization was carried out in the same manner as in the aqueous emulsion production example 1 except that 7 mol% and an ethylene-modified amount of 8 mol%) were used.
A polyvinyl acetate emulsion having a solid content of 47.2% (containing 1 part by weight of acrylic acid with respect to 100 parts by weight of vinyl acetate) was obtained. To 100 parts by weight (solid content) of this emulsion, 5 parts of phenoxyethanol was added and mixed (Em-7).

Production Example 8 of Aqueous Emulsion Instead of using PVA-1 used in Production Example 1 of Aqueous Emulsion, PVA-4 (polymerization degree: 1700, saponification degree: 88 mol%, ethylene modification amount: 4 mol%) was used. Emulsion polymerization was carried out in the same manner as in Aqueous Emulsion Production Example 1 to obtain a polyvinyl acetate emulsion having a solid content concentration of 47.2% (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 phenoxyethanol was added and mixed (Em-8).

Production Example 9 of Aqueous Emulsion 300 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.
g of PVA-1 and 19.5 g of PVA-1 were stirred at 95 ° C. for 2 hours and completely dissolved. Next, the PVA aqueous solution was cooled, replaced with nitrogen, and then stirred at 200 rpm at 60 ° C.
After the temperature was raised, 4.4 g of a 10% aqueous solution of tartaric acid and 5
10g aqueous hydrogen peroxide (based on all monomers initially charged,
After adding 0.05) in a molar ratio by shot, vinyl acetate 26 was added.
g and acrylic acid 0.26 g were charged to initiate polymerization. 30 minutes after the start of the polymerization, the end of the initial polymerization (the residual amount of vinyl acetate was less than 1%) was confirmed. Next, 0.9 g of a 10% aqueous solution of tartaric acid and 3 g of a 5% hydrogen peroxide solution were added by shots, and then 234 g of vinyl acetate and 2.34 g of acrylic acid were added.
Was continuously added over 2 hours, and the polymerization temperature was 80 ° C.
To complete the polymerization to obtain a polyvinyl acetate emulsion having a solid content of 47.2% (containing 1 part by weight of acrylic acid with respect to 100 parts by weight of vinyl acetate). 5 parts of phenoxyethanol was added to and mixed with 100 parts by weight (solid content) of this emulsion (Em-9).

Aqueous Emulsion Production Example 10 In a 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet, 300 ion-exchanged water was added.
g of PVA-1 and 19.5 g of PVA-1 were stirred at 95 ° C. for 2 hours and completely dissolved. Next, the PVA aqueous solution was cooled, replaced with nitrogen, and then stirred at 200 rpm at 60 ° C.
After the temperature was raised, 4.4 g of a 10% aqueous solution of tartaric acid and 5
After 0.1 g of a 0.1% aqueous hydrogen peroxide solution (0.0005 in molar ratio with respect to all monomers initially charged) was added, 26 g of vinyl acetate and 0.26 g of acrylic acid were charged to initiate polymerization. 30 minutes after the start of the polymerization, the end of the initial polymerization (the residual amount of vinyl acetate was less than 1%) was confirmed. Then one of tartaric acid
After adding 0.9 g of a 0% aqueous solution and 3 g of a 5% aqueous hydrogen peroxide solution by shot, 234 g of vinyl acetate and 2.30 g of acrylic acid were added.
34 g was continuously added over 2 hours, and polymerization was attempted while maintaining the polymerization temperature at 80 ° C., but the system was destabilized on the way and an emulsion could not be obtained stably.

Production Example 11 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.
g of PVA-1 and 19.5 g of PVA-1 were stirred at 95 ° C. for 2 hours and completely dissolved. Next, the PVA aqueous solution was cooled, replaced with nitrogen, and then stirred at 200 rpm at 60 ° C.
After the temperature was raised, 4.4 g of a 10% aqueous solution of tartaric acid and 5
After adding 3 g of a 3% aqueous hydrogen peroxide solution (0.015 in molar ratio to all monomers initially charged), 26 g of vinyl acetate was added.
g and acrylic acid 0.26 g were charged to initiate polymerization. 30 minutes after the start of the polymerization, the end of the initial polymerization (the residual amount of vinyl acetate was less than 1%) was confirmed. Then, 1.8 g of a 10% aqueous solution of tartaric acid and 35 g of a 5% hydrogen peroxide solution were added by shot, and then 234 g of vinyl acetate and 2.34 of acrylic acid were added.
g was continuously added over 2 hours, and the polymerization temperature was 80 ° C.
To complete the polymerization, and a polyvinyl acetate emulsion having a solid content of 47.2% (containing 1 part by weight of acrylic acid with respect to 100 parts by weight of vinyl acetate) was obtained. To 100 parts by weight (solid content) of this emulsion, 5 parts of phenoxyethanol was added and mixed (Em-10).

Production Example 12 of Aqueous Emulsion 260 g of 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.
g, 37 g of PVA-5 (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-11).

Production Example 13 of Aqueous Emulsion 260 g of 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.
g, 37 g of PVA-6 (polymerization degree: 1700, saponification degree: 97.3 mol%, ethylene modification amount: 4.0 mol%) 9
Completely dissolved at 5 ° C. Next, this PVA aqueous solution was cooled, replaced with nitrogen, and charged with 37 g of vinyl acetate and 3.7 g of acrylic acid while stirring at 200 rpm.
After polymerization, polymerization was initiated in the presence of a hydrogen peroxide / tartaric acid redox initiator system. From 15 minutes after the start of the polymerization, 333 g of vinyl acetate was continuously added over 3 hours.
The polymerization was completed. A polyvinyl acetate emulsion having a solids concentration of 48.4% (containing 1 part by weight of acrylic acid with respect to 100 parts by weight of vinyl acetate) was obtained. 5 parts of dibutyl phthalate was added to and mixed with 100 parts by weight (solid content) of this emulsion (Em-12).

Example 1 "Em-1" 10 obtained in Production Example 1 of 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). The film water resistance, solvent resistance, boiling water adhesion and viscosity stability of the obtained aqueous emulsion composition were evaluated in the following manner. Table 1 shows the results.

(Evaluation of Emulsion) (1) Water Resistance of Film 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. 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) * 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. * Absolute dry weight of film after immersion;
Weight dried in time. 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 dipping (water content) x coating water content (%) / 10
0) * Moisture content of the film: The film (a sample different from the sample immersed in water at 20 ° C) is completely dried at 105 ° C for 4 hours, and the moisture 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. 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) Water resistance and boiling water adhesive strength Test using beech wood The obtained aqueous emulsion was applied to European beech wood (straight grain) at 150 g / m ² and bonded together to 7 kg / m.
² was pressed for 16 hours. After that, depressurize, 20 ° C
After curing for 7 days under 65% RH, British Standard B
S EN204 D3 standard (Serial number of conditioning seq
uence 1, 3, 4) and D4 standard (Serialnumber of c
Tensile shear adhesive strength (N / mm ² ) was measured by onditioning sequence 5 and 6). Serial number of c
The test conditions of the onditioning sequence are shown. 1: Measured after standing for 7 days at 20 ° C and 65% RH. 3: Measured while immersed in water at 20 ° C for 4 days and kept wet. 4: After immersion in water at 20 ° C. for 4 days, air-dried at 20 ° C. and 65% RH for 7 days, and measured. 5: immersed in boiling water for 6 hours, immersed in 20 ° C. water for 2 hours, and measured while wet. 6: Dipped in boiling water for 6 hours, dipped in 20 ° C. water for 2 hours, air-dried at 20 ° C. and 65% RH for 7 days, and measured. Test using Tsuga wood 150 g of the obtained aqueous emulsion was applied to Tsuga wood (straight grain).
/ M ² applied and bonded together with a load of 7 kg / m ² for 16
Time clamped. Thereafter, the pressure was released, and the mixture was cured at 20 ° C. and 65% RH for 5 days, immersed in boiling water for 4 hours, and the compressive shear strength (kg / cm ² ) was measured in a wet state. (4) Viscosity stability 30 minutes when the emulsion was left at 5 ° C. and 50 ° C.
The change in viscosity after one day was evaluated using a B-type viscometer. (4) Gel Content The aqueous emulsion was cast on PET at 20 ° C. and 65% RH, and dried for 7 days to obtain a dried film having a thickness of 500 μm. This film was punched into a circle having a diameter of 2.5 cm,
Acetone Soxhlet extraction for 4 hours and insoluble content (% by weight) when extracted for 24 hours in 5 liters of boiling water
Was measured. Gel content (insoluble content): (weight of dried film after immersion / weight of dried film before immersion) × 100

Example 2 A test was conducted 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 nonahydrate. 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 in place 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 2.3 parts by weight of aluminum nitrate 9 hydrate was used instead of 1 part by weight of aluminum nitrate 9 hydrate used in Example 1. The results are shown in Table 1.

Comparative Example 1 A test was conducted in the same manner as in Example 1 except that aluminum nitrate 9 hydrate was not used. The results are shown in Table 1.

Example 5 A test was conducted in the same manner as in Example 1 except that Em-2 obtained in Aqueous Emulsion Production Example 2 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Example 6 A test was conducted in the same manner as in Example 1 except that Em-3 obtained in Aqueous Emulsion Production Example 3 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Example 7 A test was performed in the same manner as in Example 1 except that Em-4 obtained in Aqueous Emulsion Production Example 4 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Comparative Example 2 A test was conducted in the same manner as in Example 1 except that Em-5 obtained in Aqueous Emulsion Production Example 5 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Comparative Example 3 A test was conducted in the same manner as in Example 1 except that Em-6 obtained in Aqueous Emulsion Production Example 6 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Comparative Example 4 A test was conducted in the same manner as in Example 1 except that Em-7 obtained in Aqueous Emulsion Production Example 7 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Comparative Example 5 A test was conducted in the same manner as in Example 1 except that Em-8 obtained in Aqueous Emulsion Production Example 8 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Comparative Example 6 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.
g, acetoacetyl group modified PVA (degree of polymerization 1030, degree of saponification 98.5%, acetoacetyl group modified amount 5 mol%)
Of vinyl alcohol-based polymer was completely dissolved at 95 ° C. Next, the PVA aqueous solution was cooled and replaced with nitrogen. Then, 10 g of vinyl acetate was charged while stirring at 140 rpm, and the temperature was raised to 60 ° C., and then polymerization was started in the presence of a hydrogen peroxide / tartaric acid redox initiator system. . Initiation of polymerization 1
After 5 minutes, the end of the initial polymerization (the residual amount of vinyl acetate was less than 1) was confirmed. Next, 90 g of vinyl acetate was continuously added over 3 hours, and the polymerization temperature was maintained at 80 ° C. to complete the polymerization. A polyvinyl acetate emulsion having a solid content of 50% was obtained. To 100 parts by weight (solid content) of this emulsion, 5 parts of phenoxyethanol was added and mixed (Em-13). 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-13”. The film water resistance, the boiling water resistance and the 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 7 A test was conducted in the same manner as in Example 1 except that Em-9 obtained in Aqueous Emulsion Production Example 9 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Comparative Example 8 A test was conducted in the same manner as in Example 1 except that Em-10 obtained in Aqueous Emulsion Production Example 11 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1. Was done. The results are shown in Table 1.

Comparative Example 9 A test was conducted in the same manner as in Comparative Example 2 except that aluminum nitrate 9 hydrate was not used. The results are shown in Table 1.

Comparative Example 10 Em-11 obtained in Aqueous Emulsion Production Example 12 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1 in Example 1, and 1 part by weight of aluminum nitrate nonahydrate was further used. The test was conducted in the same manner as in Example 1 except that 0.5 parts by weight of aluminum chloride was used instead of The results are shown in Table 1.

Comparative Example 11 Em-12 obtained in Aqueous Emulsion Production Example 13 was used instead of Em-1 obtained in Aqueous Emulsion Production Example 1 in Example 1, and 1 part by weight of aluminum nitrate nonahydrate was further used. The test was conducted in the same manner as in Example 1 except that 0.5 parts by weight of aluminum chloride was used instead of The results are shown in Table 1.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

The aqueous emulsion composition of the present invention is excellent in boiling water adhesion and solvent resistance, and also excellent in water resistance and storage viscosity stability, and is useful for woodworking adhesives, plywood adhesives and papers. It is widely and suitably used for processing agents, paints, fiber processing agents and the like.

[Procedure amendment]

[Submission date] July 26, 2001 (2001.7.2)
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

In the present invention, when the aqueous emulsion composition is formed into a film at 20 ° C., it is essential that the gel content is 60% or more. Here, the gel content refers to a film having a thickness of 500 μm and a diameter of 2.5 cm obtained by casting the emulsion on a substrate at 20 ° C. and 65% RH and drying for 7 days.
It refers to the insoluble matter (% by weight) after acetone soxhlet extraction for 4 hours and further extraction for 24 hours in 5 liters of boiling water. When the gel content is less than 60%, the boiling water resistance,
Solvent resistance decreases. The gel content is preferably at least 65%,
It is more preferably at least 70%. The aqueous emulsion composition of the present invention having a gel content of 60% or more when formed into a film at 20 ° C. is obtained, for example, by the following method. That is, (1) a vinyl alcohol-based polymer having 1 to 15 mol% of an α-olefin unit having 4 or less carbon atoms in a molecule and having a saponification degree of 90 mol% to 99.5 mol% as a dispersant; Upon emulsion polymerization of an ester monomer and a monomer containing a carboxyl group and / or a monomer containing an N-alkylolamide group,
(2) At least one polymerization initiator selected from hydrogen peroxide, ammonium persulfate and potassium persulfate is used in a molar ratio of 0.001 to 0.
(3) In the early stage of the polymerization, the vinyl ester monomer is used in an amount of 5 to 20% by weight based on the total amount of the vinyl ester monomer.
By adding an aluminum compound to an aqueous emulsion (A) obtained by performing a polymerization operation in which the polymerization initiator is charged and the above polymerization initiator is added in a molar ratio of 0.005 to 0.025 with respect to all monomers initially charged. can get.

Claims (9)

[Claims] (1) a molecule containing an α-olefin unit having 4 or less carbon atoms in an amount of 1 to 15 mol% and a degree of saponification of 90 to 9 mol%;
9.5 mol% of a vinyl alcohol-based polymer is used as a dispersant, and 100 parts by weight of a vinyl ester-based monomer unit is used.
A monomer unit containing a carboxyl group and / or N
-Monomer units containing an alkylolamide group 0.1 to
An aqueous emulsion composition comprising an aqueous emulsion (A) containing a polymer containing 10 parts by weight of a dispersoid and an aluminum compound (B), and having a gel content of 60 when the composition is formed into a film at 20 ° C. % Or more of the aqueous emulsion composition. 2. A tensile shear adhesive strength of 3.5 N / m.
The aqueous emulsion composition of claim 1, wherein indicating the m ² or more. 3. The aqueous emulsion composition according to claim 1, wherein the α-olefin unit having 4 or less carbon atoms is an ethylene unit. 4. The method according to claim 1, wherein the aluminum compound (B) is added in an amount of 0.1 part by weight (solid content) based on 100 parts by weight of the aqueous emulsion (A).
The aqueous emulsion composition according to any one of claims 1 to 3, which contains from 01 to 5 parts by weight. 5. 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. 6. A dispersoid comprising a total of 0.1 part by weight of a monomer having a carboxyl group and a monomer unit having an N-alkylolamide group per 100 parts by weight of a vinyl ester monomer unit. The aqueous emulsion composition according to any one of claims 1 to 5, which is a polymer containing 10 to 10 parts by weight. 7. A vinyl alcohol polymer containing 1 to 15 mol% of an α-olefin unit having 4 or less carbon atoms in the molecule and having a saponification degree of 90 to 99.5 mol% as a dispersant. When emulsion-polymerizing a vinyl ester monomer and a monomer containing a carboxyl group and / or a monomer containing an N-alkylolamide group,
(2) At least one polymerization initiator selected from hydrogen peroxide, ammonium persulfate and potassium persulfate is used in a molar ratio of 0.001 to 0.01 with respect to all monomers, and (3) at the beginning of polymerization, The vinyl ester monomer is charged in an amount of 5 to 20% by weight based on the total amount of the vinyl ester monomer, and the polymerization initiator is added in a molar ratio of 0.005 to 0.025 with respect to the initial charged monomers. A method for producing an aqueous emulsion composition, comprising mixing an aluminum compound into the aqueous emulsion (A) obtained by performing a polymerization operation. 8. The method for producing an aqueous emulsion composition according to claim 7, wherein a polymerization initiator is added at a time in a molar ratio of 0.005 to 0.025 with respect to all monomers initially charged in the initial stage of polymerization. 9. The method for producing an aqueous emulsion composition according to claim 7, wherein the aqueous emulsion composition has a gel content of 60% or more when formed into a film at 20 ° C.