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WO2020071360A1 - Composé de moulage de feuille, matériau composite renforcé par des fibres et procédé de production d'un matériau composite renforcé par des fibres - Google Patents

Composé de moulage de feuille, matériau composite renforcé par des fibres et procédé de production d'un matériau composite renforcé par des fibres

Info

Publication number
WO2020071360A1
WO2020071360A1 PCT/JP2019/038739 JP2019038739W WO2020071360A1 WO 2020071360 A1 WO2020071360 A1 WO 2020071360A1 JP 2019038739 W JP2019038739 W JP 2019038739W WO 2020071360 A1 WO2020071360 A1 WO 2020071360A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
epoxy resin
molecular weight
molding compound
sheet molding
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/038739
Other languages
English (en)
Japanese (ja)
Inventor
明宏 花房
智 太田
隼人 小笠原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to JP2019556378A priority Critical patent/JP6835253B2/ja
Publication of WO2020071360A1 publication Critical patent/WO2020071360A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • 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
    • 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

Definitions

  • the present invention relates to a sheet molding compound, a fiber-reinforced composite material, and a method for producing a fiber-reinforced composite material.
  • Fiber-reinforced composite materials are lightweight, high-strength, and highly rigid, and thus are used in sports and leisure applications such as fishing rods and golf shafts; and in a wide range of industrial applications such as automobiles and aircraft. Used in.
  • FRP Fiber-reinforced composite materials
  • an intermediate material for FRP containing a reinforcing fiber and a matrix resin is suitably used. After cutting the FRP intermediate material into a desired shape, shaping and curing in a mold, an FRP molded product can be obtained.
  • Intermediate materials for FRP include prepregs using long fibers as reinforcing fibers; sheet molding compounds using short fibers as reinforcing fibers (hereinafter, also referred to as “SMC”). Since SMC contains short fibers, it is excellent in fluidity and moldability as compared with prepreg.
  • a method for producing an FRP by molding an intermediate material for FRP there are an autoclave molding method, a filament wind molding method, a resin injection molding method, a vacuum resin injection molding method, a press molding method and the like.
  • the press molding method has high productivity, and the FRP having an excellent design surface is easily obtained, so that the demand for the press molding method is increasing.
  • thermosetting resin a resin composition containing a thermosetting resin is often used from the viewpoint of excellent impregnation into reinforcing fibers and heat resistance after curing.
  • thermosetting resin a phenol resin, a melamine resin, a bismaleimide resin, an unsaturated polyester resin, an epoxy resin, or the like is used.
  • epoxy resin composition a resin composition containing an epoxy resin (hereinafter, also referred to as “epoxy resin composition”) is excellent in moldability and heat resistance after curing, and is capable of obtaining an FRP capable of exhibiting high mechanical properties. Therefore, it is suitable as a matrix resin.
  • An epoxy resin composition comprising a mixture of a bisphenol F-type epoxy resin and a polyfunctional epoxy resin, an acid anhydride, a Lewis acid salt (a boron trichloride amine complex), and an organic aluminum compound (Patent Document 1).
  • Patent Document 2 An epoxy resin composition mainly containing an epoxy resin, a curing agent having an activation temperature of 20 to 100 ° C., and a curing agent having an activation temperature of 100 to 200 ° C.
  • Patent Document 2 An epoxy resin composition mainly containing an epoxy resin, a curing agent having an activation temperature of 20 to 100 ° C., and a curing agent having an activation temperature of 100 to 200 ° C.
  • the epoxy resin composition of Patent Document 2 includes two types of curing agents having different activation temperatures. Therefore, a curing agent having a low activation temperature reacts at room temperature to increase the viscosity, and when heated after increasing the viscosity at room temperature, a curing agent having a high activation temperature reacts and cures.
  • the following characteristics are required for the matrix resin used for the SMC. -To have an appropriate tackiness (adhesiveness) in order to ensure handling workability as an intermediate material for FRP during press molding. -It has high mechanical properties and heat resistance after curing because it is molded in a short time and at high temperature in the press molding method. -It must have appropriate fluidity to enable complex molding of ribs and bosses in the press molding method. -In order to increase the productivity during press molding, it is necessary to suppress the generation of burrs (unnecessary portions formed at the ends of the molded product due to the resin flowing into the gaps of the mold during the press molding and solidifying). -Having high mechanical properties and heat resistance after curing in order to obtain FRP having high mechanical properties and heat resistance.
  • the present invention provides a sheet molding compound that is excellent in handling workability and fluidity of a matrix resin at the time of press molding, can suppress generation of burrs, and can obtain a fiber-reinforced composite material having excellent mechanical properties and heat resistance.
  • a fiber reinforced composite material using the sheet molding compound and a method for producing the fiber reinforced composite material is excellent in handling workability and fluidity of a matrix resin at the time of press molding, can suppress generation of burrs, and can obtain a fiber-reinforced composite material having excellent mechanical properties and heat resistance.
  • the present invention has the following aspects.
  • [1] comprising an epoxy resin composition and a reinforcing fiber, A sheet molding compound, wherein the epoxy resin composition comprises the following component (A), the following component (B), and the following component (C), and the proportion of a tetrahydrofuran-insoluble component of the epoxy resin component is less than 50% by mass.
  • Component (A) an epoxy resin component having a peak top molecular weight of 500 or less.
  • Component (B) an epoxy resin component having a peak top molecular weight of more than 500 to 10,000 or less and a ratio represented by weight average molecular weight / number average molecular weight of 1.2 or more.
  • Component (C) an epoxy resin curing agent.
  • a sheet capable of obtaining a fiber reinforced composite material having excellent handling workability, excellent fluidity of a matrix resin at the time of press molding, suppression of burrs, and excellent mechanical properties and heat resistance. Molding compound; a fiber reinforced composite material using the sheet molding compound and a method for producing the fiber reinforced composite material.
  • Weight average molecular weight is each gel permeation chromatography (hereinafter, referred to as polystyrene as a standard substance) using tetrahydrofuran (hereinafter also referred to as "THF”) as an eluent. This is a value measured by “GPC”.
  • the peak top molecular weight is a molecular weight corresponding to the maximum value of peak intensity in a chromatogram showing the relationship between retention time and peak intensity, measured by GPC using an RI (differential refractive index) detector.
  • the weight average molecular weight is also referred to as “Mw”
  • the number average molecular weight is also referred to as “Mn”
  • the peak top molecular weight is also referred to as “Mp”.
  • the “molecular weight distribution curve” is a differential molecular weight distribution curve obtained by GPC using the eluent of the epoxy resin component as THF and the standard substance as polystyrene. The GPC measurement is performed on the THF-soluble component of the epoxy resin component. The detailed measuring method is as shown in the examples.
  • the “tetrahydrofuran-insoluble matter” is a component that does not dissolve in THF at room temperature (23 ° C.).
  • tetrahydrofuran-soluble component is a component that is soluble in THF at room temperature (23 ° C.). More specifically, it is a component that does not precipitate when centrifugation is performed in the method for measuring the proportion of THF-insoluble content shown in Examples described later.
  • Liquid at 25 ° C.” means liquid at 25 ° C. and 1 atm.
  • Solid at 25 ° C.” means a solid at 25 ° C. and 1 atm.
  • epoxy resin is a compound having two or more epoxy groups in a molecule.
  • Acid anhydride is a compound having an acid anhydride group.
  • An “acid anhydride group” is a group having a structure in which one water molecule has been removed from two acid groups (such as a carboxy group).
  • “Hydrogenated phthalic anhydride” is a compound in which some or all of the unsaturated carbon bonds on the benzene ring of phthalic anhydride have been replaced by saturated carbon bonds.
  • Sheet molding compound” and “SMC” are sheet-like molding materials containing short fiber reinforcing fibers and a thermosetting resin. “Burr” is an unnecessary portion formed at an end portion of a molded product due to the epoxy resin composition flowing into the gap of the mold during the SMC press molding and solidifying. "-" Indicating a numerical range means that the numerical values described before and after the numerical range are included as the lower limit and the upper limit.
  • One embodiment of the present invention is a sheet molding compound (SMC) including an epoxy resin composition and a reinforcing fiber.
  • the epoxy resin composition contains the following component (A), the following component (B), and the following component (C).
  • the epoxy resin composition may further include other components as needed, as long as the effects of the present invention are not impaired.
  • Component (A) an epoxy resin component having an Mp of 500 or less.
  • Component (B) an epoxy resin component having Mp of more than 500 and 10,000 or less and a ratio represented by Mw / Mn of 1.2 or more.
  • Component (C) an epoxy resin curing agent.
  • Component (A) is an epoxy resin component having an Mp of 500 or less.
  • the component (A) is a component that adjusts the viscosity of the epoxy resin composition constituting the SMC of the present invention, and enhances the impregnation of the epoxy resin composition into the reinforcing fibers.
  • the component (A) may have two or more Mp within the above numerical range.
  • the lower limit of Mp of component (A) is not particularly limited, but is, for example, 100.
  • the Mw of the component (A) is preferably 500 or less, more preferably 400 or less. Although the lower limit of Mw of the component (A) is not particularly limited, it is, for example, 200.
  • the above lower limit and upper limit can be arbitrarily combined.
  • glycidyl ether of a bisphenol compound bisphenol A, bisphenol F, bisphenol AD, a halogen-substituted product thereof, etc.
  • glycidyl of a polyhydric phenol compound obtained by a condensation reaction between a phenol compound and an aromatic carbonyl compound Ethers glycidyl ethers of polyhydric alcohol compounds (such as polyoxyalkylene bisphenol A and alkanediol); and polyglycidyl compounds derived from aromatic amine compounds.
  • alkanediol a linear alkanediol having 4 to 8 carbon atoms is preferable. Specific examples include 1,6-hexanediol and the like.
  • Component (A) contains a bisphenol-type epoxy resin because it is easy to adjust the viscosity of the epoxy resin composition to a viscosity suitable for impregnating the reinforcing fibers, and it is easy to adjust the mechanical properties of FRP to a desired range. Is preferred.
  • a bisphenol type epoxy resin a bifunctional bisphenol type epoxy resin is preferable.
  • the bisphenol A type epoxy resin is more preferable because the heat resistance of FRP is further excellent and the chemical resistance is also excellent.
  • a bisphenol F type epoxy resin is more preferable because it has a lower viscosity than a bisphenol A type epoxy resin having a similar molecular weight and a higher elastic modulus of FRP.
  • bifunctional bisphenol-type epoxy resin means a bisphenol-type epoxy resin having two epoxy groups in a molecule.
  • JER registered trademark
  • Component (A) may include a trifunctional or higher functional epoxy resin.
  • the heat resistance of the fiber-reinforced composite material can be further improved without greatly changing the viscosity of the epoxy resin composition.
  • the trifunctional or higher epoxy resin include a trifunctional epoxy resin and a tetrafunctional epoxy resin.
  • trifunctional epoxy resin means a resin having three epoxy groups in the molecule.
  • tetrafunctional epoxy resin means a resin having four epoxy groups in a molecule.
  • a glycidylamine-based epoxy resin such as TETRAD-X described above is preferable.
  • the change over time in the viscosity of the epoxy resin composition can be accelerated. That is, by adjusting the content of the glycidylamine-based epoxy resin, it is possible to obtain an epoxy resin composition having a desired molecular weight distribution in a short time, and to enhance productivity when preparing the epoxy resin composition. Can be.
  • the component (A) one type may be used alone, or two or more types may be used in combination.
  • Component (B) is an epoxy resin component having an Mp of more than 500 and not more than 10,000.
  • Component (B) is a component that enhances the fluidity of the SMC of the present invention during press molding and enhances the mechanical properties of the molded product.
  • Component (B) may have two or more Mp within the above numerical range.
  • the Mp of the component (B) is preferably from 700 to 5,000, more preferably from 900 to 3,000, further preferably from 1,000 to 2,000, and particularly preferably from 1,100 to 1,500.
  • the above lower limit and upper limit can be arbitrarily combined.
  • the viscosity of the epoxy resin composition is appropriately high.
  • the reinforcing fibers and the epoxy resin composition are not easily separated during the press molding of SMC. Therefore, the reinforcing fibers reach the end of the molded article, and the mechanical properties of the molded article tend to be excellent.
  • the SMC during press molding of SMC Has good fluidity, and tends to be excellent in moldability of complicated shapes such as ribs and bosses.
  • the Mw of the component (B) is preferably more than 500 and not more than 10,000, more preferably 1,000 to 7,000, further preferably 1,500 to 5,000, and particularly preferably 2,000 to 4,000.
  • the above lower limit and upper limit can be arbitrarily combined.
  • the Mw of the component (B) is more than 500, more preferably 1,000 or more, still more preferably 1,500 or more, particularly preferably 2,000 or more
  • the SMC of the present invention tends to have an appropriate tackiness. is there.
  • Mw is 10,000 or less, more preferably 7,000 or less, still more preferably 5,000 or less, and particularly preferably 4,000 or less
  • the difference represented by (Mw of component (B)) ⁇ (Mw of component (A)) is preferably 1,000 or more, more preferably 2,000 or more.
  • the ratio represented by Mw / Mn of the component (B) is 1.2 or more.
  • the SMC of the present invention can be given an appropriate tackiness.
  • This Mw / Mn is preferably from 1.5 to 8, more preferably from 1.6 to 4, and still more preferably from 1.7 to 3.5.
  • the above lower limit and upper limit can be arbitrarily combined.
  • Mw / Mn is 1.2 or more, preferably 1.5 or more, more preferably 1.6 or more, and still more preferably 1.7 or more
  • stickiness is less likely to occur while maintaining excellent tackiness of the SMC.
  • Mw / Mn is preferably 8 or less, more preferably 4 or less, and still more preferably 3.5 or less, the SMC tends to be sufficiently soft to facilitate processing such as cutting.
  • component (B) for example, a compound having a functional group capable of reacting with the component (A) (hereinafter, also referred to as “reactive functional group”) (hereinafter, also referred to as “component (D)”). )).
  • component (B) is a reaction product of component (D) and component (A)
  • the epoxy resin composition typically comprises component (A), component (D) and component (C).
  • This is a thickened material of a raw material mixture obtained by mixing raw materials. The content of the component (A) in the thickened material is such that when the component (D) reacts with the component (A), a part of the component (A) remains without reacting with the component (D). is there.
  • component (A) and component (D) having an appropriate molecular weight distribution is generated in SMC.
  • the raw material mixture thickens with the generation of the component (B).
  • the reactive functional group of the component (D) include a functional group that reacts with an epoxy group.
  • the reactive functional group of the component (D) may be a functional group that reacts with a functional group other than the epoxy group.
  • the reactive functional group include an acid anhydride group, an amino group, and an isocyanate group.
  • Component (D) may have two or more reactive functional groups of different types.
  • Component (D) preferably has two or more reactive functional groups in the molecule. The upper limit of the number of reactive functional groups that the component (D) has in the molecule is, for example, four.
  • Component (D) is preferably a compound that is liquid at 25 ° C.
  • the composition containing the component (A), the component (D), and the component (C) can be easily impregnated into the reinforcing fiber at room temperature, and SMC with few voids can be produced.
  • the reaction with the component (A) easily proceeds uniformly, and the molecular weight and structure of the component (B) are easily controlled.
  • component (D) is an acid anhydride. That is, one preferred embodiment of the component (B) is a reaction product of an acid anhydride and the component (A). When the component (B) is a reaction product of the acid anhydride and the component (A), the reaction at the time of thickening is easy to control, and the thickening stability is excellent.
  • the acid anhydride is preferably liquid at 25 ° C.
  • the acid anhydride examples include a cyclic acid anhydride having a structure in which one or one or more water molecules are removed from two or more acid groups (such as a carboxy group) in the molecule. it can.
  • These cyclic anhydrides include compounds having one or more cyclic anhydride groups in the molecule.
  • Compounds having one cyclic acid anhydride group in the molecule include, for example, dodecenyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylhydranhydride.
  • Compounds having two cyclic acid anhydride groups in the molecule include, for example, glyceryl bisanhydrotrimellitate monoacetate, ethylene glycol bisanhydrotrimellitate, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, , 2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, diphenyl-3,3 ′ , 4,4'-Tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3 -Yl) -tetralin-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrof
  • phthalic anhydride or a hydrogenated phthalic anhydride which may have a substituent is preferable from the viewpoints of thickening stability, heat resistance of a cured product of the epoxy resin composition, and mechanical properties.
  • the compound represented by the formula (1) or the compound represented by the following formula (2) is more preferable.
  • the acid anhydride a compound having two cyclic acid anhydride groups in the molecule is preferable from the viewpoint of reducing the generation of burrs during press molding of SMC.
  • One kind of the acid anhydride may be used alone, or two or more kinds may be used in combination.
  • component (D) is an amine. That is, another preferred embodiment of the component (B) is a reaction product of an amine and the component (A). When the component (B) is a reaction product of the amine and the component (A), the reaction control at the time of thickening is easy, and the thickening stability is excellent.
  • the amine is preferably liquid at 25 ° C.
  • a primary amine having two alicyclic skeletons in the molecule is preferable from the viewpoint that the storage stability of the epoxy resin composition becomes good.
  • an alicyclic diamine having a substituent other than the amino group on the ⁇ -carbon of the amino group is preferable.
  • the substituent other than the amino group tends to inhibit the reaction of the active hydrogen of the amino group.
  • an alkyl group having 1 to 4 carbon atoms, a benzyl group, and a cyclohexyl group are preferable, and an alkyl group having 1 to 4 carbon atoms is preferable in view of prolonging the pot life of the epoxy resin composition. More preferred are a methyl group, an ethyl group and an isopropyl group.
  • a compound represented by the following formula (3) is preferable in view of having the above characteristics.
  • R 1 is a single bond, —CH 2 —, —C (CH 3 ) 2 —, —O— or —SO 2 —
  • R 2 , R 3 , R 4 and R 5 are each independently A hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Examples of the compound represented by the formula (3) include 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 3,3′-diethyl-4,4′-diaminodicyclohexylmethane, bis (4 -Amino-3-methyl-5-ethylcyclohexyl) methane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane and the like.
  • 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane is preferred from the viewpoint of the quick curing property of the epoxy resin composition.
  • One type of amine may be used alone, or two or more types may be used in combination.
  • an isocyanate can be used as the component (D). That is, another embodiment of the component (B) is a reaction product of the isocyanate and the component (A). Since the isocyanate and the component (A) react at room temperature, the component (B) can be obtained relatively easily.
  • Examples of the isocyanate include a polyisocyanate compound having two or more isocyanate groups in a molecule.
  • Examples of the polyisocyanate compound include methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, propane-1,3-diisocyanate, butane-1 , 4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2,2-dimethylpentane- 1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, octane-1,8-di
  • a bifunctional isocyanate compound or a trifunctional isocyanate compound is preferable because the storage stability of SMC and the heat resistance of the fiber-reinforced composite material as a cured product of SMC tend to be improved. More preferably, it is a bifunctional isocyanate compound, and further preferably, a bifunctional isocyanate compound having a skeleton selected from isophorone, benzene, toluene, diphenylmethane, naphthalene, norbornene, polymethylene polyphenylene polyphenyl, and hexamethylene.
  • polyisocyanate compound a commercially available product may be used.
  • Commercially available polyisocyanates include Lepranate MS, Lupranate MI, Lupranate M20S, Lupranate M11S, Lupranate M5S, Lupranate MP-102, Lupranate MM-103, Lupranate MB-301, Lupranate T -80 (manufactured by BASF INOAC Polyurethane Co., Ltd.), Takenate 500, Takenate 600 (manufactured by Mitsui Chemicals, Inc.), Burnock DN-902S, Burnock DN-955-S, Burnock DN-980S, Burnock DN-990- S, Barnock DN-992-S (manufactured by DIC Corporation), isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
  • commercially available polyisocyanate compounds are not limited to these examples.
  • the component (B) includes a structure represented by the following formula (4) (hereinafter, also referred to as “structure (4)”) as a part of the structure.
  • Structure (4) contains a rigid aromatic skeleton. Therefore, when the component (B) includes the structure (4) in a part of the structure, the cured product of the SMC has more excellent mechanical properties and heat resistance.
  • the component (B) containing the structure (4) contains, for example, at least one selected from the group consisting of phthalic anhydride which may have a methyl group and hydrogenated phthalic anhydride which may have a methyl group. It is obtained by reacting the component (D) with the component (A) containing a bifunctional bisphenol-type epoxy resin.
  • R 6 is a group represented by the following formula (41), (42) or (43).
  • X is a hydrogen atom or a methyl group.
  • the component (B) includes a structure represented by the following formula (5) (hereinafter, also referred to as “structure (5)”) as a part of the structure.
  • Structure (5) has many branched structures in the molecule. Therefore, when the component (B) includes the structure (5) as a part of the structure, the resin and the fiber are easily integrated and flow at the time of press molding, so that generation of burrs can be further suppressed. Further, since the structure has many crosslinking points when cured by heat, the mechanical properties of the cured product are further improved.
  • the component (B) containing the structure (5) contains, for example, at least one selected from the group consisting of phthalic anhydride which may have a methyl group and hydrogenated phthalic anhydride which may have a methyl group. It is obtained by reacting the component (D) with the component (A) containing a glycidylamine-based epoxy resin such as the above-mentioned TETRAD-X.
  • R 6 is a group represented by the above formula (41), (42) or (43).
  • the component (B) includes a structure represented by the following formula (6) (hereinafter, also referred to as “structure (6)”) as a part of the structure.
  • Structure (6) contains a rigid aromatic skeleton. Therefore, when the component (B) includes the structure (6) in a part of the structure, the cured product of the SMC has further excellent mechanical properties and heat resistance.
  • the component (B) containing the structure (6) is obtained, for example, by reacting the component (D) containing the compound represented by the formula (3) with the component (A) containing a bifunctional bisphenol-type epoxy resin. can get.
  • R 1 is a single bond, —CH 2 —, —C (CH 3 ) 2 —, —O— or —SO 2 —
  • R 2 , R 3 , R 4 and R 5 are each independently A hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • component (B) includes a structure represented by the following formula (7) (hereinafter, also referred to as “structure (7)”) as a part of the structure.
  • Structure (7) contains a linear, saturated hydrocarbon skeleton. Therefore, when the component (B) includes the structure (7) in a part of the structure, the cured product of the SMC has excellent toughness.
  • the component (B) containing the structure (7) reacts, for example, the component (D) containing the compound represented by the formula (3) with the component (A) containing the glycidyl ether of 1,6-hexanediol. Obtained.
  • R 1 is a single bond, —CH 2 —, —C (CH 3 ) 2 —, —O— or —SO 2 —
  • R 2 , R 3 , R 4 and R 5 are each independently A hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Component (C) is an epoxy resin curing agent.
  • Component (C) is preferably solid at 25 ° C.
  • the component (C) examples include aliphatic amines, aromatic amines, modified amines, secondary amines, tertiary amines, imidazole compounds, mercaptans, dicyandiamide, and the like.
  • dicyandiamide is preferable because it can exhibit excellent toughness and heat resistance of a cured product of the SMC without impairing the storage stability and the rapid curing property of the SMC.
  • one type may be used alone, or two or more types may be used in combination.
  • dicyandiamide and an imidazole compound may be used in combination.
  • the imidazole compound examples include 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine.
  • the content of the component (C) is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of all epoxy resin components contained in the epoxy resin composition. 0.5 to 2 parts by mass is more preferred.
  • the SMC tends to have excellent fast-curing properties.
  • the content of the component (C) is 15 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less, the fluidity of the SMC during press molding tends to be further excellent.
  • Other components include epoxy resin curing accelerators, inorganic fillers, internal mold release agents, surfactants, organic pigments, inorganic pigments, and other resins (thermoplastic resins, thermoplastic elastomers and elastomers). .
  • a urea compound is preferable because the mechanical properties (flexural strength and flexural modulus) of the fiber-reinforced composite material are increased.
  • urea compounds include 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, and 3- (3-chloro-4-methylphenyl) -1,1- Dimethylurea, 2,4-bis (3,3-dimethylureido) toluene, 1,1 ′-(4-methyl-1,3-phenylene) bis (3,3-dimethylurea) and the like can be mentioned.
  • Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, clay, barium sulfate, magnesium oxide, glass powder, hollow glass beads, and aerosil.
  • Examples of the internal release agent include carnauba wax, zinc stearate, calcium stearate and the like.
  • the releasability of the carrier film from the SMC can be improved. Further, voids in the SMC can be reduced.
  • Thermoplastic resins, thermoplastic elastomers and elastomers change the viscoelasticity of the epoxy resin composition, not only to optimize the viscosity, storage modulus and thixotropic properties of the epoxy resin composition, but also to cure the epoxy resin composition. It has the role of improving the toughness of the product.
  • the thermoplastic resin, the thermoplastic elastomer, and the elastomer may be used alone or in a combination of two or more.
  • the minimum value of W B is 20% or more, more preferably 25% or more, more preferably 30% or more, the maximum value of W B is 50% or less, 45% and more preferably less, more preferably 40% or less If present, the epoxy resin components (component (A), component (B), etc.) contained in the epoxy resin composition have an excellent balance of molecular weight distribution, exhibit appropriate fluidity during press molding, and further suppress burrs. be able to.
  • the value of W B can be adjusted component (B), when the reaction product of a compound component having a functional group capable of reacting with epoxy groups (A), the reaction temperature, the reaction time and the like.
  • W B for example, can be determined by the following procedure.
  • a chromatogram showing the relationship between the retention time and the peak intensity is measured by GPC using an RI (differential refractive index) detector.
  • RI differential refractive index
  • the peak is divided into two at a portion (minimum value) where the peak intensity of the RI detector is the lowest. I do.
  • W B as a ratio of the area value of the peak component (B) to the total area values of all peaks Is calculated.
  • ratio W Z is preferably 0.1 to 15%, more preferably 0.2 to 10%, and still more preferably from 1 to 7%.
  • the content is 7% or less, the reinforcing fibers and the epoxy resin composition tend to be hardly separated at the time of SMC press molding, and thus the SMC tends to have further excellent fluidity at the time of press molding.
  • W Z is, for example, when component (B) is a reaction product of components (D) and the component (A), the reaction temperature of the component (D) to component (A), adjusted by the reaction time, etc. it can.
  • W Z is, for example, can be determined by the following procedure.
  • a chromatogram showing the relationship between the retention time and the peak intensity is measured by GPC using an RI (differential refractive index) detector.
  • RI differential refractive index
  • WZ is calculated as the ratio of the area value of the region having a molecular weight exceeding 10,000 to the area value of the measured chromatogram.
  • the proportion of the THF-insoluble component of the epoxy resin component is less than 50% by mass, preferably 45% by mass or less, more preferably 25% by mass or less, and even more preferably 5% by mass or less, based on the total mass of the epoxy resin component. If the proportion of the THF-insoluble component is less than 50% by mass, the amount of the crosslinked product in the epoxy resin composition is small, so that the fluidity during press molding is excellent, the SMC is sufficiently soft, and processing such as cutting is easy. is there.
  • the lower limit of the THF-insoluble content is not particularly limited, but is, for example, 0.001% by mass.
  • reinforcing fibers can be employed depending on the use and purpose of use of the SMC.
  • the reinforcing fibers include carbon fibers (including graphite fibers; the same applies hereinafter), aramid fibers, silicon carbide fibers, alumina fibers, boron fibers, tungsten carbide fibers, glass fibers, and the like.
  • carbon fibers and glass fibers are preferable, and carbon fibers are particularly preferable, from the viewpoint of the mechanical properties of FRP.
  • the reinforcing fibers are usually used in the form of a reinforcing fiber bundle consisting of a single fiber of 1,000 or more and 60,000 or less.
  • the reinforcing fiber bundle may exist while maintaining the shape of the fiber bundle, or may exist in the form of a bundle composed of fewer fibers. In SMC, they are usually present in smaller bundles.
  • the reinforcing fiber a chopped reinforcing fiber bundle composed of short fibers obtained by cutting a continuous reinforcing fiber bundle is preferable.
  • the length of the short fiber is preferably 0.3 to 10 cm, more preferably 1 to 5 cm.
  • an FRP having better mechanical properties can be obtained.
  • the length of the short fiber is 10 cm or less, an SMC having better flow characteristics at the time of press molding can be obtained.
  • As the form of the reinforcing fibers in the SMC a sheet-like material in which chopped reinforcing fiber bundles are stacked two-dimensionally at random is more preferable.
  • a method for producing the SMC of the present invention for example, a raw material mixture containing components (A), (D) and (C) is mixed to prepare a raw material mixture, and the raw material mixture is impregnated into reinforcing fibers; A method of increasing the viscosity of the raw material mixture is exemplified. Thereby, SMC containing the epoxy resin composition which is a thickened material of the raw material mixture and the reinforcing fibers is obtained. This method will be described in detail below. However, the method for producing the SMC of the present invention is not limited to this method.
  • Component (A), component (D), component (C), etc. may be mixed at the same time, or a part of component (A), component (D), component (C), etc. may be mixed, and then the remainder may be mixed. You may mix. For example, a part or all of the component (A) and the component (C) may be mixed in advance to prepare a master batch of the component (C), and the master batch and the remaining components may be mixed.
  • the mixing of each component can be performed using, for example, a kneading apparatus.
  • Examples of the kneading apparatus include a grinder, an attritor, a planetary mixer, a dissolver, a three-roller, a kneader, a universal stirrer, a homogenizer, a homodispenser, a ball mill, and a bead mill. Two or more kneading apparatuses may be used in combination.
  • a grinder an attritor
  • a planetary mixer a dissolver
  • a three-roller a kneader
  • a kneader a universal stirrer
  • a homogenizer a homodispenser
  • ball mill ball mill
  • a bead mill Two or more kneading apparatuses may be used in combination.
  • Two or more kneading apparatuses may be used in combination.
  • the content of the component (A) is preferably from 70 to 95% by mass based on the total mass of the raw material mixture.
  • the content of the component (D) is preferably 3 to 20% by mass based on the total mass of the raw material mixture.
  • the content of the component (C) is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of all epoxy resin components contained in the raw material mixture.
  • various impregnation methods can be applied depending on the form of the reinforcing fiber.
  • various methods can be adopted as a method for impregnating a raw material mixture into a chopped reinforcing fiber bundle made of short fibers.
  • the following method can be mentioned. Two films prepared by uniformly applying the above-mentioned raw material mixture are prepared. A chopped reinforcing fiber bundle is randomly distributed on the surface of one of the films to which the raw material mixture is applied to form a sheet.
  • the coated surface of the raw material mixture of the other film on which the chopped reinforcing fiber bundle is not spread is stuck on a sheet, and the raw material mixture is pressed against the sheet to impregnate the chopped reinforcing fiber bundle.
  • the one in which the raw material mixture is impregnated into the reinforcing fibers is also referred to as “intermediate material precursor”.
  • Examples of the method for thickening the raw material mixture include a method in which the intermediate material precursor is allowed to stand under a temperature condition of about 15 to 80 ° C. During the standing period, a part of the component (A) and the component (D) react to generate the component (B), and the raw material mixture thickens (B-stage).
  • the period during which the intermediate precursor is allowed to stand is preferably 3 to 30 days, more preferably 5 to 15 days, and most preferably 5 to 10 days. As the period is shorter, the reactivity tends to be higher and the reaction control becomes more difficult. The longer the period, the longer the storage period, which tends to be unsuitable for industrialization.
  • the raw material mixture may be thickened by holding the intermediate precursor at a temperature of about 60 to 80 ° C. for several seconds to several tens of minutes.
  • Component (B), and the THF-insoluble content of the epoxy resin component is less than 50% by mass. Therefore, FRP which is excellent in handling workability (that is, having an appropriate tackiness), fluidity of the matrix resin at the time of press molding, generation of burrs can be suppressed, and excellent in mechanical properties and heat resistance can be obtained. be able to.
  • One embodiment of the present invention is a fiber-reinforced composite material (FRP) which is a cured product of the SMC of the present invention.
  • the FRP of the present invention can be produced, for example, by a method for producing a fiber-reinforced composite material described below.
  • the fiber-reinforced composite material of the present invention is a cured product of the SMC of the present invention. Therefore, the fiber reinforced composite material of the present invention has excellent mechanical properties and heat resistance.
  • One embodiment of the present invention is a method for producing a fiber-reinforced composite material, which comprises pressing the SMC of the present invention.
  • the fiber-reinforced composite material of the present invention is manufactured by heating or press-molding the SMC of the present invention and curing the epoxy resin composition.
  • One SMC or a stack of a plurality of SMCs is set between a pair of molds.
  • the SMC is heated and compressed at 120 to 230 ° C. for 2 to 60 minutes to cure the epoxy resin composition, thereby obtaining a fiber-reinforced composite material as a molded product.
  • a honeycomb structure such as corrugated cardboard may be used as a core material, and SMC may be arranged on both surfaces or one surface thereof.
  • the SMC of the present invention is press-formed. Therefore, a fiber-reinforced composite material having excellent mechanical properties and heat resistance can be obtained.
  • Raw material (b): jER (registered trademark) 827 bisphenol A type liquid epoxy resin, manufactured by Mitsubishi Chemical Corporation).
  • ⁇ Preparation of master batch of curing agent> The raw material (a) and the raw material (g) are mixed at a mass ratio of 1: 1 using a planetary stirring / defoaming device MAZERUSTAR (manufactured by Kurashiki Spinning Co., Ltd.), and the obtained mixture is mixed with three rolls. The mixture was refined to obtain a master batch (g).
  • a master batch (h) was obtained in the same manner as the master batch (g) except that the raw material (h) was used instead of the raw material (g).
  • the raw material (b) and the raw material (g) were mixed at a mass ratio of 1: 1 using a planetary stirring / defoaming device MAZERUSTAR (manufactured by Kurashiki Spinning Co., Ltd.), and the obtained mixture was mixed with three rolls.
  • the mixture was refined to obtain a master batch (g ′).
  • a master batch (h ′) was obtained in the same manner as the master batch (g ′), except that the raw material (h) was used instead of the raw material (g).
  • Preparation Example 2 A raw material mixture having a composition (2) was obtained in the same manner as in Preparation Example 1, except that the amount of the raw material (e) was changed from 5 parts by mass to 13 parts by mass.
  • Preparation Example 4 A raw material mixture having a composition (4) was obtained in the same manner as in Preparation Example 1, except that the amount of the raw material (e) was changed from 5 parts by mass to 25 parts by mass.
  • Apparatus Tosoh's high-speed GPC device HLC-8320GPC type, Detector: RI detector, Flow rate: 0.35 ml / min, Inlet temperature: 40 ° C, Oven temperature: 40 ° C, RI temperature: 40 ° C, Sample injection volume: 10 ⁇ L, Column: three columns connected in the order of (1) to (3) below, (1) TSKgel superHZM-M (4.6 mm ID x 15 cmL) manufactured by Tosoh Corporation (2) TSKgel superHZM-M (4.6 mm ID x 15 cmL) manufactured by Tosoh Corporation (3) TSKgel HZ2000 (4.6 mm ID x 15 cmL) manufactured by Tosoh Corporation Guard column: TSKguardcolumnsuper HZ-L (4.6 mm ID ⁇ 3.5 cmL) manufactured by Tosoh Corporation Eluent: THF (stabilizer BHT), Standard substance: monodisperse polystyrene of known molecular weight.
  • TSKgel superHZM-M 46
  • the tackiness of the SMC was evaluated according to the following criteria. The results are shown in Tables 1 to 3. A: When the SMC was touched by hand, it had an appropriate tack and the lamination work of the SMC was simple. B: When the SMC was touched by hand, the tack was slightly strong, but the lamination work of the SMC was possible. C: When the SMC was touched by hand, the stickiness was very strong and the laminating operation could not be performed.
  • the SMC is laminated by 2 ply, charged into the molding die at a charging rate (the ratio of the area of the SMC to the die area) of 65%, and heated and compressed at a die temperature of 140 ° C. and a pressure of 4 MPa for 5 minutes.
  • the composition was cured to obtain a flat FRP (molded product) having a thickness of about 2 mm and a square of 300 mm.
  • the SMCs of Examples 1 to 9 had an appropriate tackiness, were excellent in the fluidity of the matrix resin during press molding, and were able to suppress the generation of burrs. Also, the workability was excellent. Further, since the reinforcing fibers were filled up to the end of the mold at the time of press molding, it can be seen that the obtained FRP has excellent mechanical properties.
  • the SMCs of Examples 10 to 11 had slightly higher tack, but the handling workability was at a practical level. In addition, burrs were somewhat large, and there was a part of the end of the molded article where the reinforcing fibers were not sufficiently provided, but the fluidity was at a practical level.
  • the tackiness of the SMCs of Examples 12 and 13 was slightly higher, but the fluidity of the matrix resin during press molding was better than that of Comparative Examples 1 and 2.
  • the SMC of Comparative Example 1 had an appropriate tack, but was inferior in fluidity of the matrix resin at the time of press molding, so that the SMC could not be filled to the end of the mold.
  • the SMC of Comparative Example 2 had too high tack and poor handling workability. Further, since the SMC is excessively soft, it was difficult to cut the SMC into a desired shape with a cutter knife at room temperature (23 ° C.). Further, the reinforcing fibers and the matrix resin were separated during press molding, and the reinforcing fibers did not reach the end of the molded product.
  • the SMC of the present invention is excellent in mechanical properties and heat resistance after curing, it is suitable as a raw material for industrial and automotive structural parts.
  • the SMC of the present invention is excellent in handling workability, fluidity and rapid curability of the matrix resin at the time of press molding, can suppress occurrence of burrs, and obtains a fiber reinforced composite material excellent in mechanical properties and heat resistance. be able to.
  • the fiber reinforced composite material of the present invention has excellent mechanical properties and heat resistance. According to the method for producing a fiber-reinforced composite material of the present invention, a fiber-reinforced composite material having excellent mechanical properties and heat resistance can be obtained.

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Abstract

L'invention concerne : un composé de moulage de feuille qui est en mesure de supprimer la formation de bavures, tout en présentant d'excellentes propriétés de manipulation et une excellente fluidité d'une résine de matrice pendant le moulage à la presse, et qui permet l'obtention d'un matériau composite renforcé par des fibres qui présente d'excellentes caractéristiques mécaniques et une excellente résistance à la chaleur ; un matériau composite renforcé par des fibres qui présente d'excellentes caractéristiques mécaniques et une excellente résistance à la chaleur ; et un procédé de production de ce matériau composite renforcé par des fibres. L'invention porte sur un composé de moulage de feuille qui contient une composition de résine époxy et des fibres de renforcement et qui est conçu de telle sorte que : la composition de résine époxy contient un constituant (A), un constituant (B) et un constituant (C) ; et le rapport de la fraction insoluble dans le tétrahydrofuranne des constituants de résine époxy est inférieur à 50 % en masse. Constituant (A) : un constituant de résine époxy présentant un poids moléculaire au sommet du pic de 500 ou moins. Constituant (B) : un constituant de résine époxy présentant un poids moléculaire au sommet du pic supérieur à 500 mais inférieur ou égal à 10 000, tout en présentant un rapport (poids moléculaire moyen en poids)/(poids moléculaire moyen en nombre) d'au moins 1,2. Constituant (C) : un agent de durcissement de résine époxy. L'invention concerne également un matériau composite renforcé par des fibres qui utilise ce composé de moulage de feuille ; et un procédé de production de ce matériau composite renforcé de fibres.
PCT/JP2019/038739 2018-10-05 2019-10-01 Composé de moulage de feuille, matériau composite renforcé par des fibres et procédé de production d'un matériau composite renforcé par des fibres Ceased WO2020071360A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002012649A (ja) * 2000-06-28 2002-01-15 Matsushita Electric Works Ltd エポキシ樹脂組成物、シートモールディングコンパウンド及び成形品
CN101096443A (zh) * 2007-07-10 2008-01-02 武汉理工大学 一种制备环氧片状模塑料的方法及其产品
JP2008038082A (ja) * 2006-08-09 2008-02-21 Toray Ind Inc 引き抜き成形繊維強化複合材料
JP2017203108A (ja) * 2016-05-11 2017-11-16 三菱ケミカル株式会社 成形材料および繊維強化複合材料
JP2018066026A (ja) * 2016-02-29 2018-04-26 三菱ケミカル株式会社 エポキシ樹脂組成物
WO2018190329A1 (fr) * 2017-04-12 2018-10-18 三菱ケミカル株式会社 Composé de moulage en feuille et matériau composite renforcé par des fibres
WO2019176568A1 (fr) * 2018-03-16 2019-09-19 三菱ケミカル株式会社 Composé de moulage de feuille et article moulé en matériau composite de fibres de carbone

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002012649A (ja) * 2000-06-28 2002-01-15 Matsushita Electric Works Ltd エポキシ樹脂組成物、シートモールディングコンパウンド及び成形品
JP2008038082A (ja) * 2006-08-09 2008-02-21 Toray Ind Inc 引き抜き成形繊維強化複合材料
CN101096443A (zh) * 2007-07-10 2008-01-02 武汉理工大学 一种制备环氧片状模塑料的方法及其产品
JP2018066026A (ja) * 2016-02-29 2018-04-26 三菱ケミカル株式会社 エポキシ樹脂組成物
JP2017203108A (ja) * 2016-05-11 2017-11-16 三菱ケミカル株式会社 成形材料および繊維強化複合材料
WO2018190329A1 (fr) * 2017-04-12 2018-10-18 三菱ケミカル株式会社 Composé de moulage en feuille et matériau composite renforcé par des fibres
WO2019176568A1 (fr) * 2018-03-16 2019-09-19 三菱ケミカル株式会社 Composé de moulage de feuille et article moulé en matériau composite de fibres de carbone

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