JP2010077176A - Aqueous emulsion epoxide composition curable below freezing temperature - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous emulsion epoxide composition curable in a relatively short time even below the freezing temperature, and providing excellent appearance and coating film performance. <P>SOLUTION: The aqueous emulsion epoxide composition comprises (A) an epoxide having more than one average epoxy groups in the molecule, (B) a curing agent of a polyamine derivative having at least one nitrogen atom having an active hydrogen in the molecule, and (C) a glycol, a glycerol or a derivative thereof having at least one hydroxy group in the molecule, or further (D) a polyamine compound having at least one amino group in the molecule. Preferably, based on the total amount of water, and (C) the glycol, the glycerol or the derivative thereof, or the total amount of water, and (C) the glycol, the glycerol or the derivative thereof, and (D) the polyamine compound, (C) the glycol, the glycerol or the derivative thereof, or (C) the glycol, the glycerol or the derivative thereof, and (D) the polyamine compound are each contained in the concentration range of exceeding 1.5 wt.% and less than 40 wt.%; and the ratio of (C)/(D) is in the range of 1/99 to 99/1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous emulsion epoxide composition. According to the present invention, it can be cured in a short time even at a temperature below freezing, and an excellent coating film appearance can be given as a paint.

  Conventionally used organic solvent-based epoxide compositions (containing volatile organic compounds) are water-based emulsions that are friendly to the environment due to the problem of VOC emission (such as VOC regulations) in the atmosphere. Epoxide compositions have been drawing attention (Patent Document 1). Against this backdrop of environmental problems, aqueous emulsion epoxide compositions have come to be widely used as adhesives, paints and coatings, but work in the winter and cold regions where the workplace temperature is below freezing and work slowly. Since it takes a long time until it can be used later (construction time) and the emulsion epoxide composition itself freezes, it often encounters situations where it cannot be constructed. Water based emulsion epoxide compositions are desired.

  For the purpose of preventing freezing of the composition, which is one of the problems, an antifreezing effect is obtained by adding a water-soluble volatile organic solvent such as ethanol, propanol, or butanol to the aqueous emulsion epoxide composition. Things have been done.

  However, although the antifreezing effect is recognized by adding the above organic solvents to the aqueous emulsion epoxide composition, there is a problem that the appearance of the coating film is deteriorated. At the same time, the addition of the organic solvent impairs the stability of the aqueous emulsion epoxide composition, resulting in a problem that workability is significantly deteriorated.

  For the purpose of shortening the construction time in winter and cold regions, which is another problem, as a method for shortening the curing time of the aqueous emulsion epoxide composition, it has been studied to increase its solid content concentration. The aqueous emulsion epoxide composition has a high viscosity, and practically effective emulsion particles cannot be obtained. Thus, there are limitations in terms of production and workability.

  In addition, this method of increasing the solid content concentration does not provide the antifreezing effect which is a problem, it is necessary to add the organic solvents, and not only the adverse effect such as deterioration of the appearance of the coating film can be improved. There is a limit to short-time curing. Furthermore, it also goes against the suppression of the emission of volatile organic compounds to the environment, which has recently been regarded as important. In addition, for the purpose of shortening the curing time of the composition, the use of a curing accelerator has been studied, but no material that achieves a good appearance even below freezing has been found.

On the other hand, as a means of improving the appearance of the coating film, studies have been made to add a surface modifier or the like. However, in an aqueous emulsion, it is difficult to select an additive that gives a satisfactory appearance below the freezing point. In fact, no surface modifier has been found that can develop a good coating appearance.
JP-A-10-130372

As a result of intensive studies to solve the above problems, the present inventors have added glycol or glycerin having one or more hydroxyl groups in the molecule or a derivative thereof to the aqueous emulsion epoxide composition, The present inventors have found an aqueous emulsion epoxide composition that can give a good coating film appearance without freezing below freezing point. Furthermore, by adding a glycol or glycerin having one or more hydroxyl groups in the molecule or a derivative thereof and a polyamine compound having one or more amino groups in the molecule to the aqueous emulsion epoxide composition, the composition can be frozen below freezing point. Thus, an aqueous emulsion epoxide composition has been found that can be cured within 24 hours and can give a better coating appearance.
The present invention is based on such knowledge.

  Accordingly, an object of the present invention is to provide an aqueous emulsion epoxide composition that can be cured even at freezing temperatures and gives a good coating appearance.

Therefore, the present invention
(A) an epoxide having an average of more than one epoxy group in the molecule;
(B) An aqueous emulsion epoxide composition comprising a curing agent of a polyamine derivative having at least one nitrogen atom having active hydrogen in the molecule, and (C) glycol or glycerin having at least one hydroxyl group in the molecule or a derivative thereof. Related to things.

In a preferred embodiment of the aqueous emulsion epoxide composition of the present invention, the glycol or glycerin or a derivative thereof (C) is a total of water and glycol or glycerin or a derivative thereof (C) in the aqueous emulsion epoxide composition. Based on the amount, it is more than 1.5% by weight and less than 40% by weight.
Moreover, in the preferable aspect of the aqueous | water-based emulsion epoxide composition of this invention, the said glycol or glycerin, or those derivatives (C) are the water in the said aqueous | water-based emulsion epoxide composition, glycol, glycerol, or those derivatives (C). Based on the total amount of 2 to 37.5% by weight.
In a preferred embodiment of the aqueous emulsion epoxide composition of the present invention, (D) a polyamine compound having one or more amino groups in the molecule is further included.

Moreover, in the preferable aspect of the aqueous | water-based emulsion epoxide composition of this invention, the said glycol or glycerin or those derivatives (C), and the said polyamine compound (D) are the water in the said aqueous | water-based emulsion epoxide composition, glycol or glycerol, Based on the total amount of the derivative (C) and the polyamine compound (D), it is more than 1.5% by weight and less than 40% by weight.
Moreover, in the preferable aspect of the aqueous | water-based emulsion epoxide composition of this invention, the said glycol or glycerin or those derivatives (C), and the said polyamine compound (D) are the water in the said aqueous | water-based emulsion epoxide composition, and the said glycol or glycerin. Or they are 2 weight%-37.5 weight% on the basis of the total amount with those derivatives (C) and the said polyamine compound (D).
Moreover, in the preferable aspect of the aqueous | water-based emulsion epoxide composition of this invention, the weight ratio of the said glycol or glycerol or those derivatives (C), and the said polyamine compound (D) is 99/1-1/99.

  According to the aqueous emulsion epoxide composition of the present invention, by including glycol or glycerin or a derivative thereof (C), the composition can be cured in a relatively short time even under a low temperature condition without being frozen below freezing point. A coated film appearance can be obtained. In addition, by including glycol or glycerin or derivatives thereof (C) and polyamine compound (D), it can be cured within 24 hours even under low temperature conditions without freezing below freezing point, and has an excellent coating film appearance. Obtainable.

Epoxides (A) (hereinafter sometimes referred to as component (A)) that can be used in the aqueous emulsion epoxide composition of the present invention are epoxides having an average of more than one epoxy group in the molecule. Specifically, for example, bisphenol A, bisphenol F, bisphenol S, hexahydrobisphenol A, tetramethylbisphenol A, tetramethylbisphenol F, catechol, resorcin, cresol novolak, tetrabromobisphenol A, trihydroxybiphenyl, benzophenone, bisresorcinol Glycidyl ether obtained by reacting polychlorophenol such as bisphenol hexafluoroacetone, hydroquinone, triphenylmethane, tetraphenylethane, and bixylenol with epichlorohydrin; glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, Such as hexylene glycol, polyethylene glycol, polypropylene glycol Polyglycidyl ether obtained by reacting an aliphatic polyhydric alcohol and epichlorohydrin; glycidyl ether ester obtained by reacting a hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin; phthalic acid , Polyphthalates derived from polycarboxylic acids such as methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, endomethylenehexahydrophthalic acid, trimellitic acid, polymerized fatty acid Glycidyl ester; glycidyl aminoglycidyl ether obtained from aminophenol and aminoalkylphenol; glycidylaminoglycidyl ester obtained from aminobenzoic acid; aniline, toluidine, tribro Glycidylamine obtained from muaniline, xylylenediamine, diaminocyclohexane, bisaminomethylcyclohexane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, etc .; epoxidized polyolefin; glycidylhydantoin; glycidylalkylhydantoin, triglycidyl Cyanurates; or monoepoxides typified by butyl glycidyl ether, phenyl glycidyl ether, alkylphenyl glycidyl ether, benzoic acid glycidyl ester, styrene oxide, etc., and a mixture of one or more of these Can be used. Moreover, when mixing as an aqueous emulsion epoxide composition of this invention, it is preferable to use as an aqueous emulsion which disperse | distributed these epoxides in water.
The upper limit is not particularly limited as long as the epoxide has an average of more than one epoxy group in the molecule, but it is preferably 8 or less, and more preferably 6 or less.

The polyamine derivative curing agent (B) (hereinafter sometimes referred to as component (B)) that can be used in the aqueous emulsion epoxide composition of the present invention has at least one nitrogen atom having active hydrogen in the molecule. For example, metaxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, diaminocyclohexane, phenylenediamine, toluylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, piperazine, N-aminoethylpiperazine, polyethylene polyamine, etc. For example, polyamine derivatives derived from such polyamines by methods such as amidation, Mannichation, epoxy adduct formation, cyanoethylation, and the like, and one or a mixture of two or more of these can be used. .
Moreover, when mixing as an aqueous | water-based emulsion epoxide composition of this invention, it is preferable to use as an aqueous | water-based emulsion by which these polyamine derivatives were disperse | distributed to water.
The upper limit is not particularly limited as long as one or more nitrogen atoms having active hydrogen of the curing agent of the polyamine derivative are contained in the molecule.

A water-soluble glycol or glycerin having one or more hydroxyl groups in the molecule or a derivative thereof (C) (hereinafter sometimes referred to as component (C)) that can be used in the aqueous emulsion epoxide composition of the present invention. As, for example, glycols such as monoethylene glycol, diethylene glycol, monopropylene glycol, polyethylene glycol and dipropylene glycol, glycol derivatives such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether, glycerin, glycerin fatty acid ester derivatives and the like What mixed these 1 type (s) or 2 or more types can be used. These glycols or glycerin or derivatives thereof are water-soluble for use as aqueous emulsions. Among these, dipropylene glycol, glycerin, ethylene glycol, and propylene glycol are preferable, and dipropylene glycol is more preferable.
The upper limit is not particularly limited as long as one or more hydroxyl groups of glycol or glycerin or derivatives thereof are contained in the molecule.

The polyamine compound (D) having an average of more than one amino group in the molecule of the present invention (hereinafter sometimes referred to as component (D)) is, for example, metaxylylenediamine, 1,3-bis (amino Mention of monoamine compounds such as methyl) cyclohexane, isophoronediamine, diaminocyclohexane, phenylenediamine, toluylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, piperazine, N-aminoethylpiperazine, polyamines such as polyethylene polyamine, and alkylamines What mixed these 1 type (s) or 2 or more types can be used. Since these polyamine compounds are used as an aqueous emulsion, it is desirable that they are water-soluble.
Among these, metaxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, and N-aminoethylpiperazine are preferable.
The upper limit is not particularly limited as long as one or more amino groups of the polyamine compound are present in the molecule.

The glycol or glycerin or their derivative (C) is preferably more than 1.5% by weight based on the total amount of water and glycol or glycerin or their derivative (C) in the aqueous emulsion epoxide composition. It is less than 40% by weight, more preferably 2% by weight to 37.5% by weight. A concentration exceeding 1.5% by weight is preferable in that the epoxide composition does not freeze even below freezing, and a concentration less than 40% by weight is preferable in that a smooth coating film can be obtained.
The glycol or glycerin or derivatives thereof (C) and the polyamine compound (D) are the sum of water in the aqueous emulsion epoxide composition and glycol or glycerin or derivatives thereof (C) and the polyamine compound (D). Based on the amount, it is preferably more than 1.5 wt% and less than 40 wt%, more preferably 2 wt% to 37.5 wt%. A concentration of more than 1.5% by weight is preferable in that the epoxide composition does not freeze even below freezing point and is completely cured within 24 hours. A concentration of less than 40% by weight results in a smooth coating film. It is preferable in that it can be obtained.

  When the aqueous emulsion epoxide composition of the present invention contains glycol or glycerin or their derivatives (C) and a water-soluble polyamine compound (D), the water-soluble glycol or glycerin or their derivatives (C) and water-soluble The weight ratio (C / D) to the polyamine compound (D) is preferably 1/99 to 99/1 in order to have a good appearance and completely cure within 24 hours.

  In the aqueous emulsion epoxide composition of the present invention, the component (A) and the component (B) are components for curing the composition. The content of the component (A) and the component (B) in the composition is as follows: The composition is not particularly limited as long as the composition can be cured. Moreover, since the said component (D) also has a function as a hardening | curing agent, it is preferable to adjust the quantity of a component (B) according to the quantity of a component (D), such a component (B ) Can be adjusted without undue experimentation with ordinary knowledge in the technical field to which the present invention pertains.

  In addition to the components (A), (B), (C), and (D), the aqueous emulsion epoxide composition of the present invention includes a tackifier, a thickener, an emulsifying dispersant, Foaming agents, preservatives, plasticizers, colorants, extenders, organic solvents, and the like may be added.

  The aqueous emulsion epoxide composition of the present invention is a curable composition and can be used for an adhesive, a paint, or a coating agent.

  The best mode for carrying out the invention in an aqueous emulsion epoxide composition curable below freezing point and examples of the present invention are shown below together with comparative examples, but the present invention is limited to the scope of these examples. It is not something.

Example 1
As component (A), 100 parts by weight of EM-101-50 (Adeka water-based emulsion epoxide, moisture 50%), as component (B) FXS-918-FA (Fuji Kasei Kogyo Co., Ltd. polyamine derivative aqueous emulsion, 30 parts by weight of water (40%), 21.1 parts of water, and 1.8 parts of dipropylene glycol (abbreviated as DPG) as component (C) were mixed to obtain an aqueous emulsion epoxide composition.

Example 2
The procedure of Example 1 was repeated except that 9.2 parts of dipropylene glycol (abbreviated as DPG) was used as component (C).

Example 3
The procedure of Example 1 was repeated except that 35.6 parts of dipropylene glycol (abbreviated as DPG) was used as component (C).

Example 4
The procedure of Example 1 was repeated except that 49.9 parts of dipropylene glycol (abbreviated as DPG) was used as component (C).

Example 5
The procedure of Example 1 was repeated except that 9.2 parts of glycerin (abbreviated as GLY) was used as component (C).

Example 6
The procedure of Example 1 was repeated except that 35.6 parts of glycerin (abbreviated as GLY) was used as component (C).

Example 7
The procedure of Example 1 was repeated except that 9.2 parts of ethylene glycol (abbreviated EG) was used as component (C).

Example 8
The procedure of Example 1 was repeated except that 9.2 parts of diethylene glycol (abbreviated as DEG) was used as component (C).

Example 9
The procedure of Example 1 was repeated except that 9.2 parts of propylene glycol (abbreviated as PG) was used as component (C).

Example 10
As component (A), 100 parts by weight of EM-101-50 (Adeka water-based emulsion epoxide, moisture 50%), as component (B) FXS-918-FA (Fuji Kasei Kogyo Co., Ltd. polyamine derivative aqueous emulsion, 28.2 parts by weight of water (40%), 20.6 parts of water, 1.7 parts of dipropylene glycol (abbreviated as DPG) as component (C) and metaxylylenediamine (abbreviated as MXDA) as component (D) ) Was mixed to obtain an aqueous emulsion epoxide composition.

Example 11
As component (B), 15 parts by weight of FXS-918-FA (Fuji Kasei Kogyo Co., Ltd., polyamine derivative aqueous emulsion, moisture 40%), 16.1 parts of water, and dipropylene glycol (abbreviated as DPG) as component (C) ) And 6.3 parts of component (D) and 1.7 parts of metaxylylenediamine (abbreviated as MXDA) were used, and the procedure of Example 10 was repeated.

Example 12
The procedure of Example 11 was repeated except that 29.2 parts of dipropylene glycol (abbreviated as DPG) was used as component (C).

Example 13
The procedure of Example 11 was repeated except that 41.6 parts of dipropylene glycol (abbreviated as DPG) was used as component (C).

Example 14
Except for using 6.2 parts of dipropylene glycol (abbreviated as DPG) as component (C) and 1.8 parts of 1,3-bis (aminomethyl) cyclohexane (abbreviated as BAC) as component (D). Repeated the procedure of Example 11.

Example 15
Example 11 except that 5.8 parts of dipropylene glycol (abbreviated as DPG) was used as component (C) and 2.2 parts of N-aminoethylpiperazine (abbreviated as AEP) was used as component (D). The procedure of was repeated.

Example 16
As component (B), FXS-918-FA (Fuji Kasei Kogyo Co., Ltd. polyamine derivative aqueous emulsion, moisture 40%) is 29.7 parts by weight, water is 21.0 parts, and component (C) is dipropylene glycol (DPG). The procedure of Example 10 was repeated except that 9.1 parts were used) and 0.1 part metaxylylenediamine (abbreviated MXDA) was used as component (D).

Example 17
As component (B), FXS-918-FA (Fuji Kasei Kogyo Co., Ltd. polyamine derivative aqueous emulsion, water 40%) is 3.0 parts by weight, water is 12.1 parts, and component (C) is dipropylene glycol (DPG). The procedure of Example 10 was repeated except that 0.1 part was used and 13.5 parts metaxylylenediamine (abbreviated MXDA) was used as component (D).

<< Comparative Example 1 >>
As component (A), 100 parts by weight of EM-101-50 (Adeka water-based emulsion epoxide, moisture 50%), as component (B) FXS-918-FA (Fuji Kasei Kogyo Co., Ltd. polyamine derivative aqueous emulsion, A water-based emulsion epoxide composition was obtained by mixing 30 parts by weight of water (40%) and 21.1 parts of water.

<< Comparative Example 2 >>
The procedure of Example 1 was repeated except that 1.2 parts of dipropylene glycol (abbreviated as DPG) was used as component (C).

<< Comparative Example 3 >>
The procedure of Example 1 was repeated except that 48.1 parts of glycerin (abbreviated as GLY) was used as component (C).

<< Comparative Example 4 >>
The procedure of Example 1 was repeated except that 9.2 parts of normal propanol (abbreviated as NPA), which is a water-soluble alcohol, was used instead of component (C).

<< Comparative Example 5 >>
The procedure of Example 10 was repeated except that 1.2 parts of dipropylene glycol (abbreviated as DPG) was used as component (C).

<< Comparative Example 6 >>
The procedure of Example 11 was repeated except that 46.4 parts of dipropylene glycol (abbreviated as DPG) was used as component (C).

<< Comparative Example 7 >>
As component (A), 100 parts by weight of EM-101-50 (Adeka water-based emulsion epoxide, water 50%), 11.1 parts of water, 3 parts of dipropylene glycol (abbreviated as DPG) as component (C) .4 parts and 3.4 parts of metaxylylenediamine (abbreviated as MXDA) as a component (D) were mixed to obtain an aqueous emulsion epoxide composition.

<< Comparative Example 8 >>
Except for using 3.2 parts of dipropylene glycol (abbreviated as DPG) as component (C) and 3.6 parts of 1,3-bis (aminomethyl) cyclohexane (abbreviated as BAC) as component (D). Repeated the procedure of Comparative Example 7.

<< Comparative Example 9 >>
Comparative Example 7 except that 2.5 parts of dipropylene glycol (abbreviated as DPG) was used as component (C) and 4.3 parts of N-aminoethylpiperazine (abbreviated as AEP) was used as component (D). The procedure of was repeated.

  Table 1 shows the evaluation results of curability, surface condition, and composition appearance. The concentration of the added water-soluble glycol and amine in water in the composition was described as C + D%, and the ratio of the water-soluble glycol and amine was described as the C / D ratio.

Evaluation of Curability The obtained aqueous emulsion epoxide composition was applied to a glass plate with a 200 μm applicator, and the curing time at −5 ° C. was measured with an RCI-type curing / drying tester.
d1: Primary streak start time (touch curing time)
d2: Secondary streak start time (semi-curing time)
d3: Secondary streak extinction time (complete curing time)
In Table 1, the description of d3 “impossible to measure” indicates that the complete curing time could not be clearly determined because the coating film on the painted surface was relatively soft and slight scarring was observed with the needle. .

Evaluation of surface condition Similar to the evaluation of curability, the obtained water-based emulsion epoxide composition was applied to a glass plate with a 200 μm applicator and cured at −5 ° C. for 24 hours. Observed by touch.
◎: Very good ○: Good △: Slightly bad ×: Remarkably bad

Composition Appearance Observation 10 g of the obtained aqueous emulsion epoxide composition was sealed in a glass bottle with a capacity of 20 ml, and the presence or absence of freezing and the presence or absence of separation were observed when left at −5 ° C. for 6 hours.
◎: Very good ○: Good △: Slightly bad ×: Remarkably bad

In Example 1, dipropylene glycol (DPG) as a water-soluble glycol component was used at a concentration of 2%, but a coating film having a relatively good appearance could be obtained even at -5 ° C. In Examples 2 and 3, dipropylene glycol (DPG) was used at concentrations of 10% and 30%, respectively, but a coating film having a good appearance could be obtained. In Example 4, dipropylene glycol (DPG) was used at a concentration of 37.5%, but a coating film having a relatively good appearance could be obtained.
In Examples 5 and 6, glycerin (GLY) was used at 10% and 30%, but the cured coating films obtained from Examples 2 and 3 were somewhat inferior in appearance but relatively good coating films. Could get. In Examples 7 to 9, the test was conducted at a concentration of 10% by changing the water-soluble glycol component, but a cured coating film having a relatively satisfactory appearance was obtained in the same manner.
In Example 10, the total amount of the water-soluble glycol dipropylene glycol (DPG) and the water-soluble amine metaxylylenediamine (MXDA) was 2%, and the DPG / MXDA ratio was 89/11. However, it was possible to obtain a coating film having a relatively good appearance with a rapid curing. In Example 11, the total amount of DPG and MXDA was 10%, and the DPG / MXDA ratio was 79/21. However, the curing was completed within 18 hours, and the appearance of the coating film was also good. It was excellent. In Example 12, the total amount of DPG and MXDA was 30%, and the DPG / MXDA ratio was 95/5. However, the appearance of the coating film was good and curing proceeded within 24 hours. In Example 13, the total amount of DPG and MXDA was 37.5%, and the DPG / MXDA ratio was 96/4, but an almost good coating film was obtained.
In Example 14 and Example 15, the water-soluble amine was replaced with 1,3-bis (aminomethyl) cyclohexane (BAC) and N-aminoethylpiperazine (AEP), and the water-soluble polyol dipropylene glycol (DPG) and The test was conducted in such an amount that the total amount of 10% was 10%, but a cured film having a short curing time of 20 hours or less was obtained.
In Example 16, the relative amount of the water-soluble amine metaxylylenediamine (MXDA) was reduced and tested in such an amount that the DPG / MXDA ratio was 99/1. However, the appearance of the coating film was good and the curing took less than 24 hours. Progressed. In Example 17, the metaxylylenediamine (MXDA) relative amount of the water-soluble amine was increased and tested in such an amount that the DPG / MXDA ratio was 1/99, but a smooth coating film with almost good transparency was obtained. The curing time was as short as 16.5 hours.
Comparative Examples 1 and 2 were a system containing no water-soluble glycol component and a system containing 1.5% in the composition, but the composition was frozen and a cured coating film was not formed. In Comparative Example 3, glycerin (GLY) was used at 40%, but the transparency and smoothness of the obtained coating film were not satisfactory.
In Comparative Example 4, normal propanol (NPA), which is a general water-soluble alcohol, was used at 10%, but the emulsion was separated and an evaluation coating film could not be obtained.
In Comparative Example 5, the total amount of dipropylene glycol (DPG) and water-soluble amine metaxylylenediamine (MXDA) was 1.5%, but the composition was frozen and the coating film was frozen. Not formed. Comparative Example 6 was used in such an amount that the total amount of dipropylene glycol (DPG) and the water-soluble amine metaxylylenediamine (MXDA) was 40%, but the transparency and smoothness of the obtained coating film were satisfactory. It wasn't possible.
Comparative Examples 7 to 9 were tested using various water-soluble amines using dipropylene glycol (DPG) as a water-soluble glycol without using an aqueous emulsion-based curing agent. However, satisfactory transparency was not achieved.

  From the above description, the present invention can provide a coating film having a good appearance even under sub-freezing conditions, and can provide an aqueous emulsion epoxide composition curable at sub-freezing temperature that can be cured for a short time. It is clear.

  Since the aqueous emulsion epoxide composition of the present invention forms an excellent coating film even under sub-freezing conditions, it can be applied in winter and cold districts that could not be used conventionally, and the curing time at low temperatures is shortened. In addition to being able to reduce the construction period significantly, it enables construction plans that are not affected by seasonal temperature factors. In addition, unlike organic solvent-based coating compositions that have been used conventionally, since it does not contain harmful volatile organic compounds, there is also an advantage that the burden on the operator and the surrounding environment is small.

Claims (7)

(A) an epoxide having an average of more than one epoxy group in the molecule;
(B) An aqueous emulsion epoxide composition containing a curing agent of a polyamine derivative having at least one nitrogen atom having active hydrogen in the molecule, and (C) glycol or glycerin having at least one hydroxyl group in the molecule or a derivative thereof. object.   The glycol or glycerin or their derivative (C) is more than 1.5% by weight and 40% by weight based on the total amount of water and glycol or glycerin or their derivative (C) in the aqueous emulsion epoxide composition. The aqueous emulsion epoxide composition according to claim 1, which is less than%.   The glycol or glycerin or a derivative thereof (C) is 2 to 37.5% by weight based on the total amount of water and glycol or glycerin or a derivative thereof (C) in the aqueous emulsion epoxide composition. The aqueous emulsion epoxide composition according to claim 1 or 2, wherein The aqueous emulsion epoxide composition according to claim 1, further comprising (D) a polyamine compound having one or more amino groups in the molecule.   The glycol or glycerin or derivatives thereof (C) and the polyamine compound (D) are the sum of water in the aqueous emulsion epoxide composition and glycol or glycerin or derivatives thereof (C) and the polyamine compound (D). The aqueous emulsion epoxide composition according to claim 4, wherein the aqueous emulsion epoxide composition is greater than 1.5 wt% and less than 40 wt%, based on the amount.   The glycol or glycerin or a derivative thereof (C) and the polyamine compound (D) are obtained by combining water in the aqueous emulsion epoxide composition with the glycol or glycerin or a derivative thereof (C) and the polyamine compound (D). The aqueous emulsion epoxide composition according to claim 4 or 5, which is 2 wt% to 37.5 wt% based on the total amount.   The aqueous emulsion epoxide according to any one of claims 4 to 6, wherein a weight ratio of the glycol or glycerin or a derivative thereof (C) to the polyamine compound (D) is 99/1 to 1/99. Composition.