JP3118080B2 - Low foam resin emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a low-foaming property by using a sulfonate-type anionic surfactant and an amide-amine-type nonionic surfactant as emulsifiers, and has a low static stability. The present invention relates to a resin emulsion composition having excellent mechanical stability. This resin emulsion is widely used as a compounding agent for adhesives, adhesives, sealants, paints, inks, rubbers, plastics, and the like.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of improving the working environment in terms of safety, the use of resins has been changing from the use of melts and solvents to the use of emulsions.

[0003] Sulfonate-type anionic surfactants, which are generally widely used as emulsifiers, satisfy the static stability and the mechanical stability, but have a problem of many bubbles. In other words, the sulfonate-type anionic surfactant has a high surface activity and a good emulsified state, and thus has excellent standing stability and mechanical stability, but generates more foam.

Therefore, in order to suppress foaming, an antifoaming agent such as a silicone-based, polyalkylene glycol-based, alcohol-based, mineral oil-based, animal and vegetable oil-based antifoaming agent is added. However, the addition of an antifoaming agent often causes deterioration of the emulsified state, resulting in poor standing stability and mechanical stability,
In addition, the addition of an antifoaming agent or the like is not preferred because it may adversely affect the subsequent steps in the use of the emulsion.

[0005] Next, the use of low-foaming emulsifiers is mentioned. Generally, low-foaming means that the surface activity is low, so that the emulsified state is deteriorated and foaming is small. The properties and mechanical stability will be poor.

The following are examples of the properties of resin emulsions. (1) Solid content (2) pH (3) Viscosity (4) Average particle size (5) Foaming (6) Stability at rest (7) Mechanical stability

The solid content (1) refers to the amount of resin contained in the resin emulsion, and can be adjusted by the balance between the amount of resin and the amount of water at the time of production. Although the optimum amount of the solid content varies depending on the application, water is finally removed by evaporation, and therefore, in general, those having a low water content and a high solid content are preferred. However, when the solid content is 70% by weight or more, the viscosity rapidly rises in many cases, making it practically unusable. Therefore, the solid content is adjusted to an optimum value of 70% by weight or less.

The pH of (2) is generally determined by the type of emulsifier. However, in many cases, the resin emulsion is used by being mixed with another emulsion, an aqueous solution, or the like. Therefore, the optimum pH differs depending on the pH of the object to be mixed. Therefore, in order to obtain the optimum pH, the pH is adjusted by selecting an emulsifier or by adding a pH adjuster.

The viscosity of (3) is desirably 500 cP or less as an easy-to-handle viscosity, but the optimum viscosity varies depending on the application. Since the viscosity is closely related to the type and amount of the emulsifier and the type and amount of the solid content, the viscosity is adjusted by changing the combination of these types and amounts. Thickeners and thinners are also used.

Regarding the average particle diameter of (4), when mixed with other emulsions, the smaller the average particle diameter is,
In general, a finer particle size is preferred because of improved mixing and compatibility. The average particle size is determined by the type of emulsifier and the method of producing the emulsion.

The above properties (1) to (4) differ in the optimum properties required depending on the use of the resin emulsion. These properties can be dealt with by changing the emulsifier, the emulsification method and the emulsification conditions. The properties (5) to (7) described below are important factors that pose a problem in actual use of the resin emulsion, and excellent properties are required regardless of the application.

(5) Foaming refers to how much foam is formed during operations such as stirring, mixing, and transferring. Bubbles are not only difficult to handle due to the foam during operation, but they also hinder the next step.
Foaming has two properties: foaming and defoaming. Foaming refers to the ease with which the foam is formed, and defoaming refers to the ease with which the formed foam disappears. The property required for foaming is that foam cannot be formed first, that is, the foaming property is low. In this case, it can be said that the defoaming property is good because the foam is originally small. Next, even if bubbles are formed, they disappear quickly, that is, they have good defoaming properties. In any case, it is preferable that the amount of foam is always small. As a specific method for evaluating these, an emulsion diluted 10-fold with water is placed in a graduated cylinder with a stopper, and shaken vertically 10 times at a rate of 1 time / second to immediately determine the amount of foam. Foaming property, 5
The foam amount after 30 seconds and 30 seconds is evaluated as defoaming property.

The stationary stability (6) is the stability of the resin emulsion during long-term storage. Those with poor stationary stability are deteriorated and separated and cannot be used. Those that are stable for long periods are preferred.

The mechanical stability (7) is the stability against mechanical operation when the resin emulsion is handled by a device such as stirring, mixing, and pumping. Those having poor mechanical stability cause the resin emulsion to solidify due to mechanical operation. This coagulated material is not preferable in handling in an apparatus, and if the coagulated substance is large, it cannot be used in the apparatus. The mechanical stability is determined by the amount of this coagulated material,
According to SK-6392, the mixture is treated with a Malon-type stability tester, and the percentage of the weight of the coagulated material with respect to the weight of the solid content of the resin emulsion and the coagulation rate are determined, and this is used as a measure of mechanical stability. The required solidification rate varies depending on the device used and the method of use, but in each case, the lower the value, the better.

As described above, those having poor properties of (5) to (7), even those having excellent properties of (1) to (4), are unnecessarily necessary when actually used. Bubbles rise,
It separates and solidifies, making it practically unusable or limiting the applications and devices used. Therefore, as the required properties, foaming is small, and the standing stability is stable for a long time,
The coagulation rate is low from the viewpoint of mechanical stability. These properties are greatly influenced by the emulsifier, and selection of the emulsifier becomes an important problem.

[0016]

As described above, foaming and static stability and mechanical stability often have contradictory properties. If foaming is reduced, static stability and mechanical stability deteriorate. I do. Therefore, it is very difficult to obtain a resin emulsion having both properties. The present invention balances these contradictory properties, and has excellent standing stability and mechanical stability,
Moreover, it is intended to provide a resin emulsion with less foaming.

[0017]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to obtain a resin emulsion having low foaming properties and excellent in static stability and mechanical stability. The problem has been solved by combining a surfactant and an amide / amine type nonionic surfactant as an emulsifier, resulting in the present invention.

That is, the present invention provides, as an emulsifier component, an emulsifier A) one or more sulfonic acid salt type anionic surfactants; an emulsifier B) those belonging to (a) represented by the following structural formula: One or more surfactants selected from among them,
An amide-amine type nonionic surfactant comprising a mixture of one or more surfactants selected from those belonging to (b);

(A) Amide type

[0020]

Embedded image

(In the formula, R ¹ is an alkyl group having 5 to 9 carbon atoms, and R ² and R ³ are an alkylol group having 2 to ³ carbon atoms.)

(B) amine type

N- (R) ₃

(Wherein R is hydrogen or an alkylol group having 2 to 3 carbon atoms and has at least one alkylol group)

The present invention relates to a resin emulsion composition containing the emulsifier A, the emulsifier B and the resin.

The resin used in the present invention includes:
Any hydrophobic resin used in a melt system, a solvent system, and an emulsion system may be used, and specific examples include a petroleum resin, a rosin ester resin, a terpene resin, and an epoxy resin.

Next, among the emulsifiers used in the present invention, the sulfonate type anionic surfactant of the emulsifier A includes:
Emulsifiers which are generally used as emulsifiers may be used, but emulsifiers having excellent standing stability and mechanical stability are preferred. Specifically, alkylbenzene sulfonates, alpha olefin sulfonates, dialkyl sulfosuccinates, alkyl ether sulfones There are acid salts and the like, for example, sodium alkyl benzene sulfonate, sodium alpha olefin sulfonate, sodium dialkyl sulfosuccinate, sodium polyoxyethylene alkyl phenyl ether sulfonate, sodium alkyl diphenyl ether sulfonate and the like. Emulsifier A is a mixture of one or more of these sulfonate-type anionic surfactants at an arbitrary ratio.

As the amide type of the emulsifier B represented by the general formula (a), R ¹ is an alkyl group having 5 to 9 carbon atoms, and R ² and R ³ are alkylol groups having 2 to ³ carbon atoms. The alkylol group includes an ethanol group, a normal propanol group, and an isopropanol group.Specifically, fatty acid ethanol amide, fatty acid diethanol amide, fatty acid normal propanol amide, fatty acid dinormal propanol amide, fatty acid isopropanol amide, fatty acid diisopropanol There is an amide.
As the amine type represented by the general formula in (b) of the emulsifier B, R is hydrogen or an alkylol group having 2 to 3 carbon atoms, at least one of which has an alkylol group. Specifically, there are ethanolamine, diethanolamine, triethanolamine, normal propanolamine, dinormal propanolamine, trinormal propanolamine, isopropanolamine, diisopropanolamine, and triisopropanolamine. A mixture of one or more of the amide type (a) and one or more of the amine type (b) is preferable. Preferably, emulsifier B is obtained by mixing (a) and (b) at a mixing weight ratio of 1: 5 to 5: 1.

The amount of resin solid content in the resin emulsion composition of the present invention may be an amount usually used frequently. Generally, it is 30 to 70% by weight, but preferably 50 to 60% by weight. If the resin solids content is too low, the stability during standing will be degraded, and if it is too high, the viscosity will be too high and handling will be difficult.

Regarding the amount of emulsifier A, if the amount of emulsifier A is too small, the emulsified state deteriorates, and
The mechanical stability also deteriorates. Conversely, if the amount is too large, the generation of bubbles increases and the viscosity increases. Therefore, it is preferable to use 0.1 to 5.0% by weight based on the whole resin emulsion, but more preferably 0.5 to 3% by weight. It is more preferable to use 0.0% by weight. The emulsifier B is preferably used in an amount of 0.1 to 5.0% by weight based on the whole resin emulsion. It is preferable to use an amount equal to or less than that of the emulsifier A, and it is more preferable to use 50% by weight of the amount of the emulsifier A.

By using the combination of the emulsifier A and the emulsifier B in the present invention, a resin emulsion having a sufficiently low foaming property and excellent standing stability and mechanical stability can be obtained. Additives such as a thickener, a viscosity reducer, and a pH adjuster may be used.

The emulsification method in the present invention includes a high-temperature high-pressure emulsification method in which the viscosity of the resin is reduced at a high temperature to effect emulsification, a solvent emulsification method in which the resin is dissolved in a solvent to perform emulsification, / W type phase inversion emulsification method, and a method of further performing a secondary treatment by applying a high shearing force to atomize the particles. Anyway, it is not limited to these.

[0033]

First, among emulsifiers, regarding emulsifier A, a resin emulsion emulsified with only a sulfonate-type anionic surfactant of emulsifier A has many foams, but has excellent standing stability and mechanical stability. It will be. This is because the type of the emulsifier A has a very high surface activity and a good emulsified state, so that it has excellent static stability and mechanical stability. It is considered that the large amount of foam by the emulsifier A is because a strong and stable foam film is formed by the emulsifier A and the foam cannot be easily broken.

On the other hand, when the emulsifier B is emulsified with only the amide / amine type nonionic surfactant of the emulsifier B, the emulsification is temporarily performed, but the emulsified state is poor, and the stationary stability is extremely poor. What is important here is that the emulsifier B is not completely free of emulsifying power, but has some emulsifying power.

When the emulsifier A and the emulsifier B are combined and emulsified, the emulsifier A is strongly emulsified, and the emulsifier B itself has a weak emulsifying power but does not hinder the strong emulsifying power of the emulsifier A. Therefore, this emulsion has excellent standing stability and mechanical stability. This is thought to be because the foam film becomes unstable when the emulsifier B enters the strong and stable foam film by the emulsifier A, and the foam film is broken, resulting in low foamability. As described above, there are many substances that destabilize the foam film, including antifoaming agents, but in general, not only the foam film but also the emulsified state becomes unstable, resulting in static stability and mechanical stability. It causes the deterioration of the sex. However, the emulsifier A according to the present invention
When used in combination with the emulsifier B, shows a low foam without deteriorating the emulsified state by the synergistic action of these emulsifiers,
In addition, a resin emulsion having excellent standing stability and mechanical stability can be obtained.

[0036]

According to the conventional emulsifiers, it was difficult to satisfy the appropriate foaming and the excellent standing stability and mechanical stability due to the characteristics of the emulsifier, but the emulsifier was emulsified by combining different types of emulsifiers of the present invention. Can solve the problem. Since the resin emulsion of the present invention is excellent in foaming, standing stability and mechanical stability, problems in handling on a real machine are reduced, and applications, usage methods, equipment used and the like which have been conventionally limited can be expanded. .

[0037]

Next, the present invention will be described in more detail by way of examples, which are merely examples, and the present invention is not limited thereto. Various properties of the produced emulsion were evaluated by the following methods.

(1) Foaming Emulsion 3 in 100 ml graduated cylinder with stopper
g of tap water and 27 g of tap water were shaken vertically 10 times at a rate of once / second to evaluate foaming. Further, the foaming property was evaluated based on the foam amount immediately after shaking, and the defoaming property was evaluated based on the foam amounts after 5 seconds and 30 seconds.

(2) Stationary stability One emulsion was placed in a 100 ml collection vial.
After sealing at 0 cm height, the resin was allowed to stand at room temperature for 2 weeks, and the state of sedimentation of the resin was examined and judged according to the following criteria.

○: No sedimentation ×: Sedimentation occurred

(3) Mechanical stability (JIS K-6392)
Emulsion 150 previously filtered through a 45 μm wire mesh
g in a container of a Marron-type stability tester, and load 15
A mechanical force is applied for 30 minutes at kgf and a rotation speed of 1000 rpm, and then the formed coagulated product is separated by filtration with a 45 μm wire mesh, dried in a drier to a constant weight, and the amount of the coagulated product is measured. Ask for.

[0042]

(Equation 1)

CR Coagulation rate (%) WC Mass of dried coagulated material (g) W Mass of sample (g) TSC Total solid content (%)

[0044]

Example 1 Sodium alkylbenzene sulfonate was used as emulsifier A, and a mixture of fatty acid diethanolamide and diethanolamine at a weight ratio of 1: 1 was used as emulsifier B. The fatty acid diethanolamide used in the examples of the present invention refers to an emulsifier B in which (a) R ¹ represented by the amide type general formula has an alkyl group having 5 to 9 carbon atoms, It is a mixture of these fatty acid diethanolamides having different carbon numbers.

600 g of an aromatic petroleum resin having a softening point of 95 ° C. (trade name: Oligotec 1300, manufactured by Mitsubishi Petroleum Co., Ltd.) is dissolved at 160 ° C. and put into a resin emulsion production apparatus. / Cm
² Stir the pump at (gage pressure). 5 g of emulsifier A (0.5% by weight with respect to resin emulsion) and 2 g of emulsifier B with 393 g of water (tap water) (0.2 with respect to resin emulsion 0.2)
% By weight) and 20 ml of this aqueous solution of emulsifier is poured into a resin emulsion production apparatus in which the resin is stirred.
/ Min. After completion of the injection, the mixture was transferred to a cooling tank and circulated with water at 0 ° C. to 17 kgf / cm ² (gap).
The mixture was cooled to 20 ° C. under the pressure of (2) to obtain a resin emulsion composition. Various physical properties were measured according to the methods described above, and as shown in Table 1, the foaming properties were low and the static stability and the mechanical stability were good.

[0046]

EXAMPLE 2 As in Example 1, emulsifier A was sodium alkylbenzene sulfonate, and emulsifier B was a 1: 1 mixture of fatty acid diethanolamide and diethanolamine.
The mixture was converted to a resin solid content of the same resin 60 as in Example 1.
After dissolving 10 g of emulsifier A (1% by weight based on resin emulsion) and 3 g of emulsifier B (0.3% by weight based on resin emulsion) in 387 g of water using 0 g, Example 1 was used.
And emulsified by the method described in (1). As shown in Table 1, the physical properties were low in foaming property and good in static stability and mechanical stability.

[0047]

Example 3 As in Example 1, emulsifier A was sodium alkylbenzene sulfonate, and emulsifier B was a 1: 1 mixture of fatty acid diethanolamide and diethanolamine.
The mixture was converted to a resin solid content of the same resin 60 as in Example 1.
Example 1 After dissolving 10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B (0.5% by weight based on resin emulsion) in 385 g of water using 0 g.
And emulsified by the method described in (1). As shown in Table 1, the physical properties were low in foaming property and good in static stability and mechanical stability.

[0048]

EXAMPLE 4 As in Example 1, emulsifier A was sodium alkylbenzene sulfonate, and emulsifier B was a 1: 1 mixture of fatty acid diethanolamide and diethanolamine.
The mixture was converted to a resin solid content of the same resin 60 as in Example 1.
After dissolving 10 g of emulsifier A (1% by weight based on resin emulsion) and 8 g of emulsifier B (0.8% by weight based on resin emulsion) in 382 g of water using 0 g, Example 1 was used.
And emulsified by the method described in (1). As shown in Table 1, the physical properties were low in foaming property and good in static stability and mechanical stability.

[0049]

Example 5 As in Example 1, emulsifier A was sodium alkylbenzene sulfonate, and emulsifier B was a 1: 1 mixture of fatty acid diethanolamide and diethanolamine.
The mixture was converted to a resin solid content of the same resin 60 as in Example 1.
Using 0 g, 20 g of emulsifier A (2% by weight based on resin emulsion) and 10 g of emulsifier B (1% by weight based on resin emulsion) are dissolved in 370 g of water, and emulsified by the method described in Example 1. did. As shown in Table 1, the physical properties were low in foaming property and good in static stability and mechanical stability.

[0050]

Example 6 As in Example 1, emulsifier A was sodium alkylbenzene sulfonate, and emulsifier B was a 1: 1 mixture of fatty acid diethanolamide and diethanolamine.
The mixture was converted to a resin solid content of the same resin 60 as in Example 1.
After dissolving 30 g of emulsifier A (3% by weight based on resin emulsion) and 15 g of emulsifier B (1.5% by weight based on resin emulsion) in 355 g of water using 0 g, the method described in Example 1 is used. And emulsified. Physical properties are shown in Table 1.
The foaming properties were low, and the static stability and mechanical stability were good.

[0051]

Example 7 Sodium alkylbenzene sulfonate was used as emulsifier A, a 1: 1 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B, and 500 g of the same resin as in Example 1 was used as the resin solid content.
10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B (0.5% based on resin emulsion) were added to 5 g of water.
(% By weight) and then emulsified by the method described in Example 1. As shown in Table 2, the physical properties were low in foaming property and good in static stability and mechanical stability.

[0052]

Example 8 A sodium alkylbenzene sulfonate as emulsifier A, a 1: 1 mixture of fatty acid diethanolamide and diethanolamine as emulsifier B, and 300 g of the same resin as in Example 1 were used as resin solids.
10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B (0.5% based on resin emulsion) were added to 5 g of water.
(% By weight) and then emulsified by the method described in Example 1. As shown in Table 2, the physical properties were low in foaming property and good in static stability and mechanical stability.

[0053]

EXAMPLE 9 As in Example 1, emulsifier A was sodium alkylbenzene sulfonate, and emulsifier B was a 1: 1 mixture of fatty acid diethanolamide and diethanolamine.
The same resin as in Example 1 was used as the resin solid content of 6
Example 5 After dissolving 10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B (0.5% by weight based on resin emulsion) in 335 g of water using 50 g, Example 1 was used.
And emulsified by the method described in (1). As shown in Table 2, the physical properties were low in foaming property and good in static stability and mechanical stability.

[0054]

Comparative Example 1 No emulsifier B was used, only sodium alkylbenzene sulfonate was used as emulsifier A, 600 g of the same resin as in Example 1 was used as the resin solid content, and 10 g of emulsifier A was added to 390 g of water (1 wt. %)
After dissolution, emulsification was carried out by the method described in Example 1. As shown in Table 3, the physical properties were good in mechanical stability and standing stability, but high in foaming property and poor in defoaming property.

[0055]

Comparative Example 2 No emulsifier A was used, only a 1: 1 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B, and 600 g of the same resin as in Example 1 was used as the resin solid content, and 10 g of emulsifier B was added to 390 g of water. (1% by weight of resin emulsion) After dissolution, emulsification was carried out by the method described in Example 1. The produced resin emulsion had a large amount of coarse particles, and had poor standing stability that caused separation and sedimentation in about one hour. Therefore, other physical properties could not be measured.

[0056]

Comparative Example 3 A sodium alkylbenzene sulfonate was used as emulsifier A, a 1: 1 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B, and 600 g of the same resin as in Example 1 was used as the resin solid content.
5 g of emulsifier A (0.5% by weight based on resin emulsion) and 10 g of emulsifier B (1% by weight based on resin emulsion) were dissolved in 385 g of water, and emulsified by the method described in Example 1. As shown in Table 3, since the amount of the emulsifier B was larger than the amount of the emulsifier A, the physical stability was poor in static stability and mechanical stability.

[0057]

Comparative Example 4 A sodium alkylbenzene sulfonate was used as emulsifier A, a 1: 1 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B, and 600 g of the same resin as in Example 1 was used as the resin solid content.
10 g of emulsifier A (1% by weight based on resin emulsion) and 15 g of emulsifier B (1.5% by weight based on resin emulsion) were dissolved in 375 g of water, and emulsified by the method described in Example 1. As shown in Table 3, since the amount of the emulsifier B was larger than the amount of the emulsifier A, the physical stability was poor in static stability and mechanical stability.

[0058]

Example 10 Sodium alpha-olefin sulfonate was used as emulsifier A, a 1: 1 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B (shown in Table 4), and 600 g of the same resin as in Example 1 was used as the resin solid content. And 10 g of emulsifier A in 385 g of water
(1% by weight of resin emulsion) and 5 g of emulsifier B
(Based on the resin emulsion 0.5% by weight)
The emulsion was emulsified by the method described in Example 1. As shown in Table 6, the foaming properties were low and the static stability and mechanical stability were good.

[0059]

Comparative Example 5 No emulsifier B was used, only sodium alpha-olefin sulfonate was used as emulsifier A (shown in Table 4), and the same resin as in Example 10 was used as the resin solid content in the same amount as in Example 390. Was dissolved in 10 g (based on 1% by weight of the resin emulsion), and emulsified by the method described in Example 1. As shown in Table 6, the foaming property was high and the defoaming property was poor.

[0060]

EXAMPLE 11 Sodium dialkyl sulfosuccinate was used as emulsifier A and a 1: 1 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B (Table 4).
The same amount of resin as in Example 10 was used as the resin solid content, and 10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B were added to 385 g of water (0.5 g based on resin emulsion 0.5). (% By weight) and then emulsified by the method described in Example 1. As shown in Table 6, physical properties were low in foaming property, and good in static stability and mechanical stability.

[0061]

Comparative Example 6 No emulsifier B was contained, and only sodium dialkyl sulfosuccinate was used as emulsifier A (shown in Table 4).
Using the same amount of the same resin as in Example 10 as the resin solid content,
10 g of emulsifier A (1% by weight based on resin emulsion) was dissolved in 390 g of water, and emulsified by the method described in Example 1. As shown in Table 6, the foaming property was high and the defoaming property was poor.

[0062]

Example 12: Sodium polyoxyethylene alkylphenyl ether sulfonate as emulsifier A, emulsifier B
As a resin solid content, the same resin as in Example 10 was used in the same amount as in Example 10, and 10 g of emulsifier A was added to 385 g of water (based on resin emulsion 1). weight%)
And 5 g of emulsifier B (based on 0.5% by weight of resin emulsion) were dissolved and emulsified by the method described in Example 1. As shown in Table 6, physical properties were low in foaming property, and good in static stability and mechanical stability.

[0063]

Comparative Example 7 Only 390 g of the same resin as in Example 10 was used as the emulsifier A without sodium emulsifier A, using only sodium polyoxyethylene alkylphenyl ether sulfonate (shown in Table 4). Emulsifier A in water
Was dissolved in 10 g (1% by weight with respect to the resin emulsion),
The emulsion was emulsified by the method described in Example 1. As shown in Table 6, the foaming property was high and the defoaming property was poor.

[0064]

Example 13 Using emulsifier A as a sodium alkyldiphenyl ether disulfonate and emulsifier B using a 1: 1 mixture of fatty acid diethanolamide and diethanolamine (shown in Table 4), the resin solid content of Example 10 was used.
Using the same amount of the same resin as above, 10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B (0.5% by weight based on resin emulsion) were dissolved in 385 g of water. Emulsified by the method described in 1. As shown in Table 6, physical properties were low in foaming property, and good in static stability and mechanical stability.

[0065]

Comparative Example 8 No emulsifier B was used, only sodium alkyldiphenyl ether disulfonate was used as the emulsifier A (shown in Table 4), and the same resin as in Example 10 was used as the resin solid content in 390 g of water. Was dissolved in 10 g (based on 1% by weight of the resin emulsion), and emulsified by the method described in Example 1. As shown in Table 6, the foaming properties were low and the defoaming property was poor.

[0066]

Example 14 A 1: 1 mixture of sodium alkylbenzenesulfonate and sodium alpha-olefinsulfonate was used as emulsifier A, and a 1: 1 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B (shown in Table 5). Using the same amount of the same resin as in Example 10, 10 g of emulsifier A in 385 g of water
(1% by weight of resin emulsion) and 5 g of emulsifier B
(Based on the resin emulsion 0.5% by weight)
The emulsion was emulsified by the method described in Example 1. As shown in Table 6, physical properties were low in foaming property, and good in static stability and mechanical stability.

[0067]

Example 15 A 1: 1 mixture of sodium alkylbenzenesulfonate and sodium dialkylsulfosuccinate was used as emulsifier A, and a 1: 1 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B (shown in Table 5). Using the same amount of the same resin as in Example 10, 10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B (0.5% by weight based on resin emulsion) were dissolved in 385 g of water. Example 1
And emulsified by the method described in (1). As shown in Table 6, physical properties were low in foaming property, and good in static stability and mechanical stability.

[0068]

EXAMPLE 16 Sodium alkylbenzene sulfonate was used as emulsifier A, a 1: 2 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B (shown in Table 5), and the same resin as in Example 10 was used as the resin solid content. Then, 10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B (0.5% by weight based on resin emulsion) were dissolved in 385 g of water.
And emulsified by the method described in (1). As shown in Table 6, physical properties were low in foaming property, and good in static stability and mechanical stability.

[0069]

Example 17 Sodium dialkyl sulfosuccinate was used as emulsifier A, and a 1: 2 mixture of fatty acid diethanolamide and diethanolamine was used as emulsifier B (Table 5).
The same amount of resin as in Example 10 was used as the resin solid content, and 10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B were added to 385 g of water (0.5 g based on resin emulsion 0.5). (% By weight) and then emulsified by the method described in Example 1. As shown in Table 6, physical properties were low in foaming property, and good in static stability and mechanical stability.

[0070]

Example 18 Sodium alkylbenzene sulfonate was used as emulsifier A, and a 1: 1: 1 mixture of fatty acid diethanolamide, diethanolamine and triethanolamine was used as emulsifier B (shown in Table 5). Resin solid content was the same as in Example 10. 385g using the same amount of resin
After 10 g of emulsifier A (1% by weight based on resin emulsion) and 5 g of emulsifier B (0.5% by weight based on resin emulsion) were dissolved in water, the mixture was emulsified by the method described in Example 1. As shown in Table 6, physical properties were low in foaming property, and good in static stability and mechanical stability.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

[Table 5]

[0076]

[Table 6]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08K 5/17 C08K 5/17 5/20 5/20 5/42 5/42 (56) References JP-A-59-74154 ( JP, A) JP-A-57-155253 (JP, A) JP-B-46-14742 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 B01F 17/00-17/22 B01J 13/00

Claims (3)

(57) [Claims] The emulsifier component is selected from emulsifiers A) one or more sulfonate type anionic surfactants, and emulsifiers B) those belonging to (a) represented by the following structural formula. One or more surfactants,
Amide-amine type nonionic surfactant comprising a mixture of one or more surfactants selected from those belonging to (b), (a) amide type (In the formula, R ¹ is an alkyl group having 5 to 9 carbon atoms, R ² · R ³
Is an alkylol group having 2 to 3 carbon atoms. (B) amine type N- (R) ₃ (wherein R is hydrogen or an alkylol group having 2 to 3 carbon atoms, at least one of which is an alkylol group) A resin emulsion composition containing these emulsifiers A, B and a resin. 2. The content of the emulsifier A is 0.1 to 5.0% by weight based on the whole part of the emulsion, and the content of the emulsifier B is equal to or less than the content of the emulsifier A based on the whole part of the emulsion. And a mixture weight ratio of (a) the amide type nonionic surfactant and (b) the amine type nonionic surfactant is in the range of 1: 5 to 5: 1. A resin emulsion composition. 3. The emulsifier component, wherein the surfactant of the emulsifier A) is one or more of alkyl benzene sulfonate, alpha olefin sulfonate, dialkyl sulfosuccinate, and alkyl ether sulfonate. And the content is 0.5 with respect to the total amount of the emulsion.
(A) Amide-type nonionic surfactant of emulsifier B) is a fatty acid ethanolamide, a fatty acid diethanolamide, a fatty acid normal propanol amide, a fatty acid dinormal propanol amide, a fatty acid isopropanol amide, or a fatty acid diisopropanol amide And one or more of (a) and (b) the amine-type nonionic surfactant are ethanolamine, diethanolamine,
Triethanolamine, normal propanolamine,
It comprises one or a mixture of two or more of dinormal propanolamine, trinormal propanolamine, isopropanolamine, diisopropanolamine, and triisopropanolamine, and the mixing weight ratio of (a) and (b) is 1: 1 to 1 : 2, and the content of the emulsifier B is 50% by weight of the emulsifier A.
A resin emulsion composition comprising an emulsifier B and a resin.