JP2003327661A - Modifier for aqueous epoxy resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a self-emulsifiable epoxy resin composition which excels in emulsification stability, and can obtain a coating film having excellent adhesion to a substrate and water resistance when used as a coating material, and a modifier for an aqueous epoxy resin necessary to obtain the same. <P>SOLUTION: The modifier for the aqueous epoxy resin is composed of a primary amino group-containing polyether compound represented by formula (1). The self-emulsifiable epoxy resin is obtained by reacting this modifier for the aqueous epoxy resin with an epoxy resin, and the aqueous epoxy resin composition is obtained by emulsifying or dispersing this self-emulsifiable epoxy resin into water. An epoxy group-containing surface active agent is obtained by reacting the above modifier for the aqueous epoxy resin with 1.5-2.2 mol, based on 1 mol of the primary amino group of the primary amino group- containing polyether compound represented by formula (1), of the polyepoxy compound having two or more epoxy groups. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modifier for an aqueous epoxy resin, a self-emulsifying epoxy resin and an aqueous epoxy resin composition. The present invention also relates to a surfactant obtained by reacting a modifier for an aqueous epoxy resin with a polyepoxy compound.

[0002]

2. Description of the Related Art Epoxy resins are widely used as paints, adhesives, fiber treating agents, etc. because they are excellent in adhesion to various substrates, heat resistance, chemical resistance, electrical properties, mechanical properties, etc. ing. Further, among the epoxy resins, polyglycidyl ethers such as phenol novolac and cresol novolac are excellent in heat resistance of the cured product, and therefore are preferably used for applications requiring high heat resistance such as automobiles. When the epoxy resin is used for the above-mentioned uses, a solvent type in which the epoxy resin is dissolved in various low boiling point solvents is generally used for easy handling. However, the use of low boiling point solvents has come to be restricted due to problems such as fire risk, harmfulness to humans, and adverse effects on the global environment.In recent years, water-based epoxy resins obtained by emulsifying epoxy resin in water have been developed. Being developed.

As a method for emulsifying an epoxy resin,
(A) a method using a non-reactive surfactant, (b) a method using a reactive surfactant, and (c) a method in which a hydrophilic group is introduced into an epoxy resin to make the epoxy resin itself self-emulsifying. Be separated. In the present invention, a compound that reacts with an epoxy resin to introduce a hydrophilic group is referred to as a water-based epoxy resin modifier, and an epoxy resin that can be emulsified in water without using a surfactant is referred to as a self-emulsifying epoxy resin.

[0004]

Among these, the method (a) is a method of emulsifying an epoxy resin with a surfactant having no reactive group with an epoxy group or an amino group, a so-called non-reactive surfactant. Is. As the non-reactive surfactant, a nonionic surfactant such as nonylphenol polyethylene oxide adduct, octylphenol polyethylene oxide adduct, or polypropylene glycol polyethylene oxide adduct is used. However, the stability of an aqueous epoxy resin using these surfactants as an emulsion was not sufficiently satisfactory. Further, when such an aqueous epoxy resin is used for applications such as paints, the adhesion between the coating film and the substrate and the water resistance of the coating film are insufficient. It is considered that this is because the surfactant used for emulsification remains free in the resin even after the epoxy resin is cured.

The method (b) uses a surfactant having reactivity with the epoxy resin or its curing agent, that is, a so-called reactive surfactant, and the residual amount of the free surfactant in the cured epoxy resin. The purpose is to reduce For example, in JP-A-59-98125, a reactive surfactant having a phenolic hydroxyl group at a terminal obtained by reacting a polyether diol, a diisocyanate and a dihydric phenol; in JP-A-7-256845, an alkylphenol is disclosed. Reactive surfactant consisting of terminal glycidyl ether such as ethoxylate and polypropylene glycol ethoxylate; JP-A-6-212059
In JP-A-7-206982, a polyether polyol, a hydroxyl group-containing epoxy compound and a reactive surfactant obtained by reacting a polyisocyanate are disclosed; in JP-A-7-206982, a polyether polyol, a hydroxyl group-containing epoxy compound and an acid anhydride. A reactive surfactant and the like obtained by reacting a compound are disclosed. However, when the water-based epoxy resin using these reactive surfactants is used for coating applications, the adhesion between the coating film and the substrate and the water resistance of the coating film are improved, but the emulsion stability is not sufficient. Absent.

In the method (c), since the epoxy resin itself is self-emulsifying, it is not necessary to use a surfactant, and when it is used for paints, the adhesion between the coating film and the substrate is low. The water resistance of coatings and coatings is improved. Japanese Patent Laid-Open No. 61-2438
No. 22 discloses a self-emulsifying epoxy resin obtained by reacting diglycidyl ether of dihydric phenol, dihydric phenol, diglycidyl ether of polyoxyalkylene glycol, and alkylphenol-formaldehyde novolac resin. However, these have problems such as insufficient emulsification property, low film strength of the cured product, and slow curing speed of the cured product. In addition, Japanese Examined Japanese Patent Sho 63
No. 20448, No. 9-507873, and the like include the following general formula (3). A self-emulsifying epoxy resin obtained by reacting a secondary amino group-containing polyether compound represented by and an epoxy resin is disclosed.

The secondary amino group-containing polyether compound represented by the general formula (3) can be obtained by converting the terminal hydroxyl group of the polyether monool compound into an amino group. However, since the conversion of the alcoholic hydroxyl group to the amino group is limited to the secondary or tertiary hydroxyl group, the amino group of the compound represented by the general formula (3) has a high steric hindrance and has a high reactivity with the epoxy resin. It needs to be reacted at low and high temperatures. Further, two epoxy groups can react with the secondary amino group of the compound represented by the general formula (3), but the imino group formed by the reaction of one epoxy group with the secondary amino group is further steric. Since the obstacle becomes high and the second epoxy group becomes very difficult to react, the general formula (3)
Even if the compound represented by and the epoxy resin are reacted at a high temperature, the reaction may not proceed sufficiently, and when used as a paint, the adhesion to the substrate and the water resistance were insufficient. Since the compound represented by the general formula (3) has a hydrocarbon group at the structural terminal of the molecule, the reaction product with the epoxy resin has insufficient emulsion stability.

On the other hand, JP-A-2-58534, JP-A-10-279967 and JP-A-11-26375.
No. 6, JP-A No. 2002-20768, etc.
Polyether compounds having a primary amino group and a hydroxyl group are disclosed. However, in JP-A-2-58534, a curing agent for epoxy resin, a crosslinking agent for urethane resin, a modifier for polyamide resin; JP-A-10-279967, JP-A-11-263756, and JP-A-2002.
No. 20768 discloses only the use of a fuel oil for an internal combustion engine as an additive, and does not disclose the use as a modifier for an aqueous epoxy resin as in the present invention. Therefore, the object of the present invention is excellent in emulsion stability, when used as a coating,
It is to provide a self-emulsifying epoxy resin composition that can obtain a coating film having excellent adhesion to a base material and water resistance, and to provide a modifier for an aqueous epoxy resin necessary for obtaining the same. .

In the present invention, the modifier for an aqueous epoxy resin means a part of the epoxy group in the epoxy resin (or
A compound which makes the epoxy resin self-emulsifying by reacting with a reactive group other than the epoxy group. Therefore,
An epoxy resin (self-emulsifying epoxy resin) obtained by reacting a modifier for an aqueous epoxy resin becomes a liquid at ordinary temperature or becomes a liquid by heating, and an aqueous epoxy resin composition can be obtained by emulsifying or dispersing in water. On the other hand, the curing agent for epoxy resin refers to a compound that reacts with all or most of the epoxy groups in the epoxy resin to increase the molecular weight and crosslink to cure the epoxy resin. Therefore, the epoxy resin cured with the curing agent for epoxy resin does not liquefy even when heated, and cannot be emulsified or dispersed in water.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a primary amino group-containing polyether compound having a specific structure has good reactivity with an epoxy resin,
Epoxy resin modified by this has excellent self-emulsification and emulsion stability, when used as a paint,
The present invention has been completed by finding that a coating film having excellent adhesion to a substrate and excellent water resistance of the coating film can be obtained. That is, the present invention provides the following general formula (1) A modifier for a water-based epoxy resin comprising a primary amino group-containing polyether compound represented by Further, the present invention is a self-emulsifying epoxy resin obtained by reacting the modifier for an aqueous epoxy resin with an epoxy resin, and an aqueous epoxy resin composition obtained by emulsifying or dispersing the self-emulsifying epoxy resin in water. It is a thing.

The present invention further comprises a primary amino group-containing polyether compound represented by the general formula (1), which comprises the above-mentioned modifier for an aqueous epoxy resin and a polyepoxy compound having two or more epoxy groups. With respect to 1 mol of the primary amino group,
Polyepoxy compound having two or more epoxy groups 1.
An epoxy group-containing surfactant, which is obtained by reacting 5 to 2.2 mol.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to preferred embodiments. In the general formula (1), R ¹ represents an alkylene group. Examples of the alkylene group include methylene, ethylene, propylene, butylene, pentene, hexene, heptene, octene, etc., preferably an alkylene group having 1 to 5 carbon atoms, and an alkylene group having 1 to 3 carbon atoms. More preferably,

X represents a hydrocarbon group, a group represented by --R ² O (AO ² ) _c H, or a group represented by --R ³ --CH ₂ NH ₂ . Hydrocarbon groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2
Butyl, tert-butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tert-pentyl, hexyl, secondary hexyl, heptyl, secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl Second grade decyl, undecyl,
Secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl,
Secondary tetradecyl, hexadecyl, secondary hexadecyl,
Stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl,
2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl, 2-hexadecyloctadecyl, 2-tetradecyloctadecyl, monomethyl Branched-alkyl groups such as isostearyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl; Phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylpheni Aryl groups such as hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, styrenated phenyl, p-cumylphenyl, phenylphenyl, benzylphenyl, α-naphthyl and β-naphthyl groups; Examples of cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, and methylcycloheptenyl groups, and cycloalkenyl groups. To be

R ² and R ³ represent an alkylene group. Examples of the alkylene group include the alkylene groups mentioned for R ¹ . R ² and R ³ are preferably alkylene groups having 1 to 5 carbon atoms, and more preferably alkylene groups having 1 to 3 carbon atoms. R ¹ , R ² and R ³ may be different or the same.

AO¹And AO²Represents an oxyalkylene group
Eagle, (AO¹)_bAnd (AO²)_cPolyoxya represented by
The alkylene group is ethylene oxide or propylene oxa.
Id, butylene oxide, tetrahydrofuran (1,
4-butylene oxide), long-chain α-olefin oxa
And alkylene oxides such as styrene oxide
Can be obtained by addition-polymerizing
Renoxide is preferred. Alkylene oxide, etc.
By adding (AO¹)_bOr (AO²)_cRepresented by
Group to form a alkylene oxide
AO ¹Or AO²Is determined. To add
There is no particular limitation on the form of polymerization of alkylene oxide, etc.
Homopolymerization of two types of alkylene oxides, two or more types
Random copolymerization of alkylene oxide, etc., block
It may be copolymerization or random / block copolymerization.
(AO¹)_bOr (AO²)_cGroups represented by
When formed by copolymerization of alkylene oxide,
One of the alkylene oxides is ethylene oxide
Is preferred.

The group represented by (AO ¹ ) _b or (AO ² ) _c is
When it is formed by copolymerization of ethylene oxide and another alkylene oxide, the content of the oxyethylene group in the group represented by (AO ¹ ) _b or (AO ² ) _c is (AO ¹ ) _b or It is preferably 40% by mass or more, and 60% by mass based on the total amount of the unit represented by (AO ² ) _c.
More preferably, it is more than 70% by mass, most preferably 70% by mass or more. The content of the oxyethylene group in the group represented by (AO ¹ ) _b or (AO ² ) _c is
When it is less than 40% by mass based on the total amount of units represented by O ¹ ) _b or (AO ² ) _c , the emulsion stability of the aqueous epoxy resin composition obtained by the modifier for an aqueous epoxy resin of the present invention May be insufficient. b and c are 1
It is the above number, preferably the number of 1 to 500, more preferably the number of 2 to 250, and 3 to 8
Most preferably, it is a number of zero. (AO ¹ ) _b and (A
The groups represented by O ² ) _c may be the same as or different from each other. When there are two or more groups represented by (AO ¹ ) _b in the molecule (when a is 2 or more), they may be the same or different.

In a, X is a hydrocarbon group or --R³-CH₂N
H₂When the group is represented by, a number of 1 or more; X is -R²
O (AO²)_c0 or 1 or more when the group is represented by H
Represents the number of. However, if a is too large,
Polyether containing primary amino group represented by general formula (1)
The viscosity of the compound was too high, making it difficult to manufacture.
Obtained by the modifier for an aqueous epoxy resin of the present invention
When the emulsion stability of the aqueous epoxy resin composition becomes insufficient.
There is a match. Therefore, X is a hydrocarbon group or -R ³-CH₂
NH₂When the group is represented by, a is a number from 1 to 3.
Is preferable, and a number of 1 to 2 is more preferable.
Most preferably, it is 1. Also, -R²O
(AO²)_cWhen it is a group represented by H, a is 0 or
It is preferable that the number is 1 to 3, and 0 or the number is 1 to 2.
It is more preferable that the number is 0 or 1, and it is most preferable that the number is 0 or 1.
Is also preferable.

Of these, X is --R ² O (A
O ² ) _c H group, a group represented by -R ³ -CH ₂ NH ₂ or a linear alkyl group or a linear alkenyl group having 1 to 18 carbon atoms is preferable, and -R ² O (AO ² ) _c A group represented by H or a linear alkyl group having 1 to 8 carbon atoms is more preferable, and a group represented by —R ² O (AO ² ) _c H or a group having 1 to 8 carbon atoms is preferable.
Most preferred is a straight chain alkyl group of 4.

The method for producing the primary amino group-containing polyether compound represented by the general formula (1) is, for example,
(A) A polyether polyol compound in which the terminal hydroxyl group is substituted with halogen and ammonia or the following general formula (2) A method of reacting an amine compound represented by the formula (B), wherein the primary amino group of the amine compound represented by the general formula (2) is reacted with a ketone compound to protect it as a ketimine group, and then the secondary amino group is converted to an alkylene oxide. And the like to give a ketimine group-containing polyether compound, and then removing the ketone compound from the ketimine group to give a primary amino group. Among them, the method (A) is a method in which, when a is a number of 1 or more, a polyether polyol compound in which a hydroxyl group is substituted with a halogen in the primary amino group and the secondary amino group of the general formula (2) is used. There is no difference in reactivity, and it is difficult to selectively convert only secondary amino groups into polyether. For this reason, the amine compound obtained by the method (A) has a higher emulsion stability of the aqueous epoxy resin when used as an aqueous epoxy resin modifier than that obtained by the method (B). Not enough.

On the other hand, in the method (B), since the primary amino group is protected as a ketimine group with a ketone compound and then reacted with alkylene oxide, the secondary amino group is selectively polyetherified. You can Therefore,
The method (B) is preferable as the method for producing the primary amino group-containing polyether compound represented by the general formula (1). The ketimine group means "primary amino (R ¹ NH ₂ ).
And a ketone (R ² COR ³ ) are reacted and condensed to obtain a structure of R ¹ N = CR ² R ³ ”(Seikagaku Dictionary, 1st edition 5).
Page 72, Tokyo Kagaku Dojin).

Among the amine compounds represented by the general formula (2), examples of the amine compound in which Y is a hydrocarbon group include, for example, N-methylethylenediamine, N-ethylethylenediamine, N-methyl-1,3-propanediamine. ,
N-cyclohexyl-1,3-propanediamine, N-
Decyl-1,3-propanediamine, N-dodecyl-
1,3-propanediamine, N-isotridecyl-1,
Examples include 3-propanediamine, N-tetradecyl-1,3-propanediamine, N-octadecyl-1,3-propanediamine and the like.

The amine compound in which Y is a group represented by -R ² O-H includes, for example, monoethanolamine, monopropanolamine, monoisopropanolamine,
2-hydroxybutylamine, 4-hydroxybutylamine, N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) -1,3-propanediamine and the like can be mentioned.

The amine compound in which Y is a group represented by -R ³ -NH ₂ includes, for example, diethylenetriamine, N- (2-aminoethyl) -1,3-propanediamine and N- (3-amino. Propyl) -1,3-propanediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, N, N "-
1,2-ethylenediyl- (1,3-propanediamine) and the like can be mentioned.

The ketone compound used in the method (B) is represented by the following general formula (4) It is a ketone compound represented by. In the general formula (4), R ⁴ and R ⁵ are hydrocarbon groups, and specific examples thereof include the hydrocarbon groups listed for X in the general formula (1). R ⁴ and R ⁵ are independent of each other and may be the same or different. Examples of the ketone used in the present invention include:
Acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, dibutyl ketone, diisobutyl ketone, methylhexyl ketone, acetophenone and the like can be mentioned. Further, a ketone having a structure in which R ⁴ and R ⁵ are linked, for example, cyclohexanone,
Cycloheptanone or the like may be used. Among these ketone compounds, a ketone compound in which R ⁴ and R ⁵ are hydrocarbon groups having 1 to 10 carbon atoms is preferable. Furthermore, the ketone compound in which either R ⁴ or R ⁵ is a hydrocarbon group having a secondary or tertiary carbon has few side reactions such as elimination of the ketimine group when the alkylene oxide is reacted with the ketimine compound, More preferable.

The reaction in which the primary amino group of the amine compound represented by the general formula (2) is ketiminated with a ketone compound is
It can be performed by a usual method. As a reaction example, 1 to 4 equivalents of a ketone are present in the presence of a ketone in an amount of 10 equivalents to 1 equivalent of a primary amino group of an amine compound represented by the general formula (2).
The primary amino group can be easily ketiminated by heating to 0 to 140 ° C. and dehydration reaction. In this reaction, a reflux solvent azeotropic with water, for example, toluene, xylene, pseudocumene or the like may be allowed to coexist. The ketimine compound obtained by reacting the amine compound represented by the general formula (2) with the ketone compound can be represented by the following general formula (5).

The reaction of reacting the ketimine compound represented by the general formula (5) with an alkylene oxide to form a polyether is similar to the reaction of reacting an alkylene oxide with an ordinary amine compound to form a polyether. In the presence of, alkylene oxide may be added while heating. As the catalyst, an alkali metal catalyst is preferable. Examples of the alkali metal catalyst include sodium hydroxide, potassium hydroxide, sodium methylate, cesium hydroxide and the like. Reaction temperature is 70-1
40 degreeC is preferable and 90-130 degreeC is more preferable.
When toluene, xylene, pseudocumene or the like is used in the ketiminization, the solvent may be removed before the reaction with the alkylene oxide, or the alkylene oxide may be directly reacted without being removed. .

Thereafter, the polyetherified ketimine compound can be hydrolyzed to obtain a primary amino group-containing polyether compound represented by the general formula (1). The hydrolysis is carried out by heat treatment in the presence of excess water. Water is 1. to 1 equivalent of ketimine group.
The amount is preferably 2 to 10 equivalents, more preferably 1.5 to 5 equivalents. The reaction temperature is preferably 60 to 120 ° C, more preferably 80 to 100 ° C. After completion of hydrolysis, water, ketone and solvent produced by hydrolysis,
It can be removed by heating and reducing the pressure.

The modifier for an aqueous epoxy resin of the present invention comprising a primary amino group-containing polyether compound represented by the general formula (1) has a primary amino group which is less sterically hindered and has good reactivity with an epoxy group. . Further, by reacting the epoxy resin with the modifier for a water-based epoxy resin of the present invention, self-emulsification can be imparted to the epoxy resin.

Examples of the epoxy resin capable of imparting the self-emulsifying property by reacting with the modifier for an aqueous epoxy resin of the present invention include, for example, polynuclear polyphenol compounds such as hydroquinone, resorcin, pyrocatechol and phloroglucinol. Glycidyl ether compound; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3- Bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl)
Butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac,
Polyglycidyl ether compounds of polynuclear polyphenol compounds such as orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, bisphenol A novolac, bisphenol F novolac, and terpene diphenols;

Polyglycidyl ether compounds of the above mononuclear polyhydric phenol compounds or ethylene oxide and / or propylene oxide adducts to the polynuclear polyhydric phenol compounds; polyglycidyl ether compounds of hydrogenated mononuclear polyhydric phenol compounds; ethylene Glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol,
Polyglycidyl ethers of polyhydric alcohols such as sorbitol and bisphenol A-ethylene oxide adducts;

Maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid Acid, pyromellitic acid, tetrahydrophthalic acid,
Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as hexahydrophthalic acid and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate; N, N-diglycidylaniline, bis ( An epoxy compound having a glycidylamino group such as 4- (N-methyl-N-glycidylamino) phenyl) methane; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxy Epoxidized cyclic olefin compounds such as cyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; Epo Shi polybutadiene, epoxidized styrene - epoxidized conjugated diene polymer such as butadiene copolymer, heterocyclic compounds such as triglycidyl isocyanurate. Further, these epoxy resins may be internally cross-linked with a prepolymer having a terminal isocyanate.

Among the above epoxy resins, especially high molecular weight epoxy resins have been difficult to emulsify with known emulsifiers until now. However, by reacting with the aqueous epoxy resin modifier of the present invention, emulsion stability is improved. It is possible to obtain an excellent self-emulsifying epoxy resin. As such an epoxy resin which is difficult to emulsify, for example, a number average molecular weight of 50
Bisphenol A type epoxy resin of about 0 to 4,000; polyglycidyl ether of phenol novolac compound such as phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, bisphenol A novolac and bisphenol F novolac. A compound etc. are mentioned.

When the self-emulsifying epoxy resin is produced by reacting the modifier for an aqueous epoxy resin of the present invention with an epoxy resin, the ratio of the modifier for an aqueous epoxy resin of the present invention to the epoxy resin is particularly limited. However, the ratio of the modifier for an aqueous epoxy resin of the present invention to 100 parts by mass of the epoxy resin is preferably 1 to 30 parts by mass,
It is more preferably 1.5 to 20 parts by mass, and 2-1.
Most preferably, it is 0 part by mass. When the amount of the modifier for an aqueous epoxy resin of the present invention is less than 1 part by mass,
When the self-emulsifying epoxy resin of the present invention is used as a coating material, the water resistance may decrease when the emulsion stability is insufficient.

The reaction method for reacting the epoxy resin with the water-based epoxy resin modifier of the present invention to form a self-emulsifying epoxy resin is, for example, either the epoxy resin or the water-based epoxy resin modifier of the present invention. A method in which one is heated and stirred at a predetermined reaction temperature and then the other is added and reacted; an epoxy resin and an aqueous epoxy resin modifier of the present invention are mixed, and then gradually heated. A reaction method and the like can be mentioned, but it is particularly preferable to heat and stir the epoxy resin to a predetermined reaction temperature and gradually add the aqueous epoxy resin modifier of the present invention to the reaction. The reaction temperature is preferably 50 to 130 ° C, more preferably 70 to 100 ° C. The reaction time is about 0.5 to 5 hours.

The self-emulsifying epoxy resin obtained by reacting the epoxy resin with the aqueous epoxy resin modifier of the present invention can be emulsified by mixing with water to give an aqueous epoxy resin composition. The ratio of the self-emulsifying epoxy resin and water is not particularly limited, but water is preferably 40 to 700 parts by mass, and 50 to 400 parts by mass with respect to 100 parts by mass of the self-emulsifying epoxy resin of the present invention. Is more preferable and 60 to 200 parts by mass is most preferable. If the amount of water is less than 30 parts by mass, the emulsification may be insufficient or the viscosity may be high and handling may be difficult. If the amount is more than 700 parts by mass, drying when used in paints or the like may occur. Sex decreases.

The method for producing the aqueous epoxy resin composition of the present invention is, for example, a method of gradually mixing one of the self-emulsifying epoxy resin and water with the other while stirring, or a method of batch-mixing at the time of stirring. Although various methods such as a method of blending are used, the method is not particularly limited. Here, examples of the stirrer used for the stirring include a disper, a homomixer, a rotary homogenizer, a high-pressure homogenizer, and the like.

Further, in the aqueous epoxy resin composition of the present invention, a curing agent usually used as a curing agent for epoxy resin can be used. Examples of such a curing agent include chain aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine and polyoxypropylenetriamine; menthenediamine, isophoronediamine, bis (4-amino). -3-Methyldicyclohexyl)
Methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4
Cycloaliphatic amines such as 8,10-tetraoxosuspyro (5.5) undecane and m-xylenediamine; metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethylphenylmethane, α, α′-bis ( 4-aminophenyl)
A polyamine curing agent such as aromatic polyamine such as p-diisopropylbenzene; a polyamide polyamine curing agent obtained by reacting these polyamines with a dicarboxylic acid such as dimer acid by a conventional method; or an epoxy resin to these polyamines Examples thereof include added epoxy addition-modified polyamine curing agents and Michael addition-modified polyamine curing agents to which acrylonitrile and the like are added, and latent curing agents such as dicyandiamide and imidazoles can also be used.

If desired, the aqueous epoxy resin composition of the present invention may contain an organic solvent. Solvents that can be preferably used include, for example, lower alcohols such as ethanol and isopropanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl acetoacetate, and 2-ethoxyethyl acetate; ethylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether,
Glycol ethers such as dipropylene glycol monomethyl ether and propylene glycol monoethyl ether; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; esters of glycol ethers such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; ethylene carbonate and propylene Carbonates such as carbonates; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, isooctane, decane, dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane; N, N- Dimethylformamide, N, N-dimethylacetamide, N-
Examples include methylpyrrolidone and terpenes. These solvents may be used alone or may be optionally used as a mixed solvent of two or more kinds.

In order to add a solvent, a step of reacting the modifier for an aqueous epoxy resin of the present invention with an epoxy resin to obtain a self-emulsifying epoxy resin; a step of making the self-emulsifying epoxy resin into water to obtain an aqueous epoxy resin composition It may be carried out at any step such as a step of adding an additive such as a curing agent to the aqueous epoxy resin composition. By adding a solvent, the emulsion stability of the water-based epoxy resin composition of the present invention can be improved, and the viscosity can be reduced and the handling can be facilitated.

Further, the aqueous epoxy resin composition of the present invention contains, if necessary, glass fiber, cellulose, silica sand,
Fillers such as cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, bituminous substances; γ-aminopropyltriethoxysilane, γ-methacryl Roxypropyltrimethoxysilane,
Vinyltrichlorosilane, vinyltriethoxysilane,
Coupling agents such as γ-glycidoxypropyltrimethoxysilane; polymer emulsions such as acrylate emulsions; pigments, lubricants, antistatic agents, light stabilizers,
Antioxidants, UV absorbers, thickeners, thixotropic agents, dispersants, flame retardants, defoamers, antibacterial agents, antifungal agents, preservatives, conventional additives such as reactive or non-reactive diluents It is also possible to use a combination agent such as a xylene resin, a petroleum resin and the like.

The aqueous epoxy resin composition of the present invention is a paint or adhesive for concrete, cement mortar, various metals, leather, glass, etc .; adhesive tape for packaging, adhesive label, frozen food label, removable label, POS label. Adhesives for adhesive wallpaper, adhesive flooring; art paper, coated paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copying paper, impregnated paper, etc .; natural fiber, synthetic fiber, glass fiber, It can be used for a wide range of applications such as sizing agents such as carbon fibers and metal fibers, fiber treatment agents such as anti-raveling agents and processing agents; building materials such as sealing materials, cement admixtures and waterproof materials. Among these applications, it can be particularly suitably used as a paint, an adhesive, a fiber treatment agent, and the like.

The aqueous epoxy resin composition of the present invention is excellent in emulsion stability. This is because the modifier for an aqueous epoxy resin of the present invention that has reacted with an epoxy resin, that is, the primary amino group-containing polyether compound represented by the general formula (1) that has reacted with a polyepoxide compound has an epoxy group-containing surfactant. This is because it has an excellent emulsifying action as an agent.
Moreover, the coating material using the water-based epoxy resin composition of the present invention exhibits excellent water resistance even though it is a water-based coating material. This is because the surfactant having this epoxy group has an epoxy group as a reactive group, so it is fixed in the coating film by the curing agent and free in the resin like a non-reactive surfactant. It is considered that this is because they do not remain.

Surfactant having such an epoxy group
In order to obtain a high-purity
2 or more epoxies per 1 equivalent of primary amino group of agent
1.5 to 2.2 mol of a polyepoxy compound having a group,
Preferably, 1.8 to 2.1 mol may be reacted. This
An epoxy group-containing surfactant (
Below, the epoxy group-containing surfactant of the present invention is an epoxy
In addition to emulsifiers for resins, monomers for radical polymerization
Used as an emulsifier for emulsion polymerization, an emulsifier for aqueous urethane resins, etc.
Can be suitably used. Epoxy group-containing surfactant of the present invention
Polyepoxy having two or more epoxy groups used in the agent
The compound is a diepoxy compound.
The emulsifying performance of Mitsui's epoxy group-containing surfactant can be improved.
It is preferable because Among diepoxy compounds, in particular,
Diphenols of sphenols or hydrogenated bisphenols
Glycidyl ether is more preferable, and bisphenol A is used.
Or diglycidyl ether of bisphenol F is the best
Is also preferable. Further, the epoxy group-containing surfactant of the present invention
Used as a modifier for the aqueous epoxy resin of the present invention
Is a hydrocarbon group or -R in the general formula (1).²
O (AO ²)_cA group represented by H is preferable.

The structure of the epoxy group-containing surfactant of the present invention can be represented by the following general formula (6) when the epoxy resin is bisphenol A diglycidyl ether. In the general formula (6), X ′ represents a group represented by —R ² O (AO ² ) _c H or a group represented by the following general formula (7), and R ¹ , R ² , AO ¹ , AO ² , a, b and c have the same meaning as in the general formula (1), and in the general formula (7), R ³ is
It is synonymous with general formula (1).

When the epoxy group-containing surfactant of the present invention is used as an emulsifying agent for emulsion polymerization, the radically polymerizable monomers include (meth) acrylic acid, (meth) acrylic acid esters, and (meth) acrylic acid. Examples thereof include amides, styrene, vinyl alcohol esters, vinyl ethers, acrylonitrile, butadiene, maleic acid (esters), itaconic acid (esters), crotonic acid (esters), and the like.

[0046]

EXAMPLES Hereinafter, the present invention will be described more specifically by way of examples.
In the structural formulas below, EO represents an oxyethylene group, PO represents an oxypropylene group, and (EO) ₁₈ / (PO) ₃ represents 1
It represents a polyoxyalkylene group in which an oxyethylene group of 8 and an oxypropylene group of 3 are randomly bonded. The epoxy equivalent is the molecular weight of the epoxy resin per one epoxy group, and the active hydrogen equivalent is defined as the molecular weight of the amine compound per one N—H group capable of reacting with the epoxy group. The molecular weight or the number of moles of the amine compound was calculated from the number of amino groups in the structural formula and the measured value of active hydrogen equivalent. Further, in the following examples, parts and% are based on mass unless otherwise specified.

<Synthesis Example 1: Inventive product 1> 61 g (1 mole) of monoethanolamine and 400 g (4 moles of methyl isobutyl ketone) were placed in a 5 liter autoclave equipped with a nitrogen gas inlet tube, a thermometer, a water divider and a stirrer. ) Was charged and reacted at 140 ° C. and normal pressure for 8 hours. The water flowing out during the reaction was removed at any time with a water divider while blowing nitrogen gas. After completion of the reaction, remove excess methyl isobutyl ketone by 12
It was evaporated under reduced pressure at 0 ° C. Next, 4 g of potassium hydroxide was charged as a catalyst, and 968 g of ethylene oxide (2
2 mol) was added at a temperature of 130 ° C. and a pressure of 10 kg / cm ² . After completion of the ethylene oxide reaction, the catalyst was removed by a conventional method, 60 g of water was added, and hydrolysis was carried out at 110 ° C. for 4 hours. After completion of the hydrolysis, the released methyl isobutyl ketone and excess water were removed under reduced pressure to obtain a product 1 of the present invention which is a modifier for an aqueous epoxy resin.

<Synthesis Example 2: Inventive Product 2> In Synthesis Example 1, 75 g (1 mol) of monoisopropanolamine instead of monoethanolamine, 290 g (5 mol) of propylene oxide instead of ethylene oxide,
Next, the same operation as in Synthesis Example 1 was carried out except that 1,188 g (27 mol) of ethylene oxide was reacted in a block form to obtain a product 2 of the present invention as a modifier for an aqueous epoxy resin.

<Synthesis Example 3 of the present invention 3> In Synthesis Example 1, 104 g (1 mol) of N- (2-hydroxyethyl) ethylenediamine was used instead of monoethanolamine.
Instead of ethylene oxide, 1,584 g (36 mol) of ethylene oxide and 34 parts of propylene oxide
The same operation as in Synthesis Example 1 was carried out except that 8 g (6 mol) of the mixture was reacted randomly to obtain a product 3 of the present invention which is a modifier for an aqueous epoxy resin.

<Synthesis Example 4: Inventive Product 4> In Synthesis Example 1, instead of monoethanolamine, N-methyl-
88 g (1 mol) of 1,3-propylenediamine, instead of ethylene oxide, ethylene oxide 1,67
2 g (38 mol) and 290 g of propylene oxide (5
The same operation as in Synthesis Example 1 was carried out except that the mixture of (mol) was randomly reacted to obtain a product 4 of the present invention as a modifier for an aqueous epoxy resin.

<Synthesis Example 5: Inventive product 5> In Synthesis Example 1, diethylenetriamine (103 g, 1 mol) was used instead of monoethanolamine, propylene oxide was 290 g (5 mol), and ethylene oxide 1 was used instead of ethylene oxide. , 188 g (27 mol) were reacted in a block form, and the same operation as in Synthesis Example 1 was carried out to obtain a product 5 of the present invention which is a modifier for an aqueous epoxy resin.

<Synthesis Example 6: Product 6 of the present invention> Adekaresin EP-4100 (bisphenol A diglycidyl manufactured by Asahi Denka Co., Ltd.) was placed in a 500 mL glass reaction container equipped with a nitrogen gas inlet tube, a thermometer and a stirrer. 152 g (0.4 mol) of an ether type epoxy resin and an epoxy equivalent of 190) were charged and heated to 80 ° C. To this, 206 g (0.2 mol) of the product (1) of the present invention was added over 2 hours,
After completion of the addition, the product of the present invention, which is an epoxy group-containing surfactant, is further stirred by aging at 100 ° C. for 2 hours for aging.
Got

<Synthesis Example 7: Present Invention Product 7> In Synthesis Example 6, 206 g of the present invention product (1) was replaced with 386 g of the present invention product (3).
The same operation as in Synthesis Example 6 was carried out except that the amount was changed to (0.2 mol) to obtain a product 7 of the present invention which was an epoxy group-containing surfactant.

<Comparative Product 1> Nonylphenol ethoxylate (30).

<Comparative product 2> 1 mol of Pluronic F-8
8 (polyethylene glycol adduct of ethylene oxide, number average molecular weight 10,800, content of oxyethylene group in molecule 80%), reaction product of 2 mol of bisphenol A and 2 mol of isophorone diisocyanate. The reaction conditions were based on Example 1 of Japanese Examined Patent Publication No. 3-65808.

<Comparative Product 3> A modifier for an aqueous epoxy resin represented by the following formula.

<Comparative product 4> A modifier for an aqueous epoxy resin represented by the following formula.

<Comparative Product 5> In Synthesis Example 6, 206 g of the product of the present invention (1) was mixed with 192 g (0.2 mol) of the comparative product (4).
Instead of the reaction temperature and aging temperature of 120 ℃,
The same operation as in Synthesis Example 6 was performed to obtain comparative product 5 which is a comparative epoxy group-containing surfactant.

<Comparative Product 6> Sulfate Na salt of nonylphenol ethoxylate (10)

<Epoxy Resin> Epoxy Resin A: Adeka Resin EP-4100 (Asahi Denka Kogyo Co., Ltd., bisphenol A diglycidyl ether type epoxy resin, epoxy equivalent 190) Epoxy Resin B: Adeka Resin EP-5100-75X
(Asahi Denka Kogyo KK, low molecular weight bisphenol A type epoxy resin, containing 25% xylene as a solvent, epoxy equivalent 630)

<< Analysis Method >> The following values were measured for the products 1 to 7 of the present invention and the comparative products 3 to 5. The results are shown in Table 1. <Hydroxyl value> The hydroxyl value was measured according to JIS K1557 (polyether test method for polyurethane). <Epoxy equivalent> Measured in accordance with JIS K7236 (method for determining epoxy equivalent of epoxy resin). <Active hydrogen equivalent> JIS K7245 (Plastic-
Amine-based curing agent for epoxy resin-determination of primary, secondary, and tertiary amino group nitrogen content)) and primary amino group nitrogen content (%) and secondary amino group nitrogen content (%) Then, the primary amino group was converted into bifunctional and the secondary amino group was converted into monofunctional.

[0062]

<Preparation of Self-Emulsifying Epoxy Resin> [In the case of products 1 to 5 of the invention] The products 1 to 5 of the invention and the epoxy resin were placed in a reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer. The mixture was charged at the ratio shown in Table 2 and reacted by stirring at 90 ° C. for 2 hours.

[In case of Inventive Products 6, 7 and Comparative Products 1, 5] Inventive Products 6, 7 or Comparative Products 1, 5 and epoxy were placed in a mixing container equipped with a nitrogen gas introducing pipe, a thermometer and a stirring device. The resin was charged in the ratio shown in Table 2 and mixed by stirring at 80 ° C. for 1 hour.

[Comparative product 2] In a reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, the comparative product 2 and the epoxy resin were charged at the ratios shown in Table 2 and stirred at 130 ° C for 2 hours. Was reacted with. Triphenylphosphine (0.5 part with respect to 100 parts of epoxy resin) was used as a catalyst.

[Comparative Products 3 and 4] [Comparative Products 3 to 4 were used instead of Comparative Products 3 to 4 and the reaction temperature was 120 ° C.] ] And reacted.

[0067]

(Test 1: Emulsion Stability of Aqueous Epoxy Resin Composition) 100 g of the emulsifying epoxy resin of Examples 1 to 13 or Comparative Examples 1 to 10 was sampled in a 1 L beaker, and 66 g of water was gradually added using a homogenizer. In addition to 20-40 ℃
Each aqueous epoxy resin composition was prepared by emulsifying with, and the emulsifying property was evaluated. In addition, the storage stability of each aqueous epoxy resin composition was evaluated. The results are shown in Table 3.

<Emulsification Test> In the preparation of the above aqueous epoxy resin composition, the ease of emulsification was evaluated according to the following criteria. ◯: The resin has a low viscosity and is easily emulsified. Δ: The resin has a high viscosity and is difficult to emulsify. X: Emulsification is insufficient and cannot be emulsified, or a gel-like material is generated.

<Storage Stability Test> Each aqueous epoxy resin composition was stored in a constant temperature bath at 50 ° C. for 30 days, and the presence or absence of separation was visually observed and evaluated according to the following criteria. ◯: Separation is not seen. X: Separation is seen in the upper or lower part of the emulsion.

[0071]

(Test 2: Coating film test) <Coating film drying test> Polyamideamine was added to the aqueous epoxy resin compositions of Examples 1 to 11 and Comparative Examples 1 to 10 produced in Test 1 as a curing agent. Type curing agent (Asahi Denka Kogyo Co., Ltd.,
Trade name: ADEKA HARDNER EH-203, active hydrogen equivalent 133) was blended in a ratio shown in Table 4. Apply this to a tin plate so that the thickness of the dry coating film is 50 μm,
It was air-dried at room temperature for 24 hours, and the dryness to the touch was evaluated. ◯: No stickiness and good drying property. Δ: Slightly sticky and slightly dry. X: There is stickiness and the drying property is poor.

<Coating film water resistance test> The test piece used for the coating film drying test was immersed in water at 40 ° C for 2 hours and 24 hours,
The coating film water resistance was evaluated by whitening the coating film surface. ◯: No whitening is observed in both coating films after 2 hours of immersion and 24 hours after immersion. Δ: No whitening was observed in the coating film 2 hours after the immersion, but whitening was observed in the coating film 24 hours after the immersion. X: Whitening was observed in the coating film 2 hours after immersion.

<Adhesion Test> The test piece used for the coating film dryness test was further stored at 80 ° C. for 1 hour, and then 10 cuts were made on the coating film at intervals of 1 mm to make 100 cuts.
Individual grids were made, cellophane tape was applied, and after sufficient pressure bonding, the tape was peeled off, the number of peeled measurement points out of 100 measurement points was counted, and the evaluation was made according to the following criteria. ◯: No peeling was observed, and the adhesion of the coating film was good. (Triangle | delta): Peeling is recognized in the point of 1-20, and the adhesiveness of a coating film is a little bad. X: Peeling was observed at 21 or more points, and the adhesion of the coating film was poor.

[0075]

(Test 3: Evaluation as Emulsifier for Emulsion Polymerization) In order to see the performance as the emulsifier for emulsion polymerization of the inventive products 6, 7 and the comparative products 1, 5, 6 which are the surfactants of the present invention. , And a mixture of styrene / ethyl acrylate / acrylic acid (styrene / ethyl acrylate / acrylic acid = 49/49/2 mass ratio) was used as a monomer to carry out emulsion polymerization. The particle size, amount of aggregates, mechanical stability, foamability, and water resistance of the film obtained from the polymer emulsion were measured. The results are shown in Table 5.

<Polymerization method> 120 g of deionized water was placed in a reaction vessel equipped with a reflux condenser, a stirrer, a dropping funnel and a thermometer.
Was charged, and the inside of the system was replaced with nitrogen gas. Separately, 4 g of the surfactant is dissolved in 100 g of the mixed monomer, and 10 g of this is dissolved.
And 0.08 g ammonium persulfate were added to the reaction vessel,
Polymerization was initiated at 0 ° C. Then, the remaining mixture of the monomer and the surfactant was continuously dropped into the reactor over 2 hours, and after the dropping was completed, the mixture was aged for 2 hours to obtain a polymer emulsion.

<Amount of Aggregate> The above polymer emulsion after polymerization was filtered through a wire mesh of 325 mesh, the filtration residue was washed with water and dried at 105 ° C. for 2 hours, and this mass was measured and expressed in mass% based on the solid content. expressed.

<Mechanical Stability> The polymer emulsion after polymerization was stirred with a disper at 2,000 rpm for 2 minutes, and the amount of aggregate was measured by the above method to evaluate the mechanical stability.

<Water resistance of film> The above polymer emulsion after polymerization was applied to a glass plate to form a coating film having a thickness of 0.2 mm, air-dried at room temperature, and further stored at 80 ° C. for 30 minutes. The glass plate having the coating film was dipped in water at 50 ° C., and the time required for whitening to make it impossible to distinguish 8-point characters through the coating film was measured to evaluate the water resistance. The evaluation criteria are as follows. ◯: Characters could be identified even after 24 hours had passed. Δ: Characters could not be identified after 1 hour or more. X: Characters could not be identified in less than 1 hour.

[0081]

(Test 4: Evaluation as Emulsifier for Aqueous Polyurethane Resin) Each of the surfactants of the invention products 6 and 7 and the comparative products 1 and 5 was prepared by the following production method and evaluation method.
It was evaluated as an emulsifier for an aqueous polyurethane resin.
The results are shown in Table 6.

<Production of Prepolymer> Nitrogen gas inlet pipe,
In a reaction vessel equipped with a thermometer and a stirrer, polyester polyol (isophthalic acid / adipic acid = 1: 1 and 1,
Condensate of 6-hexanediol, number average molecular weight 1,50
0) 100 g, methylene bis (4-cyclohexyl isocyanate) 30.8 g and dimethylol propionic acid 0.92 g were charged, heated and stirred, and reacted at 90 to 100 ° C. for 3 hours to obtain a prepolymer.

<Preparation of Aqueous Polyurethane Resin Composition> 60 g of water, 9 g of the surfactant of the present invention or comparative product were placed in a reaction vessel equipped with a nitrogen gas inlet tube, a thermometer and a stirrer.
Triethylamine (1.08 g) was added, and the mixture was stirred and uniformly mixed.
It was added over a period of time, and then 0.58 g of ethylenediamine was added as a cross-linking agent, and the mixture was stirred at 30 ° C. for 1 hour to carry out a cross-linking reaction to obtain an aqueous polyurethane resin composition.

<Storage Stability Test> The above-mentioned aqueous polyurethane resin composition was placed in a 20 mL glass bottle with a tight stopper, and 40
Store in a constant temperature bath at ℃, visually determine the occurrence of precipitation,
The following criteria evaluated. ◯: No precipitation occurs even after 200 days. Δ: Precipitation occurred between 30 and 199 days. X: Precipitation occurred within 29 days.

<Water Resistance Test> Each of the above water-based polyurethane resins was applied to a glass plate to prepare a film having a length of 30 mm, a width of 30 mm and a thickness of 100 μm. The mass of the polyurethane resin film was precisely weighed, immersed in warm water at 50 ° C. for 1 hour, and again weighed precisely after the immersion. The mass change rate before and after the immersion of the film was calculated by the following formula, and the water resistance was evaluated according to the following criteria. Weight change ratio (%) = 100 × (M S -M 0) / M 0 M 0: mass before immersion in hot water film M _S: mass of the film after immersion in hot water ○: weight change rate is more than 100% to 110 Is less than%,
Good water resistance. Δ: The mass change rate is 110% or more and less than 120%,
Water resistance is slightly poor. X: The mass change rate is 120% or more, and the water resistance is poor.

[0087]

[0088]

The modifier for an aqueous epoxy resin of the present invention is
The reactivity with the epoxy resin is good, and the epoxy resin modified by the modifier for an aqueous epoxy resin of the present invention is
A coating film having excellent self-emulsifying property and emulsion stability and having excellent adhesion to a substrate and water resistance of the coating film is obtained when used as a coating material. Further, the epoxy group-containing surfactant obtained by reacting the modifier for an aqueous epoxy resin of the present invention with an epoxy resin in a specific ratio is an emulsifier for a resin emulsion such as an aqueous epoxy resin or an aqueous polyurethane resin, or an emulsion polymerization. It is useful as an emulsifying agent.

Continued front page    (72) Inventor Tamotsu Nagamatsu             7-35 Higashiokyu, Arakawa-ku, Tokyo Asahiden             Chemical Industry Co., Ltd. F-term (reference) 4F070 AA53 AB01 AB08 AB13 CA01                       CB01 CB12                 4J031 AA47 AA53 AB04 AC03 AC07                       AC09 AD01 AF07 AF30                 4J036 AA01 AB00 AC00 AD00 AD01                       AD08 AD09 AD20 AD21 AF01                       AF06 AG03 AH04 AJ08 AK02                       AK03 CD12 JA15

Claims (8)

[Claims] 1. The following general formula (1): A modifier for an aqueous epoxy resin, comprising a primary amino group-containing polyether compound represented by: 2. In the general formula (1), (AO ¹ ) _b or
(AO ²⁾ the content of oxyethylene groups in the groups represented by _c are each of (AO ¹⁾ _b or (AO ²⁾ according to claim 1 is 40 mass% or more with respect to units based on the total amount represented by _c The modifier for an aqueous epoxy resin described. 3. A self-emulsifying epoxy resin obtained by reacting the modifier for an aqueous epoxy resin according to claim 1 or 2 with an epoxy resin. 4. A water-based epoxy resin composition obtained by emulsifying or dispersing the self-emulsifying epoxy resin according to claim 3 in water. 5. A primary amino group-containing polyether represented by the general formula (1), comprising the modifier for an aqueous epoxy resin according to claim 1 or 2 and a polyepoxy compound having two or more epoxy groups. An epoxy group-containing surfactant, which is obtained by reacting 1.5 to 2.2 mol of a polyepoxy compound having two or more epoxy groups with 1 mol of a primary amino group of the compound. 6. A surfactant for an aqueous epoxy resin, which comprises the epoxy group-containing surfactant according to claim 5. 7. An emulsifying agent for emulsion polymerization, which comprises the epoxy group-containing surfactant according to claim 5. 8. A surfactant for an aqueous urethane resin, which comprises the epoxy group-containing surfactant according to claim 5.