Classifications

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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
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  • 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
  • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3227—Compounds containing acyclic nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—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
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
  • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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  • 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/14—Solid materials, e.g. powdery or granular
• • 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
  • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
  • C08J2481/06—Polysulfones; Polyethersulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
  • C08K2003/382—Boron-containing compounds and nitrogen
  • C08K2003/385—Binary compounds of nitrogen with boron
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/30—Applications used for thermoforming

Definitions

• the present invention relates to an epoxy resin composition, a prepreg, and a fiber reinforced composite material with excellent fire resistance.
• thermosetting resins such as epoxy resins and phenolic resins as matrix resins are used for everything from sports and leisure goods such as fishing rods, tennis and badminton rackets, to various industrial equipment, and civil engineering. It is used in a wide range of applications, from architecture to the aerospace field.
• thermosetting resins used in most composite materials are easily flammable and can cause fires, so flame-retardant composite materials are used to prevent accidents caused by ignition and combustion, especially for structural materials such as aircraft and vehicles. It has been demanded.
• materials are required to be flame retardant in order to prevent the casings and parts from catching fire and burning due to internal heat generation, leading to accidents.
• flame retardants As a means of promoting char formation in the matrix resin, additives that make the material less flammable, so-called flame retardants, are often added. Phosphorus compounds are commonly used as flame retardants, and some phosphorus compounds are used industrially. It is believed that during combustion, the phosphorus compound converts into polyphosphoric acid, which has a dehydration and carbonization effect, thereby promoting char formation. Flame retardant technologies using such phosphorus compounds include technologies that add additive flame retardants such as red phosphorus and phosphoric acid esters to epoxy resin compositions, or reactions that contain phosphorus atoms in the molecule and react with the resin. There is a technique to introduce phosphorus atoms into the crosslinked structure by using a type flame retardant.
• metal hydroxides are commonly used as endothermic agents and are used industrially.
• Patent Document 1 a flame retardant technology using a resin composition containing a reactive diluent having a specific structure and an amine curing agent containing a phosphorus atom having a specific structure provides excellent viscosity stability.
• a technique has been reported to obtain a cured resin product that has a char formation promoting effect and also has excellent mechanical properties.
• Patent Document 2 reports a technique for obtaining a fire-resistant resin containing an epoxy resin containing phosphorus atoms having a specific structure.
• Patent Document 3 reports a flame-retardant resin containing a specific epoxy resin, red phosphorus, and aluminum hydroxide, and a technique for obtaining a fire-resistant fiber-reinforced composite material using the same.
• An object of the present invention is to provide an epoxy resin composition from which a fiber-reinforced composite material having excellent mechanical properties and excellent fire resistance can be obtained, as well as prepregs and fiber-reinforced composite materials using the same.
• the epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin, and the cured resin obtained by curing at a temperature of 180°C for 2 hours was measured based on ASTM E1461-01 (2001).
• the epoxy resin composition has a thermal diffusivity of 0.17 mm 2 /s or more and less than 0.30 mm 2 /s at 25°C, and a char formation rate of 20% or more and less than 50% at 600°C under air.
• such an epoxy resin composition contains an inorganic filler made of boron nitride or graphite as a component other than the epoxy resin.
• 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 prepreg described above, or a fiber-reinforced composite material comprising a cured resin material obtained by curing the above-mentioned epoxy resin composition and reinforcing fibers.
• the thickness of the fiber-reinforced composite material is 0.5 mm or more and less than 2 mm.
• the present invention provides an epoxy resin composition that can be cured to obtain a cured resin product that has a high char-forming effect, thermal conductivity, and excellent mechanical properties, and a prepreg using the same. becomes possible. Furthermore, the present invention makes it possible to provide a fiber-reinforced composite material with excellent mechanical properties and fire resistance.
• the epoxy resin composition of the present invention has a thermal diffusivity of 0.17 mm 2 /s or more and 0.30 mm at 25°C for a resin cured product obtained by curing the epoxy resin composition at a temperature of 180°C for 2 hours. less than 2 /s.
• the thermal diffusivity is within this range, heat radiation in the thickness direction is sufficiently promoted, and a fiber reinforced composite material with excellent fire resistance can be obtained.
• the above-mentioned thermal diffusivity is the thermal diffusivity in the thickness direction when a cured resin material is measured based on the standard of ASTM E1461-01 (2001).
• the lower limit of the thermal diffusivity is preferably 0.18 mm 2 /s or more, more preferably 0.19 mm 2 /s or more. Most preferably, the thermal diffusivity is 0.20 mm 2 /s or more and less than 0.30 mm 2 /s.
• the epoxy resin composition of the present invention has a 600°C char formation rate under air of 20% or more and less than 50% for the resulting cured resin product.
• the char production rate is within this range, thermal diffusion of decomposed gas is sufficiently suppressed, and a fiber-reinforced composite material with excellent fire resistance can be obtained.
• the char production rate at 600°C in air means when the cured resin is heated at a rate of 10°C/min from room temperature in an air atmosphere using a thermogravimetric measuring device to reach 600°C. This is the residual rate of thermal decomposition residue in .
• the lower limit of the char production rate is preferably 25% or more, more preferably 30% or more. Most preferably, the char production rate is 35% or more and less than 50%.
• the fiber-reinforced composite material of the present invention is a fiber-reinforced composite material consisting of a cured epoxy resin and reinforcing fibers, and the cured resin has a temperature at 25°C measured based on ASTM E1461-01 (2001).
• Thermal diffusivity is 0.17 mm 2 /s or more and less than 0.30 mm 2 /s, and the char formation rate at 600°C in air is 20% or more and less than 50%, and the thickness of the fiber reinforced composite material is 0.5 mm. It is at least 2 mm.
• the fiber-reinforced composite material of the present invention has an excellent heat dissipation effect in the thickness direction, so it is possible to exhibit the effect of improving fire resistance even when the thickness of the material is within the above range. .
• the epoxy resin composition in the present invention preferably contains an inorganic filler made of boron nitride or graphite as component [A] in addition to the epoxy resin.
• an inorganic filler made of graphite is more preferred. By adding such an inorganic filler, the thermal conductivity of the resin is improved.
• component [A] examples include scaly boron nitride, spherical graphite, scaly graphite, and scaly graphite. Among them, flaky graphite is particularly preferable because it is highly graphitized and has high thermal conductivity.
• These components [A], boron nitride and graphite, may be used alone as an inorganic filler, or both 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 volume average particle diameter of component [A] in the present invention as determined by a particle size distribution measuring device using a laser diffraction method is preferably 10 nm to 100 ⁇ m from the viewpoint of obtaining high thermal conductivity and mechanical properties, and more preferably 1 ⁇ m. ⁇ 20 ⁇ m.
• the content of component [A] in the present invention is preferably 0.5% to 50% by mass in the total epoxy resin composition, more preferably from the viewpoint of obtaining high thermal conductivity and mechanical properties. It is 1% by mass to 10% by mass.
• the epoxy resin composition of the present invention further includes, as component [B], an amine curing agent having a structure represented by the following general formula (1), and an amine curing agent having a structure represented by the following general formula (2). It is preferable that at least one amine curing agent selected from the group consisting of a curing agent and an amine curing agent having a structure represented by general formula (3) is included. By adding such an amine curing agent to the epoxy resin composition, char formation is promoted. In addition, it functions as a curing agent for epoxy resin, and a cured product with a high degree of curing can be obtained.
• R 1 represents a hydrocarbon group having 1 to 4 carbon atoms.
• R 2 represents a hydrogen atom or an amino group.
• the number of carbon atoms in R 1 decreases, the hydrophobicity of the amine curing agent having the structure represented by general formula (1) decreases, so the moisture absorption resistance of the resulting cured resin product decreases. It may decrease. Therefore, the number of carbon atoms in R 1 is preferably 4.
• hydrocarbon group having 1 to 4 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, and the like.
• Examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, etc. It will be done.
• R 3 to R 6 are preferably hydrogen atoms or groups having 1 carbon number, ie, methyl groups. Note that R 3 to R 6 do not all need to be the same.
• Examples of the amine curing agent having the structure represented by the general formula (1) as component [B] in the present invention include bis(4-aminophenyl)ethylphosphine oxide and bis(3-aminophenyl)ethylphosphine oxide.
• Examples of the amine curing agent having the structure represented by the general formula (2) include tris(4-aminophenyl)phosphine oxide, tris(3-aminophenyl)phosphine oxide, and tris(2-aminophenyl)phosphine oxide. , bis(4-aminophenyl)phenylphosphine oxide, bis(3-aminophenyl)phenylphosphine oxide, and the like.
• Examples of the amine curing agent having the structure represented by the general formula (3) include biphenylaralkyl aromatic amines in which R 3 to R 6 are hydrogen atoms (BAN, manufactured by Nippon Kayaku Co., Ltd.) and R Examples include biphenylaralkyl aromatic amines (BXN, manufactured by Nippon Kayaku Co., Ltd.) in which 3 to R 6 are methyl groups.
• tris(3-aminophenyl)phosphine oxide or bis(3-aminophenyl)phenylphosphine oxide is preferably used because of its excellent mechanical properties and heat resistance. Of these two compounds, the latter is more preferably used.
• the content of component [B] in the present invention is 10 to 100 parts by mass based on 100 parts by mass of the total amount of epoxy resin. It is preferred from the viewpoint of ensuring flame retardancy and mechanical properties, and more preferably 25 to 100 parts by mass.
• the phosphorus atom content in the epoxy resin composition is 0.
• a content of 1 to 5.0% by mass is preferable because the obtained cured product or fiber-reinforced composite material can have both flame retardancy and mechanical properties.
• the phosphorus atom content is preferably 0.3 to 4.0% by mass.
• the phosphorus atom content (mass %) here is determined by mass (g) of phosphorus atoms in the total epoxy resin composition/mass (g) of the total epoxy resin composition ⁇ 100.
• the mass of the phosphorus atom is determined by calculating the mass of the phosphorus atom per molecule of the compound of component [B] from the atomic weight of the phosphorus atom, and adding to this the mass of the phosphorus atom per molecule of the compound of component [B], which is added to the mass of the compound of component [B] contained in the entire epoxy resin composition. It is obtained by calculating the number of molecules from the number of moles and multiplying them.
• the epoxy resin composition of the present invention can also contain a curing agent other than the above component [B].
• the curing agent here is a curing agent for epoxy resin, and is a compound having an active group that can react with an epoxy group.
• Examples of 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, and tetramethylguanidine.
• thiourea-adducted amines carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, carboxylic acid hydrazides, carboxylic acid amides, polymercaptans, and Lewis acid complexes such as boron trifluoride ethylamine complex.
• carboxylic acid anhydrides such as methylhexahydrophthalic anhydride
• carboxylic acid hydrazides carboxylic acid amides
• polymercaptans and Lewis acid complexes
• Lewis acid complexes such as boron trifluoride ethylamine complex.
• the content of the curing agent other than the component [B] is 90 parts by mass or less based on 100 parts by mass of the total amount of the curing agent including the component [B] and the curing agent other than the component [B]. This is preferable because it makes it easier to ensure the flame retardancy of cured products and fiber-reinforced composite materials.
• the epoxy resin composition of the present invention can contain a difunctional glycidylamine type epoxy resin as component [C] in order to impart excellent flame retardance and mechanical properties to the resulting cured resin product.
• aniline compounds are preferably used. It is particularly preferable to use the epoxy resin component [C] represented by the following general formula (4) as the aniline compound because a cured resin product having excellent heat resistance, flame retardance, and mechanical properties can be obtained.
• R 7 represents one selected from a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a halogen atom, an acyl group, a trifluoromethyl group, and a nitro group.
• X represents a hydrogen atom or a substituent having a ring structure of 4 or more members.
• substituents having a ring structure of 4 or more members include phenyl group, 1-naphthyl group, 2-naphthyl group, phenoxy group, 1-naphthoxy group, 2-naphthoxy group, biphenyl group, phenylsulfonyl group, benzyl group. Examples include groups.
• R 7 is an aliphatic hydrocarbon group
• R 7 is a hydrogen atom or a methyl group.
• R 7 is a halogen atom such as Br or Cl.
• X is preferably a substituent having one benzene ring, from the viewpoint that as the number of carbon atoms increases, the viscosity of the resin composition may increase and become difficult to handle, and from the viewpoint of flame retardancy.
• component [C] include N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, N,N-diglycidyl-m-toluidine, N,N-diglycidyl-p-toluidine, and N,N-diglycidyl-p-toluidine.
• Monoamine type epoxy resins such as diglycidyl-2,3-xylidine, N,N-diglycidyl-2,4-xylidine, N,N-diglycidyl-3,4-xylidine, and N,N-diglycidyl-4-phenoxyaniline Can be mentioned.
• N,N-diglycidylaniline and N,N-diglycidyl-4-phenoxyaniline are particularly preferred because they have excellent flame retardancy and mechanical properties.
• These epoxy resins as component [C] may be used alone or in combination of two or more.
• the content of component [C] in the present invention is preferably 10 to 60 parts by mass based on 100 parts by mass of the total amount of epoxy resin in order to ensure excellent heat resistance and mechanical properties. More preferably, it is 25 to 40 parts by mass.
• the epoxy resin composition of the present invention can also contain the following epoxy resins other than the above component [C].
• epoxy resins other than the above component [C].
• bisphenol type epoxy resins having less than two functional groups bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, epoxy resins having a biphenyl skeleton, Examples include epoxy resins having a naphthalene skeleton and epoxy resins having a dicyclopentadiene skeleton.
• N,N,O-triglycidyl-m-aminophenol N,N,O-triglycidyl-p-aminophenol
• N,N,O-triglycidyl-4-amino- Examples include aminophenol type epoxy resins such as 3-methylphenol.
• N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane N,N,N',N'-tetraglycidyl-2,2'-diethyl-4,4 Examples include diamine type epoxy resins such as '-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-m-xylylenediamine.
• the epoxy resin composition of the present invention is used to control the tackiness of the obtained prepreg, to control the fluidity of the resin when impregnating reinforcing fibers with the epoxy resin composition, and to impart toughness to the obtained fiber reinforced composite material.
• the epoxy resin composition may further contain a thermoplastic resin soluble in component [D].
• the thermoplastic resin of component [D] is preferably a thermoplastic resin having a polyarylether skeleton. Specific examples include polysulfone, polyphenylsulfone, polyethersulfone, polyetherimide, polyphenylene ether, polyetheretherketone, polyetherethersulfone, and the like. These thermoplastic resins having a polyarylether skeleton may be used alone or in appropriate combinations. Among them, polyether sulfone and polyetherimide can be preferably used because they can impart toughness to the resulting fiber-reinforced composite material without deteriorating its heat resistance or mechanical properties.
• the blending amount of component [D] in the present invention is preferably 5 to 40 parts by weight, more preferably 10 to 35 parts by weight, even more preferably 14 to 30 parts by weight, based on 100 parts by weight of the total amount of epoxy resin. be.
• the viscosity of the epoxy resin composition at 80° C. is preferably in the range of 0.5 to 200 Pa ⁇ s from the viewpoint of tack and drape of the prepreg. If the viscosity at 80° C. is less than 0.5 Pa ⁇ s, excessive resin flow tends to occur during molding of the fiber-reinforced composite material, resulting in large variations in the basis weight of the reinforcing fibers. In addition, if the viscosity at 80°C exceeds 200 Pa ⁇ s, it becomes difficult to impregnate the reinforcing fibers with the epoxy resin composition when producing prepreg, and voids are likely to occur in the resulting fiber reinforced composite material.
• the strength of the reinforced composite material is likely to decrease.
• the viscosity at 80° C. here is determined by the following method. That is, using a dynamic viscoelasticity measuring device such as ARES:TA Instruments Japan, using flat parallel plates with a diameter of 40 mm, epoxy resin was placed between the upper and lower plates so that the distance between the plates was 1 mm. After setting the composition and confirming that it reached 40°C, measurement was performed by simple heating in torsion mode (angular frequency: 3.14 rad/s) at a heating rate of 1.5°C/min until the temperature reached 80°C. Let us calculate the complex viscosity ⁇ * at the time when the temperature reaches °C.
• the epoxy resin composition according to the present invention contains particles containing a thermoplastic resin as a main component (thermoplastic resin particles) as component [E] in order to improve the impact resistance of the fiber-reinforced composite material obtained. It is preferable. Such thermoplastic resin particles are insoluble in the epoxy resin composition, and remain as particles even after the epoxy resin composition is made into a prepreg and further made into a fiber-reinforced composite material.
• the particles whose main component is a thermoplastic resin here refer to particles in which the mass percentage of thermoplastic resin is the highest among the components constituting the particles, and thermoplastic resin particles consisting only of a thermoplastic resin. Also included.
• Polyamide is the most preferable material for the thermoplastic resin particles, and among polyamides, polyamide 12, polyamide 6, polyamide 11, polyamide 66, polyamide 6/12 copolymer, and polyamide (semi-IPN) made of epoxy resin and semi-IPN are most preferable.
• IPN polyamide is preferred. By using particles made of epoxy resin and semi-IPN polyamide, it is possible to impart excellent heat resistance and impact resistance to the prepreg.
• IPN is an abbreviation for interpenetrating polymer network, which is a type of polymer blend, in which the blend component polymers are cross-linked polymers, and each different type of cross-linked polymer is partially or It refers to something that is intertwined with each other to form a multi-network structure.
• Semi-IPN is one in which a heavy network structure is formed by a cross-linked polymer and a linear polymer.
• Semi-IPN thermoplastic resin particles can be obtained, for example, by dissolving a thermoplastic resin and a thermosetting resin in a common solvent, mixing them uniformly, and then re-precipitating the mixture.
• semi-IPN polyamide particles can be obtained by the method described in Example 1 of JP-A-1-104624.
• thermoplastic resin particles may be spherical particles, non-spherical particles, or porous particles, but spherical particles have better viscoelasticity because they do not reduce the flow characteristics of the resin, and there is no starting point for stress concentration. This is a preferred embodiment in that it provides high impact resistance.
• Commercially available polyamide particles include SP-500, SP-10, TR-1, TR-2, 842P-48, 842P-80, "Trepearl (registered trademark)” TN (manufactured by Toray Industries, Inc.), “Orgasol (registered trademark)” 1002D, 2001UD, 2001EXD, 2002D, 3202D, 3501D, 3502D (all manufactured by Arkema), etc. can be used. These polyamide particles may be used alone or in combination.
• the epoxy resin composition of the present invention may contain components other than the above, such as coupling agents, thermosetting resin particles, silica gel, carbon black, clay, carbon nanotubes, graphene, etc., to the extent that the effects of the present invention are not impaired.
• Inorganic fillers such as carbon particles and metal powder can be blended.
• the prepreg of the present invention is made by impregnating reinforcing fibers with the epoxy resin composition of the present invention. That is, the above-mentioned epoxy resin composition is used as a matrix resin, and this epoxy resin composition is composited with reinforcing fibers.
• Preferred examples of reinforcing fibers include carbon fibers, graphite fibers, aramid fibers, and glass fibers. Among them, carbon fiber is particularly preferred from the viewpoint of mechanical properties.
• Commercially available carbon fiber products include “Torayca (registered trademark)” T700SC-24K, “Torayca (registered trademark)” “T800SC-24K”, and “Torayca (registered trademark)” “T1100GC-24K” (manufactured by Toray Industries, Inc.). Can be mentioned.
• the prepreg of the present invention can be produced by various known methods, such as a wet method or a hot melt method.
• the hot-melt method is preferable in that it easily exhibits the effects of the present invention.
• the hot melt method is a method in which the viscosity of the matrix resin is reduced by heating without using a solvent, and the matrix resin is impregnated into reinforcing fibers.
• the hot-melt method involves directly impregnating reinforcing fibers with a matrix resin whose viscosity has been reduced by heating, or by first creating a release paper sheet with a resin film by coating the matrix resin on release paper, etc., and then There is a method of stacking the reinforcing fibers from both sides or one side and applying heat and pressure to impregnate the reinforcing fibers with the matrix resin.
• the reinforcing fiber has a basis weight of 100 to 1000 g/m 2 . If the reinforcing fiber basis weight is less than 100 g/m 2 , it is necessary to increase the number of sheets to be laminated to obtain a predetermined thickness when molding the fiber-reinforced composite material, and the lamination work may become complicated. On the other hand, when the reinforcing fiber basis weight exceeds 1000 g/m 2 , the drapeability of the prepreg tends to deteriorate. Further, the fiber mass content of the prepreg is preferably 40 to 90% by mass, more preferably 50 to 80% by mass.
• the fiber mass content is less than 40% by mass, the ratio of resin is too high, so the excellent mechanical properties of the reinforcing fibers cannot be taken advantage of, and the amount of heat generated during curing of the fiber reinforced composite material may become too high. There is sex. Furthermore, if the fiber mass content exceeds 90% by mass, poor resin impregnation occurs, and the resulting fiber-reinforced composite material may have many voids.
• the form of the prepreg of the present invention may be any of UniDirection (UD) prepregs, woven prepregs, nonwoven fabric prepregs such as sheet molding compounds, etc.
• UD UniDirection
• the first aspect of the fiber-reinforced composite material of the present invention is a fiber-reinforced composite material obtained by curing the prepreg of the present invention.
• a fiber-reinforced composite material can be obtained, for example, by laminating the prepregs of the present invention in a predetermined form and then applying heat and pressure to harden the matrix resin.
• known methods such as an autoclave molding method, a press molding method, a bagging molding method, a wrapping tape method, and an internal pressure molding method can be used.
• a second embodiment of the fiber-reinforced composite material of the present invention is a fiber-reinforced composite material containing a cured resin obtained by curing the epoxy resin composition of the present invention and reinforcing fibers.
• a fiber-reinforced composite material can be obtained by directly impregnating a reinforcing fiber base material with a liquid epoxy resin and curing it, without using prepreg.
• such a fiber-reinforced composite material can be obtained by, for example, a resin transfer molding method, a filament winding method, a pultrusion method, a hand layup method, or the like.
• the thickness of the fiber reinforced composite material of the present invention is 0.5 mm or more and less than 2 mm, preferably 0.5 mm or more and less than 1 mm.
• the thickness of the fiber-reinforced composite material is less than 0.5 mm, flame tends to propagate in the vertical direction of the material, and fire resistance tends to deteriorate.
• the thickness is 2 mm or more, the weight of the member becomes too large and the weight of the structural member cannot be reduced sufficiently.
• the material is thick, it becomes difficult for flame to propagate in the vertical direction even without using the fiber-reinforced composite material of the present invention, so the fire-resistant effect of the fiber-reinforced composite material of the present invention cannot be utilized. That is, the fiber-reinforced composite material of the present invention is characterized in that it has sufficient fire resistance even when the thickness is reduced.
• the fiber reinforced composite material of the present invention preferably has a surface combustion length of 10 mm or more and less than 50 mm in the JIS T8022 flame propagation test (method A (surface ignition), 50 seconds of flame contact). More preferably, it is 10 mm or more and less than 46 mm. Further, the length of damage on the back surface is preferably 10 mm or more and less than 60 mm. More preferably, it is 10 mm or more and less than 56 mm.
• the surface combustion length referred to herein is the maximum length in the vertical direction of the region where the resin has decomposed on the flame-contacting surface of the measurement sample, and this region does not include the soot-attached portion.
• the back surface damage length referred to herein is the maximum length in the vertical direction of the discolored region on the surface of the measurement sample on the side opposite to the flame contact side.
• BF-3AK volume average particle diameter 3 ⁇ m
• CBR volume average particle diameter 18 ⁇ m
• ⁇ Component [B] Amine curing agent having a structure represented by general formula (2)> ⁇ Bis(3-aminophenyl)phenylphosphine oxide (BAPPO, manufactured by Katayama Chemical Industry Co., Ltd.) ⁇ Tris(3-aminophenyl)phosphine oxide (TAPPO, manufactured by Katayama Chemical Industry Co., Ltd.) ⁇ Component [B]: Amine curing agent having a structure represented by general formula (3)> ⁇ Biphenylaralkyl aromatic amine (BAN) ⁇ Biphenylaralkyl aromatic amine (BXN) ⁇ Curing agent other than component [B]> -4,4'-diaminodiphenylsulfone (Seika Cure S, manufactured by Wakayama Seika Kogyo Co., Ltd.).
• ⁇ Component [C] Epoxy resin having a structure represented by general formula (4)> ⁇ N,N-diglycidylaniline (GAN, manufactured by Nippon Kayaku Co., Ltd.) ⁇ N,N-diglycidyl-4-phenoxyaniline (TOREP A-204E, manufactured by Toray Fine Chemical Co., Ltd.) ⁇ Epoxy resin other than component [C]> ⁇ Bisphenol A epoxy resin (“jER (registered trademark)” 825, manufactured by Mitsubishi Chemical Corporation) ⁇ N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane ("Araldite (registered trademark)” MY721, manufactured by Huntsman Advanced Materials) - N,N,O-triglycidyl-p-aminophenol (“Araldite (registered trademark)” MY510, manufactured by Huntsman Advanced Materials).
• thermoplastic resin Particles containing thermoplastic resin as main component> ⁇ Polyamide particles (“Trepearl (registered trademark)” TN, manufactured by Toray Industries, Inc.) ⁇ Other ingredients> ⁇ Red phosphorus (“Novared (registered trademark)” 120UF, manufactured by Rin Kagaku Kogyo Co., Ltd.) - Carbon fiber (“Torayka (registered trademark)” T800SC-24K manufactured by Toray Industries, Inc.).
• the temperature of the resin composition in the kneading device is lowered to 80°C or less, and then it is charged into the kneading device before adding the curing agent. and stirred.
• the epoxy resin composition prepared in (1) After defoaming the epoxy resin composition prepared in (1) in vacuum, it is cured under predetermined curing conditions in a mold set to a thickness of 2 mm with a 2 mm thick "Teflon (registered trademark)" spacer. In this way, a cured epoxy resin product with a thickness of 2 mm was obtained.
• Flame retardancy was evaluated using a thermogravimetric measuring device TG-DSC (PerkinElmer STA6000 system). Approximately 10 mg of test pieces were cut out from the cured epoxy resin, and the temperature was simply raised at a temperature increase rate of 10° C./min in air, and the char formation rate (%) at 600° C. was used as an index of flame retardancy.
• the char production rate here is a value expressed by (mass (g) of thermal decomposition residue at 600° C.)/(mass (g) of cured epoxy resin before measurement) ⁇ 100.
• the cured epoxy resin produced in (2) was cut into a size of 10 mm x 10 mm square, and the surface was blackened using Black Guard Spray (manufactured by Fine Chemical Japan Co., Ltd.) to prepare measurement samples.
• the thermal diffusivity of the sample at 25° C. was measured based on ASTM E1461-01 (2001) using a thermal diffusivity measuring device LFA467HyperFlash (manufactured by NETZSCH).
• the cured epoxy resin product prepared in (2) was cut into a 10 mm x 60 mm square size to prepare a test piece. Based on JIS K7171 (2006), using an Instron 5565 universal testing machine (manufactured by Instron), the test was carried out under the conditions of crosshead speed 2.5 mm/min, span length 40 mm, indenter diameter 10 mm, and fulcrum diameter 4 mm. A three-point bending test was performed on the test piece, and the bending elastic modulus was measured.
• Examples 1 to 14, Comparative Examples 1 to 5 An epoxy resin composition was prepared using each component in the proportions (parts by mass) shown in Tables 1 to 3 according to the above method (1) for preparing an epoxy resin composition.
• the obtained epoxy resin composition was cured at a temperature of 180° C. for 2 hours, and the char production rate and thermal diffusivity of the cured resin product were measured.
• the evaluation results are shown in Tables 1 to 3.
• Example 15 In a kneading device, 9.5 parts by mass of flaky graphite (component [A]), 35 parts by mass of N,N-diglycidylaniline (GAN) (component [C]), and 65 parts by mass of tetraglycidyldiaminodiphenylmethane ( After kneading and dissolving epoxy resins other than component [C] and 19 parts by mass of "VIRANTAGE (registered trademark)" VW-10700RFP (component [D]), 28 parts by mass of bis(3-aminophenyl)phenyl Phosphine oxide (BAPPO) (component [B]) and 33 parts by mass of 4,4'-diaminodiphenylsulfone were added and kneaded to prepare a primary resin composition.
• component [A] flaky graphite
• GAN N,N-diglycidylaniline
• BAPPO bis(3-aminophenyl)
• This primary resin composition does not contain particles whose main component is a thermoplastic resin (component [E]).
• the 80°C viscosity of the obtained primary resin composition was 15.5 Pa ⁇ s.
• the obtained primary resin composition was coated onto a release paper using a knife coater at a resin basis weight of 29 g/m 2 to produce a primary resin film.
• This primary resin film was set in a prepreg making machine, and superimposed on both sides of carbon fibers (fabric weight: 190 g/m 2 ) aligned in one direction to be impregnated with the primary resin composition to obtain a primary prepreg.
• thermoplastic resin A secondary resin composition whose composition was adjusted by adding component [E]) was prepared.
• the secondary resin composition was coated onto a release paper using a knife coater at a resin basis weight of 20 g/m 2 to produce a secondary resin film.
• This secondary resin film was laminated and pasted on both sides of the primary prepreg to obtain a final prepreg.
• the surface burning length and the back surface damage length of the obtained prepreg were measured according to the method described in (6) Flame retardancy evaluation of carbon fiber reinforced composite materials (flame propagation test) above. The results are shown in Table 4.
• Example 15 (Comparative example 6) In Example 15, the blending amount of flaky graphite (component [A]) was set to 0 parts by mass, and the amount of "Trepearl (registered trade)" TN (particles mainly composed of thermoplastic resin) in the entire resin composition (component [A]) was set to 0 parts by mass. Example 15 was carried out in the same manner as in Example 15, except that the composition shown in Table 4 was made so that the mass % of E])) and the mass % of "VIRANTAGE (registered trademark)" VW-10700RFP (component [D]) were constant. A prepreg was produced. The surface burning length and the back surface damage length of the obtained prepreg were measured according to the method described in (6) Flame retardancy evaluation of carbon fiber reinforced composite materials (flame propagation test) above. The results are shown in Table 4.
• Example 7 the amount of bis(3-aminophenyl)phenylphosphine oxide (BAPPO) (component [B]) was set to 0 parts by mass, and the mass of flaky graphite (component [A]) in the entire resin composition was %, mass % of "TREPEARL (registered trademark)" TN (particles mainly composed of thermoplastic resin (component [E])) and mass % of "VIRANTAGE (registered trademark)" VW-10700RFP (component [D])
• the composition shown in Table 4 was made so that the ratio H/E of the active hydrogen mole number (H) of the curing agent to the epoxy group mole number (E) in the epoxy resin was constant.
• a prepreg was produced in the same manner as in Example 15 except for this.
• the 80°C viscosity of the obtained primary resin composition was 9.1 Pa ⁇ s.
• the surface burning length and the back surface damage length of the obtained prepreg were measured according to the method described in (6) Flame retardancy evaluation of carbon fiber reinforced composite materials (flame propagation test) above. The results are shown in Table 4.

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