TWI480305B - A method for producing a latent hardener for a powdery epoxy resin, a latent hardener for a powdered epoxy resin, and a hardened epoxy resin composition - Google Patents

Description

Method for producing latent hardener for powdered epoxy resin, latent hardener for powdered epoxy resin, and curable epoxy resin composition

The present invention relates to a method for producing a latent hardener for a powdery epoxy resin. In particular, the hardener is a fine powder of an epoxy adduct amine, or an epoxy addition amine and a phenol. The fine powder of the mixture of the resin, and the mixture of the epoxy resin and the water are treated with an isocyanate and then treated with a non-polar solvent, which is suitable for the hardenability which is excellent in storage stability and excellent in heat curability. The epoxy resin composition, the present invention relates to a method for producing a latent curing agent for a powdery epoxy resin, a latent curing agent for a powdery epoxy resin obtained by the manufacturing method, and hardening using the curing agent Epoxy resin composition.

The epoxy resin is excellent in adhesion to various substrates, and the cured product obtained by hardening the epoxy resin with a hardener is excellent in heat resistance, chemical resistance, electrical property, mechanical properties, etc. It is recommended for a wide range of applications such as adhesives and various molding materials.

Conventional epoxy resin compositions have been mainstreamed by adding a hardener or a hardening accelerator before use. Although the two-component system has the characteristics of being hardenable at normal temperature or low temperature, on the other hand, it must be metered and mixed before being used, and it can be used for a short time after mixing, so it is suitable for automatic machinery. Difficulties such as difficulties. As a result, the two-component epoxy resin composition has a problem in that its use conditions are limited, and in order to eliminate this problem, development of a one-component curable epoxy resin composition has been desired.

In order to obtain a component curable resin composition as described above, it is necessary to have a hardener which does not react at room temperature, but which is heated to initiate reaction and harden, which is a so-called latent curing agent. In terms of latent hardeners, there are proposals such as dicyanodiamine, Adipic acid dihydrazide, boron trifluoride amine complex salt, guanamine, melamine, imidazole and the like.

However, for example, in the case where dicyanodiamine, melamine, and guanamine are mixed with an epoxy resin, although the storage stability is excellent, the disadvantage is that the hardening conditions must be heated for a long time at a high temperature of 150 ° C or higher. On the other hand, the method of shortening the hardening time by using these latent hardeners and hardening accelerators is also widely used, and in this case, it is understood that the storage stability is remarkably impaired.

On the one hand, in the case of using a dibasic acid dioxime or an imidazole, although hardening is carried out at a relatively low temperature, but storage stability is lacking, in the case of using a boron trifluoride amine complex salt, although storage stability is obtained The advantage of being excellent and the hardening time is short, however, there is a problem that water resistance is deteriorated, and corrosion such as metal is present. In addition, there are many proposals for surface-treating an amine-based curing agent such as an amine epoxy-based compound with a polyisocyanate, and a latent curing agent for a microcapsule-type epoxy resin. However, in storage stability and heat hardening, Sex and other performance aspects, have not yet been able to obtain sufficient to meet the needs of the object.

There are proposals, for example, a microcapsule-type hardener in which a hardener is contained as a core component and a thermoplastic resin as a shell component (Patent Document 1); a compound having a primary amine group or a secondary amine group, and a tertiary amine group An epoxy resin hardener obtained by reacting a mixture of a compound having no primary amino group and a secondary amine group with an isocyanate compound (Patent Document 2); and a solid synthesized from an amine compound and an epoxy compound The product is in the form of a spherical powder hardener for epoxy resin (Patent Document 3). However, in any of the above cases, there is a problem that the solvent (solvent) lacks stability.

[Patent Document 1] Japanese Patent Laid-Open No. 9-3164

[Patent Document 2] Japanese Patent Laid-Open No. 4-314724

[Patent Document 3] Japanese Patent No. 3098760

Therefore, a first object of the present invention is to provide a method for producing a latent curing agent for a powdery epoxy resin which is excellent in storage stability and excellent in heat curability and which is suitable for a curable epoxy resin composition.

A second object of the present invention is to provide a latent curing agent for a powdery epoxy resin which is excellent in storage stability and excellent in heat curability and which is suitable for a curable epoxy resin composition.

A third object of the present invention is to provide a curable epoxy resin composition which is excellent in storage stability and excellent in heat curability, and which can provide a cured product having high heat resistance, excellent adhesion and electrical properties.

The inventors of the present invention have repeatedly conducted research on the above-mentioned respective objects, and as a result, have found that a mixture of a fine powder of an epoxy-addition amine, an epoxy resin, and water mixed with a phenol resin which can be used as needed is firstly carried out. After the isocyanate treatment, a latent curing agent for a powdery epoxy resin which achieves the above object can be produced by treatment with a non-polar solvent, and thus the present invention has been completed.

That is, the feature of the present invention is a method for producing a latent hardener for a powdery epoxy resin having the following steps (A) to (F), a latent hardener for a powdery epoxy resin, and a hardenable epoxy resin. Resin composition.

(A) a step of heating an amine compound (a2) with an epoxy resin (a3) in a solvent (a1),

(B) Any of the following steps (B1) to (B3):

(B1) removing the solvent (a1), and taking out a step of reacting the solid compound (b1) obtained by reacting the amine compound (a2) with the epoxy resin (a3),

(B2) The solvent (a1) is removed, the reactant (b1) of the amine compound (a2) and the epoxy resin (a3) is taken out, and the phenol resin (b2) is added to the reactant (b1) to be heated, dissolved, and dehydrated. The step of taking out the solid matter (b3), and

(B3) After adding the phenol resin (b2) to the reactant in the step (A), the solvent (a1) is removed, heated, dissolved, and dehydrated, and the reactant of the amine compound (a2) and the epoxy resin (a3) is taken out. a step of solid matter (b3) of a mixture of (b1) and a phenol resin (b2),

(C) a step of pulverizing the solid matter (b1) or (b3) to obtain a fine powder (c1) having a volume average particle diameter of 0.1 to 10 μm,

(D) a step of adding water (1) to the epoxy resin (d1) and adding the fine powder (c1) to obtain a uniform mixture (d2),

(E) a step of reacting the polyisocyanate (e1) in the mixture (d2) to obtain a reactant (e2) by infrared absorption of NCO until the disappearance of the polyisocyanate (e1) is confirmed, and

(F) A step of adding/mixing a nonpolar solvent (f1) to the reactant (e2), followed by filtration and drying to obtain a latent curing agent for a powdery epoxy resin.

The curable epoxy resin composition using the latent curing agent for a powdery epoxy resin obtained by the production method of the present invention is excellent in storage stability and heat curability, and can be used, for example, for concrete, cement mortar, various metals, Wide range of applications such as leather, glass, rubber, plastic, wood, cloth, paper and other coatings or adhesives. The cured product of the curable epoxy resin composition using the latent curing agent of the present invention has high heat resistance, excellent adhesion and electrical properties, and thus can be suitably used for packaging for semiconductor protection, bonding of electronic parts, and the like. Use of electronic materials or automotive materials.

Hereinafter, a method for producing a latent curing agent for a powdery epoxy resin, a latent curing agent for a powdery epoxy resin, and a curable epoxy resin composition will be described in detail.

The solvent (a1) used in the step (A) of the present invention may, for example, be a nonpolar solvent such as toluene, xylene or ethylbenzene; an alcohol such as methanol, ethanol, propanol or isopropanol or the like.

In the solvent, a nonpolar solvent such as toluene, xylene or ethylbenzene may be used singly or in order to improve the reactivity, a nonpolar solvent such as toluene, xylene or ethylbenzene may be used, and methanol, ethanol or propanol may be used. A mixed solvent of an alcohol such as isopropyl alcohol or propylene glycol monomethyl ether is preferred.

The amine compound (a2) used in the step (A) of the present invention is an amine compound having one or more primary or secondary amino groups, such as ethylenediamine, 1,2-diaminopropane, 1, Olefinic diamines such as 3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane; diethylenetriamine, triamethylenetriamine, tetraamethyleneamine Polyalkyl polyamines; 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane An alicyclic polyamine such as isophorone diamine; an aromatic polyamine such as m-xylylenediamine, diaminodiphenylmethane or diaminodiphenyl hydrazine; 2-methylimidazole, 2 -ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2- An imidazole such as aminopropyl imidazole or the like.

In the epoxy resin (a3) used in the step (A) of the present invention, there is a polynuclear polyvalent phenol compound such as hydroquinone, resorcin, pyrocatechol or phloroglucinol. A epoxidized propyl ether compound; dihydroxynaphthalene, bisphenol, methylene bisphenol (bisphenol F), methylene bis (o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol) A), isopropylidene bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxyisopropyl (phenyl) benzene), 1,4-bis(4-hydroxyisopropyl) Phenylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, bisthiol, sulfobisphenol, Hydroxy bisphenol, phenol novolac, orthocresol novolac, ethyl phenol novolac, butyl phenol novolac, octyl phenol novolac, resorcinol novolac, terpene phenol, etc. Polyglycidyl ether compound of polyvalent phenol compound; ethylene glycol, propylene glycol, butanediol, hexanediol, polyethylene glycol, thiodiglycol, glycerol, trimethylol Propane, neopentyl alcohol, sorbitol, bisphenol A-ethylene oxide plus a polyepoxypropyl ether of a polyvalent alcohol such as a maleic acid; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid (azelaic) Acid), azelaic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,4,-benzenetricarboxylic acid, trimesic acid Acid), epoxy propyl esters of aliphatic, aromatic or alicyclic polybasic acids such as pyromellitic acid, tetrahydrofurfuric acid, hexahydrononanoic acid, and methylenetetrahydrofurfuric acid, and epoxy a single polymer or copolymer of propyl methacrylate; N,N-diepoxypropyl aniline, bis(4-(N-methyl-N-epoxypropylamino)phenyl)methane, two Epoxy compound having a glycidylamino group such as epoxypropyl o-toluidine; ethylene cyclohexenyl diepoxide, dicyclopentadienyl diepoxide, 3,4-epoxy group Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3) Epoxide of a cyclic olefin compound such as 4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized poly Dienes, epoxidized styrene - butadiene copolymer epoxidized conjugated diene polymer, a heterocyclic compound three epoxy propyl cyanurate and the like.

Among these epoxy resins, a liquid bisphenol type epoxy resin is preferably used in order to obtain a latent curing agent for a powdery epoxy resin having superior performance.

In the step (A) of the present invention, the epoxy resin (a3) is used in an amount of 0.1 to 5 equivalents, particularly preferably 0.5 to 2 equivalents, per mol of the polyamine compound (a2). Further, the solvent (a1) is used in an amount of from 1 to 10,000 parts by mass, particularly preferably from 10 to 1,000 parts by mass, per 100 parts by mass of the total of the polyamine compound (a2) and the epoxy resin (a3) component.

In the step (A) of the present invention, the heating reaction of the amine compound (a2) and the epoxy resin (a3) in the solvent (a1) is carried out at 40 to 150 ° C for 1 to 20 hours, particularly 60 to 120. °C is preferably 2 to 15 hours.

In the present invention, the step (B) is any one of the following steps (B1) to (B3).

(B1) The solvent (a1) used in the step (A) is removed, and the solid matter (b1) obtained by reacting the amine compound (a2) with the epoxy resin (a3) is taken out.

(B2) removing the solvent (a1) used in the step (A), taking out the reactant (b1) of the amine compound (a2) and the epoxy resin (a3), and adding the phenol resin (b2) to the reactant (b1), The step of heating, dissolving, and dehydrating the solid matter (b3) is taken out.

(B3) After adding the phenol resin (b2) to the reactant in the step (A), the solvent (a1) is removed, heated, dissolved, and dehydrated, and the reactant of the amine compound (a2) and the epoxy resin (a3) is taken out. (b1), a step of solid matter (b3) of a mixture with a phenol resin (b2).

In the present invention, any of the above steps (B1) to (B3) may be used, and in the step (B1), when the steps (B2) and (B3) are selected without using the phenol resin (b2), Since the phenol resin (b2) is used, in the case of selecting the step (B1) and the step of selecting (B2) or (B3), the composition of the final powdery epoxy resin is not the same as that of the latent hardener. In summary, there is no substitute for a latent curing agent for a powdery epoxy resin which can achieve the object of the present invention.

The phenol resin (b2) which can be used in the step (B2) or (B3) of the present invention may, for example, be a phenol resin synthesized from a phenol monomer and an aldehyde.

Examples of the phenolic monomer include phenol, cresol, ethyl phenol, n-propanol, isopropyl phenol, butanol, tertiary butyl phenol, octyl phenol, decyl phenol, dodecyl phenol, cyclohexyl phenol, and chlorophenol. , bromophenol, resorcinol, catechol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-thiodiphenol, dihydroxydiphenylmethane, naphthol, anthracene Terpene phenol, phenolated dicyclopentadiene, etc., and the aldehyde is exemplified by formaldehyde.

Further, a phenol resin obtained by copolymerizing a phenolic monomer and dicyclopentadiene using Lewis acid as a catalyst can also be used.

The amount of the phenol resin which can be used in the step (B2) or (B3) of the present invention is preferably 5 to 200 parts by mass based on 100 parts by mass of the reactant of the amine compound (a2) and the epoxy resin (a3) component. It is preferable to use 20 to 100 parts by mass.

In the step (B2) or (B3) of the present invention, the solid (b3) of the mixture of the amine compound (a2) and the epoxy resin (a3) reactant (b1) and the phenol resin (b2) is at atmospheric pressure. Or under reduced pressure, at 100 to 250 ° C, preferably 150 to 230 ° C, after heating, dissolution, under reduced pressure at 100 to 250 ° C, preferably 150 to 230 ° C, by dehydration take out.

In the step (B) of the present invention, the method of removing the solvent (a1) is not particularly limited, and it is preferred to carry out heating at 100 to 250 ° C, particularly 150 to 230 ° C under normal pressure or reduced pressure. .

In the step (C) of the present invention, the method of pulverizing the solid matter (b1) or (b3) is not particularly limited, and a method of pulverizing using a jet mill pulverizer is particularly preferable.

The volume average particle diameter of the fine powder (c1) obtained by pulverizing the solid matter (b1) or (b3) can obtain a powdery epoxy latent hardener having more excellent properties, from 0.1 to 10 μm. It is better. Further, in the present invention, the volume average particle diameter is a volume average particle diameter measured by Microtrack MT3300 (trade name) manufactured by Nikkiso Co., Ltd.

In the epoxy resin (d1) used in the step (D), there are polyepoxypropyl ethers of mononuclear polyvalent phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucin. Compound; dihydroxynaphthalene, bisphenol, methylene bisphenol (bisphenol F), methylene bis(o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A), iso-Asia Propyl bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1 , 3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, bisthiophenol, sulfobisphenol, hydroxybisphenol, phenol novolac, a polyepoxypropyl ether compound of a polynuclear polyvalent phenol compound such as o-cresol novolac, cresol novolac, butyral novolac, octylphenol novolak, resorcinol novolac, terpene phenol; Glycol, propylene glycol, butanediol, hexanediol, polyethylene glycol, diethanol sulfide, glycerin, trimethylolpropane, neopentyl alcohol, sorbitol, bisphenol A-ethylene oxide addition Polyepoxypropyl ether of polyvalent alcohols such as males; maleic acid, fumaric acid, and ikon Acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, citric acid, isophthalic acid, terephthalic acid, 1, 2 , 4,-benzenetricarboxylic acid, trimesic acid, pyromellitic acid, tetrahydrofurfuric acid, hexahydrophthalic acid, terminal methylene tetrahydrofurfuric acid, etc., aliphatic, aromatic or alicyclic A single polymer or copolymer of a polybasic acid glycidyl ester and a glycidyl methacrylate; N,N-diepoxypropylaniline, bis(4-(N-methyl-N) -epoxypropylamino)phenyl)methane, diepoxypropyl o-toluidine, etc. epoxy compound having a glycidylamino group; ethylene cyclohexene diepoxide, dicyclopentadiene bicyclo Oxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methyl Epoxide of a cyclic olefin compound such as cyclohexane carboxylate or bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized polybutadiene, epoxidized benzene Epoxidized conjugated diene polymer such as ethylene-butadiene copolymer, heterocyclic ring such as triepoxypropyl isocyanate Compounds.

From the viewpoint of obtaining a powdery epoxy latent curing agent having more excellent properties, a liquid bisphenol type epoxy resin is preferably used among the epoxy resins.

In the step (D), the amount of water added is preferably from 0.01 to 5 parts by mass, particularly preferably from 0.1 to 3 parts by mass, per 100 parts by mass of the epoxy resin (d1). When it is less than 0.01 part by mass, storage stability and solvent stability tend to be insufficient, and in the case of more than 5 parts by mass, there is a case where hardening failure occurs, which is not preferable.

The amount of the fine powder (c1) to be added in the step (D) is preferably 10 to 100 parts by mass, particularly preferably 20 to 80 parts by mass, per 100 parts by mass of the epoxy resin (d1). When the amount is less than 10 parts by mass, the hardening is insufficient, and when it exceeds 100 parts by mass, the hardening failure is liable to be unsatisfactory.

In terms of the polyisocyanate (e1) to be added in the step (E), there are, for example, 1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methyl group. Pentane-2,4-diisocyanate, 3,6-diisocyanate, 3,3-dinitropentane-1,5-diisocyanate, 1,6-diisocyanate, 1,6 - hexamethylene diisocyanate (HDI), trimethyl methylene diisocyanate, diazonic acid diisocyanate, tolylene diisocyanate (TDI), xylene diisocyanate, xylylene diisocyanate Meta-tetramethyl, isophorone diisocyanate (3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate), 1,3- or 1,4-bis(isocyanate) Methyl ester) cyclohexane, 4,4'-diphenylmethyl diisocyanate (MDI), cyclo 4,4'-diisocyanate (hydrogenated MDI), hydrogenated toluene (tolylene) Isocyanates, etc., and such mixtures. Further, the polyisocyanates may be trimerized to form isomeric cyanurics.

From the viewpoint of allowing the reaction to proceed sufficiently in the step (E), it is preferred to use an aromatic polyisocyanate among the polyisocyanates.

The amount of the polyisocyanate (e1) to be added in 100 parts by mass of the mixture (d2) in the step (E) is from 1 to 20 parts by mass, particularly preferably from 2 to 10 parts by mass. When the amount is less than 1 part by mass, the storage stability tends to be lowered, and when it exceeds 20 parts by mass, the case where the curing failure occurs is not preferable.

Further, in the step (E), the infrared absorption of the NCO was examined, and the reaction was carried out until the disappearance of the polyisocyanate (e1) was confirmed.

In the non-polar solvent (f1) to be added in the step (F), there are, for example, benzene, toluene, xylene, ethylbenzene, cumene, pentylbenzene, dodecanebenzene, styrene, decalin, and tetra An aromatic hydrocarbon such as hydrogenated naphthalene; an aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, decane, undecane, dodecane or petroleum ether; cyclopentane, ring A mixture of these may be used as an alicyclic hydrocarbon such as hexane. In the case of using such aromatic, aliphatic or alicyclic hydrocarbons, a suitable hardening agent for a powdery epoxy resin is obtained, and this is a suitable embodiment of the present invention.

The amount of the nonpolar solvent (f1) to be added in 100 parts by mass of the reactant (e1) in the step (F) is preferably 10 to 1,000 parts by mass, particularly preferably 50 to 700 parts by mass. If it is less than 10 parts by mass, it may not be sufficiently washed. When it exceeds 1,000 parts by mass, the storage stability may be impaired.

In the step (F), after the above nonpolar solvent (f1) is added/mixed, the latent curing agent for a powdery epoxy resin of the present invention can be obtained by filtration and drying.

In the present invention, after the amine compound (a2) and the epoxy resin (a3) are reacted in the step (A), an additional amine compound (a2') and a blocked isocyanate (a4) may be further subjected to a heating reaction.

The amine compound (a2') may, for example, be a compound exemplified as the amine compound (a2).

Further, in the case of the above-mentioned blocked isocyanate (a4), a compound exemplified as the polyisocyanate (e4) and a blocker as exemplified below may be blocked.

Examples of the above blocking agent include active methylene compounds such as malonic acid diester (diethyl malonate), acetamylacetone, acetamidine acetate (ethyl acetate, etc.); Anthraquinone compounds such as acetamidine, methyl ethyl ketone oxime (MEK 肟), methyl isobutyl ketone oxime (MIBK 肟); methanol, ethanol, propanol, butanol, heptanol, hexanol, octanol, 2 a monovalent alcohol such as ethylhexanol, isodecyl alcohol or stearyl alcohol or such isomers; methyl glycol, ethyl glycol, ethyl diethylene glycol, ethyl triethylene glycol , ethylene glycol derivatives such as ethylene glycol butyl ether and butyl diethylene glycol; amine compounds such as dicyclohexylamine; phenol, cresol, ethyl phenol, n-propanol, isopropyl phenol, butanol, tertiary Butyl phenol, octyl phenol, decyl phenol, dodecyl phenol, cyclohexyl phenol, chlorophenol, bromophenol, resorcinol, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, naphthol Such as phenols; ε-caprolactone and the like.

In order to obtain the block reaction of the above blocked isocyanate, it can be carried out by a known method. The amount of the blocking agent added is usually from 1 equivalent to 2 equivalents, and preferably from 1.05 to 1.5 equivalents, per equivalent of the free isocyanate group.

Further, in the present invention, a stabilizer may be added in the step (A). Examples of the stabilizer include boric acid esters such as trimethyl borate, triethyl borate, tributyl borate, and monophenyl borate; adipic acid, glutaric acid, pemelilic acid, and suberic acid. And polycarboxylic acids such as azelaic acid, maleic acid, itaconic acid, citric acid, isophthalic acid, terephthalic acid, 1,2,4,-benzenetricarboxylic acid, and pyromellitic acid. In the present invention, one or more of these stabilizers may be used in combination.

The latent curing agent for a powdery epoxy resin obtained by the present invention can be used in combination with a main component containing a polyepoxy compound as a main component. In particular, since it is excellent in storage stability, it is suitable as a component of a one-component curing type curable resin composition.

For the polyepoxy compound of the curable epoxy resin composition of the present invention, there is a polyepoxypropyl group of a mononuclear polyvalent phenol compound such as hydroquinone, resorcin, pyrocatechol or phloroglucin. Ether ether compound; dihydroxynaphthalene, bisphenol, methylene bisphenol (bisphenol F), methylene bis(o-cresol), ethylene bisphenol, isopropylidene bisphenol (bisphenol A), Hexamethylene bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1 , 1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, bisthiophenol, sulfobisphenol, hydroxybisphenol, phenol novolac Polyepoxypropyl ether compound of nucleating polyphenolic compound such as varnish, o-cresol novolac, cresol novolac, butyral novolac, octanophenol novolac, resorcinol novolac, terpene phenol ; ethylene glycol, propylene glycol, butanediol, hexanediol, polyethylene glycol, diethanol sulfide, glycerin, trimethylolpropane, neopentyl alcohol, sorbitol, bisphenol A-ethylene oxide a polyepoxy propyl ether of a polyvalent alcohol such as an adduct; maleic acid, anti Arogate, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, citric acid, isophthalic acid, para-benzene Aliphatic, aromatic or aliphatic such as dicarboxylic acid, 1,2,4,-benzenetricarboxylic acid, trimesic acid, pyromellitic acid, tetrahydrofurfuric acid, hexahydrophthalic acid, terminal methylene tetrahydrofurfuric acid a single polymer or copolymer of a cyclopropyl polybasic acid glycidyl ester and a glycidyl methacrylate; N,N-diepoxypropylaniline, bis(4-(N-methyl) -N-epoxypropylamino)phenyl)methane, diepoxypropyl o-toluidine, etc. epoxy compound having a glycidylamino group; ethylene cyclohexene diepoxide, dicyclopentadiene Diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6- Epoxide of a cyclic olefin compound such as methylcyclohexane carboxylate or bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized polybutadiene, ring Epoxidized conjugated diene polymer such as styrene-butadiene copolymer, triepoxypropyl iso-cyanate, etc. Compound.

Further, the epoxy resins may be internally crosslinked by a prepolymer of a terminal isocyanate, or may be polymerized by a polyvalent active hydrogen compound (polyvalent phenol, polyamine, polyphosphate, etc.). .

Further, the polyepoxy compound used in the curable epoxy resin composition of the present invention preferably has an epoxy equivalent of from 100 to 2,000, particularly preferably from 150 to 1,500. When the epoxy equivalent is less than 100, the hardenability is lowered. When the epoxy equivalent is more than 2,000, the case where sufficient coating property cannot be obtained is not preferable.

The curable epoxy resin composition of the present invention can be dissolved in various solvents for easy handling.

In addition to the aforementioned solvents (a1) and (f1), such solvents include, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether. Ketones such as acetate and cyclohexanone; esters such as ethyl acetate and n-butyl acetate; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; High-grade paraffinic solvent such as mineral spirit, Swazol #310 (trade name of Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (trade name of Exxon Chemical Co., Ltd.), and the like.

The solvent is used in an amount of from 0 to 40 parts by mass, preferably from 0 to 20 parts by mass, per 100 parts by mass of the polyepoxy compound. When the amount is more than 200 parts by mass, it is not preferable because it may be volatilized and dangerous or harmful.

In the present invention, a reactive or non-reactive diluent may be used in combination. As the reactive diluent, there are, for example, phenol, cresol, ethyl phenol, propyl phenol, tertiary butyl phenol, p-tripentyl phenol, hexyl phenol, octyl phenol, decyl phenol, dodecyl phenol, stearyl phenol or hydrazine. A monoepoxypropyl ether compound such as terpene phenol. Further, as the non-reactive diluent, there are, for example, dioctyl phthalate, dibutyl phthalate, benzyl alcohol and the like.

In the curable epoxy resin composition of the present invention, the polyepoxy compound and the latent curing agent of the present invention are used in an amount such that the former epoxy equivalent is equal to the latter active hydrogen equivalent. The amount of the latent hardener to be used may be changed in any range as needed, however, the ratio of use of the main component of the polyepoxide and the hardener (the former: the latter, the mass basis) is (90 to 10): (10 - 90) The range should be better.

In the curable epoxy resin composition of the present invention, in order to improve the hardenability, a curing accelerator may be used in combination.

Examples of the above hardening accelerator include trimethylamine, ethyldimethylamine, propyldimethylamine, and N,N'-dimethylhexahydropyridyl. , pyridine, picoline, 1,8-diazobicyclo(5,4,0) undecene-1 (DBU), benzyldimethylamine, 2-(dimethylaminomethyl)phenol Tertiary amines such as (DMP-10), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30); phenol novolac, o-cresol novolac, p-cresol novolac, three a phenol such as a butyl phenol novolak or a dicyclopentadienyl cresol; a 1-aminopyrrolidine salt of p-toluic acid or thiocyanate (manufactured by Otsuka Chemical Co., Ltd.; NR-S).

The amount of the hardening accelerator to be used is preferably from 1 to 30% by mass based on the total solid content, and particularly preferably from 2 to 20% by mass.

As the curable epoxy resin composition of the present invention, a known curing agent which is usually used as an epoxy resin can be used. Especially dicyandiamide; anhydride; bismuth oxalate, diammonium malonate, diterpene succinate, diammonium glutarate, diammonium adipate, dinononic acid, A dibasic acid diterpene such as diterpene sebacate, diterpene sebacate or diterpene niobate; a so-called latent hardener such as melamine can be suitably used.

The curable epoxy resin composition of the present invention may contain, as needed, glass fiber, carbon fiber, cellulose, siliceous sand, cement, kaolin, clay, aluminum hydroxide, bentonite (Bentonite). ), talc, cerium oxide, fine powder of cerium oxide, titanium dioxide, carbon black, graphite, iron oxide, asphalt, etc. filler or pigment; tackifier; thixotropic agent; flame retardant; defoaming Defoaming agent; rust inhibitor; additive commonly used in colloidal cerium oxide, colloidal alumina, and the like. Further, an adhesive resin such as a xylene resin or a petroleum resin may be used in combination.

The latent hardener for epoxy resin of the present invention is combined with a main agent mainly composed of a polyepoxide, for example, relative to concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc. Coatings or adhesives; adhesive tapes for packaging, adhesive labels, frozen food labels, removable labels, POS labels, adhesive wallpapers, flooring materials, etc.; art paper, lightweight Processing paper such as coated paper, cast coated paper, coated paper board, carbonless printer, impregnated paper, etc.; natural fiber, synthetic fiber, glass fiber, carbon fiber, metal fiber, etc. , bundling agent, fray agent, processing agent and other fiber treatment agents; sealing materials, cement tight mixes, waterproof materials and other building materials, etc., can be used for a wide range of applications.

The present invention will be further illustrated by the following examples, but the invention is not limited by the examples. Further, in the examples, the volume average particle diameter is a value measured by using Microtrack MT3300 (trade name manufactured by Nikkiso Co., Ltd.).

[Example 1]

After dissolving 102 g of dimethylaminopropylamine in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (Acetone bisepoxypropyl ether type manufactured by ADEKA Co., Ltd.) was added at 60-100 °C. The trade name of epoxy resin: 190 g of epoxy equivalent: 190 g, aging and further heating to 180 ° C and removal of xylene and isopropanol to obtain a solid having a melting point of 70 ° C. Next, the obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

In 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.: epoxy equivalent 170), 1.6 g of water was added and uniformly mixed, and the obtained was added. 60 g of the fine powder was further uniformly mixed. Next, 8.1 g of toluene diisocyanate (TDI) was added, and after the reaction was carried out at 40 to 50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared. Then, 500 g of toluene was added/mixed, and after filtration/drying, a powder having a volume average particle diameter of 4 μm (product 1 of the present invention) was obtained.

[Example 2]

After dissolving 82 g of 2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (made by ADEKA, bisphenol A diglycidyl ether type) was added at 60-100 °C. The trade name of the epoxy resin: 190 g of an epoxy group equivalent: 190), aged and reacted, and further heated to 180 ° C, and xylene and isopropyl alcohol were removed to obtain a solid matter having a melting point of 95 ° C. Next, the obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

In 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.: epoxy equivalent 170), 1.6 g of water was added thereto, and the mixture was uniformly mixed. 60 g of fine powder was further uniformly mixed. Next, 8.1 g of toluene diisocyanate (TDI) was added, and after reacting at 40-50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared. Next, 500 g of toluene was added/mixed, and after filtration/drying, a powder having a volume average particle diameter of 4 μm (product 2 of the present invention) was obtained.

[Example 3]

After dissolving 125 g of 1-aminoethyl-2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (bisphenol A manufactured by Adeka Co., Ltd.) was added at 60-100 °C. Diethylene oxide propyl type epoxy resin trade name: epoxide equivalent 190) 190 g, aged and reacted. Further, the mixture was heated to 180 ° C and xylene and isopropanol were removed to obtain a solid having a melting point of 80 ° C. Next, the obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

In 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether type epoxy resin, epoxy resin equivalent: 170), 1.6 g of water was added and uniformly mixed, and the obtained result was added. 60 g of the fine powder was further uniformly mixed. Next, 8.1 g of toluene diisocyanate (TDI) was added, and after the reaction was carried out at 40 to 50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared. Then, 500 g of toluene was added/mixed, and after filtration/drying, a powder having a volume average particle diameter of 3 μm (product 3 of the present invention) was obtained.

[Embodiment 4]

After dissolving 112 g of 1,2-diaminopropane in 200 g of xylene, Adeca resin EP-4100E (trade name of bisphenol A diepoxypropyl ether type epoxy resin manufactured by ADEKA Co., Ltd.) was added at 60-100 °C. : epoxide equivalent 190) 190 g, aged and reacted. Next, 102 g of dimethylaminopropylamine, 221 g of isophorone diisocyanate and 174 g of methyl ethyl ketone oxime were added, and 395 g of a previously prepared reaction product was added, and further heated to 180 ° C and removed. Xylene and methyl ethyl ketone oxime to obtain a solid matter having a melting point of 90 °C. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

In the Adeca resin EP-4901E (trade name: epoxide F diglycidyl ether epoxy resin, manufactured by Adeka Co., Ltd., trade name: epoxy equivalent 170), 133.1 g, 1.6 g of water was added thereto, and the mixture was uniformly mixed. 60 g of fine powder was further uniformly mixed. Next, 8.1 g of toluene diisocyanate (TDI) was added, and after reacting at 40-50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared. Then, 500 g of toluene was added/mixed, and after filtration/drying, a powder having a volume average particle diameter of 5 μm (product 4 of the present invention) was obtained.

[Comparative Example 1]

After dissolving 82 g of 2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (bisphenol A diglycidyl ether ring made by ADEKA) was added at 60-100 °C. Oxygen resin trade name: epoxide equivalent 190) 190 g, aged and reacted. Further, the mixture was heated to 180 ° C to remove xylene and isopropyl alcohol to obtain a solid having a melting point of 95 ° C. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm (Comparative Product 1).

[Comparative Example 2]

After dissolving 82 g of 2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (made by ADEKA, bisphenol A diglycidyl ether type) was added at 60-100 °C. Epoxy resin trade name: epoxide equivalent 190) 190 g, aged and reacted. Further, the mixture was heated to 180 ° C to remove xylene and isopropyl alcohol to obtain a solid having a melting point of 95 ° C. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

In 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.: epoxy equivalent 170), 1.6 g of water was added thereto, and the mixture was uniformly mixed. 60 g of fine powder (f-1) was further uniformly mixed. Next, 8.1 g of toluene diisocyanate (TDI) was added, and after reacting at 40-50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared, and Comparative Product 2 was obtained.

[usage]

The following evaluation test was carried out using the latent curing agent for epoxy resin (the present invention and the comparative product) obtained in the above Examples 1 to 4 and Comparative Example 1-2. Further, the viscosity increasing ratio (%) was calculated based on the measured viscosity using a BM type rotational viscometer.

[Embodiment 5] (relative to the storage stability of epoxy resin)

In 100 parts by mass of Adeca resin EP-4901E (trade name of bisphenol F epoxy propyl ether type epoxy resin manufactured by ADEKA Co., Ltd.: epoxy equivalent 170), the epoxy resin latent curing agent 20 obtained above is mixed. In parts by mass, a hardenable epoxy resin composition was obtained. The obtained curable epoxy resin composition was stored at 40 ° C and evaluated for viscosity increase rate (%) after 1 day, 3 days, and 7 days later. Further, in Comparative Example 5-2, since the abrasion of the epoxy resin caused by the step (F) was not performed, 40 parts by mass of the above-mentioned Adeca resin EP-4901E and 80 parts by mass of the latent curing agent for epoxy resin were used. The results are shown in [Table 1].

[Embodiment 6] (solvent stability)

The above-mentioned epoxy resin latent hardener 20 is mixed in 100 parts by mass of Adeca resin EP-4901E (trade name: epoxide F epoxy epoxide type epoxy resin, manufactured by Adeka Co., Ltd.). A part by mass and toluene to obtain a curable epoxy resin composition. The obtained curable epoxy resin composition was stored at 40 ° C and evaluated for a viscosity increase ratio (%) after 6 hours. Further, in Comparative Example 6-2, since the epoxy resin was not worn by the step (F), 40 parts by mass of the above Adeca resin EP-4901E and 80 parts by mass of the latent curing agent for epoxy resin were used. The results are shown in [Table 2].

[Embodiment 7] (solvent stability)

The evaluation of the tack-increasing ratio (%) was carried out in the same manner as in Example 6 except that ethyl acetate was used instead of toluene. The results are shown in [Table 3].

[Embodiment 8] (hardening speed)

The above-mentioned epoxy resin latent hardener 20 is mixed in 100 parts by mass of Adeca resin EP-4901E (trade name: epoxide F epoxy epoxide type epoxy resin, manufactured by Adeka Co., Ltd.). In parts by mass, a hardenable epoxy resin composition was obtained. The obtained curable epoxy resin composition was measured for the time (seconds) until it was completely cured by heating at 150 ° C and 180 ° C. Further, in Comparative Example 8-2, since the epoxy resin was not worn by the step (F), 40 parts by mass of the above Adeca resin EP-4901E and 80 parts by mass of the latent curing agent for epoxy resin were used. The results are shown in [Table 4].

As is apparent from the above-described Examples 5 to 8, in the case where a latent curing agent for powdery epoxy resin (Comparative Product 1) obtained by pulverizing a polyamine epoxy adduct was used, storage stability and solvent stability were remarkably lowered. Further, in the case where a fine powder obtained by pulverizing a polyamine epoxy adduct is surface-treated with a polyisocyanate to obtain a masterbatch type epoxy resin latent curing agent (Comparative Product 2), a comparative product is used. In comparison with the case of 1, the storage stability and the solvent stability are improved at the same time, but the performance as a product is not sufficient.

On the other hand, the fine powder obtained by pulverizing the polyamine epoxy adduct is surface-treated with a polyisocyanate, and further washed with a non-polar solvent to obtain a latent curing agent for a powdery epoxy resin (inventive products 1 to 4). In other cases, it was confirmed that not only the storage stability and the solvent stability were remarkably improved, but also the hardenability was excellent.

[Embodiment 9]

After dissolving 102 g of dimethylaminopropylamine in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (bisphenol A digoxypropyl group manufactured by Adeka Co., Ltd.) was added at 60 to 100 °C. The name of the ether type epoxy resin is 190 g of epoxy equivalent 190, which is aged and reacted. Next, it was heated to 180 ° C and xylene and isopropyl alcohol were removed.

Further, 125 g of a phenol resin (trade name: PSM-4326, melting point: 126 ° C) was added, and after dissolving and dehydrating at 180 ° C, a solid matter having a melting point of 80 ° C was obtained. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

1.6 g of water was added to 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.), and uniformly mixed, and the volume obtained above was added. 60 g of fine powder having an average particle diameter of 2 μm was uniformly mixed.

Next, 8.1 g of toluene diisocyanate (TDI) was added, and after reacting at 40 to 50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared. Further, 500 g of toluene was added thereto, and after filtration and drying, a powder having a volume average particle diameter of 4 μm (product 5 of the present invention) was obtained.

[Embodiment 10]

After dissolving 82 g of 2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (bisphenol A diglycidyl ether ring made by ADEKA) was added at 60 to 100 °C. Oxygen resin trade name: epoxide equivalent 190) 190 g, aged and reacted. Next, it was heated to 180 ° C and xylene and isopropyl alcohol were removed.

Further, 117 g of dicyclopentadiene phenol resin (manufactured by Shin-Nippon Chemical Co., Ltd.; trade name: DPP-6125, melting point: 120 ° C) was added, and the mixture was dissolved at 180 ° C to obtain a solid matter having a melting point of 125 ° C. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

In 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.: epoxy equivalent 170), 1.6 g of water was added thereto, and the mixture was uniformly mixed. 60 g of a fine powder having a volume average particle diameter of 2 μm was uniformly mixed.

Next, 8.1 g of toluene diisocyanate (TDI) was added and reacted at 40 to 50 ° C for 2 hours, and it was confirmed that the NCO absorption of IR disappeared. Further, 500 g of toluene was added thereto, and after filtration and drying, a powder having a volume average particle diameter of 3 μm (product 6 of the present invention) was obtained.

[Embodiment 11]

After dissolving 125 g of 1-aminoethyl-2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (made by Adeka Co., Ltd., bisphenol A) was added at 60 to 100 °C. Diethylene oxide propyl type epoxy resin trade name: epoxide equivalent 190) 190 g, aged and reacted. Next, it was heated to 180 ° C and xylene and isopropyl alcohol were removed.

Further, 135 g of a phenol resin (manufactured by Kyoei Chemical Co., Ltd.; trade name: PSM-4326, melting point: 126 ° C) was added, and after dissolving and dehydrating at 180 ° C, a solid matter having a melting point of 95 ° C was obtained. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

1.6 g of water was added to 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether type epoxy resin) to be uniformly mixed, and the above-mentioned volume was added. 60 g of fine powder having an average particle diameter of 2 μm was uniformly mixed.

Next, 8.1 g of toluene diisocyanate (TDI) was added, and after reacting at 40 to 50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared. Here, 500 g of toluene was further added, and after filtration and drying, a powder having a volume average particle diameter of 5 μm (product 7 of the present invention) was obtained.

[Embodiment 12]

After dissolving 112 g of 1,2-diaminopropane in 200 g of xylene, Adeca resin EP-4100E (trade name of bisphenol A diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.) was added at 60 to 100 °C. : Epoxy equivalent 190) 190 g, aged and reacted. Next, 102 g of dimethylaminopropylamine, 221 g of isophorone diisocyanate and 174 g of methyl ethyl ketone oxime were added, and 395 g of a previously prepared reaction product was added, and further heated to 180 ° C. And removing xylene and methyl ethyl ketone oxime.

Next, 129 g of a phenol resin (trade name: PSM-4326, melting point: 126 ° C) was added, and after dissolving and dehydrating at 180 ° C, a solid matter having a melting point of 90 ° C was obtained. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

1.6 g of water was added to 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.), and uniformly mixed, and the volume obtained above was added. 60 g of fine powder having an average particle diameter of 2 μm was uniformly mixed.

Next, 8.1 g of toluene diisocyanate (TDI) was added and reacted at 40 to 50 ° C for 2 hours, and it was confirmed that the NCO absorption of IR disappeared. Here, 500 g of toluene was further added, and after filtration and drying, a powder having a volume average particle diameter of 4 μm (product 8 of the present invention) was obtained.

[Comparative Example 3]

After dissolving 82 g of 2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (bisphenol A diglycidyl ether ring made by ADEKA) was added at 60 to 100 °C. Oxygen resin trade name: epoxide equivalent 190) 190 g, aged and reacted. Subsequently, the mixture was heated to 180 ° C and xylene and isopropanol were removed to obtain a solid having a melting point of 95 ° C. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm (Comparative Product 3).

[Comparative Example 4]

After dissolving 82 g of 2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (bisphenol A diglycidyl ether ring made by ADEKA) was added at 60 to 100 °C. Oxygen resin trade name: epoxide equivalent 190) 190 g, aged and reacted. Subsequently, the mixture was heated to 180 ° C, and xylene and isopropyl alcohol were removed to obtain a solid matter having a melting point of 95 ° C. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.: epoxy equivalent 170) 133.1 g of water added 1.6 g was uniformly mixed, and the volume average obtained above was added. 60 g of a fine powder having a particle diameter of 2 μm was uniformly mixed.

Next, 8.1 g of toluene diisocyanate (TDI) was added, and after reacting at 40 to 50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared. Here, 500 g of toluene was further added, and after filtration and drying, a powder having a volume average particle diameter of 3 μm (Comparative Product 4) was obtained.

[Comparative Example 5]

After dissolving 82 g of 2-methylimidazole in a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, Adeca resin EP-4100E (bisphenol A diglycidyl ether ring made by ADEKA) was added at 60 to 100 °C. Oxygen resin trade name: epoxide equivalent 190) 190 g, aged and reacted. Subsequently, the mixture was heated to 180 ° C and xylene and isopropanol were removed to obtain a solid having a melting point of 95 ° C. The obtained solid matter was pulverized to obtain a fine powder having a volume average particle diameter of 2 μm.

1.6 g of water was added to 133.1 g of Adeca resin EP-4901E (trade name of bisphenol F diglycidyl ether epoxy resin manufactured by Adeka Co., Ltd.), and uniformly mixed, and the volume obtained above was added. 60 g of fine powder having an average particle diameter of 2 μm was uniformly mixed.

Next, 8.1 g of toluene diisocyanate (TDI) was added, and after reacting at 40 to 50 ° C for 2 hours, it was confirmed that the NCO absorption of IR disappeared, and Comparative Product 5 was obtained.

[usage]

The following evaluation tests were carried out using the latent curing agents for epoxy resins (Inventive Products 5 to 8 and Comparative Products 3 to 5) obtained in the above Examples 9 to 12 and Comparative Examples 3 to 5. Further, the viscosity increasing ratio (%) was calculated based on the measured viscosity using a BM type rotational viscometer.

[Example 13] (relative to the storage stability of epoxy resin)

100 parts by mass of Adeca resin EP-4901E (trade name of bisphenol F epoxy propyl ether type epoxy resin manufactured by Adeka Co., Ltd.: epoxy equivalent 170), and 20 parts by mass of the latent curing agent for epoxy resin obtained above A curable epoxy resin composition is obtained. The obtained curable epoxy resin composition was stored at 40 ° C and evaluated for the viscosity increase rate (%) after 1 day, 3 days, and 7 days later. Further, with respect to Comparative Example 13-3, since the epoxy resin was not worn by the step (F), the Adeca resin was used in order to make the use ratio of the epoxy resin and the latent hardener different from those of the other examples. EP-4901E 40 parts by mass and 80 parts by mass of a latent curing agent for epoxy resin.

The results are shown in [Table 5].

[Embodiment 14] (solvent stability)

100 parts by mass of the Adeca resin EP-4901E (made by ADEKA Co., Ltd., bisphenol F epoxy propyl ether type epoxy resin: epoxy equivalent 170), 20 parts by mass of the latent curing agent for epoxy resin obtained, and toluene 20 parts by mass, a hardenable epoxy resin composition was obtained. With respect to the obtained curable epoxy resin composition, the tack-increasing ratio (%) after six hours was stored and evaluated at 4 ° C. Further, regarding Comparative Example 14-3, the epoxy resin was not subjected to the step (F). Since the ratio of the use ratio of the epoxy resin to the latent curing agent is the same as the other examples, the Adeca resin EP-4901E is used in an amount of 40 parts by mass and the epoxy resin latent curing agent is used in an amount of 80 parts by mass.

The results are shown in [Table 6].

[Example 15]

The tack-increasing ratio (%) was evaluated in the same manner as in Example 14 except that 20 parts by mass of ethyl acetate was used instead of 20 parts by mass of toluene. The results are shown in [Table 7].

[Example 16] (shear test)

20 parts by mass of the latent curing agent for epoxy resin obtained by mixing the above-mentioned epoxy resin latent curing agent in 100 parts by mass of Adeca resin EP-4901E (trade name of bisphenol F epoxy propyl ether type epoxy resin manufactured by Adeka Co., Ltd.) A curable epoxy resin composition is obtained. With respect to the obtained curable epoxy resin composition, a test piece was produced under the curing conditions of 180 ° C and 60 minutes, and the shear adhesive strength of the soft steel plate was determined by the method of JIS K6850. Further, in Comparative Example 16-3, since the epoxy resin was not worn by the step (F), the Adeca resin EP was used in order to match the use ratio of the epoxy resin to the latent curing agent to other examples. -4901E 40 parts by mass and 80 parts by mass of a latent curing agent for epoxy resin.

(glass transition temperature; Tg)

The above-mentioned epoxy resin latent hardener 20 is mixed in 100 parts by mass of Adeca resin EP-4901E (trade name of bisphenol F epoxy propyl ether type epoxy resin, manufactured by Adeka Co., Ltd.). A hardening epoxy resin composition was obtained. Regarding the hardened material of the curable epoxy resin composition obtained under the same hardening conditions as in the case of the shear test, a differential scanning calorimeter DSC6220 (manufactured by Seiko Instruments Inc.) was used at a temperature increase rate of 10 The DSC was measured at ° C/min and the scanning temperature range of 25 to 300 °C. Further, the temperature was raised twice under the same conditions, and the glass transition temperature was measured from the change in the heat capacity. Further, in Comparative Example 16-3, since the epoxy resin was not worn by the step (F), the Adeca resin EP was used in order to match the use ratio of the epoxy resin to the latent curing agent to other examples. -4901E 40 parts by mass and 80 parts by mass of a latent curing agent for epoxy resin.

The shearing force (MPa) and the glass transition temperature [Tg] of the cured product with respect to each of the curable resin compositions are as shown in [Table 8].

From the results of the above-mentioned Examples 9 to 16, it is understood that storage stability and solvent stability are remarkable in the case where a latent curing agent (Comparative Product 3) for a powdery epoxy resin obtained by pulverizing a polyamine epoxy adduct is used. Lowering is not sufficient in the physical surface of the cured product. Further, the fine powder obtained by pulverizing the polyamine epoxy adduct is subjected to surface treatment with a polyisocyanate, and further, when a latent curing agent for a powdery epoxy resin (Comparative Product 4) is obtained by washing with a non-polar solvent, Although improvement in storage stability and solvent stability was observed, the physical properties of the cured product were insufficient. Further, in the case of using a master batch type latent curing agent (Comparative Product 5) of a master batch type obtained by subjecting a fine powder obtained by pulverizing a polyamine epoxy adduct to a polyisocyanate. Although the storage stability and the solvent stability were observed to be improved at the same time, the physical properties of the cured product were insufficient for the completely insufficient performance .

On the other hand, the fine powder obtained by pulverizing a mixture of a polyamine epoxy adduct and a phenol resin is surface-treated with a polyisocyanate, and further used as a latent hardener for washing a powdery epoxy resin obtained by washing with a non-polar solvent (this) In the case of Inventions 5 to 8), it was confirmed that not only the storage stability and the solvent stability were remarkably improved, but also the physical properties of the cured product were excellent.

In this way, the curable epoxy resin composition of the present invention using the latent curing agent for a powdery epoxy resin obtained by the production method of the present invention is excellent in storage stability and heat curability, for example, for concrete, cement mortar, A variety of coatings or adhesives for metals, leather, glass, rubber, plastic, wood, cloth, paper, etc. are useful. The cured product of the curable epoxy resin composition of the present invention obtained by using the latent curing agent for a powdery epoxy resin of the present invention has high heat resistance, excellent adhesion and electrical properties, and is therefore sealed for semiconductor protection. Suitable for electronic materials such as electronic component bonding or automotive materials.

The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and the equivalent technical changes of the present invention and the contents of the drawings are included in the scope of protection of the present invention. Within, combined with Chen Ming.

Claims (12)

A method for producing a latent hardener for a powdery epoxy resin, comprising the following steps (A) to (F): (A) an amine compound (a2) and an epoxy resin (a3) in a solvent (a1) a step of heating the reaction, (B) any one of the following steps (B2) to (B3): (B2) removing the solvent (a1), and removing the reactant of the amine compound (a2) and the epoxy resin (a3) ( B1), adding a phenol resin (b2) to the reactant (b1), heating, dissolving, dehydrating and removing the solid matter (b3), and (B3) adding the phenol resin (b2) to the step (A) After the reactant, the solvent (a1) is removed, heated, dissolved, and dehydrated, and a solid (solid) of a mixture of the amine compound (a2) and the epoxy resin (a3) (b1) and the phenol resin (b2) is taken out. (b3) a step of (C) pulverizing the solid matter (b3) to obtain a fine powder (c1) having a volume average particle diameter of 0.1 to 10 μm, and (D) adding water to the epoxy resin (d1) and After homogenization, the fine powder (c1) is added to obtain a uniform mixture (d2), and (E) is absorbed by infrared absorption of NCO until the disappearance of the polyisocyanate (e1) is confirmed to cause polyisocyanate ( E1) reacted in the mixture (d2) Reaction step (e2) of, and (F) after addition / mixing non-polar solvent (f1) to the reactant (e2), filtered and dried to obtain a powdery epoxy resin latent curing agent of step. The method for producing a latent hardener for a powdery epoxy resin according to claim 1, wherein the solvent (a1) is a nonpolar solvent or an alcohol or a mixture thereof. The method for producing a latent curing agent for a powdery epoxy resin according to the second aspect of the invention, wherein the non-polar solvent used in the (a1) is at least one selected from the group consisting of toluene, xylene, and ethylbenzene. The method for producing a latent curing agent for a powdery epoxy resin according to the second aspect of the invention, wherein the alcohol used in the (a1) is at least one selected from the group consisting of methanol, ethanol, propanol and isopropanol. . The method for producing a latent curing agent for a powdery epoxy resin according to the above aspect of the invention, wherein the amine compound (a2) is an amine compound having one or more primary or secondary amine groups. The method for producing a latent curing agent for a powdery epoxy resin according to the first aspect of the invention, wherein the epoxy resin (a3) is a bisphenol epoxy resin. The method for producing a latent curing agent for a powdery epoxy resin according to the first aspect of the invention, wherein the epoxy resin (d1) is a bisphenol epoxy resin. The method for producing a latent curing agent for a powdery epoxy resin according to the first aspect of the invention, wherein the polyisocyanate (e1) is an aromatic polyisocyanate. The method for producing a latent curing agent for a powdery epoxy resin according to the first aspect of the invention, wherein the non-polar solvent (f1) is at least one selected from the group consisting of aromatic, aliphatic or alicyclic hydrocarbons. The method for producing a latent curing agent for a powdery epoxy resin according to claim 1, wherein in the step (A), after reacting the amine compound (a2) with the epoxy resin (a3), Further, an additional amine compound (a2') and a blocked isocyanate (a4) are added and heated. A latent hardening agent for a powdery epoxy resin, which is obtained by the method according to any one of the above claims. A curable epoxy resin composition comprising a polyepoxy compound and a latent curing agent for a powdery epoxy resin according to claim 11 of the patent application.