JP2016079273A - Epoxy resin and method for producing the same, composition containing epoxy resin, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for producing an epoxy resin, in which, when reacting an epoxy compound and a phenol-based compound by an advancement process, the reaction proceeds sufficiently and an epoxy resin obtained has excellent storage stability in the presence of other materials; an epoxy resin obtained by the production method; a composition containing the epoxy resin; and a cured product.SOLUTION: Provided is a method for producing an epoxy resin, comprising reacting an epoxy compound (A) and a phenol-based compound (B) in the presence of a trialkylphosphine (C1), a dialkylarylphosphine (C2), or an alkyldiarylphosphine (C3).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an epoxy resin having excellent reaction activity and excellent storage stability when the resulting epoxy resin is mixed with other components, particularly a curing agent, and an epoxy resin obtained by the production method. Moreover, this invention relates to the epoxy resin containing composition and hardened | cured material which are obtained using this epoxy resin.

Epoxy resins are widely used in fields such as paints, civil engineering, adhesion, and electrical materials because they are excellent in heat resistance, adhesion, chemical resistance, water resistance, mechanical strength, electrical properties, and the like.
Generally, epoxy resin is produced by a toffee method (one-step method) in which an epihalohydrin is reacted with a phenol compound in the presence of an alkali, or an advanced method (two-step method) in which an epoxy compound and a phenol compound are reacted in the presence of a catalyst. Law) etc. are known. The advanced method is known to be a method suitable for the production of a high molecular weight epoxy resin that is difficult to purify after synthesis because it hardly produces by-products such as sodium chloride compared to the toffee method. Non-Patent Document 1 describes that onium salt compounds, alkaline compounds and the like are generally used as a catalyst for producing an epoxy resin by the advance method.

  When the epoxy resin is used in the fields of paint, civil engineering, adhesion, electrical material and the like as described above, it is generally used as a mixture with multiple materials including a curing agent. According to the detailed study by the present inventors, an epoxy resin using an onium salt-based compound or an alkaline compound as a catalyst as described in Non-Patent Document 1 when produced by the advanced method, It has been found that the storage stability may be insufficient when mixed with other materials.

  Although it is also described in Non-Patent Document 1 that triphenylphosphine is used as a catalyst as a phosphorus compound, it has been found that triphenylphosphine has insufficient activity as a catalyst for the advance method.

Review Epoxy Resin Volume 1 Basics I Epoxy Resin Technology Association (2003)

  The present invention has been made in view of the above problems of the prior art. That is, an object of the present invention is to provide an epoxy resin in which the reaction proceeds sufficiently when the epoxy compound and the phenol compound are reacted by the advance method, and the obtained epoxy resin is excellent in storage stability with other materials. It is providing the manufacturing method and the epoxy resin obtained by this manufacturing method, an epoxy resin containing composition, and hardened | cured material.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a method for producing an epoxy resin that is reacted in the presence of a specific phosphine compound when an epoxy resin is obtained using an epoxy compound and a phenolic compound as raw materials. Thus, the inventors have found that the above-described problems can be solved, and have completed the invention. That is, the gist of the present invention resides in the following [1] to [8].
[1] An epoxy compound (A) and a phenolic compound (B) are converted into a trialkylphosphine (C1), a dialkylarylphosphine (C2) or an alkyldiarylphosphine (C
A method for producing an epoxy resin to be reacted in the presence of 3).
[2] 0.05-1.25 mol of phenolic compound (B) is used per 1.00 mol of epoxy compound (A), and trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine The method for producing an epoxy resin according to [1], wherein the amount of (C3) used is 10 to 50000 ppm by weight of the amount of the epoxy compound (A) used. [3] An epoxy resin obtained by the method for producing an epoxy resin according to any one of [1] to [2].
[4] Epoxy equivalent is 100 to 200,000 g / eq. The epoxy resin according to [3].
[5] An epoxy resin-containing composition comprising the epoxy resin according to claim [3] or [4] and a curing agent.
[6] The epoxy resin-containing composition according to [5], including 0.1 to 1000 parts by weight of a curing agent with respect to 100 parts by weight of the epoxy resin.
[7] The curing agent is selected from the group consisting of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, cationic polymerization initiators, and organic phosphines. The epoxy resin-containing composition according to [5] or [6], which is at least one.
[8] A cured product obtained by curing the epoxy resin-containing composition according to any one of [5] to [7].

[Method for producing epoxy resin]
In the method for producing an epoxy resin of the present invention, an epoxy compound (A) and a phenol compound (B) are reacted in the presence of a trialkylphosphine (C1), a dialkylarylphosphine (C2) or an alkyldiarylphosphine (C3). It is.
In the present invention, the method for producing an epoxy resin of the present invention may be referred to as “the production method of the present invention”. Moreover, the epoxy resin obtained by the manufacturing method of the epoxy resin of this invention may be called "the epoxy resin of this invention." The epoxy resin of the present invention has the effect of being remarkably excellent in storage stability when blended with other components, particularly a curing agent. This is presumably because the phosphine compound used in the present invention is susceptible to oxidation and deactivates rapidly after completion of the reaction. In addition, the phosphine compound used in the present invention has higher activity in the advance method than triphenylphosphine. This is presumably because the phosphorus atom of the trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3) of the present invention is directly bonded to at least one alkyl group.

[Epoxy compound (A)]
In the present invention, the epoxy compound (A) may be a compound having two or more epoxy groups in the molecule, and a bifunctional epoxy compound and a polyfunctional epoxy compound (in the present invention, "polyfunctional epoxy compound" It means a trifunctional or higher functional epoxy compound.).

For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, bisphenol Z diglycidyl ether, bisphenol S diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol acetophenone diglycidyl ether, Bisphenols such as bisphenol trimethylcyclohexane diglycidyl ether, bisphenol fluorenediglycidyl ether, tetramethyl bisphenol A diglycidyl ether, tetramethyl bisphenol F diglycidyl ether, tetra-t-butyl bisphenol A diglycidyl ether, tetramethyl bisphenol S diglycidyl ether Diglycidyl ether Biphenyl diglycidyl ethers such as biphenol diglycidyl ether, tetramethyl biphenol diglycidyl ether, dimethyl biphenol diglycidyl ether, tetra-t-butylbiphenol diglycidyl ether; hydroquinone diglycidyl ether, dihydroanthracene diglycidyl ether, methyl hydroquinone Benzenediol diglycidyl ethers such as diglycidyl ether, dibutyl hydroquinone diglycidyl ether, resorcin diglycidyl ether, methyl resorcin diglycidyl ether; dihydroanthrahydroquinone diglycidyl ether, dihydroxydiphenyl ether diglycidyl ether, thiodiphenol diglycidyl ether, Dihydroxy naphthalene diglycol Jill ether, and the like.

  As the bifunctional epoxy compound, an epoxy compound in which hydrogen is added to the aromatic ring of the epoxy compound listed above, adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, terephthalic acid, isophthalic acid, Epoxy resins produced from various carboxylic acids such as orthophthalic acid, biphenyldicarboxylic acid, dimer acid and the like and epihalohydrin, various amine compounds such as diaminodiphenylmethane, aminophenol and xylenediamine, and epoxy compounds produced from epihalohydrin , Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycol Dil ether, polytetramethylene glycol diglycidyl ether, 1,5-pentanediol diglycidyl ether, polypentamethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyhexamethylene glycol diglycidyl ether, 1,7 -Heptanediol diglycidyl ether, polyheptamethylene glycol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether Alkylene having a cyclic structure such as (poly) alkylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, etc. consisting only of a chain structure such as Recall diglycidyl ether may be mentioned.

  Examples of the polyfunctional epoxy compound include a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, a naphthol novolak type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl aralkyl type epoxy resin, and a dicyclopentadiene type. Epoxy resin, phenol-modified xylene type epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, and these various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal. Various phenolic compounds such as polycondensation resins obtained from polyhydric phenol resins, heavy oil or pitches, phenols and formaldehyde Epoxy resins obtained by use.

The epoxy compound (A) mentioned above can be used alone or in combination of two or more.
Among the epoxy compounds listed above, a bifunctional epoxy compound is preferable from the viewpoint of suppressing gelation during the reaction between the epoxy compound (A) and the phenolic compound (B).

[Phenolic compound (B)]
In the present invention, the phenolic compound (B) may be a compound having two or more hydroxyl groups bonded to an aromatic ring.
Examples of the phenolic compound (B) include bisphenol A, bisphenol F, bisphenol E, bisphenol Z, bisphenol S, bisphenol AD, bisphenol acetophenone, bisphenol trimethylcyclohexane, bisphenol fluorene, tetramethyl bisphenol A, tetramethyl bisphenol F, tetra Bisphenols such as t-butyl bisphenol A and tetramethyl bisphenol S; biphenols such as biphenol, tetramethyl biphenol, dimethyl biphenol, and tetra-t-butyl biphenol; hydroquinone, methyl hydroquinone, dibutyl hydroquinone, resorcin, methyl resorcin, and the like Benzenediols (here, “benzenediols” means one ben A compound having two ring groups, in which two hydroxyl groups are directly bonded to the benzene ring.); Dihydroanthrahydroquinones; dihydroxydiphenyl ethers such as dihydroxydiphenyl ether; thiodiphenols such as thiodiphenol; Dihydroxynaphthalenes such as dihydroxynaphthalene; dihydroxystilbenes such as dihydroxystilbene; phenol novolac resins, cresol novolac resins, bisphenol novolac resins such as bisphenol A novolac resins; naphthol novolac resins, phenol aralkyl resins, terpene phenol resins, Various phenol resins such as dicyclopentadiene phenol resin, phenol biphenylene resin, phenol-modified xylene resin, and these species Polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc., co-condensation resin of heavy oil or pitches with phenols and formaldehyde, etc. Various phenolic compounds are mentioned. The phenolic compounds (B) listed above can be used alone or in combination of two or more.

[Amount of use of epoxy compound (A) and phenolic compound (B)]
The amount of the phenol compound (B) used in the present invention is preferably 0.05 mol or more, more preferably 0.10 mol or more, relative to 1.00 mol of the epoxy compound (A), The amount is more preferably 0.15 mol or more, and particularly preferably 0.20 mol or more. On the other hand, the amount of the phenolic compound (B) used in the present invention is desirably 1.25 mol or less and 1.20 mol or less with respect to 1.00 mol of the epoxy compound (A). Preferably, it is more preferably 1.15 mol or less, and particularly preferably 1.10 mol or less. The blending amount of the phenolic compound (B) to be used is preferably the lower limit or more from the viewpoint of molecular weight elongation by the advance method, and the upper limit or less is preferable because an epoxy compound having good curability is easily obtained.

[Trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3)]
The trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3) used in the present invention acts as a catalyst for the reaction between the epoxy compound (A) and the phenolic compound (B).

  The trialkylphosphine (C1) may have a structure in which a phosphorus atom is bonded to three alkyl groups. All three alkyl groups bonded to the phosphorus atom of the trialkylphosphine (C1) may be the same or different. The alkyl group preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, preferably 20 or less carbon atoms, and more preferably 15 or less carbon atoms. The structure of the alkyl group may be any of linear, branched, and cyclic structures, may have a substituent, and may have an unsaturated bond.

Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, 2-methyl-n-butyl, n-hexyl, cyclohexyl, Examples include n-octyl and n-dodecyl.
Examples of trialkylphosphine (C1) include triallylphosphine, tributylphosphine, trimethylphosphine, tribenzylphosphine, triisobutylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri-n. -Propylphosphine, di-t-butylmethylphosphine, tri-n-butylphosphine, cyclohexyl di-tert-butylphosphine and the like.

  The dialkylaryl phosphine (C2) may have a structure in which a phosphorus atom is bonded to two alkyl groups and is bonded to one aryl group. Two alkyl groups bonded to the phosphorus atom of the dialkylarylphosphine (C2) may be the same or different. As the alkyl group, those described above can be used. The aryl group may have a substituent and preferably has 6 to 21 carbon atoms. Examples of the aryl group include phenyl, 4-methylphenyl, 2,4-dimethylphenyl and the like.

Examples of dialkylarylphosphine (C2) include diethylphenylphosphine, di-n-butylphenylphosphine, di-tert-butylphenylphosphine, didicyclohexylphenylphosphine and the like.
The alkyldiarylphosphine (C3) may have a structure in which a phosphorus atom is bonded to one alkyl group and bonded to two aryl groups. As the alkyl group, those described above can be used, and as the aryl group, those described above can be used.

Examples of the alkyldiarylphosphine (C3) include methyldiphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, cyclohexyldiphenylphosphine and the like.
The trialkylphosphine (C1), dialkylarylphosphine (C2), or alkyldiarylphosphine (C3) can be used alone or in combination of two or more.

  The amount of trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3) used in the present invention is preferably 10 ppm by weight or more based on the amount of the epoxy compound (A). 50 ppm by weight or more is more preferable, and 100 ppm by weight or more is particularly preferable. On the other hand, the blending amount of the trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3) used in the present invention is 50000 ppm by weight or less based on the blending amount of the epoxy compound (A). It is preferably 20000 ppm by weight or less, more preferably 10,000 ppm by weight or less, and particularly preferably 5000 ppm by weight or less. If the blending amount of the trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3) to be used is equal to or higher than the above lower limit, the molecular weight is increased by the advance method, and the storage stability tends to be good. Preferably, it is preferably at most the upper limit value in that the storage stability tends to be good.

[Other catalysts]
In the present invention, other catalysts may be used in combination with trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3). The other catalyst is not particularly limited as long as it is usually used as a catalyst for the advance method. For example, an alkali metal compound, a trialkylphosphine (C1), a dialkylarylphosphine (C2) or an alkyldiarylphosphine (C3) Organic phosphorus compounds other than the above, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like.

  Specific examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride; sodium Examples thereof include alkali metal alkoxides such as methoxide and sodium ethoxide; alkali metal hydrides such as alkali metal phenoxide, sodium hydride and lithium hydride; alkali metal salts of organic acids such as sodium acetate and sodium stearate. Specific examples of organic phosphorus compounds other than trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3) include triphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydro Oxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium The Amide, triphenyl ethyl phosphonium iodide, triphenyl benzyl phosphonium chloride, triphenyl benzyl phosphonium bromide, and the like. Specific examples of the tertiary amines include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like. Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride Id, and phenyl trimethylammonium chloride and the like. Specific examples of cyclic amines include 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5 diazabicyclo (4,3,0) -5-nonene. Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

The other catalysts mentioned above may be used alone or in combination of two or more. Moreover, the usage-amount of another catalyst is 10,000 weight ppm or less of the usage-amount of an epoxy compound (A) normally.
As other usage methods of the catalyst mentioned above, it can be used after diluting with an organic solvent or water. As the organic solvent, any organic solvent can be used as long as it can dissolve the raw materials. Specifically, trialkylphosphine (C1), dialkylarylphosphine (C2), or alkyldiarylphosphine (C3) is used. The same organic solvent can be used.

[Reaction conditions]
The reaction between the epoxy compound (A) and the phenolic compound (B) can be carried out under normal pressure, pressure, or reduced pressure. Moreover, reaction temperature is 80-240 degreeC normally, Preferably it is 100-220 degreeC, More preferably, it is 120 degreeC-200. It is preferable that the reaction temperature is equal to or higher than the above lower limit because the reaction can easily proceed. Moreover, side reaction is hard to advance that reaction temperature is below the said upper limit, and it is preferable from a viewpoint of obtaining a highly purified epoxy resin.
Although it does not specifically limit as reaction time, Usually, it is 0.5 to 24 hours, Preferably it is 1 to 22 hours, More preferably, it is 1.5 to 20 hours. When the reaction time is not more than the above upper limit, it is preferable from the viewpoint of improving production efficiency, and when the reaction time is not less than the above lower limit, it is preferable from the viewpoint that unreacted components can be reduced.

[solvent]
The epoxy resin of the present invention may use a solvent in the reaction step. Any solvent can be used as long as it dissolves the raw material, but it is usually an organic solvent.
Examples of the organic solvent include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, and the like. Specific examples of the aromatic solvent include benzene, toluene, xylene and the like. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone, and acetylacetone. Specific examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like. Specific examples of the glycol ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Examples include mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like.
The solvent mentioned above may use only 1 type, or may be used in combination of 2 or more type. In addition, when a highly viscous product is generated during the reaction, a solvent can be further added to continue the reaction.

[solvent]
The epoxy resin of this invention may adjust a solid content concentration by mixing a solvent after completion | finish of reaction. The solvent is not particularly limited as long as it can dissolve the epoxy resin, but is usually an organic solvent. As specific examples of the organic solvent, the same organic solvents as those mentioned above can be used. In the present invention, the terms “solvent” and “solvent” are used as the “solvent” when used in the reaction of the epoxy resin, and as the “solvent” as used after the completion of the reaction. Alternatively, different types may be used.
The solvent is preferably used so that the solid content is 10 to 90% by weight with respect to the epoxy resin. Moreover, it is more preferable to use it so that it may become 20 to 80 weight%.

[Epoxy equivalent]
The epoxy resin of the present invention preferably has an epoxy equivalent of 100 g / eq or more, more preferably 200 g / eq or more, still more preferably 300 g / eq or more, and 500 g / eq or more. Is particularly preferred. On the other hand, it is preferably 200,000 g / eq or less, more preferably 150,000 g / eq or less, still more preferably 100,000 g / eq or less, and 50,000 g / eq or less. Particularly preferred. It is preferable from the viewpoint of flexibility of the epoxy resin that the epoxy equivalent is equal to or higher than the lower limit, and when the epoxy resin-containing composition described later is cured as the epoxy equivalent is equal to or lower than the upper limit, the density between cross-linking points between epoxy groups is It is preferable in that it becomes high and it is easy to obtain cured physical properties. In the present invention, “epoxy equivalent” is defined as “the mass of an epoxy resin containing one equivalent of an epoxy group” and can be measured according to JIS K7236.

[Epoxy resin-containing composition]
The epoxy resin-containing composition of the present invention (in the present invention, sometimes referred to as “the epoxy resin-containing composition of the present invention”) contains at least the epoxy resin of the present invention described above and a curing agent. Moreover, the epoxy resin containing composition of this invention can mix | blend suitably another epoxy resin, a hardening accelerator, another component, etc. as needed. The epoxy resin-containing composition of the present invention is excellent in storage stability.

[Curing agent]
The curing agent used in the epoxy resin-containing composition of the present invention is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of the epoxy resin. In the present invention, even if what is usually called a “curing accelerator” is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of an epoxy resin, it is regarded as a curing agent. To do.

The content of the curing agent in the epoxy resin-containing composition of the present invention is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin of the present invention. Further, it is more preferably 80 parts by weight or less, and still more preferably 60 parts by weight or less.
Moreover, in the epoxy resin containing composition of this invention, when other epoxy resin mentioned later is contained, Preferably content of a hardening | curing agent is 0.1 to 100 weight part of all the epoxy resin components as solid content. 100 parts by weight. Further, it is more preferably 80 parts by weight or less, and still more preferably 60 parts by weight or less. In the present invention, the “solid content” means a component excluding a solvent, and includes not only a solid epoxy resin but also a semi-solid or viscous liquid material. The “total epoxy resin component” means the total of the epoxy resin of the present invention and other epoxy resins described later.

In the epoxy resin-containing composition of the present invention, polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, cationic polymerization initiators, and organic phosphines are used as curing agents. Preferably, at least one of the group consisting of:
Examples of polyfunctional phenols include bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol AD, bisphenol Z, tetrabromobisphenol A, bisphenols, 4,4′-biphenol, 3,3 ′, 5, Biphenols such as 5′-tetramethyl-4,4′-biphenol; catechol, resorcin, hydroquinone, dihydroxynaphthalene; and these are halogen groups, alkyl groups, aryl groups, ether groups, ester groups, sulfur, phosphorus, silicon And the like substituted with a non-interfering substituent such as an organic substituent containing a hetero element such as. Furthermore, novolaks and resoles which are polycondensates of monofunctional phenols such as phenols, phenols, cresols, alkylphenols, and aldehydes can be used.

  Specific examples of polyisocyanate compounds include tolylene diisocyanate, methylcyclohexane diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate. And polyisocyanate compounds such as lysine triisocyanate. Furthermore, the polyisocyanate compound obtained by the reaction of these polyisocyanate compounds with a compound having at least two active hydrogen atoms such as amino group, hydroxyl group, carboxyl group and water, or 3 to 5 amount of the above polyisocyanate compound The body etc. can be mentioned.

  Examples of amine compounds include aliphatic primary, secondary, tertiary amines, aromatic primary, secondary, tertiary amines, cyclic amines, guanidines, urea derivatives, and the like. Ethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, metaxylenediamine, dicyandiamide, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-nonene, dimethyl Examples include urea and guanylurea.

Examples of the acid anhydride compound include phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and a condensate of maleic anhydride and an unsaturated compound.
Examples of imidazole compounds include 1-isobutyl-2-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole and the like. It is done. The imidazole compound also functions as a curing accelerator described later, but in the present invention, it is classified as a curing agent.

Examples of amide compounds include dicyandiamide and its derivatives, polyamide resins, and the like.
Cationic polymerization initiators generate cations by heat or active energy ray irradiation, and include aromatic onium salts. _{Specifically, SbF 6 -, BF 4 -} , AsF 6 -, PF 6 -, CF 3 SO 3, B (C 6 F 5) anionic component of iodine 4 such as sulfur, nitrogen, atom such as phosphorus And a compound comprising an aromatic cation component containing In particular, diaryl iodonium salts and triaryl sulfonium salts are preferred.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

When using polyfunctional phenols, amine compounds, and acid anhydride compounds, the functional groups in the curing agent for all epoxy groups in the epoxy resin-containing composition (hydroxy groups of polyfunctional phenols, amino groups of amine compounds) Or an acid anhydride group of an acid anhydride compound) is preferably used so as to be in a range of 0.8 to 1.5. When an imidazole compound is used, it is preferably used in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the total epoxy resin component as a solid content. When using an amide-type compound, it is preferable to use it in the range of 0.1-20 weight% with respect to the total amount of all the epoxy resin components and amide-type compounds as solid content. When using a cationic polymerization initiator, it is preferable to use in 0.01-15 weight part with respect to 100 weight part of all the epoxy resin components as solid content. When using organic phosphines, it is preferably used in the range of 0.1 to 20% by weight based on the total amount of all epoxy resin components and organic phosphines as a solid content.
In addition to the curing agents listed above, for example, mercaptan compounds, organic acid dihydrazides, boron halide amine complexes, and the like can also be used in the epoxy resin-containing composition of the present invention. These curing agents may be used alone or in combination of two or more.

[Other epoxy resins]
In the epoxy resin-containing composition of the present invention, an epoxy resin other than the epoxy resin of the present invention (sometimes referred to as “other epoxy resin” in the present specification) can be used. Other epoxy resins were obtained by reacting the epoxy compound (A) and the phenolic compound (B) in the presence of a trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3). If not, the kind of the compound may be the same compound as the epoxy resin of the present invention.

Other epoxy resins include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin. , Glycidyl ether type epoxy resins such as tetrabromobisphenol A type epoxy resins, other polyfunctional phenol type epoxy resins, epoxy resins obtained by hydrogenating aromatic rings of the above aromatic epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxies Examples thereof include epoxy resins such as resins, linear aliphatic epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. The other epoxy resins mentioned above may be used alone or in combination of two or more. In addition, from the viewpoint of storage stability, it is preferable that other epoxy resins are not included when the epoxy resin-containing composition is stored, or the amount is smaller than that of the epoxy resin of the present invention.

[Other ingredients]
The epoxy resin-containing composition of the present invention can contain other components in addition to the components listed above. Examples of these various additives include coupling agents, flame retardants, plasticizers, reactive diluents, pigments, inorganic fillers, and the like.

[Cured product]
A cured product can be obtained by curing the epoxy resin-containing composition of the present invention. The term “curing” as used herein means that the epoxy resin composition is intentionally cured by heat and / or light or the like, and the degree of curing may be controlled by desired physical properties and applications. Further, the degree of curing may be in a completely cured state or in a semi-cured state, but the reaction rate of the curing reaction between the epoxy group and the curing agent is usually 5 to 95%.

The curing method of the epoxy resin-containing composition when making the cured product obtained by curing the epoxy resin-containing composition of the present invention varies depending on the blending component and blending amount in the epoxy resin-containing composition, but is usually 80 to Examples include heating conditions at 200 ° C. for 60 to 180 minutes. This heating may be performed in a two-stage process of primary heating at 80 to 160 ° C. for 10 to 30 minutes and secondary heating at 120 to 200 ° C. that is 40 to 120 ° C. higher than the primary heating temperature for 60 to 150 minutes, This is preferable from the viewpoint of reducing curing failure.
When producing a cured product as a semi-cured product, the curing reaction of the epoxy resin-containing composition may be advanced to such an extent that the shape can be maintained by heating or the like. When the epoxy resin-containing composition contains a solvent, most of the solvent is removed by techniques such as heating, reduced pressure, and air drying, but 5% by weight or less of the solvent may be left in the semi-cured product. .

[Use]
The epoxy resin of this invention is excellent in the storage stability at the time of mix | blending another component, especially a hardening | curing agent. Therefore, the epoxy resin obtained by the method for producing an epoxy resin of the present invention and the epoxy resin-containing composition containing the epoxy resin are used in the fields of paints, electrical / electronic materials, adhesives, carbon fiber reinforced resins (CFRP), and the like. Can be suitably used.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Raw materials]
The raw materials, catalysts, solvents and solvents used in the following examples are as follows.
[Epoxy compound (A)]
A: Bisphenol A diglycidyl ether (JER (registered trademark) 828US manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq)

[Phenolic compound (B)]
B: Bisphenol F (phenolic hydroxyl group equivalent: 100 g / eq)
C1-1: Tri-n-octylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 10% by weight toluene solution (an example of trialkylphosphine (C1))
C1-2: Tri-t-butylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 10% by weight toluene solution (an example of trialkylphosphine (C1))
C1-3: Tricyclohexylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 10% by weight toluene solution (an example of trialkylphosphine (C1))
C2-4: 10% by weight toluene solution of dicyclohexylphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) (an example of dialkylarylphosphine (C2))
C3-5: Ethyldiphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 10% by weight toluene solution (an example of alkyldiarylphosphine (C3))

[Other catalysts (for comparative example)]
c-1: Tetramethylammonium hydroxide 27% by weight aqueous solution (manufactured by Nippon Specialty Chemicals)
c-2: 50% by weight aqueous solution of tetramethylammonium chloride (manufactured by Nippon Special Chemical Industry Co., Ltd.) c-3: 20% ethanol solution of ethyl triphenylphosphonium iodide (manufactured by Hokuko Chemical Co., Ltd.) c-4: triphenylphosphine ( Hokuko Chemical Co., Ltd.) 10 wt% toluene solution

[Solvent (D)]
D-1: Methyl isobutyl ketone D-2: Toluene [Solvent (E)]
E: Methyl ethyl ketone

〔Evaluation method〕
Evaluation methods in the following examples and comparative examples are as follows.
[Epoxy equivalent]
About the epoxy resin obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4, the epoxy equivalent was measured based on JIS K 7236.

[Reaction activity]
○: Reached the theoretical epoxy equivalent
X: What did not reach the theoretical epoxy equivalent The theoretical epoxy equivalent is the epoxy equivalent of the epoxy resin produced when the epoxy group of the epoxy compound (A) and the hydroxyl group of the phenolic compound (B) react 1: 1. is there.

[Storage stability]
About the epoxy resin containing composition obtained in Examples 1-5 and Comparative Examples 1-4, the state after leaving to stand at 23 degreeC for 24 hours was observed visually, and the storage stability was evaluated on the following references | standards.
○: Fluidity without gelation Δ: Not gelled but thickened and fluidity decreased ×: Gelled and no longer fluidity

[Manufacture and evaluation of epoxy resins]
Example 1
400.0 parts by weight of bisphenol A diglycidyl ether (A), bisphenol F (
B) 179.2 parts by weight, trioctylphosphine (C1-1) 10% by weight toluene solution 2.0 parts by weight, methyl isobutyl ketone (D-1) 25.1 parts by weight were put in a pressure-resistant reaction vessel, and a nitrogen gas atmosphere A polymerization reaction was carried out at 170 ° C. for 6 hours to obtain the desired epoxy resin. This was dissolved in 548.7 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.

  5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

(Example 2)
Bisphenol A diglycidyl ether (A) 400.0 parts by weight, bisphenol F (B) 208.8 parts by weight, tri-t-butylphosphine (C1-2) 10% by weight toluene solution 10.0 parts by weight, methyl isobutyl ketone (D-1) 146.8 parts by weight were put in a pressure resistant reactor and subjected to a polymerization reaction at 170 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy resin. This was dissolved in 456.6 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.

  5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

(Example 3)
Bisphenol A diglycidyl ether (A) 400.0 parts by weight, bisphenol F (B) 197.3 parts by weight, tricyclohexylphosphine (C1-3) 10% by weight toluene solution 6.0 parts by weight, toluene (D-2) 27.8 parts by weight were placed in a pressure resistant reactor and subjected to a polymerization reaction at 170 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy resin. This was dissolved in 565.9 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.

  5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

Example 4
Bisphenol A diglycidyl ether (A) 400.0 parts by weight, bisphenol F (B) 197.3 parts by weight, dicyclohexylphenylphosphine (C2-4) 10% by weight toluene solution 6.0 parts by weight, toluene (D-2) 27.8 parts by weight were placed in a pressure resistant reactor and subjected to a polymerization reaction at 170 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy resin. This was dissolved in 565.9 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.

5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

(Example 5)
Bisphenol A diglycidyl ether (A) 400.0 parts by weight, bisphenol F (B) 197.3 parts by weight, ethyldiphenylphosphine (C3-5) 10% by weight toluene solution 6.0 parts by weight, toluene (D-2) 27.8 parts by weight were placed in a pressure resistant reactor and subjected to a polymerization reaction at 170 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy resin. This was dissolved in 565.9 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.
5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

(Comparative Example 1)
Bisphenol A diglycidyl ether (A) 526.0 parts by weight, bisphenol F (B) 264.3 parts by weight, tetramethylammonium hydroxide (c-1) 27% by weight aqueous solution 3.0 parts by weight, methyl isobutyl ketone (D -1) 197.6 parts by weight were put into a pressure resistant reactor and subjected to a polymerization reaction at 170 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy resin. This was dissolved in 597.8 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.
5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

(Comparative Example 2)
Bisphenol A diglycidyl ether (A) 500.0 parts by weight, bisphenol F (B) 246.6 parts by weight, tetramethylammonium chloride (c-2) 50% by weight aqueous solution 1.6 parts by weight, toluene (D-2) 39.4 parts by weight was placed in a pressure resistant reactor and subjected to a polymerization reaction at 170 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy resin. This was dissolved in 707.3 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.
5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

(Comparative Example 3)
Bisphenol A diglycidyl ether (A) 500.0 parts by weight, bisphenol F (B) 246.6 parts by weight, ethyltriphenylphosphonium iodide (c-3) 10% by weight ethanol solution (c-3) 2.5 parts by weight Part and 38.5 parts by weight of toluene (D-2) were put in a pressure resistant reactor and subjected to a polymerization reaction at 165 ° C. for 6 hours under a nitrogen gas atmosphere to obtain a target epoxy resin. This was dissolved in 707.3 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.
5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

(Comparative Example 4)
Bisphenol A diglycidyl ether (A) 500.0 parts by weight, bisphenol F (B) 246.6 parts by weight, triphenylphosphine (c-4) 10% by weight toluene solution (c-3) 10.0 parts by weight, 31 0.0 part by weight of toluene (D-2) was put in a pressure-resistant reaction vessel, and a polymerization reaction was performed at 165 ° C. for 6 hours in a nitrogen gas atmosphere to obtain a target epoxy resin. This was dissolved in 707.3 parts by weight of methyl ethyl ketone (E) (solid content 50% by weight). About the obtained epoxy resin solution, epoxy equivalent was evaluated by the said method, and the result was shown in Table-1.

  5 parts by weight of an adduct of isophorone diisocyanate (Mittech (registered trademark) NY260A NCO group amount: 10.8 (% by weight) manufactured by Mitsubishi Chemical Corporation) is blended with 10 parts by weight of the obtained epoxy resin solution. A resin-containing composition was obtained, and the storage stability was evaluated by the method described above, and the results are shown in Table-1.

[Evaluation results]
As can be seen from Table 1, in Examples 1 to 5 using trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3), the reaction activity is high, and the epoxy resin-containing composition is stored. It was excellent in stability.
On the other hand, Comparative Examples 1 to 4 did not satisfy both the reaction activity and the storage stability of the epoxy resin-containing composition.

  The production method of the present invention has an excellent reaction rate as an advance method. Moreover, the epoxy resin obtained by the manufacturing method of this invention is excellent in the storage stability at the time of mix | blending another component, especially a hardening | curing agent. Therefore, the epoxy resin obtained by the method for producing an epoxy resin of the present invention and the epoxy resin-containing composition containing the epoxy resin are used in the fields of paints, electrical / electronic materials, adhesives, carbon fiber reinforced resins (CFRP), and the like. Can be suitably used.

Claims (8)

  A method for producing an epoxy resin, comprising reacting an epoxy compound (A) and a phenolic compound (B) in the presence of a trialkylphosphine (C1), a dialkylarylphosphine (C2) or an alkyldiarylphosphine (C3).   0.05-1.25 mol of phenolic compound (B) is used per 1.00 mol of epoxy compound (A), and trialkylphosphine (C1), dialkylarylphosphine (C2) or alkyldiarylphosphine (C3) The manufacturing method of the epoxy resin of Claim 1 whose usage-amount of is 10-50000 weight ppm of the usage-amount of an epoxy compound (A).   The epoxy resin obtained by the manufacturing method of the epoxy resin of any one of Claim 1 thru | or 2.   The epoxy resin of Claim 3 whose epoxy equivalent is 100-200,000 g / equivalent.   An epoxy resin-containing composition comprising the epoxy resin according to claim 3 and 4 and a curing agent.   The epoxy resin containing composition of Claim 5 containing 0.1-1000 weight part of hardening | curing agents with respect to 100 weight part of said epoxy compounds.   The curing agent is at least one selected from the group consisting of polyfunctional phenols, polyisocyanate compounds, amine compounds, acid anhydride compounds, imidazole compounds, amide compounds, cationic polymerization initiators, and organic phosphines. The epoxy resin-containing composition according to claim 5 or 6, wherein   Hardened | cured material formed by hardening | curing the epoxy resin containing composition of any one of Claims 5 thru | or 7.