JP2008001758A - Novel oligomer-containing epoxy compound and curable epoxy resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel oligomer-containing epoxy compound excellent in flexibility, impact resistance, and water resistance and a curable epoxy resin composition using the same. <P>SOLUTION: The oligomer-containing epoxy compound (A) is obtained by adding a catalyst to an epoxy resin having, as the main component, a compound represented by formula (1) (wherein n is an integer of 3 to 35 and G1 and G2 are each hydrogen or a glycidyl group, provided that G1 and G2 are simultaneously not hydrogens) obtained by reacting a polyoxytetramethylene glycol with an epihalohydrin to effect self-polymerization. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel oligomer-containing epoxy compound excellent in flexibility, impact resistance, and water resistance, and further, a curable epoxy resin composition comprising the oligomer-containing epoxy compound and a curing agent as essential components. It is about things.

  Conventionally, epoxy resins have been used in a wide range of fields due to their cured products having high strength and elastic modulus, high adhesive strength, excellent heat resistance, and excellent chemical resistance. However, although the composition using an epoxy resin has the above-mentioned features, it has been pointed out that the cured product is brittle. In fields where flexibility and impact resistance are required, dimer acid type epoxy resins and polypropylene glycol diglycidyl ether, which are generally excellent in flexibility, are blended and used. Flexibility and impact resistance are insufficient.

  The epoxy resin composition (see Patent Document 1) containing an epoxy compound obtained by reacting polyoxytetramethylene glycol and epihalohydrin previously proposed by the present inventors is acceptable when compared with a known epoxy resin composition. Although it was excellent in flexibility, impact resistance, and water resistance, flexibility and impact resistance were still insufficient.

In addition, an epoxy resin composition containing a compound obtained by modifying a bisphenol A type epoxy resin with dimer acid has been proposed as an epoxy resin having excellent flexibility (see Patent Document 2). Therefore, it was easily hydrolyzed and poor in water resistance.
Japanese Patent Application No. 2006-139304 JP-A-8-53533

  An object of the present invention is to provide a novel oligomer-containing epoxy compound excellent in flexibility, impact resistance and water resistance, and a curable epoxy resin composition using the same.

（ｎは３〜３５の整数、Ｇ１、Ｇ２は水素原子又はグリシジル基を示す。但し 、Ｇ１、Ｇ２共に水素原子であることはない。） As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained an epoxy resin mainly composed of a compound represented by the following general formula (1), which is obtained by reacting polyoxytetramethylene glycol and epihalohydrin. The inventors found that the oligomer-containing epoxy compound (A) obtained by adding a catalyst to self-polymerization to achieve the above object, and completed the present invention.

(N is an integer of 3 to 35, G1 and G2 each represent a hydrogen atom or a glycidyl group. However, neither G1 nor G2 is a hydrogen atom.)

  The novel oligomer-containing epoxy compound (A) of the present invention is a resin having excellent flexibility, impact resistance and water resistance, and a curable epoxy resin composition containing the resin has excellent flexibility and resistance. Gives a cured product with impact and water resistance.

（ｎは３〜３５の整数、Ｇ１、Ｇ２は水素原子又はグリシジル基を示す。但し、Ｇ１、Ｇ２共に水素原子であることはない。） The novel oligomer-containing epoxy compound <also referred to as component (A)> in the present invention is represented by the following general formula (1) by reacting polyoxytetramethylene glycol with epihalohydrin using a known technique. After obtaining an epoxy resin containing a compound as a main component, it can be synthesized by diluting in a solvent and self-polymerizing with a catalyst such as Lewis acid.

(N is an integer of 3 to 35, G1 and G2 each represent a hydrogen atom or a glycidyl group. However, neither G1 nor G2 is a hydrogen atom.)

  The synthesis method of the present invention will be described in more detail. First, as a first step, a hydroxyl group of polyoxytetramethylene glycol and epihalohydrin are reacted by a generally known method to obtain an glycidyl ether to obtain an epoxy compound. For example, polyoxytetramethylene glycol is dissolved in excess epichlorohydrin, and epichlorohydrin is added to the hydroxyl group of polyoxytetramethylene glycol using sodium hydroxide or the like, and the resulting chlorohydrin group is closed to form an epoxy compound. Convert. Furthermore, the generated NaCl, unreacted sodium hydroxide, and the like are washed with water to remove and remove the solvent, thereby obtaining an epoxy compound before self-polymerization. As another method, polychlorotetramethylene glycol is dissolved or dispersed in an inert solvent such as toluene, xylene, or methyl isobutyl ketone, and epichlorohydrin is prepared using a Lewis acid catalyst such as boron trifluoride etherate or tin tetrachloride. React with. Thereafter, the chlorohydrin group generated using sodium hydroxide or the like is converted into an epoxy group. Furthermore, the generated NaCl, unreacted sodium hydroxide, and the like are washed with water to remove and remove the solvent, thereby obtaining an epoxy compound before self-polymerization.

  Next, the reaction product obtained as a result of the above reaction is self-polymerized. In the self-polymerization reaction, an alcohol residue of polyoxytetramethylene glycol or a hydroxyl group generated after ring opening of an epoxy group reacts with an epoxy group. The reaction conditions include an inert solvent such as toluene, xylene and methyl isobutyl ketone, a boron acid trifluoride etherate, a Lewis acid catalyst such as tin tetrachloride, an alkali metal hydroxide catalyst such as sodium hydroxide, and triethylamine. Amine catalysts, quaternary ammonium salt catalysts such as tetramethylammonium chloride, phosphorus catalysts such as triphenylphosphine and tetrabutylphosphonium bromide, etc., depending on the activity of each catalyst and the desired degree of polymerization Set the temperature and time. After the reaction, if necessary, the catalyst is neutralized and removed, and then the solvent is removed to obtain the desired oligomer-containing epoxy compound.

  The content of total chlorine contained as an impurity in the oligomer-containing epoxy compound in the present invention is not particularly limited, but if the content of total chlorine is large, the corrosion of the metal becomes a problem in the electrical and electronic fields. Since it becomes difficult to use, 0.5 wt% or less is preferable.

  The viscosity of the oligomer-containing epoxy compound in the present invention can be arbitrarily adjusted depending on the reaction conditions so as to obtain the intended performance, but a range of 500 to 500,000 mPa · s (25 ° C.) is preferable. If the amount is less than 500 mPa · s, the amount of oligomers produced is too small. Therefore, depending on the application, flexibility and impact resistance may be insufficient. If the amount exceeds 500,000 mPa · s, a high polymer will be produced too much. Difficult to handle in use.

  Those obtained by curing the component (A) of the present invention as an epoxy resin have good flexibility, impact resistance, and water resistance, and are a sealing material, a resin for laminates, a casting material, an electric material. It can be used in various fields such as insulating materials, adhesives, paint resins, and the like.

  The curable epoxy resin composition containing the component (A) produced according to the present invention contains a curing agent <hereinafter also referred to as the component (B)> as an essential component.

  The component (A) can be used in combination with any other epoxy resin. Specific examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, bisphenol fluorene type epoxy resin. Biscresol fluorene type epoxy resin, bisphenol S diglycidyl ether, halogenated bisphenol type epoxy resin, halogenated cresol novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated phenol novolak type epoxy resin, polyethylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butyl Diol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, sorbitol polyglycidyl ether, butyl glycidyl ether, phenyl Glycidyl ether, triglycidyl isocyanurate, N, N′-diglycidyl derivatives of cyclic alkylene ureas, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, 3, 4 -Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxysilane B hexyl methyl) adipate, and the like.

  As the component (B), polycarboxylic acid which can be cured by normal temperature or heating after blending and / or its acid anhydride, amine curing agent, phenol curing agent, latent curing agent, heating after blending or ultraviolet ray, etc. And a cationic polymerization initiator that can be cured by irradiation with light.

  Specific examples of the polycarboxylic acid and / or acid anhydride thereof in the present invention include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, norbornane-2,3-dicarboxylic acid Anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,3,4-tricarboxylic acid-3, 4-Anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, dodecyl succinic anhydride, pyromellitic anhydride, trimellitic anhydride, etc. can be mentioned. Among these, in consideration of workability of handling of the blended resin composition, characteristics after curing, and the like, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride which are liquid at normal temperature are preferable.

  The content of polycarboxylic acid and / or acid anhydride thereof is 0.5 to 1 equivalent of epoxy group of the entire epoxy resin (total of component (A) and other epoxy components in the present invention). The range is preferably 1.5 equivalents, more preferably 0.8 to 1.2 equivalents in view of curability and physical properties of the cured product.

  Specific examples of amine curing agents include polyoxyethylene diamine, polyoxypropylene diamine, polyoxybutylene diamine, polyoxypentylene diamine, polyoxyethylene triamine, polyoxypropylene triamine, polyoxybutylene triamine, polyoxypentylene triamine. , Diethylenetriamine <DETA>, triethylenetetramine <TETA>, tetraethylenepentamine <TEPA>, m-xylenediamine <MXDA>, trimethylhexamethylenediamine <TMD>, 2-methylpentamethylenediamine <2-MPMDA>, diethylamino Propylamine <DEAPA>, Isophoronediamine <IPDA>, 1,3-bisaminomethylcyclohexane <1,3-BAC>, Bis (4-aminocyclohex Sil) methane <PACM>, norbornenediamine <NBDA>, 1,2-diaminocyclohexane <1,2-DCH>, diaminodiphenylmethane <DDM>, metaphenylenediamine <MPDA>, diaminodiphenylsulfone <DDS>, N-amino Examples include ethyl piperazine <N-AEP>. These modified products such as MXDA modified products and IPDA modified products may also be used.

  The content of the amine curing agent is in the range of 0.5 to 1.5 equivalents with respect to 1 equivalent of the epoxy group of the entire epoxy resin (the sum of the component (A) in the present invention and the other epoxy components). In view of curability and physical properties of the cured product, a range of 0.8 to 1.2 equivalents is more preferable.

  Specific examples of phenolic curing agents include phenol novolac resins made from various phenols, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolac resins, fluorene skeleton-containing phenol novolak resins, and the like. Is mentioned. The various phenols used above include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethyl. Bisphenol S, tetramethyl-4,4′-biphenol, dimethyl-4,4′biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl ) Phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, Resor Phenols having a fluorene skeleton such as diol, hydroquinone, pyrogallol, diisopropylidene, 1,1-di-4-hydroxyphenylfluorene, phenolized polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol Various phenols such as A, bisphenol F, bisphenol S, and naphthols can be mentioned.

  Content of a phenol type hardening | curing agent is the range of 0.5-1.5 equivalent with respect to 1 equivalent of epoxy groups of the whole epoxy resin ((A) component in this invention, and the sum total of other epoxy components). In view of curability and physical properties of the cured product, a range of 0.8 to 1.2 equivalents is more preferable.

  Specific examples of the latent curing agent include dicyandiamide, imidazole compound, dihydrazide compound, amine adduct-based latent curing agent, ketimine compound and the like. These latent curing agents are preferable because they can be stored for a long period of time in a state of being mixed with an epoxy resin in advance, so that they are easy to handle.

  The content of the latent curing agent may be in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the entire epoxy resin (the sum of the component (A) in the present invention and the other epoxy components). Preferably, in view of curability and physical properties of the cured product, a range of 5 to 20 equivalents is more preferable.

As the cationic polymerization initiator, at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, and the like, and at least one selected from BF ₄ ⁻ , PF ₆ ⁻ , and SbF ₆ ^— An onium salt composed of the anion. Such a cationic polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of the aromatic sulfonium salt-based cationic polymerization initiator include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate. Bis [4- (diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, (2-ethoxy-1-methyl-2-oxoethyl) ) Methyl-2-naphthalenylsulfonium hexafluorophosphate, (2-ethoxy-1-methyl-2-oxoethyl) methyl-2-naphthalenylsulfonium hexafluoroatimonate, (2-ethoxy-1-methyl) 2-oxoethyl) methyl-2-naphthalenylsulfonium tetrafluoroborate, (2-ethoxy-1-methyl-2-oxoethyl) methyl-2-naphthalenylsulfonium tetrakis (pentafluorophenyl) borate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroatimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) ) Borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenyls Honium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- ( Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoro Examples thereof include borates and bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate.

  Specific examples of aromatic iodonium salt-based cationic polymerization initiators include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) Iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1- Methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl- -(1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis ( Pentafluorophenyl) borate and the like.

  Specific examples of the aromatic diazonium salt-based cationic polymerization initiator include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.

  Specific examples of the aromatic ammonium salt cationic polymerization initiator include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetra Fluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, Examples thereof include 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.

  (B) A component may be used individually by 1 type and may be used together 2 or more types as needed.

  In the range which does not impair the physical property of hardened | cured material, a hardening accelerator <henceforth (C) component> can be added to the curable epoxy resin composition of this invention in addition to said component. By adding the component (C), the curing speed can be increased, leading to an improvement in productivity.

  Although it does not specifically limit as a compound which can be used as (C) component, Specifically, Triphenyl benzyl phosphonium tetraphenyl borate, tetrabutyl phosphonium diethyl phosphorodithioate, tetraphenyl phosphonium bromide, tetrabutyl phosphonium acetate, Tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide , Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, n-butyltriphenylphosphonium Phosphines such as mubromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium tetraphenylborate and quaternary salts thereof, 2-ethyl-4-methylimidazole <2E4MZ>, 2-phenylimidazole, 1- (2-cyanoethyl) 2-ethyl-4-methylimidazole <2E4MZ-CN>, 2,4-diamino-6- [2-methylimidazolyl- (1)] ethyl-s-triazine <2MZ-A>, 2-phenylimidazoline <2PZL > Imidazoles such as 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole <TBZ>, tris (dimethylaminomethyl) phenol <DMP-30>, benzyldimethylamine <BDMA>, 1,8 -Diazabicyclo (5,4,0) undecene-7 <DBU Metal amines such as tertiary amines such as zinc octylate, zinc laurate, zinc stearate, tin octylate, benzoylacetone zinc chelate, dibenzoylmethane zinc chelate, ethyl zinc acetoacetate chelate Well-known compounds, such as a chelate compound, are mentioned. These accelerators are appropriately selected with respect to the requirements for the resin composition such as time required for curing and pot life.

  (C) It is preferable to mix | blend 0 to 5.0 weight% of the compounding ratio of a component with respect to the whole epoxy resin.

  In the curable epoxy resin composition of the present invention, if necessary, a colorant, an antioxidant, a leveling agent, a surfactant, an ultraviolet absorber, a silane coupling agent, an inorganic filler, resin particles, and wettability improvement. An agent or the like can be added.

  Hereinafter, the details of the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

<Synthesis Example 1>
In a 1 L four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen introduction tube, 324 g (1.0 equivalent) of polyoxytetramethylene glycol (PolyTHF 650 (manufactured by BASF Japan Ltd.) hydroxyl value 173 mgKOH / g) ), 370 g (4.0 mol) of epichlorohydrin was charged, and 2.0 g of triethylbenzylammonium chloride was further added as a phase transfer catalyst. Next, 60 g (1.5 mol) of sodium hydroxide was added over 5 minutes at an internal temperature of 50 ° C., and the mixture was reacted at the same temperature for 2 hours. After the reaction, the generated NaCl, unreacted sodium hydroxide, catalyst, and the like are removed by washing with water, and then epichlorohydrin is distilled off under reduced pressure to obtain 373 g of a liquid semi-product (polyoxytetramethylene glycol diglycidyl ether). Obtained. Subsequently, 373 g of the semi-finished product (polyoxytetramethylene glycol diglycidyl ether) synthesized above and 560 g of toluene were charged into a 1 L four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen introduction tube. The temperature was raised to 60 ° C. with stirring, and 0.47 g of boron trifluoride / ethyl ether complex was added little by little as a catalyst, followed by further aging at the same temperature for 4 hours. After the reaction, the remaining catalyst was removed by washing with water, and then toluene was distilled off under reduced pressure to obtain 358 g of a viscous liquid product (hereinafter abbreviated as A-1). This product had an epoxy equivalent of 823 g / eq, a viscosity of 15800 mPa · s (25 ° C.), and a total chlorine content of 0.25%.

<Synthesis Example 2>
When synthesized in the same manner as in Synthesis Example 1 except that the amount of boron trifluoride / ethyl ether complex added was 0.37 g, 362 g of a liquid product (hereinafter abbreviated as A-2) was obtained. The epoxy equivalent of this product was 722 g / eq, the viscosity was 1970 mPa · s (25 ° C.), and the total chlorine content was 0.25%.

<Synthesis Example 3>
In a 1 L four-necked flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser, and a nitrogen introduction tube, 324 g (1) 0.0 equivalent) and 260 g of toluene were charged, and 4.0 g of tin tetrachloride was added as a Lewis acid catalyst with stirring. While maintaining the internal temperature at 60 to 65 ° C., 111 g (1.2 mol) of epichlorohydrin was dropped from the dropping funnel over 1 hour, and the reaction was continued at the same temperature until the epichlorohydrin peak disappeared by gas chromatography. Next, after adding 4.0 g of triethylbenzylammonium chloride as a phase transfer catalyst, 296 g (2.2 mol) of 30% aqueous sodium hydroxide solution was added from the dropping funnel over 1 hour while maintaining the internal temperature at 60 to 65 ° C. The solution was added dropwise and further aged for 3 hours at the same temperature. Next, the generated NaCl, unreacted sodium hydroxide, catalyst and the like are removed by washing with water, and then toluene is distilled off under reduced pressure to obtain 374 g of a liquid semi-product (polyoxytetramethylene glycol diglycidyl ether). Obtained. Subsequently, 374 g of the semi-finished product (polyoxytetramethylene glycol diglycidyl ether) synthesized above and 560 g of toluene were charged into a 1 L four-necked flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen introduction tube. The temperature was raised to 60 ° C. with stirring, and 0.67 g of boron trifluoride / ethyl ether complex was added little by little as a catalyst, followed by further aging at the same temperature for 4 hours. After the reaction, the remaining catalyst was removed by washing with water, and then toluene was distilled off under reduced pressure to obtain 360 g of a viscous liquid product (hereinafter abbreviated as A-3). This product had an epoxy equivalent of 780 g / eq, a viscosity of 9800 mPa · s (25 ° C.), and a total chlorine content of 1.40%.

<Comparative Synthesis Example 1>
When synthesized in the same manner as in Synthesis Example 1 up to the semi-finished product (polyoxytetramethylene glycol diglycidyl ether) stage, 373 g of a liquid product (hereinafter abbreviated as A-4) was obtained. The epoxy equivalent of this product was 425 g / eq, the viscosity was 161 mPa · s (25 ° C.), and the total chlorine content was 0.25%.

<Example 1>
According to the formulation shown in Table 1, 50 parts of A-1 obtained in Synthesis Example 1 as component (A), 50 parts of bisphenol A type epoxy resin (epoxy equivalent: 185 g / eq), and methyl as component (B) Hexahydrophthalic anhydride (acid anhydride equivalent: 165 g / eq) 55 parts (1 equivalent to 1 equivalent of epoxy group), (C) component 2-ethyl-4-methylimidazole (Curesol 2E4MZ, Shikoku Chemical Industries ( A curable resin composition according to the present invention was obtained by uniformly stirring and mixing 1 part). Furthermore, the said composition was heated over 120 degreeC * 3 hours +150 degreeC * 15 hours, the hardened | cured material was created, and physical property evaluation was performed. The results are shown in Table 1.

<Examples 2-3 and Comparative Examples 1-3>
According to the formulation shown in Table 1, a cured product was prepared and evaluated for physical properties in the same manner as in Example 1 except that each component was stirred and mixed. The results are shown in Table 1.

Below, the evaluation method in the above-mentioned Example etc. is demonstrated.
<Tensile strength, tensile elongation>
The obtained cured product was evaluated according to JIS K7113.
<Bending strength, bending deflection rate>
The obtained cured product was evaluated according to JIS K 7171.
<Izod impact strength>
The obtained cured product was evaluated according to JIS K 7110.
<Water resistance>
The obtained cured product was allowed to stand for 24 hours under the conditions of a temperature of 121 ° C., a pressure of 2 atm, and a humidity of 100%. The state of the cured product after being left to stand was observed, and the case where there was no change compared to before the test was marked with ◯, and the case where it was soft compared with before testing was marked with ×.

  As shown in Table 1, a novel oligomer-containing epoxy compound obtained by adding a catalyst to self-polymerization of an epoxy compound obtained by reacting polyoxytetramethylene glycol and epihalohydrin, and this novel compound It has been found that the curable epoxy resin composition containing can provide a cured product having excellent elongation, flexibility having impact strength, impact resistance, and water resistance.

It can be applied to sealing materials, resin for laminates, casting materials, electrical insulating materials, adhesives, resins for paints, etc., and has an extremely high industrial utility value.

Claims (5)

An oligomer-containing epoxy compound obtained by reacting polyoxytetramethylene glycol and epihalohydrin, which is obtained by adding a catalyst to an epoxy resin containing a compound represented by the following general formula (1) as a main component and performing self-polymerization ( A).

(N is an integer of 3 to 35, G1 and G2 each represent a hydrogen atom or a glycidyl group. However, neither G1 nor G2 is a hydrogen atom.)   The oligomer-containing epoxy compound (A) according to claim 1, wherein the content of total chlorine contained as impurities is 0.5% by weight or less.   The oligomer-containing epoxy compound (A) according to claim 1 or 2, which has a viscosity at 25 ° C of 500 to 500,000 mPa · s.   The curable epoxy resin composition which contains the oligomer body containing epoxy compound (A) and hardening | curing agent (B) as described in any one of Claims 1-3 as an essential component. The curable epoxy resin composition according to claim 4, wherein the curing agent (B) is an acid anhydride curing agent.