JPH06102748B2 - Epoxy resin emulsion composition and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an epoxy resin emulsion composition used as a paint, an adhesive, a fiber processing agent, a glass fiber sizing agent, etc., and a method for producing the same.

[Conventional technology]

Conventionally, epoxy resins have been widely used as paints and adhesives. Such epoxy resin adhesives (paints, etc.) are usually used by curing the epoxy resin itself with an amine-based curing agent, but recently, the epoxy resin is phase-shifted with an emulsifier to form emulsion. The epoxy resin emulsion composition has been developed and put into practical use. For example, JP-A-54-15956 and JP-A-58-111831.
The publication discloses an epoxy resin emulsion composition containing 3 to 20 parts of a nonionic emulsifier with respect to 100 parts by weight of epoxy resin (hereinafter abbreviated as "part").

[Problems to be Solved by the Invention]

However, in the epoxy resin emulsion composition, in order to secure the emulsion stability, the compounding ratio of the emulsifier is very large, 3 to 20 parts (when the emulsifier is less than 3 parts, the resin and water are emulsified). Because of phase separation immediately after), it is inferior in physical properties such as water resistance, chemical resistance, film strength, etc. compared to the conventional epoxy resin which is cured as it is. In addition, there is a problem that the heat treatment tends to cause yellowing and a decrease in adhesive strength.

Further, Japanese Patent Application Laid-Open No. 61-243822 discloses a self-emulsifying type modified with an epoxy resin, which has low film strength, slow curing speed, high cost, etc. It has drawbacks.

As described above, in the conventional epoxy resin emulsion composition, it is the fact that no one having water resistance, chemical resistance, thermal stability and the like comparable to the original epoxy resin has been obtained.

The present invention has been made in view of such circumstances, and by suppressing the amount of the emulsifier used to a necessary minimum, an epoxy resin emulsion having excellent physical properties comparable to an epoxy resin without impairing the stability of the emulsion. The purpose is to provide a composition.

[Means for Solving the Problems]

In order to achieve the above object, the present invention has a softening point of 100 ° C.
For 100 parts by weight of the following epoxy resin, the following (A)
0.3 to 0.9 parts by weight of component, 0.3 to 0.9 part by weight of component (B) below, 0.4 to 1.2 parts by weight of component (C) below, 20 to 70 parts of water
An O / W type epoxy resin emulsion composition obtained by mixing 0 part by weight, wherein the average particle size of the dispersoid is set to 0.6 μm or less
(A) A polymeric emulsifier with a molecular weight of 7,000 or more.

(B) At least one of a nonionic emulsifier and an anionic emulsifier having a molecular weight of 7,000 or less and an HLB of 17 or more.

(C) A nonionic emulsifier having a molecular weight of 7,000 or less and an HLB of 14 to 17.

0.3 to 0.9 parts by weight of the following component (A) and 100 parts by weight of the epoxy resin having a softening point of 100 ° C. or less and the following (C) component
Prepare a liquid epoxy resin by mixing at a ratio of 0.4 to 1.2 parts by weight, prepare 200 to 700 parts by weight of water for 100 parts by weight of the epoxy resin, and add a part of this water to 100 parts by weight of the epoxy resin. On the other hand, a step of dissolving 0.3 to 0.9 parts by weight of the following component (B) to obtain a component (B) aqueous solution, and blending the liquid epoxy resin with the component (B) aqueous solution to prepare a system from a W / O emulsion The second gist is a method for producing an epoxy resin emulsion composition, which comprises a step of phase inversion into an O / W emulsion and further compounding the rest of the water.

(A) A polymeric emulsifier having a molecular weight of 7,000 or more.

(B) At least one of a nonionic emulsifier and an anionic emulsifier having a molecular weight of 7,000 or less and an HLB of 17 or more.

(C) A nonionic emulsifier having a molecular weight of 7,000 or less and an HLB of 14 to 17.

[Action]

That is, the present invention uses a combination of the above-mentioned special three kinds of emulsifiers as an emulsifier, and further, emulsification method
By mixing liquid epoxy resin in which two of two types of emulsifiers are mixed with epoxy resin and one remaining emulsifier dissolved in a small amount of water, W / O type emulsion is changed to O / W type emulsion. Since a special method of phase inversion is used, it is possible to obtain a very fine emulsion having an average particle diameter of 0.6 μm or less of the epoxy resin as a dispersoid, although the amount of the emulsifier is small. Therefore, the epoxy resin emulsion composition of the present invention does not have an excessive emulsifier liberated in the emulsion, is excellent in water resistance, chemical resistance, film strength, and is not discolored by heat treatment and has excellent adhesive strength. It becomes a thing. Moreover,
Since the emulsion has a fine texture, it has an advantage that it has excellent storage stability.

Next, the present invention will be described in detail.

Examples of the epoxy resin having a softening point of 100 ° C. or less used in the present invention include a bisphenol A epichlorohydrin type epoxy resin represented by the following formula (1) and a novolak type epoxy resin represented by the following formula (2). Can be given.

In addition to the above resins, halogenated epoxy resin, resorcin-type epoxy resin, bisphenol F-type epoxy resin, tetrahydroxyphenylethane-type epoxy resin, glycerin triether-type epoxy resin, polyolefin-type epoxy resin and the like can be mentioned. These epoxy resins need to have a softening point of 100 ° C. or lower, and even if they have the above structure, the softening point is 100.
Those having a temperature above 0 ° C cannot be emulsified by the method of the present invention described below.

The emulsifier for emulsifying the epoxy resin is the following 3
It is necessary to use a combination of different types of emulsifiers.

(A) A polymeric emulsifier having a molecular weight of 7,000 or more.

(B) At least one of a nonionic emulsifier and an anionic emulsifier having a molecular weight of 7,000 or less and an HLB of 17 or more.

(C) A nonionic emulsifier having a molecular weight of 7,000 or less and an HLB of 14 to 17.

Examples of the above-mentioned (A) high molecular weight emulsifier having a molecular weight of 7,000 or more include block polymers of ethylene oxide and other alkylene oxides such as propylene oxide and butylene oxide, and polyvinyl alcohol. Among them, ethylene oxide-propylene oxide block polymers represented by the following formula (3) are preferable.

The nonionic emulsifiers used in (B) and (C) above include lauryl ether ethylene oxide adduct, cetyl ether ethylene oxide adduct, stearyl ether ethylene oxide adduct, oleyl ether ethylene oxide adduct, octyl phenyl ether. Ethylene oxide adduct, nonylphenyl ether Ethylene oxide adduct, sorbitan monolaurate sorbitan monopalmitate, sorbitan monostearate, sorbitan tristeareate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, sorbitan disteare Rate, sorbitan monolaurate ethylene oxide adduct, sorbitan monopalmitate ethylene oxide adduct, sorbitan monostea Over preparative ethylene oxide adducts, sorbitan tristearate-ethylene oxide adducts,
Sorbitan monooleate ethylene oxide adduct,
Sorbitan trioleate ethylene oxide adduct,
Tetraoleic acid polyoxyethylene sorbite, glycerol monostearate, glycerol monooleate, polyethylene glycol monourearate, polyethylene glycol monostearate polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, castor oil Examples thereof include ethylene oxide adducts and hydrogenated castor oil ethylene oxide adducts. In the present invention, these are properly used according to the molecular weight and HLB. Among them, as the nonionic emulsifier having a molecular weight of 7,000 or less and HLB of 17 or more in the above (B), a lauryl ether ethylene oxide adduct represented by the following formula (4) and an oleyl ether ethylene oxide represented by the following formula (5) are used. An adduct, an octylphenyl ether ethylene oxide adduct represented by the following formula (6), a nonylphenyl ether ethylene oxide adduct represented by the following formula (7), and the like are preferable.

_{C 12 H 25 -OCH 2 CH 2} O n H ...... (4) C 18 H 37 -OCH 2 CH 2 O n H ...... (5) Then, as the nonionic emulsifier having a molecular weight of 7,000 or less and HLB14 to 17 in the above (C), an ethylene oxide adduct of a sorbitan fatty acid ester represented by the following formula (8),
An ethylene oxide adduct of castor oil represented by the following formula (9), an ethylene oxide adduct of hydrogenated castor oil represented by the following formula (10), and the like are preferable.

Further, as the anionic emulsifier having a molecular weight of 7,000 or less and HLB of 17 or more in the above (B), sodium lauryl sulfate, higher sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate sodium dodecylbenzenesulfonate, alkylsulfonate, alkylsulfosuccinic acid are used. Examples thereof include salts, sodium alkyldiphenyl ether disulfonate, potassium alkylphosphate salt, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and the like. Of these, sodium alkyl sulfonate represented by the following formula (11) and sodium alkyl sulfosuccinate represented by the following formula (12) are preferable.

The epoxy resin emulsion composition of the present invention can be produced, for example, as follows using the epoxy resin emulsion composition and the above-mentioned three kinds of emulsifiers (A, B, C). That is, first with respect to the epoxy resin,
The above polymeric emulsifier having a molecular weight of 7,000 or more (component A) and the nonionic emulsifier having a molecular weight of 7,000 or less and HLB 14 to 17 (component C) are mixed to obtain a liquid state. Further, the nonionic emulsifier and the anionic emulsifier (B component) having a molecular weight of 7,000 or less and an HLB of 17 or more are dissolved in a small amount of water. Then, the liquid epoxy resin containing the component A and the component C is mixed with the aqueous solution of the component B, and the system is phase-shifted from the W / O type emulsion to the O / W type emulsion. Then, the remaining water is gradually added and stirred uniformly. In this way
A very stable epoxy resin emulsion composition having a dispersoid (epoxy resin) particle size of, for example, 0.6 μm or less can be obtained.

By the way, it has been found that the epoxy resin emulsion composition thus obtained has no storage and precipitation of the resin phase even after 90 days from the production and is excellent in storage stability.
Further, as in the conventional case, when the emulsifier is used in an amount of 3 to 10 parts, when it is used for a purpose such as a fiber processing agent or a glass fiber sizing agent where heat treatment is indispensable, the compounding amount of the emulsifier is Although many yellowing, coloring, etc. were seen, since the epoxy resin emulsion composition of the present invention has a small emulsifier content of 1 to 3 parts, there is almost no discoloration during heat treatment,
It was discovered that it has excellent thermal stability. It was also found that the adhesive strength was as strong as that of the epoxy resin alone.

In addition, in the said manufacturing method, it is necessary to set the compounding quantity of A component to 0.3-0.9 part with respect to 100 parts of epoxy resins. Further, it is necessary to set the blending amount of the component B to 0.3 to 0.9 part per 100 parts of the epoxy resin. Furthermore, C
It is necessary to set the compounding amount of the components to 0.4 to 1.2 with respect to 100 parts of the epoxy resin. By blending the above-mentioned three kinds of emulsifiers within the above-mentioned range, it is possible to obtain an emulsion having excellent stability without excess or deficiency even when the amount of the emulsifier used is very small.

Next, examples will be described together with comparative examples.

Example 1 An ethylene oxide-propylene block polymer (MW = 7000) was added to 100 parts of Epicoat # 828 (produced by Yuka Shell Co., Ltd.).
3 parts and castor oil ethylene oxide 100 mol adduct (MW =
4600, HLB = 15.0) 0.4 parts were mixed and heated to 50 ° C., and stirred until the emulsifier was sufficiently and uniformly dispersed in the epoxy resin. Then, the mixture was cooled to room temperature, and 15 parts of water was added with 30 mol of nonylphenyl ether ethylene oxide (MW =
1800, HLB17.5) 0.3 part was added and immediately stirred with a motor. After continuing the stirring for a while, the remaining 85 parts of water was added every 10 minutes by a quarter to obtain an epoxy resin emulsion composition having an average molecular diameter of the dispersoid of 0.59 μm. The emulsion composition was stable after being left for 90 days. A film obtained by curing the emulsion composition with an amine-based curing agent has a water absorption rate of 0.8% by weight (hereinafter abbreviated as "%"), an acetone absorption rate of 14%, a toluene absorption rate of 14.5%, and 4% NaOH. The alkali absorption rate used is 0.
The film strength was 7% and the film strength was 350 kg / cm ² . No coloring was observed even when this film was heat-treated. Furthermore, the initial curing time when curing with an amine curing agent is 180 minutes,
The adhesion was good.

The evaluation of each physical property was performed as follows (the same applies to the following Examples and Comparative Examples).

<Stability after 90 days storage> The emulsion composition was placed in a test tube so that the depth was 20 cm, and left at room temperature for 90 days, and then the separated state of the resin phase and the aqueous phase was examined. The evaluation was made into the following four-level evaluation.

◎… No separation is observed ○… Almost no separation is observed △… Separation is observed ×… Completely separated <Average particle size> Light scattering using LPA system 3000/3100 manufactured by Otsuka Electronics Co., Ltd. It measured according to the method.

<Film water absorption> The emulsion composition is cured with an amine-based curing agent to a thickness of 1 m.
A film of m was obtained. Then, this film was cut into 2.5 cm square pieces and immersed in water for 48 hours, and then the weight increase rate after immersion was shown.

<Acetone absorption rate of film> Acetone was used instead of water, and the weight increase rate after immersion was shown in the same manner as above.

<Film Absorption Toluene Rate> Toluene was used instead of water, and the weight increase rate after immersion was shown in the same manner as above.

<Film absorption rate> The 4% NaOH aqueous solution was used instead of water, and the weight increase rate after immersion was shown in the same manner as above.

<Film colorability> The emulsion composition is cured with an amine curing agent to a thickness of 1 m.
A film of m was obtained. Then, cut this film into 2.5 Cm squares, and
The film was treated at 0 ° C. for 5 minutes and the coloration of the film was observed. The evaluation was made into the following four-level evaluation.

◎… No discoloration is observed ○… Almost no discoloration is observed △… Discoloration is considerably discolored ×… Discoloration is completely discolored <Film strength> The emulsion composition is cured with an amine-based curing agent to a thickness of 1 m.
A film of m was obtained. This film is molded with a No. 3 dampener, 20
The tensile strength was measured under the conditions of ℃ and 200 mm / min.

<Initial Curing Required Time> Steel sheets were laminated by mixing and curing an amine-based curing agent in the same amount as the epoxy equivalent of the epoxy resin contained in the emulsion composition. At that time, the time required to obtain 80% of the adhesive strength of the final cured product was measured.

<Adhesive Strength> Steel plates were laminated in the same manner as in the case of measuring the above initial curing time. The adhesive strength was evaluated according to the following four grades.

⊚: excellent ○: good Δ: somewhat inferior [Example 2] The amount of ethylene-propylene block polymer was changed to 0.6 part, and the amount of nonylphenyl ether ethylene oxide 30 mol adduct was changed to 0.6 part. The amount of castor oil ethylene oxide 100 mole adduct was changed to 0.8 parts. Otherwise in the same manner as in Example 1, a good emulsion composition having an average particle diameter of 0.33 μm was obtained. This emulsion composition is 90
It was stable even after being left for days. Further, the water absorption of the film obtained by curing the emulsion composition with an amine-based curing agent is 0.8.
%, Acetone absorption rate was 14%, toluene absorption rate was 14.5%, alkali absorption rate was 0.8%, and film strength was 345 kg / cm ² . No coloring was observed even when this film was heat-treated. Furthermore, the initial curing time required for curing with an amine curing agent was 180 minutes, and the adhesiveness was good.

Example 3 The amount of ethylene-propylene block polymer was changed to 0.9 part, the amount of nonylphenyl ether ethylene oxide 30 mol adduct was changed to 0.9 part, and the amount of castor oil ethylene oxide 100 mol adduct was changed to 1.2 part. changed. Otherwise in the same manner as in Example 1, a good emulsion composition having an average particle diameter of 0.28 μm was obtained. This emulsion composition is 90
It was stable even after being left for days. Further, the water absorption rate of the film obtained by curing the emulsion composition with an amine-based curing agent is 0.9.
%, The acetone absorption rate was 15%, the toluene absorption rate was 15.5%, the alkali absorption rate was 0.8%, and the film strength was 395 kg / cm ² . No coloring was observed even when this film was heat-treated. Further, the initial curing time required for curing with an amine curing agent was 185 minutes, and the adhesiveness was good.

Example 4 0.6 part of ethylene-propylene block polymer (MW = 460
0), hydrogenated castor oil ethylene oxide 80 mol adduct (M
0.8 part of W = 4600, HLB = 15) was mixed with Epicoat # 1001 (manufactured by Yuka Shell Co., Ltd.) preheated to 85 ° C. and stirred, and the emulsifier was dispersed sufficiently uniformly and then cooled to 75 ° C. Then, to this was added 15 parts of water at 75 ° C. in which 0.6 part of a nonylphenyl ether ethylene oxide 35 mol adduct (MW = 1800, HLB17.5) was dissolved, and stirring was immediately started by a motor. After confirming the phase inversion, continue stirring for a while, and
Parts were added in quarters with heating to 75 ° C. After adding all the water, cool gently to room temperature and then average particle size 0.41
A good emulsion composition having a thickness of μm was obtained. The emulsion composition was stable after being left for 90 days. A film obtained by curing this emulsion composition with an amine curing agent has a water absorption of 0.7%, an acetone absorption of 14%, a toluene absorption of 15.5%, an alkali absorption of 0.8%, and a film strength of 360 kg / cm. ²
It was. No coloring was observed even when this film was heat-treated. Further, the initial curing time required for curing with the amine curing agent was 195 minutes, and the adhesiveness was good.

[Example 5] A novolak type epoxy resin was used as the epoxy resin. Otherwise, in the same manner as in Example 4 above, the average particle size was 0.
A good emulsion composition of 38 μm was obtained. The emulsion composition was stable after being left for 90 days. A film obtained by curing the emulsion composition with an amine curing agent has a water absorption rate of 0.8%, an acetone absorption rate of 14%, a toluene absorption rate of 15.5%, an alkali absorption rate of 0.7%, and a film strength of 380 kg / c.
It was m ² . No coloring was observed even when this film was heat-treated. Further, the initial curing time required for curing with the amine-based curing agent was 200 minutes, and the adhesiveness was good.

[Example 6] Ethylene oxide-propylene block polymer (MW = 7000) was added to 100 parts of Epicoat # 828 (produced by Yuka Shell Co., Ltd.).
6 parts and 0.6 part of hydrogenated castor oil ethylene oxide 100 mol adduct (MW = 4600, HLB = 15.0) were mixed and heated to 50 ° C., and stirred until the emulsifier was sufficiently and uniformly dispersed in the epoxy resin. Then, the mixture was cooled to room temperature, to which was added 15 parts of water in which 0.2 parts of nonylphenyl ether ethylene oxide 35 mol adduct (MW = 1800, HLB17.5) and 0.4 parts of alkyl ether sulfate sodium salt were dissolved. , Immediately stirred by the motor. After continuing the stirring for a while, the remaining 85 parts of water was added every 10 minutes by a quarter to obtain a good emulsion composition having an average molecular diameter of 0.59 μm. The emulsion composition was stable after being left for 90 days.
A film obtained by curing the emulsion composition with an amine curing agent has a water absorption rate of 0.8%, an acetone absorption rate of 14%, a toluene absorption rate of 14.5%, an alkali absorption rate of 0.7%, and a film strength of 350 kg / cm. ^{It was 2} . No coloring was observed even when this film was heat-treated. Furthermore, the initial curing time required for curing with an amine curing agent was 180 minutes, and the adhesiveness was good.

Comparative Example 1 The amount of ethylene-propylene block polymer was changed to 0.6 part, the amount of nonylphenyl ether ethylene oxide 30 mol adduct was changed to 0.6 part, and the amount of castor oil ethylene oxide 100 mol adduct was changed to 0.8 part. changed. Otherwise in the same manner as in Example 1, an emulsion composition having an average particle diameter of 2.98 μm was obtained. In this emulsion composition, resin separation and sedimentation were immediately observed.

Comparative Example 2 The amount of ethylene-propylene block polymer was changed to 1.2 parts, the amount of nonylphenyl ether ethylene oxide 30 mol adduct was changed to 1.2 parts, and the amount of castor oil ethylene oxide 100 mol adduct was changed to 1.6 parts. changed. Otherwise in the same manner as in Example 1, a good emulsion composition having an average particle diameter of 0.28 μm was obtained. However, this emulsion composition was extremely colored by heat treatment and could not be used as a fiber processing agent or a glass fiber sizing agent.

[Comparative Examples 3 to 7] An emulsion composition was obtained in the same manner as in Example 1 by using an emulsifier other than the combination of emulsifiers of the present invention (see Table << Part 2 >> described later). However, in all of these emulsion compositions, the average particle size was larger than 0.6 μm, and the resin phase and the aqueous phase were immediately separated and settled.

[Comparative Examples 8 to 10] 100 parts of Epicoat # 828 (manufactured by Yuka Shell Co., Ltd.) were mixed with the same three kinds of emulsifiers as in Example 2 at the same ratio.
However, in Comparative Example 8, the above three kinds of emulsifiers were dispersed in the resin in advance, in Comparative Example 9, the ethylene-propylene block polymer and nonylphenyl ether ethylene oxide adduct were dissolved in water, and in Comparative Example 10, three kinds of emulsifiers were used. All were dissolved in water and other conditions were the same as in Example 1 to obtain an emulsion composition. All of these emulsion compositions had an average particle size of more than 0.6 μm and immediately separated and precipitated the resin phase and the aqueous phase.

[Comparative Examples 11 to 16] The same three kinds of emulsifiers as in Example 2 were mixed with 100 parts of Epicoat # 828 (produced by Yuka Shell Co., Ltd.). However, any one of the blending amounts of each emulsifier was set outside the range of the present invention. As a result, all the emulsion compositions obtained had an average particle size of more than 0.6 μm and immediately separated the resin phase and the aqueous phase.

[Comparative Example 17] 100 parts of Epicoat # 828 (produced by Yuka Shell Co., Ltd.) were mixed with the same three kinds of emulsifiers as in Example 2 at the same ratio.
However, nonylphenyl ether was dissolved in 45 parts of water and then blended in the emulsion resin. An emulsion composition was obtained in the same manner as in Example 2 except for the above. This emulsion composition had an average particle diameter of 2.65 μm and immediately separated the resin phase and the aqueous phase.

[Comparative Example 18] With respect to 100 parts of Epicoat # 828 (produced by Yuka Shell Co., Ltd.), the same three kinds of emulsifiers as in Example 4 were blended in the same proportion and in a total amount of 10 parts. Otherwise in the same manner as in Example 4, a good emulsion composition having an average particle size of 0.23 μm was obtained. The emulsion composition was stable after being left for 90 days. A film obtained by curing this emulsion composition with an amine-based curing agent has a water absorption of 4% and an acetone absorption of
The toluene absorption rate was 30%, the alkali absorption rate was 4%, and the film strength was 200 kg / cm ² . Further, when this film was heat-treated, the coloration was considerably worse. When cured with an amine-based curing agent, the initial curing time was 350 minutes and the adhesion was inferior to that according to the present invention.

[Comparative Example 19] Epicoat # 828 itself was cured with an amine curing agent.
The water absorption of this film is 0.8%, the acetone absorption is 14%, the toluene absorption is 14.5%, the alkali absorption is 0.7%, and the film strength is 3%.
It was 50 kg / cm ² . No coloring was observed even when this film was heat-treated. Furthermore, the initial curing time required for curing with an amine-based curing agent was 175 minutes, indicating good adhesion.

The compositions and evaluation results of the above Examples and Comparative Examples are summarized in the table below. However, in the table, ethylene oxide is abbreviated as “EO”.

[Effects of the Invention] As described above, the epoxy resin emulsion composition of the present invention has the amount of the emulsifier suppressed to the minimum necessary amount as compared with the conventional composition, and all the emulsifiers contribute to the emulsifier without excess or deficiency. There is. For this reason, there is no excessively liberated emulsifier, the curing speed is fast, and there is no coloration such as yellowing during heat treatment, which is excellent in thermal stability. Also, it has the same adhesive strength as the epoxy resin alone and has high adhesiveness. It is also excellent in various physical properties such as water resistance, chemical resistance, and film strength. Furthermore, since the average particle size of the epoxy resin, which is the dispersoid, is as small as 0.6 μm or less, the emulsion structure is extremely stable and
Even after 90 days, there is no separation and settling of the resin phase, and storage stability is excellent. Moreover, since the content of the emulsifier having a higher unit price is smaller than that of the other components, there is an advantage that the price per unit weight of the entire composition is low.

According to the production method of the present invention, among the three types (A, B, C) used as emulsifiers, A and C are dispersed in an epoxy resin, B is dispersed in a small amount of water, and both are mixed. By doing so, the emulsion is obtained after phase inversion, so that a very fine emulsion having an average particle diameter of 0.6 μm or less can be easily obtained.

Continuation of front page (56) Reference JP 61-87722 (JP, A) JP 57-36161 (JP, A) JP 50-19856 (JP, A) JP 63-223025 (JP , A) JP 63-31750 (JP, A) JP 54-15956 (JP, A) JP 58-111831 (JP, A) JP 61-243822 (JP, A) JP 50-15487 (JP, B1)

Claims (2)

[Claims] 1. A softening point of 100 to 100 parts by weight of an epoxy resin, 0.3 to 0.9 parts by weight of the following component (A), 0.3 to 0.9 parts by weight of the following component (B), and (C) ) Component 0.4
˜1.2 parts by weight and 20 to 700 parts by weight of water in an O / W type epoxy resin emulsion composition, wherein the average particle size of the dispersoid is set to 0.6 μm or less. Epoxy resin emulsion composition. (A) A polymeric emulsifier having a molecular weight of 7,000 or more. (B) At least one of a nonionic emulsifier and an anionic emulsifier having a molecular weight of 7,000 or less and an HLB of 17 or more. (C) A nonionic emulsifier having a molecular weight of 7,000 or less and an HLB of 14 to 17. 2. The following component (A) is added in an amount of 0.3 to 0.9 parts by weight and the following component (C) is added in an amount of 0.4 to 1.2 parts by weight with respect to 100 parts by weight of an epoxy resin having a softening point of 100 ° C. or less. To obtain liquid epoxy resin, and 2 per 100 parts by weight of epoxy resin
Prepare 00 to 700 parts by weight of water, and add 0.3 to 0.9 parts by weight of (B) below to 100 parts by weight of epoxy resin in a part of this water.
A step of dissolving the components to obtain a component (B) aqueous solution, and mixing the liquid epoxy resin with the component (B) aqueous solution to form a system.
A process for producing an epoxy resin emulsion composition, which comprises a step of phase inversion from a W / O emulsion to an O / W emulsion and further blending the balance of the water. (A) A polymeric emulsifier having a molecular weight of 7,000 or more. (B) At least one of a nonionic emulsifier and an anionic emulsifier having a molecular weight of 7,000 or less and an HLB of 17 or more. (C) A nonionic emulsifier having a molecular weight of 7,000 or less and an HLB of 14 to 17.