JPH09235515A - Aqueous resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing an aqueous resin, a polyether-modified polysiloxane and a carbonic acid salt ammonium complex, capable of reducing a drying time of a coated membrane, especially a time required for the completion of the drying of a thick coated membrane to reduce a cost for forming the coated membrane. SOLUTION: This aqueous resin composition is obtained by blending (A) an aqueous resin with (B) a polyether-modified polysiloxane as a heat sensitive gelating agent, and (C) a carbonic acid salt ammonium complex (suitably, zinc carbonate ammonium complex) as an assistant of the heat sensitive gelation. As the component (A), it is preferable to use a substance obtained by performing a multiple-staged emulsion polymerization of a polymerizable monomer mixture consisting of a polymerizable monomer component containing carboxyl group such as (meth)acrylic acid and another polymerizable monomer component different from the previous component in an aqueous medium. It is preferable to blend 0.1-20 pts.wt. component (B) and 0.1-10 pts.wt. component (C) based on 100 pts.wt. component (A).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous resin composition having a heat-sensitive gelling property, which is suitably used as an interior coating material for civil engineering and construction products, a protective coating material for exterior coating materials such as automobiles and building materials, and a coating material. It is about.

[0002]

2. Description of the Related Art Conventionally, when a water-based coating material that has been used as a coating material or paint is used for line coating that is applied to a substrate and then dried at high temperature, the water-based coating material is
It has a first problem that a film is formed on the surface during drying and the internal drying is difficult to proceed, and a second problem that blisters and cracks are likely to occur in the coating layer such as a coating film during drying.

In order to avoid the above-mentioned first problem, Japanese Patent Application Laid-Open No. 4-261453 discloses a synthetic resin latex composition which imparts a heat-sensitive gelation property to a coating material and can suppress the formation of a film during drying. It is disclosed.

The above synthetic resin latex composition was prepared by mixing a carboxylic acid-containing synthetic resin latex having a chemical stability index of 24 or less, an aqueous solution of a polyvalent metal complex, and an alkylene oxide adduct of an alkylphenol-formalin condensate. It is a thing.

In order to avoid the second problem,
Japanese Unexamined Patent Publication (Kokai) No. 6-299000 discloses a heat-sensitive gelling copolymer latex capable of imparting heat-sensitive gelling property to a coating material to reduce generation of blisters and cracks on a coating layer.

The above heat-sensitive gelling copolymer latex is
First monomer component 1 to 99.9% by weight, second monomer component 0.1 to 20% by weight and third monomer component 0 to 98.9% by weight
100% by weight of a monomer mixture consisting of 10% by weight and emulsion polymerization in the presence of 0.1 to 20 parts by weight of an ethylenically unsaturated surfactant, having a glass transition point of +30 to -70 ° C.
The heat-sensitive gelling agent is contained in the latex of the copolymer.

The first monomer component is an aliphatic conjugated diene monomer and / or a (meth) acrylic acid alkyl ester monomer, and the second monomer component is a functional group. And the third monomer component is the first
It is a monomer copolymerizable with the monomer component and the second monomer component.

[0008]

However, in the structure of each of the above-mentioned conventional publications, the formation of a film on the surface is avoided at the time of drying by the provision of the heat-sensitive gelling property, and the drying also progresses inside, so that reliable drying can be achieved. It can be realized,
The drying time of the coating film is long, which causes a problem of increasing the cost in drying when forming a coating film, especially a coating film having a large thickness.

[0009]

In order to solve the above problems, the aqueous resin composition of the present invention comprises an aqueous resin, a polyether-modified polysiloxane for imparting heat-sensitive gelation property, and a heat-sensitive gelation. It is characterized by containing an ammonium carbonate complex for imparting properties.

According to the above constitution, by containing the polyether-modified polysiloxane and the ammonium carbonate complex, the coating film has a drying time while imparting the heat-sensitive gelation property,
In particular, it is possible to shorten the drying time of a thick film having a thickness of 2 to 20 mm.

In order to solve the above problems, the aqueous resin composition of the present invention is characterized by containing an aqueous resin obtained by multistage polymerization and a heat-sensitive gelling agent.

According to the above-mentioned constitution, by containing the heat-sensitive gelling agent, the heat-sensitive gelling property can be exhibited and the aqueous resin is multi-stage polymerized, so that the drying time of the coating film, especially the thickness of the coating film It is possible to shorten the drying time of a thick coating film having a thickness of 2 to 20 mm.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below. Aqueous resin composition of the present invention, an aqueous resin obtained by multi-stage polymerization of a polymerizable monomer,
It contains a heat-sensitive gelling agent. The aqueous resin is a resin which is soluble in a solvent containing water or suspended in the above solvent as an emulsion. As the above-mentioned aqueous resin, those obtained by multi-stage emulsion polymerization of a polymerizable monomer containing a first polymerizable monomer component (a) having a carboxyl group in the molecule are preferable.

If the first polymerizable monomer component (a) is a polymerizable monomer having a carboxyl group in the molecule,
It is not particularly limited, and for example, unsaturated carboxylic acid salts such as (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, monomethyl myate, and monoethyl myate, Or its derivative can be mentioned, and these 1
One kind or a mixture of two or more kinds can be used.

The amount of the first polymerizable monomer component (a) used is
0.1-10% by weight, based on the total amount of polymerizable monomers used
Used within the range of. When the amount of the first polymerizable monomer component (a) used is less than 0.1% by weight, the stability of multi-stage emulsion polymerization may be reduced, and the adhesion to various coated objects may be reduced. On the contrary, when the amount of the first polymerizable monomer component (a) used exceeds 10% by weight, the water resistance of the obtained coating film is lowered, which is not preferable.

In the aqueous resin composition of the present invention, the aqueous resin contains, if necessary, the first polymerizable monomer component (a) and a second polymerizable monomer component (b) which is different from the first polymerizable monomer component (b). It may be polymerized.

Examples of the second polymerizable monomer component (b) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth).
(Meth) acrylic acid esters such as acrylates; aromatic unsaturated monomers such as styrene, α-chlorostyrene, vinyltoluene; unsaturated cyan compounds such as (meth) acrylonitrile; hydroxyethyl (meth) acrylate, Vidroxyl group-containing unsaturated monomers such as hydroxypropyl (meth) acrylate; glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate, acrylic glycidyl ether, and allyl glycidyl ether, divinylbenzene, ethylene glycol di (meth) ) Polyfunctional unsaturated monomers such as acrylate may be mentioned, and one kind or a mixture of two or more kinds thereof may be used. The second polymerizable monomer component (b) is used within the range of 90 to 99.9% by weight based on the total amount of the polymerizable monomer.

The aqueous resin composition of the present invention comprises a multi-stage emulsification of a polymerizable monomer component comprising a first polymerizable monomer component (a) and a second polymerizable monomer component (b) in an aqueous medium. The product obtained by the polymerization is preferable because a spherical particle shape (particle size 1 μm or less) can be obtained and desired characteristics can be exhibited. In such multi-stage polymerization, for example, in the case of the first stage polymerization, At this time, it is desirable that the first polymerizable monomer component (a) contains the above-mentioned polyfunctional unsaturated monomer having a group capable of reacting with a carboxyl group in the second polymerization which is a separate step. .

If the first polymerizable monomer component (a) having a carboxyl group is omitted from the first-stage polymerization, the polymerization stability may decrease, and the polyfunctionality from the second-stage polymerization may be decreased. If the water-unsaturated monomers are omitted, the water resistance of the coating film may decrease. Furthermore, when the first polymerizable monomer component (a) and the polyfunctional unsaturated monomer are simultaneously used in the same stage in the multi-stage polymerization, the resulting synthetic resin emulsion of an aqueous resin is obtained. In some cases, unfavorable drawbacks in handling such as excessive increase in viscosity may occur.

Therefore, the aqueous resin composition is subjected to multi-stage emulsion polymerization as described above to separately polymerize the necessary functional groups to polymerize them separately, thereby shortening the drying time and keeping the drying time from 2 to 20 m.
It is possible to more surely realize both the heat-sensitive gelling property capable of easily forming a thick film of m by drying for a short time and the water resistance property showing durability at a high level.

Examples of the above heat-sensitive gelling agent include polyether modified polysiloxane, alkylene oxide adduct of alkylphenol formalin condensate, polyether formal, polyvinyl methyl ether, polypropylene glycol, water-soluble polyamide, starch, methyl cellulose, hydroxy. Examples thereof include ethyl cellulose, carboxymethyl cellulose, proteins, carbonates, bicarbonates, polyphosphates, and nonionic surfactants having a cloud point.

Of these, polyether-modified polysiloxanes and alkylene oxide adducts of alkylphenol formalin condensates are preferable, and polyether-modified polysiloxanes are more preferable.

The heat-sensitive gelling agent is added in an amount of 0.
1 to 20 parts by weight is preferred. Within this range, the use of the following heat-sensitive gelling aid in combination does not consider thickening of the film to a thickness of, for example, 2 mm to 20 mm, particularly 5 mm to 20 mm. A thick film can be easily achieved. In addition, it is possible to maintain the storage stability at room temperature.

The above-mentioned heat-sensitive gelling aid, together with the heat-sensitive gelling agent, is for further improving the heat-sensitive gelling property of the aqueous resin composition. As a heat-sensitive gelling aid,
A polyvalent metal, particularly a polyvalent metal complex salt, and specifically, a carbonate complex salt such as a zinc carbonate complex salt, a zirconium carbonate complex salt, a zinc acetate complex salt, a zinc acrylate complex salt, a zinc glycinate complex salt, a zinc malate complex salt. Among them, zinc carbonate complex salt is particularly preferable.

As such a polyvalent metal complex salt, those used in an aqueous solution are preferable since the aqueous resin composition of the present invention is used in an aqueous solvent, and from the viewpoint of water solubility, the polyvalent metal carbonate salt is used. An ammonium complex is preferable, and it is particularly preferable to use zinc ammonium carbonate as the ammonium polyvalent metal carbonate complex.

The amount of the polyvalent metal complex salt added is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the aqueous resin. Within this range, a thick film can be easily formed by using the heat-sensitive gelling agent in combination. In addition, since metal cross-linking due to the polyvalent metal complex salt occurs between the polyvalent metal and each carboxylic acid in the aqueous resin, it becomes possible to significantly improve the water resistance of the coating film formed by the aqueous resin composition.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Each embodiment of the present invention will be described below. The aqueous resin composition of the present invention comprises a first polymerizable monomer component (a) having a carboxyl group in the molecule,
A synthetic resin emulsion which is an aqueous resin obtained by multistage polymerization of the first polymerizable monomer component (a) and a different second polymerizable monomer component (b), if necessary, and a heat-sensitive gelling agent. And a heat-sensitive gelling aid, if necessary.

Example 1 An example of the above synthetic resin emulsion will be described as the synthetic resin emulsion (A) of Example 1. First, a stirrer, a reflux condenser, a dropping funnel,
Into a 1 liter separable flask equipped with a thermometer, 100 parts of deionized water and 0.1 part of an ethylenically unsaturated surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: AQUARON HS-10) ) Was charged, and then the temperature was raised to 70 ° C. with stirring while blowing nitrogen gas.

Then, as the first stage polymerization step, 30
A polymerizable monomer first mixture consisting of 1 part methyl methacrylate, 18 parts 2-ethylhexyl acrylate, 2 parts acrylic acid, 100 parts deionized water, and 1.0 part of the above ethylenically unsaturated surfactant. The liquid was uniformly added dropwise over 1 hour. At the same time, 30 parts of a 5% aqueous solution of potassium persulfate and 30 parts of a 2% aqueous solution of sodium hydrogen sulfite were added dropwise uniformly over 1 hour.

Then, after aging for 30 minutes while maintaining the temperature in the separable flask, as a second polymerization step, 16 parts of methyl methacrylate and 32 parts of 2-methacrylate were used.
A polymerizable monomer second consisting of ethylhexyl acrylate, 2 parts of glycidyl methacrylate, 20 parts of deionized water, and 1.0 part of the above ethylenically unsaturated surfactant.
The mixture was uniformly added dropwise over 1 hour. At the same time, 30 parts of a 5% aqueous solution of potassium persulfate and 30 parts of a 2% aqueous solution of sodium hydrogen sulfite were added dropwise uniformly over 1 hour.

Subsequently, aging is carried out for 60 minutes while maintaining the temperature in the separable flask, and after cooling, 4 parts of 25% aqueous ammonia is added to neutralize the mixture to obtain a nonvolatile content of 5%.
A synthetic resin emulsion (A) having 0% by weight, pH 7.0, and a viscosity of 1000 mPa · s and having good polymerization stability was obtained. Table 1 shows the composition and polymerization stability results of the synthetic resin emulsion (A).

Next, with respect to 100 parts of the above synthetic resin emulsion (A), an aqueous solution of zinc ammonium carbonate which becomes 5 parts in terms of zinc oxide, and 1 part of polyether-modified polysiloxane (Toshiba Silicone Co., Ltd., product Name: TPA-
And 4390) were sequentially added with stirring to obtain an aqueous resin composition (1).

This aqueous resin composition (1) has the above-mentioned aqueous resin composition (1) in order to measure the storage stability at room temperature.
Was left for 1 month in an atmosphere of 40 ° C., but no change was observed in the viscosity or appearance of the aqueous resin composition (1), and the storage stability at room temperature was good.

Next, when the drying time of the aqueous resin composition (1) was measured, it was confirmed that the drying was completed in 10 minutes, which is a short time, although the coating film was as thick as 10 mm. I understood. The results are shown in Table 2.
In addition, when the dried state of the coating film was observed, the coating film had no appearance of blisters and blisters, and the obtained coating film had an excellent appearance.

Explaining the method for measuring the drying time, first, the aqueous resin composition (1) is poured onto a glass plate in a mold so that the coating film has a thickness of 10 mm,
The coating film was dried at 80 ° C. (air velocity 1 m / s) by changing the drying time, and the coating film immediately after drying was scratched to expose the inside, that is, the inside in the thickness direction in a planar manner. The drying time until the aqueous resin composition (1) was not redissolved in water when immersed in water was observed as the drying completion time. The results are shown in Table 2.

[0036]

[Table 1]

[0037]

[Table 2]

Subsequently, the water resistance (water whitening resistance test) of the above aqueous resin composition (1) was measured, and it was found that the water resistance was exhibited for a long period of time. The results are shown in Table 2.

The water whitening resistance test is carried out by applying the aqueous resin composition (1) on a glass plate so that the film thickness becomes 100 μm, and
After drying at 3 ° C. for 24 hours to form a coating film, a cylindrical transparent spot glass having openings at both ends was placed on the coating film, and 50 ml of deionized water was put into the spot glass. Is a test for observing whether or not the interface between the water in the spot glass and the water on the coating film is whitened.

In Table 2, “◯” indicates that redissolution was not observed at all, and water was in a transparent state, and “Δ” in Table 2 was redissolved and slightly clouded. The “X” in Table 2 indicates that the substance is re-dissolved and remarkably becomes cloudy.

(Example 2) Another example of the above synthetic resin emulsion will be described as a synthetic resin emulsion (B) of Example 2. In Example 2, instead of 2 parts of acrylic acid and 30 parts of methyl methacrylate in the polymerizable monomer first mixed solution of Example 1, 3 parts of methacrylic acid, 29
Example 1 above, except that part of methyl methacrylate was used.
In the same manner as above, non-volatile content 50% by weight, pH 7.0,
A synthetic resin emulsion (B) having a viscosity of 1000 mPa · s and good polymerization stability was obtained. Table 1 shows the composition and polymerization stability results of the synthetic resin emulsion (B).

Next, with respect to 100 parts of the above synthetic resin emulsion (B), an aqueous solution of zinc ammonium carbonate, which is 5 parts in terms of zinc oxide, and 1 part of the polyether-modified polysiloxane are sequentially stirred. Addition gave an aqueous resin composition (2).

When the storage stability of this aqueous resin composition (2) at room temperature was measured in the same manner as in Example 1, no change was observed in the viscosity or appearance of the above aqueous resin composition (2), and the aqueous resin composition (2) was stored. The stability was good.

When the drying time of the above-mentioned aqueous resin composition (2) was measured in the same manner as in Example 1, it was found that the drying was completed in a short time. The results are shown in Table 2. Further, when the dried state was observed, it was found that the appearance was excellent without the occurrence of blisters and blisters. Example 1
When the water resistance property (water whitening resistance test) of the aqueous resin composition (2) was measured in the same manner as in, it was found that the water resistance property was exhibited for a long period of time. The results are shown in Table 2.

(Example 3) Still another example of the synthetic resin emulsion will be described as a synthetic resin emulsion (C) of Example 3. In Example 3, 2 parts of acrylic acid in the first mixed liquid of the polymerizable monomer of Example 1 was used.
2.5 parts methacrylic acid, 20 parts methyl methacrylate and 10 parts instead of 0 parts methyl methacrylate
0.5 parts of methacrylic acid, 9 parts of methyl methacrylate, and 6 parts of styrene were used instead of 16 parts of methyl methacrylate in the second polymerizable liquid mixture of Example 1 above. A synthetic resin emulsion (C) having a nonvolatile content of 50% by weight, a pH of 7.0 and a viscosity of 2000 mPa · s and having good polymerization stability was obtained by the same procedure as in Example 1 except that the above was used. Table 1 shows the composition and polymerization stability results of the synthetic resin emulsion (C).

Next, with respect to 100 parts of the above synthetic resin emulsion (C), an aqueous solution of zinc ammonium carbonate, which is 5 parts in terms of zinc oxide, and 1 part of the polyether-modified polysiloxane are sequentially stirred. Addition gave an aqueous resin composition (3).

When the storage stability of this aqueous resin composition (3) was measured at room temperature in the same manner as in Example 1, no change was observed in the viscosity or appearance of the aqueous resin composition (3), and the storage stability was evaluated. The stability was good.

When the drying time of the aqueous resin composition (3) was measured in the same manner as in Example 1, it was found that the drying was completed in a short time. The results are shown in Table 2. Further, when the dried state was observed, it was found that the appearance was excellent without the occurrence of blisters and blisters. Example 1
When the water resistance property (water whitening resistance test) of the aqueous resin composition (3) was measured in the same manner as in, it was found that the water resistance property was exhibited over a long period of time. The results are shown in Table 2.

Next, each comparative example for explaining the characteristics of the aqueous resin composition of the present invention will be described. (Comparative Example 1) In Comparative Example 1, a nonvolatile content of 50 was obtained in the same manner as in Example 1 except that 2 parts of the glycidyl methacrylate of the second polymerizable liquid mixture of Example 1 was omitted.
A synthetic resin emulsion (D) having a good polymerization stability having a weight% of pH 7.0 and a viscosity of 1000 mPa · s was obtained.
The results of composition and polymerization stability of the synthetic resin emulsion (D) are shown in Table 1.

Next, with respect to 100 parts of the above synthetic resin emulsion (C), an aqueous solution of zinc ammonium carbonate, which is 5 parts in terms of zinc oxide, and 1 part of the polyether-modified polysiloxane are sequentially stirred. Addition gave comparative composition (4).

When the storage stability of this comparative composition (4) was measured at room temperature in the same manner as in Example 1, no change was observed in the viscosity or appearance of the above-mentioned comparative composition (4), and the storage stability was Was good.

The comparative composition (4) was prepared in the same manner as in Example 1.
When the drying time was measured in the same manner as above, it was found that at least 20 minutes were required to complete the drying. The results are shown in Table 2. When the water resistance property (water whitening test) of the comparative composition (4) was measured in the same manner as in Example 1, it was found that the water resistance property was decreased in a short period of one day. The results are shown in Table 2.

(Comparative Example 2) In Comparative Example 2, in Example 1
The same procedure as in Example 1 was conducted except that 2 parts of the acrylic acid in the first mixture of the polymerizable monomer of Example 1 was omitted. Polymerization stability was remarkably poor, and a good synthetic resin emulsion was obtained. There wasn't. Therefore, in Comparative Example 2, it was impossible to measure the storage stability, drying time, and water resistance of the aqueous resin composition using the synthetic resin emulsion.

(Comparative Example 3) The synthetic resin emulsion of Comparative Example 3 was prepared by a single step polymerization step and omitting the monomer component having a carboxyl group in the above polymerization step.

That is, for a 1 liter separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts of deionized water and 0.1 part of an ethylenically unsaturated surfactant (first After being charged with Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, the temperature was raised to 70 ° C. with stirring while blowing nitrogen gas.

Then, as the first stage polymerization step, 52
A polymerizable monomer mixture consisting of 1 part of methyl acrylate, 48 parts of 2-ethylhexyl alkylate, 200 parts of deionized water, and 2 parts of the above ethylenically unsaturated surfactant was uniformly added dropwise over 3 hours. At the same time, 60 parts of a 5% aqueous solution of potassium persulfate and 60 parts of a 2% aqueous solution of sodium hydrogen sulfite were added dropwise uniformly over 3 hours.

Then, when aging was carried out for 120 minutes while maintaining the temperature in the separable flask, the polymerization stability was remarkably poor and a good synthetic resin emulsion could not be obtained. From this, in Comparative Example 3, it was impossible to measure the storage stability, drying time, and water resistance of the aqueous resin composition using the synthetic resin emulsion.

(Comparative Example 4) The synthetic resin emulsion of Comparative Example 4 was produced by a polymerization process having only one stage. That is, in place of 2 parts of acrylic acid, 30 parts of methyl acrylate, and 18 parts of 2-ethylhexyl alkylate in the polymerizable monomer mixed solution in Example 1, 2 parts were prepared as the polymerizable monomer mixed solution. Acrylic acid, 4
Polymerization was performed using 8 parts of methyl acrylate and 50 parts of 2-ethylhexyl alkylate, omitting the second step of the polymerization step in Example 1, dropping the polymerizable monomer mixture solution for 3 hours, and adding persulfuric acid. The same operation as in Example 1 was carried out except that 5% aqueous potassium solution and 2% aqueous sodium hydrogen sulfite solution were added dropwise for 3 hours and aging for 120 minutes. As a result, the nonvolatile content was 50 wt%, pH 7.0, and viscosity was 1000 mPa.
A synthetic resin emulsion (E) having a good polymerization stability of s was obtained.

Next, with respect to 100 parts of the above synthetic resin emulsion (E), an aqueous solution of zinc ammonium carbonate, which is 5 parts in terms of zinc oxide, and 1 part of the polyether-modified polysiloxane are sequentially stirred. Addition gave a comparative composition (5).

When the storage stability of this comparative composition (5) was measured at room temperature in the same manner as in Example 1, no change was observed in the viscosity or appearance of the above-mentioned comparative composition (5), and the storage stability was Was good.

The comparative composition (5) was prepared according to Example 1
When the drying time was measured in the same manner as above, it was found that even if the drying time was 20 minutes, the drying was inferior, and that it took more than 20 minutes to complete the drying of the coating film.
The results are shown in Table 2. When the water resistance physical property (water whitening resistance test) of the comparative composition (5) was measured in the same manner as in Example 1, it was found that the water resistance physical property was decreased in a short period of not even one day. The results are shown in Table 2.

(Comparative Example 5) The synthetic resin emulsion of Comparative Example 5 has a polymerization step having only one step, a monomer component having a carboxyl group, and a polyfunctional group which reacts with the carboxyl group in the polymerization step. It is produced by mixing and polymerizing with a monomer component.

That is, for a 1 liter separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 100 parts of deionized water and 0.1 part of an ethylenically unsaturated surfactant (first After being charged with Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, the temperature was raised to 70 ° C. with stirring while blowing nitrogen gas.

Then, as the first polymerization step, 48
Parts methyl acrylate, 48 parts 2-ethylhexyl acrylate, 2 parts acrylic acid (monomer component having a carboxyl group), 2 parts glycidyl methacrylate (monomer component having a polyfunctional group that reacts with a carboxyl group) , 100 parts of deionized water, and 1.0 part of the above ethylenically unsaturated surfactant were uniformly added dropwise over 3 hours. At the same time, 3
0 parts of a 5% aqueous solution of potassium persulfate and 30 parts of a 2% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 3 hours.

Then, when aging was carried out for 120 minutes while maintaining the temperature in the separable flask, the polymerization stability was remarkably poor and a good synthetic resin emulsion could not be obtained. From this, in Comparative Example 5, it was impossible to measure the storage stability, the drying time and the water resistance of the aqueous resin composition using the synthetic resin emulsion.

From the above, acrylic acid as a polymerizable monomer component having a carboxyl group and glycidyl methacrylate as a polyfunctional unsaturated monomer capable of reacting with the carboxyl group in the same weight part. It was found that the polymerization stability was lowered when used as a mixture.

Therefore, this Comparative Example 5 and the above-mentioned Example 3
From the results, when the polymerizable monomer component having a carboxyl group and the polyfunctional unsaturated monomer capable of reacting with the carboxyl group are used in the same polymerization stage, the compound has a carboxyl group. It is preferable that the polymerizable monomer component is used in an amount of not more than half the weight part of the polyfunctional unsaturated monomer capable of reacting with the carboxyl group, and in a molar ratio of 0.8 or less. I understand.

As described above, in the constitution of each of the above-mentioned examples, the synthetic resin emulsion which is an aqueous resin obtained by multi-stage polymerization, the heat-sensitive gelling agent, and preferably the heat-sensitive gelling aid are added to the surface of the coating film. While avoiding the inconvenience of poor internal drying due to the formation of a film, even in the case of a thick film having a thickness of 10 mm, the drying is completed in a drying time of about 10 minutes and It is possible to prevent the formation of blisters and blisters, and to form a coating film with excellent appearance, water resistance, and durability.

From the above, in the above-mentioned constitution, when it is used as a coating film for a base material such as a binder for factory coating, various coating materials for interior and exterior, a binder for fiber treatment, a binder for synthetic leather, etc. Since the drying time can be shortened, the productivity and mass productivity of the base material can be improved, the cost for drying can be reduced, and the cost can be reduced.

Further, in the above-mentioned constitution, the hardness of the obtained coating film can be increased by setting the glass transition temperature of the synthetic resin emulsion to a high level. Especially, since the drying time of a thick film can be shortened, a tougher coating film can be formed in a short time and a coating film having excellent durability can be formed.

From the above, in the above structure, since a thick coating film can be formed by increasing its hardness, it has excellent machinability, and when used as various interior and exterior coating materials. Further, it becomes possible to easily impart the decorative property to the coating material.

[0072]

As described above, the aqueous resin composition of the present invention is configured to contain an aqueous resin obtained by multistage polymerization and a heat-sensitive gelling agent.

Therefore, the above-mentioned constitution includes the aqueous resin obtained by the multi-stage polymerization which is separately polymerized and the heat-sensitive gel laxative, so that the drying time of the coating film, especially the drying of the thick coating film is completed. The time can be shortened. Therefore, in the above-mentioned composition, there is an effect that the cost at the time of forming a coating film can be reduced.

As described above, the aqueous resin composition of the present invention comprises the aqueous resin, the polyether-modified polysiloxane for imparting the heat-sensitive gelling property, and the carbonate for imparting the heat-sensitive gelling property. It is a structure including an ammonium complex.

Therefore, in the above constitution, by including both the polyether-modified polysiloxane and the ammonium carbonate complex, it is possible to shorten the drying time of the coating film, particularly the drying completion time of the thick coating film. it can. Therefore, in the above-mentioned composition, there is an effect that the cost at the time of forming a coating film can be reduced.

Claims (6)

[Claims] 1. An aqueous resin composition comprising an aqueous resin, a polyether-modified polysiloxane, and an ammonium carbonate complex. 2. An aqueous resin composition comprising an aqueous resin obtained by multistage polymerization and a heat-sensitive gelling agent. 3. A polyfunctional resin capable of reacting the first polymerizable monomer component (a) having a carboxyl group in the molecule with the carboxyl group of the first polymerizable monomer component (a). 3. The aqueous resin composition according to claim 1 or 2, which is obtained by multi-stage polymerization with a second polymerizable monomer component (b) containing at least a polyunsaturated monomer. 4. A polyether-modified polysiloxane is contained as a heat-sensitive gelling agent.
Alternatively, the aqueous resin composition according to the item 3. 5. The aqueous resin resin composition according to claim 2, which further comprises a polyvalent metal as a heat-sensitive gelling aid. 6. The aqueous resin composition according to claim 1, wherein the coating film has a thickness of 2 to 20 mm.