CN116457386A

CN116457386A - Modified epoxy resin, modified epoxy resin dispersion containing the modified epoxy resin, and method for producing modified epoxy resin

Info

Publication number: CN116457386A
Application number: CN202180079260.0A
Authority: CN
Inventors: 远藤弘隆; 伊本刚
Original assignee: Adeka Corp
Current assignee: Adeka Corp
Priority date: 2020-11-30
Filing date: 2021-11-25
Publication date: 2023-07-18
Also published as: WO2022114056A1; JPWO2022114056A1

Abstract

The invention provides a modified epoxy resin and a manufacturing method thereof, wherein the modified epoxy resin is obtained by the following steps: an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq is reacted with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate, a cationic group-introducing agent (c-1) having a molecular weight of less than 300 or an anionic group-introducing agent (c-2) having a molecular weight of less than 300 is reacted with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate, and the obtained ionized modified epoxy resin intermediate is neutralized with an anionic compound (d-1) having a molecular weight of less than 300 or a cationic compound (d-2) having a molecular weight of less than 300.

Description

Modified epoxy resin, modified epoxy resin dispersion containing the modified epoxy resin, and method for producing modified epoxy resin

Technical Field

The present invention relates to a modified epoxy resin excellent in self-emulsifying property, corrosion resistance, water resistance, blocking resistance and other properties, and a modified epoxy resin dispersion.

Background

Epoxy resins are excellent in adhesion to various substrates, heat resistance, chemical resistance, electrical characteristics, mechanical characteristics, and the like, and therefore are widely used particularly as coating materials, adhesives, fiber treatment agents, and the like. In the case of using an epoxy resin for the above-mentioned applications, the epoxy resin is usually dissolved in various low boiling point solvents (also referred to as "solvent type") for easy handling. However, the use of low boiling point solvents has been limited in view of the problems such as the risk of fire, the harm to the human body, and the adverse effect on the global environment, and in recent years, aqueous epoxy resins in which an epoxy resin is emulsified in water have been developed.

As a method of emulsifying an epoxy resin, there are roughly classified: a method of using a non-reactive surfactant, a method of using a reactive surfactant, and a method of making an epoxy resin itself self-emulsifiable by introducing a hydrophilic group into the epoxy resin. Among them, the method of using a non-reactive surfactant is a method of emulsifying an epoxy resin with a surfactant having no reactive group that reacts with an epoxy group or an amino group, so-called a non-reactive surfactant. As the non-reactive surfactant, a nonionic surfactant such as a polyethylene oxide adduct of nonylphenol, a polyethylene oxide adduct of octylphenol, or a polyethylene oxide adduct of polypropylene glycol can be used. However, aqueous epoxy resins using these surfactants do not sufficiently satisfy the stability as an emulsion. In addition, when such an aqueous epoxy resin is used for a coating material or the like, the adhesion between the coating film and the substrate and the water resistance of the coating film are insufficient. The reason for this is considered that the surfactant used for emulsification remains in the resin in a free state even after the epoxy resin is cured.

The method of using a reactive surfactant aims at reducing the amount of surfactant remaining in a free state in the cured epoxy resin by using a surfactant reactive with the epoxy resin or its curing agent, so-called a reactive surfactant. For example, patent document 1 discloses a reactive surfactant having a phenolic hydroxyl group at the end, which is obtained by reacting polyether glycol, diisocyanate, and dihydric phenol, and patent document 2 discloses a reactive surfactant containing a terminal glycidyl ether such as alkylphenol ethoxylate or polypropylene glycol ethoxylate. However, when the aqueous 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 insufficient.

In the method of introducing a hydrophilic group into an epoxy resin to make the epoxy resin itself self-emulsifiable, the epoxy resin itself self-emulsifiable is not required, and therefore, when the epoxy resin is used as a coating material, the adhesion between a coating film and a substrate and the water resistance of the coating film are improved. Patent document 4 discloses a self-emulsifying epoxy resin obtained by reacting a diglycidyl ether of a dihydric phenol, a polyoxyalkylene glycol, and an alkylphenol-formaldehyde novolac resin. However, these have problems such as insufficient emulsifying properties and low film strength of the cured product, and also have problems such as low curing speed of the cured product.

Patent documents 5 and 6 disclose self-emulsifiable epoxy resins obtained by reacting a specific secondary amino group-containing polyether compound obtained by converting a terminal hydroxyl group of a polyether monol compound into an amino group with an epoxy resin. However, the conversion of an alcoholic hydroxyl group into an amino group is limited to a secondary hydroxyl group or a tertiary hydroxyl group, and therefore the steric hindrance of the amino group of the obtained polyether monol compound becomes high, the reactivity with an epoxy resin is low, and it is necessary to react it at a high temperature. Further, the secondary amino group of the polyether monol compound can react with two epoxy groups, but the steric hindrance of the imino group generated by the reaction of one epoxy group with the secondary amino group becomes further high, and the second epoxy group is very difficult to react, so that the reaction with the epoxy resin may not be sufficiently performed even if it is caused to react at a high temperature, and in the case of using as a coating material, the adhesion with a substrate and the water resistance are insufficient. In addition, in the reaction product of the polyether monol compound and the epoxy resin, the emulsion stability is still insufficient.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 59-98125

Patent document 2: japanese patent laid-open No. 7-256845

Patent document 3: japanese patent laid-open No. 7-206982

Patent document 4: japanese patent laid-open No. 61-243822

Patent document 5: japanese patent publication No. 63-20448

Patent document 6: japanese patent laid-open No. 9-507873

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a modified epoxy resin and a modified epoxy resin dispersion liquid, each of which has excellent self-emulsifying properties, corrosion resistance, water resistance, blocking resistance and other properties.

Solution for solving the problem

Accordingly, the present inventors have conducted intensive studies and have found a modified epoxy resin excellent in self-emulsifying property, corrosion resistance, water resistance, blocking resistance and other properties, and have completed the present invention. Namely, the present invention is a modified epoxy resin obtained by: an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq is reacted with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate, a cationic group-introducing agent (c-1) having a molecular weight of less than 300 or an anionic group-introducing agent (c-2) having a molecular weight of less than 300 is reacted with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate, and the obtained ionized modified epoxy resin intermediate is neutralized with an anionic compound (d-1) having a molecular weight of less than 300 or a cationic compound (d-2) having a molecular weight of less than 300.

Effects of the invention

The modified epoxy resin of the present invention is excellent in self-emulsifying property, and the modified epoxy resin dispersion can provide a product excellent in various properties such as corrosion resistance, water resistance, and blocking resistance.

Detailed Description

< modified epoxy resin intermediate >

In the present invention, the modified epoxy resin intermediate is a modified epoxy resin intermediate obtained by reacting an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq with an amine compound (b) of at least one selected from the group consisting of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more.

The epoxy resin (a) which can be used in the present invention is an epoxy resin having an epoxy equivalent of 600g/eq to 6000 g/eq. The epoxy resin is not particularly limited as long as it has at least one epoxy group in the molecule and has an epoxy equivalent of 600g/eq to 6000g/eq, and examples thereof include: bisphenol type epoxy resins such as bisphenol a type epoxy resins and bisphenol F type epoxy resins; biphenyl type epoxy resins such as biphenyl type epoxy resin and tetramethyl biphenyl type epoxy resin; dicyclopentadiene type epoxy resins; naphthalene type epoxy resin; alicyclic epoxy resins obtained from cyclohexanedimethanol, hydrogenated bisphenol a, and the like; novolac type epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol a novolac type epoxy resins, epoxides which are condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, and biphenyl novolac type epoxy resins; triphenylmethane type epoxy resin; tetraphenylethane type epoxy resin; dicyclopentadiene-phenol addition reaction type epoxy resins; phenol aralkyl type epoxy resins, and the like. These compounds may be used alone or in combination of two or more. In the present invention, the epoxy equivalent is according to JIS K7236: 2009.

The number of epoxy groups contained in the epoxy resin (a) is not limited as long as the effect of the present invention is exhibited, and the number of epoxy groups contained in one molecule of the epoxy resin is 1 to 10, preferably 2 to 6, more preferably 2 to 4, and most preferably 2.

Among these, from the viewpoint of the effect of the present invention, at least one epoxy resin selected from the group consisting of bisphenol-type epoxy resins, biphenyl-type epoxy resins, and alicyclic epoxy resins is preferably used, the epoxy equivalent of which is 600g/eq to 6000g/eq, more preferably bisphenol-type epoxy resins having an epoxy equivalent of 600g/eq to 6000g/eq, and even more preferably bisphenol-a-type epoxy resins having an epoxy equivalent of 600g/eq to 6000 g/eq.

From the viewpoint of each characteristic of the obtained modified epoxy resin, it is preferable to use an epoxy resin having an epoxy equivalent of 700 or more, more preferably an epoxy resin having an epoxy equivalent of 900 or more, still more preferably an epoxy resin having an epoxy equivalent of 1200 or more, and particularly preferably an epoxy resin having an epoxy equivalent of 1600 or more as the epoxy resin (a). From the viewpoints of self-emulsifying properties and various characteristics of the obtained modified epoxy resin, it is preferable to use an epoxy resin having an epoxy equivalent of 5000 or less, more preferably an epoxy resin having an epoxy equivalent of 4000 or less, still more preferably an epoxy resin having an epoxy equivalent of 3000 or less, and still more preferably an epoxy resin having an epoxy equivalent of 2000 or less.

More specifically, as the epoxy resin (a), a bisphenol A type epoxy resin having an epoxy equivalent of 700g/eq to 5000g/eq is preferably used, a bisphenol A type epoxy resin having an epoxy equivalent of 900g/eq to 5000g/eq is more preferably used, a bisphenol A type epoxy resin having an epoxy equivalent of 900g/eq to 3000g/eq is more preferably used, a bisphenol A type epoxy resin having an epoxy equivalent of 1200g/eq to 3000g/eq is still more preferably used, a bisphenol A type epoxy resin having an epoxy equivalent of 1600g/eq to 3000g/eq is still more preferably used, and a bisphenol A type epoxy resin having an epoxy equivalent of 1600g/eq to 2000g/eq is most preferably used.

The amine compound (b) which can be used in the present invention is at least one amine compound selected from the group consisting of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more. Examples of the primary amine compound having a molecular weight of 300 or more include: aliphatic amines having a molecular weight of 300 or more and having a primary amino group in the molecule, aromatic amines having a molecular weight of 300 or more and having a primary amino group in the molecule, heterocyclic amines having a molecular weight of 300 or more and having a primary amino group in the molecule, alkanolamines having a molecular weight of 300 or more and having a primary amino group in the molecule, etheramines having a molecular weight of 300 or more and having a primary amino group in the molecule, polyetherpolyamines having a molecular weight of 300 or more and having a primary amino group in the molecule, polyamidoamines having a molecular weight of 300 or more and having a primary amino group in the molecule, amino acid derivatives having a molecular weight of 300 or more and having a primary amino group in the molecule, and these primary amine compounds may have two or more primary amino groups in the molecule, and may further contain secondary amino groups and tertiary amino groups in the molecule. Examples of the secondary amine compound having a molecular weight of 300 or more include: aliphatic amines having a molecular weight of 300 or more and having a secondary amino group in the molecule, aromatic amines having a molecular weight of 300 or more and having a secondary amino group in the molecule, heterocyclic amines having a molecular weight of 300 or more and having a secondary amino group in the molecule, alkanolamines having a molecular weight of 300 or more and having a secondary amino group in the molecule, etheramines having a molecular weight of 300 or more and having a secondary amino group in the molecule, polyetherpolyamines having a molecular weight of 300 or more and having a secondary amino group in the molecule, polyamidoamines having a molecular weight of 300 or more and having a secondary amino group in the molecule, amino acid derivatives having a molecular weight of 300 or more and having a secondary amino group in the molecule, and these secondary amine compounds may have two or more secondary amino groups in the molecule or may further have tertiary amino groups in the molecule. The upper limit of the molecular weight of the amine compound is not particularly limited, but from the viewpoint of the effect of the present invention, the molecular weight of the amine compound is preferably 100000 or less, more preferably 10000 or less, and even more preferably 6000 or less.

The amine compound (b) may be composed of only one or two or more primary amine compounds having a molecular weight of 300 or more, may be composed of only one or two or more secondary amine compounds having a molecular weight of 300 or more, or may be composed of one or two or more primary amine compounds having a molecular weight of 300 or more and one or two or more secondary amine compounds having a molecular weight of 300 or more. In the present invention, the use of such an amine compound as the amine compound (b) can improve the self-emulsifying property and various characteristics of the resulting modified epoxy resin.

In the present invention, from the viewpoint of properly controlling the hydrophobicity and hydrophilicity of the resulting modified epoxy resin and improving the self-emulsifying property and various characteristics of the modified epoxy resin, it is preferable to use an amine compound containing a polyether amine compound having a molecular weight of 300 or more having a primary amino group in the molecule as the amine compound (b). The amine compound including a polyether amine compound having a molecular weight of 300 or more and a primary amino group in the molecule is not particularly limited as long as it is a compound having a primary amino group and a polyether moiety in the molecule. Among such compounds, polyether amine compounds having a molecular weight of 300 or more, represented by the following general formula (1), can be preferably used.

Wherein X represents a hydrogen atom, an amino group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms in which one hydrogen atom is substituted with an amino group, a, b, and c represent average molar values of addition of the respective unit cells, and each independently represents a number of 0 to 100, and the arrangement of the respective unit cells may be either a block form or a random form.

In the general formula (1), X represents a hydrogen atom, an amino group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms in which one hydrogen atom is substituted with an amino group. From the viewpoint of self-emulsifying properties of the resulting modified epoxy resin, X is preferably an amino group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms in which one hydrogen atom is substituted with an amino group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

In the general formula (1), a represents a number of 0 to 100. From the viewpoints of self-emulsifying property and respective characteristics of the obtained modified epoxy resin, a is preferably a number of 1 to 100, more preferably a number of 1 to 70, and still more preferably a number of 10 to 60.

In the general formula (1), b represents a number of 0 to 100. From the viewpoints of self-emulsifying property and respective characteristics of the obtained modified epoxy resin, b is preferably a number of 1 to 100, more preferably a number of 1 to 50, still more preferably a number of 1 to 20, and still more preferably a number of 1 to 10.

In the general formula (1), c represents a number of 0 to 100. From the viewpoints of self-emulsifying property and various characteristics of the obtained modified epoxy resin, c is preferably a number of 0 to 50, more preferably a number of 0 to 30, and still more preferably 0.

In the general formula (1), the total value of a, b, and c is not particularly limited, but from the viewpoints of self-emulsifying property and respective characteristics of the obtained modified epoxy resin, the total value of a, b, and c is preferably 10 to 200, more preferably 10 to 100, and even more preferably 15 to 70.

In the present invention, from the viewpoints of self-emulsifying property and various characteristics of the obtained modified epoxy resin, a polyether amine compound having a number of 1 to 100, b number of 1 to 100 and c number of 0 in the general formula (1) is preferably used. In this case, from the viewpoints of self-emulsifying property and various characteristics of the obtained modified epoxy resin, a polyether amine compound having a number of 1 to 70, b number of 1 to 50, and a total value of a and b of 10 to 80 is preferably used, and a polyether amine compound having a number of 10 to 60, b number of 1 to 20, and a total value of a and b of 15 to 75 is more preferably used.

The weight average molecular weight of the polyether amine compound represented by the general formula (1) is not particularly limited as long as the effect of the present invention is exhibited, and is preferably 400 to 8000, more preferably 600 to 6000, still more preferably 800 to 4000, and still more preferably 1000 to 3100.

The method for measuring the weight average molecular weight may be a method of measuring the weight average molecular weight by GPC (Gel Permeation Chromatography: gel permeation chromatography) in terms of standard polystyrene. In the case of using a commercially available product, the catalog value may be referred to.

The polyether amine compound represented by the general formula (1) and having a molecular weight of 300 or more may be produced by a known method or may be commercially available. Examples of such commercial products include: huntsman Corporation JEFFAMINE (registered trademark) M-600, JEFFAMINE (registered trademark) M-1000, JEFFAMINE (registered trademark) M-2005, JEFFAMINE (registered trademark) M-2070, JEFFAMINE (registered trademark) M-3085, etc.), JEFFAMINE (registered trademark) D-400, JEFFAMINE (registered trademark) D-2000, JEFFAMINE (registered trademark) D-3000, etc.), JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, etc.), PEGylamine M-1000, CAM-2005, CAM-2070, etc. manufactured by Yangzhou morning new material company, polyether amine D (CAD-400, CAD-2000, etc.), polyether amine (CAD-600, CAED-2003, CAED-900, etc.), CAED-1200, etc.

Among these, JEFFAMINE (registered trademark) M-1000 (in the general formula (1), X is methyl, a has a value (average value) of 19, b has a value (average value) of 3, c has a value of 0, a polyether amine compound having a weight average molecular weight of 1041) and JEFFAMINE (registered trademark) M-3085 (in the general formula (1), X is methyl, a has a value (average value) of 58, b has a value (average value) of 8,c of 0, a polyether amine compound having a weight average molecular weight of 3047) are preferably used, and JEFFAMINE (registered trademark) M-3085 is more preferably used.

In the present invention, the modified epoxy resin intermediate is a modified epoxy resin intermediate obtained by reacting an epoxy resin (a) with an amine compound (b), the amount and ratio of the epoxy resin (a) and the amine compound (b) used are not particularly limited, and from the viewpoints of self-emulsifying properties and respective characteristics of the obtained modified epoxy resin, the modified epoxy resin intermediate is preferably a modified epoxy resin intermediate obtained by reacting the epoxy resin (a) and the amine compound (b) in an amount of 0.01 to 0.95 mole relative to 1 mole of the epoxy groups in the epoxy resin (a) with respect to 1 mole of the amino groups in the amine compound (b). Since the modified epoxy resin intermediate used in the present invention has an unreacted epoxy group by using the modified epoxy resin intermediate obtained as described above, a modified epoxy resin excellent in self-emulsifying property and various characteristics can be obtained by a method described later. From the viewpoint of further excellent self-emulsifying properties, improving properties such as corrosion resistance, water resistance, and blocking resistance, the modified epoxy resin intermediate is more preferably a modified epoxy resin intermediate obtained by reacting the epoxy resin (a) with the amine compound (b) in an amount of 0.05 to 0.90 mole relative to 1 mole of the amino groups in the amine compound (b) with respect to 1 mole of the epoxy groups in the epoxy resin (a), and even more preferably a modified epoxy resin intermediate obtained by reacting the amino groups in the amine compound (b) with respect to 1 mole of the epoxy groups in the epoxy resin (a) in an amount of 0.10 to 0.80 mole, and particularly preferably a modified epoxy resin intermediate obtained by reacting the amino groups in the amine compound (b) with respect to 1 mole of the epoxy groups in the epoxy resin (a) with respect to 0.15 to 0.70 mole. The modified epoxy resin intermediate has a structure in which an epoxy group in the epoxy resin (a) as a raw material reacts with an amino group in the amine compound (b), but the structure differs depending on the number and amount of epoxy groups or amino groups of the epoxy resin (a) and the amine compound (b) used, so that it is not practical to specifically show the structure of the modified epoxy resin intermediate.

In the present invention, the method of reacting the epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq with the amine compound (b) of at least one selected from the group consisting of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more is not particularly limited, and the reaction can be carried out by a known method. Examples of such a method include: and a method in which the epoxy resin (a) and the amine compound (b) are reacted under reduced pressure, normal pressure or elevated pressure at a temperature of from room temperature to 180 ℃ for 1 hour to 10 hours. In this reaction, the epoxy resin (a) and the amine compound (b) may be used in the whole amount at one time or may be used in multiple times.

The reaction of the epoxy resin (a) with the amine compound (b) may be performed in a solvent which does not react with the epoxy resin (a) and the amine compound (b). Examples of the solvent that can be used in the present reaction include: hydrocarbon solvents such as hexane, cyclohexane, toluene, and xylene; ethyl acetate, butyl acetate, methyl branched butyl ketone, branched propyl myristate, triglycerides and other ester solvents. The amount of the solvent used in the case of using the solvent is not particularly limited, but from the viewpoints of self-emulsifying property and various characteristics of the obtained modified epoxy resin, the amount of the solvent used is preferably 5 to 95% by mass, more preferably 10 to 60% by mass, relative to the whole system. In the case where the solvent is used for the reaction between the epoxy resin (a) and the amine compound (b), the solvent may be removed after the reaction, or the solvent may be used continuously in the step of obtaining the ionization-modified epoxy resin intermediate.

The reaction of the epoxy resin (a) and the amine compound (b) may be carried out using a catalyst. Examples of the catalyst that can be used in the present reaction include: phosphines such as triphenylphosphine; phosphonium salts such as tetraphenyl phosphonium bromide; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, and imidazolylsilane; imidazole salts as salts of the above imidazoles with trimellitic acid, isocyanuric acid, boron and the like; amines such as benzyl dimethylamine and 2,4, 6-tris (dimethylaminomethyl) phenol; quaternary ammonium salts such as trimethylammonium chloride; ureas such as 3-p-chlorophenyl-1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3-phenyl-1, 1-dimethylurea, isophorone diisocyanate-dimethylurea, toluene diisocyanate-dimethylurea, and the like; and complexes of boron trifluoride with amines, ether compounds and the like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used in the case of using the catalyst is not particularly limited, and may be, for example, about 0.01 to 1% by mass relative to the whole system.

Ionization modified epoxy resin intermediate

In the present invention, the ionizing, modified epoxy resin intermediate is an ionizing, modified epoxy resin intermediate obtained by reacting a cationic group-introducing agent (c-1) having a molecular weight of less than 300 or an anionic group-introducing agent (c-2) having a molecular weight of less than 300 with the above-mentioned modified epoxy resin intermediate.

The cationic group-introducing agent (c-1) having a molecular weight of less than 300 which can be used in the present invention is not particularly limited as long as it is a compound having a group in the molecule which forms a cationic group by protonation, and examples thereof include: a compound having a molecular weight of less than 300 having a primary amino group in the molecule, a compound having a molecular weight of less than 300 having a secondary amino group in the molecule, a compound having a tertiary amino group in the molecule, a compound having a molecular weight of less than 300 having a cyclic amino group in the molecule, a compound having a molecular weight of less than 300 having a hydrazine group in the molecule, a compound having an ammonium group in the molecule, and a compound having a molecular weight of less than 300. Examples of such a compound include: monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, dimethylaminoethanol, diglycolamine, 2-amino-2-methyl-1-propanol, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylpiperazine, morpholine, aminopropylmorpholine, dimethylaminopropylamine, diisobutylamine, N-methylhexylamine, benzylamine, dibenzylamine, N-methylbenzylamine, aniline, N-ethylaniline, diphenylamine, diethylhydroxylamine, monoethylamine, diethylamine, triethylamine, dipropylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine, tributylamine, pentylamine, neopentylamine, hexylamine, ethylbutylamine, dihexylamine, dicyclohexylamine, aminoethoxysilane, piperidine, piperazine, 2- (2-aminoethylamino) ethanol, oleylamine, di-2-ethylhexyl amine, furfuryl amine, and the like.

From the viewpoint of self-emulsifying properties of the resulting modified epoxy resin, the cationic group-introducing agent (c-1) preferably contains at least one compound selected from the group consisting of a compound having a primary amino group in the molecule of less than 300 and a compound having a secondary amino group in the molecule of less than 300, more preferably contains at least one compound selected from the group consisting of monoethanolamine, diethanolamine, diisopropanolamine, N-methylethanolamine, morpholine, diisobutylamine, N-methylhexylamine, benzylamine, N-methylbenzylamine, dipropylamine, diisopropylamine, dibutylamine, dicyclohexylamine, and 2-ethylhexylamine, still more preferably contains at least one selected from the group consisting of monoethanolamine, diethanolamine, 2-ethylhexylamine, benzylamine, dicyclohexylamine, N-methylbenzylamine, and dibutylamine.

The lower limit of the molecular weight of the cationic group-introducing agent (c-1) is not particularly limited, and the cationic group-introducing agent (c-1) preferably has a molecular weight of 50 or more, more preferably 60 or more.

The anionic group-introducing agent (c-2) having a molecular weight of less than 300 which can be used in the present invention is not particularly limited as long as it is a compound having a group in the molecule which forms an anionic group by deprotonation, and examples thereof include: a compound having a carboxyl group in a molecule and a molecular weight of less than 300, a compound having a sulfonyl group in a molecule and a molecular weight of less than 300, a compound having a phosphate group in a molecule and a molecular weight of less than 300, and the like. Among these, from the viewpoint of self-emulsifying properties of the resulting modified epoxy resin, the anionic group-introducing agent (c-2) preferably contains at least one selected from the group consisting of phosphoric acid, acetic acid, lactic acid, boric acid, and formic acid, a compound having a molecular weight of less than 300 having a carboxyl group in a molecule, a compound having a molecular weight of less than 300 having a boric acid group in a molecule, or a compound having a molecular weight of less than 300 having a phosphoric acid group in a molecule, and more preferably contains at least one selected from the group consisting of phosphoric acid, acetic acid, and lactic acid.

The lower limit of the molecular weight of the anionic group-introducing agent (c-2) is not particularly limited, and the anionic group-introducing agent (c-2) preferably has a molecular weight of 40 or more, more preferably 45 or more.

In the present invention, the method of reacting the modified epoxy resin intermediate with the cationic group-introducing agent (c-1) having a molecular weight of less than 300 or the anionic group-introducing agent (c-2) having a molecular weight of less than 300 is not particularly limited, and the reaction may be carried out by a known method. Examples of such a method include: and a method in which the modified epoxy resin intermediate is reacted with the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2) under reduced pressure, normal pressure or elevated pressure at a temperature of from room temperature to 180 ℃ for 1 hour to 10 hours. In the present reaction, the modified epoxy resin intermediate and the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2) may be used in all amounts at once or in multiple times, respectively.

Generally, in the present invention, the modified epoxy resin intermediate is reacted with the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2). Further, it is preferable not to use both the cationic group-introducing agent (c-1) and the anionic group-introducing agent (c-2) at the same time.

The reaction of the modified epoxy resin intermediate with the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2) may be carried out in a solvent which does not react with the modified epoxy resin intermediate, the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2). Examples of the solvent that can be used in the present reaction include: hydrocarbon solvents such as hexane, cyclohexane, toluene, and xylene; ethyl acetate, butyl acetate, methyl branched butyl ketone, branched propyl myristate, triglycerides and other ester solvents. The amount of the solvent used in the case of using the solvent is not particularly limited, but from the viewpoints of self-emulsifying property and various characteristics of the obtained modified epoxy resin, the amount of the solvent used is preferably 5 to 95% by mass, more preferably 10 to 60% by mass, relative to the whole system. In the case where a solvent is used for the reaction of the modified epoxy resin intermediate with the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2), the solvent may be removed after the reaction or may be used continuously as a solvent in the step of obtaining the modified epoxy resin.

In addition, the reaction of the modified epoxy resin intermediate with the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2) may be carried out using a catalyst. Examples of the catalyst that can be used in the present reaction include: phosphines such as triphenylphosphine; phosphonium salts such as tetraphenyl phosphonium bromide; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, and imidazolylsilane; imidazole salts as salts of the above imidazoles with trimellitic acid, isocyanuric acid, boron and the like; amines such as benzyl dimethylamine and 2,4, 6-tris (dimethylaminomethyl) phenol; quaternary ammonium salts such as trimethylammonium chloride; ureas such as 3-p-chlorophenyl-1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3-phenyl-1, 1-dimethylurea, isophorone diisocyanate-dimethylurea, toluene diisocyanate-dimethylurea, and the like; and complexes of boron trifluoride with amines, ether compounds and the like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used in the case of using the catalyst is not particularly limited, and may be, for example, about 0.01 to 1% by mass relative to the whole system.

In the present invention, the ionizing, modified epoxy resin intermediate is preferably an ionizing, modified epoxy resin intermediate obtained by reacting a modified epoxy resin intermediate with a cationic group-introducing agent (c-1) having a molecular weight of less than 300 or an anionic group-introducing agent (c-2) having a molecular weight of less than 300 in the following amounts: the amount of the cationic groups (groups such as amino groups, hydrazine groups, ammonium groups and the like which form cationic groups by protonation) in the cationic group introducing agent or the anionic groups (groups such as carboxyl groups, sulfonyl groups, phosphate groups and the like which form anionic groups by deprotonation) in the anionic group introducing agent when the amount of the epoxy groups in the modified epoxy resin intermediate (the amount of the epoxy groups in the epoxy resin (a) excluding the epoxy groups which react with the amine compound (b)) is 1 is set to 0.1 to 2.0. By using the ionizing radiation-modified epoxy resin intermediate of the present invention as the ionizing radiation-modified epoxy resin intermediate obtained as described above, a modified epoxy resin excellent in self-emulsifying property and various characteristics can be obtained by a method described later. The ionizing, modified epoxy resin intermediate is more preferably one obtained by reacting the modified epoxy resin intermediate with the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2) in such an amount that the number of cationic groups in the cationic group-introducing agent or the number of anionic groups in the anionic group-introducing agent is 0.2 to 1.5, and even more preferably one obtained by reacting the modified epoxy resin intermediate with the cationic group-introducing agent (c-1) or the anionic group-introducing agent (c-2) in such an amount that the number of epoxy groups in the modified epoxy resin intermediate is 1, and particularly preferably one obtained by reacting the modified epoxy resin intermediate with the cationic group-introducing agent in such an amount that the number of epoxy groups in the modified epoxy resin intermediate is 0.4 to 0.9, from the viewpoint of further excellent self-emulsifying property and improving various properties such as corrosion resistance, water resistance and blocking resistance.

The ionizing, modified epoxy resin intermediate has a structure in which the epoxy groups remaining in the epoxy resin (a) used in the production of the modified epoxy resin intermediate are reacted with the cationic groups of the cationic group introducing agent (c-1) or the anionic groups of the anionic group introducing agent (c-2), but it is not realistic to determine the structure of the modified epoxy resin intermediate and the positions of the epoxy groups in the modified epoxy resin intermediate, and therefore it is not realistic to determine the structure of the ionizing, modified epoxy resin intermediate.

< modified epoxy resin >)

The modified epoxy resin of the present invention is a modified epoxy resin obtained by neutralizing the above-mentioned ionizing modified epoxy resin intermediate with an anionic compound (d-1) having a molecular weight of less than 300 or a cationic compound (d-2) having a molecular weight of less than 300.

In the present invention, "neutralization" means that at least a part or all of the cationic groups derived from the cationic group-introducing agent (c-1) in the above-mentioned ionization-modified epoxy resin intermediate is neutralized by the anionic groups of the above-mentioned anionic compound (d-1), or at least a part or all of the anionic groups derived from the anionic group-introducing agent (c-2) in the above-mentioned ionization-modified epoxy resin intermediate is neutralized by the cationic groups of the above-mentioned cationic compound (d-2).

The anionic compound (d-1) having a molecular weight of less than 300 which can be used in the present invention is not particularly limited as long as it has a group showing an anionic property by deprotonation, and examples thereof include: a compound having a carboxyl group in a molecule and a molecular weight of less than 300, a compound having a sulfonyl group in a molecule and a molecular weight of less than 300, a compound having a phosphate group in a molecule and a molecular weight of less than 300, and the like. From the viewpoint of self-emulsifying properties of the obtained modified epoxy resin, the anionic compound preferably contains a compound having a carboxyl group in a molecule and a molecular weight of less than 300, a compound having a boric acid group in a molecule and a molecular weight of less than 300, or a compound having a phosphoric acid group in a molecule and a molecular weight of less than 300, more preferably contains at least one selected from the group consisting of phosphoric acid, acetic acid, lactic acid, boric acid, and formic acid, and particularly preferably contains at least one selected from the group consisting of phosphoric acid, acetic acid, boric acid, and formic acid.

The lower limit of the molecular weight of the anionic compound (d-1) is not particularly limited, and the anionic compound (d-1) preferably has a molecular weight of 40 or more, more preferably 45 or more.

The cationic compound (d-2) having a molecular weight of less than 300 which can be used in the present invention is not particularly limited as long as it has a group exhibiting cationic property by protonation in the molecule, and examples thereof include: a compound having a molecular weight of less than 300 having a primary amino group in the molecule, a compound having a molecular weight of less than 300 having a secondary amino group in the molecule, a compound having a tertiary amino group in the molecule, a compound having a molecular weight of less than 300 having a cyclic amino group in the molecule, a compound having a molecular weight of less than 300 having a hydrazine group in the molecule, a compound having an ammonium group in the molecule, and the like. Examples of such a compound include: monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, dimethylaminoethanol, diglycolamine, 2-amino-2-methyl-1-propanol, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, aminoethylpiperazine, morpholine, aminopropylmorpholine, dimethylaminopropylamine, diisobutylamine, N-methylhexylamine, benzylamine, dibenzylamine, N-methylbenzylamine, aniline, N-ethylaniline, diphenylamine, diethylhydroxylamine, monoethylamine, diethylamine, triethylamine, dipropylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine, tributylamine, pentylamine, neopentylamine, hexylamine, ethylbutylamine, dihexylamine, dicyclohexylamine, aminoethoxysilane, piperidine, piperazine, 2- (2-aminoethylamino) ethanol, oleylamine, di-2-ethylhexyl amine, furfuryl amine, and the like. From the viewpoint of self-emulsifying properties of the resulting modified epoxy resin, the cationic compound preferably contains at least one compound having a molecular weight of less than 300 and having a primary amino group in the molecule, a compound having a secondary amino group in the molecule and a compound having a molecular weight of less than 300, or a compound having a tertiary amino group in the molecule, more preferably contains at least one selected from the group consisting of monoethanolamine, diethanolamine, diisopropanolamine, N-methylethanolamine, dimethylaminoethanol, morpholine, triethylamine, diisobutylamine, N-methylhexylamine, benzylamine, N-methylbenzylamine, dipropylamine, diisopropylamine, dibutylamine, dicyclohexylamine, and 2-ethylhexylamine, still more preferably contains at least one selected from the group consisting of monoethanolamine, dimethylaminoethanol, triethylamine, diethanolamine, 2-ethylhexylamine, benzylamine, dicyclohexylamine, N-methylbenzylamine, and dibutylamine, and particularly preferably contains at least one selected from the group consisting of dimethylaminoethanol and triethylamine.

The lower limit of the molecular weight of the cationic compound (d-2) is not particularly limited, and the cationic compound (d-2) preferably has a molecular weight of 50 or more, more preferably 60 or more.

The modified epoxy resin of the present invention is a modified epoxy resin obtained by neutralizing an ionized modified epoxy resin intermediate with an anionic compound (d-1) or a cationic compound (d-2), and the amount of the anionic compound (d-1) or the cationic compound (d-2) used is not particularly limited and may be appropriately adjusted. From the viewpoints of self-emulsifying property and various characteristics of the obtained modified epoxy resin, the amount of the anionic compound (d-1) or the cationic compound (d-2) to be used is preferably set to be: the amount of the cationic groups in the cationic group introducing agent (c-1) or the amount of the anionic groups in the anionic group introducing agent (c-2) used for the ionization of the modified epoxy resin intermediate is set to 1, the amount of the anionic groups (groups showing an anionic property by deprotonation) in the anionic compound (d-1) or the amount of the cationic groups (groups showing a cationic property by protonation) in the cationic compound (d-2) is set to 0.3 to 2.0, more preferably to 0.4 to 1.5, still more preferably to 0.5 to 1.2. The modified epoxy resin of the present invention is a modified epoxy resin obtained as described above, and thus a modified epoxy resin excellent in self-emulsifying property and various characteristics can be obtained.

In the case where the ionization-modified epoxy resin intermediate has an epoxy group, at least a part of the anionic compound (d-1) or the cationic compound (d-2) reacts with the epoxy group, and the anionic group or the cationic group may be introduced into the ionization-modified epoxy resin intermediate. However, in the present invention, a compound for neutralizing a cationic group or an anionic group of the ionization-modified epoxy resin intermediate is defined as an anionic compound (d-1) or a cationic compound (d-2), respectively.

The modified epoxy resin has a structure in which the cationic group or the anionic group in the intermediate of the ionizing modified epoxy resin is neutralized with the anionic group in the anionic compound (d-1) or the cationic group in the cationic compound (d-2), but it is not realistic to determine the structure of the intermediate of the ionizing modified epoxy resin and the position of the cationic group or the anionic group in the intermediate of the ionizing modified epoxy resin, and thus it is not realistic to determine the structure of the intermediate of the modified epoxy resin.

When the ionizing, modified epoxy resin intermediate obtained by using the cationic group-introducing agent (c-1) is neutralized with the anionic compound (d-1), it is preferable that a compound corresponding to the cationic compound (d-2) is not added. In the case of neutralizing the ionization-modified epoxy resin intermediate obtained by using the anionic group-introducing agent (c-2) with the cationic compound (d-2), it is preferable that the compound corresponding to the anionic compound (d-1) is not added.

In the present invention, the method for neutralizing the ionization-modified epoxy resin intermediate with the anionic compound (d-1) or the cationic compound (d-2) is not particularly limited, and the reaction can be carried out by a known method. Examples of such a method include: and a method in which the ionizing, modified epoxy resin intermediate is reacted with the anionic compound (d-1) or the cationic compound (d-2) under reduced pressure, normal pressure or elevated pressure at a temperature of from room temperature to 180℃for 1 hour to 10 hours. In this reaction, the ionizing, modified epoxy resin intermediate and the anionic compound (d-1) or the cationic compound (d-2) may be used in a single-use or multiple-use amount.

The step of neutralizing the ionization-modified epoxy resin intermediate with the anionic compound (d-1) or the cationic compound (d-2) may be performed in a solvent which does not react with the ionization-modified epoxy resin intermediate, the anionic compound, or the cationic compound. Examples of the solvent that can be used in the present neutralization step include: hydrocarbon solvents such as hexane, cyclohexane, toluene, and xylene; ethyl acetate, butyl acetate, methyl branched butyl ketone, branched propyl myristate, triglycerides and other ester solvents. The amount of the solvent used in the case of using the solvent is not particularly limited, but the amount of the solvent used is preferably 5 to 95% by mass, more preferably 10 to 60% by mass, based on the whole system. In the case where a solvent is used for the reaction of the epoxy resin (a) and the amine compound (b), the solvent may be removed after the reaction, or may be used as a solvent for the modified epoxy resin dispersion.

More specifically, the modified epoxy resin of the present invention is a modified epoxy resin as follows: an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq is reacted with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate, and a cationic group introducing agent (c-1) having a molecular weight of less than 300 is reacted with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate, and the obtained ionized modified epoxy resin intermediate is neutralized with an anionic compound (d-1) having a molecular weight of less than 300 to obtain a modified epoxy resin, or the modified epoxy resin of the present invention is a modified epoxy resin as follows: an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq is reacted with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate, an anionic group-introducing agent (c-2) having a molecular weight of less than 300 is reacted with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate, and the obtained ionized modified epoxy resin intermediate is neutralized with a cationic compound (d-2) having a molecular weight of less than 300 to obtain a modified epoxy resin.

Wherein an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq is reacted with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate, a cationic group introducing agent (c-1) having a molecular weight of less than 300 is reacted with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate, and the obtained ionized modified epoxy resin intermediate is neutralized with an anionic compound (d-1) having a molecular weight of less than 300 to obtain a modified epoxy resin, and when the modified epoxy resin of the present invention is the modified epoxy resin, the epoxy resin (a), the amine compound (b), and the cationic group introducing agent (c-1) can be simultaneously reacted to obtain an ionized modified epoxy resin intermediate. In this case, in terms of the amounts of the epoxy resin (a), the amine-based compound (b), and the cationic group-introducing agent (c-1) to be used, from the viewpoints of self-emulsifying property and various characteristics of the modified epoxy resin obtained, it is preferable that the amount of the amine-based compound (b) is an amount in which the amino group in the amine-based compound (b) is 0.01 to 0.95 mole relative to 1 mole of the epoxy group in the epoxy resin (a), and the amount of the cationic group-introducing agent (c-1) is an amount in which the amount of the cationic group-introducing agent (c-1) is 0.01 to 0.95 when the number of the epoxy groups in the epoxy resin (a) is 1. The amount of the amine compound (b) is more preferably an amount of 0.05 to 0.80 mole based on 1 mole of the epoxy groups in the epoxy resin (a), still more preferably an amount of 0.10 to 0.60 mole based on 1 mole of the epoxy groups in the epoxy resin (a), and particularly preferably an amount of 0.15 to 0.50 mole based on 1 mole of the epoxy groups in the epoxy resin (a), from the viewpoint of obtaining a modified epoxy resin having more excellent self-emulsifying properties, improving corrosion resistance, water resistance, blocking resistance, and the like. In addition, from the viewpoint of obtaining a modified epoxy resin having more excellent self-emulsifying properties and improved properties such as corrosion resistance, water resistance, blocking resistance, etc., the amount of the cationic group-introducing agent (c-1) is more preferably an amount in which the number of cationic groups of the cationic group-introducing agent (c-1) is 0.2 to 0.9, still more preferably an amount in which the number of cationic groups of the cationic group-introducing agent (c-1) is 0.3 to 0.85, and particularly preferably an amount in which the number of cationic groups of the cationic group-introducing agent (c-1) is 0.5 to 0.85, when the number of epoxy groups in the epoxy resin (a) is 1.

Method for producing modified epoxy resin

The method for producing a modified epoxy resin of the present invention is a method for producing a modified epoxy resin comprising the steps of: a step of reacting an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate; a step of reacting a cationic group-introducing agent (c-1) having a molecular weight of less than 300 or an anionic group-introducing agent (c-2) having a molecular weight of less than 300 with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate; and a step of neutralizing the resulting ionization-modified epoxy resin intermediate with an anionic compound (d-1) having a molecular weight of less than 300 or a cationic compound (d-2) having a molecular weight of less than 300. In this case, the epoxy resin (a), the amine-based compound (b), the cationic group-introducing agent (c-1), the anionic group-introducing agent (c-2), the anionic compound (d-1) and the cationic compound (d-2) used in the present production method may be the aforementioned compounds, respectively. The step of obtaining the modified epoxy resin intermediate, the step of obtaining the ionized modified epoxy resin intermediate, and the step of neutralizing the ionized modified epoxy resin intermediate may be performed by the methods described above.

More specifically, the method for producing a modified epoxy resin of the present invention comprises the steps of: a step of reacting an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate; a step of reacting a cationic group-introducing agent (c-1) having a molecular weight of less than 300 with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate; and a step of neutralizing the resulting ionized modified epoxy resin intermediate with an anionic compound (d-1) having a molecular weight of less than 300, or the method for producing a modified epoxy resin of the present invention is a method comprising the steps of: a step of reacting an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate; a step of reacting an anionic group-introducing agent (c-2) having a molecular weight of less than 300 with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate; and a step of neutralizing the obtained ionization-modified epoxy resin intermediate with a cationic compound (d-2) having a molecular weight of less than 300.

The method for manufacturing the modified epoxy resin comprises the following steps: a step of reacting an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq with an amine compound (b) selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate; a step of reacting a cationic group-introducing agent (c-1) having a molecular weight of less than 300 with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate; and a step of neutralizing the obtained intermediate of the ionized modified epoxy resin with an anionic compound (d-1) having a molecular weight of less than 300, wherein in the case where the method for producing a modified epoxy resin of the present invention is the method for producing a modified epoxy resin described above, a step of reacting an amine-based compound (b) and a cationic group-introducing agent (c-1) with an epoxy resin (a) to obtain an intermediate of the ionized modified epoxy resin may be used instead of the step of reacting an epoxy resin (a) with an amine-based compound (b) to obtain an intermediate of the modified epoxy resin and the step of reacting a cationic group-introducing agent (c-1) with the obtained intermediate of the modified epoxy resin to obtain an intermediate of the ionized modified epoxy resin. In this case, in terms of the amounts of the epoxy resin (a), the amine-based compound (b), and the cationic group-introducing agent (c-1) to be used, from the viewpoints of self-emulsifying property and various characteristics of the modified epoxy resin obtained, it is preferable that the amount of the amine-based compound (b) is an amount in which the amino group in the amine-based compound (b) is 0.01 to 0.95 mole relative to 1 mole of the epoxy group in the epoxy resin (a), and the amount of the cationic group-introducing agent (c-1) is an amount in which the amount of the cationic group-introducing agent (c-1) is 0.01 to 0.95 when the number of the epoxy groups in the epoxy resin (a) is 1. The amount of the amine compound (b) is more preferably an amount of 0.05 to 0.90 mole based on 1 mole of the epoxy groups in the epoxy resin (a), still more preferably an amount of 0.10 to 0.80 mole based on 1 mole of the epoxy groups in the epoxy resin (a), and particularly preferably an amount of 0.15 to 0.70 mole based on 1 mole of the epoxy groups in the epoxy resin (a), from the viewpoint of obtaining a modified epoxy resin having more excellent self-emulsifying properties, improving corrosion resistance, water resistance, blocking resistance, and the like. In addition, from the viewpoint of obtaining a modified epoxy resin having more excellent self-emulsifying properties and improved properties such as corrosion resistance, water resistance, blocking resistance, etc., the amount of the cationic group-introducing agent (c-1) is more preferably an amount such that the number of cationic groups of the cationic group-introducing agent (c-1) is 0.2 to 0.9, still more preferably an amount such that the number of cationic groups of the cationic group-introducing agent (c-1) is 0.3 to 0.85, and particularly preferably an amount such that the number of cationic groups of the cationic group-introducing agent (c-1) is 0.5 to 0.85, when the number of epoxy groups in the epoxy resin (a) is 1.

The modified epoxy resin of the present invention can be used for various products to which epoxy resin is generally applied, and is not particularly limited, and for example, can be used for: paints, coating agents, sealants, adhesives, binders, fiber bundles, building materials, electronic parts and the like. Among these, a paint or coating agent for concrete, cement, mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, or the like is preferable.

< modified epoxy resin Dispersion >

The modified epoxy resin dispersion of the present invention is a modified epoxy resin dispersion containing the modified epoxy resin and water. The content of water in the modified epoxy resin dispersion of the present invention is not particularly limited, but from the viewpoint of the effect of the present invention, the content of water in the modified epoxy resin dispersion is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, and even more preferably 40 to 80% by mass, relative to the total amount of the modified epoxy resin dispersion. The content of the modified epoxy resin in the modified epoxy resin dispersion of the present invention is not particularly limited, but from the viewpoints of various characteristics such as emulsion stability, corrosion resistance, water resistance, and blocking resistance of the obtained modified epoxy resin dispersion, the content of the modified epoxy resin in the modified epoxy resin dispersion is preferably 0.1 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 3 to 40% by mass, relative to the total amount of the modified epoxy resin dispersion.

The modified epoxy resin dispersion of the present invention may further contain at least one organic solvent. Examples of such an organic solvent include: 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; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and tetrahydrofuran; esters of glycol ethers such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; carbonates such as ethylene carbonate and propylene carbonate; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, isooctane, decane, dodecane, etc.; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, and the like; n, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, terpenes and the like. From the viewpoints of stability and various characteristics of the modified epoxy resin dispersion liquid, the modified epoxy resin dispersion liquid of the present invention preferably contains an organic solvent selected from at least one of the group consisting of propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, ethylene glycol monobutyl ether, N-ethyl pyrrolidone, and isopropyl alcohol, more preferably contains an organic solvent selected from at least one of the group consisting of propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and ethylene glycol monobutyl ether, and still more preferably contains an organic solvent selected from at least one of the group consisting of propylene glycol monomethyl ether, diethylene glycol dimethyl ether, and ethylene glycol monobutyl ether.

When the modified epoxy resin dispersion of the present invention contains at least one organic solvent, the content of the organic solvent in the modified epoxy resin dispersion is not particularly limited, but from the viewpoints of the emulsion stability and various characteristics of the modified epoxy resin dispersion, the content of the organic solvent in the modified epoxy resin dispersion is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 10% by mass, relative to the total amount of the modified epoxy resin dispersion.

In the case where the modified epoxy resin dispersion of the present invention contains at least one organic solvent, the ratio of the water content in the modified epoxy resin dispersion to the organic solvent content is not particularly limited, but from the viewpoints of stability and each property of the modified epoxy resin dispersion, operability at the time of use, reduction in environmental load, and the like, the ratio of the water content in the modified epoxy resin dispersion to the organic solvent content is preferably 60:40 to 99:1, more preferably 70:30 to 98:2, and still more preferably 80:20 to 97:3, in terms of mass ratio.

The modified epoxy resin dispersion of the present invention preferably contains, as an organic solvent, at least one organic solvent selected from the group consisting of propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, ethylene glycol monobutyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, and isopropanol, and preferably contains, as an organic solvent, diethylene glycol monomethyl ether, and at least one organic solvent selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, and isopropanol, when the modified epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq is reacted with at least one amine compound (b) selected from the group consisting of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more, and the obtained ionized modified epoxy resin is neutralized with an anionic compound (d-1) having a molecular weight of less than 300.

Further, when the epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq is reacted with at least one amine compound (b) selected from the group consisting of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate, the anionic group introducing agent (c-2) having a molecular weight of less than 300 is reacted with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate, the obtained ionized modified epoxy resin intermediate is neutralized with the cationic compound (d-2) having a molecular weight of less than 300 to obtain a modified epoxy resin, and when the modified epoxy resin in the modified epoxy resin dispersion of the present invention is the modified epoxy resin, the organic solvent is preferably selected from the group consisting of propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, ethylene glycol monobutyl ether, N-methyl pyrrolidone, N-ethyl pyrrolidone, and isopropyl alcohol, and the organic solvent is preferably selected from the group consisting of at least one methyl glycol monomethyl ether, diethylene glycol monoethyl ether and ethylene glycol monoethyl ether is further preferably selected from the group consisting of methyl glycol monomethyl ether, diethylene glycol monoethyl ether and ethylene glycol monoethyl ether.

The modified epoxy resin dispersion of the present invention can be used for various products to which epoxy resins are generally applied, and is not particularly limited, and for example, can be used for: paints, coating agents, surface treatment agents, sealants, adhesives, binders, fiber bundles, building materials, electronic parts and the like. Among these, a paint, a coating agent or a surface treatment agent for concrete, cement, mortar, various metals, leather, glass, rubber, plastics, wood, cloth, paper, or the like is preferable.

In the case where the modified epoxy resin dispersion of the present invention is used in a paint, a coating agent or a surface treatment agent, the content of the modified epoxy resin in the paint, the coating agent or the surface treatment agent containing the modified epoxy resin dispersion is preferably 0.1 to 90% by mass, more preferably 0.5 to 70% by mass, still more preferably 1 to 50% by mass, relative to the total amount of the paint, the coating agent or the surface treatment agent.

Examples

The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples, and may be modified within the scope of the present invention. In the following examples and the like, unless otherwise specified,% is a mass basis.

< manufacture of epoxy resin 1 >

A separable round-bottomed flask equipped with a Dimroth Luo Lengning apparatus (Dimroth), a stirring blade, and a nitrogen line was charged with 745.5g of bisphenol A type epoxy resin (epoxy equivalent: 190 g/eq), 272.6g of bisphenol A, and 0.27g of triphenylphosphine as a catalyst and mixed. Thereafter, it was reacted at 120℃for 6 hours, whereby bisphenol A-type epoxy resin a-1 was obtained. The epoxy equivalent of the obtained epoxy resin a-1 was 631g/eq.

< manufacture of epoxy resin 2 >

A separable round-bottomed flask equipped with a Dimu Luo Lengning vessel, stirring blade, nitrogen line was charged with 711.7g of bisphenol A type epoxy resin (epoxy equivalent: 190 g/eq), 308.5g of bisphenol A, and 0.19g of triphenylphosphine as a catalyst and mixed. Thereafter, it was reacted at 120℃for 6 hours, whereby bisphenol A-type epoxy resin a-2 was obtained. The epoxy equivalent of the obtained epoxy resin a-2 was 920g/eq.

< manufacture of epoxy resin 3 >)

A separable round-bottomed flask equipped with a Dimu Luo Lengning vessel, stirring blade, nitrogen line was charged with 711.7g of bisphenol A type epoxy resin (epoxy equivalent: 190 g/eq), 366.0g of bisphenol A, and 0.30g of triphenylphosphine as a catalyst and mixed. Thereafter, it was reacted at 140℃for 6 hours, whereby bisphenol A-type epoxy resin a-3 was obtained. The epoxy equivalent of the obtained epoxy resin a-3 was 1795g/eq.

< manufacture of epoxy resin 4 >

A separable round-bottomed flask equipped with a Dimu Luo Lengning vessel, stirring blade, nitrogen line was charged with 785.7g of bisphenol A type epoxy resin (epoxy equivalent: 190 g/eq), 215.2g of bisphenol A, and 0.21g of triphenylphosphine as a catalyst and mixed. Thereafter, it was reacted at 120℃for 6 hours, whereby bisphenol A-type epoxy resin a-4 was obtained. The epoxy equivalent of the obtained epoxy resin a-4 was 464g/eq.

The raw materials used in producing the modified epoxy resin and the modified epoxy resin dispersion of the present invention are shown below.

Epoxy resin (a) >

Epoxy resin a-1

An epoxy resin having an epoxy equivalent of 631g/eq was obtained from the production 1 of an epoxy resin.

Epoxy resin a-2

The epoxy resin obtained in the production 2 of an epoxy resin had an epoxy equivalent of 920 g/eq.

Epoxy resin a-3

An epoxy resin having an epoxy equivalent of 1795g/eq was obtained from the epoxy resin production 3.

Epoxy resin a-4 (Compound for comparative example)

An epoxy resin having an epoxy equivalent of 464g/eq was obtained from production 4 of an epoxy resin.

Amine compound (b)

Amine compound b-1

Polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman Co., ltd.) represented by the general formula (1), X is methyl, a value (average value) of a is 19, b value (average value) is 3, c value is 0, and weight average molecular weight is 1041.

Amine compound b-2

Polyetheramine (JEFFAMINE (registered trademark) M-3085, manufactured by huntsman Co., ltd.) represented by the general formula (1), X is methyl, a value (average value) of a is 58, b value (average value) is 8, c value is 0, and weight average molecular weight is 3047.

Cationic group-introducing agent (c-1) >

Cationic group-introducing agent c-1

Diethanolamine.

Cationic group-introducing agent c-1-2

2-ethylhexyl amine.

Cationic group-introducing agent c-1-3

Benzyl amine.

Cationic group-introducing agent c-1-4

Monoethanolamine.

Cationic group-introducing agent c-1-5

Dicyclohexylamine.

Cationic group-introducing agent c-1-6

N-methylbenzylamine.

Cationic group-introducing agent c-1-7

Dibutylamine.

< anionic group-introducing agent (c-2) >

Anionic group-introducing agent c-2-1

Phosphoric acid.

Anionic group-introducing agent c-2

Acetic acid.

Anionic group-introducing agent c-2-3

Lactic acid.

< anionic Compound (d-1) >)

Anionic Compound d-1

Phosphoric acid.

Anionic Compound d-1-2

Acetic acid.

Anionic Compound d-1-3

Formic acid.

Anionic Compound d-1-4

Boric acid.

< cationic Compound (d-2) >)

Cationic compound d-2-1

And triethylamine.

Cationic compound d-2

Dimethylaminoethanol.

< organic solvent >)

Organic solvent 1

Propylene glycol monomethyl ether.

Organic solvent 2

Diethylene glycol dimethyl ether.

Organic solvent 3

Ethylene glycol monobutyl ether.

Example 1 >

To 255.0g of epoxy resin a-1 (epoxy resin equivalent 631 g/eq) was added 85.0g of propylene glycol monomethyl ether as a solvent, and the mixture was stirred at 120℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman corporation) having a value of X as methyl group, a as average value of 19, b as average value of 3, c as average value of 0 and a weight average molecular weight of 1041, and 30.0g of diethanolamine as a cationic group-introducing agent, which were represented by the general formula (1), were added and reacted at 120℃for 4 hours, thereby obtaining an ionization-modified epoxy resin intermediate 1. Next, 16.7g of phosphoric acid as an anionic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 1. Thereafter, 735.0g of water was added and stirred using a homomixer, whereby a modified epoxy resin dispersion 1 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 1 and the modified epoxy resin dispersion 1 are shown in table 1. The numerical values in the table indicate the mass (g) of each raw material used.

Example 2 >

To 255.0g of epoxy resin a-1 (epoxy resin equivalent 631 g/eq) was added 85.0g of propylene glycol monomethyl ether as a solvent, and the mixture was stirred at 120℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman Co., ltd.) represented by the general formula (1), X is methyl, a (average value) is 19, b (average value) is 3, c is 0, and weight average molecular weight is 1041 was added as an amine compound, and reacted at 120℃for 6 hours to obtain a modified epoxy resin intermediate 2. Next, 16.6g of phosphoric acid as an anionic group-introducing agent was added and reacted at 80℃for 1 hour, thereby obtaining an ionization-modified epoxy resin intermediate 2. Next, 11.5g of triethylamine as a cationic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 2. Thereafter, 650.0g of water was added and stirred by a homomixer, whereby a modified epoxy resin dispersion 2 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 2 and the modified epoxy resin dispersion 2 are shown in table 1. The numerical values in the table indicate the mass (g) of each raw material used.

Example 3 >

To 255.0g of epoxy resin a-1 (epoxy resin equivalent 631 g/eq) was added 85.0g of propylene glycol monomethyl ether as a solvent, and the mixture was stirred at 120℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman corporation) having a value of X as methyl group, a as average value of 19, b as average value of 3, c as average value of 0 and a weight average molecular weight of 1041, and 18.5g of 2-ethylhexyl amine as a cationic group-introducing agent, which were represented by the general formula (1), were added and reacted at 140℃for 6 hours, thereby obtaining an ionization-modified epoxy resin intermediate 3. Then, 17.0g of acetic acid as an anionic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 3. Thereafter, 710.0g of water was added and stirred by a homomixer, whereby a modified epoxy resin dispersion 3 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 3 and the modified epoxy resin dispersion 3 are shown in table 1. The numerical values in the table indicate the mass (g) of each raw material used.

Example 4 >

To 255.0g of epoxy resin a-1 (epoxy resin equivalent 631 g/eq) was added 85.0g of propylene glycol monomethyl ether as a solvent, and the mixture was stirred at 120℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman corporation) having a value of X as methyl group, a as average value of 19, b as average value of 3, c as average value of 0 and a weight average molecular weight of 1041, and 15.3g of benzylamine as a cationic group introducing agent, which were represented by the general formula (1), were added and reacted at 140℃for 6 hours, thereby obtaining an ionization modified epoxy resin intermediate 4. Next, 13.3g of formic acid as an anionic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 4. Thereafter, 695.0g of water was added and stirred by a homomixer, whereby a modified epoxy resin dispersion 4 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 4 and the modified epoxy resin dispersion 4 are shown in table 1. The numerical values in the table indicate the mass (g) of each raw material used.

Example 5 >

To 255.0g of epoxy resin a-1 (epoxy resin equivalent 631 g/eq) was added 85.0g of propylene glycol monomethyl ether as a solvent, and the mixture was stirred at 120℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman Co., ltd.) represented by the general formula (1), X being a methyl group, a value (average value) of a being 19, b being a value (average value) of 3, c being a value of 0, and a weight average molecular weight of 1041, and 8.7g of monoethanolamine as a cationic group introducing agent were added and reacted at 140℃for 6 hours to obtain an ionization modified epoxy resin intermediate 5. Then, 17.7g of boric acid as an anionic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 5. Thereafter, 690.0g of water was added and stirred using a homomixer, whereby a modified epoxy resin dispersion 5 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 5 and the modified epoxy resin dispersion 5 are shown in table 1. The numerical values in the table indicate the mass (g) of each raw material used.

Example 6 >

To 255.0g of epoxy resin a-2 (epoxy resin equivalent: 920 g/eq) was added 85.0g of diethylene glycol dimethyl ether as a solvent, and the mixture was stirred at 140℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman corporation) having a value of X as methyl group, a as average value of 19, b as average value of 3, c as average value of 0 and a weight average molecular weight of 1041, and 30.0g of dicyclohexylamine as a cationic group-introducing agent, which were represented by the general formula (1), were added and reacted at 140℃for 4 hours, thereby obtaining an ionization-modified epoxy resin intermediate 6. Then, 9.2g of acetic acid as an anionic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 6. Thereafter, 686.0g of water was added and stirred by a homomixer, whereby a modified epoxy resin dispersion 6 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 6 and the modified epoxy resin dispersion 6 are shown in table 2. The numerical values in the table indicate the mass (g) of each raw material used.

Example 7 >

To 255.0g of epoxy resin a-2 (epoxy resin equivalent: 920 g/eq) was added 85.0g of diethylene glycol dimethyl ether as a solvent, and the mixture was stirred at 140℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman Co., ltd.) represented by the general formula (1), X is methyl, a (average value) is 19, b (average value) is 3, c is 0, and weight average molecular weight is 1041 was added as an amine compound, and reacted at 140℃for 4 hours to obtain a modified epoxy resin intermediate 7. Next, 10.0g of acetic acid as an anionic group-introducing agent was added and reacted at 80℃for 1 hour, thereby obtaining an ionization-modified epoxy resin intermediate 7. Next, 10.0g of dimethylaminoethanol as a cationic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 7. After that, 675.0g of water was added and stirred by a homomixer, thereby obtaining a modified epoxy resin dispersion 7 (the content of the modified epoxy resin was 30 mass%). The compositions of the raw materials used for producing the modified epoxy resin 7 and the modified epoxy resin dispersion 7 are shown in table 2. The numerical values in the table indicate the mass (g) of each raw material used.

Example 8 >

To 255.0g of epoxy resin a-2 (epoxy resin equivalent: 920 g/eq) was added 85.0g of diethylene glycol dimethyl ether as a solvent, and the mixture was stirred at 140℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman corporation) having a value of X as methyl group, a as average value of 19, b as average value of 3, c as average value of 0 and a weight average molecular weight of 1041, and 20.0g of N-methylbenzylamine as a cationic group introducing agent, which were represented by the general formula (1), were added and reacted at 140℃for 4 hours, thereby obtaining an ionization-modified epoxy resin intermediate 8. Then, 12.0g of formic acid as an anionic compound was added to neutralize the resultant mixture, thereby obtaining a modified epoxy resin 8. After that, 700.0g of water was added and stirred by a homomixer, thereby obtaining a modified epoxy resin dispersion 8 (the content of the modified epoxy resin was 30 mass%). The compositions of the raw materials used for producing the modified epoxy resin 8 and the modified epoxy resin dispersion 8 are shown in table 2. The numerical values in the table indicate the mass (g) of each raw material used.

Example 9 >

To 255.0g of epoxy resin a-2 (epoxy resin equivalent: 920 g/eq) was added 85.0g of diethylene glycol dimethyl ether as a solvent, and the mixture was stirred at 140℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman Co., ltd.) represented by the general formula (1), X is methyl, a value (average value) is 19, b value (average value) is 3, c value is 0, and weight average molecular weight is 1041 was added as an amine compound, and reacted at 140℃for 4 hours, thereby obtaining a modified epoxy resin intermediate 9. Subsequently, 15.0g of lactic acid as an anionic group-introducing agent was added and reacted at 80℃for 1 hour, thereby obtaining an ionization-modified epoxy resin intermediate 9. Then, 15.0g of triethylamine as a cationic compound was added thereto for neutralization, whereby a modified epoxy resin 9 was obtained. Then, 675.0g of water was added and stirred by a homomixer, whereby a modified epoxy resin dispersion 9 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 9 and the modified epoxy resin dispersion 9 are shown in table 2. The numerical values in the table indicate the mass (g) of each raw material used.

Example 10 >

To 255.0g of epoxy resin a-3 (epoxy resin equivalent 1795 g/eq) was added 85.0g of ethylene glycol monobutyl ether as a solvent and stirred at 140℃for 1 hour. Next, 53.0g of polyetheramine (JEFFAMINE (registered trademark) M-3085, manufactured by huntsman corporation) having a value of X as methyl group, a as average value of 58, b as average value of 8, c as average value of 0, and a weight average molecular weight of 3047, and 13.5g of dibutylamine as a cationic group-introducing agent were added as amine-based compounds, and reacted at 140℃for 6 hours to obtain an ionization-modified epoxy resin intermediate 10. Next, 13.5g of phosphoric acid as an anionic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 10. Thereafter, 660.0g of water was added and stirred by a homomixer, whereby a modified epoxy resin dispersion 10 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 10 and the modified epoxy resin dispersion 10 are shown in table 3. The numerical values in the table indicate the mass (g) of each raw material used.

Example 11 >

To 255.0g of epoxy resin a-3 (epoxy resin equivalent 1795 g/eq) was added 85.0g of ethylene glycol monobutyl ether as a solvent and stirred at 140℃for 1 hour. Next, 53.0g of polyetheramine (JEFFAMINE (registered trademark) M-3085, manufactured by huntsman Co., ltd.) represented by the general formula (1), wherein X is a methyl group, a has a value (average value) of 58, b has a value (average value) of 8, c has a value of 0, and a weight average molecular weight of 3047 was added as an amine compound, and reacted at 140℃for 6 hours to obtain a modified epoxy resin intermediate 11. Next, 6.0g of phosphoric acid as an anionic group-introducing agent was added and reacted at 80℃for 1 hour, thereby obtaining an ionization-modified epoxy resin intermediate 11. Then, 6.0g of dimethylaminoethanol as a cationic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 11. Thereafter, 715.0g of water was added and stirred by a homomixer, whereby a modified epoxy resin dispersion 11 (the content of the modified epoxy resin was 30 mass%) was obtained. The compositions of the raw materials used for producing the modified epoxy resin 11 and the modified epoxy resin dispersion 11 are shown in table 3. The numerical values in the table indicate the mass (g) of each raw material used.

Comparative example 1 >

To 255.0g of epoxy resin a-4 (epoxy resin equivalent 464 g/eq) was added 85.0g of propylene glycol monomethyl ether as a solvent, and the mixture was stirred at 120℃for 1 hour. Next, 50.0g of polyetheramine (JEFFAMINE (registered trademark) M-1000, manufactured by huntsman corporation) having a value of X as methyl group, a as average value of 19, b as average value of 3, c as average value of 0 and a weight average molecular weight of 1041, and 46.0g of diethanolamine as a cationic group-introducing agent, which were represented by the general formula (1), were added and reacted at 120℃for 4 hours, thereby obtaining an ionization-modified epoxy resin intermediate 12. Next, 20.0g of phosphoric acid as an anionic compound was added to neutralize the mixture, thereby obtaining a modified epoxy resin 12. Then, 715.0g of water was added and stirred by a homomixer to obtain a modified epoxy resin dispersion 12 (content of modified epoxy resin: 30 mass%). The compositions of the raw materials used for producing the modified epoxy resin 12 and the modified epoxy resin dispersion 12 are shown in table 3. The numerical values in the table indicate the mass (g) of each raw material used.

Comparative example 2 >

To 255.0g of epoxy resin a-3 (epoxy resin equivalent 1795 g/eq) was added 85.0g of ethylene glycol monobutyl ether as a solvent and stirred at 140℃for 1 hour. Next, 53.0g of polyetheramine (JEFFAMINE (registered trademark) M-3085, manufactured by huntsman Co., ltd.) having a value of X as a methyl group, a value of a (average value) 58, b as an average value of 8, c as a value of 0, and a weight average molecular weight of 3047, and 12.0g of diethanolamine as amine-based compounds were added and reacted at 120℃for 4 hours to obtain a modified epoxy resin 13. Then, 683.0g of water was added and stirred by a homomixer to obtain a modified epoxy resin dispersion 13 (the content of the modified epoxy resin was 30 mass%). The compositions of the raw materials used for producing the modified epoxy resin 13 and the modified epoxy resin dispersion 13 are shown in table 3. The numerical values in the table indicate the mass (g) of each raw material used.

< evaluation of dispersibility >

The dispersibility of each of the produced modified epoxy resin dispersions 1 to 13 was evaluated. Specifically, the average particle diameter of the modified epoxy resin in each of the modified epoxy resin dispersions 1 to 13 was measured by a laser diffraction/scattering method using a particle diameter measuring apparatus (LA-950V 2, manufactured by horiba, ltd.). Based on the measured average particle diameter of the modified epoxy resin, the dispersibility of the modified epoxy resin dispersion was evaluated based on the following evaluation criteria. The evaluation results are shown in tables 1 to 3. When the evaluation criterion of dispersibility is Δ or more, it is indicated that the modified epoxy resin dispersion is practical.

Evaluation criterion of dispersibility

And (3) the following materials: the average particle size is less than 300nm.

O: the average particle diameter is 300nm or more and less than 1000nm.

Delta: the average particle diameter is 1000nm or more and less than 10000nm.

X: the average particle diameter is 10000nm or more or the average particle diameter cannot be measured.

< evaluation of Corrosion resistance >

Corrosion resistance was evaluated for each of the modified epoxy resin dispersions 1 to 13 produced. Specifically, the modified epoxy resin dispersions 1 to 13 were applied to 100mm×100mm sandblasted steel plates each having a dry film thickness of about 100 μm by a bar coater, and then dried at room temperature at 25℃for 5 days, to prepare test pieces. Next, using each test piece, a salt spray test was performed in accordance with JIS K5600-7-9 (2006). The corrosion resistance of the coating film on the surface of the test piece after the 7-day cycle test was evaluated by visual observation based on the following evaluation criteria. The evaluation results are shown in tables 1 to 3. Among them, the modified epoxy resin dispersion 13 was not dispersed with the modified epoxy resin, and therefore could not be applied to a sandblasted steel sheet, and this test could not be performed. When the evaluation criterion of corrosion resistance is Δ or more, it is indicated that the modified epoxy resin dispersion is practical.

Evaluation criterion for Corrosion resistance

And (3) the following materials: no bulge and rust were observed.

O: no bulge was observed, but rust was slightly observed.

Delta: some bulge and rust were observed.

X: swelling and rust were observed over the whole surface.

< evaluation of Water resistance >

The water resistance of each of the produced modified epoxy resin dispersions 1 to 13 was evaluated. Specifically, the modified epoxy resin dispersions 1 to 13 were applied to 100mm×100mm sandblasted steel plates each having a dry film thickness of about 100 μm by a bar coater, and then dried at room temperature at 25℃for 5 days, to prepare test pieces. Then, a drop of water was dropped onto each test piece, and the mixture was allowed to stand at 25℃for 24 hours. The state of the coating film on the surface of the test piece after standing was visually observed, and the water resistance was evaluated based on the following evaluation criteria. The evaluation results are shown in tables 1 to 3. Among them, the modified epoxy resin dispersion 13 was not dispersed with the modified epoxy resin, and therefore could not be applied to a sandblasted steel sheet, and this test could not be performed. When the evaluation criterion of the water resistance is Δ or more, it is indicated that the modified epoxy resin dispersion is practical.

Evaluation criterion for Water resistance

And (3) the following materials: no white haze or the like was observed while maintaining the transparency before the test.

O: a light white mist was observed on a part of the surface of the test piece.

Delta: a light white fog was observed on the entire surface of the test piece.

X: the test piece surface whitened as a whole.

< evaluation of blocking resistance >

The modified epoxy resin dispersions 1 to 13 thus produced were evaluated for blocking resistance. Specifically, two test pieces were produced by applying the modified epoxy resin dispersions 1 to 13 to 100mm×100mm sandblasted steel plates each having a dry film thickness of about 100 μm by a bar coater, and then drying the steel plates at room temperature for 5 days at 25 ℃. Next, according to JIS K5600-6 (general test method for paint-fifth part: mechanical properties of coating film-sixth section adhesion (cross-cut method)), the coating film was cut into 100 lattices by using a cutter guide with a gap spacing of 10mm, and then the coating film portions of the two test pieces were laminated and 10kgf/cm was applied ² Is used for the load of the (a),while the mixture was allowed to stand in a constant temperature and humidity tank at 60℃and a relative humidity of 80%. After 72 hours, the overlapped test pieces were peeled off, and the broken state of the coating films on the surfaces (total 200 grids) of the two test pieces was visually observed, and the blocking resistance was evaluated based on the following evaluation criteria. The evaluation results are shown in tables 1 to 3. Among them, the modified epoxy resin dispersion 13 was not dispersed with the modified epoxy resin, and therefore could not be applied to a sandblasted steel sheet, and this test could not be performed. When the evaluation criterion of blocking resistance is Δ or more, it is indicated that the modified epoxy resin dispersion is practical.

Evaluation criterion for blocking resistance

And (3) the following materials: the number of broken cells in the coating film is less than 2.

O: the coating film is broken in 2 or more and less than 20 cells in the whole area of the lamination.

Delta: the coating film is broken in 20 or more and less than 100 cells in the whole area of the lamination.

X: over 100 grids of the coating film are broken in the whole overlapping area.

TABLE 1

TABLE 2

TABLE 3

As shown in the above results, the epoxy resin obtained by using an epoxy resin having an epoxy resin equivalent of 464g/eq as the epoxy resin and the epoxy resin dispersion (comparative example 1) were excellent in self-emulsifying property, but were not practical in various properties, such as significantly deteriorated blocking resistance. Even when an epoxy resin having an epoxy resin equivalent of 1795g/eq is used as the epoxy resin, the self-emulsifying properties of the obtained epoxy resin and the epoxy resin dispersion (comparative example 2) are also poor, and the dispersibility of the modified epoxy resin is also poor when the dispersion is produced, unlike the case of the modified epoxy resin obtained by neutralizing the ionized modified epoxy resin intermediate in the present invention, and the use as a modified epoxy resin dispersion is not available. On the other hand, the modified epoxy resin and the modified epoxy resin dispersion obtained by the present invention are excellent in self-emulsifying property, corrosion resistance, water resistance, blocking resistance and other properties, and can be preferably used for paints, coating agents, surface treatment agents, sealants, adhesives, fiber bundles, building materials, electronic parts and the like.

Claims

1. A modified epoxy resin is obtained by the following steps:

an epoxy resin (a) having an epoxy equivalent of 600g/eq to 6000g/eq is reacted with an amine compound (b) of at least one selected from the group consisting of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate,

reacting a cationic group-introducing agent c-1 having a molecular weight of less than 300 or an anionic group-introducing agent c-2 having a molecular weight of less than 300 with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate,

the resulting ionization-modified epoxy resin intermediate is neutralized with an anionic compound d-1 having a molecular weight of less than 300 or a cationic compound d-2 having a molecular weight of less than 300.

2. The modified epoxy resin of claim 1, wherein,

the amine compound b contains a polyether amine compound having a molecular weight of 300 or more.

3. The modified epoxy resin according to claim 1 or 2, wherein,

the cationic group introducing agent c-1 contains at least one selected from the group consisting of monoethanolamine, diethanolamine, 2-ethylhexyl amine, benzylamine, dicyclohexylamine, N-methylbenzylamine, and dibutylamine.

4. A modified epoxy resin according to any one of claim 1 to 3, wherein,

the anionic group-introducing agent c-2 contains at least one selected from the group consisting of phosphoric acid, acetic acid, lactic acid, boric acid, and formic acid.

5. The modified epoxy resin according to any one of claims 1 to 4, wherein,

the modified epoxy resin intermediate is obtained by reacting the epoxy resin a with the amine compound b in such an amount that the amino group in the amine compound b is 0.01 to 0.95 mole relative to 1 mole of the epoxy group in the epoxy resin a.

6. A modified epoxy resin dispersion comprising the modified epoxy resin according to any one of claims 1 to 5 and water.

7. The modified epoxy resin dispersion according to claim 6, further comprising an organic solvent selected from at least one of the group consisting of propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and ethylene glycol monobutyl ether.

8. A method for producing a modified epoxy resin comprises the following steps:

a step of reacting an epoxy resin a having an epoxy equivalent of 600g/eq to 6000g/eq with an amine compound b selected from at least one of a primary amine compound having a molecular weight of 300 or more and a secondary amine compound having a molecular weight of 300 or more to obtain a modified epoxy resin intermediate;

A step of reacting a cationic group-introducing agent c-1 having a molecular weight of less than 300 or an anionic group-introducing agent c-2 having a molecular weight of less than 300 with the obtained modified epoxy resin intermediate to obtain an ionized modified epoxy resin intermediate; and

and a step of neutralizing the obtained ionization-modified epoxy resin intermediate with an anionic compound d-1 having a molecular weight of less than 300 or a cationic compound d-2 having a molecular weight of less than 300.