Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
  • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
  • B29C39/10—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
  • B29C39/22—Component parts, details or accessories; Auxiliary operations
  • B29C39/24—Feeding the material into the mould
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
  • B29C39/22—Component parts, details or accessories; Auxiliary operations
  • B29C39/42—Casting under special conditions, e.g. vacuum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/28—Shaping operations therefor
  • B29C70/40—Shaping or impregnating by compression not applied
  • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
  • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
  • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • C—CHEMISTRY; METALLURGY
  • 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

Definitions

• the present invention relates to an epoxy resin composition suitably used for aerospace members, automobile members, etc., a fiber-reinforced composite material using the same, and a method for producing the same.
• Fiber-reinforced composite materials consisting of reinforced fibers and matrix resins can be designed to take advantage of the advantages of reinforced fibers and matrix resins, so their applications are expanding to the aerospace field, sports field, general industrial field, etc. ..
• the reinforcing fiber glass fiber, aramid fiber, carbon fiber, boron fiber, etc. are used.
• the matrix resin both a thermosetting resin and a thermoplastic resin are used, but a thermosetting resin that can be easily impregnated into the reinforcing fiber is often used.
• the thermosetting resin an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a bismaleimide resin, a cyanate resin and the like are used.
• a method for forming the fiber-reinforced composite material As a method for forming the fiber-reinforced composite material, a method such as a prepreg method, a hand lay-up method, a filament winding method, a plutrusion method, or an RTM (Resin Transfer Molding) method is applied.
• the prepreg method is a method of obtaining a molded product by laminating a prepreg in which a reinforcing fiber is impregnated with an epoxy resin composition into a desired shape and heating the prepreg.
• this prepreg method is suitable for the production of fiber-reinforced composite materials having high material strength required for structural material applications such as aircraft and automobiles, it goes through many processes such as prepreg production and laminating.
• the RTM method is a method in which a liquid epoxy resin composition is injected into a reinforcing fiber base material placed in a heated molding mold, impregnated, and heat-cured in the molding mold to obtain a molded product.
• Each molding step of the RTM method includes a step of injecting and impregnating a liquid epoxy resin composition into a reinforcing fiber base material placed in a heated molding die, and a step of heating and curing the epoxy resin composition in the molding die. The process is divided into a step of obtaining a molded product and removing the molded product from the molding die.
• the epoxy resin composition In order to shorten the time for injecting and impregnating the epoxy resin composition into the reinforcing fiber base material, the epoxy resin composition should have a low viscosity so as to be impregnated in a short time, and the epoxy resin composition being injected has a low viscosity. It is necessary to maintain the condition. Further, in order to shorten the heat curing time, it is required that the epoxy resin composition is sufficiently cured in a short time and high heat resistance is imparted so that the epoxy resin composition can be smoothly demolded.
• an epoxy resin composition containing methylenebis (3-chloro-2,6-diethylaniline) (M-CDEA) as a curing agent has been disclosed, and there is a method of suppressing an increase in viscosity for a long time. It has been proposed (Patent Document 1). Further, an epoxy resin composition containing diaminodiphenyl sulfone as a curing agent is disclosed, which has excellent impregnation property, can be cured at high speed at 180 ° C., and the resin is sufficiently cured in the demolding step after molding. A method has been proposed (Patent Document 2).
• Patent Document 1 Although the method described in Patent Document 1 can suppress an increase in viscosity for a long time, the resin composition has a high viscosity, so that the impregnation property is insufficient and the reactivity is low. Since it contains (3-chloro-2,6-diethylaniline) (M-CDEA), it has a problem that its curability at a high temperature of 180 ° C. is low and sufficient high strength is not developed in a short time.
• M-CDEA (3-chloro-2,6-diethylaniline)
• Patent Document 2 Although the method described in Patent Document 2 described above is excellent in impregnation property, it may not be sufficiently good for high-speed curing property required at a high level.
• an object of the present invention is that the viscosity is very low, the impregnation property is excellent, the viscosity increase is suppressed even at the injection temperature, the viscosity can be sufficiently cured in a short time, and the resin is used in the demolding step after molding. It is an object of the present invention to provide an epoxy resin composition that can be smoothly demolded by sufficiently curing and imparting high heat resistance. Furthermore, it is an object of the present invention to provide a fiber-reinforced composite material having excellent compressive strength, impact resistance and microcrack resistance during moist heat.
• the present invention has the following configuration in order to solve the above problems. That is, an epoxy resin composition containing at least the following constituents [A] to [C] as an epoxy resin and at least the following constituents [D] and [E] as a curing agent.
• A] is contained in an amount of 30 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component
• the component [B] is contained in an amount of 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component.
• the constituent component [D] is contained in 55 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the total curing agent component, and is contained in the total number of epoxy groups (E) contained in the epoxy resin and in the curing agent.
• It is an epoxy resin composition in which H / E which is the ratio with the total number of active hydrogens (H) of an amine compound is 1.1 or more and 1.4 or less.
• H / E which is the ratio with the total number of active hydrogens (H) of an amine compound is 1.1 or more and 1.4 or less.
• the fiber-reinforced composite material of the present invention is a fiber-reinforced composite material containing the cured product of the epoxy resin composition and the reinforced fiber base material.
• the first aspect of the method for producing a fiber-reinforced composite material of the present invention is a main agent solution containing at least the constituent components [A] to [C] as an epoxy resin, and at least the constituent components [D] and the curing agent.
• a molding die in which a curing agent solution consisting of a liquid containing the component [E] and in which the component [D] is uniformly dissolved is mixed at 70 ° C. or higher and 130 ° C. or lower and then heated to 110 ° C. or higher and 150 ° C. or lower. It is a method for producing a fiber-reinforced composite material which is injected into a reinforcing fiber base material arranged inside, impregnated, and cured at 110 ° C.
• constituent component [A] is an all-epoxy resin.
• 30 parts by mass or more and 50 parts by mass or less are contained with respect to 100 parts by mass of the component
• the component [B] is contained by 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component
• the component [B] is contained.
• D] is contained in an amount of 55 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the total curing agent component, and the total number of epoxy groups (E) contained in the epoxy resin and the total number of active hydrogens of the amine compound contained in the curing agent.
• This is a method for producing a fiber-reinforced composite material having an H / E ratio of (H) of 1.1 or more and 1.4 or less.
• the second aspect of the method for producing a fiber-reinforced composite material of the present invention is a main agent solution containing at least the constituent components [A] to [C] as an epoxy resin, and at least the constituent components [D] and the curing agent.
• a molding die in which a curing agent solution consisting of a liquid containing the component [E] and in which the component [D] is uniformly dissolved is mixed at 70 ° C. or higher and 130 ° C. or lower and then heated to 90 ° C. or higher and 130 ° C. or lower. It is a method for producing a fiber-reinforced composite material which is injected into a reinforcing fiber base material arranged inside, impregnated, and cured at 160 ° C.
• constituent component [A] is an all-epoxy resin.
• 30 parts by mass or more and 50 parts by mass or less are contained with respect to 100 parts by mass of the component
• the component [B] is contained by 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component
• the component [B] is contained.
• D] is contained in an amount of 55 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the total curing agent component, and the total number of epoxy groups (E) contained in the epoxy resin and the total number of active hydrogens of the amine compound contained in the curing agent.
• This is a method for producing a fiber-reinforced composite material having an H / E ratio of (H) of 1.1 or more and 1.4 or less.
• the viscosity is very low, the impregnation property is excellent, the viscosity increase is suppressed even at the injection temperature, the viscosity is stable, sufficient curing can be performed in a short time, and the resin is sufficient in the demolding step after molding. It becomes possible to provide an epoxy resin composition which can be smoothly demolded by being cured and imparted with high heat resistance, and a fiber-reinforced composite material having excellent compression strength and impact resistance at the time of moist heat can be obtained.
• the fiber-reinforced composite material composed of the epoxy resin composition and the reinforcing fiber is excellent in compressive strength, impact resistance, and microcrack resistance during moist heat, it should be suitably used for aeronautical / spacecraft members, automobile members, and the like. Can be done.
• the constituent component [A] used in the present invention is a tetrafunctional glycidyl diamine type epoxy resin, which is a necessary component for imparting high heat resistance and mechanical properties to a cured resin product and a fiber-reinforced composite material.
• a tetrafunctional glycidyl diamine type epoxy resin which is a necessary component for imparting high heat resistance and mechanical properties to a cured resin product and a fiber-reinforced composite material.
• N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane N, N, N', N'-tetraglycidyl-3,3'-dimethyl-4,4'-diaminodiphenylmethane.
• N, N, N', N'-tetraglycidyl-m-xylylene diamine N, N, N', N'-tetraglycidyl-p-xylylene diamine, etc.
• N, N, N', N'-tetraglycidylxylylenediamine isomers or derivatives thereof, 1,3-bis (diglycidylaminomethyl) cyclohexane, 1,4-bis (diglycidylaminomethyl) cyclohexane, Examples thereof include tetraglycidylates of various alicyclic diamines such as 2,5-bis (diglycidylaminomethyl) norbornane and 2,6-bis (diglycidylaminomethyl) norbornane.
• the constituent component [A] two or more kinds of these tetrafunctional glycidyl diamine type epoxy resins may be used in combination.
• the constituent [A1] N, N, N', N'-tetraglycidyldiaminodiphenylmethane is preferably contained as the constituent [A], and the constituent [A1] is used as the constituent [A]. Is more preferable.
• tetrafunctional glycidyl diamine type epoxy resins include "Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), YH434L (manufactured by Nittetsu Chemical & Materials Co., Ltd.), and "jER (registered trademark)”. 604 (manufactured by Mitsubishi Chemical Co., Ltd.), "Araldite (registered trademark)” MY720, “Araldite (registered trademark)” MY721 (all manufactured by Huntsman Japan Co., Ltd.), TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) ) Etc. can be used.
• the constituent component [A] in the present invention needs to be contained in an amount of 30 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component.
• the constituent component [A] is contained in an amount of 30 parts by mass or more with respect to 100 parts by mass of all the epoxy resin components, the cured resin material exhibits high heat resistance and the compressive strength of the fiber-reinforced composite material during moist heat is improved. do.
• the constituent component [A] is 50 parts by mass or less, the viscosity of the resin composition at the time of resin injection is reduced, and the impregnation property into the reinforcing fiber base material is improved. From this point of view, the blending amount of the constituent component [A] is more preferably in the range of 40 parts by mass or more and 50 parts by mass or less.
• the constituent component [B] in the present invention is an aminophenol type epoxy resin, which is a necessary component for lowering the viscosity of the resin composition and giving high mechanical properties to the cured resin product and the fiber-reinforced composite material.
• N N-diglycidyl-4-glycidyloxyaniline
• N N-diglycidyl-2-methyl-4-glycidyloxyaniline
• N N-diglycidyl-3-methyl-4-glycidyloxyaniline
• N- Diglycidyl-2,6-dimethyl-4-glycidyloxyaniline N, N-diglycidyl-3,5-dimethyl-4-glycidyloxyaniline
• N N-diglycidyl-2-ethyl-4-glycidyloxyaniline
• constituent component [B] two or more kinds of these aminophenol type epoxy resins may be used in combination.
• constituent [B1] triglycidyl-p-aminophenol is preferably contained as the constituent [B]
• constituent [B1] is more preferably used as the constituent [B].
• aminophenol type epoxy resin examples include "jER (registered trademark)” 630 (all manufactured by Mitsubishi Chemical Corporation), “Araldite (registered trademark)” MY0500, “Araldite (registered trademark)” MY0510, and “Araldite”. (Registered trademark) "MY0600”, “Araldite (registered trademark)” MY0610 (all manufactured by Huntsman Japan Co., Ltd.), ELM100 (manufactured by Sumitomo Chemical Corporation) and the like can be used.
• the constituent component [B] in the present invention needs to be contained in an amount of 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component.
• the constituent component [B] When the constituent component [B] is contained in an amount of 20 parts by mass or more with respect to 100 parts by mass of all the epoxy resin components, the cured resin exhibits high heat resistance, and the viscosity of the resin composition at the resin impregnation temperature is reduced. The impregnation property into the reinforcing fiber base material is improved.
• the constituent component [B] is 40 parts by mass or less, the deterioration of the physical properties at the time of moist heat is suppressed, and the compressive strength of the fiber-reinforced composite material at the time of moist heat is improved. From this point of view, the blending amount of the constituent component [B] is more preferably in the range of 20 parts by mass or more and 30 parts by mass or less.
• the epoxy resin composition of the present invention contains both the constituent component [A] and the constituent component [B], and the constituent component [A] is 30 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of all the epoxy resin components. It is essential that the constituent component [B] is contained in an amount of 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component.
• the viscosity is very low and the impregnation property is excellent, the increase in viscosity is suppressed even at the injection temperature, and it is stable, and it is sufficient in a short time.
• the resin is sufficiently cured during the demolding process after molding, and by imparting high heat resistance, it can be demolded smoothly and has excellent compression strength and impact resistance during moist heat. It becomes possible to provide an epoxy resin composition obtained by obtaining a fiber-reinforced composite material.
• the constituent component [C] in the present invention is a bisphenol F type epoxy resin, and in order to reduce the viscosity of the resin composition at the resin impregnation temperature and improve the impregnation property into the reinforcing fiber base material, the resin cured product and the fiber are further prepared. It is a necessary component to give high mechanical properties to reinforced composite materials.
• the bisphenol F type epoxy resin of the constituent component [C] is one in which two phenolic hydroxyl groups of bisphenol F are glycidylated.
• bisphenol F-type epoxy resins include "jER (registered trademark)” 806, “jER (registered trademark)” 807, “jER (registered trademark)” 1750, “jER (registered trademark)” 4004P, and “jER (registered)”.
• Examples of commercially available products of the tetramethylbisphenol F type epoxy resin which is an alkyl substituent include "Epototo (registered trademark)" YSLV-80XY (Nittetsu Chemical & Materials Co., Ltd.).
• the constituent component [C] in the present invention is preferably contained in an amount of 20 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component.
• the constituent component [C] is contained in an amount of 20 parts by mass or more with respect to 100 parts by mass of all the epoxy resin components, the viscosity of the resin composition at the resin impregnation temperature is reduced, and the impregnation property into the reinforcing fiber base material is improved. It is preferable because it can prevent unimpregnation and further exhibits high toughness and elastic modulus in the cured resin product, and when it is 40 parts by mass or less, it is preferable because it exhibits high heat resistance. From this point of view, the blending amount of the constituent component [C] is more preferably in the range of 20 parts by mass or more and 30 parts by mass or less.
• bisphenol type epoxy resin other than bisphenol F type phenol novolac type epoxy resin, cresol novolac type epoxy resin, resorcinol type epoxy resin, which are epoxy resins other than the constituents [A] to [C]
• It is selected from phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin having a biphenyl skeleton, isocyanate-modified epoxy resin, tetraphenylethane type epoxy resin, triphenylmethane type epoxy resin, etc. 1
• the epoxy resin of more than one species may be contained, and the content thereof is preferably less than 30 parts by mass with respect to 100 parts by mass of the total epoxy resin component.
• epoxy resins other than the constituents [A] to [C] include bisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, 2, 2', 6,6.
• bisphenol type epoxy resins other than bisphenol F type are preferably used because they contribute to an excellent balance between toughness and heat resistance of the cured resin, and liquid bisphenol type epoxy resins are particularly excellent in impregnation into reinforcing fibers. Since it contributes, it is preferably used as an epoxy resin other than the constituents [A] to [C].
• liquid means that the viscosity at 25 ° C is 1000 Pa ⁇ s or less
• solid means that there is no fluidity at 25 ° C or the fluidity is extremely low. Specifically, it means that the viscosity at 25 ° C. is larger than 1000 Pa ⁇ s.
• the viscosity is determined according to the "conical-viscosity measuring method using a flat plate type rotational viscometer” in JIS Z8803 (1991), and an E-type viscometer equipped with a standard cone rotor (1 ° 34'x R24) (for example, Tokyo Keiki). Measured using TVE-30H manufactured by Co., Ltd.).
• the bisphenol type epoxy resin other than bisphenol F type is a glycidylated two phenolic hydroxyl groups of a bisphenol compound other than bisphenol F, and is bisphenol A type, bisphenol AD type, bisphenol S type, or these. Examples thereof include halogens of bisphenols, alkyl substituents, hydrogenated products and the like.
• these bisphenol type epoxy resins not only monomers but also high molecular weight bodies having a plurality of repeating units can be preferably used. From the viewpoint of the balance between toughness and heat resistance of the cured resin, when a bisphenol type epoxy resin other than the bisphenol F type is contained, it is preferably less than 30 parts by mass with respect to 100 parts by mass of the total epoxy resin component.
• Examples of commercially available bisphenol S-type epoxy resins include "EPICLON (registered trademark)" EXA-1515 (manufactured by DIC Corporation).
• the epoxy resin composition of the present invention contains at least two kinds of curing agents in order to impart excellent heat resistance and mechanical strength to the fiber-reinforced composite material while enhancing the impregnation property into the reinforcing fiber base material.
• the curing agent refers to a compound having an active group that can react with an epoxy group to form a crosslinked structure with an epoxy resin.
• one type of curing agent is the crystalline aromatic diamine of the constituent component [D].
• the component [D] is a component necessary for imparting high mechanical properties to a cured resin product and a fiber-reinforced composite material while having a low viscosity and excellent handleability and improving the impregnation property into a reinforcing fiber base material.
• crystalline aromatic diamines are 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 2,2'-diethyldiaminodiphenylmethane, 4,4'.
• the constituent component [D1] 4,4'-methylenebis (2-isopropyl-6-methylaniline) is preferably contained as the constituent component [D]
• the constituent component [D1] is used as the constituent component [D]. It is more preferable to be used.
• Commercially available crystalline aromatic diamines include "Lonza Cure (registered trademark)” M-MIPA, “Lonza Cure (registered trademark)” M-DIPA (all manufactured by Lonza Co., Ltd.), and Seika Cure S (manufactured by Seika Co., Ltd.). ), 3,3'-DAS (manufactured by Mitsui Kagaku Fine Co., Ltd.) and the like.
• the constituent component [D] in the present invention needs to be contained in an amount of 55 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the total curing agent component.
• the constituent component [D] is contained in an amount of 55 parts by mass or more with respect to 100 parts by mass of the total curing agent component, the viscosity at the resin impregnation temperature at the time of injection is sufficiently low, the impregnation property is good, and the fiber-reinforced composite material is obtained. The compressive strength during moist heat is improved.
• the curing agent can be treated as a liquid at 25 ° C., so that it is excellent in handling and can exhibit high-speed curing at high temperature. From this point of view, it is more preferably in the range of 60 parts by mass or more and 70 parts by mass or less.
• the other type of curing agent is the liquid aromatic diamine of the constituent component [E].
• the constituent component [E] is liquid at 25 ° C., and the constituent component [D] can be dissolved to form a uniform curing agent liquid. Since the curing agent can be treated as a liquid at 25 ° C., the handleability is improved. It is an essential ingredient.
• the uniformly dissolved state refers to a liquid state in which the constituent component [D] has not reached the solubility at 23 ° C. and no solid component is deposited.
• this curing agent liquid remains liquid for a long time, it can be suitably used in a method for producing a fiber-reinforced composite material such as the RTM method.
• diethyltoluenediamine such as 2,4-diethyl-6-methyl-m-phenylenediamine and 4,6-diethyl-2-methyl-m-phenylenediamine.
• the constituent [E1] diethyltoluenediamine and / or the constituent [E2] 4,4'-diamino-3,3'-dimethyldiphenylmethane are preferably used as the constituent [E], and the constituent [E2].
• 4,4'-Diamino-3,3'-dimethyldiphenylmethane is more preferably used as the constituent component [E].
• a cured epoxy resin having a high glass transition temperature and a high elastic modulus can be obtained.
• the epoxy resin composition of the present invention may also contain a curing agent other than the constituent component [D] and the constituent component [E].
• a curing agent other than the constituent component [D] and the constituent component [E] include an aliphatic diamine curing agent such as hexamethylenediamine, 1,3-pentanediamine, and 2-methylpentamethylenediamine, and isophoronediamine, 4. , 4'-Methylenebiscyclohexylamine, 4,4'-methylenebis (2-methylcyclohexylamine), bis (aminomethyl) norbornan, 1,2-cyclohexanediamine, 1,3-bisaminomethylcyclohexane and the like.
• diamine curing agents include diamine curing agents. These curing agents may be used alone or in combination of two or more.
• the epoxy resin composition of the present invention contains, as other components, a curing accelerator, a plasticizer, a dye, a pigment, an inorganic filler, an antioxidant, an ultraviolet absorber, a coupling agent, a surfactant and the like, if necessary. Can be included.
• H / E which is the ratio of the total number of epoxy groups (E) contained in the epoxy resin to the total number of active hydrogens (H) of the amine compound contained in the curing agent, is 1.1 or more and 1.4 or less. , 1.2 or more and 1.3 or less is more preferable.
• H / E is 1.1 or more, it is preferable because a good effect of improving curability and an effect of improving the plastic deformation ability of the cured resin product can be obtained, and when it is 1.4 or less, it has high heat resistance. Is preferable because it expresses.
• the epoxy resin composition of the present invention contains core-shell rubber particles containing an epoxy group in the shell portion, in which the volume average particle diameter is in the range of 50 nm or more and 300 nm or less as the constituent component [F].
• the core-shell rubber particles are excellent in that they give high toughness to the fiber-reinforced composite material, and have the effects of improving impact resistance and suppressing the generation of microcracks, which will be described later.
• the core-shell rubber particles are particles in which a part or the whole of the core surface is covered by a method such as graft-polymerizing a particulate core portion mainly composed of a polymer such as crosslinked rubber and a polymer different from the core portion. Means.
• a polymer polymerized from one or more selected from a conjugated diene-based monomer, an acrylic acid ester-based monomer, and a methacrylic acid ester-based monomer, a silicone resin, or the like can be used.
• Specific examples thereof include butadiene, isoprene, and chloroprene, and a crosslinked polymer composed of these alone or by using a plurality of kinds thereof is preferable.
• butadiene as the conjugated diene-based monomer, that is, a polymer polymerized from a monomer containing butadiene as a core component. ..
• the shell component constituting the core-shell rubber particles is graft-polymerized with the above-mentioned core component and chemically bonded to the polymer particles constituting the core component.
• the component constituting such a shell component is, for example, a polymer polymerized from one or more selected from (meth) acrylic acid ester, aromatic vinyl compound and the like.
• a component contained in the epoxy resin composition of the present invention that is, a functional group that reacts with the epoxy resin or a curing agent component thereof is introduced into the shell component.
• Such a functional group When such a functional group is introduced, the affinity with the epoxy resin is improved, and finally it can react with the epoxy resin composition and be incorporated into the cured product, so that the dispersion is good. Sex can be achieved. As a result, a sufficient effect of improving toughness can be obtained even with a small amount of compounding, and it is possible to improve toughness while maintaining Tg and elastic modulus.
• a functional group include a hydroxyl group, a carboxyl group, and an epoxy group.
• a method for introducing such a functional group into the shell portion one or more components such as acrylic acid esters and methacrylic acid esters containing such functional groups are added to the core surface as a part component of the monomer. Examples thereof include a method such as graft polymerization.
• the core-shell rubber particles of the component [F] in the present invention preferably have a volume average particle diameter of 50 nm or more and 300 nm or less, and preferably 50 nm or more and 150 nm or less.
• the volume average particle size can be measured using a nanotrack particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., dynamic light scattering method).
• a nanotrack particle size distribution measuring device manufactured by Nikkiso Co., Ltd., dynamic light scattering method.
• the volume average particle diameter is 50 nm or more, the specific surface area of the core-shell rubber particles is moderately small, which is energetically advantageous, so that aggregation is unlikely to occur and the toughness improving effect is high.
• the volume average particle diameter is 300 nm or less, the distance between the core-shell rubber particles is appropriately small, and the toughness improving effect is high.
• core-shell rubber particles there are no particular restrictions on the method for producing core-shell rubber particles, and those produced by a well-known method can be used.
• Commercially available core-shell rubber particles include, for example, "Paraloid (registered trademark)" EXL-2655 (manufactured by Dow Chemical Co., Ltd.) composed of a butadiene / alkyl methacrylate / styrene copolymer, and an acrylic acid ester / methacrylic acid ester copolymer weight.
• the core layer of a glassy polymer having a glass transition temperature of room temperature or higher such as Staphyroid IM-601 and IM-602 (manufactured by Aica Kogyo Co., Ltd.), is covered with an intermediate layer of a rubber-like polymer having a low Tg.
• a core-shell rubber particle having a three-layer structure, which is surrounded by a shell layer can also be used.
• these core-shell rubber particles are treated as powder by crushing the lumps taken out, and the powder-like core-shell rubber is often dispersed again in the thermosetting resin composition.
• this method has a problem that it is difficult to stably disperse the particles in a state without agglomeration, that is, in a state of primary particles.
• it should be handled in the state of a masterbatch in which one component of a thermosetting resin, for example, primary particles is dispersed in an epoxy resin, without taking it out in a lump form from the manufacturing process of core-shell rubber particles.
• a preferable dispersed state can be obtained by using a material capable of producing the same.
• the core-shell rubber particles that can be handled in such a masterbatch state can be produced, for example, by the method described in JP-A-2004-315572.
• a suspension in which core-shell rubber particles are dispersed is obtained by using a method of polymerizing core-shell rubber in an aqueous medium typified by emulsion polymerization, dispersion polymerization, and suspension polymerization.
• the suspension is mixed with water and an organic solvent exhibiting partial solubility, for example, a ketone solvent such as acetone or methyl ethyl ketone, or an ether solvent such as tetrahydrofuran or dioxane, and then a water-soluble electrolyte such as sodium chloride or chloride.
• the organic solvent layer and the aqueous layer are phase-separated by contacting with potassium, and the aqueous layer is separated and removed to obtain an organic solvent in which the core-shell rubber particles obtained are dispersed. Then, after mixing the epoxy resin, the organic solvent is evaporated and removed to obtain a masterbatch in which the core-shell rubber particles are dispersed in the epoxy resin in the form of primary particles.
• a masterbatch in which the core-shell rubber particles are dispersed in the epoxy resin in the form of primary particles.
• Kaneka registered trademark
• the content of the core-shell rubber particles is preferably 1 part by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the total epoxy resin component.
• a cured resin product having high toughness is obtained, and when it is 10 parts by mass or less, a cured product having a high elastic modulus is obtained, and the dispersibility of the core-shell rubber particles in the resin is also good. Therefore, it is preferable.
• a generally used dispersion method can be used. For example, a method using a three-roll, a ball mill, a bead mill, a jet mill, a homogenizer, a rotation / revolution mixer, or the like can be mentioned. Further, the above-mentioned method of mixing the core-shell rubber particle-dispersed epoxy masterbatch can also be preferably used. However, even if the particles are dispersed in the state of primary particles, reaggregation may occur due to excessive heating or a decrease in viscosity.
• the core-shell rubber particles are dispersed / blended and mixed / kneaded with other components after the dispersion, it is preferable to carry out the process within a temperature and viscosity range in which reaggregation of the core-shell rubber particles does not occur.
• a temperature and viscosity range in which reaggregation of the core-shell rubber particles does not occur.
• the viscosity of the composition may decrease and aggregation may occur, so that it is preferable to knead at a lower temperature.
• gelation occurs at the time of temperature rise to prevent reaggregation, so that there is no problem in exceeding 150 ° C. at that time.
• the epoxy resin composition of the present invention has 1 ⁇ ⁇ ⁇ 20 when the resin viscosity after 30 minutes at a constant temperature of 110 ° C., which is obtained by isothermal measurement with an E-type viscometer, is ⁇ (unit: mPa ⁇ s). Is preferable.
• the epoxy resin composition of the present invention is injected into a preform made of a reinforcing fiber base material placed in a molding mold, if the epoxy resin composition of the present invention is highly reactive at the injection temperature, the viscosity is increased during the injection process. May become difficult to mold, for example, the impregnation property may decrease, an unimpregnated portion may be formed, or the molding may take a long time.
• the viscosity 30 minutes after mixing the main agent and the curing agent is preferably 1 ⁇ ⁇ ⁇ 20 mPa ⁇ s at 110 ° C., and more preferably 1 ⁇ ⁇ ⁇ . It is 18 mPa ⁇ s.
• the viscosity is measured by an E-type viscometer (Tokyo) equipped with a standard cone rotor (1 ° 34'x R24) according to the "conical-viscosity measurement method using a plate-shaped rotary viscometer" in JIS Z8803 (1991). Viscosity measured at a rotation speed of 50 rpm using a TVE-30H manufactured by Viscometer Co., Ltd.
• the lower limit of the viscosity at 110 ° C. is not particularly limited, and the lower the viscosity, the easier the injection impregnation of the epoxy resin composition in the method for producing the fiber-reinforced composite material of the present invention described later, particularly the RTM method, and the better the moldability. ..
• the epoxy resin composition in the present invention is cured at 180 ° C. for 30 minutes.
• the glass transition temperature Tg of the object is preferably 170 ° C. or higher and 190 ° C. or lower.
• the heat resistance of the fiber-reinforced composite material depends on the glass transition temperature of the epoxy resin cured product obtained by curing the epoxy resin composition, and by setting the Tg to 170 ° C. or higher, the heat resistance of the resin cured product is ensured. By setting the temperature to 190 ° C.
• the curing shrinkage of the epoxy resin composition can be suppressed, and the deterioration of the surface quality of the fiber-reinforced composite material caused by the difference in thermal expansion between the epoxy resin composition and the reinforcing fiber can be prevented. .. Further, from the relationship between heat resistance and surface quality, it is more preferably 175 ° C. or higher and 190 ° C. or lower.
• the glass transition temperature of the cured resin product obtained by curing the epoxy resin composition is determined by measurement using a dynamic viscoelastic measurement (DMA) device. That is, using a rectangular test piece cut out from a resin-cured plate, DMA measurement is performed under high temperature, and the temperature of the inflection point of the obtained storage elastic modulus G'is defined as Tg. The measurement conditions are as described in the examples.
• DMA dynamic viscoelastic measurement
• the epoxy resin composition of the present invention can be demolded after the precure. Therefore, it is preferable that the glass transition temperature Tg of the cured resin product cured at 130 ° C. for 120 minutes is 120 ° C. or higher and 140 ° C. or lower.
• the glass transition temperature Tg of the epoxy resin cured product obtained by curing the epoxy resin composition is 120 ° C. or higher, the resin is sufficiently cured during the demolding step after precure, and high heat resistance is imparted. Therefore, the mold can be smoothly removed, and when the temperature is 140 ° C.
• the curing shrinkage of the epoxy resin composition is suppressed, and the surface quality of the fiber-reinforced composite material resulting from the difference in thermal expansion between the epoxy resin composition and the reinforcing fiber is obtained. Can be prevented from deteriorating. Further, from the relationship between heat resistance and surface quality, it is more preferably 120 ° C. or higher and 135 ° C. or lower.
• the preform used for the fiber-reinforced composite material of the present invention it is preferable to use a preform in which a reinforcing fiber base material is linked with a hot-melt binder (tack fire).
• a sheet-like base material such as a reinforced fiber woven fabric is often laminated and shaped, and processed into a shape close to a desired product to form a preform.
• a thermoplastic resin and a thermosetting resin can be applied.
• the thermoplastic resin include resins such as polyamide, polysulfone, polyetherimide, polyphenylene ether, polyimide and polyamideimide.
• thermosetting resin examples include epoxy resin, vinyl ester resin, unsaturated polyester resin, and phenol resin.
• the form of the binder is not particularly limited, but forms such as films, tapes, long fibers, short fibers, spun yarns, woven fabrics, knits, non-woven fabrics, mesh bodies, and particles can be adopted. Among them, the particle form or the non-woven fabric form can be particularly preferably used.
• binder particles The case where the binder is in the form of particles
• the binder resin composition is a non-woven fabric is referred to as a binder non-woven fabric.
• the average particle size thereof is preferably 10 ⁇ m or more and 500 ⁇ m or less.
• the average particle size refers to the median size, and the average particle size of the binder particles can be measured using, for example, a laser diffraction type particle size distribution meter or the like. If the average particle size is smaller than 10 ⁇ m, the adhesive strength and workability of the preform may decrease. From this point of view, the average particle size is more preferably 30 ⁇ m or more. When the average particle size is larger than 500 ⁇ m, the reinforcing fibers may be wavy when preformed, and the mechanical properties of the obtained fiber-reinforced composite material may be deteriorated. From this point of view, the average particle size is more preferably 300 ⁇ m or less.
• the average diameter thereof is preferably 10 ⁇ m or more and 300 ⁇ m or less.
• the average diameter is a value obtained by observing the cross section of the binder nonwoven fabric with a scanning electron microscope, measuring the diameter of 100 arbitrarily selected fibers, and calculating the average value. If the cross-sectional shape of the fiber is not a perfect circle, measure the minor axis as its diameter and use it as the average value. If the average diameter is smaller than 10 ⁇ m, the adhesive strength of the preform may decrease.
• the average diameter is larger than 300 ⁇ m, the reinforcing fibers of the preform may be wavy and the mechanical properties of the obtained fiber-reinforced composite material may be deteriorated. From this point of view, the average diameter is more preferably 100 ⁇ m or less.
• the binder is attached to at least the surface of the reinforcing fiber base material and is used as the reinforcing fiber base material with a binder. Further, the reinforcing fiber base material with a binder has the above-mentioned binder at least on the surface and is used for preform.
• the binder when a non-woven fabric is used as the form of the binder, the binder can be uniformly arranged on the base material, so that the impregnation flow path of the matrix resin is secured, the impregnation property is particularly excellent, and voids are extremely unlikely to occur. Furthermore, even when the amount of binder adhered is smaller than in the case of particle morphology, the effect of morphological fixing when preformed is equivalently maintained, and the original high value of matrix resin when used as a fiber-reinforced composite material. It is preferable because it can exhibit heat resistance and mechanical properties.
• the adhesion amount in case of attaching the conventional binders, including particle morphology on the surface, on one or both sides, per side 0.5 g / m 2 or more 50 g / m 2 or less, preferably 1 g / m 2 While it is preferable to have a texture of 30 g / m 2 or less, the non-woven fabric has a texture of 0.5 g / m 2 or more and 10 g / m 2 or less while maintaining the same effect of fixing the shape when it is made into a preform. It is also possible.
• the preform is formed by laminating a reinforcing fiber base material with a binder having at least the above-mentioned binder on the surface and fixing the form.
• a binder is attached to at least one surface of the reinforcing fiber base material by heating to form a reinforcing fiber base material with a binder, and then a plurality of the binders are laminated to obtain a laminate having the binder at least between the laminated layers. .. This is heated and cooled, and the binder adheres between the base material layers to fix the morphology, whereby a preform having the binder at least between the laminated layers can be obtained.
• the preform can be produced by cutting a reinforcing fiber base material with a binder to which a binder is attached into a predetermined shape, laminating it on a mold, and applying appropriate heat and pressure.
• a press can be used, or a method of surrounding the inside with a vacuum bag film and sucking the inside with a vacuum pump to pressurize with atmospheric pressure can also be used.
• the fiber volume content of the reinforcing fibers is preferably in the range of 45% or more and 70% or less, and more preferably in the range of 50% or more and 65% or less.
• the fiber volume content is 45% or more, a fiber-reinforced composite material having a higher elastic modulus and excellent weight reduction effect can be obtained, and when it is 70% or less, there is no decrease in strength due to rubbing between the reinforcing fibers, and further tensile strength.
• a fiber-reinforced composite material having excellent mechanical properties such as the above can be obtained.
• the temperature at which the epoxy resin composition is not gelled is set. It is preferably an existing epoxy resin composition.
• gelation of the epoxy resin composition means that the reaction between the epoxy resin in the resin and the curing agent proceeds and the fluidity is lost, and heat curing such as ATD-1000 (manufactured by Alpha Technologies Co., Ltd.)
• ATD-1000 manufactured by Alpha Technologies Co., Ltd.
• the complex viscosity obtained from the increase in torque as the curing reaction progresses reaches 1.0 ⁇ 10 5 Pa ⁇ s.
• the temperature be the gelling temperature.
• the binder in the form of a non-woven fabric When the binder in the form of a non-woven fabric is heated to a temperature higher than the melting point, the entanglement of the polymer molecular chains forming the binder becomes loose. If a non-gelled epoxy resin composition is present around this, the epoxy resin composition enters the gaps between the loosened polymer molecular chains, and in that state, the epoxy resin cures through gelation, resulting in resin and polymer molecules. It is preferable because the chains may be entangled to improve the interfacial adhesive strength, and the impact resistance and the microcrack resistance may be improved.
• the binder in the form of a non-woven fabric used in the fiber-reinforced composite material of the present invention is preferably made of polyamide having a melting point of 165 ° C. or higher and 180 ° C. or lower.
• the melting point of the polyamide is 165 ° C or higher, the morphology can be maintained during curing in the manufacturing process of the fiber-reinforced composite material, the interlayer thickness capable of sufficient plastic deformation can be uniformly secured, and the non-woven fabric is a continuous phase, so that cracks occur. Is preferable because it can efficiently block the heat and impact resistance is exhibited.
• the melting point of the polyamide is 180 ° C.
• the polyamide begins to melt at a temperature lower than the gelation temperature of the epoxy resin composition, so that the epoxy resin composition enters the gaps between the loosened polyamide molecular chains, and the epoxy resin is in that state. It is preferable that the resin and the polyamide molecular chain are entangled with each other by being cured through gelation to improve the interfacial adhesion strength, and the impact resistance and the microcrack resistance may be improved.
• the reinforcing fiber in the present invention is not particularly limited, and examples thereof include glass fiber, carbon fiber, graphite fiber, aramid fiber, boron fiber, alumina fiber, and silicon carbide fiber. Two or more of these reinforcing fibers may be mixed and used. Above all, it is preferable to use carbon fiber or graphite fiber in order to obtain a fiber-reinforced composite material that is lighter and has higher durability. In particular, carbon fiber is preferably used because it has an excellent specific elastic modulus and specific strength in applications where there is a high demand for weight reduction and high strength of the material.
• the carbon fiber any kind of carbon fiber can be used depending on the application, but it is preferable that the carbon fiber has a tensile elastic modulus of at most 400 GPa from the viewpoint of impact resistance. Further, from the viewpoint of strength, since a composite material having high rigidity and mechanical strength can be obtained, it is preferable that the carbon fiber has a tensile strength of 4.4 GPa or more and 6.5 GPa or less. Further, the tensile elongation is also an important factor, and it is preferable that the carbon fiber has a high strength and a high elongation of 1.7% or more and 2.3% or less. Therefore, carbon fibers having the characteristics of a tensile elastic modulus of at least 230 GPa, a tensile strength of at least 4.4 GPa, and a tensile elongation of at least 1.7% are most suitable.
• the fiber-reinforced composite material of the present invention is a combination of a cured product of an epoxy resin composition and a reinforcing fiber.
• the fiber-reinforced composite material is used especially in the aircraft field, high heat resistance and mechanical properties are required. Since the fiber-reinforced composite material of the present invention has excellent heat resistance and reflects the high mechanical properties of the cured epoxy resin, it has a high compressive strength during moist heat and is said to be 1100 MPa or more, more preferably 1200 MPa or more. It can show 0 ° compressive strength at high moist heat. Further, the post-impact compressive strength can be 260 MPa or more, more preferably 265 MPa or more, which is a high post-impact compressive strength.
• microcracks are minute cracks of about several tens of ⁇ m that may occur in fiber-reinforced composite materials used in aircraft applications, and range from a high temperature of about 70 ° C to a low temperature of about -50 ° C. It is known that it is likely to occur when exposed to an environment where temperature changes are repeated.
• the matrix resin in the fiber-reinforced composite material is exposed to a high temperature of about 70 ° C. to a low temperature of about -50 ° C, the matrix resin itself tends to shrink, but is surrounded by reinforcing fibers that hardly shrink.
• step c As a specific calculation method for the number of microcracks, the following a. b. After being exposed to the environmental conditions as shown in step c, a width of 25 mm was cut out from a region ⁇ 10 mm from the vertical center of the test piece, and the cut surface was polished as an observation surface, and 200 times using a commercially available microscope. It is obtained by observing the observation surface at a magnification and measuring the number of cracks that have occurred.
• the cells are transferred to a commercially available environmental tester and first exposed to an environment of ⁇ 54 ° C. for 1 hour. After that, the temperature is raised to 71 ° C. at a heating rate of 10 ° C. ⁇ 2 ° C./min. After raising the temperature, the temperature is maintained at 71 ° C. for 5 minutes ⁇ 1 minute, the temperature is lowered to ⁇ 54 ° C. at 10 ° C. ⁇ 2 ° C./min, and the temperature is maintained at ⁇ 54 ° C. for 5 minutes ⁇ 1 minute.
• This cycle of raising the temperature from ⁇ 54 ° C. to 71 ° C. and lowering the temperature to ⁇ 54 ° C. is defined as one cycle, and this cycle is repeated 200 times.
• the environmental exposure in the constant temperature and humidity chamber and the cycle in the environmental tester are defined as 1 block, and 5 blocks are repeated.
• the number of microcracks observed by the above method is preferably 5 or less, and more preferably 3 or less, from the viewpoint of long-term durability of the fiber-reinforced composite material.
• Specific examples of the method for producing a fiber-reinforced composite material using the epoxy resin composition of the present invention include a liquid composite molding method, a resin film infusion method, a filament winding method, a hand lay-up method, and a pull-fusion method. , Prepreg method, etc.
• the liquid composite molding method is a so-called preform made of reinforced fibers, that is, a sheet-like or three-dimensional curved fabric, mat, etc. that has been preformed to a position almost close to the shape of the final molded product. This is a method of injecting a liquid epoxy resin composition and then curing the epoxy resin composition to obtain a fiber-reinforced composite material.
• This manufacturing method is a molding method that is often used because it can mold a member having a complicated shape and has good productivity.
• This manufacturing method includes an RTM method, an SRI (Structural Reaction Injection Molding) method, a VaRTM (Vacum-assisted Resin Transfer Molding) method, an SCRIMP (Seeman's Complex Method Molding) method, and SCRIMP (Seeman's Compression Molding) method.
• CAPRI to better control the resin injection process, especially the vacuum auxiliary resin transfer forming process, by evacuating the resin supply tank to a pressure below atmospheric pressure, using circulating compression and controlling the net forming pressure.
• the filament winding method is a method in which a reinforcing fiber bundle is impregnated with an epoxy resin composition, wound around a core metal, and then cured to form a fiber-reinforced composite material.
• This manufacturing method is a molding method that is often used because a cylindrical member can be easily molded and the productivity is good.
• a preform made of reinforced fibers is impregnated with a required and sufficient amount of an epoxy resin composition by rolling it with a roller, and then the epoxy resin composition is cured to obtain a fiber reinforced composite material.
• the method In the hand lay-up method, a preform made of reinforced fibers is impregnated with a required and sufficient amount of an epoxy resin composition by rolling it with a roller, and then the epoxy resin composition is cured to obtain a fiber reinforced composite material.
• the plutovieron method is a method in which a reinforcing fiber bundle is impregnated with an epoxy resin composition, the epoxy resin composition is cured through the reinforcing fiber bundle in a heating mold, and then the molded product is withdrawn using a take-up machine. , A method of using a fiber-reinforced composite material. Since the plutotulon method uses continuous reinforcing fibers, it is easy to obtain a fiber-reinforced composite material with high strength and high rigidity.
• the epoxy resin composition of the present invention is preferably applied to the RTM method from the viewpoint of efficiently obtaining a fiber-reinforced composite material having a complicated shape.
• a reinforcing fiber base material or preform is placed in a molding die, a liquid matrix resin is injected into the molding die to impregnate the reinforcing fiber base material or preform, and then the reinforcing fiber base material or preform is heated.
• a molding mold having a plurality of injection ports is used, and the epoxy resin composition is injected simultaneously from the plurality of injection ports or sequentially with a time lag, etc., to obtain a fiber-reinforced composite material. It is preferable to select appropriate conditions according to the conditions, because the degree of freedom that can be applied to compacts of various shapes and sizes can be obtained. There is no limit to the number and shape of such injection ports, but the larger the number of injection ports, the better to enable injection in a short time, and the arrangement is such that the flow length of the resin can be shortened according to the shape of the molded product. Is preferable.
• a closed mold made of a rigid material may be used as a molding mold when the RTM method is applied, and an open mold of the rigid material and a flexible film (bag) may be used. It is also possible to use. In the latter case, the reinforcing fiber substrate can be placed between the open mold of the rigid material and the flexible film.
• the rigid material various existing materials such as metal such as steel and aluminum, fiber reinforced plastic (FRP), wood, and gypsum are used.
• FRP fiber reinforced plastic
• Polyamide, polyimide, polyester, fluororesin, silicone resin and the like are used as the material of the flexible film.
• the VaRTM method when an open mold of a rigid material and a flexible film are used, the VaRTM method is usually used in which suction is performed and the epoxy resin is injected only at atmospheric pressure without using special pressurizing means.
• a method of adjusting the injection pressure to a pressure lower than the atmospheric pressure is also possible, as in the CAPRI method cited in WO01 / 41993A2.
• the inside of the molding mold means the inside of a cavity formed by the closed mold, and when an open mold made of a rigid material and a flexible film are used, the molding mold is used.
• the inside means the space surrounded by the open mold and the flexible film.
• foam cores, honeycomb cores, metal parts, etc. can be installed in the molding mold to obtain a composite material integrated with these.
• a sandwich structure obtained by arranging reinforcing fibers on both sides of a foam core or a honeycomb core and forming the sandwich structure is useful because it is lightweight and has a large bending rigidity.
• a single liquid in which all the components are mixed in a batch can be injected into a mold from a single container, or a main agent containing at least the constituent components [A] to [C] as an epoxy resin.
• a liquid and a curing agent liquid consisting of a liquid containing at least the constituent component [D] and the constituent component [E] as a curing agent and in which the constituent component [D] is uniformly dissolved are stored in separate containers and mixed. It is possible to inject into the mold via a container, or to store the main agent liquid and the curing agent liquid in separate containers and inject into the mold from the container at atmospheric pressure while injecting into the container via the mixer. be.
• the mixture of the main agent liquid and the curing agent liquid can also be made into a low-viscosity liquid, and it is easy to impregnate the reinforcing fibers. Become. Moreover, since the epoxy main agent liquid and the curing agent liquid are stored separately, long-term storage is possible without any particular limitation on the storage conditions.
• both the container and the mold of the epoxy resin composition are kept at a constant temperature in the resin injection step.
• the mold temperature in the injection step that is, the injection temperature, is from the range of 70 ° C. or higher and 130 ° C. or lower based on the relationship between the initial viscosity and the viscosity increase of the epoxy resin composition from the viewpoint of enhancing the impregnation property into the reinforcing fiber base material. It is preferably the selected temperature.
• Heat curing in the mold is performed by holding the mold at the time of injection for a certain period of time, raising the temperature to the maximum curing temperature and holding it for a certain period of time to cure, the temperature of the mold at the time of injection and the maximum curing temperature. It is possible to use any of the methods of raising the temperature to an intermediate temperature, holding the temperature for a certain period of time, raising the temperature again, and holding the temperature for a certain period of time after reaching the maximum curing temperature.
• the holding time of the maximum curing temperature in the curing in the mold is preferably 15 minutes or more and 2 hours or less, and more preferably 15 minutes or more and 90 minutes or less.
• the curing in the mold is precure.
• the aftercure time is preferably 15 minutes or more and 2 hours or less, and more preferably 15 minutes or more and 1 hour or less.
• a fiber-reinforced composite material that requires heat resistance is manufactured, it is finally cured at a temperature of 160 ° C. or higher and 190 ° C. or lower.
• the maximum curing temperature in the molding mold is preferably 160 ° C. or higher and 190 ° C. or lower
• the after-cure temperature is preferably 160 ° C. or higher and 190 ° C. or lower.
• the maximum temperature in precure is preferably 110 ° C or higher and 150 ° C or lower.
• the main agent solution and the curing agent solution are mixed at 70 ° C. or higher and 130 ° C. or lower.
• the temperature of the mold in the injection step that is, the injection temperature is 110 ° C. or higher and 150 ° C. or higher based on the relationship between the initial viscosity and the viscosity increase of the epoxy resin composition from the viewpoint of enhancing the impregnation property into the reinforcing fiber base material. It is preferable that the temperature is selected from the range of ° C. or lower, and it is preferable to perform heat curing at a temperature of 110 ° C. or higher and 150 ° C. or lower in the molding die.
• the temperature is raised to the maximum curing temperature and held for a certain period of time to cure, the main agent solution and the curing agent solution are mixed at 70 ° C. or higher and 130 ° C. or lower.
• the temperature of the mold in the injection step that is, the injection temperature is 90 ° C. or higher and 130 ° C. or higher based on the relationship between the initial viscosity and the increase in viscosity of the epoxy resin composition from the viewpoint of enhancing the impregnation property into the reinforcing fiber base material. It is preferable that the temperature is selected from the range of ° C. or lower, and it is preferable to perform heat curing at a temperature of 160 ° C. or higher and 200 ° C. or lower in the molding die.
• the pressure at the time of injecting the epoxy resin composition is usually 0.1 MPa or more and 1.0 MPa or less, and the VaRTM method in which the resin composition is injected by vacuum suctioning the inside of the molding die can also be used. From the viewpoint of economy, 0.1 MPa or more and 0.6 MPa is preferable. Further, even in the case of pressure injection, it is preferable to suck the inside of the molding mold into a vacuum before injecting the resin composition because the generation of voids is suppressed.
• the vacuum suction referred to here means that the inside of the molding die is usually in a pressure state of 0.1 MPa or more and 1.0 MPa or less.
• the epoxy resin composition of the present invention is preferably used in a preform composed of a reinforced fiber base material arranged in a molding die in an arbitrary range of 70 ° C. or higher and 130 ° C. or lower. It is preferred to inject at temperature. At that time, if the reactivity of the epoxy resin composition of the present invention is high at the injection temperature, the viscosity may increase during the injection process and molding may become difficult. Therefore, the epoxy resin composition of the present invention preferably has a resin viscosity of 20 mPa ⁇ s or less, more preferably 18 mPa ⁇ s or less, after 30 minutes at a constant temperature of 110 ° C.
• the viscosity is measured by an E-type viscometer (Tokyo) equipped with a standard cone rotor (1 ° 34'x R24) according to the "conical-viscosity measurement method using a plate-shaped rotary viscometer" in JIS Z8803 (1991). Viscosity measured at a rotation speed of 50 rpm using a TVE-30H manufactured by Viscometer Co., Ltd. If the viscosity 30 minutes after the start of injection is higher than the above range, the impregnation property of the epoxy resin composition may be insufficient.
• the lower limit of the resin viscosity after a constant 30 minutes at 110 ° C. is not particularly limited, and the lower the viscosity, the easier the injection impregnation of the epoxy resin composition of the present invention in the RTM method, and the better the moldability.
• the fiber-reinforced composite material of the present invention has excellent mechanical properties, compression strength during wet and heat, impact resistance, and microcrack resistance, the fuselage, main wings, tail wings, moving blades, fairings, cowls, doors, seats, interior materials, etc.
• Epoxy resin (a) The tetrafunctional glycidyl diamine type epoxy resin represented by the component [A] ⁇ "Araldite (registered trademark)" MY721 (N, N, N', N'-tetraglycidyl-4,4' -Diaminodiphenylmethane, epoxy equivalent: 113 g / mol, manufactured by Huntsman Japan Corporation) (B) Aminophenol type epoxy resin represented by the component [B] ⁇ "jER (registered trademark)” 630 (N, N-diglycidyl-4-glycidyloxyaniline, epoxy equivalent: 98 g / mol, Mitsubishi Chemical Corporation Made) (C) Bisphenol F type epoxy resin represented by the component [C] ⁇ "EPICLON (registered trademark)” 830 (diglycidyl ether of bisphenol F, epoxy equivalent: 170 g / mol, manufactured by DIC Corporation) (D) Other epoxy resins- "EPICLON (registered trademark)"
• Curing agent (a) Crystalline aromatic diamine represented by component [D] "Lonza Cure (registered trademark)" M-MIPA (3,3'-diisopropyl-5,5'-dimethyl-4,4 '-Diaminodiphenylmethane, active hydrogen equivalent: 78 g / mol, manufactured by Lonza Co., Ltd.) -"Lonza Cure (registered trademark)” M-DEA (3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, active hydrogen equivalent: 78 g / mol, manufactured by Lonza Co., Ltd.) "Lonza Cure (registered trademark)” M-CDEA (4,4'-methylenebis (3-chloro-2,6-diethylaniline, active hydrogen equivalent: 95 g / mol, manufactured by Lonza Co., Ltd.)) (B) Liquid aromatic diamine represented by the component [E] ⁇
• a binder was produced according to the following production method.
• PA-1 crystalline polyamide, melting point: 170 ° C.
• fibers discharged from a mouthpiece provided with one orifice are stretched using an aspirator with an impact plate at the tip and compressed air, and then formed into a wire mesh. It was sprayed and collected.
• the fiber sheets collected on the wire mesh were heat-bonded using a heating press to prepare a binder 1 in the form of a non-woven fabric.
• PES amorphous polyether sulfone, melting point: none
• PA-2 crystalline polyamide, melting point: 225 ° C.
• fibers discharged from a mouthpiece provided with one orifice are stretched using an aspirator with an impact plate at the tip and compressed air, and then formed into a wire mesh. It was sprayed and collected.
• the fiber sheets collected on the wire mesh were heat-bonded using a heating press to prepare a binder 3 in the form of a non-woven fabric.
• PA-3 crystalline polyamide, melting point: 110 ° C.
• fibers discharged from a mouthpiece provided with one orifice are stretched using an aspirator with an impact plate at the tip and compressed air, and then formed into a wire mesh. It was sprayed and collected.
• the fiber sheets collected on the wire mesh were heat-bonded using a heating press to prepare a binder 4 in the form of a non-woven fabric.
• the prepared binder resin composition was freeze-milled using a hammer mill (PULVERIZER, manufactured by Hosokawa Micron Co., Ltd.) using a screen having a pore size of 1 mm and using liquid nitrogen to obtain a binder 5 in the form of particles. Such particles were passed through a sieve having an opening size of 150 ⁇ m and 75 ⁇ m, and the binder particles remaining on the sieve having an opening size of 75 ⁇ m were used for evaluation.
• a hammer mill PULVERIZER, manufactured by Hosokawa Micron Co., Ltd.
• the obtained binder was used as a carbon fiber unidirectional fabric (plain weave, warp: carbon fiber T800S-24K-10C manufactured by Toray Industries, Inc., carbon fiber grain 295 g / m 2 , warp density 7.2 / 25 mm, weft: glass fiber. ECE225 1/0 1Z Nitto Boseki Co., Ltd., weft density 7.5 yarns / 25 mm) was attached to one side. Coating weight, when the binder 1 of the binder 4 5 g / m 2, in the case of binder 5 was 10 g / m 2. Then, it was heated using a far-infrared heater to fuse the binder, and a reinforced fiber base material with a binder having a binder on one side surface was obtained.
• a carbon fiber unidirectional fabric plain weave, warp: carbon fiber T800S-24K-10C manufactured by Toray Industries, Inc., carbon fiber grain 295 g / m 2 , warp density 7.2 / 25
• Tg glass transition temperature
• the temperature was lowered to 30 ° C., and the mold was removed. After demolding, the temperature is raised from 30 ° C to 180 ° C at a rate of 1.5 ° C / min for post-curing, and after curing at 180 ° C for 30 minutes, the temperature is lowered to 30 ° C and post-curing is performed.
• a test piece having a width of 12.7 mm and a length of 79.4 mm is cut so that the 0 ° direction and the length direction are the same, and is used for 0 ° compressive strength.
• a test piece was prepared. This test piece was immersed in warm water at 72 ° C. for 14 days, and then the 0 ° compressive strength of the fiber-reinforced composite material was measured. The measurement of 0 ° compressive strength conforms to ASTM D695, and a universal material testing machine (4208 type Instron manufactured by Instron Japan Co., Ltd.) is used as a testing machine, and the crosshead speed at the time of measurement is 1.27 mm /. The measurement temperature was set to 82 ° C.
• a test piece having a width of 101.6 mm and a length of 152.4 mm was cut so that the 0 ° direction and the length direction were the same, and made into SACMA SRM 2R-94. According to this, the compressive strength after impact was measured.
• a testing machine a universal material testing machine (1128 type Tencilon manufactured by Instron Japan Co., Ltd.) was used. Here, the energy of the impact of the falling weight was set to 6.7 J / mm, and the crosshead speed was set to 1.27 mm / min.
• the cells are transferred to a commercially available environmental tester and first exposed to an environment of ⁇ 54 ° C. for 1 hour. After that, the temperature is raised to 71 ° C. at a heating rate of 10 ° C. ⁇ 2 ° C./min. After raising the temperature, the temperature is maintained at 71 ° C. for 5 minutes ⁇ 1 minute, the temperature is lowered to ⁇ 54 ° C. at 10 ° C. ⁇ 2 ° C./min, and the temperature is maintained at ⁇ 54 ° C. for 5 minutes ⁇ 1 minute.
• This cycle of raising the temperature from ⁇ 54 ° C. to 71 ° C. and lowering the temperature to ⁇ 54 ° C. is defined as one cycle, and this cycle is repeated 200 times.
• the environmental exposure in the constant temperature and humidity chamber and the cycle in the environmental tester are defined as 1 block, and 5 blocks are repeated.
• a width of 25 mm is cut out from a region ⁇ 10 mm from the center of the vertical direction of the test piece subjected to the above environmental exposure, the cut surface is polished as an observation surface, and the observation surface is observed at a magnification of 200 times using a commercially available microscope. The number of cracks occurring was measured.
• Example 1 As shown in Table 1, 40 parts of "Araldite (registered trademark)” MY721 as a component [A], 30 parts of “jER (registered trademark)” 630 as a component [B], and “EPICLON” as a component [C]. 30 parts of “830 (registered trademark)” was added, and the mixture was stirred at 70 ° C. for 1 hour to prepare a main agent solution. In addition, 40 parts of “Lonza Cure (registered trademark)” M-MIPA as a constituent component [D] and 18 parts of "jER Cure (registered trademark)” W as a constituent component [E] are added to a container separate from the main agent solution. , 80 ° C.
• the mixture cooled to 70 ° C. was used as a curing agent solution.
• 100 parts of the main agent solution and 58 parts of the curing agent solution were mixed to obtain an epoxy resin composition, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured and found to be 179 ° C. and 18 mPa ⁇ s, respectively. rice field.
• the Tg of the cured product cured at 130 ° C. for 120 minutes was 135 ° C.
• Examples 2 to 9 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 1, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change in Examples 1 to 9 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, the viscosity after holding at 110 ° C. for 30 minutes was 20 mPa ⁇ s or less, and the impregnation property into the reinforcing fiber was also good.
• it had a Tg that could be demolded by curing at 130 ° C for 120 minutes, and showed sufficient heat resistance even when cured at 180 ° C for 30 minutes.
• the fiber-reinforced composite material also had good heat resistance, mechanical properties, and durability, with a 0 ° compressive strength during moist heat of 1100 MPa or more, a post-impact compressive strength of 260 MPa or more, and a number of microcracks of 3 or less.
• Example 10 As shown in Table 1, 25 parts of "Araldite (registered trademark)” MY721 as a component [A], 30 parts of “jER (registered trademark)” 630 as a component [B], and “EPICLIN” as a component [C]. 30 parts of (registered trademark) "830 and 20 parts of” Kaneace (registered trademark) "MX-416 as a constituent component [F] were added, and the mixture was stirred at 70 ° C. for 1 hour to prepare a main agent solution.
• the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured. It was higher than the binder melting point of the material, the viscosity after holding at 110 ° C. for 30 minutes was 20 mPa ⁇ s or less, and the impregnation property into the reinforcing fiber was also good. In addition, it had a Tg that could be demolded by curing at 130 ° C for 120 minutes, and showed sufficient heat resistance even when cured at 180 ° C for 30 minutes.
• the compressive strength at 0 ° during moist heat was 1100 MPa or more
• the compressive strength after impact was 260 MPa or more
• the number of microcracks was 0, and the heat resistance, mechanical properties, and durability were also good.
• Example 11 and 12 An epoxy resin composition was prepared in the same manner as in Example 10 except that the blending amount of each component was changed as shown in Table 2, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• the blending amount of each component was changed as shown in Table 2, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• the component [A] is contained in an amount of 35 parts by mass.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the changes between Examples 10 and Examples 11 and 12 are the content ratio of each component and the core-shell rubber type.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, but the viscosity after holding at 110 ° C. for 30 minutes exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was in Example 10. It was a little inferior to.
• the fiber-reinforced composite material had a Tg that could be demolded by curing at 130 ° C for 120 minutes, and showed sufficient heat resistance even when cured at 180 ° C for 30 minutes.
• the compressive strength at 0 ° during moist heat was 1100 MPa or more
• the compressive strength after impact was 260 MPa or more
• the number of microcracks was 0, and the heat resistance, mechanical properties, and durability were also good.
• Example 13 to 16 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 2, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Examples 13-16 is the binder species. In each case, the viscosity after holding at 110 ° C.
• Example 13 the adhesiveness between the resin and the binder is slightly inferior to that in Example 1 because the melting point of the binder of the reinforcing fiber base material does not exist or is higher than the gelation temperature of the resin.
• the compressive strength after impact and the number of microcracks of the fiber-reinforced composite material were slightly inferior to those of Example 1.
• Example 15 although the gelation temperature of the resin is higher than the melting point of the binder of the reinforcing fiber base material, the melting point of the polyamide as a binder is less than 165 ° C., so that the thickness between the layers of the fiber-reinforced composite material is in Example 1.
• the results were slightly non-uniform, and the post-impact compression strength and the number of microcracks of the fiber-reinforced composite material were slightly inferior to those of Example 1.
• Example 17 As shown in Table 2, 40 parts of "Araldite (registered trademark)” MY721 as a component [A], 30 parts of “jER (registered trademark)” 630 as a component [B], and “EPICLON” as a component [C]. 30 parts of “830 (registered trademark)” was added, and the mixture was stirred at 70 ° C. for 1 hour to prepare a main agent solution. In addition, in a container separate from the main agent solution, 45 parts of "Ronza Cure (registered trademark)” M-MIPA as the constituent component [D] and 22 parts of "Kayahard (registered trademark)” AA (PT) as the constituent component [E].
• the mixture was added in portions, stirred at 80 ° C. for 1 hour to uniformly dissolve, and then the temperature was lowered to 70 ° C. to prepare a curing agent solution.
• 100 parts of the main agent solution and 58 parts of the curing agent solution were mixed to obtain an epoxy resin composition, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured and found to be 177 ° C. and 20 mPa ⁇ s, respectively. rice field. Further, as a result of preparing a cured resin product by the above method and measuring the Tg of the cured product, the Tg of the cured product cured at 130 ° C.
• Example 18 An epoxy resin composition was prepared in the same manner as in Example 17, except that the blending amount of each component was changed as shown in Table 2, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change in Examples 17 to 25 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, the viscosity after holding at 110 ° C. for 30 minutes was 18 mPa ⁇ s or less, and the impregnation property into the reinforcing fiber was also good. In addition, it had a Tg that could be demolded by curing at 130 ° C for 120 minutes, and showed sufficient heat resistance even when cured at 180 ° C for 30 minutes.
• the fiber-reinforced composite material also had good heat resistance, mechanical properties, and durability, with a 0 ° compressive strength during moist heat of 1100 MPa or more, a post-impact compressive strength of 260 MPa or more, and a number of microcracks of 3 or less.
• Examples 19 to 25 An epoxy resin composition was prepared in the same manner as in Example 17, except that the blending amount of each component was changed as shown in Tables 2 and 3, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured. bottom.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change in Examples 17 to 25 is the content ratio of each component.
• the gelation temperature of the resin is higher than the melting point of the binder of the reinforcing fiber base material, and the viscosity after holding at 110 ° C. for 30 minutes is slightly higher than 20 mPa ⁇ s only in Examples 21 and 25, but 20 mPa ⁇ s in the others. It was s or less, and the impregnation property into the reinforcing fiber was generally good. In addition, it had a Tg that could be demolded by curing at 130 ° C for 120 minutes, and showed sufficient heat resistance even when cured at 180 ° C for 30 minutes.
• the fiber-reinforced composite material also had good heat resistance, mechanical properties, and durability, with a 0 ° compressive strength during moist heat of 1100 MPa or more, a post-impact compressive strength of 260 MPa or more, and a number of microcracks of 3 or less.
• Example 26 As shown in Table 3, 25 parts of "Araldite (registered trademark)” MY721 as a component [A], 30 parts of "jER (registered trademark)” 630 as a component [B], and “EPICLON” as a component [C]. (Registered trademark) "830 parts and 20 parts of” Kaneace (registered trademark) "MX-416 as a constituent component [F] were added, and the mixture was stirred at 70 ° C. for 1 hour to prepare a main agent solution. As described in Example 10, since “Kaneace (registered trademark)” MX-416 contains 75% by mass of "Araldite (registered trademark)” MY721, 100 parts by mass of the main agent solution of this example contains.
• the component [A] is contained in an amount of 40 parts by mass.
• the mixture was added in portions, stirred at 80 ° C. for 1 hour to uniformly dissolve, and then the temperature was lowered to 70 ° C. to prepare a curing agent solution.
• 105 parts of the main agent liquid and 67 parts of the curing agent liquid were mixed to obtain an epoxy resin composition, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• the viscosity is 22 mPa ⁇ s, and the impregnation property is slightly inferior.
• the Tg of the cured product cured at 130 ° C. for 120 minutes was 131 ° C.
• the Tg of the cured product cured at 180 ° C. for 30 minutes was 173 ° C. It had sufficient heat resistance.
• a fiber-reinforced composite material was produced using this epoxy resin composition, and the compressive strength at 0 ° during moist heat and the compressive strength after impact were measured.
• Example 27 and 28 An epoxy resin composition was prepared in the same manner as in Example 26 except that the blending amount of each component was changed as shown in Table 3, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• the blending amount of each component was changed as shown in Table 3, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• the component [A] is contained in an amount of 40 parts by mass.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the changes between Examples 26 and 27 and 28 are the content ratio of each component and the core-shell rubber type.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, but the viscosity after holding at 110 ° C. for 30 minutes exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was Example 26. It was a little inferior to.
• the fiber-reinforced composite material also had good heat resistance, mechanical properties, and durability, with a 0 ° compressive strength during moist heat of 1100 MPa or more, a post-impact compressive strength of 260 MPa or more, and a number of microcracks of 3 or less.
• Examples 29 to 32 An epoxy resin composition was prepared in the same manner as in Example 17, except that the blending amount of each component was changed as shown in Tables 3 and 4, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured. bottom.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 17 and Examples 29-32 is the binder species. In each case, the viscosity after holding at 110 ° C.
• Example 31 although the gelation temperature of the resin is higher than the melting point of the binder of the reinforcing fiber base material, the melting point of the polyamide as a binder is less than 165 ° C., so that the thickness between the layers of the fiber-reinforced composite material is in Example 17.
• the results were slightly non-uniform, and the post-impact compression strength and the number of microcracks of the fiber-reinforced composite material were slightly inferior to those of Example 17.
• Example 1 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Comparative Example 1 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, the viscosity after holding at 110 ° C. for 30 minutes was 20 mPa ⁇ s or less, and the impregnation property into the reinforcing fiber was also good. In addition, it had Tg that could be demolded by curing at 130 ° C. for 120 minutes, and the number of microcracks was as good as 3 or less.
• Example 2 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Comparative Example 2 is the content ratio of each component.
• the cured product obtained by curing at 180 ° C. for 30 minutes was sufficiently cured, but the Tg was 159 ° C. and the heat resistance was low.
• Example 3 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during wet and heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Comparative Example 3 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, the viscosity after holding at 110 ° C. for 30 minutes was 20 mPa ⁇ s or less, and the impregnation property into the reinforcing fiber was also good. In addition, it had a Tg that could be demolded by curing at 130 ° C for 120 minutes, and showed good heat resistance even when cured at 180 ° C for 30 minutes.
• the post-impact compressive strength and the number of microcracks of the fiber-reinforced composite material were also good. However, the 0 ° compressive strength at the time of moist heat was 1060 MPa, which was a defect.
• Example 4 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Comparative Example 4 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, it had a Tg that could be demolded by curing at 130 ° C. for 120 minutes, and showed good heat resistance even when cured at 180 ° C. for 30 minutes.
• the viscosity after holding at 110 ° C. for 30 minutes was 34 mPa ⁇ s, which exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was inferior. Voids due to impregnation defects were observed in the obtained fiber-reinforced composite material, and the compressive strength after impact was as poor as 255 MPa.
• Example 5 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Comparative Example 5 is the content ratio of each component.
• the cured product obtained by curing at 180 ° C. for 30 minutes was sufficiently cured, but the Tg was 158 ° C. and the heat resistance was low.
• Example 6 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Comparative Example 6 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material.
• Example 7 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Comparative Example 7 is the content ratio of each component.
• the gelation temperature of the resin was lower than the binder melting point of the reinforced fiber base material, the post-impact compressive strength of the fiber reinforced composite material was 258 MPa, and the number of microcracks was 5, which was poor.
• Example 8 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 1 and Comparative Example 8 is the content ratio of each component.
• the gelation temperature of the resin was higher than the binder melting point of the reinforced fiber base material, and the post-impact compressive strength of the fiber reinforced composite material and the number of microcracks were good.
• the viscosity after holding at 110 ° C. for 30 minutes was 25 mPa ⁇ s, which exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was inferior.
• curing at 130 ° C. for 120 minutes did not cure sufficiently and could not be smoothly removed. Further, it was not sufficiently cured by curing at 180 ° C. for 30 minutes, the Tg of the cured resin product was 164 ° C., and the fiber-reinforced composite material also had a poor compressive strength of 0 ° at wet heat of 1090 MPa.
• Example 9 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 5, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the changes between Example 1 and Comparative Example 9 are the content ratio of each component and the epoxy resin type.
• the gelation temperature of the resin is higher than the melting point of the binder of the reinforcing fiber base material, the viscosity after holding at 110 ° C. for 30 minutes is 20 mPa ⁇ s or less, the impregnation property into the reinforcing fiber is good, and the mold is removed by curing at 130 ° C. for 120 minutes. It had a possible Tg and showed good heat resistance even when cured at 180 ° C for 30 minutes.
• the post-impact compressive strength and the number of microcracks of the fiber-reinforced composite material were also good. However, the 0 ° compressive strength at the time of moist heat was 1010 MPa, which was poor.
• Example 10 a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the changes between Example 10 and Comparative Example 10 are the content ratio of each component and the epoxy resin species.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, it had a Tg that could be demolded by curing at 130 ° C. for 120 minutes, and showed good heat resistance even when cured at 180 ° C. for 30 minutes. However, the viscosity after holding at 110 ° C.
• Example 11 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 17 and Comparative Example 11 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, but the viscosity after holding at 110 ° C. for 30 minutes exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was somewhat insufficient. In addition, it had Tg that could be demolded by curing at 130 ° C. for 120 minutes, and the number of microcracks was as good as 3 or less.
• Example 12 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 17 and Comparative Example 12 is the content ratio of each component.
• the cured product obtained by curing at 180 ° C. for 30 minutes was sufficiently cured, but the Tg was 154 ° C. and the heat resistance was low.
• Example 13 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 17 and Comparative Example 13 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, the viscosity after holding at 110 ° C. for 30 minutes was 20 mPa ⁇ s or less, and the impregnation property into the reinforcing fiber was also good.
• it had a Tg that could be demolded by curing at 130 ° C. for 120 minutes, and the post-impact compressive strength and the number of microcracks of the fiber-reinforced composite material were also good.
• the Tg after curing at 180 ° C. for 30 minutes was low at 168 ° C., and the compressive strength at 0 ° at wet heat was also poor at 1080 MPa.
• Example 14 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured. In addition, a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured. The only change between Example 17 and Comparative Example 14 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, it had a Tg that could be demolded by curing at 130 ° C. for 120 minutes, and showed good heat resistance even when cured at 180 ° C. for 30 minutes.
• the viscosity after holding at 110 ° C. for 30 minutes was 34 mPa ⁇ s, which exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was inferior. Voids due to poor impregnation were observed in the obtained fiber-reinforced composite material, and the compressive strength after impact was 252 MPa, which was poor.
• Example 15 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 17 and Comparative Example 15 is the content ratio of each component.
• the cured product obtained by curing at 180 ° C. for 30 minutes was sufficiently cured, but the Tg was 153 ° C. and the heat resistance was low.
• Example 16 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 17 and Comparative Example 16 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material.
• the fiber-reinforced composite material had good 0 ° compressive strength and the number of microcracks during moist heat, but the post-impact compressive strength was 227 MPa, which was poor.
• Example 17 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the only change between Example 17 and Comparative Example 17 is the content ratio of each component.
• Example 18 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured. In addition, a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured. The only change between Example 17 and Comparative Example 18 is the content ratio of each component.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, and the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks of the fiber-reinforced composite material were good.
• the viscosity after holding at 110 ° C. for 30 minutes was 25 mPa ⁇ s, which exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was inferior.
• curing at 130 ° C. for 120 minutes did not cure sufficiently and could not be smoothly removed. Further, it was not sufficiently cured by curing at 180 ° C. for 30 minutes, the Tg of the cured resin product was 159 ° C., and the heat resistance was insufficient.
• Example 19 An epoxy resin composition was prepared in the same manner as in Example 17 except that the blending amount of each component was changed as shown in Table 6, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured. In addition, a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured. The changes between Example 17 and Comparative Example 19 are the content ratio of each component and the epoxy resin species.
• the gelation temperature of the resin is higher than the melting point of the binder of the reinforcing fiber base material, the viscosity after holding at 110 ° C. for 30 minutes is 20 mPa ⁇ s or less, the impregnation property into the reinforcing fiber is good, and the mold is removed by curing at 130 ° C. for 120 minutes. It had a possible Tg and showed good heat resistance even when cured at 180 ° C for 30 minutes.
• the post-impact compressive strength and the number of microcracks of the fiber-reinforced composite material were also good. However, the 0 ° compressive strength at the time of moist heat was 1030 MPa, which was a defect.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the changes between Example 26 and Comparative Example 20 are the content ratio of each component and the epoxy resin species.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, it had a Tg that could be demolded by curing at 130 ° C for 120 minutes, and showed good heat resistance even after curing at 180 ° C for 30 minutes, but it showed good heat resistance at 110 ° C for 30 minutes.
• the viscosity after holding was over 20 mPa ⁇ s, and the impregnation property into the reinforcing fibers was inferior.
• the compressive strength at 0 ° during moist heat was 1170 MPa, which was sufficient, but the compressive strength after impact was 250 MPa, and the number of microcracks was 6, which was poor.
• Example 21 An epoxy resin composition was prepared in the same manner as in Example 1 except that the blending amount of each component was changed as shown in Table 7, and the gelation temperature of the resin and the viscosity after holding at 110 ° C. for 30 minutes were measured.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the changes between Example 1 and Comparative Example 21 are the content ratio of each component and the type of curing agent.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, but the viscosity after holding at 110 ° C. for 30 minutes was 37 mPa ⁇ s, which greatly exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was inferior.
• curing at 130 ° C. for 120 minutes did not cure sufficiently and could not be smoothly removed. Further, it was not sufficiently cured by curing at 180 ° C. for 30 minutes, and the Tg of the cured resin product was 162 ° C.
• Voids due to impregnation defects were observed in the obtained fiber-reinforced composite material, and the compressive strength at 0 ° during moist heat was 1080 MPa, the compressive strength after impact was 220 MPa, and the number of microcracks was 7.
• a cured resin product and a fiber-reinforced composite material were prepared using each of the epoxy resin compositions, and the Tg of the cured product, the compressive strength at 0 ° during moist heat, the compressive strength after impact, and the number of microcracks were measured.
• the changes between Example 10 and Comparative Example 22 are the content ratio of each component and the type of curing agent.
• the gelation temperature of the resin was higher than the melting point of the binder of the reinforcing fiber base material, but the viscosity after holding at 110 ° C. for 30 minutes was 25 mPa ⁇ s, which exceeded 20 mPa ⁇ s, and the impregnation property into the reinforcing fiber was inferior.
• Example 10 and Comparative Example 23 are the content ratio of each component and the type of curing agent.
• the viscosity after holding at 110 ° C. for 30 minutes is 20 mPa ⁇ s or less, but it does not cure sufficiently at 130 ° C. for 120 minutes and cannot be removed smoothly, and it does not cure sufficiently even at 180 ° C. for 30 minutes.
• the heat resistance is inferior at 146 ° C.
• the gelation temperature of the resin was lower than the melting point of the binder of the reinforcing fiber base material, the adhesiveness between the resin and the binder was slightly inferior, and the compressive strength after impact and the number of microcracks of the fiber-reinforced composite material were slightly insufficient.
• the 0 ° compressive strength during moist heat was also poor at 990 MPa.
• the epoxy resin composition of the present invention has a very low viscosity and excellent impregnation property, is stable even at an injection temperature with suppressed increase in viscosity, can be sufficiently cured in a short time, and is used in a demolding step after molding. It is possible to provide an epoxy resin composition that can be smoothly demolded by sufficiently curing the resin and imparting high heat resistance, and can obtain a fiber-reinforced composite material having excellent compression strength and impact resistance during moist heat. Become.
• the fiber-reinforced composite material composed of the epoxy resin composition and the reinforcing fiber is excellent in compressive strength at the time of moist heat, impact resistance, and microcrack resistance, it can be suitably used for aeronautical / spacecraft members, automobile members, and the like. can.

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