WO2023053834A1 - Composition de résine époxy, préimprégné, matériau composite renforcé par des fibres, structure composite, élément résistant aux chocs et élément d'amortissement - Google Patents

Composition de résine époxy, préimprégné, matériau composite renforcé par des fibres, structure composite, élément résistant aux chocs et élément d'amortissement Download PDF

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Publication number
WO2023053834A1
WO2023053834A1 PCT/JP2022/032775 JP2022032775W WO2023053834A1 WO 2023053834 A1 WO2023053834 A1 WO 2023053834A1 JP 2022032775 W JP2022032775 W JP 2022032775W WO 2023053834 A1 WO2023053834 A1 WO 2023053834A1
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epoxy resin
fiber
resin composition
formula
composite material
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PCT/JP2022/032775
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English (en)
Japanese (ja)
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三好雅幸
平野啓之
本間雅登
中山義文
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東レ株式会社
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Publication of WO2023053834A1 publication Critical patent/WO2023053834A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof

Definitions

  • the present invention provides an epoxy resin composition preferably used as a matrix resin for a fiber-reinforced composite material, a prepreg and a fiber-reinforced composite material using this as a matrix resin, and a composite structure and an impact-resistant member using the fiber-reinforced composite material. and damping members.
  • epoxy resin is suitably used as a matrix resin for fiber-reinforced composite materials that are combined with reinforcing fibers such as carbon fiber, glass fiber, and aramid fiber.
  • a sheet-like intermediate base material in which reinforcing fibers are impregnated with epoxy resin, is commonly used for the production of fiber-reinforced composite materials. Molded products are obtained by laminating prepregs and then heating and curing the epoxy resin, and various characteristics can be expressed by prepreg lamination design, so it is applied to various fields such as aircraft, automobiles, sports and medicine.
  • Rubber-like polymers and thermoplastic elastomers are known as matrix resins for fiber-reinforced composite materials suitable for applications requiring such flexibility and impact resistance (Patent Document 1).
  • Patent Document 1 Rubber-like polymers and thermoplastic elastomers have high resin viscosities, there has been a demand for improved impregnation of reinforcing fibers.
  • Patent Documents 2 to 5 low-viscosity flexible epoxy resin compositions are sometimes used as such matrix resins.
  • the epoxy resin compositions described in Patent Documents 2 to 5 sacrifice heat resistance in order to increase flexibility. Therefore, the glass transition temperature of the epoxy resin composition is greatly exceeded when demolding after molding, and the shape cannot be maintained, resulting in poor demoldability after molding, which affects process stability during mass production.
  • an object of the present invention is to overcome the drawbacks of the prior art and to provide an epoxy resin composition that has excellent flexibility, sufficient heat resistance, and excellent releasability.
  • a further object of the present invention is to provide a prepreg and a fiber-reinforced composite material with excellent productivity by using the epoxy resin composition as a matrix resin.
  • the present invention is as follows. [1] An epoxy resin composition containing the following components [A], [B], and [C].
  • [C]: Aromatic urea The epoxy resin composition according to [1], containing 45 to 100 parts by mass of the epoxy resin of component [A] based on 100 parts by mass of the total epoxy resin. [3] The epoxy resin composition according to [1] or [2], wherein the cured product has a glass transition temperature of 80°C or higher. [4] The epoxy resin according to any one of [1] to [3], including both an epoxy resin having a structure of formula (I) and an epoxy resin having a structure of formula (II) as component [A]. Composition.
  • the structure has at least one shape selected from a spherical shape, a hemispherical shape, an eggplant shape, a cylinder, a cylinder, a cone, a prism, a prism, and a pyramid, and is integrated with [14] or [15] Composite structure as described.
  • an epoxy resin composition that has excellent flexibility, sufficient heat resistance, and excellent releasability.
  • the epoxy resin composition of the present invention contains component [A]: epoxy resin, component [B]: dicyandiamide, and component [C]: aromatic urea compound as essential components. Each component will be described below.
  • Component [A] used in the present invention is an epoxy resin having a structure of formula (I) or formula (II).
  • “including an epoxy resin having a structure of formula (I) or formula (II)” means an epoxy resin having a structure of formula (I) and an epoxy resin having a structure of formula (II). (meaning it contains one or both of the epoxy resins.)
  • R 1 and R 2 represent a hydrogen atom, a methyl group, or an ethyl group.
  • X represents a divalent aliphatic group containing 6 or more carbon atoms.
  • n is 1 to 15 represents an integer of.
  • the average epoxy equivalent of formula (I) is 300 to 420.
  • R 3 and R 4 represent a hydrogen atom, a methyl group, or an ethyl group, and n represents an integer of 1 to 10.
  • the epoxy resin having the structure of formula (I) is simply referred to as “the epoxy resin of formula (I)” and the like.
  • the average epoxy equivalent of the epoxy resin of formula (I) is 300-420.
  • an epoxy resin composition having excellent balance between flexibility and heat resistance and excellent demoldability can be obtained.
  • R 1 and R 2 in the epoxy resin of formula (I) are a hydrogen atom, a methyl group, or an ethyl group
  • an epoxy resin composition having an excellent balance between flexibility and heat resistance can be obtained.
  • X in formula (I) is a divalent aliphatic group containing 6 or more carbon atoms, and n is an integer of 1 to 15, the epoxy resin composition has an excellent balance of flexibility and heat resistance. you get something.
  • R 3 and R 4 in the epoxy resin of formula (II) are a hydrogen atom, a methyl group, or an ethyl group, an epoxy resin composition having an excellent balance between flexibility and heat resistance can be obtained. Further, when n in the epoxy resin of formula (II) is an integer of 1 to 10, an epoxy resin composition having an excellent balance of flexibility and heat resistance can be obtained.
  • the component [A] epoxy resin used in the present invention is preferably contained in an amount of 45 to 100 parts by mass based on 100 parts by mass of the total epoxy resin. By including a predetermined amount of these epoxy resins, it is possible to obtain an epoxy resin composition which has an excellent balance between flexibility and heat resistance, and which is also excellent in releasability.
  • the epoxy resin composition of the present invention preferably contains both an epoxy resin having the structure of formula (I) and an epoxy resin having the structure of formula (II) as component [A].
  • the weight mixing ratio of the epoxy resin having the structure of formula (I) and the epoxy resin having the structure of formula (II) as component [A] is 3:2 to 5: 1 is preferred. By setting the weight blending ratio within this range, an epoxy resin composition having a better balance between flexibility and heat resistance can be obtained.
  • component [A] Commercially available products of component [A] include EXA-4850-1000 (manufactured by DIC Corporation), EXA-4816 (manufactured by DIC Corporation), LCE-2615 (manufactured by Nippon Kayaku Co., Ltd.), and the like. .
  • the cured epoxy resin composition of the present invention preferably has a glass transition temperature of 80°C or higher.
  • the glass transition temperature of the cured product By setting the glass transition temperature of the cured product to 80° C. or higher, it is possible to obtain an epoxy resin cured product with a smooth surface without causing deformation or warping during demolding.
  • the cured epoxy resin used for measuring the glass transition temperature shall be prepared by the method described in the examples below.
  • Epoxy resins that can be used in combination with the epoxy resin of component [A] include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, novolak type epoxy resin, and fluorene.
  • Epoxy resins having skeletons epoxy resins made from copolymers of phenol compounds and dicyclopentadiene, glycidyl ether type epoxy resins such as diglycidylresorcinol, tetrakis(glycidyloxyphenyl)ethane, tris(glycidyloxyphenyl)methane , tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylene diamine, glycidylamine type epoxy resins, polypropylene glycol type epoxy resins, polyethylene glycol type epoxy resins, and long-chain aliphatic epoxy resins. . Epoxy resins other than component [A] may be used alone or in combination.
  • Component [B] in the present invention is dicyandiamide.
  • Dicyandiamide is excellent in that it imparts high mechanical properties and heat resistance to cured resins, and is widely used as a curing agent for epoxy resins.
  • Commercial products of such dicyandiamide include DICY7 and DICY15 (manufactured by Mitsubishi Chemical Corporation).
  • Blending dicyandiamide [B] as a powder into the epoxy resin composition is preferable from the viewpoint of storage stability at room temperature and viscosity stability during prepreg production. Further, it is preferable to disperse dicyandiamide [B] in a part of the epoxy resin of component [A] in advance using a triple roll or the like, in order to make the epoxy resin composition uniform and to improve the physical properties of the cured product. .
  • the average particle size is preferably 10 ⁇ m or less, more preferably 7 ⁇ m or less.
  • the average particle size as used herein means a volume average, and can be measured by a laser diffraction particle size distribution analyzer.
  • Component [C] aromatic urea compound
  • the epoxy resin composition of the present invention must contain an aromatic urea compound as component [C].
  • Component [C] functions as a curing accelerator, and can shorten the curing time when used in combination with component [B].
  • aromatic urea compounds for component [C] include 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and phenyldimethylurea. , toluenebisdimethylurea, and the like.
  • aromatic urea compounds include DCMU99 (manufactured by Hodogaya Chemical Industry Co., Ltd.), “Omicure (registered trademark)” 24 (manufactured by PTI Japan Co., Ltd.), “Omicure (registered trademark) )”94 (manufactured by PTI Japan Co., Ltd.), “Dyhard (registered trademark)” UR505 (4,4′-methylenebis(phenyldimethylurea, manufactured by AlzChem) and the like can be used.
  • the epoxy resin composition of the present invention is used for the purpose of adjusting the viscoelasticity, improving the tag and drape properties of the prepreg, and improving the mechanical properties and toughness of the resin composition, as long as the effects of the present invention are not lost.
  • It may contain thermoplastic resin, rubber particles, inorganic particles such as silica, nanoparticles such as CNT and graphene, and the like.
  • thermoplastic resins soluble in epoxy resins include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resins, polyamides, polyimides, polyvinylpyrrolidone, polysulfones, and polyethersulfones.
  • rubber particles include crosslinked rubber particles and core-shell rubber particles obtained by graft-polymerizing a different polymer on the surface of crosslinked rubber particles.
  • kneading may be carried out using a machine such as a kneader, planetary mixer, three-roll and twin-screw extruder. You can mix by hand using a spatula or the like.
  • the prepreg of the present invention contains at least one selected from the group consisting of carbon fibers, glass fibers, and aramid fibers as reinforcing fibers in the epoxy resin composition. Further, the reinforcing fibers may be surface-treated.
  • the surface treatment includes, in addition to metal adhesion treatment as a conductor, treatment with a coupling agent, treatment with a sizing agent, treatment with a binding agent, adhesion treatment with additives, and the like.
  • one type of these reinforcing fibers may be used alone, or two or more types may be used in combination.
  • carbon fibers such as polyacrylonitrile (PAN)-based, pitch-based, and rayon-based carbon fibers, which are excellent in specific strength and specific rigidity, are preferably used from the viewpoint of weight reduction effect.
  • glass fibers are preferably used, and it is particularly preferable to use carbon fibers and glass fibers in combination from the viewpoint of the balance between mechanical properties and economic efficiency.
  • aramid fibers are preferably used, and in particular, carbon fibers and aramid fibers are used in combination from the viewpoint of the balance between mechanical properties and impact resistance. is preferred.
  • reinforcing fibers coated with a metal such as nickel, copper, or ytterbium can also be used.
  • a metal such as nickel, copper, or ytterbium
  • PAN-based carbon fibers which are excellent in mechanical properties such as strength and elastic modulus, can be used more preferably.
  • the prepreg of the present invention can be obtained by impregnating a reinforcing fiber base material with the epoxy resin composition of the present invention.
  • the impregnation method include a hot melt method (dry method) and the like.
  • the hot-melt method is a method of directly impregnating reinforcing fibers with an epoxy resin composition whose viscosity has been reduced by heating, or a film is prepared by coating an epoxy resin composition on release paper or the like, and then both sides of the reinforcing fibers.
  • Another method is to stack the films from one side and impregnate the reinforcing fibers with the resin by applying heat and pressure.
  • a method for molding the prepreg for example, a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, etc. can be used as appropriate.
  • the reinforcing fibers contained in the prepreg of the present invention may be discontinuous fibers.
  • discontinuous fibers By using discontinuous fibers as the reinforcing fibers, it becomes easy to form a complex shape when the sheet-like prepreg is molded by applying an external force.
  • the reinforcing fibers are preferably bundled and randomly dispersed in the prepreg. By doing so, when the prepreg is molded by applying an external force, molding into a complicated shape is facilitated.
  • the reinforcing fibers are substantially monofilament-like and randomly dispersed in the prepreg.
  • the number of reinforcing fibers existing as fiber bundles in the prepreg is reduced, so the weak points at the fiber bundle ends of the reinforcing fibers can be minimized, resulting in excellent reinforcement efficiency and isotropy.
  • substantially monofilament-like means that the reinforcing fiber single yarn exists in fine fineness strands of less than 500 strands.
  • the reinforcing fibers are in the form of monofilaments, that is, they are dispersed so as to exist as single yarns, and it is even more preferable that the monofilament-like single fibers are randomly dispersed.
  • the reinforcing fibers are discontinuous fibers, the reinforcing fibers may be in the form of a non-woven fabric.
  • a fiber-reinforced composite material that is one aspect of the present invention is a fiber-reinforced composite material in which a cured product of the epoxy resin composition of the present invention (hereinafter referred to as "cured epoxy resin product of the present invention") is used as a matrix resin. Specifically, it is obtained by curing the prepreg of the present invention described above. More specifically, prepregs made of the epoxy resin composition of the present invention are laminated as necessary, and then cured by heating to obtain a fiber-reinforced composite material containing the cured epoxy resin of the present invention as a matrix resin. be able to.
  • the fiber-reinforced composite material of the present invention is preferably a porous structure having voids inside. Typically, it is a porous structure having voids formed by overlapping or intersecting discontinuous reinforcing fibers coated with a cured epoxy resin.
  • a porous structure such a fiber-reinforced composite material is referred to as a "porous structure" in the present specification.
  • the voids of the porous structure are formed, for example, by raising the reinforcing fibers due to the low viscosity of the epoxy resin component accompanying heating when heating the prepreg in which the reinforcing fibers are pre-impregnated with the epoxy resin composition. . This is based on the property that, in the prepreg, the internal reinforcing fibers that have been in a compressed state under pressure are raised by the raising force derived from their elastic modulus.
  • the reinforcing fibers have a mass-average fiber length of 1 to 15 mm, because the reinforcing efficiency of the reinforcing fibers can be increased and excellent mechanical properties can be obtained.
  • the mass-average fiber length of the reinforcing fibers is less than 1 mm, it becomes difficult to efficiently form the voids described above, and the density tends to increase.
  • the mass average fiber length of the reinforcing fibers is longer than 15 mm, the reinforcing fibers tend to bend due to their own weight in the porous structure, which may hinder the development of mechanical properties.
  • the reinforcing fiber strands and/or the intersections of the monofilaments that are in contact with each other are preferably coated with the epoxy resin cured product of the present invention, and the coating thickness is 1 ⁇ m or more and 15 ⁇ m or less.
  • the coating thickness is 1 ⁇ m or more and 15 ⁇ m or less.
  • the density of the porous structure is preferably 0.01 g/cm 3 or more and 0.9 g/cm 3 or less.
  • the density ⁇ is 0.9 g/cm 3 or less, lightness can be ensured, and when the density is 0.01 g/cm 3 or more, sufficient mechanical strength can be maintained.
  • the density of the porous structure of the present invention is 0.2 to 0.5 g/cm 3 .
  • the porous structure preferably has a tear strength of 3.0 N/m or more in a trouser type tear test according to JIS-K6252-1 (2015). There is a correlation between tear strength and impact resistance, and a tear strength of 3.0 N/m or more indicates excellent impact resistance.
  • the composite structure of the present invention is preferably one in which the fiber-reinforced composite material of the present invention is arranged and integrated over 25% or more of the surface area of the structure.
  • the arrangement relationship between the fiber-reinforced composite material and the structure in the composite structure in the present invention, there is no particular limitation as long as the fiber-reinforced composite material is arranged on at least one surface of the structure.
  • a canape structure in which fiber reinforced composite materials are placed only on one surface side of the structure, a structure in which one surface side and the other surface side of the structure are sandwiched between fiber reinforced composite materials, or a structure in which fiber reinforced composite materials are used
  • a sandwich structure which is a sandwiching structure, can be adopted.
  • a sandwich structure which is a structure in which a fiber-reinforced composite material is sandwiched between structures. Furthermore, a sandwich structure is preferable from the viewpoint of a high effect of improving impact resistance and vibration damping properties, and a canape structure is preferable from the viewpoint of achieving both impact resistance and vibration damping properties and light weight.
  • composite structures made of canape structures can be suitably used for flying objects and drones, where light weight is important, and can be easily imparted with excellent impact resistance, so that the composite structure can withstand falls and collisions. It is preferable because it is possible to prevent a failure such as breaking the body.
  • the composite structure of the present invention has at least one shape selected from a spherical shape, a hemispherical shape, an eggplant shape, a cylinder, a cylinder, a cone, a prism, a prism, and a pyramid.
  • the structure has at least one shape selected from spherical, hemispherical, cylindrical, columnar, prismatic, and prismatic. These shapes enable continuous molding of the structure.
  • a hemispherical shape, a cylindrical shape, and a rectangular shape are preferable for use in flying objects and drones.
  • the fiber-reinforced composite material is preferably arranged on 25% or more of the surface area of the structure, and the fiber-reinforced composite material is arranged on 40% or more of the surface area of the structure. is more preferred. Such arrangement makes it possible to easily obtain a composite structure having excellent impact resistance and vibration damping properties.
  • Materials for the structure in the present invention include steel, stainless steel, aluminum alloys, magnesium alloys, copper alloys, titanium alloys, glass, ceramics, thermoplastic resins, GFRP, and CFRP.
  • steel, magnesium alloys, aluminum alloys, and CFRP are preferable from the viewpoint of improving impact resistance and vibration damping properties.
  • the impact-resistant member of the present invention preferably uses the fiber-reinforced composite material of the present invention or a composite structure having this material arranged on the surface.
  • the fiber-reinforced composite material of the present invention has the effect of attenuating impact, and can maintain the shape of the composite structure without being damaged even when an impact that would otherwise damage the structure by itself is applied.
  • the damping member of the present invention preferably uses the fiber-reinforced composite material of the present invention or a composite structure having this material arranged on the surface.
  • the fiber-reinforced composite material of the present invention has the effect of damping vibration, and by arranging it, it can be preferably used for damping applications.
  • the fiber-reinforced composite material which is one aspect of the present invention, is preferably used for sports, aerospace and general industrial applications. More specifically, in sports applications, it is preferably used for golf shafts, fishing rods, shoe soles, tennis and badminton rackets, hockey sticks, and ski poles. In addition, in aerospace applications, it is preferably used for aircraft primary structural material applications such as flying objects, UAM (Urban Air Mobility), drones, main wings, tail wings and floor beams, and secondary structural material applications such as interior materials. Furthermore, in general industrial applications, it is preferably used for structural materials such as automobiles, bicycles, windmills, ships, and railroad vehicles, and electronic device members such as IC trays and notebook computer housings.
  • aircraft primary structural material applications such as flying objects, UAM (Urban Air Mobility), drones, main wings, tail wings and floor beams
  • secondary structural material applications such as interior materials.
  • structural materials such as automobiles, bicycles, windmills, ships, and railroad vehicles, and electronic device members such as IC
  • a continuous carbon fiber having a total of 12,000 single filaments was obtained by subjecting a copolymer containing PAN as a main component to spinning, baking treatment, and surface oxidation treatment.
  • the properties of this continuous carbon fiber were as follows. Average fiber diameter: 7 ⁇ m Mass per unit length: 0.8g/m Specific gravity: 1.8.
  • ⁇ Method for preparing epoxy resin composition Predetermined amounts of components other than [B] dicyandiamide and [C] aromatic urea were placed in a stainless steel beaker, heated to 40 to 150° C., and appropriately kneaded until each component was dissolved. Separately, a predetermined amount of [A] (eg, "EPICLON (registered trademark)" EXA-4816) and [B] dicyandiamide are added to a polyethylene cup, and the mixture is passed through the rolls twice using a triple roll to A master was created.
  • [A] eg, "EPICLON (registered trademark)" EXA-4816
  • the main component prepared above and the dicyandiamide master were kneaded at 60°C or less so as to have a predetermined mixing ratio, and finally [C] aromatic urea was added and kneaded at 60°C for 30 minutes to obtain an epoxy resin composition. got stuff
  • the epoxy resin composition was defoamed in a vacuum, and then poured into a mold set to have a thickness of 2 mm with a "Teflon (registered trademark)" spacer.
  • the temperature was raised from 30° C. to 150° C. by 2.5° C. per minute in a hot air oven, and then held at 150° C. for 90 minutes to cure the epoxy resin composition.
  • the temperature was lowered to 30° C. and removed from the mold to prepare a resin cured product having a thickness of 2 mm.
  • ⁇ Method for measuring glass transition temperature> A test piece with a width of 12.7 mm and a length of 45 mm was cut out from the 2 mm-thick resin cured product obtained by the above ⁇ Method for producing cured resin product>, and a viscoelasticity measuring device (ARES, TA Instruments) DMA measurement was performed in a temperature range of -15 to 250°C under the conditions of a torsional vibration frequency of 1.0 Hz and a heating rate of 5.0°C/min.
  • the glass transition temperature (Tg) was taken as the temperature at the intersection of the tangent line in the glass state and the tangent line in the transition state in the storage modulus G' curve.
  • the demoldability evaluation method of the epoxy resin composition was as follows: The epoxy resin composition obtained by the above method was cast into a fluororubber O-ring (manufactured by ESCO) having an inner diameter of 3 cm and a thickness of 4 mm, and heated at 150°C for 90 minutes. After curing, the epoxy resin cured product released from the mold was visually evaluated according to the following criteria. The surface is smooth, and there is no deformation or warping in the epoxy resin cured product S The surface is almost smooth, but there are slight deformations and warps...A The surface is almost smooth, but there are some deformations and warps ... B Remarkable deformation, warpage and cracking in cured epoxy resin...C.
  • ⁇ Method for producing carbon fiber web The carbon fibers were cut to a length of 6.5 mm with a cartridge cutter to obtain chopped carbon fibers. A dispersion having a concentration of 0.1% by mass consisting of water and a surfactant (polyoxyethylene lauryl ether (trade name), manufactured by Nacalai Tesque Co., Ltd.) was prepared, and this dispersion and the chopped carbon fiber were used. , a papermaking base material was manufactured with a papermaking base material manufacturing apparatus. The manufacturing apparatus includes a cylindrical container with a diameter of 1000 mm having an opening cock at the bottom of the container serving as a dispersing tank, and a linear transport section (tilt angle of 30 degrees) connecting the dispersing tank and the papermaking tank.
  • a stirrer is attached to the opening on the upper surface of the dispersion tank, and the chopped carbon fibers and the dispersion liquid can be introduced through the opening.
  • the papermaking tank is a tank provided with a mesh conveyor having a papermaking surface with a width of 500 mm at the bottom, and a conveyor capable of transporting a carbon fiber base material (papermaking base material) is connected to the mesh conveyor.
  • the mass per unit area was adjusted by adjusting the carbon fiber concentration in the dispersion. If necessary, about 5% by mass of polyvinyl alcohol aqueous solution (Kuraray Poval, manufactured by Kuraray Co., Ltd.) is applied as a binder to the paper-made carbon fiber substrate, and dried in a drying oven at 140° C. for 1 hour to form a carbon fiber web. Obtained.
  • the mass per unit area of the carbon fiber web was 50 g/m 2 .
  • a prepreg sheet was obtained by impregnating a carbon fiber web (fiber length: 6.5 mm, basis weight: 50 g/m 2 ) with the epoxy resin composition prepared according to ⁇ Method for preparing epoxy resin composition>. The obtained sheet was cut into a length of 200 mm and a width of 200 mm. Then, a porous structure was obtained through the following steps (1) to (5). (1) Place the prepreg sheet in a press molding mold cavity preheated to 60° C. and close the mold. (2) A pressure of 5 MPa is applied to the mold and held for an additional 300 seconds.
  • step (2) the mold cavity is opened and metal spacers are inserted into the ends thereof to adjust the thickness of the resulting porous structure to 0.8 mm.
  • step (3) the mold cavity is closed again, and the temperature of the mold is raised to 150° C. while the pressure is maintained, and curing is performed for 90 minutes.
  • step (3) Open the mold and take out the porous structure.
  • the density of the resulting porous structure was 0.2-0.5 g/cm 3 .
  • Vfi fiber volume content
  • JIS K7075 testing method for fiber content and void content of carbon fiber reinforced plastics, 1991.
  • Vfi Va/Vb ⁇ 100 (%)
  • Va fiber volume in the porous structure (mm 3 )
  • Vb Volume of porous structure (mm 3 ).
  • Example 1 [A] 100 parts by mass of "EPICLON (registered trademark)" EXA-4816 as an epoxy resin, [B] 5.2 parts by mass of DICY7 as dicyandiamide, and [C] "Omicure (registered trademark)" as an aromatic urea compound Using 3.1 parts by mass of 24, an epoxy resin composition was prepared according to the above ⁇ Method for preparing epoxy resin composition>. Using this epoxy resin composition, an epoxy resin cured product was prepared according to ⁇ Method for preparing cured epoxy resin>, and measured according to ⁇ Method for measuring glass transition temperature>. showed good heat resistance.
  • Example 2 An epoxy resin composition, a cured epoxy resin and a porous structure were produced in the same manner as in Example 1, except that the resin composition was changed as shown in Table 1. The evaluation results are shown in Table 1.
  • Epoxy resin composition was prepared in the same manner as in Example 1 except that "EPICLON (registered trademark)" EXA-4850-150 and 100 parts of the epoxy resin represented by the formula (I) having an average epoxy equivalent weight of 450 were used as the epoxy resin. A product and an epoxy resin cured product were prepared. The resin composition and evaluation results are shown in Table 2. The resulting resin composition had good flexibility, but was insufficient in heat resistance and releasability.
  • Example 2 An epoxy resin composition and an epoxy resin cured product were prepared in the same manner as in Example 1, except that "Denacol (registered trademark)" EX-991L and 100 parts of an epoxy resin that is a long-chain aliphatic epoxy resin were used as the epoxy resin. made.
  • the resin composition and evaluation results are shown in Table 2. Since the obtained resin composition was not cured, the releasability was insufficient, and the characteristics of the epoxy resin composition could not be evaluated.
  • Example 4 An epoxy resin composition, a cured epoxy resin and a porous structure were produced in the same manner as in Example 1, except that the resin composition was changed as shown in Table 2. The evaluation results are shown in Table 2. The heat resistance and releasability of the obtained resin composition were good, but the resin elongation was as low as 3.2%, which was insufficient. Moreover, the resulting porous structure had a low tear strength of 2.4 N/m and insufficient impact resistance.
  • surface is a mass part when all the epoxy resin components contained in an epoxy-resin composition are set to 100 mass parts.

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  • Reinforced Plastic Materials (AREA)

Abstract

Le but de la présente invention est de fournir une composition de résine époxy ayant une résistance à la chaleur adéquate et des propriétés exceptionnelles de démoulage tout en ayant également une flexibilité exceptionnelle. La présente invention concerne une composition de résine époxy comprenant les composants suivants [A], [B] et [C]. [A] : Une résine époxy ayant une structure représentée par la formule (I) ou la formule (II). (Dans la formule (I), R1 et R2 représentent un atome d'hydrogène, un groupe méthyle ou un groupe éthyle. X représente un groupe aliphatique divalent comprenant six atomes de carbone ou plus. n représente un nombre entier de 1 à 15. L'équivalent époxy moyen est de 300 à 420.) (Dans la formule (II), R3 et R4 représentent un atome d'hydrogène, un groupe méthyle ou un groupe éthyle. n représente un nombre entier de 1 à 10.) [B] : Dicyandiamide. [C] : Une urée aromatique.
PCT/JP2022/032775 2021-09-29 2022-08-31 Composition de résine époxy, préimprégné, matériau composite renforcé par des fibres, structure composite, élément résistant aux chocs et élément d'amortissement WO2023053834A1 (fr)

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Citations (7)

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JP2016504472A (ja) * 2013-01-07 2016-02-12 東レ株式会社 エポキシ樹脂組成物、プリプレグ、繊維強化プラスチック材料、および繊維強化プラスチック材料の製造方法
JP2017536441A (ja) * 2014-12-02 2017-12-07 東レ株式会社 エポキシ樹脂組成物、プリプレグ、繊維強化プラスチック材料および繊維強化プラスチック材料の製造方法
JP2018104482A (ja) * 2016-12-22 2018-07-05 東レ株式会社 構造体
JP2019189750A (ja) * 2018-04-25 2019-10-31 三菱ケミカル株式会社 エポキシ樹脂組成物、エポキシ樹脂組成物を含むプリプレグおよびその硬化物
WO2020003926A1 (fr) * 2018-06-26 2020-01-02 東レ株式会社 Corps stratifié
JP2021004314A (ja) * 2019-06-26 2021-01-14 味の素株式会社 樹脂組成物
WO2021106562A1 (fr) * 2019-11-29 2021-06-03 東レ株式会社 Conducteur thermique et son procédé de fabrication

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016504472A (ja) * 2013-01-07 2016-02-12 東レ株式会社 エポキシ樹脂組成物、プリプレグ、繊維強化プラスチック材料、および繊維強化プラスチック材料の製造方法
JP2017536441A (ja) * 2014-12-02 2017-12-07 東レ株式会社 エポキシ樹脂組成物、プリプレグ、繊維強化プラスチック材料および繊維強化プラスチック材料の製造方法
JP2018104482A (ja) * 2016-12-22 2018-07-05 東レ株式会社 構造体
JP2019189750A (ja) * 2018-04-25 2019-10-31 三菱ケミカル株式会社 エポキシ樹脂組成物、エポキシ樹脂組成物を含むプリプレグおよびその硬化物
WO2020003926A1 (fr) * 2018-06-26 2020-01-02 東レ株式会社 Corps stratifié
JP2021004314A (ja) * 2019-06-26 2021-01-14 味の素株式会社 樹脂組成物
WO2021106562A1 (fr) * 2019-11-29 2021-06-03 東レ株式会社 Conducteur thermique et son procédé de fabrication

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