Classifications

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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3227—Compounds containing acyclic nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3218—Carbocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/06—Polysulfones; Polyethersulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
  • C08J2481/06—Polysulfones; Polyethersulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

• the present invention relates to an epoxy resin composition preferably used as a matrix resin of a fiber-reinforced composite material suitable for sports use, general industrial use, and aerospace use, and a prepreg and a fiber-reinforced composite material using the same as a matrix resin. It is.
• thermosetting resin used as a matrix resin of a prepreg
• an epoxy resin is widely used because of its excellent heat resistance, adhesiveness, and mechanical strength.
• Patent Document 1 discloses a technique in which a polyfunctional bisphenol-type epoxy resin and an amine-type epoxy resin are used in combination to achieve both flexural modulus and fracture strength of a cured epoxy resin.
• Patent Document 2 discloses a technique of increasing the elastic modulus of a cured epoxy resin by using a trifunctional or higher amine type epoxy resin and a high molecular weight bisphenol F type epoxy resin.
• Patent Document 3 discloses a technique of curing an aminophenol-type epoxy resin with an aromatic amine compound to increase the flexural modulus and the breaking strength of a cured epoxy resin.
• Patent Document 4 discloses that an epoxy resin composition containing an amine type epoxy resin and a thermoplastic resin as essential components is cured with an aromatic amine, thereby increasing the deformability while maintaining the heat resistance of the cured epoxy resin. The technology is described.
• Patent Document 5 discloses a technique for improving the heat resistance and fracture toughness of a fiber-reinforced composite material by using an epoxy resin having an oxazolidone ring structure in a molecule and a triblock copolymer in combination.
• Patent Document 6 discloses a resin prepreg for improving CFRP 90-degree bending in order to increase the breaking strength of a CFRP tubular body.
• Patent Document 4 The epoxy resin composition disclosed in Patent Document 4 has high heat resistance of the cured resin, but has insufficient flexural modulus, and has low mechanical properties of the fiber-reinforced composite material.
• the epoxy resin composition disclosed in Patent Literature 5 has a high degree of deformation of the cured resin, but has a low flexural modulus, so that the fiber-reinforced composite material has a low bending strength in the 0 ° direction. Was.
• the present invention improves the disadvantages of the prior art, achieves a high level of flexural modulus and flexural strain, and provides an epoxy resin composition capable of obtaining a cured resin having excellent heat resistance, and the epoxy resin.
• An object of the present invention is to provide a prepreg comprising a composition and a reinforcing fiber, and a fiber-reinforced composite material obtained by curing the prepreg and having particularly excellent flexural strengths of 0 ° and 90 °.
• the present inventors have conducted intensive studies to solve the above problems, and as a result, have found an epoxy resin composition having the following constitution, and have completed the present invention. That is, the epoxy resin composition of the present invention has any one of the following aspects 1 to 4.
• Embodiment 1 is an epoxy resin composition that includes the following components [A], [B] and [C], and satisfies all of the following conditions 1, 2 and 3.
• Condition 1 Epoxy resin composition is reacted at 180 ° C. for 120 minutes Flexural modulus of the cured resin obtained by the reaction is 4.4 GPa or more
• Condition 2 Flexural strength of the cured resin obtained by reacting the epoxy resin composition at 180 ° C.
• An embodiment 2 is an epoxy resin composition containing the following components [A], [B], and [C], and satisfies all of the following conditions 4, 5, and 6: Component [A]: Trifunctional amine type epoxy resin component [B]: Bisphenol F type epoxy resin component solid at 25 ° C. [C]: Aromatic amine compound Condition 4: Epoxy resin composition reacted at 180 ° C. for 120 minutes The bending strain of the cured resin obtained by the above is 6% or more.
• Condition 5 The average epoxy equivalent of the component [B] is 600 to 1000 g / eq.
• Condition 6 The glass transition temperature X (° C.) of the cured resin obtained by reacting the epoxy resin composition at 180 ° C. for 120 minutes and the storage elastic modulus Y (MPa) in a rubber state obtained from dynamic viscoelasticity measurement. Satisfies the following equation (2): 0.087X-6 ⁇ Y ⁇ 0.087X-4 (2).
• Aspect 3 is an epoxy resin composition that includes the following components [A], [B], and [C] and satisfies the following conditions 5 and 7.
• Aspect 4 is an epoxy resin composition that includes the following components [A], [E] and [F] and satisfies all of the following conditions 8, 9 and 10.
• Component [A] Trifunctional amine type epoxy resin component [E]: Sorbitol type epoxy resin component [F]: Dicyandiamide or a derivative thereof
• Condition 8 Curing of resin obtained by reacting epoxy resin composition at 130 ° C. for 90 minutes
• Condition 9 Flexural strength of resin cured product obtained by reacting the epoxy resin composition at 130 ° C. for 90 minutes is 190 MPa or more
• Condition 10 Total epoxy resin 100 in epoxy resin composition The total of the component [A] and the component [E] is at least 40 parts by mass.
• the prepreg of the present invention is a prepreg comprising the epoxy resin composition and reinforcing fibers.
• the fiber-reinforced composite material of the present invention is a fiber-reinforced composite material obtained by curing the prepreg.
• the epoxy resin composition of the present invention is an epoxy resin composition that can achieve both a high flexural modulus and a high flexural strain and can obtain a cured resin having excellent heat resistance.
• the fiber reinforced composite material using the epoxy resin composition of the present invention as a matrix resin exhibits excellent bending strength in the 0 ° direction and the 90 ° direction.
• Embodiments 1 to 3 of the epoxy resin composition of the present invention include a component [A] trifunctional amine type epoxy resin, a component [B] a bisphenol F type epoxy resin solid at 25 ° C., and a component [C] an aromatic amine compound. As an essential component.
• the fiber-reinforced composite material using the epoxy resin composition of the present invention in the form of Embodiment 1 to Embodiment 3 as a matrix resin also has excellent interlayer toughness.
• Embodiment 4 of the epoxy resin composition of the present invention contains, as essential components, component [A] a trifunctional amine type epoxy resin, component [E] sorbitol type epoxy resin, and component [F] dicyandiamide or a derivative thereof.
• embodiments 1 to 3 of the epoxy resin composition of the present invention will be described.
• embodiments 1 to 4 of the epoxy resin composition of the present invention may be simply referred to as embodiments 1 to 4 of the present invention. Further, when the present invention is simply referred to without specifying the embodiment, it indicates all the embodiments 1 to 4.
• the component [A] in the present invention is a trifunctional amine type epoxy resin.
• triglycidylaminophenol type epoxy resin triglycidylaminocresol type epoxy resin and the like can be mentioned.
• triglycidyl aminophenol type epoxy resin examples include "Sumiepoxy (registered trademark)” ELM100 and ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY0500, MY0510, and MY0600 (Huntsman Advanced. Materials Co., Ltd.).
• component [A] is preferably an aminophenol-type epoxy resin.
• component [A] is an aminophenol-type epoxy resin, the flexural modulus of the cured resin becomes high, and a fiber-reinforced composite material having a high 0 ° bending strength is easily obtained.
• the component [A] is contained in an amount of 50 to 80 parts by mass, more preferably 55 to 65 parts by mass, based on 100 parts by mass of the total epoxy. It is. By satisfying the above range, it becomes easy to obtain a cured epoxy resin having a good balance between the bending elastic modulus and the bending strength of the cured resin.
• Component [B] in Embodiments 1 to 3 of the present invention is a bisphenol F epoxy resin which is solid at 25 ° C.
• Examples of the bisphenol F epoxy resin include “jER (registered trademark)” 4004P, 4005P, and 4010P (all manufactured by Mitsubishi Chemical Corporation) and “Epototo (registered trademark)” YDF-2001, YDF-2004, and YDF-2005RD. (Above, manufactured by Toto Kasei Co., Ltd.).
• the flexural strength can be easily increased without impairing the flexural modulus of the cured resin.
• Component [C] in Embodiments 1 to 3 of the present invention is an aromatic amine compound.
• aniline diethyltoluenediamine, 4,4′-methylene-bis (2-isopropyl-6-methylaniline), diaminodiphenylsulfone and the like can be mentioned.
• component [C] is preferably diaminodiphenylsulfone, and more preferably 3,3'-diaminodiphenylsulfone.
• component [C] is diaminodiphenyl sulfone, the flexural modulus of the cured resin product tends to increase, and a fiber-reinforced composite material having a higher 0 ° flexural strength can be easily obtained.
• the relationship between the number of moles of active hydrogen (Mc) of the component [C] and the number of moles of active epoxy groups (Ma) in 100 parts by mass of the total epoxy resin in the aspects 1 to 3 of the present invention is shown by the following formula (4). It is preferable to be within the range. 0.95 ⁇ Ma / Mc ⁇ 1.05 (4) By setting the content in such a range, the reaction between the epoxy resin and the curing agent easily occurs efficiently, so that the bending strength of the cured resin material tends to be high, and a fiber reinforced composite material having a higher 90 ° bending strength is obtained. It becomes easy to be.
• the number of moles of active epoxy groups (Ma) in 100 parts by mass of all epoxy resins is the sum of the number of moles of each epoxy resin active group, and is represented by the following formula.
• Ma (mass of epoxy resin A / epoxy equivalent of epoxy resin A) + (mass of epoxy resin B / epoxy equivalent of epoxy resin B) + .... + (mass of epoxy resin W / epoxy equivalent of epoxy resin W) ).
• Embodiment 1 of the epoxy resin composition of the present invention contains the above components [A], [B] and [C], and satisfies all of the following conditions 1, 2 and 3.
• the cured resin obtained by curing the epoxy resin composition at 180 ° C. for 120 minutes has a flexural modulus of 4.4 GPa or more (condition 1) and a flexural strength of 190 MPa or more (condition 2).
• condition 1 a flexural modulus of 4.4 GPa or more
• condition 2 a flexural strength of 190 MPa or more
• the flexural modulus and the flexural strength of the cured resin are in the above ranges, a fiber-reinforced composite material having both a 0 ° flexural strength and a 90 ° flexural strength at a high level can be easily obtained.
• the flexural modulus is 4.4 GPa or more, sufficient bending characteristics in the 0 ° direction can be easily obtained.
• the bending strength is 190 MPa or more
• sufficient bending characteristics in the 0 ° and 90 ° directions can be easily obtained.
• the flexural modulus and flexural strength of the cured resin of the present invention can be evaluated, for example, by performing a three-point bending test according to JIS K7171 (1994).
• the relationship between the average epoxy equivalent (Ea) of the component [A] and the average epoxy equivalent (Eb) of the component [B] needs to satisfy the following formula (1) (condition 3). 6 ⁇ Eb / Ea ⁇ 10 (1)
• Eb / Ea 6 or more
• a sufficient flexural modulus of the cured epoxy resin is easily obtained, and the 0 ° bending strength of the fiber-reinforced composite material is likely to be sufficient.
• Eb / Ea is 10 or less, the deformability of the cured resin material is not easily lost, and the bending strength is not easily reduced, so that a sufficient 90 ° bending strength of the fiber-reinforced composite material is easily obtained.
• Embodiment 1 of the epoxy resin composition of the present invention when the average epoxy equivalent of the component [A] and the component [B] satisfies the above range, both the flexural modulus and the bending strength of the cured resin can be achieved at a higher level. It becomes possible to make it easier.
• the Eb / Ea when the Eb / Ea is in a specific range, the number of bonding points formed by the reaction between the epoxy resin and the curing agent increases, which is generated when the cured epoxy resin is deformed. It is presumed that the fragile portion, which is the starting point of the destruction, was reduced and the deformability was improved.
• the average epoxy equivalent of the component [A] and the component [B] can be evaluated, for example, by performing a potentiometric titration according to JIS K7236 (2001).
• Embodiment 2 of the epoxy resin composition of the present invention includes the above components [A], [B], and [C], and satisfies all of the following conditions 4, 5, and 6.
• the flexural strain of the cured resin obtained by curing the epoxy resin composition at 180 ° C. for 120 minutes is 6% or more (condition 4).
• condition 4 The flexural strain of the cured resin obtained by curing the epoxy resin composition at 180 ° C. for 120 minutes.
• the bending strain of the cured resin is within the above range, the fiber-reinforced composite material using the epoxy resin composition as a matrix resin tends to have excellent 90 ° bending strength.
• the bending strain is 6% or more, sufficient bending characteristics in the 90 ° direction can be easily obtained.
• the above condition 4 can be achieved by mixing the above components [A], [B], and [C] at an appropriate ratio.
• the bending strain amount of the resin cured product of the present invention can be evaluated by, for example, performing a three-point bending test according to JIS K7171 (1994).
• the bending strain amount in the present invention can be calculated from the displacement amount when the maximum load is shown in the three-point bending test.
• the average epoxy equivalent weight (hereinafter, EEW) of the component [B] is in the range of 600 to 1000 g / eq (condition 5).
• EEW of the component [B] is 600 g / eq or more, a sufficient bending elastic modulus is easily obtained.
• the EEW of the component [B] is 1000 g / eq or less, the flexural modulus and the amount of strain are easily improved.
• the cured resin obtained by curing at 180 ° C. for 120 minutes has a glass transition temperature X (° C.) obtained from dynamic viscoelasticity measurement and a storage elastic modulus Y in a rubber state. (MPa) satisfies the following expression (condition 6).
• X glass transition temperature
• MPa storage elastic modulus Y in a rubber state.
• the storage elastic modulus Y in the rubber state satisfies the above range
• a fiber-reinforced composite material having an excellent balance between bending strength and heat resistance can be easily obtained.
• the relationship between the storage elastic modulus in the rubber state and the glass transition temperature is in a specific range, so that the density of crosslinking points in the epoxy resin cured product becomes appropriate. I have.
• the glass transition temperature of the cured resin of the present invention and the storage elastic modulus in a rubber state are obtained by performing a temperature rise measurement in a DMA measurement (dynamic viscoelasticity measurement). Can be calculated from The glass transition temperature is the temperature at the intersection of the tangent drawn in the glass region and the tangent drawn in the glass transition region in the scatter diagram.
• the storage elastic modulus in the rubber state is the storage elastic modulus at a temperature 50 ° C. higher than the glass transition temperature.
• Embodiment 3 of the epoxy resin composition of the present invention contains the above-mentioned components [A], [B] and [C], and satisfies the above condition 5 and the following condition 7 simultaneously.
• the storage elastic modulus Y (MPa) in the rubber state obtained from the dynamic viscoelasticity measurement and the number of moles of active epoxy group (Ma) in 100 parts by mass of the total epoxy resin ) Satisfies the following equation (condition 7).
• the storage elastic modulus in a rubber state and the number of moles of active epoxy groups in 100 parts by mass of the total epoxy resin satisfy the above ranges, so that the bending elastic modulus and the bending elastic modulus are higher. It is easy to balance strength. Although the reason is not clear, it is speculated that when the Y / Ma is in a specific range, the consumption of the epoxy group accompanying the curing reaction proceeds efficiently. It is considered that the cured resin obtained by curing the epoxy resin composition has a small amount of unreacted epoxy resin remaining and shows a homogeneous crosslinked state, that is, it can disperse the stress generated at the time of deformation.
• a cured resin obtained by curing the epoxy resin composition at 180 ° C. for 120 minutes has a flexural modulus of 4.6 GPa or more, and a bending strain of 6% or more.
• a flexural modulus and flexural strain amount of the cured resin are within such ranges, the flexural strength is likely to be excellent.
• the fiber reinforced composite material comprising the epoxy resin composition has high flexural strength and interlayer toughness. Easy to hold together.
• the aspect 1 of the epoxy resin composition of the present invention includes the component [A], the component [B], and the component [C].
• the following (i) ), (Ii) and (iii) are preferably satisfied.
• (I) Condition 4, Condition 5, and Condition 6 are satisfied.
• (Ii) Condition 5 and Condition 7 are satisfied.
• (Iii) Condition 4, Condition 5, Condition 6, and Condition 7 are satisfied.
• the fiber-reinforced composite material made of the epoxy resin composition has both 0 ° and 90 ° bending strength. In addition, it has excellent interlayer toughness.
• Embodiment 4 of the epoxy resin composition of the present invention contains, as essential components, component [A] a trifunctional amine type epoxy resin, component [E] sorbitol type epoxy resin, and component [F] dicyandiamide. It is preferable that the fiber-reinforced composite material using the epoxy resin composition of the present invention in aspect 4 as a matrix resin has excellent interlayer toughness.
• a triglycidylaminophenol-type epoxy resin, a triglycidylaminocresol-type epoxy resin and the like can be mentioned as in the above-described embodiments 1 to 3 of the present invention.
• component [A] is preferably an aminophenol-type epoxy resin.
• component [A] is an aminophenol-type epoxy resin, the flexural modulus of the cured resin is likely to be high, and a fiber-reinforced composite material having high 0 ° bending strength is easily obtained.
• the epoxy resin composition preferably contains 50 to 80 parts by mass of the component [A] based on 100 parts by mass of the total epoxy resin. By satisfying this range, the balance between the bending elastic modulus and the bending strength of the cured resin can be increased.
• the component [E] in the embodiment 4 of the present invention is a sorbitol type epoxy resin.
• Examples of the component [E] include "Denacol (registered trademark)" EX-614 and EX-614B (all manufactured by Nagase ChemteX Corporation).
• the component [E] is contained in an amount of 20 to 40 parts by mass based on 100 parts by mass of the total epoxy resin in the epoxy resin composition. By satisfying this range, the balance between bending strain and bending strength of the cured resin can be further improved.
• a cured resin obtained by curing the epoxy resin composition at 130 ° C. for 90 minutes has a flexural modulus of 4.3 GPa or more (condition 8) and a bending strength of 190 MPa. This is (condition 9).
• condition 8 When the flexural modulus and the flexural strength of the cured resin are in the above ranges, a fiber-reinforced composite material having both a 0 ° flexural strength and a 90 ° flexural strength at a high level can be easily obtained.
• the flexural modulus is 4.3 GPa or more, sufficient bending characteristics in the 0 ° direction can be easily obtained.
• the bending strength is 190 MPa or more, sufficient bending characteristics in 0 ° and 90 ° directions are easily obtained.
• Component [D] In the aspect 4 of the present invention, it is preferable to include the following component [D] -1 and / or component [D] -2 as the component [D].
• the glass transition temperature is a temperature that is an index of the heat resistance of the cured epoxy resin, and can be evaluated by DMA or DSC measurement of the cured resin.
• Component [D] -1 Naphthalene type epoxy resin
• Component [D] -2 Isocyanuric acid type epoxy resin.
• ⁇ Component [D] -1 in Embodiment 4 of the present invention is a naphthalene type epoxy resin.
• naphthalene type epoxy resin examples include “EPICLON (registered trademark)” HP-4032D, HP-4700, HP-4770, HP-5000, and HP-4710 (all manufactured by DIC Corporation).
• ⁇ Component [D] -2 in Embodiment 4 of the present invention is an isocyanuric acid type epoxy resin.
• Examples of the isocyanuric acid type epoxy resin include “TEPIC (registered trademark)”-S, -G, -L, -PAS, -UC, -FL (all manufactured by Nissan Chemical Industries, Ltd.).
• Component [F] in aspect 4 of the present invention is dicyandiamide or a derivative thereof.
• Dicyandiamide is excellent in that it can impart high mechanical properties and heat resistance to a cured epoxy resin obtained using the same as a curing agent, and is widely used as a curing agent for epoxy resins.
• Commercial products of dicyandiamide include DICY7 and DICY15 (all manufactured by Mitsubishi Chemical Corporation).
• the component [F] can be used together with the component [I] curing accelerator such as aromatic urea to lower the curing temperature of the epoxy resin composition as compared with the case where the component [F] is blended alone.
• the component [I] curing accelerator for example, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (sometimes abbreviated as DCMU), 3- (4-chlorophenyl) -1,1- Examples include dimethylurea, phenyldimethylurea (sometimes abbreviated as PDMU), and toluenebisdimethylurea (sometimes abbreviated as TBDMU).
• aromatic ureas include DCMU99 (manufactured by Hodogaya Chemical Industry Co., Ltd.), “Omicure (registered trademark)” 24 (manufactured by PTI Japan Ltd.), and “Dyhard (registered trademark)”. "UR505 (4,4'-methylenebis (phenyldimethylurea, CVC)) and the like.
• aspects 1 to 4 of the epoxy resin composition of the present invention include component [A], component [B], component [C], and component [D] as component [G] as long as the effects of the present invention are not lost.
• an epoxy resin different from the component [E] may be used.
• epoxy resins examples include aniline type epoxy resin, diaminodiphenylmethane type epoxy resin, diaminodiphenyl sulfone type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin liquid at 25 ° C., phenol novolak type epoxy resin, Cyclopentadiene type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more.
• aniline type epoxy resins include GAN (N, N-diglycidylaniline) and GOT (N, N-diglycidyl-o-toluidine) (all manufactured by Nippon Kayaku Co., Ltd.).
• diaminodiphenylmethane type epoxy resin Commercial products of the diaminodiphenylmethane type epoxy resin include “Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), YH434L (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and “jER (registered trademark)” 604 ( Mitsubishi Chemical Corporation), “Araldite (registered trademark)” MY720, MY721 (all manufactured by Huntsman Advanced Materials Co., Ltd.) and the like.
• TG3DAS manufactured by Konishi Chemical Industry Co., Ltd.
• bisphenol A type epoxy resins include “jER (registered trademark)” 828, 1001, 1007 (all manufactured by Mitsubishi Chemical Corporation) and the like.
• phenol novolac type epoxy resins include jER (registered trademark) "152, 154, 180S (all manufactured by Mitsubishi Chemical Corporation) and the like.
• an isocyanuric acid type epoxy resin may be used, and an epoxy resin exemplified as the aforementioned component [D] -2 may be used.
• the epoxy resin composition of the present invention has the purpose of adjusting the viscosity to be suitable for the process of producing the fiber reinforced composite material, adjusting the viscoelasticity, adjusting the tag and drape properties, and the mechanical properties and toughness of the resin composition. It is preferable to include a thermoplastic resin as the component [H] for the purpose of, for example, increasing the viscosity.
• a thermoplastic resin include polyvinyl acetal resin such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resin, polyamide, polyimide, polyvinyl pyrrolidone, polysulfone, and polyether sulfone.
• aspect 4 of the epoxy resin composition of the present invention preferably contains a thermoplastic resin as the component [H] from the viewpoint of adjusting the flexural modulus of the cured resin and other properties without impairing the strength. More preferably, the thermoplastic resin is polyether sulfone.
• the fiber-reinforced composite material of the present invention is obtained by curing the prepreg of the present invention.
• a prepreg comprising the epoxy resin composition of the present invention and a reinforcing fiber, that is, after laminating the prepreg of the present invention, heating and curing to obtain the fiber-reinforced composite material of the present invention.
• kneading may be performed using a machine such as a kneader, a planetary mixer, a three-roll extruder, and a twin-screw extruder. It may be mixed by hand using a spatula or the like.
• the prepreg of the present invention comprises the epoxy resin composition of the present invention and reinforcing fibers.
• the prepreg of the present invention can be obtained, for example, by impregnating a reinforcing fiber base with the epoxy resin composition prepared by the above method.
• Examples of the method of impregnation include a hot melt method (dry method) and the like.
• the hot melt method is a method of directly impregnating a reinforcing fiber with a thermosetting resin composition whose viscosity has been reduced by heating, or preparing a film in which an epoxy resin composition is coated on release paper or the like, and then reinforcing fibers.
• This method is a method of impregnating the reinforcing fibers with a resin by laminating this film from both sides or one side of the film and heating under pressure. At this time, the fiber mass content of the prepreg can be adjusted by changing the amount of the resin applied to the release paper.
• the reinforcing fiber used in the present invention is not particularly limited, and glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like can be used. These fibers may be used as a mixture of two or more kinds. From the viewpoint of obtaining a lightweight and highly rigid fiber reinforced composite material, it is preferable to use carbon fibers.
• a press molding method as a method for applying heat and pressure, a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, or the like can be appropriately used.
• the fiber-reinforced composite material of the present invention is preferably used for sports applications, aerospace applications and general industrial applications. More specifically, in sports applications, it is preferably used for golf shafts, fishing rods, rackets for tennis and badminton, and the like. In aerospace applications, it is preferably used for primary structural materials such as main wings, tail fins and floor beams, and secondary structural materials such as interior materials. Further, in general industrial applications, it is preferably used for structural materials such as automobiles, bicycles, ships, and railway vehicles. Among them, taking advantage of the feature that a fiber-reinforced composite material having a high bending strength in 0 ° and 90 ° directions can be obtained, it is suitably used for various structural members.
• Component [B] bisphenol F type epoxy resin component [B] -1 “Epototo (registered trademark)” YDF-2001 (manufactured by Toto Kasei Co., Ltd.) which is solid at 25 ° C.
• Component [B] -2 “jER (registered trademark)” 4004P manufactured by Mitsubishi Chemical Corporation
• Component [B] -3 “Epototo (registered trademark)” YDF-2004 manufactured by Toto Kasei Co., Ltd.
• Component [B] -4 “Epototo (registered trademark)” YDF-2005RD manufactured by Toto Kasei Co., Ltd.
• Component [B] -5 “jER (registered trademark)” 4007P manufactured by Mitsubishi Chemical Corporation
• Component [B] -6 “jER (registered trademark)” 4010P manufactured by Mitsubishi Chemical Corporation.
• Component [C] aromatic amine compound component [C] -1 Seika Cure-S (4,4′-diaminodiphenyl sulfone, manufactured by Seika Co., Ltd.), Component [C] -2 3,3 'DAS (3,3'-diaminodiphenyl sulfone, manufactured by Mitsui Chemicals Fine Co., Ltd.), Component [C] -3 “Lonacure (registered trademark)” M-MIPA (4,4′-methylene-bis (2-isopropyl-6-methylaniline), manufactured by Lonza), Component [C] -4 "jER Cure (registered trademark)” W (diethyltoluenediamine, manufactured by Mitsubishi Chemical Corporation).
• Component [E] sorbitol type epoxy resin “Denacol (registered trademark)” EX-614B (manufactured by Nagase ChemteX Corporation).
• Component [G] Other epoxy resin component [G] -1 GAN (diglycidylaniline type epoxy resin, manufactured by Nippon Kayaku Co., Ltd.), Component [G] -2 “Sumiepoxy (registered trademark)” ELM434 (diaminodiphenylmethane type epoxy resin, manufactured by Sumitomo Chemical Co., Ltd.), Component [G] -3 TG3DAS (diaminodiphenyl sulfone type epoxy resin, manufactured by Konishi Chemical Industry Co., Ltd.), Component [G] -4 “jER (registered trademark)” 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation), Component [G] -5 “jER (registered trademark)” 1001 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation), Component [G] -6 “jER (registered trademark)” 1004 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation), Component [G] -7 “jER (registered trademark
• Component [I] curing accelerator DCMU99 (3- (3,4-dichlorophenyl) -1,1-dimethylurea, manufactured by Hodogaya Chemical Industry Co., Ltd.).
• the electrode is immersed in the above solution, potentiometric titration is performed with a perchloric acid-acetic acid standard solution (0.1 mol / L), and the average epoxy equivalent of the component [A] and the component [B] according to JIS K7236 (2001). Was calculated.
• the average epoxy equivalent is as shown in Tables 1, 2, 6, and 7. Note that, in this specification, Table 1 indicates Table 1-1 and Table 1-2. The same applies to Tables 2, 6, and 7.
• ⁇ Preparation method of epoxy resin composition> In a kneader, a predetermined amount of the component [C], the aromatic amine compound, the component [F] and other curing agents, and the components other than the component [I] curing accelerator are added, and the temperature is raised to 60 to 150 ° C. It was kneaded appropriately until dissolved. That is, when the temperature was raised to a temperature at which the respective components were compatible according to the respective compositions in the examples and comparative examples, the respective components were heated at any temperature in the range of 60 to 150 ° C. in any of the compositions. Compatible.
• the epoxy resin composition is as shown in Tables 1 to 8.
• a test piece having a width of 10 mm and a length of 60 mm was cut out, and using an Instron universal testing machine (manufactured by Instron), the span was 32 mm, the crosshead speed was 10 mm / min, and JIS K7171 (1994).
• a test piece having a width of 12.7 mm and a length of 45 mm was cut out, and the test piece was placed on a solid torsion jig using a dynamic viscoelasticity measuring device (ARES W / FCO: manufactured by TA Instruments).
• the temperature was set at a heating rate of 5 ° C./min, a frequency of 1 Hz, and a strain of 0.08%, and the temperature was measured in a temperature range of 40 to 260 ° C.
• the glass transition temperature was the temperature at the intersection of the tangent drawn in the glass state and the tangent drawn in the glass transition temperature region in the obtained graph of storage modulus and temperature.
• the storage elastic modulus in the rubber state was defined as the storage elastic modulus at a temperature 50 ° C. higher than the glass transition temperature in the obtained graph of the storage elastic modulus and the temperature.
• ⁇ Preparation method of prepreg> The epoxy resin composition obtained according to the above ⁇ Preparation method of epoxy resin composition> was applied on release paper using a knife coater to prepare two resin films having a predetermined basis weight. The basis weight of the resin film was adjusted to be 39 g / m 2 . Next, two pieces of the obtained resin films were put on carbon fibers “Treca (registered trademark)” T700S-12K-60E (manufactured by Toray Industries, Ltd., basis weight 150 g / m 2 ) arranged in one direction in a sheet shape. The fibers were overlaid on both sides and heated under pressure at a temperature of 110 ° C. and a pressure of 2 MPa to impregnate the epoxy resin composition to obtain a unidirectional prepreg. The fiber mass content of the obtained prepreg was 67%.
• ⁇ Method of measuring composite characteristics> (1) 0 ° bending strength of CFRP
• the unidirectional prepreg prepared according to the above ⁇ Preparation method of prepreg> is aligned in the fiber direction, 13 plies are laminated, and is autoclaved at 180 ° C. or 130 ° C. for 2 hours at 0 ° C. for 2 hours. Under a pressure of 6 MPa, molding was performed at a temperature increasing rate of 1.7 ° C./min to produce a 2-mm-thick unidirectional CFRP.
• the laminate was cut out to have a width of 15 mm and a length of 100 mm, and was subjected to three-point bending using an Instron universal testing machine (manufactured by Instron) in accordance with JIS K7017 (1988). The measurement was performed at a crosshead speed of 5.0 mm / min, a span of 80 mm, a thickness of 10 mm, and a fulcrum diameter of 4 mm, and the bending strength was measured. The 0 ° bending strength was measured for six samples, calculated as a conversion value when the fiber mass content was 60% by mass, and the average was determined as the 0 ° bending strength.
• the curing temperature when a curing agent not used in Examples and Comparative Examples is used is appropriately selected from temperatures higher than a temperature at which an exothermic peak appears in differential scanning calorimetry.
• the laminated board was cut out so as to have a width of 20 mm and a length of 200 mm, and an aluminum block was adhered to the end where the film was inserted so as to be perpendicular to the fiber direction, and an Instron universal testing machine (manufactured by Instron) A double cantilever beam test was performed according to JIS K7086 (1993). The measurement was performed at a crosshead speed of 1.0 mm / min, and the fracture toughness value was measured. Such fracture toughness values were measured on six samples, the average value was calculated as G 1c.
• Example 1 As the epoxy resin, 10 parts by mass of "Araldite (registered trademark)” MY0500, 45 parts by mass of “Araldite (registered trademark)” MY0600, 18 parts by mass of “Epototo (registered trademark)” YDF-2004, and “Sumiepoxy (registered trademark)” 10 parts by mass of "ELM434, 17 parts by mass of EPICLON (registered trademark)” 830, 41.5 parts by mass of Seikacure-S as an aromatic amine compound, and 5.0 of "Vinilec (registered trademark)” K as a thermoplastic resin.
• An epoxy resin composition was prepared according to the above ⁇ Method for preparing epoxy resin composition> using parts by mass.
• component [A] was 117 g / eq
• component [B] was 980 g / eq
• the average epoxy equivalent of the component [B] represented by the formula (1) / the average epoxy equivalent of the component [A] was 8.4.
• the flexural properties of the cured epoxy resin cured at 180 ° C. were obtained according to ⁇ Evaluation method of flexural properties of cured epoxy resin>.
• the flexural modulus was 4.7 GPa and the flexural strength was 205 MPa and the bending strain amount was 6.9%.
• the glass transition temperature and the storage elastic modulus in a rubber state were measured according to ⁇ Evaluation method of glass transition temperature and storage elastic modulus of cured epoxy resin>, and were 175 ° C. and 10.0 MPa, respectively.
• X glass transition temperature
• Y storage elastic modulus
• X 175 C., 9.2 ⁇ Y ⁇ 11.2
• the storage elastic modulus of the epoxy resin cured product in the rubber state satisfied the range of Expression (2).
• a prepreg having a fiber mass content of 67% by mass was prepared according to the ⁇ prepreg preparation method>, 13 ply of the obtained prepreg was laminated, cured at 180 ° C, and cured in one direction.
• a fiber reinforced composite material (CFRP) was produced.
• the 0 ° bending strength was 1810 MPa and the 90 ° bending strength was 132 MPa, which was good.
• Examples 2 to 15 Except that the resin composition was changed as shown in Tables 1 and 2, respectively, an epoxy resin composition, a prepreg, a cured resin, and a CFRP were produced in the same manner as in Example 1, and the bending properties of the cured resin, Average epoxy equivalent of component [B] / average epoxy equivalent of component [A] (formula (1)), relationship between glass transition temperature and storage elastic modulus in rubber state (formula (2)), 1100 ⁇ Y / Ma ⁇ 2000 (Equation (3)) was obtained, and all of Equations (1) to (3) were satisfied.
• Examples 16 to 38 The resin composition was changed as shown in Tables 3 to 5, and an epoxy resin composition and a prepreg were produced in the same manner as in Example 1. According to the above ⁇ Evaluation method of bending property of epoxy resin cured product>, cured at 130 ° C. to obtain a cured epoxy resin product, and CFRP was obtained according to the ⁇ Evaluation method of composite property>.
• the value of the formula (1) is 20.1, and the bending properties of the cured epoxy resin cured at 130 ° C. are obtained in accordance with ⁇ Evaluation method of bending properties of cured epoxy resin>.
• the elastic modulus was 4.5 GPa, but the bending strength was as low as 180 MPa.
• a prepreg having a fiber mass content of 67% by mass was prepared according to ⁇ Prepreg preparation method>, 13 ply of the obtained prepreg was laminated, cured at 130 ° C, and cured in one direction.
• a fiber reinforced composite material (CFRP) was produced.
• the 0 ° bending strength was 1701 MPa
• the 90 ° bending strength was 113 MPa
• the 90 ° bending strength was low.
• G 1c was 228 J / m 2 and G 2c was 483 J / m 2 , which was insufficient.
• Comparative Example 4 With respect to the resin compositions shown in Table 6-2, an epoxy resin composition, a prepreg, a cured resin, and CFRP were prepared in the same manner as in Comparative Example 1, and the bending properties of the cured resin, Formula (2), and Formula ( The relationship of 3) and the characteristics of CFRP were obtained.
• the epoxy resin composition does not contain the component [B].
• the cured resin did not satisfy the relations of the formulas (2) and (3) and had a glass transition temperature of 170 ° C., but had a flexural modulus of 3.7 GPa, a flexural strain of 5.8% and a flexural strength of 181 MPa. And it was low. Further, the 0 ° and 90 ° flexural strengths and interlayer toughness values of CFRP were also low.
• Comparative Example 9 With respect to the resin compositions shown in Table 7-1, an epoxy resin composition, a prepreg, a cured resin, and CFRP were prepared in the same manner as in Comparative Example 1, and the bending properties of the cured resin, Formula (2), and Formula ( The relationship of 3) and the characteristics of CFRP were obtained.
• the epoxy resin composition does not contain the component [B], but contains 40 parts by mass of a bisphenol A type epoxy resin solid at 25 ° C.
• the cured resin did not satisfy the relations of the formulas (2) and (3) and had a high glass transition temperature of 180 ° C. but a low flexural modulus of 4.0 GPa. Further, the 0 ° and 90 ° flexural strengths and interlayer toughness values of CFRP were also insufficient.
• Comparative Example 12 did not contain the component [E], so that the flexural modulus and strain were insufficient and the flexural strength was insufficient.
• Comparative Example 13 did not contain the component [A] and had insufficient flexural modulus, resulting in insufficient flexural strength.
• the 0 ° and 90 ° physical properties of CFRP were also low.
• the units of each component in the table are parts by mass.
• the epoxy resin composition of the present invention has both a high elastic modulus and bending strain at a high level, and gives a cured resin having excellent heat resistance.Therefore, a fiber-reinforced composite material using the epoxy resin composition has excellent properties. It has 0 ° bending strength and 90 ° bending strength. As a result, the weight of the fiber-reinforced composite material can be reduced, so that the degree of freedom in structural design is increased, and it is expected that the possibility of application to various structures is expanded.

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