KR102309169B1 - Epoxy resin composition, cured product, fiber-reinforced composite material, fiber-reinforced resin molded article, and method for producing fiber-reinforced resin molded article - Google Patents

Abstract

An epoxy resin composition capable of exhibiting excellent mechanical strength, heat resistance, and heat-and-moisture resistance properties in the obtained cured product while having low viscosity, a cured product having the above performance, a fiber-reinforced composite material, a fiber-reinforced resin molded article, and a fiber-reinforced resin molded article A manufacturing method is provided. Specifically, it has an epoxy resin (a) having an average functional group number of 2.3 or more, an epoxy resin (a-1) or an alicyclic epoxy resin (a-2), an acid anhydride (b), and two or more alcoholic hydroxyl groups in the molecule, In addition, an epoxy resin composition comprising a polyol compound (c) having a hydroxyl equivalent weight of 30 g/eq to 650 g/eq and a curing accelerator (d), a cured product thereof, and a fiber-reinforced composite material using the same, fiber reinforcement A resin molded article and a method for manufacturing a fiber-reinforced resin molded article are provided.

Description

Epoxy resin composition, cured product, fiber-reinforced composite material, fiber-reinforced resin molded article, and method for manufacturing fiber-reinforced resin molded article TECHNICAL FIELD FIBER-REINFORCED RESIN MOLDED ARTICLE}

The present invention provides an epoxy resin composition capable of exhibiting excellent mechanical strength, heat resistance, and heat-and-moisture resistance in a cured product obtained with low viscosity, a cured product having the above performance, a fiber-reinforced composite material, a fiber-reinforced resin molded article, and a fiber-reinforced product It relates to a method for manufacturing a resin molded article.

Fiber-reinforced resin molded articles reinforced with reinforcing fibers are noted for their light weight and excellent mechanical strength, and their use in various structural applications including automobile and aircraft casings and various members is expanding.

A fiber-reinforced resin molded article can be manufactured by applying a molding method such as a filament winding method, a press molding method, a hand layup method, a pull-through method, and an RTM method to a fiber-reinforced composite material.

The fiber-reinforced composite material consists of a structure in which the reinforcing fibers are impregnated with a resin, and as a resin used in the fiber-reinforced composite material, stability at room temperature and durability or strength of the cured product are usually required, so a thermosetting resin is generally used. is being used

In addition, when using a thermosetting resin as a resin for a fiber-reinforced composite material, since it is essential that the resin for a fiber-reinforced composite material can be impregnated into the reinforcing fibers as described above, the thermosetting resin is required to have a low viscosity. .

In addition, when a fiber-reinforced resin molded article is used for structural parts such as an engine or an electric wire core material, the thermosetting resin has excellent mechanical strength in the obtained cured product so that the fiber-reinforced resin molded article can withstand a harsh use environment for a long period of time. , heat resistance, and it is required to exhibit heat-and-moisture resistance properties.

As a material that can be used for such a use, for example, (a) an epoxy resin, (b) an anionic polymerization initiator, (c) a proton donor, and the compounding amount of (c) is (a) 100 parts by weight 1 to 30 parts by weight, the epoxy resin is a liquid, and (b) and (c) are provided an epoxy resin composition which is uniformly dissolved in the epoxy resin (for example, refer to Patent Document 1). However, the epoxy resin composition provided by the said patent document 1 has a viscosity higher than the viscosity requested|required by the market, and it was difficult to use it as resin for fiber-reinforced composite materials.

In addition, as a low-viscosity thermosetting resin composition, (a) an epoxy resin, (b) an acid anhydride, and (c) an epoxy resin composition for pultrusion molding comprising an imidazole derivative, (a) an epoxy resin (a) is an epoxy resin containing 60 to 100 parts by weight of a bifunctional epoxy resin having a viscosity at 25°C of 3000 mPa·s or less in 100 parts by weight of the epoxy resin, (c) the imidazole derivative has a substituent at the 1-position There is provided an epoxy resin composition for a pultrusion molded article characterized in that it is an imidazole derivative containing an imidazole derivative (see, for example, Patent Document 2). However, the epoxy resin composition provided by the said patent document 2 had the problem that heat resistance was insufficient in the hardened|cured material obtained.

That is, it was difficult to obtain a thermosetting resin capable of exhibiting excellent mechanical strength, heat resistance, and heat-and-moisture resistance properties in a cured product while having a low viscosity.

International Publication No. 2002/081540 Japanese Patent Laid-Open No. 2008-38082

Therefore, the problem to be solved by the present invention is an epoxy resin composition capable of expressing excellent mechanical strength, heat resistance and heat-and-moisture resistance in a cured product obtained with low viscosity, a cured product having the above performance, a fiber-reinforced composite material, and a fiber It is providing the manufacturing method of a reinforced resin molded article and a fiber reinforced resin molded article.

The present inventors, in order to solve the above problems, by using an epoxy resin composition having a predetermined epoxy resin, an acid anhydride, a predetermined polyol compound, and a curing accelerator as a result of earnest examination, the above problems can be solved found out, and came to complete the present invention.

That is, the present invention relates to an epoxy resin (a) having an average number of functional groups of 2.3 or more, an acid anhydride (b), and a polyol compound (c) having two or more alcoholic hydroxyl groups in the molecule and having a hydroxyl equivalent of 30 g/eq to 650 g/eq ), and an epoxy resin composition comprising a curing accelerator (d), a cured product thereof, and a fiber-reinforced composite material, a fiber-reinforced resin molded article, and a method for manufacturing the same comprising reinforcing fibers.

According to the present invention, an epoxy resin composition capable of exhibiting excellent mechanical strength, heat resistance, and heat-and-moisture resistance in a cured product obtained with low viscosity, a cured product having the above performance, a fiber-reinforced composite material, a fiber-reinforced resin molded article, and a fiber The manufacturing method of a reinforced resin molded article can be provided.

In the epoxy resin composition of the present invention, an epoxy resin (a-1) or an alicyclic epoxy resin (a-2) having an average number of functional groups of 2.3 or more is used as the epoxy resin (a), and an acid anhydride (b) and a molecule It is an epoxy resin composition which has a polyol compound (c) which has two or more alcoholic hydroxyl groups in it, and a hydroxyl equivalent is 30 g/eq - 650 g/eq, and a hardening accelerator (d).

・Epoxy resin (a)

As said epoxy resin (a), if the average number of functional groups is 2.3 or more epoxy resin (a-1) or alicyclic epoxy resin (a-2), it will not specifically limit. The epoxy resin (a-1) is preferably an epoxy resin having an average number of functional groups of 2.3 or more and 5 or less from the viewpoint of workability, and particularly preferably an epoxy resin having an average number of functional groups in the range of 2.3 to 4.0. When using a mixture of two or more types of epoxy resins, it is preferable to use them so that the average number of functional groups is 2.3 or more, or to use multiple types of alicyclic epoxy resins (a-2), and the above epoxy resins (a- It is also preferable to use 1) and an alicyclic epoxy resin (a-2) together.

As the epoxy resin (a-1) having an average number of functional groups of 2.3 or more, for example, a novolak type epoxy resin, a triphenylmethane type epoxy resin, a dicyclopentadiene-phenol addition reaction type epoxy resin, a phenol aralkyl type epoxy resin, Examples of the molecular structure include an epoxy resin having a naphthalene skeleton, a glycidylamine-type epoxy resin, and the like, but from the viewpoint of a low-viscosity and still higher heat resistance of the cured product obtained, a triphenylmethane-type epoxy resin, glycidylamine It is preferable to use a type|mold epoxy resin.

As said novolak-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a bisphenol A novolak-type epoxy resin, a biphenyl novolak-type epoxy resin, etc. are mentioned, for example.

As said triphenylmethane type epoxy resin, the epoxy resin etc. which epoxidized the condensate of phenols and the aromatic aldehyde which have a phenolic hydroxyl group are mentioned, for example.

As the epoxy resin having a naphthalene skeleton in the molecular structure, for example, a naphthol novolak type epoxy resin, a naphthol aralkyl type epoxy resin, a naphthol-phenol coaxial novolak type epoxy resin, a naphthol-cresol coaxial novolak type epoxy resin, digly Cydyloxynaphthalene, 1,1-bis(2,7- diglycidyloxy-1-naphthyl)alkane, etc. are mentioned.

Although it does not specifically limit as said glycidylamine type epoxy resin, From a viewpoint of improving heat resistance and mechanical strength in the hardened|cured material obtained, a trifunctional or more than trifunctional glycidylamine type epoxy resin is preferable.

As a trifunctional or more than trifunctional glycidylamine type epoxy resin, the epoxy resin represented by following structural formula (1) is mentioned, for example.

wherein Q is -CO-, -SO ₂ -, -CH ₂ -, -O-, -S-, -CH(CH ₃ )-, or -C(CH ₃ ) ₂ -.

Among these, as a glycidylamine type epoxy resin, workability|operativity is favorable, and the diaminodiphenylmethane type epoxy resin represented by the following structural formula (2) from a viewpoint of further increasing the heat resistance of the hardened|cured material obtained is fiber-reinforced Since it is excellent in the balance between workability|operativity at the time of manufacturing a composite material or a fiber reinforced resin molded article, and the heat resistance and mechanical strength in the hardened|cured material obtained, it is especially preferable.

As a commercially available product of such diaminodiphenylmethane type epoxy resin, for example, Sumiepoxy ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), Araldite MY720, Araldite MY721, Araldite MY9512, Araldite and Araldite MY9634, Araldite MY9663 (manufactured by Huntsman Advanced Materials), and Epicoat 604 (manufactured by Japan Epoxy Resins), and these commercially available products can be used as they are.

The alicyclic epoxy resin (a-2) is, for example, a resin having an alicyclic structure and two or more epoxy groups in one molecule, for example, 3',4'-epoxycyclohexylmethyl3,4- Epoxycyclohexanecarboxylate, vinylcyclohexene diepoxide, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate, etc. are mentioned. Among these, it is preferable to use 3', 4'- epoxy cyclohexyl methyl 3,4- epoxy cyclohexane carboxylate from a viewpoint that the heat resistance of the hardened|cured material obtained becomes still higher.

In addition, when the epoxy resin (a) is composed of one type of epoxy resin, it is preferable that it is composed of any one of a glycidylamine type epoxy resin and an alicyclic epoxy resin from the viewpoint of workability and heat resistance of the cured product. .

Moreover, as said epoxy resin (a), when comprised from several types of epoxy resins, from the point which is more excellent in the impregnation property to a reinforcing fiber, workability|operativity, and the heat resistance of the hardened|cured material obtained, a phenol novolak-type epoxy resin, triphenyl It is preferably composed of at least one or more epoxy resins selected from methane type epoxy resins and alicyclic epoxy resins, and particularly preferably composed of triphenylmethane type epoxy resins and alicyclic epoxy resins.

・Acid anhydride (b)

The acid anhydride (b) used in the present invention may be a compound having an acid anhydride group in the molecule and capable of curing an epoxy resin (a so-called curing agent for an epoxy resin), and is not particularly limited. As such an acid anhydride (b), unsaturated carboxylic acid anhydrides, such as a cyclic aliphatic acid anhydride, an aromatic acid anhydride, and maleic anhydride, etc. are mentioned, for example. Examples of the cyclic aliphatic acid anhydride include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylnadic anhydride, and the like. can be heard As said aromatic acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned. Maleic anhydride etc. are mentioned as said unsaturated carboxylic acid anhydride. Among these, it is preferable to use a cyclic aliphatic acid anhydride from the point from which the hardened|cured material more excellent in mechanical properties is obtained. Moreover, since the epoxy resin composition becomes excellent in the impregnation property to a reinforcing fiber, among the said cyclic aliphatic acid anhydrides, the compound whose viscosity in 25 degreeC is 500 mPa*s or less is more preferable.

・Polyol compound (c)

As a polyol compound (c) used by this invention, it has two or more alcoholic hydroxyl groups in a molecule|numerator, and what is necessary is just to have a hydroxyl equivalent of 30 g/eq - 650 g/eq, and it is not specifically limited. Examples of such a polyol compound (c) include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, and 1,6-hexane as a dihydric alcohol compound. diol, 2-butyl-2-ethyl-1,3-propanediol, a compound having an aromatic ring or a cyclo ring and two alcoholic hydroxyl groups in the molecule; and the like, trimethylolpropane, glycerin, etc. and pentaerythritol etc. are mentioned as a tetravalent alcohol compound.

Among these, it is preferable to use a dihydric alcohol compound from the viewpoint that the epoxy resin composition has a lower viscosity and is more excellent in heat resistance and heat-and-moisture resistance of the obtained cured product. It is preferable to use the compound which has a hydroxyl group. Moreover, since the mechanical strength of hardened|cured material is more excellent especially, it is preferable to use the compound which has an aromatic ring or a cyclo ring, a polyalkylene oxide chain, and two alcoholic hydroxyl groups in a molecule|numerator as said polyol compound (c). . As such a compound, it can be represented by General formula (3), for example.

However, A in Formula (3) represents the divalent coupling group containing an aromatic ring or a cyclo ring, B represents the divalent coupling group containing a polyalkylene oxide, OH represents an alcoholic hydroxyl group.

Although it will not specifically limit if it is a bivalent coupling group containing an aromatic ring or a cyclo ring as above-mentioned as A in the said General formula (3), 2 represented by the structure represented by the following structural formula (A-1) - (A-7) It is preferable from a viewpoint of the heat resistance of the hardened|cured material obtained, and a moldability being favorable that it is a valent coupling group.

However, in Structural Formulas (A-1) to (A-7), *B represents a bonding point with B in Structural Formula (3).

In addition, as A in the said general formula (3), among the bivalent coupling groups represented by the said structural formula (A-1) - (A-7), the epoxy resin composition obtained is a lower viscosity more than in the hardened|cured material obtained Since high mechanical strength and heat resistance can be expressed, it is more preferable that it is a divalent linking group represented by the structural formulas (A-4) to (A-7), and among these, 2 represented by (A-4) It is especially preferable that it is a valent linking group.

Although it will not specifically limit if it is a bivalent coupling group containing a polyalkylene oxide as mentioned above as B in the said General formula (3), From the point from which hardened|cured material with higher mechanical strength is obtained, two polyalkylene oxides in 1 molecule It is preferable that the average value of the number of repeating units of a chain|strand is the range of 1-9, and it is more preferable that the average value is 1-3. The polyalkylene oxide chain may have an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide as a repeating unit, and may have the same structure, may be different for each repeating unit, or block polymerization. It may take a form.

Although there is no restriction|limiting in particular about carbon number of the alkylene part in the repeating unit of the said polyalkylene oxide chain, Preferably carbon number is 2-12, More preferably, carbon number is 2-6, More preferably, carbon number is It is 2-4, Especially preferably, they are C2-C3 ethylene oxide and propylene oxide.

That is, as B in the said General formula (3), the divalent coupling group containing the polyalkylene oxide chain represented by (B-1) and (B-2) is especially preferable.

In said formulas (B-1) and (B-2), it is preferable that x and y are the number of repeating units, respectively independently represent an integer of 1 or more, and it is preferable that the average value is the range of 1-9. In addition, *A and *OH in formulas (B-1) and (B-2) represent a bonding point with A and OH in said Formula (3), respectively.

Accordingly, the polyol compound is particularly preferably a compound having a structure represented by the following structural formulas (3-1) to (3-2).

In the structural formulas (3-1) to (3-2), x1, x2, y1, and y2 are each independently an integer of 1 or more, and the average value thereof is 1 to 9.

Examples of the polyol compound having the above structure include 2,2-bis(4-polyoxyethylene-oxyphenyl)propane, 2,2-bis(4-polyoxypropylene-oxyphenyl)propane, and the like. can Moreover, from a viewpoint that the hardened|cured material obtained is further excellent in heat resistance and heat-and-moisture resistance among these, 2, 2-bis (4-polyoxypropylene-oxyphenyl) propane is especially preferable.

The hydroxyl equivalent of the polyol compound (c) used in the present invention is in the range of 30 g/eq to 650 g/eq from the viewpoint of ensuring a sufficient pot life of the composition and balancing the fracture toughness of the resulting cured product. It is essential, and it is preferable that it is the range of 30 g/eq - 450 g/eq from the point which especially those performance expresses further.

Moreover, it is preferable that the said polyol compound has a boiling point in normal pressure of 100 degreeC or more, Preferably it is 140 degreeC or more, More preferably, it is 180 degreeC or more. When the boiling point of the polyol compound is too low, in the case of manufacturing a fiber-reinforced resin molded article, the polyol compound is vaporized in the process of injecting the epoxy resin composition into the mold or the epoxy resin composition is cured, fiber-reinforced resin obtained Voids may form in the molded part. Moreover, when mix|blending multiple types of said polyol compound, it is preferable that any one satisfy|fills the above-mentioned conditions.

· Hardening accelerator (d)

The curing accelerator (d) used in the present invention is a compound capable of improving curing activity such as the acid anhydride contained in the epoxy resin composition. The curing accelerator is not particularly limited as long as it promotes the reaction of the epoxy group with the acid anhydride or the carboxyl group. Examples of the curing accelerator include urea derivatives, imidazole derivatives, phosphorus compounds, tertiary amines, organic acid metal salts, Lewis acids, An amine complex salt etc. are mentioned. When the curing accelerator as described above is used, in the epoxy resin composition, the curing reaction proceeds at a lower temperature or faster than when the curing accelerator is not used. For example, a hardened|cured material can be obtained in 150 degreeC - 170 degreeC, about 2 to 10 minutes, and heat resistance may improve in the hardened|cured material.

In particular, an imidazole derivative is mentioned as a hardening accelerator (d) generally used in the epoxy/acid anhydride hardening system. Specifically, imidazole, 2-methylimidazole, 2-ethyl4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, etc. are mentioned. In addition, when a high storage stability is required, a latent catalyst which is a mixture of an imidazole compound and a compound having a hydroxyl group such as phosphorous acid, phosphorous acid monoester, and phosphorous acid diester can be used.

・Epoxy resin composition

The epoxy resin composition of the present invention includes the above-mentioned epoxy resin (a), an acid anhydride (b), and a polyol compound (c) having two or more alcoholic hydroxyl groups in the molecule and having a hydroxyl equivalent weight of 30 g/eq to 650 g/eq. And, the curing accelerator (d) is essential, otherwise, although not particularly limited, the epoxy resin composition has a low viscosity, so that the impregnability into the reinforcing fibers is good, the curing reaction proceeds quickly, and the productivity From the viewpoint of being able to have good balance and better mechanical strength of the obtained cured product, the curing accelerator (d) is the epoxy resin (a), the acid anhydride (b), and the polyol When the total mass of a compound (c) and the said hardening accelerator (d) is 100 mass parts, it is preferable that it is contained in the ratio of 0.1 mass parts - 5.0 mass parts.

Further, in the epoxy resin composition of the present invention, the diol compound (c) is the epoxy resin (a), the acid anhydride (b) and When the total mass with a hardening accelerator (d) is 100 mass parts, it is preferable to be contained in the ratio of 1 mass part - 20 mass parts.

Further, in the epoxy resin composition of the present invention, as a compounding ratio of the epoxy resin (a), the acid anhydride (b), and the diol compound (c), the total functional group equivalent of the epoxy resin (a) and the diol compound and It is preferable that ratio of the functional group equivalent of the said acid anhydride is 1.0/0.7-1.0/1.0.

・Other resins

The epoxy resin composition of this invention may contain compounds other than the essential components mentioned above. Examples of such a compound include acid-modified polybutadiene (e-1), polyether sulfone resin (e-2), polycarbonate resin, polyphenylene ether resin, and phenol resin. In particular, it is preferable to use together acid-modified polybutadiene (e-1) and polyethersulfone resin (e-2) from the viewpoint of further enhancing the heat resistance and mechanical strength of the obtained cured product. Hereinafter, these compounds will be described.

・Acid-modified polybutadiene (e-1)

Since acid-modified polybutadiene (e-1) has reactivity with an epoxy resin, it is a compound included in the crosslinking network during the curing reaction of the epoxy resin composition. Therefore, when acid-modified polybutadiene (e-1) is used together, the obtained hardened|cured material WHEREIN: More excellent mechanical strength, heat resistance, and heat-and-moisture resistance can be expressed.

Examples of the acid-modified polybutadiene (e-1) include those having, in a butadiene skeleton, a skeleton derived from 1,3-butadiene and 2-methyl-1,3-butadiene. Examples of the 1,3-butadiene-derived ones include those having a structure of any one of 1,2-vinyl, 1,4-trans, and 1,4-cis, and those having two or more of these structures. As those derived from 2-methyl-1,3-butadiene, those having a structure of any one of 1,2-vinyl, 3,4-vinyl, 1,4-cis, and 1,4-trans; What has 2 or more types of these structures is mentioned.

Although it does not specifically limit as an acid-modified component of the said acid-modified polybutadiene (e-1), An unsaturated carboxylic acid is mentioned. As unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride are preferable, and itaconic anhydride and maleic anhydride are preferable from a reactive point, and maleic anhydride is more preferable.

The content of the unsaturated carboxylic acid in the acid-modified polybutadiene (e-1) is, from the viewpoint of reactivity with the epoxy resin (a) and the polyol compound (c), the acid-modified polybutadiene is derived from 1,3-butadiene. In this case, the acid value is preferably 5 mgKOH/g to 400 mgKOH/g, more preferably 20 mgKOH/g to 300 mgKOH/g, and more preferably 50 mgKOH/g to 200 mgKOH/g. It is more preferable that

When an acid value is 5 mgKOH/g or more, it is excellent in reactivity with an epoxy resin etc., In the hardened|cured material obtained, heat resistance and heat-and-moisture resistance improve. On the other hand, when an acid value is 400 mgKOH/g or less, mechanical strength, such as an elongation characteristic, in the hardened|cured material obtained by reacting moderately with an epoxy resin etc. improves.

In addition, the unsaturated carboxylic acid component should just be copolymerized in acid-modified polybutadiene, and the form is not limited. For example, random copolymerization, block copolymerization, graft copolymerization (graft modification), etc. are mentioned.

The average molar mass of the acid-modified polybutadiene (e-1) is preferably 1,000 to 8,000, more preferably 2,000 to 7,000, when the acid-modified polybutadiene is composed of a 1,3-butadiene-derived one. When the acid-modified polybutadiene is constituted by a thing derived from 2-methyl-1,3-butadiene, it is preferable that it is 1,000-60,000, and it is more preferable that it is 15,000-40,000. The average molar mass can be determined using gel permeation chromatography (GPC).

Although acid-modified polybutadiene (e-1) is obtained by modifying polybutadiene with unsaturated carboxylic acid, a commercially available one may be used as it is. Commercially available ones include, for example, maleic anhydride-modified liquid polybutadiene (polyvest MA75, Polyvest EP MA120, etc.) manufactured by Evonik Degussa, maleic anhydride-modified polyisoprene (LIR-403, LIR-410) manufactured by Crare Corporation. etc. can be used.

Moreover, as said acid-modified polybutadiene (e-1), since elongation of the hardened|cured material obtained, heat resistance, and heat-and-moisture resistance become favorable, the epoxy resin (a) in an epoxy resin composition, acid anhydride (b), acid modification When the total mass of polybutadiene (e-1) is 100 mass parts, it is preferable to contain in the ratio of 1 mass part - 40 mass parts, and it is more preferable to contain in the ratio of 3 mass parts - 30 mass parts.

・Polyethersulfone resin (e-2)

Polyethersulfone resin (e-2) is a thermoplastic resin, and in the curing reaction of the epoxy resin, it is not included in the crosslinking network, but in the cured product obtained by the excellent modifier effect having high Tg, Excellent mechanical strength and heat resistance can be expressed.

Moreover, as said polyether sulfone resin (e-2), since the mechanical strength and heat resistance of the hardened|cured material obtained become favorable, the epoxy resin (a) in an epoxy resin composition, an acid anhydride (b), polyether sulfone When the total mass of resin (e-2) is 100 mass parts, it is preferable to contain in the ratio of 1 mass part - 30 mass parts, and it is more preferable to contain in the ratio of 3 mass parts - 20 mass parts.

・Polycarbonate resin

Examples of the polycarbonate resin include a polycondensate of a divalent or difunctional phenol and a carbonyl halide, or a polycarbonate resin obtained by polymerizing a divalent or bifunctional phenol and a diester carbonate by transesterification. have.

Here, as a bivalent or bifunctional phenol which is a raw material of a polycarbonate resin, 4,4'- dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis( 4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5- Dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4- Hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, hydroquinone, resorcinol, catechol, etc. are mentioned. Among these divalent phenols, bis(hydroxyphenyl)alkanes are preferable, and those containing 2,2-bis(4-hydroxyphenyl)propane as a main raw material are particularly preferable.

On the other hand, as a carbonyl halide or diester carbonate made to react with a dihydric or bifunctional phenol, For example, phosgene; diaryl carbonates such as dihaloformate of dihydric phenol, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and m-crezyl carbonate; and aliphatic carbonate compounds such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, diamyl carbonate, and dioctyl carbonate.

In addition, the said polycarbonate resin may have a branched structure in addition to the molecular structure of the polymer chain being a linear structure. This branched structure is, as a raw material component, 1,1,1-tris(4-hydroxyphenyl)ethane, α,α′,α″-tris(4-hydroxyphenyl)-1,3,5-triiso It can be introduced by using propylbenzene, phlorogucine, trimellitic acid, isatinbis(o-cresol) or the like.

・Polyphenylene ether resin

Examples of the polyphenylene ether resin include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-14-phenylene) ether, poly(2,6). -diethyl-1,4-phenylene)ether, poly(2-ethyl-6-n-propyl-1,4-phenylene)ether, poly(2,6-di-n-propyl-1,4- Phenylene)ether, poly(2-methyl-6-n-butyl-1,4-phenylene)ether, poly(2-ethyl-6-isopropyl-1,4-phenylene)ether, poly(2- and methyl-6-hydroxyethyl-1,4-phenylene) ether.

Among these, poly(2,6-dimethyl-1,4-phenylene) ether is preferable, 2-(dialkylaminomethyl)-6-methylphenylene ether unit and 2-(N-alkyl-N-phenylamino). Polyphenylene ether containing a methyl)-6-methylphenylene ether unit etc. as a partial structure may be sufficient.

The polyphenylene ether resin is a modified polyphenyl in which a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a mercapto group, a silyl group, a hydroxyl group, and an anhydrous dicarboxyl group is introduced into the resin structure by any method such as a graft reaction or copolymerization. A lenether resin can also be used in the range which does not impair the objective of this invention.

・Phenolic resin

Examples of the phenol resin include resol-type phenol resins, novolak-type phenol resins, etc., phenol aralkyl resins, polyvinyl phenol resins, triazine-modified phenol novolac resins modified with melamine or benzoguanamine, and the like. have.

When the epoxy resin composition of the present invention contains the polycarbonate resin or polyphenylene ether resin as described above, it becomes possible to express more excellent mechanical strength in the obtained cured product, and is obtained by containing the phenol resin as described above. Hardened|cured material WHEREIN: It becomes possible to express more excellent flame retardance.

The epoxy resin composition of this invention can contain a flame retardant/flame retardant auxiliary|assistant, a filler, an additive, and an organic solvent in the range which does not impair the effect of this invention. The compounding order at the time of manufacturing an epoxy resin composition will not be specifically limited if it is a method which can achieve the effect of this invention. That is, you may mix and use all the components beforehand, and you may mix and use it in an appropriate order. In addition, the mixing|blending method can knead-manufacture, for example using kneading machines, such as an extruder, a heating roll, a kneader, a roller mixer, a Banbury mixer. Hereinafter, various members which can be contained in the epoxy resin composition of this invention are demonstrated.

・Flame retardant/flame retardant aid

The epoxy resin composition of this invention may contain the non-halogen type flame retardant which does not contain a halogen atom substantially in order to exhibit a flame retardance.

Examples of the non-halogen-based flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organometallic salt-based flame retardants, etc. A plurality of flame retardants of the same type may be used, and it is also possible to use a combination of flame retardants of different types.

As said phosphorus flame retardant, both an inorganic type and an organic type can be used. Examples of the inorganic compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate, and inorganic nitrogen-containing compounds such as amide phosphate.

Moreover, it is preferable that the said red phosphorus is surface-treated for the purpose of prevention of hydrolysis etc. As a surface treatment method, For example, (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, oxide A method of coating with an inorganic compound such as bismuth, bismuth hydroxide, bismuth nitrate or a mixture thereof, (ii) a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and a thermosetting resin such as a phenol resin A method of coating treatment, (iii) a method of double coating treatment with a thermosetting resin such as a phenol resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide, etc. are mentioned.

Examples of the organophosphorus compound include general-purpose organophosphorus compounds such as a phosphoric acid ester compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphorane compound, and an organic nitrogen-containing compound, 9,10-dihydro -9-oxa-10-phosphaphenanthrene = 10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10-(2 and cyclic organophosphorus compounds such as ,7-dihydrooxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene = 10-oxide.

In addition, when using the phosphorus-based flame retardant, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. may be used in combination with the phosphorus-based flame retardant.

As said nitrogen-type flame retardant, a triazine compound, a cyanuric acid compound, an isocyanuric acid compound, phenothiazine etc. are mentioned, for example, A triazine compound, a cyanuric acid compound, and an isocyanuric acid compound are preferable. do.

Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, etc., for example, guanyl sulfate and aminotriazine sulfate compounds such as melamine, melem sulfate and melam sulfate, the aminotriazine-modified phenol resin, and those obtained by further modifying the aminotriazine-modified phenolic resin with tung oil, isomerized linseed oil, or the like.

As a specific example of the said cyanuric acid compound, cyanuric acid, melamine cyanurate, etc. are mentioned, for example.

The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, components other than the epoxy resin composition, and the desired degree of flame retardancy, for example, an epoxy resin, a curing agent, a non-halogen-based flame retardant, and other fillers and additives. It is preferable to mix|blend in the range of 0.05 mass part - 10 mass parts among 100 mass parts of epoxy resin compositions which mix|blended all these, and it is especially preferable to mix|blend in the range of 0.1 mass part - 5 mass parts.

Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

The silicone-based flame retardant may be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

The blending amount of the silicone-based flame retardant is appropriately selected depending on the type of silicone-based flame retardant, components other than the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix|blend in the range of 0.05 mass parts - 20 mass parts among 100 mass parts of epoxy resin compositions which mix|blended. Moreover, when using the said silicone type flame retardant, you may use together a molybdenum compound, alumina, etc.

As said inorganic flame retardant, a metal hydroxide, a metal oxide, a metal carbonate compound, a metal powder, a boron compound, low-melting-point glass etc. are mentioned, for example.

Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

Specific examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Chromium oxide, nickel oxide, copper oxide, tungsten oxide, etc. are mentioned.

Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

As a specific example of the said low melting point glass, For example, Cipri (Bokusui Braunsha), hydrated glass SiO ₂ -MgO-H ₂ O, PbO-B ₂ O _{3 type} , ZnO-P ₂ O ₅ -MgO type , P ₂ O ₅ -B ₂ O ₃ -PbO-MgO type, P-Sn-OF type, PbO-V ₂ O ₅ -TeO _{2 type} , Al ₂ O ₃ -H ₂ O type, glassy compound such as lead borosilicate type can be heard

The compounding amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, components other than the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix|blend in the range of 0.05 mass parts - 20 mass parts among 100 mass parts of epoxy resin compositions which mix|blended, and it is especially preferable to mix|blend in 0.5 mass parts - 15 mass parts.

As the organometallic salt flame retardant, for example, ferrocene, an acetylacetonate metal complex, an organometallic carbonyl compound, an organocobalt salt compound, an organosulfonic acid metal salt, a metal atom and an aromatic compound or a heterocyclic compound are ionic or coordinated. compounds, and the like.

The compounding amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, components other than the epoxy resin composition, and the desired degree of flame retardancy, for example, an epoxy resin, a curing agent, a halogen-free flame retardant and other fillers. It is preferable to mix|blend in the range of 0.005 mass parts - 10 mass parts among 100 mass parts of epoxy resin compositions which mix|blended all, such as an additive.

·filling

The epoxy resin composition of this invention may contain the filler. When the epoxy resin composition of this invention contains a filler, in the hardened|cured material obtained, it will become possible to express the outstanding mechanical property.

Examples of the filler include titanium oxide, glass beads, glass flakes, glass fibers, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, potassium titanate, aluminum borate, magnesium borate, fused silica, crystalline silica, alumina, silicon nitride, and fibrous reinforcing agents such as aluminum hydroxide, kenaf fibers, carbon fibers, alumina fibers and quartz fibers, and non-fibrous reinforcing agents. These may be used individually by 1 type, and may use 2 or more types together. Moreover, these may be coat|covered with an organic substance, an inorganic substance, etc.

Moreover, when using glass fiber as a filler, it can select from long fiber type rubbing, short fiber type chopped strand, milled fiber, etc. and can be used. It is preferable to use the glass fiber surface-treated for the resin to be used. By blending the filler, the strength of the non-combustible layer (or carbonized layer) generated during combustion can be further improved. The incombustible layer (or carbonized layer) generated once during combustion is less likely to be damaged, and stable thermal insulation ability can be exhibited, and a greater flame retardant effect is obtained. In addition, high rigidity can be imparted to the material.

·additive

The epoxy resin composition of this invention may contain the additive. When the epoxy resin composition of this invention contains an additive, in the hardened|cured material obtained, other characteristics, such as rigidity and dimensional stability, will improve. Examples of additives include stabilizers such as plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, conductivity imparting agents, stress relievers, mold release agents, crystallization accelerators, hydrolysis inhibitors, lubricants, impact agents, and sliding properties.性) improving agent, compatibilizer, nucleating agent, reinforcing agent, reinforcing agent, flow regulator, dye, sensitizer, coloring pigment, rubber polymer, thickener, anti-settling agent, anti-sagging agent, defoaming agent, coupling agent, rust inhibitor, antibacterial/fungal agent, antifouling agent It is also possible to add an agent, a conductive polymer, etc.

・Organic solvent

The epoxy resin composition of this invention may contain the organic solvent, when manufacturing a fiber reinforced resin molded article using the filament winding method. Examples of the organic solvent that can be used here include methyl ethyl ketone acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. can

<Use of the epoxy resin composition>

The epoxy resin composition of the present invention has a low viscosity and can exhibit excellent mechanical strength, heat resistance, and heat-and-moisture resistance in the cured product obtained. Below, these manufacturing methods are demonstrated.

1. Fiber Reinforced Composite Materials

The fiber-reinforced composite material of the present invention is a material in a state before curing after impregnating the reinforcing fibers with an epoxy resin composition. Here, the reinforcing fiber may be any one such as a flexible yarn, a untwisted yarn, or a non-twisted yarn. Since it has a surname, it is preferable. In addition, as the form of the reinforcing fibers, the fiber direction may be aligned in one direction, or a woven fabric may be used. As for the woven fabric, it can be freely selected from a plain weave, a main weave, etc. according to the site|part to be used and a use. Specifically, since it is excellent in mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, etc. are mentioned, These 2 or more types can also be used together. Among these, carbon fibers are preferable from the viewpoint that the strength of the molded article is particularly good, and various kinds of such carbon fibers such as polyacrylonitrile, pitch, and rayon can be used.

Although it does not specifically limit as a method of obtaining the fiber reinforced composite material from the epoxy resin composition of this invention, For example, each component which comprises an epoxy resin composition is mixed uniformly to adjust a varnish, Next, the varnish obtained above A method of immersing a unidirectional reinforcing fiber in which the reinforcing fibers are aligned in one direction (state before curing in the pull-through method or filament winding method), or a fabric of reinforcing fibers stacked and set in a concave shape, and then closed in a convex shape and a method of pouring resin and impregnating under pressure (state before curing in RTM method) and the like.

In the fiber-reinforced composite material of the present invention, the epoxy resin composition is not necessarily impregnated to the inside of the fiber bundle, and the epoxy resin composition may be localized near the surface of the fiber.

Further, in the fiber-reinforced composite material of the present invention, it is preferable that the volume content of reinforcing fibers with respect to the total of the fiber-reinforced composite material is 40% to 85%, more preferably in the range of 50% to 70% in terms of strength do. When the volume content is less than 40%, the content of the epoxy resin composition is too high, the flame retardancy of the obtained cured product is insufficient, or the various properties required for a fiber-reinforced composite material having excellent specific elastic modulus and specific strength may not be satisfied. . Moreover, when the volume content exceeds 85 %, the adhesiveness of a reinforcing fiber and a resin composition may fall.

2. Fiber-reinforced resin molded products

The fiber-reinforced resin molded article of the present invention is a molded article having reinforcing fibers and a cured product of an epoxy resin composition, and is obtained by thermosetting a fiber-reinforced composite material. As the fiber-reinforced resin molded article of the present invention, specifically, the volume content of the reinforcing fibers in the fiber-reinforced molded article is preferably in the range of 40% to 85%, and from the viewpoint of strength, it is in the range of 50% to 70% Especially preferred. As such a fiber reinforced resin molded article, For example, automobile parts, such as a front subframe, a rear subframe, a front pillar, a center pillar, a side member, a cross member, a side sill, a roof rail, a propeller shaft, and the core of an electric wire cable A member, a pipe material for a subsea oil field, a roll pipe material for a printing machine, a robot fork material, a primary structure material of an aircraft, a secondary structure material, etc. are mentioned.

Although it does not specifically limit as a method of obtaining a fiber reinforced molded article from the epoxy resin composition of this invention, It is preferable to use the pultrusion method (pull truss method), the filament winding method, the RTM method, etc. The pultrusion molding method (pull truss method) is a method of molding a fiber-reinforced resin molded article by introducing a fiber-reinforced composite material into a mold, heat-curing, and then drawing with a pultrusion device, and the filament winding method is a fiber-reinforced composite material ( (including unidirectional fibers) is wound while rotating on an aluminum liner or plastic liner, etc., and then heat-hardened to form a fiber-reinforced resin molded article. , a method of molding a fiber-reinforced resin molded article by heating and curing the fiber-reinforced composite material in the mold. Moreover, when shape|molding a large size product or a fiber reinforced resin molded article of a complicated shape, it is preferable to use the RTM method.

As molding conditions of a fiber-reinforced resin molded article, it is preferable to thermoset and shape|mold a fiber reinforced composite material in the temperature range of 50 degreeC - 250 degreeC, and it is more preferable to shape|mold in the temperature range of 70 degreeC - 220 degreeC. This is because, if the molding temperature is too low, sufficient rapid curing may not be obtained. Conversely, if the molding temperature is too high, warpage due to thermal deformation may easily occur. As another molding condition, the fiber-reinforced composite material is pre-cured at 50 ° C. to 100 ° C., a tack-free cured product, and further cured in two steps, such as treatment at a temperature condition of 120 ° C. to 200 ° C. and the like.

As another method of obtaining a fiber-reinforced molded article from the epoxy resin composition of the present invention, a hand lay-up method or spray-up method in which a fiber aggregate is laid in a mold and multi-layered of the resin composition or fiber aggregate is used, and either male or female type is used. , a vacuum bag method in which a base material made of reinforcing fibers is impregnated with varnish while stacked and molded, covered with a flexible mold capable of applying pressure to the molded product, and vacuum (reduced pressure) molding of the airtight seal, a resin composition containing reinforcing fibers in advance and the SMC press method in which a sheet-like material is compression-molded with a die.

3. Cured product

As a method of obtaining a cured product from the epoxy resin composition of the present invention, it may be based on a general curing method of an epoxy resin composition, for example, the heating temperature condition may be appropriately selected according to the type and use of the curing agent to be combined. For example, the method of heating an epoxy resin composition in the temperature range of about room temperature - 250 degreeC is mentioned. It is possible to use the general method of an epoxy resin composition also for a shaping|molding method etc., and conditions specific to the epoxy resin composition of this invention especially are unnecessary.

(Example)

Next, although an Example and a comparative example demonstrate this invention concretely, in the following, "part" and "%" are based on mass unless it specifically limits.

Examples 1 to 10, and Comparative Examples 1 to 2

Examples 1 to 10 and Comparative Examples by putting an epoxy resin, an acid anhydride, a polyol compound, a curing accelerator, an acid-modified polybutadiene, and a polyethersulfone resin in a kiln according to the formulations shown in Tables 1 and 2 below and stirring to homogenize them. The epoxy resin composition of 21- was obtained. Moreover, after heat-dissolving polyethersulfone resin previously at 110 degreeC for 5 hours in an acid anhydride, what cooled was used. Next, the epoxy resin composition obtained above was poured into a mold processed so as to have a thickness according to the evaluation items, and was molded for 10 minutes under conditions of 160° C. to obtain a cured product.

The epoxy resins, acid anhydrides, polyol compounds, curing accelerators, and other compounds used in combination used in Examples and Comparative Examples are as follows.

Epoxy resin (a)

·a-1-1: triphenylmethane type epoxy resin EPICLON EXA-7250 (manufactured by DIC Corporation, average number of functional groups 3.5)

·a-2-1: alicyclic epoxy resin CEL2021P (manufactured by Daicel Chemical Industries, Ltd.)

a-1-2: glycidylamine type epoxy resin S-720 (manufactured by Synasia Ink, average number of functional groups 4)

·a-1-3: dicyclopentadiene type epoxy resin EPICLON HP-7200 (manufactured by DIC Corporation, average number of functional groups 2.3)

·a-1-4: naphthalene type epoxy resin EPICLON HP-4710 (manufactured by DIC Corporation, average number of functional groups 5)

Acid anhydride (b)

·b-1: tetrahydromethylphthalic anhydride B-570H (manufactured by DIC Corporation)

b-2: methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride MHAC-P (manufactured by Hitachi Chemical Co., Ltd.)

b-3: 3 or 4-methyl-hexahydrophthalic anhydride HN-5500E (manufactured by Hitachi Chemical Co., Ltd.)

·b-4: Hexahydrophthalic anhydride Riga Sidd HH (New Nippon Rica Co., Ltd.)

polyol compound (c)

·c-1: 2,2-bis(4-polyoxypropyleneoxyphenyl)propane BA-P13U glycol (Nippon New Chemicals Co., Ltd., hydroxyl equivalent 468 g/eq)

-c-2: 2,2-bis (4-polyoxyethylene oxyphenyl) propane BA-3U glycol (Nippon New Chemical Co., Ltd., hydroxyl equivalent 179 g/eq)

-c-3: 2,2-bis (4-polyoxyethylene oxyphenyl) propane BA-2 glycol (Nippon New Chemical Co., Ltd., hydroxyl equivalent 165 g/eq)

·c-4: trimethylolpropane TMP (manufactured by Mitsubishi Gas Chemical Co., Ltd., hydroxyl equivalent weight of 45 g/eq)

hardening accelerator (d)

·d-1: 1,2-dimethylimidazole 1,2DMZ (manufactured by Shikoku Chemical Co., Ltd.)

d-2: 1-methylimidazole 1MI (Nippon Kosei Chemical Co., Ltd.)

·d-3: amine-based epoxy accelerator Fuji Cure 7000 (manufactured by T&K TOKA)

Acid-modified polybutadiene (e-1)

·e-1-1: Maleic anhydride-modified liquid polybutadiene POLYVEST EP MA 120 (manufactured by Evonik Degussa Japan Co., Ltd.)

·e-1-2: Maleic anhydride-modified liquid polybutadiene POLYBEST MA75 (manufactured by Evonik Degusa Japan Co., Ltd.)

Polyethersulfone resin (e-2)

・e-2-1: Polyethersulfone resin Sumika Excel PES5003PS (manufactured by Sumitomo Chemical Co., Ltd.)

Unmodified polybutadiene: POLYBEST 110 (manufactured by Evonik Degusa Japan Co., Ltd.)

Aliphatic alkylene oxide: ADEKA Pluronic F-108 (made by ADEKA Co., Ltd., hydroxyl equivalent 8000 g/eq)

<Measurement of viscosity>

The viscosity in 25 degreeC of the epoxy resin composition obtained above was measured using the viscometer (TOKI SANGYO CO.LTD.VISCOMETER TV-22).

<Measurement of heat-and-moisture resistance>

The hardened|cured material obtained above was cut out to the magnitude|size of thickness 2mm, width 10mm, and length 80mm, and this was set as the test piece 1. Next, the operation of putting the test piece 1 into the wet heat tester set to 100 degreeC and the conditions of 100% for 24 hours, and putting it in the dryer set to the conditions of 180 degreeC after that for 24 hours was repeated 5 times. After completion of the operation, the decrease in mass of Test Specimen 1 was measured on a percent basis.

<Measurement of mechanical strength>

According to JIS K6911, the bending strength of the test piece 1 was measured. In addition, Shimadzu Corporation's AUTOGRAPH AG-I was used for the measurement.

<Measurement of heat resistance>

The hardened|cured material obtained above was cut out to thickness 2mm, width 5mm, and length 50mm with a diamond cutter, and this was set as the test piece 2. Next, using a viscoelasticity measuring apparatus ("DMS6100" manufactured by SII Nanotechnology Co., Ltd.), the dynamic viscoelasticity by bending of both sides of the test piece 2 is measured, and the temperature (glass transition point temperature) at which tan δ is the maximum value and , the temperature at which the elastic modulus decreases (onset temperature of the storage elastic modulus: E') was measured. The results are shown in Table 1. Moreover, the measurement conditions of the dynamic viscoelasticity measurement were made into temperature range: room temperature-260 degreeC, temperature increase rate: 3 degreeC/min, frequency: 1 Hz, and strain amplitude: 10 micrometers.

[Table 1]

[Table 2]

Claims (21)

An epoxy resin (a) whose average number of functional groups is 2.3 or more of an epoxy resin (a-1) or an alicyclic epoxy resin (a-2);
acid anhydride (b);
A polyol compound (c) having two or more alcoholic hydroxyl groups in the molecule and having a hydroxyl equivalent of 30 g/eq to 650 g/eq and having at least an aromatic ring or a cyclo ring in the molecule;
An epoxy resin composition comprising a curing accelerator (d). According to claim 1,
The epoxy resin composition in which the said epoxy resin (a-1) is an epoxy resin whose average number of functional groups is 2.3 or more and 5 or less. According to claim 1,
The epoxy resin composition in which the said epoxy resin (a-1) is a triphenylmethane type epoxy resin or a glycidylamine type epoxy resin. 4. The method of claim 3,
The epoxy resin composition which uses together a triphenylmethane type epoxy resin and an alicyclic epoxy resin (a-2) as an epoxy resin (a). 4. The method of claim 3,
The glycidylamine-type epoxy resin has the following structural formula (1)

[In Structural Formula (1), Q is -CO-, -SO ₂ -, -CH ₂ -, -O-, -S-, -CH(CH ₃ )- or -C(CH ₃ ) ₂ -]
An epoxy resin composition represented by. delete According to claim 1,
The epoxy resin composition in which the said polyol compound (c) is a compound which has polyalkylene oxide at least in a molecule|numerator. 8. The method of claim 7,
The epoxy resin composition whose average value of the number of repeating units of the alkylene oxide which comprises the said polyalkylene oxide is 1-9. 9. The method of claim 7 or 8,
The epoxy resin composition wherein the polyalkylene oxide is polyethylene oxide or polypropylene oxide. 9. The method according to any one of claims 1 to 5 and 7 to 8,
Further, an epoxy resin composition comprising an acid-modified polybutadiene (e-1) or a polyethersulfone resin (e-2). 11. The method of claim 10,
The epoxy resin composition wherein the acid-modified polybutadiene (e-1) is maleic anhydride-modified polybutadiene. 11. The method of claim 10,
When the total mass of the epoxy resin (a), the acid anhydride (b), and the acid-modified polybutadiene (e-1) is 100 parts by mass, 1 mass of the acid-modified polybutadiene (e-1) The epoxy resin composition contained in the ratio of parts - 40 mass parts. 11. The method of claim 10,
When the total mass of the epoxy resin (a), the acid anhydride (b), and the polyethersulfone resin (e-2) is 100 parts by mass, 1 part by mass of the polyethersulfone resin (e-2) The epoxy resin composition contained in the ratio of -30 mass parts. Hardened|cured material formed by hardening|curing the epoxy resin composition in any one of Claims 1-5 and 7-8. A fiber-reinforced composite material comprising the epoxy resin composition according to any one of claims 1 to 5 and 7 to 8 and reinforcing fibers as essential components. 16. The method of claim 15,
A fiber-reinforced composite material having a volume content of the reinforcing fibers in the range of 40% to 85%. A fiber-reinforced resin molded article comprising the cured product according to claim 14 and reinforcing fibers as essential components. 18. The method of claim 17,
A fiber-reinforced resin molded article having a volume content of the reinforcing fibers in the range of 40% to 85%. 18. The method of claim 17,
A fiber-reinforced resin molded product that is a core member of an electric wire and cable. A method for producing a fiber-reinforced resin molded article in which the fiber-reinforced composite material according to claim 15 is thermosetted. A method for producing a fiber-reinforced resin molded article in which the fiber-reinforced composite material according to claim 15 is pultruded.