JPH1160892A - Aqueous emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aq. emulsion compsn. which has such a fluidity that a lowering in apparent viscosity with an increase in shear rate is inhibited and the apparent viscosity increases with an increase in shear rate. SOLUTION: This aq. emulsion compsn. comprises a dispersoid of a (co)polymer comprising at least one monomer unit selected from an ethylenically unsatd. monomer and a diene monomer and a dispersant of a polyvinyl alcohol polymer (A), wherein an alkali metal salt of an arom. sulfonic acid/formaldehyde condensate (B) (degree of condensation: 2 to 20) is incorporated with the wt. ratio of component A to B being (100:0.05) to (100:100) on a solid content basis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous emulsion composition, and more particularly, to an aqueous emulsion composition having dilatancy.

[0002]

2. Description of the Related Art Polyvinyl alcohol polymers (hereinafter referred to as P
An aqueous emulsion containing a VA polymer as a dispersant has extremely high mechanical stability, chemical stability, and pigment miscibility due to the high protective colloidal properties of the PVA polymer. Since the film formed from the aqueous emulsion is extremely tough, it has long been used in many applications such as paints, adhesives, fiber processing agents, and paper processing agents. In addition, the viscosity (flowability) of an aqueous emulsion using a PVA-based polymer as a dispersant is generally referred to as a so-called shear thinning property (hereinafter referred to as a thixotropic property) in which the apparent viscosity decreases with an increase in shear rate. ), And this fluidity may be preferred in practical use.
However, recently, in the case of products produced using an aqueous emulsion containing a PVA-based polymer as a dispersant (for example, wood-bonded products, paper-bonded products, textile products, etc.), a production line (roll) is used for the purpose of improving productivity. As the speed of rotation is increased, the problem of controlling the coating amount during roll coating and scattering of the water-based emulsion from the roll has become apparent in the conventional shear-thinning aqueous emulsion.

[0003] In order to solve this problem, the fluidity of an aqueous emulsion has a Newtonian property in which the apparent viscosity does not depend on the shear rate, or a shear thickening property in which the apparent viscosity increases with an increase in the shear rate (hereinafter referred to as dilatancy property). (Sometimes expressed). P
As a method of bringing an aqueous emulsion using a VA polymer as a dispersant from a thixotropic property to a newtonian property, there is a method of improving an emulsion polymerization method (amount of an initiator, an amount of a dispersant, etc.) and a PVA polymer used as a dispersant. Can be controlled to some extent by selecting the type of (the degree of saponification, molecular weight, etc.).

Further, in order to change the fluidity of the aqueous emulsion from a Newtonian property to a dilatancy property, the dispersion stability of the aqueous emulsion is maintained only by the above-mentioned emulsion polymerization method or the selection of the PVA polymer. It is generally difficult to change only the liquidity in a state where it has been set. Therefore, a method of post-adding a gelling agent (for example, boric acid or Congo Red) of a PVA-based polymer to an aqueous emulsion using a thixotropic PVA-based polymer as a dispersant to make the fluidity dilatancy-resistant. There are cases used. However, these gelling agents have a problem of safety and a problem of coloring, and may be restricted in use in use. Also, JP-A-6-2119
No. 11 discloses an aqueous copolymer emulsion for paper coating with excellent high-speed coating properties obtained by using a naphthalene sulfonate formaldehyde condensate and a polyoxyethylene alkylphenyl ether sulfate during emulsion polymerization. Are listed. The publication also describes that PVA can be optionally blended,
It does not disclose the significance of blending PVA with a naphthalene sulfonate formaldehyde condensate, the proportion thereof, and the fact that the blending amount of PVA is greater than the blending amount of the condensate.

[0005]

SUMMARY OF THE INVENTION The present invention has been made under the above circumstances and has few problems as described above, and suppresses a decrease in apparent viscosity with respect to the shear rate of an aqueous emulsion.
Alternatively, it is intended to provide an aqueous emulsion composition capable of increasing the apparent viscosity.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to develop an aqueous emulsion composition having the above-mentioned preferable properties, and as a result, have found that the dispersoids are ethylenically unsaturated monomers and diene-based monomers. An aqueous emulsion in which the dispersing agent is (A) a polyvinyl alcohol-based polymer, and (B) an alkali metal salt of aromatic sulfonic acid formaldehyde. Containing a condensate and (A) /
The weight ratio of (B) is 100 / 0.05 to 10 in terms of solid content ratio.
It has been found that an aqueous emulsion composition characterized by being 0/100 has the desired performance. The present invention has been completed based on such findings.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous emulsion composition of the present invention comprises a (co) polymer comprising at least one monomer unit selected from ethylenically unsaturated monomers and diene monomers as a dispersoid. contains. As the ethylenically unsaturated monomer or diene-based monomer constituting the dispersoid, various types can be used. Preferred examples of the ethylenically unsaturated monomer include olefins such as ethylene, propylene and isobutylene. Halogenated olefins such as vinyl chloride, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate, acrylic acid, methacrylic acid, methyl acrylate, acrylic acid Acrylates such as ethyl, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodemethacrylate Methacrylates such as 2-hydroxyethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and quaternary products thereof, furthermore, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethyl Acrylamide monomers such as acrylamide, acrylamide-2-methylpropanesulfonic acid and its sodium salt, styrene monomers such as styrene, α-methylstyrene, p-styrenesulfonic acid and its sodium and potassium salts, and other N -Vinylpyrrolidone and the like, and preferable examples of the diene monomer include butadiene, isoprene, chloroprene and the like. These monomers are used alone or in combination of two or more. Examples of (co) polymers composed of these monomers include ethylene-vinyl acetate copolymers, vinyl ester-based (co) polymers represented by polyvinyl acetate,
(Meth) acrylate-based (co) polymers and styrene-diene-based copolymers are preferably used.

[0008] The aqueous emulsion composition of the present invention contains a PVA polymer as a dispersant. The PVA-based polymer constituting the dispersant is not particularly limited, and various types can be used. Usually, PVA obtained by polymerizing a vinyl ester-based monomer represented by vinyl acetate and then saponifying it is used. A system polymer is used. In addition, as the above-mentioned vinyl ester monomer, in addition to vinyl acetate, vinyl formate, vinyl propionate, vinyl versatate, vinyl pivalate and the like can also be used.

Further, the PVA-based polymer as a dispersant constituting the aqueous emulsion composition of the present invention contains a monomer copolymerizable with a vinyl ester-based monomer within a range not to impair the effects of the present invention. It is also possible to coexist and copolymerize. For example, olefins such as ethylene, propylene, 1-butene, isobutene, acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate Acrylates such as 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, Methacrylates such as t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, methyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether,
vinyl ethers such as n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether;
Acrylonitrile, nitriles such as methacrylonitonyl, vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl halides such as vinylidene fluoride, allyl acetate, allyl compounds such as allyl chloride, fumaric acid, maleic acid,
Carboxyl group-containing compounds such as itaconic acid, maleic anhydride, phthalic anhydride, trimetic anhydride or itaconic anhydride and esters thereof, ethylenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamide-2-methylpropanesulfone Examples thereof include a sulfonic acid group-containing compound such as an acid, a vinylsilane compound such as vinyltrimethoxysilane, isopropenyl acetate, 3-acrylamidopropyltrimethylammonium chloride, and 3-methacrylamidopropyltrimethylammonium chloride.

Further, a terminal modified product obtained by polymerizing a vinyl ester monomer such as vinyl acetate in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid and saponifying the same can also be used.

The degree of polymerization of the PVA-based polymer as a dispersant constituting the aqueous emulsion composition of the present invention is not particularly limited, but is preferably in the range of 50 to 8,000,
A range of 0 to 4000 is more preferred, and optimally 200
３3500. When the degree of polymerization is less than 50, the protective colloid property of the PVA polymer is low, and the dispersion stability of the aqueous emulsion is deteriorated. When the degree of polymerization is 8000 or more, the viscosity of the aqueous emulsion increases and the dispersion stability also decreases. Is not preferred. The degree of saponification of the PVA-based polymer cannot be generally limited but is generally at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol% from the viewpoint of water solubility. For the upper limit,
It is at most 100 mol%, preferably at most 98 mol%, more preferably at most 96 mol%.

The formaldehyde condensate of the alkali metal salt of aromatic sulfonic acid contained in the aqueous emulsion composition of the present invention is not particularly limited as long as it is a condensate of various alkali metal salts of aromatic sulfonic acid and formaldehyde. As for the naphthalene sulfonate sodium formaldehyde condensate, benzene sulfonate sodium formaldehyde condensate, and lignin sulfonate sodium formaldehyde condensate are used. Here, examples of the sodium naphthalene sulfonate include sodium α-naphthalene sulfonate and sodium β-naphthalene sulfonate. Of these formaldehyde condensates, sodium naphthalene sulfonate formaldehyde condensate is the best. The aromatic sulfonic acid alkali metal salt formaldehyde condensate used in the present invention may be water-soluble or water-dispersible, and may contain two or more aromatic sulfonic acid alkali metal salt units in one molecule. . Further, the condensation degree (n) of the aromatic sulfonic acid alkali metal salt formaldehyde condensate is preferably from 2 to 20,
More preferably, it is 4-18, most preferably 8-16. As the component (B), a formaldehyde condensate of a heterocyclic sulfonic acid alkali metal salt such as a formaldehyde condensate of a melamine sulfonic acid alkali metal salt can also be used.

The ratio of the (A) PVA polymer to the (B) alkali metal sulfonate formaldehyde condensate in the aqueous emulsion composition of the present invention is (A) /
(B) = 100 / 0.05 to 100/100 (solid content ratio). (A) / (B) = 100/0.
When the ratio of (B) is smaller than 05, the desired effect (the effect of suppressing the decrease in the apparent viscosity with respect to the shear rate of the aqueous emulsion or increasing the apparent viscosity)
Is not sufficiently expressed, and the ratio of (B) is 100/10
If it exceeds 0, the water resistance of the aqueous emulsion film decreases,
In addition, there is a problem that aggregation occurs. The preferred ratio is
(A) / (B) = 100 / 0.1 to 100/80, and optimally (A) / (B) = 100 / 0.2 to 100
/ 50.

The aqueous emulsion composition of the present invention is a (co) polymer in which the dispersoid comprises at least one monomer unit selected from an ethylenically unsaturated monomer and a diene monomer. Is composed of (A) a polyvinyl alcohol-based polymer and (B) a formaldehyde condensate of an alkali metal salt of aromatic sulfonic acid, and the weight ratio of (A) / (B) is 100 / 0.05 to 100/100 in terms of solid content ratio. The production method is not particularly limited. For example, in the presence of a PVA-based polymer and an aromatic sulfonic acid alkali metal salt formaldehyde condensate, at least one monomer selected from an ethylenically unsaturated monomer and a diene-based monomer is prepared by a conventionally known method. A method of emulsifying (copolymerizing), emulsifying (copolymerizing) at least one monomer selected from an ethylenically unsaturated monomer and a diene-based monomer by a conventionally known method in the presence of a PVA-based polymer. A method of post-adding an aromatic sulfonic acid alkali metal salt formaldehyde condensate to the aqueous emulsion obtained, selected from ethylenically unsaturated monomers and diene monomers in the presence of the aromatic sulfonic acid alkali metal salt formaldehyde condensate For example, a method of post-adding a PVA-based polymer to an aqueous emulsion obtained by emulsifying (copolymerizing) at least one type of monomer by a conventionally known method can be performed.

[0015] The aqueous emulsion composition of the present invention (A)
The total amount of (B) and (B) is from 1 to 50 parts by weight based on 100 parts by weight of the polymer of the ethylenically unsaturated monomer. It is preferable because it is possible to prevent a decrease in the amount, and the range is more preferably 2 to 30 parts by weight.

The emulsion (co) polymerization carried out to obtain the aqueous emulsion composition of the present invention is carried out by adding the above ethylenically unsaturated monomer temporarily or continuously to an emulsion polymerization system. An emulsion polymerization method in which an ethylenically unsaturated monomer previously emulsified with an aqueous dispersant solution used in emulsion polymerization and then continuously added to the polymerization reaction system can also be employed. Conventionally known initiators can be used for the emulsion polymerization. For example, water-soluble initiators such as persulfate, hydrogen peroxide, tertiary butyl hydroperoxide, and various azo- or peroxide-based oil-soluble initiators alone or tartaric acid, ascorbic acid, Rongalit,
Used in redox systems in combination with reducing agents such as ferrous iron ions. The emulsion polymerization temperature varies depending on the type of the initiator and the like, and cannot be limited unconditionally.
It is selected from the range of 00 ° C. The aqueous emulsion composition of the present invention thus obtained has Newtonian properties or dilatancy properties. Here, the dilatancy refers to, for example, 6 rpm
ratio of m to 60 rpm at 30 ° C. (6 rpm) /
(60 rpm) is smaller than 1.

The aqueous emulsion composition of the present invention may contain, if necessary, a conventionally known anionic, nonionic, cationic or amphoteric surfactant, starch, modified starch, oxidized starch, sodium alginate, carboxymethylcellulose. , Methylcellulose, hydroxymethylcellulose, maleic anhydride / isobutene copolymer,
Maleic anhydride / styrene copolymer, maleic anhydride /
A water-soluble polymer compound such as a methyl vinyl ether copolymer and a thermosetting resin such as a urea / formaldehyde resin, a urea / melamine / formaldehyde resin, and a phenol / formaldehyde resin can also be used together. Further, the aqueous emulsion composition of the present invention includes fillers such as clay, kaolin, talc, calcium carbonate, and wood flour; fillers such as flour; pigments such as titanium oxide; Various additives such as a foaming agent can be appropriately added.

The solid concentration of the aqueous emulsion composition of the present invention is preferably from 20 to 75% by weight. Solid concentration 2
If it is lower than 0% by weight, there is a problem that the drying speed is slow in practical use, and if it exceeds 75% by weight, there is a problem that the viscosity is excessively increased and the dispersion stability is lowered.

The aqueous emulsion composition of the present invention is suitably used particularly in various applications such as paper adhesives, woodworking adhesives, fiber treatment agents, and paints used for products produced on high-speed production lines.

[0020]

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. The flowability of the aqueous emulsion was evaluated as follows.

(Evaluation of Flowability of Aqueous Emulsion) BM
The viscosity at 60 ° C. and 6 rpm at 30 ° C. was measured using a viscometer, and the ratio (6 rpm viscosity) / (60 rpm)
m viscosity) was determined as a fluidity index.

Example 1 A 1-liter glass polymerization vessel equipped with a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet was charged with 320 g of water and polyvinyl alcohol (PVA-1: polymerization degree 1700, saponification degree 8).
(8.0 mol%), 20 g, and completely dissolved at 95 ° C. Next, the PVA aqueous solution was cooled and replaced with nitrogen.
While stirring at 0 rpm, 40 g of vinyl acetate was charged.
After the temperature was raised to 0 ° C., 10 g of a 10% aqueous solution of tartaric acid was added, and polymerization was started by continuously dropping 1% aqueous hydrogen peroxide. After 0.5 hour, the temperature was raised to 80 ° C., and continuous dropping of 360 g of vinyl acetate was started. Continuous dropping of vinyl acetate was completed in 2 hours (during this period, 1% aqueous hydrogen peroxide was added.
0g continuously), solid content concentration 52.0%, viscosity 500
A polyvinyl acetate emulsion (Em-1) using 0 mPas · s of PVA as a dispersant was obtained. Em-1 contains 5% by weight of PVA-1 per solid content. E
m-1 is a sodium formaldehyde condensate of sodium naphthalenesulfonate having a degree of condensation (n) of 10 to 12 (Sanyo Levelon:
PVA1 in emulsion with 5% aqueous solution of Sanyo Chemical
5 parts by weight (solid content) was added per 00 parts by weight, and water was further added to prepare an aqueous emulsion composition having a solids concentration of 45%, and the fluidity was evaluated by the above method.

Example 2 A 5% aqueous solution of sodium naphthalenesulfonate formaldehyde condensate having a degree of condensation (n) of 10 to 12 (Sanyo Leveron: manufactured by Sanyo Chemical Co., Ltd.) was added to Em-1 of Example 1 per 100 parts by weight of PVA in the emulsion. 0.5 parts by weight (solid content)
, And water is further added to obtain a solid concentration of 4
A 5% aqueous emulsion composition was prepared and evaluated for fluidity in the same manner as in Example 1.

Example 3 A 5% aqueous solution of sodium naphthalenesulfonate formaldehyde condensate having a degree of condensation (n) of 10 to 12 (Sanyo Levelon: Sanyo Chemical Co., Ltd.) was added to Em-1 of Example 1 per 100 parts by weight of PVA in the emulsion. 20 parts by weight (solid content), and further, water was added to the solid content concentration of 45 parts.
% Aqueous emulsion composition was prepared and the fluidity was determined as in Example 1.
Was evaluated in the same way as

Comparative Example 1 Water was added to Em-1 of Example 1 to prepare an aqueous emulsion having a solid content of 45%, and the fluidity was evaluated in the same manner as in Example 1.

Example 4 Polyvinyl alcohol (PVA-2: polymerization degree 1000,
(Saponification degree: 94.2 mol%) 14.4 g of ion-exchanged water 23
The mixture was heated to 0 g and dissolved in a pressure-resistant autoclave equipped with a nitrogen inlet and a thermometer. PH 4.
After adjustment to 0, 300 g of vinyl acetate was charged, and then the pressure of ethylene was increased to 45 kg / cm ² G (the charged amount of ethylene corresponds to 60 g). After raising the temperature to 60 ° C., polymerization was started with a hydrogen peroxide-Rongalit redox initiator. After 2 hours, the polymerization was completed and the solid concentration was 56.2%.
Poly (vinyl acetate-ethylene) copolymer emulsion using PVA having a viscosity of 2100 mPas · s as a dispersant (Em
-2) was obtained. Em-2 contains 4% by weight of PVA-2 per solid content. A 5% aqueous solution of sodium naphthalenesulfonate formaldehyde condensate having a degree of condensation (n) of 10 to 12 (Sanyo Levelon: manufactured by Sanyo Chemical Co., Ltd.) was added to Em-2 at a concentration of 10 parts by weight (solid content) per 100 parts by weight of PVA in the emulsion. And an aqueous emulsion composition having a solid content of 50% was prepared by adding water, and the fluidity was evaluated by the above method.

Example 5 In Example 4, 14.4 g of PVA-2 powder and 13.0 g of sodium naphthalenesulfonate formaldehyde condensate having a degree of condensation (n) of 10 to 12 (Sanyo Leveron: manufactured by Sanyo Chemical Co., Ltd.) were ionized. A poly (vinyl acetate-ethylene) copolymer emulsion was obtained in the same manner as in Example 4 except that a solution dissolved in 250 g of exchanged water was used as a dispersant (Em-3). Em-3 contains 90 parts by weight of sodium formaldehyde naphthalenesulfonate per 100 parts by weight of PVA. Water was added to Em-3 to prepare an aqueous emulsion composition having a solid content of 50%, and the fluidity was evaluated by the above method.

Comparative Example 2 Water was added to Em-2 of Example 4 to prepare an aqueous emulsion having a solid concentration of 50%, and the fluidity was evaluated in the same manner as in Example 1.

Comparative Example 3 A 5% aqueous solution of sodium naphthalenesulfonate formaldehyde condensate having a degree of condensation (n) of 10 to 12 (Sanyo Levelon: manufactured by Sanyo Chemical Co.) was added to Em-3 of Example 5 per 100 parts by weight of PVA in the emulsion. Add 20 parts by weight,
Further, water was added to prepare an aqueous emulsion having a solid content of 50%. PVA is contained in the aqueous emulsion composition.
It contains 110 parts by weight (solid content) of sodium formaldehyde naphthalenesulfonate per 100 parts by weight. Using the aqueous emulsion composition, fluidity was evaluated by the above method.

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 400 g of water and a thiol-terminated polyvinyl alcohol (PVA-3:
24 g of a polymerization degree of 500 and a saponification degree of 85.7 mol%) were charged and completely dissolved at 95 ° C. Next, after cooling the aqueous solution of polynyl alcohol, the pH was adjusted to 4.0 with dilute sulfuric acid,
After purging with nitrogen and stirring at 140 rpm, 80 g of methyl methacrylate and 80 g of n-butyl acrylate were charged. After the temperature was raised to 70 ° C., 5 g of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. Then, 120 g of methyl methacrylate and 120 g of n-butyl acrylate
Was added sequentially over 2 hours. The polymerization is completed in 4 hours,
PVA having a solid content of 51.5% and a viscosity of 750 mPas · s
Was used as a dispersant to obtain a poly (methyl methacrylate / butyl acrylate) copolymer emulsion (Em-4). Em-4 is 6% by weight of PVA-3 per solid content.
It contains. A 5% aqueous solution of sodium naphthalenesulfonate formaldehyde condensate having a degree of condensation (n) of 10 to 12 (Sanyo Levelon: manufactured by Sanyo Chemical Co., Ltd.) was added to Em-4 at a concentration of 3 parts by weight (solid content) per 100 parts by weight of PVA in the emulsion. And an aqueous emulsion composition having a solid content of 45% was prepared by adding water, and the fluidity was evaluated by the above method.

Comparative Example 4 Water was added to Em-4 of Example 6 to prepare an aqueous emulsion having a solid content of 45%, and the fluidity was evaluated by the above method.

Example 7 A sulfone group-modified polyvinyl alcohol having a thiol group at the terminal (PVA-4: polymerization degree 300, saponification degree 98.
0 mol%, allylsulfonic acid sodium salt 1.0 mol%
15 g of (random copolymerized modification) was heated and dissolved in 290 g of ion-exchanged water and charged in a pressure-resistant autoclave equipped with a nitrogen inlet and a thermometer. After adjusting the pH to 4.0 with dilute sulfuric acid, 165 g of styrene was charged, then 135 g of butadiene was charged from a pressure gauge, the temperature was raised to 70 ° C., and 10 g of a 2% aqueous solution of potassium persulfate was injected to initiate polymerization. The internal pressure decreased from 4.8 kg / cm ² G with the progress of polymerization, and decreased to 0.4 kg / cm ² G after 15 hours.
A poly (styrene-butadiene) copolymer emulsion (Em-5) using PVA having a solid content of 49.3% and a viscosity of 1500 mPas · s was obtained. Em-5 contains 5% by weight of PVA-4 per solid content.
A 5% aqueous solution of sodium naphthalenesulfonate formaldehyde condensate having a degree of condensation (n) of 10 to 12 (Sanyo Reveron: manufactured by Sanyo Chemical Co., Ltd.) was emulsified into Em-5 by emulsification.
A was added in an amount of 10 parts by weight (solid content) per 100 parts by weight of A, and water was further added to prepare an aqueous emulsion composition having a solid content of 45%, and the fluidity was evaluated by the above method.

Comparative Example 5 Water was added to Em-5 of Example 7 to prepare an aqueous emulsion having a solid content of 45%, and the fluidity was evaluated by the above method.

Comparative Example 6 In Example 4, the degree of condensation (n) was replaced with PVA-2.
Sodium naphthalene sulfonate formaldehyde condensate of 10 to 12 (Sanyo Levelon: manufactured by Sanyo Chemical) 14.4
Example 4 was repeated except that g was used, but aggregation occurred and a stable aqueous emulsion was not obtained.

Comparative Example 7 In Example 4, 10% by weight of a 5% aqueous solution of a sodium formaldehyde naphthalenesulfonate condensate having a degree of condensation (n) of 10 to 12 (manufactured by Sanyo Reveron, manufactured by Sanyo Chemical Industries) was added to 100 parts by weight of PVA in the emulsion. (Solid content) The same procedure as in Example 4 was carried out except that a 5% aqueous solution of the same condensate was added in an amount of 0.01 part by weight (solid content) per 100 parts by weight of PVA in the emulsion. No emulsion was obtained.

Comparative Example 8 In Example 4, the degree of condensation (n) was replaced with PVA-2.
7.2 g of 10-12 sodium naphthalenesulfonate formaldehyde condensate (Sanyo Levelon: manufactured by Sanyo Chemical)
And poly (vinyl acetate-ethylene) having a solids concentration of 55.3% and a viscosity of 4800 mPas · s in the same manner as in Example 4 except that 7.2 g of sodium alkyldiphenyl ether disulfonate (Sandet BL: manufactured by Sanyo Chemical Industries) is used.
A copolymer emulsion was obtained. Using this, Example 4
However, an aqueous emulsion exhibiting dilatancy was not obtained.

Example 8 In Example 4, instead of the sodium naphthalenesulfonate formaldehyde condensate having a degree of condensation (n) of 10 to 12 (Sanyo Levelon: manufactured by Sanyo Chemical Co., Ltd.), a degree of condensation (n) of 4 to 5 was used.
An aqueous emulsion was obtained under the same conditions as in Example 4 except that sodium naphthalenesulfonate formaldehyde condensate (Roma D: manufactured by San Nopco) was used. The fluidity of the obtained emulsion was evaluated by the above method.

[0038]

[Table 1]

[0039]

According to the aqueous emulsion composition of the present invention, the decrease in apparent viscosity with respect to the increase in shear rate is suppressed,
Further, it has fluidity such that the apparent viscosity increases with an increase in the shear rate. Therefore, the aqueous emulsion composition of the present invention has no problems at the time of high-speed coating, a paper adhesive,
It can be widely and effectively used for woodworking adhesives, fiber treatment agents, paper coating agents, paints and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08F 2/44 C08F 2/44 C

Claims (3)

[Claims] 1. The dispersoid is a (co) polymer comprising at least one monomer unit selected from an ethylenically unsaturated monomer and a diene monomer, and the dispersant is (A) a polyvinyl alcohol-based monomer. An aqueous emulsion which is a polymer contains (B) a formaldehyde condensate of an alkali metal salt of aromatic sulfonic acid, and the weight ratio of (A) / (B) is 100 / 0.05 to 100/100 in terms of solid content. An aqueous emulsion composition, characterized in that: 2. The aqueous emulsion composition according to claim 1, wherein the condensation degree of the formaldehyde condensate of (B) the alkali metal salt of aromatic sulfonic acid is from 2 to 20. 3. An aqueous emulsion composition having dilatancy, comprising the aqueous emulsion composition according to claim 1.