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WO2025041753A1 - Composition de résine époxy, préimprégné et matériau composite renforcé par des fibres - Google Patents

Composition de résine époxy, préimprégné et matériau composite renforcé par des fibres Download PDF

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Publication number
WO2025041753A1
WO2025041753A1 PCT/JP2024/029419 JP2024029419W WO2025041753A1 WO 2025041753 A1 WO2025041753 A1 WO 2025041753A1 JP 2024029419 W JP2024029419 W JP 2024029419W WO 2025041753 A1 WO2025041753 A1 WO 2025041753A1
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Prior art keywords
epoxy resin
resin composition
component
mass
general formula
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Japanese (ja)
Inventor
明彦 伊藤
宏明 坂田
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Toray Industries Inc
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Toray Industries Inc
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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
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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, a prepreg, and a fiber-reinforced composite material with excellent fire resistance.
  • an intermediate substrate in which the reinforcing fibers are impregnated with resin is used in a wide range of applications, from sports and leisure goods such as fishing rods and tennis and badminton rackets to various industrial equipment, civil engineering and construction, and the aerospace industry.
  • mechanical properties such as strength and elastic modulus have traditionally been considered important from the perspective of reducing weight, and they have been particularly well suited for use as structural materials for aircraft and vehicles.
  • functionality such as flame retardancy, heat conductivity, and electrical conductivity is also being required.
  • methods for making composite materials flame retardant include a method of promoting the formation of char, which is a graphite-like carbonized layer that forms on the surface of the matrix resin during combustion, thereby suppressing the diffusion of decomposition gases when the resin is thermally decomposed, a method of suppressing heat generation when the resin is burned, or a method of suppressing the decomposition of the resin in the early stages of combustion by the heat absorbing effect of an inorganic filler containing a heat absorbing agent.
  • flame retardants In order to promote char formation in matrix resins, additives that make the material less flammable, so-called flame retardants, are often added. Phosphorus compounds are commonly used as flame retardants, and several phosphorus compounds are used industrially. Phosphorus compounds are converted to polyphosphoric acid, which has a dehydrating carbonization effect, during combustion, and it is believed that this promotes char formation. Flame retardant technologies using such phosphorus compounds include a technology in which additive flame retardants such as red phosphorus and phosphate esters are added to epoxy resin compositions, and a technology in which phosphorus atoms are introduced into the crosslinking structure of the resin by using a reactive flame retardant that contains phosphorus atoms in the molecule and reacts with the resin.
  • Patent Document 1 reports a technology for obtaining a material that has excellent viscosity stability and char formation promotion effects as well as excellent mechanical properties, by using a flame retardant technology that uses an epoxy resin composition that contains a reactive diluent having a specific structure and an amine-based curing agent that contains a phosphorus atom and has a specific structure.
  • Methods for improving the thermal conductivity of composite materials include using a thermally conductive filler to form a thermally conductive path inside the resin, and using a resin with high thermal conductivity.
  • Patent Document 2 reports a technology that uses boron nitride particles as a thermally conductive filler in combination with a specific phenoxy resin and a phenolic hardener to obtain a thermally conductive resin sheet with excellent thermal conductivity, heat resistance, and adhesive strength.
  • Patent Document 3 introduces a technology for obtaining an epoxy resin composition for LED heat dissipation components that has excellent thermal conductivity, fluidity, and moldability, and a cured product thereof, by using a resin that contains a large amount of graphite particles and has a low melt viscosity as a thermally conductive filler.
  • the present invention aims to solve the above problems, that is, to provide an epoxy resin composition that can give an epoxy resin cured product that has an excellent balance of flame retardancy, thermal conductivity, mechanical properties, and heat resistance, as well as a prepreg and a fiber-reinforced composite material that use the same.
  • the epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin and has the following configuration. 1. Contains the following components [A] to [C]. [A] Bifunctional naphthalene type epoxy resin [B] Phosphorus-containing curing agent [C] Thermally conductive particles 2.
  • the epoxy resin composition according to the above item 1 in which the mass content ratio of component [A] to component [B] is 0.3 to 1.5, and further contains, as component [A'], a tri- or tetra-functional epoxy resin having two or less benzene ring structures, and contains a total of 90 parts by mass or more of components [A] and [A'] per 100 parts by mass of the total amount of the epoxy resins.
  • R1 represents a hydrocarbon group having 1 to 4 carbon atoms, and l represents an integer of 0 to 3.
  • R2 and R3 each independently represent a hydrocarbon group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3.
  • component [B] contains at least one amine-based curing agent selected from the group consisting of amine-based curing agents having a structure represented by the following general formula (3) and amine-based curing agents having a structure represented by the following general formula (4):
  • R 4 represents a hydrocarbon group having 1 to 4 carbon atoms.
  • R 5 represents a hydrogen atom or an amino group.
  • the prepreg of the present invention is a prepreg obtained by impregnating reinforcing fibers with the above-mentioned epoxy resin composition.
  • the fiber-reinforced composite material of the present invention is a fiber-reinforced composite material obtained by curing the above-mentioned prepreg, or a fiber-reinforced composite material containing a cured epoxy resin obtained by curing the above-mentioned epoxy resin composition, and reinforcing fibers.
  • the present invention makes it possible to provide an epoxy resin composition that, when cured, gives an epoxy resin cured product that has an excellent balance of flame retardancy, thermal conductivity, mechanical properties, and heat resistance, as well as a prepreg made from the same.
  • the epoxy resin composition of the present invention contains component [A] a difunctional naphthalene-type epoxy resin, component [B] a phosphorus-containing curing agent, and component [C] thermally conductive particles.
  • Component [A] a bifunctional naphthalene type epoxy resin, is a bifunctional epoxy resin having one or more naphthalene ring structures, and epoxy resins having one or two naphthalene ring structures are preferably used.
  • the structure of component [A] is represented by the following general formula (1) or (2), it is preferable because the epoxy resin cured product obtained by curing has excellent flame retardancy, thermal conductivity, heat resistance, or mechanical properties.
  • R1 represents a hydrocarbon group having 1 to 4 carbon atoms, and l represents an integer of 0 to 3.
  • R 1 is preferably a hydrocarbon group having 1 or 2 carbon atoms, and l is preferably 0 or 1, in order to obtain excellent flame retardancy and appropriate viscosity.
  • R2 and R3 each independently represent a hydrocarbon group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3.)
  • R2 and R3 each independently represent a hydrocarbon group having 1 or 2 carbon atoms, and it is preferable that m and n each independently represent 0 or 1.
  • component [A] include epoxy resins having a structure obtained by reacting precursors such as 1,2-naphthalenediol, 1,3-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 1,8-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, 2-methyl-1,4-naphthalenediol, 3-methyl-1,8-naphthalenediol, 1-(2-hydroxy-naphthalen-1-ylmethyl)-naphthalen-2-ol, 1-(2-hydroxy-naphthalen-1-ylmethyl)-naphthalen-7-ol, and 1-(7-hydroxy-naphthalen-1-ylmethyl)-naphthalen-7-ol with epichlorohydrin using a basic catalyst to convert the hydroxyl groups of
  • epoxy resins containing two naphthalene ring structures are preferably used.
  • epoxy resins having a structure obtained using 1-(2-hydroxy-naphthalen-1-ylmethyl)-naphthalen-2-ol as a precursor are particularly preferred because they have two rigid naphthalene skeletons and therefore tend to provide excellent heat resistance.
  • the epoxy resins listed above as examples of component [A] may be used alone or in combination of two or more types.
  • the epoxy resin composition of the present invention preferably further contains a tri- or tetra-functional epoxy resin having two or less benzene ring structures as component [A'].
  • the benzene ring structure refers to a structure in which a benzene ring exists isolated as an aromatic ring, and does not include a ring structure in which an aromatic ring is condensed.
  • Representative examples of such tri- or tetra-functional epoxy resins having two or less benzene ring structures include tri- or tetra-functional epoxy resins having one benzene ring structure and tetra-functional epoxy resins having two benzene ring structures.
  • tri- or tetra-functional epoxy resins having one benzene ring structure include aminophenol-type epoxy resins such as N,N,O-triglycidyl-m-aminophenol, N,N,O-triglycidyl-p-aminophenol, and N,N,O-triglycidyl-4-amino-3-methylphenol.
  • aminophenol-type epoxy resins such as N,N,O-triglycidyl-m-aminophenol, N,N,O-triglycidyl-p-aminophenol, and N,N,O-triglycidyl-4-amino-3-methylphenol.
  • Examples of tetrafunctional epoxy resins having two benzene ring structures include diamine-type epoxy resins such as N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-2,2'-diethyl-4,4'-diaminodiphenylmethane, and N,N,N',N'-tetraglycidyl-m-xylylenediamine.
  • diamine-type epoxy resins such as N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-2,2'-diethyl-4,4'-diaminodiphenylmethane, and N,N,N',N'-tetraglycidyl-m-xylylenedi
  • tetrafunctional epoxy resins having two benzene ring structures is preferred because it improves the crosslink density and makes it easier to obtain an epoxy resin cured product with high heat resistance and thermal diffusivity.
  • the epoxy resins listed above as examples of component [A'] may be used alone or in combination of two or more types.
  • the epoxy resin composition of the present invention may contain epoxy resins other than components [A] and [A'].
  • epoxy resins other than components [A] and [A'] include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, and bisphenol S type epoxy resins, epoxy resins having a biphenyl skeleton, monofunctional or trifunctional or higher epoxy resins having a naphthalene skeleton, and epoxy resins having a dicyclopentadiene skeleton.
  • the content of component [A] in the epoxy resin composition of the present invention is preferably 10 to 50 parts by mass relative to 100 parts by mass of the total epoxy resin, i.e., when the total mass of all epoxy resins, including component [A], contained in the epoxy resin composition is taken as 100 parts by mass, in order to improve the mechanical properties of the resulting epoxy resin cured product and fiber-reinforced composite material.
  • the above content is more preferably 20 to 40 parts by mass.
  • the total content of component [A] and component [A'] in the epoxy resin composition of the present invention is preferably 90 parts by mass or more per 100 parts by mass of the total amount of epoxy resin, from the viewpoint of improving the heat resistance of the cured epoxy resin product obtained by curing.
  • Component [B] used in the epoxy resin composition of the present invention is a phosphorus-containing curing agent, which is a curing agent that contains a phosphorus atom in its molecular structure.
  • the curing agent referred to here is a curing agent for epoxy resins, and is a compound that has an active group that can react with an epoxy group.
  • component [B] it is preferable for component [B] to contain at least one amine-based curing agent selected from the group consisting of amine-based curing agents having a structure represented by the following general formula (3) and amine-based curing agents having a structure represented by general formula (4), since excellent flame retardancy and mechanical properties can be obtained, and an embodiment in which it is used in combination with component [A] represented by general formula (1) or (2) is more preferable.
  • R 4 represents a hydrocarbon group having 1 to 4 carbon atoms.
  • R 5 represents a hydrogen atom or an amino group.
  • the number of carbon atoms in R 4 is preferably 2 to 4. More preferably, the number of carbon atoms in R 4 is 4.
  • R 5 is preferably a hydrogen atom.
  • Examples of phosphorus-containing curing agents represented by general formula (3) include bis(4-aminophenyl)methylphosphine oxide, bis(3-aminophenyl)methylphosphine oxide, bis(2-aminophenyl)methylphosphine oxide, bis(4-aminophenyl)ethylphosphine oxide, bis(3-aminophenyl)ethylphosphine oxide, bis(2-aminophenyl)ethylphosphine oxide, bis(4-aminophenyl)n-propylphosphine oxide, bis(3-aminophenyl)n-propylphosphine oxide, bis(4-aminophenyl)isopropylphosphine oxide, bis(3-aminophenyl)isopropylphosphine oxide, bis(4-aminophenyl)n-butylphosphine oxide, bis(3-aminophenyl)n-
  • Amine-based curing agents having a structure represented by general formula (4) include tris(4-aminophenyl)phosphine oxide, tris(3-aminophenyl)phosphine oxide, tris(2-aminophenyl)phosphine oxide, bis(4-aminophenyl)phenylphosphine oxide, bis(3-aminophenyl)phenylphosphine oxide, etc.
  • tris(3-aminophenyl)phosphine oxide or bis(3-aminophenyl)phenylphosphine oxide is preferably used because of its excellent mechanical properties, and of these two compounds, the latter is more preferably used.
  • the content of component [B] in the epoxy resin composition of the present invention is preferably 10 to 100 parts by mass per 100 parts by mass of the total epoxy resin, from the viewpoints of improving the viscosity stability of the epoxy resin composition and the flame retardancy and mechanical properties of the resulting epoxy resin cured material and fiber-reinforced composite material.
  • the above content is more preferably 25 to 100 parts by mass.
  • the mass content ratio of component [A] to component [B] is preferably 0.3 to 1.5 in order to improve the flame retardancy and thermal conductivity of the resulting epoxy resin cured product, and the above content ratio is more preferably 0.3 to 1.4.
  • the mass content ratio of component [A] to component [B] is the value obtained by dividing the mass proportion of component [A] contained in the entire epoxy resin composition by the mass proportion of component [B].
  • the resulting epoxy resin cured material and fiber-reinforced composite material can have both flame retardancy and mechanical properties.
  • the phosphorus atom content is preferably 0.3 to 4.0 mass%.
  • the phosphorus atom content (mass%) referred to here is calculated by mass (g) of phosphorus atoms in the total epoxy resin composition / mass (g) of the total epoxy resin composition ⁇ 100.
  • the mass of phosphorus atoms in the total epoxy resin composition is obtained by calculating the mass of phosphorus atoms per molecule of the compound of component [B] from the atomic weight of the phosphorus atoms, and multiplying this by the number of molecules of the compound of component [B] contained in the total epoxy resin composition, calculated from the number of moles.
  • a curing agent other than component [B] can be contained in addition to component [B].
  • the curing agent here is a curing agent for epoxy resins, and is a compound having an active group capable of reacting with an epoxy group.
  • curing agents other than component [B] include dicyandiamide, aromatic polyamines, aminobenzoic acid esters, various acid anhydrides, phenol novolac resins, cresol novolac resins, polyphenol compounds, imidazole derivatives, aliphatic amines, tetramethylguanidine, thiourea adduct amines, carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, carboxylic acid hydrazides, carboxylic acid amides, polymercaptans, and Lewis acid complexes such as boron trifluoride ethylamine complexes.
  • aromatic polyamines as a curing agent makes it easier to obtain epoxy resin cured products with good heat resistance.
  • various isomers of diaminodiphenyl sulfone, such as 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone, among aromatic polyamines it becomes easier to obtain a cured epoxy resin with good heat resistance.
  • the content of the curing agent other than the above component [B] is preferably 90 parts by mass or less relative to the total amount of the curing agents including component [B] and the curing agents other than component [B], that is, when the total amount of the curing agents including component [B] contained in the epoxy resin composition is taken as 100 parts by mass, because this makes it easier to obtain high flame retardancy in the obtained epoxy resin cured product and fiber reinforced composite material.
  • the epoxy resin composition of the present invention may contain a curing accelerator to enhance the curing activity of the curing agent.
  • the curing accelerator here is a compound that acts as a catalyst for the reaction between the epoxy resin and the curing agent and does not have an active group that can react with the epoxy group.
  • curing accelerator examples include urea derivatives such as 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 4,4'-methylenebis(diphenyldimethylurea), and 2,4-toluenebis(3,3-dimethylurea), imidazole derivatives, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, and tetraphenylphosphonium tetra(4-methylphenyl)borate.
  • urea derivatives such as 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 4,4'-m
  • Component [C] of the epoxy resin composition of the present invention is a thermally conductive particle.
  • the thermally conductive particle is preferably a filler made of boron nitride or graphite.
  • graphite filler is more preferable. Its addition improves the thermal conductivity of the resin.
  • component [C] include flake boron nitride, spherical graphite, scaly graphite, and scaly graphite. Of these, flake graphite is particularly preferred because it is highly graphitized and has high thermal conductivity.
  • boron nitride and graphite components [C] may be used alone as a filler, or the two may be used in combination. It is also possible to use a mixture of two or more types of boron nitride, graphite, or a combination of both.
  • the average particle size of component [C] in the epoxy resin composition of the present invention is preferably 10 nm to 100 ⁇ m in terms of obtaining high thermal conductivity and mechanical properties, and is more preferably 1 ⁇ m to 20 ⁇ m. Most preferably, it is 1 ⁇ m to 5 ⁇ m.
  • the content of component [C] in the epoxy resin composition of the present invention is preferably 0.5% by mass to 25% by mass of the total epoxy resin composition in terms of high thermal conductivity, mechanical properties, fluidity of the epoxy resin composition, and tackiness of the resulting prepreg.
  • the above content is more preferably 1% by mass to 10% by mass.
  • a filler made of graphite is used as component [C]
  • the above content is particularly preferable.
  • the epoxy resin composition of the present invention preferably further contains a thermoplastic resin as component [D] in order to control the tackiness of the resulting prepreg, control the fluidity of the resin when the epoxy resin composition is impregnated into the reinforcing fibers during the production of the prepreg, and increase the toughness of the resulting fiber-reinforced composite material.
  • the thermoplastic resin is preferably dissolved in the epoxy resin composition and used.
  • the thermoplastic resin as component [D] may be any compound that is soluble in the epoxy resin used at room temperature, and specific examples include polysulfone, polyphenylsulfone, polyethersulfone, polyetherimide, polyphenylene ether, polyetheretherketone, and polyetherethersulfone.
  • thermoplastic resins composed of a polyarylether skeleton are preferred. These thermoplastic resins composed of a polyarylether skeleton may be used alone or in combination as appropriate.
  • polyethersulfone and polyetherimide are preferably used because they can impart toughness without reducing the heat resistance and mechanical properties of the resulting fiber-reinforced composite material.
  • polyetherimide is preferably used from the viewpoint of improving thermal diffusivity.
  • the amount of component [D] in the epoxy resin composition of the present invention is preferably 5 to 40 parts by mass, more preferably 10 to 35 parts by mass, and even more preferably 14 to 30 parts by mass, per 100 parts by mass of the total epoxy resin.
  • Polyamide is the most preferred material for the thermoplastic resin particles, and among polyamides, polyamide 12, polyamide 6, polyamide 11, polyamide 66, polyamide 6/12 copolymer, and polyamides that have been semi-IPN (interpenetrating polymer network structure) formed with the epoxy compound described in Example 1 of JP-A-1-104624 (semi-IPN polyamides) provide particularly good adhesive strength with epoxy resins.
  • polyamide particles may be used alone or in combination of multiple types.
  • the epoxy resin composition of the present invention can contain coupling agents, thermosetting resin particles, or inorganic fillers such as silica gel, carbon black, clay, carbon nanotubes, graphene, carbon particles, and metal powder, to the extent that the effects of the present invention are not impaired.
  • the prepreg of the present invention can be manufactured by various known methods, such as the wet method and hot melt method. Among them, the hot melt method is preferred because it is easy to achieve the effects of the present invention.
  • the weight of the reinforcing fiber is preferably 100 to 1000 g/m 2. If the weight of the reinforcing fiber is less than 100 g/m 2 , the number of layers needs to be increased to obtain a predetermined thickness when molding the fiber-reinforced composite material, and the lamination work may become complicated. On the other hand, if it exceeds 1000 g/m 2 , the drapeability of the prepreg tends to deteriorate.
  • the fiber mass content in the prepreg is preferably 40 to 90 mass%, more preferably 50 to 80 mass%.
  • the fiber mass content is less than 40 mass%, the ratio of the resin is relatively high, so that it is not possible to take advantage of the excellent mechanical properties of the reinforcing fiber, and the amount of heat generated during curing to obtain a fiber-reinforced composite material may be too high.
  • the fiber mass content exceeds 90 mass%, impregnation of the resin is poor, and the obtained fiber-reinforced composite material may have many voids.
  • the prepreg of the present invention may be in the form of a unidirectional (sometimes abbreviated as UD) prepreg, a woven prepreg, or even a nonwoven prepreg.
  • UD unidirectional
  • the epoxy resin composition prepared in (1) was degassed in a vacuum, and then 2 mm thick Teflon (registered trademark) spacers were inserted into the mold so that the thickness of the resulting epoxy resin cured product was limited to 2 mm.
  • the epoxy resin cured product was cured under the specified curing conditions described below to obtain a 2 mm thick epoxy resin cured product.
  • Flame retardancy was evaluated using a thermogravimetric analyzer TG-DSC (PerkinElmer STA6000 system). A test piece of about 10 mg was cut out from the epoxy resin cured product and heated simply in air at a heating rate of 10°C/min.
  • the char generation rate (%) at 600°C was used as an index of flame retardancy.
  • the char generation rate here is a value expressed as (mass (g) of thermal decomposition residue at 600°C)/(mass (g) of epoxy resin cured product before heating) x 100.
  • the measured value was rounded off to the nearest tenth to get the nearest tenth.
  • the epoxy resin cured product prepared in (2) was cut into a size of 10 mm x 10 mm square, and the surface was blackened using Blackguard Spray (Fine Chemical Japan Co., Ltd.).
  • the thermal diffusivity of the sample was measured based on ASTM E1461-01 (2001).
  • the thermal diffusivity at 25°C was measured using a thermal diffusivity measuring device LFA467HyperFlash (NETZSCH Co., Ltd.) and calculated to two decimal places in mm2 /s.
  • thermo conductivity S: "Thermal diffusivity is 0.22 mm 2 /s or more.” A: “Thermal diffusivity is 0.19 mm 2 /s or more and less than 0.22 mm 2 /s.” B: “Thermal diffusivity is 0.16 mm 2 /s or more and less than 0.19 mm 2 /s.” C: “Thermal diffusivity is less than 0.16 mm 2 /s.”
  • the epoxy resin cured product prepared in (2) was cut into test pieces measuring 10 mm x 60 mm square, and a three-point bending test was performed based on JIS K7171 (2006) to evaluate the mechanical properties.
  • the bending test was performed using an Instron 5565 universal testing machine (manufactured by Instron) under the conditions of a crosshead speed of 2.5 mm/min, a span length of 40 mm, an indenter diameter of 10 mm, and a support diameter of 4 mm, and the bending modulus was measured.
  • the measured value was rounded off to the first decimal place in gigapascal units.
  • Judgment criteria (mechanical properties): S: “Flexural modulus of elasticity is 4.7 GPa or more.” A: “Flexural modulus is 4.1 GPa or more and less than 4.7 GPa.” B: “Flexural modulus is 3.5 GPa or more and less than 4.1 GPa.” C: “Flexural modulus is less than 3.5 GPa.” (5) Evaluation of Heat Resistance of Cured Epoxy Resin Material The heat resistance of the cured epoxy resin material was evaluated as follows.
  • the epoxy resin cured product prepared in (2) was cut into test pieces measuring 12.7 mm x 45 mm square, and the glass transition temperature was measured by dynamic mechanical analysis (DMA) in accordance with ASTM 7028-07.
  • DMA dynamic mechanical analysis
  • the measurement value was rounded off to the nearest tenth in degrees Celsius.
  • Judgment criteria (heat resistance): S: “Glass transition temperature is 210°C or higher.” A: “The glass transition temperature is 190° C. or higher and less than 210° C..” B: “The glass transition temperature is 170° C. or higher and less than 190° C..” C: “Glass transition temperature is less than 170° C.”
  • Examples 1 to 8, Comparative Examples 1 to 6 An epoxy resin composition was prepared by the above (1) method for preparing an epoxy resin composition using the components in the ratios (parts by mass) shown in Tables 1 and 2.
  • the epoxy resin cured product obtained by curing at a temperature of 180°C for 2 hours was evaluated for flame retardancy, thermal conductivity, mechanical properties, and heat resistance according to the above (2) to (5).
  • the evaluation results are shown in Tables 1 and 2.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le but de la présente invention est de fournir une composition de résine époxy qui peut être durcie afin d'obtenir un produit durci de résine époxy présentant un excellente équilibre entre ignifugation, conductivité thermique et résistance à la chaleur, et un préimprégné et un matériau composite renforcé par des fibres l'utilisant.　La composition de résine époxy comprenant une résine époxy qui atteint ce but contient [A] une résine époxy naphtalène bifonctionnelle, [B] un agent de durcissement contenant du phosphore et [C] des particules thermoconductrices.
PCT/JP2024/029419 2023-08-23 2024-08-20 Composition de résine époxy, préimprégné et matériau composite renforcé par des fibres Pending WO2025041753A1 (fr)

Applications Claiming Priority (2)

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JP2023135219 2023-08-23
JP2023-135219 2023-08-23

Publications (1)

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WO2025041753A1 true WO2025041753A1 (fr) 2025-02-27

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Country Link
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001151991A (ja) * 1999-11-25 2001-06-05 Matsushita Electric Works Ltd エポキシ樹脂組成物、プリプレグ、多層プリント配線板
JP2001348420A (ja) * 2000-06-06 2001-12-18 Matsushita Electric Works Ltd エポキシ樹脂組成物、プリプレグ、多層プリント配線板
JP2002249641A (ja) * 2001-02-23 2002-09-06 Matsushita Electric Works Ltd エポキシ樹脂組成物、樹脂フィルム、樹脂付き金属箔、プリプレグ及び積層板
JP2012241179A (ja) * 2011-05-24 2012-12-10 Panasonic Corp プリプレグ用エポキシ樹脂組成物、プリプレグ、および多層プリント配線板
US20150057393A1 (en) * 2013-08-26 2015-02-26 Samsung Electro-Mechanics Co., Ltd. Insulating resin composition for printed circuit board and products manufactured by using the same
JP2018168262A (ja) * 2017-03-29 2018-11-01 味の素株式会社 樹脂組成物
CN111777746A (zh) * 2020-09-04 2020-10-16 中国科学院宁波材料技术与工程研究所 无卤阻燃型环氧树脂组合物、模塑料制品、其制法与应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001151991A (ja) * 1999-11-25 2001-06-05 Matsushita Electric Works Ltd エポキシ樹脂組成物、プリプレグ、多層プリント配線板
JP2001348420A (ja) * 2000-06-06 2001-12-18 Matsushita Electric Works Ltd エポキシ樹脂組成物、プリプレグ、多層プリント配線板
JP2002249641A (ja) * 2001-02-23 2002-09-06 Matsushita Electric Works Ltd エポキシ樹脂組成物、樹脂フィルム、樹脂付き金属箔、プリプレグ及び積層板
JP2012241179A (ja) * 2011-05-24 2012-12-10 Panasonic Corp プリプレグ用エポキシ樹脂組成物、プリプレグ、および多層プリント配線板
US20150057393A1 (en) * 2013-08-26 2015-02-26 Samsung Electro-Mechanics Co., Ltd. Insulating resin composition for printed circuit board and products manufactured by using the same
JP2018168262A (ja) * 2017-03-29 2018-11-01 味の素株式会社 樹脂組成物
CN111777746A (zh) * 2020-09-04 2020-10-16 中国科学院宁波材料技术与工程研究所 无卤阻燃型环氧树脂组合物、模塑料制品、其制法与应用

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