Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T50/00—Aeronautics or air transport
  • Y02T50/40—Weight reduction

Definitions

• the present invention relates to an epoxy resin composition, and a prepreg and fiber-reinforced composite material using the epoxy resin composition, which are suitably used for fiber-reinforced composite materials for aerospace applications, general industrial applications, sports applications, and the like. .
• Fiber-reinforced composite materials using carbon fiber, aramid fiber, etc. as reinforcing fibers utilize their high specific strength and specific elastic modulus to be used as structural materials for aircraft and automobiles, as well as tennis rackets, golf shafts, fishing rods, bicycles, etc. It is widely used for sports and general industrial applications such as housings.
• thermosetting resins are mainly used from the viewpoint of heat resistance and productivity, and among them, epoxy resins are preferable from the viewpoint of mechanical properties such as adhesion to reinforcing fibers. Used.
• Patent Document 1 a method of improving the strength of a cured resin product by combining an epoxy resin and a phosphite or phosphate compound has been studied.
• Patent Document 1 When the technique of Patent Document 1 is used, the strength of the resulting fiber-reinforced composite material is improved, but mechanical properties under high temperature and/or high humidity conditions are not considered. That is, as described in the specification of Patent Document 1, the technology of Patent Document 1 is based on the fact that "the phosphate ester or the phosphite ester improves the adhesion between the carbon fiber and the matrix resin, resulting in a cured It is intended to improve the flexural modulus or flexural strength of a material, and attention is paid to the interaction between the crosslinked structure formed by curing the epoxy resin in the fiber reinforced composite material and the phosphate ester compound. Therefore, the above characteristics were not sufficient.
• the present invention provides an epoxy resin composition that has an excellent balance of strength, elastic modulus, elastic modulus in a moist heat environment, and heat resistance after moisture absorption, which can be suitably used for prepreg and fiber-reinforced composite material applications.
• the task is to provide
• the present invention employs the following configuration in order to solve such problems. That is, it is an epoxy resin composition that contains the following components [A], [B] and [C] and satisfies the following conditions (1) and (2).
• the present invention also provides a prepreg comprising the epoxy resin composition of the present invention and reinforcing fibers, and a fiber-reinforced composite material comprising a cured product of the epoxy resin composition of the present invention and reinforcing fibers.
• an epoxy resin composition that can be suitably used for prepregs and fiber-reinforced composite materials and that has an excellent balance of strength, elastic modulus, elastic modulus in a moist heat environment, and heat resistance after moisture absorption is provided. can get.
• the resin composition of the present invention contains component [A], component [B], and component [C] as essential components.
• "constituent element” means an individual component contained in the resin composition.
• the component [A] in the present invention is an epoxy resin.
• the epoxy resin of the component [A] one containing two or more epoxy groups in one molecule increases the glass transition temperature of the cured product obtained by heating and curing the resin composition, and improves the heat resistance. It is preferable because it can Also, an epoxy resin containing one epoxy group in one molecule may be blended. These epoxy resins may be used alone or in combination.
• Epoxy resins of the component [A] include, for example, glycidylamine types such as diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, metaxylenediamine type and 1,3-bisaminomethylcyclohexane type, bisphenol type, phenol Epoxy resins such as novolak type, ortho cresol novolak type, glycidyl ether type such as trishydroxyphenylmethane type and tetraphenylolethane type, isocyanurate type, and hydantoin type epoxy resins.
• glycidylamine types such as diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, metaxylenediamine type and 1,3-bisaminomethylcyclohexane type
• bisphenol type bisphenol type
• phenol Epoxy resins such as novolak type, ortho cresol no
• glycidylamine type and glycidyl ether type epoxy resins are preferably used because of their well-balanced physical properties.
• diaminodiphenylmethane type, aminophenol type and bisphenol type epoxy resins are particularly preferably used.
• a glycidyl ether type epoxy resin is contained in 100 parts by mass of the component [A], and 20 to 60 parts by mass. is more preferably included.
• diaminodiphenylmethane type epoxy resins include "Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY720 (manufactured by Huntsman Advanced Materials Co., Ltd.), “ Araldite (registered trademark) "MY721 (manufactured by Huntsman Advanced Materials Co., Ltd.), “Araldite (registered trademark)” MY9512 (manufactured by Huntsman Advanced Materials Co., Ltd.), “Araldite (registered trademark)” MY9663 (manufactured by Huntsman Advanced Materials Co., Ltd.) Huntsman Advanced Materials Co., Ltd.), and “Epototo (registered trademark)” YH-434 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), “jER (registered trademark)” 630 (manufactured by Y
• diaminodiphenylsulfone type epoxy resins include TG3DAS (manufactured by Mitsui Chemicals Fine Co., Ltd.).
• aminophenol-type epoxy resins Commercial products of aminophenol-type epoxy resins include ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), ELM100 (manufactured by Sumitomo Chemical Co., Ltd.), "jER (registered trademark)” 630 (manufactured by Mitsubishi Chemical Corporation), and “Araldite (registered trademark) "MY0500 (manufactured by Huntsman Advanced Materials Co., Ltd.), “Araldite (registered trademark)” MY0510 (manufactured by Huntsman Advanced Materials Co., Ltd.), “Araldite (registered trademark)” MY0600 (manufactured by Huntsman Advanced Materials Co., Ltd.), “Araldite (registered trademark)” MY0610 (Huntsman Advanced Materials Co., Ltd.), and the like.
• ELM120 manufactured by Sumitomo Chemical Co., Ltd.
• ELM100 manufactured by Sumitomo Chemical Co., Ltd.
• bisphenol A type epoxy resins include "EPON (registered trademark)” 825 (manufactured by Mitsubishi Chemical Corporation), “Epiclon (registered trademark)” 850 (manufactured by DIC Corporation), and “Epotote (registered trademark)”. "YD-128 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), DER-331 and DER-332 (manufactured by Dow Chemical Co., Ltd.), and the like.
• bisphenol F type epoxy resins include "Araldite (registered trademark)” GY282 (manufactured by Huntsman Advanced Materials), "jER (registered trademark)” 806, “jER (registered trademark)” 807, “jER (registered trademark) ”1750 (manufactured by Mitsubishi Chemical Corporation), “Epiclon (registered trademark)” 830 (manufactured by DIC Corporation) and “Epotote (registered trademark)” YD-170 (Nippon Steel Chemical & Materials ( Co., Ltd.) and the like.
• isocyanurate epoxy resins include “TEPIC (registered trademark)”-S (manufactured by Nissan Chemical Industries, Ltd.), “TEPIC (registered trademark)”-G (manufactured by Nissan Chemical Industries, Ltd.), “ TEPIC (registered trademark)”-L (manufactured by Nissan Chemical Industries, Ltd.) and the like.
• epoxy resin that can be used in the epoxy resin composition of the present invention is not limited to the epoxy resins described above, and it goes without saying that epoxy resins other than those described above can also be used.
• Component [A] has an average epoxy equivalent of 160 g/eq or less, as will be described later, but an epoxy resin having an epoxy equivalent of 130 g/eq or less in 100% by mass of component [A] is used. It is preferable to contain 40% by mass or more. By containing 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more of an epoxy resin having an epoxy equivalent of 130 g/eq or less, excellent curing with a sufficient glass transition temperature even after moisture absorption you get something.
• the epoxy equivalent is understood as the mass of an epoxy resin containing 1 mol of epoxy groups (using (g/eq) as a unit).
• Examples of commercially available epoxy resins having an epoxy equivalent weight of 130 g/eq or less include "Sumiepoxy (registered trademark)” ELM434 (epoxy equivalent weight: 119 g/eq), “Araldite (registered trademark)” MY720 (epoxy equivalent weight: 119 g/eq).
• the component [B] is an amine curing agent.
• the amine curing agent has an amino group capable of reacting with an epoxy group and functions as a curing agent by reacting with the epoxy group.
• amine curing agents examples include aliphatic polyamines and aromatic polyamines. Among them, aromatic polyamines are preferably used because they can impart high mechanical properties and heat resistance to cured epoxy resins. These amine curing agents may be used alone or in combination.
• Those classified as aromatic polyamines include 2,2′-diethyldiaminodiphenylmethane, 2,4-diethyl-6-methyl-m-phenylenediamine, 4,6-diethyl-2-methyl-m-phenylenediamine, 4 ,6-diethyl-m-phenylenediamine and other diethyltoluenediamines, 4,4′-methylenebis(N-methylaniline), 4,4′-methylenebis(N-ethylaniline), 4,4′-methylenebis(N- sec-butylaniline), N,N'-di-sec-butyl-p-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3, 3'-diisopropyl-4,4'-diaminodiphenylmethan
• aromatic polyamines include Seikacure S (manufactured by Wakayama Seika Kogyo Co., Ltd.), MDA-220 (manufactured by Mitsui Chemicals, Inc.), and “jER Cure (registered trademark)” W (manufactured by Mitsubishi Chemical Corporation). ), and 3,3′-DAS (manufactured by Mitsui Chemicals, Inc.), “Lonzacure (registered trademark)” M-DEA (manufactured by Lonza Co., Ltd.), “Lonzacure (registered trademark)” M-DIPA (manufactured by Lonza Co., Ltd.
• E (mol) is the total number of moles of epoxy groups possessed by the epoxy resin of component [A], and the total number of active hydrogens possessed by the amine curing agent of component [B] is The number of moles is H (mol), and their ratio (H/E) is preferably 0.50 or more and 1.30 or less, more preferably 0.70 or more and 1.20 or less, and still more preferably 0 0.80 or more and 1.10 or less.
• H/E ratio
• the component [C] is a phosphate ester compound with a molecular weight of 250 or less.
• the constituent element [C] is not chemically incorporated into the crosslinked structure itself, but is contained within the network formed by the crosslinked structure (the constituent element [ A] and the constituent element [B] (the same applies hereinafter), and this state is maintained even after curing. Thereby, the elastic modulus of the obtained cured epoxy resin is increased.
• it is possible to obtain a cured epoxy resin product having not only elastic modulus but also excellent balance of strength, elastic modulus under wet heat, and heat resistance after moisture absorption. The reason for this is not clear, but the inventor believes as follows.
• the molecular weight of the component [C] is 250 or less, and the component [C] is suitable within the network formed by the crosslinked structure formed by the reaction of the epoxy resin and the amine curing agent. , a dense cured product can be obtained without voids, and the cured product has a high elastic modulus. In addition, when strain is applied to the cured product, the constituent element [C] moves freely in the crosslinked structure, and the strain energy until breakage can be alleviated, increasing the strength of the cured product.
• Intermolecular interactions work between the polar functional groups inside, and the state of being properly maintained within the network formed by the crosslinked structure can be maintained even when moisture is absorbed or in a high-temperature environment. It is considered that the heat resistance becomes higher.
• the epoxy resin and the amine curing agent react to form a crosslinked structure.
• the constituent element [C] is appropriately retained in the formed network, and a cured product having excellent strength, elastic modulus, and wet heat elastic modulus can be obtained.
• the molecular weight of the component [C] is 100 or more, the component [C] is appropriately retained in the network formed by the crosslinked structure formed by the reaction of the epoxy resin and the amine curing agent, It is preferable because a cured product having excellent strength, elastic modulus, and wet heat elastic modulus can be obtained.
• the boiling point of the component [C] is 180° C. or higher, more preferably 200° C. or higher, and still more preferably 230° C. or higher, thereby suppressing volatilization of the component [C] when the epoxy resin composition is cured. It is possible to obtain a resin cured product and a fiber-reinforced composite material having excellent mechanical properties, and furthermore, it is possible to suppress the generation of voids and the deterioration of mechanical properties in the obtained fiber-reinforced composite material, which is preferable.
• the boiling point is the value at normal pressure (101 kPa). Moreover, when the boiling point at normal pressure cannot be measured, the boiling point converted to 101 kPa in the boiling point conversion chart can be used.
• Examples of such component [C] include trimethyl phosphate, triethyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, and dimethyl methylphosphonate.
• a phenylphosphonic acid alkyl ester compound such as dimethyl phenylphosphonate and diethyl phenylphosphonate having an aromatic ring in the molecule is blended, the mechanical properties of the obtained resin cured product are particularly excellent, which is preferable.
• the phenylphosphonic acid alkyl ester compound has a high boiling point and is preferable in that it can suppress the generation of voids in the fiber-reinforced composite material. These compounds may be used alone or in combination.
• component [C] in the epoxy resin composition of the present invention it is important to include 1 part by mass or more and 15 parts by mass or less of component [C] with respect to 100 parts by mass of component [A]. is.
• amount of component [C] By setting the amount of component [C] to be 1 part by mass or more, more preferably 5 parts by mass or more, a cured product having excellent strength and elastic modulus can be obtained. Further, by setting the amount of component [C] to be 15 parts by mass or less, more preferably 12 parts by mass or less, a cured product having excellent wet heat elastic modulus and heat resistance after moisture absorption can be obtained.
• the component [D] is a thermoplastic resin.
• the epoxy resin composition of the present invention preferably further contains component [D].
• thermoplastic resin composed of a polyaryl ether skeleton is preferable as such a thermoplastic resin.
• examples include polysulfone, polyphenylsulfone, polyethersulfone, polyetherimide, polyphenylene ether, polyetheretherketone, and polyetherethersulfone.
• These thermoplastic resins having a polyarylether skeleton may be used alone, or may be used in combination.
• polyethersulfone can be preferably used because it can impart toughness to the obtained fiber-reinforced composite material without lowering its heat resistance and mechanical properties.
• Examples of commercially available products of the component [D] include Sumika Excel (registered trademark) "PES5003P (manufactured by Sumitomo Chemical Co., Ltd.)” and “Sumika Excel (registered trademark)” PES2603P (manufactured by Sumitomo Chemical Co., Ltd.). , Virantage (registered trademark) "VW10700RFP (manufactured by Solvay Advanced Polymers Co., Ltd.), and the like.
• component [D] As for the content of component [D], it is preferable to include 2 parts by mass or more of component [D] with respect to 100 parts by mass of component [A].
• component [D] is 2 parts by mass or more, more preferably 5 parts by mass or more, tackiness can be imparted to the prepreg, and in addition to obtaining a prepreg with excellent handleability, the flow of the resin during heat curing is improved. It is possible to obtain a fiber-reinforced composite material in which the properties can be suppressed and the resin content is uniform.
• the component [D] By setting the component [D] to 20 parts by mass or less, more preferably 16 parts by mass or less, it is possible to suppress an excessive decrease in the fluidity of the resin during heat curing, and a fiber-reinforced composite material with few voids can be obtained. be done.
• the epoxy resin composition of the present invention preferably contains component [A], component [B], component [C], and component [D]. , component [A], component [B], component [C], and component [D]. At this time, additives and the like may be contained within a range that does not affect the effects of the invention.
• the average epoxy equivalent weight of all epoxy resins used as component [A] is 160 g/eq or less.
• the average epoxy equivalent of the epoxy resin which is the component [A] is 160 g/eq or less, more preferably 140 g/eq or less, curing with excellent strength, elastic modulus, wet heat elastic modulus, and heat resistance after moisture absorption you get something.
• the average epoxy equivalent of the epoxy resin, which is the constituent element [A] is 120 g/eq or more, the curing reaction is less likely to run out of control during curing of the epoxy resin, and a decrease in the mechanical strength of the resulting cured product can be suppressed. preferable.
• the average epoxy equivalent is defined as the value obtained by the following formula.
• n is a positive integer and indicates the number of epoxy resin species to be used. .
• the average epoxy equivalent of the component [A] is 160 g/eq or less, the number of epoxy groups contained in the resin composition increases, so the number of hydroxyl groups generated by the ring-opening addition reaction between the epoxy group and the amine curing agent will also increase.
• the resulting cured epoxy resin has a high crosslink density, so the network size of the crosslinked epoxy resin is small.
• the component [C] is firmly held in the network formed by the crosslinked structure, and the strength, elastic modulus, elastic modulus under wet heat, and heat resistance after moisture absorption of the cured resin obtained are excellent.
• the average epoxy equivalent of the constituent element [A] is 110 g/eq or more, the curing heat generated when the epoxy resin composition is cured is reduced, so that the runaway reaction can be suppressed, and the strength of the cured product obtained. It is preferable because it is excellent in elastic modulus, elastic modulus under wet heat, and heat resistance after moisture absorption.
• the epoxy resin composition of the present invention has excellent elastic modulus, strength, and elongation, and is suitably used as a matrix resin for fiber-reinforced composite materials. That is, the fiber-reinforced composite material of the present invention comprises a cured epoxy resin composition of the present invention and continuous reinforcing fibers.
• Methods for obtaining a fiber-reinforced composite material include a method in which reinforcing fibers are impregnated with a resin composition in the molding process, such as a hand lay-up method, an RTM method, a filament winding method, a pultrusion method, and a method in which reinforcing fibers are preliminarily coated with a resin composition.
• a method of molding the impregnated prepreg by an autoclave method or a press molding method it is preferable to prepare a prepreg consisting of an epoxy resin composition and reinforcing fibers in advance, because the arrangement of fibers and the ratio of resin can be precisely controlled and the properties of the composite material can be maximized. That is, the prepreg of the present invention comprises the epoxy resin composition of the present invention and continuous reinforcing fibers. However, this does not exclude the inclusion of other components as long as the object of the present invention is not impaired.
• continuous reinforcing fiber used in the prepreg of the present invention and the fiber-reinforced composite material of the present invention
• carbon fiber graphite fiber, aramid fiber, glass fiber, etc.
• the form and arrangement of the continuous reinforcing fibers are not particularly limited as long as the fibers are continuous. things are used.
• reinforcing fibers two or more types of carbon fibers, glass fibers, aramid fibers, boron fibers, PBO fibers, high-strength polyethylene fibers, alumina fibers, silicon carbide fibers, and the like may be used in combination.
• carbon fibers include acrylic, pitch, and rayon carbon fibers, with acrylic carbon fibers having particularly high tensile strength being preferably used.
• Untwisted yarn or untwisted yarn which has a good balance between the moldability and strength characteristics of the carbon fiber reinforced composite material, is preferably used because it causes a decrease in the mechanical properties of the carbon fiber reinforced composite material.
• the carbon fiber preferably has a tensile modulus of 200 GPa or more and 440 GPa or less.
• the tensile elastic modulus of carbon fibers is affected by the crystallinity of the graphite structure that constitutes the carbon fibers, and the higher the crystallinity, the higher the elastic modulus. This range is preferable because the rigidity and strength of the carbon fiber reinforced composite material are well balanced at a high level. More preferably, the elastic modulus is 230 GPa or more and 400 GPa or less, and more preferably 260 GPa or more and 370 GPa or less.
• the tensile modulus of carbon fiber is a value measured according to JIS R7608 (2008).
• the prepreg of the present invention can be produced by various known methods.
• a prepreg can be produced by a hot-melt method in which a resin composition is heated to have a low viscosity without using an organic solvent, and reinforcing fibers are impregnated with the resin composition.
• the content of the continuous reinforcing fiber in 100 parts by mass of the prepreg is preferably 30 parts by mass or more and 90 parts by mass or less.
• the amount is set to 30 parts by mass or more, more preferably 35 parts by mass or more, and even more preferably 65 parts by mass or more, it is easy to obtain the advantages of a fiber-reinforced composite material having excellent specific strength and specific elastic modulus.
• the fiber-reinforced composite material is molded, it is possible to prevent the amount of heat generated during curing from becoming too high.
• the content is 90 parts by mass or less, more preferably 85 parts by mass or less, it is possible to suppress the occurrence of voids in the composite material due to impregnation failure of the resin. Moreover, the tackiness of the prepreg can be maintained.
• the fiber-reinforced composite material of the present invention can be produced by laminating the prepregs of the present invention described above in a predetermined form and applying pressure and heat to cure the resin.
• a method for applying heat and pressure a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, or the like is employed.
• the fiber-reinforced composite material of the present invention can be widely used for aerospace applications, general industrial applications and sports applications. More specifically, in general industrial applications, it is suitably used for structures such as automobiles, ships and railroad vehicles. In sports applications, it is suitably used for golf shafts, fishing rods, tennis and badminton rackets.
• Component [B] Amine curing agent, Seikacure S (4,4'-diaminodiphenylsulfone, active hydrogen equivalent: 62 g/eq, manufactured by Wakayama Seika Kogyo Co., Ltd.).
• Component [C] a phosphate ester compound having a molecular weight of 250 or less.
• ⁇ Trimethyl phosphate molecular weight: 140, boiling point: 197°C, manufactured by Tokyo Chemical Industry Co., Ltd.
• Dimethyl phenylphosphonate molecular weight: 186, boiling point: 247°C, manufactured by Tokyo Chemical Industry Co., Ltd.
• Diethyl phenylphosphonate molecular weight: 214, boiling point: 267°C, manufactured by Tokyo Chemical Industry Co., Ltd.
• test piece with a width of 10 mm and a length of 60 mm was cut out from the cured resin, immersed in boiling water under 1 atm for 20 hours to absorb moisture, and then the test piece was heated to 82°C using a constant temperature bath.
• Instron universal testing machine manufactured by Instron
• the span is 32 mm
• JIS K7171 (1994) three-point bending is performed under the same conditions as above.
• Tg glass transition temperature
• a test piece with a width of 12.7 mm and a length of 55 mm was cut out from the prepared resin cured plate, immersed in boiling water under 1 atm for 48 hours, and then glass transition temperature (Tg after moisture absorption) was determined by the DMA method according to SACMA SRM18R-94. asked for In the storage modulus G' curve, the temperature value at the intersection of the tangent line in the glass state and the tangent line in the transition state was defined as the glass transition temperature. Here, the temperature was measured at a temperature increase rate of 5° C./min and a frequency of 1 Hz.
• the average epoxy equivalent of the epoxy groups of the component [A] was 137 g/eq.
• Examples 2 to 5> According to the compounding ratio in Table 1, each component [A], component [B], component [C] and component [D] were blended in the same manner as in Example 1 above to obtain a resin composition. .
• Examples 6 to 9 According to the compounding ratio in Table 1, each component [A], component [B], component [C] and component [D] were blended in the same manner as in Example 1 above to obtain a resin composition. . Various measurement results of Examples are shown in Table 1. Even when the compounding ratio of the glycidylamine type epoxy resin and the glycidyl ether type epoxy resin of the component [A] was changed as in Examples 6 to 9, A cured resin product having an excellent balance of strength and elastic modulus, elastic modulus under wet heat, and Tg after moisture absorption was obtained.
• Example 10 The components [A], [B] and [C] were blended in the same manner as in Example 1 according to the compounding ratio shown in Table 1 to obtain a resin composition.
• the various measurement results of Examples are shown in Table 1. Compared to the case containing the component [D], although the cured product strength and wet heat breaking strain are slightly inferior, a sufficiently excellent cured resin product was obtained. was taken.
• Comparative Example 1 the component corresponding to [C] is not blended. Comparing Comparative Example 1 and Example 1, it can be seen that by blending the component [C], the strength, elastic modulus, and wet heat elastic modulus are improved without impairing the Tg after moisture absorption of the resin cured product. .
• Comparative Example 2 PX-200 was blended instead of the component [C]. PX-200 does not meet the requirement that the molecular weight of component [C] be 250 or less. Comparing Comparative Example 2 and Example 1, it can be seen that when the molecular weight of the component [C] is 250 or less, the strength, elastic modulus, elastic modulus under wet heat, and Tg after moisture absorption of the resulting resin cured product are excellent. I understand.
• Comparative Example 3 1,2-hexanediol was blended instead of the component [C]. Comparing Comparative Example 3 and Example 1, it can be seen that the elastic modulus under wet heat and the Tg after moisture absorption are excellent by blending the phosphoric acid ester compound as the component [C].
• Comparative Example 4 18 parts by mass of dimethyl phenylphosphonate was blended as the component [C]. Comparative Example 4 does not satisfy the requirement that 1 part by mass or more and 15 parts by mass or less of component [C] is included with respect to 100 parts by mass of component [A]. Comparing Comparative Example 4 and Example 4, by including 1 part by mass or more and 15 parts by mass or less of component [C] with respect to 100 parts by mass of component [A], after moisture absorption of the cured resin obtained It turns out that Tg is excellent.
• Comparative Example 5 the component [A] had an average epoxy equivalent weight of 172 g/eq and did not satisfy the requirement that the component [A] had an average epoxy equivalent weight of 160 g/eq. Comparing Comparative Example 5 and Example 3, in which 5 parts of dimethyl phenylphosphonate were blended, the cured resin material obtained by satisfying the requirement that the average epoxy equivalent of the component [A] is 160 g/eq or less. It can be seen that the strength, elastic modulus, wet heat elastic modulus, and Tg after moisture absorption are excellent.

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• 2022
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