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WO2018131300A1 - Préimprégné et matériau composite renforcé par des fibres - Google Patents

Préimprégné et matériau composite renforcé par des fibres Download PDF

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Publication number
WO2018131300A1
WO2018131300A1 PCT/JP2017/042434 JP2017042434W WO2018131300A1 WO 2018131300 A1 WO2018131300 A1 WO 2018131300A1 JP 2017042434 W JP2017042434 W JP 2017042434W WO 2018131300 A1 WO2018131300 A1 WO 2018131300A1
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WO
WIPO (PCT)
Prior art keywords
prepreg
epoxy resin
fiber
epoxy
resin composition
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
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PCT/JP2017/042434
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English (en)
Japanese (ja)
Inventor
小柳静恵
三角潤
坂田宏明
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Toray Industries Inc
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Toray Industries Inc
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Publication date
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Priority to JP2017562787A priority Critical patent/JPWO2018131300A1/ja
Publication of WO2018131300A1 publication Critical patent/WO2018131300A1/fr
Anticipated expiration legal-status Critical
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    • 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 prepreg in which a ladder-type silsesquioxane is introduced into a matrix resin and a fiber-reinforced composite material.
  • fiber reinforced composite materials using carbon fibers, aramid fibers, and the like as reinforcing fibers have been used for structural materials such as aircraft and automobiles, tennis rackets, golf shafts, fishing rods, etc. by utilizing their high specific strength and specific elastic modulus. It has been used for sports and general industrial applications.
  • a method of curing a prepreg which is a sheet-like intermediate material impregnated with an uncured matrix resin in a reinforcing fiber, or a liquid resin in a reinforcing fiber disposed in a mold.
  • a resin transfer molding method or the like is used in which an intermediate is obtained by pouring the resin to cure the intermediate.
  • the method using a prepreg has an advantage that it is easy to obtain a high-performance fiber-reinforced composite material because the orientation of the reinforcing fibers can be strictly controlled and the design freedom of the laminated structure is high.
  • a thermosetting resin is mainly used from the viewpoint of heat resistance and productivity, and an epoxy resin is preferably used from the viewpoint of mechanical properties such as adhesion to the reinforcing fiber.
  • a technique of adding an additive for making a material difficult to burn into a matrix resin a so-called flame retardant
  • a flame retardant a silicon compound, a halogen compound, a phosphorus compound, a metal hydroxide, a nitrogen compound, etc. are generally used.
  • a silicon compound is preferable because the obtained resin cured product has excellent heat resistance and elastic modulus. Has been used.
  • Patent Document 1 As an example of blending a silicon compound into a matrix resin, a technique of blending silica particles (Patent Document 1 and Patent Document 2) and a technique of blending a cage silsesquioxane (Patent Document 3) are disclosed. Moreover, the technique (patent document 4) which melt
  • Patent Document 1 and Patent Document 2 when the silica particles described in Patent Document 1 and Patent Document 2 are used, the silica particles have thixotropic properties, so that they thicken during curing, or separate and precipitate during curing, and the elongation of the matrix resin cured product. Sometimes became insufficient. Moreover, when the cage-type silsesquioxane described in Patent Document 3 is used, the effect of improving the elongation of the cured product of the matrix resin may be insufficient, and the blending amount is limited. In Patent Document 4, a wet method in which a matrix resin is dissolved in a solvent is used to reduce the viscosity at the time of preparing a prepreg.
  • the solvent volatilizes during curing and the volume of the fiber reinforced composite material shrinks and voids and cracks are generated due to the residual solvent. May be damaged.
  • the honeycomb material volatile components gasified in the honeycomb at the time of surface formation are sealed, and the volatile matter expands in the honeycomb without an outlet, which may be a factor that hinders adhesion between the surface material and the honeycomb core material.
  • it is required to produce a prepreg without using a solvent.
  • An object of the present invention is to solve the above-mentioned problems, that is, to provide a prepreg and a fiber-reinforced composite material having high flame retardancy and heat resistance without using a solvent and excellent in mechanical properties.
  • the present invention has the following configuration in order to solve the above problems. That is, a prepreg obtained by impregnating a reinforcing fiber with an epoxy resin composition containing at least the following components [A], [B], and [C], and the total amount of epoxy resin in the epoxy resin composition is 100 parts by mass. On the other hand, it is a prepreg containing 1 to 40 parts by mass of [A] and having a volatile content of 0.8% by mass or less.
  • [A] Ladder-type silsesquioxane having a structure represented by the formula (1)
  • the fiber-reinforced composite material of the present invention is a fiber-reinforced composite material obtained by curing the above prepreg.
  • the prepreg of the present invention includes the following components [A], [B], and [C].
  • the component [A] in the present invention is a ladder-type silsesquioxane, and flame retardancy and heat resistance are imparted by blending it with the epoxy resin composition.
  • the ratio of the substituent R having an epoxy ring structure to the substituent R in the formula (1) is 50 to 100%, more preferably 60 to 100%. More preferably, it is 75 to 100%.
  • the ratio (%) of the epoxy ring structure here means the number (number) of substituents R having an epoxy group in the constituent element [A] / the number of total substituents R in the constituent element [A] ⁇ 100 is required.
  • the proportion of the epoxy ring structure in the component [A] can also be determined by organic element analysis of the epoxy resin composition, ICP-MS (inductively coupled plasma mass spectrometry), or the like.
  • examples of the substituent R having an epoxy ring structure include ⁇ -glycidoxyethyl group, ⁇ -glycidoxypropyl group, ⁇ -glycidoxybutyl group and the like.
  • Such as an alkyl group of the number 3 or less carbon atoms substituted with a kill group Such as an alkyl group of the number 3 or less carbon atoms substituted with a kill group.
  • ⁇ -glycidoxyethyl group, ⁇ -glycidoxypropyl group, and ⁇ - (3,4-epoxycyclohexyl) ethyl group are preferable.
  • examples of the substituent R not containing an epoxy ring structure include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group, and the like. Is mentioned.
  • examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group.
  • examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • examples of the aryl group include a phenyl group, a benzyl group, a tolyl group, and a naphthyl group.
  • the weight average molecular weight of the component [A] used in the present invention is preferably 1500 to 30000, more preferably 1500 to 15000, and still more preferably 2000 to 8000.
  • the weight average molecular weight of the component [A] is preferably 1500 to 30000, more preferably 1500 to 15000, and still more preferably 2000 to 8000.
  • the weight average molecular weight means a molecular weight in terms of polystyrene that can be determined by GPC (gel permeation chromatography).
  • the component [A] used in the present invention can be produced by, for example, the method described in JP-A-2007-9079.
  • the amount of the epoxy group contained can be controlled by blending trialkoxysilane having no epoxy ring structure and trialkoxysilane having an epoxy ring structure in a predetermined molar ratio, and performing cohydrolysis and cocondensation. it can.
  • the blending amount of the constituent element [A] is set to the constituent element [A] from the viewpoint that the obtained fiber-reinforced composite material exhibits flame retardancy, heat resistance and mechanical properties at a high level.
  • the total amount of the epoxy resin including the component [B] is required to be 1 to 40 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 20 parts by weight. .
  • Two or more types of components [A] may be used.
  • the component [B] used in the present invention is an epoxy resin other than the component [A], and is an epoxy resin having two or more epoxy groups in one molecule.
  • the glass transition temperature of a fiber-reinforced composite material obtained by heat-curing a fiber impregnated with a mixture with a curing agent described later is sufficiently high. Therefore, it is preferable.
  • the component [B] used in the present invention include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, bisphenol S type epoxy resins, and other bisphenol type epoxy resins, tetrabromobisphenol A diglycidyl.
  • Brominated epoxy resins such as ether, epoxy resins having a biphenyl skeleton, epoxy resins having a naphthalene skeleton, epoxy resins having a dicyclopentadiene skeleton, novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins, N , N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4-amino-3-methylphenol, etc.
  • Nophenol type epoxy resin N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline, N, N, N ′, N′-tetraglycidyl-2,2′-diethyl-4, Examples thereof include diamine type epoxy resins such as 4′-methylenedianiline and N, N, N ′, N′-tetraglycidyl-m-xylylenediamine. These epoxy resins may be used alone or in combination of two or more.
  • the epoxy resin may be in any form from liquid to solid, crystalline or amorphous. Here, the liquid state has a melting point or glass transition temperature below room temperature.
  • the component [B] used in the present invention preferably contains a tri- or higher functional glycidylamine type epoxy resin from the viewpoint of improving heat resistance and mechanical properties.
  • trifunctional or more means that the number of epoxy rings in one molecule is 3 or more.
  • Examples of the tri- or higher functional glycidylamine type epoxy resin include diaminodiphenylmethane type, diaminodiphenyl ether type, diaminodiphenyl sulfone type, and aminophenol type epoxy resins.
  • diaminodiphenylmethane type diaminodiphenyl ether type
  • diaminodiphenyl sulfone type diaminodiphenyl sulfone type
  • aminophenol type epoxy resins at least one selected from the group consisting of diaminodiphenylmethane type and aminophenol type epoxy resins is particularly preferably used because of the good balance between processability when producing the prepreg, heat resistance and mechanical properties.
  • tetraglycidyldiaminodiphenylmethane is used as the diaminodiphenylmethane type epoxy resin
  • various isomers of triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, and triglycidylaminocresol are used as the aminophenol type epoxy resin. It is done.
  • diaminodiphenylmethane type epoxy resins include ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldite (registered trademark)” MY720, “Araldite (registered trademark)” MY721, “Araldite (registered trademark)” MY725, “Araldite” (Registered trademark) "MY9512", “Araldite (registered trademark)” MY9663 (manufactured by Huntsman Advanced Materials), “Epototo (registered trademark)” YH-434 (manufactured by Toto Kasei Co., Ltd.) and the like It is done.
  • ELM434 manufactured by Sumitomo Chemical Co., Ltd.
  • Aldite (registered trademark)” MY720 “Araldite (registered trademark)” MY721, “Araldite (registered trademark)” MY725, “Araldite” (Registered trademark) "MY9512", “Aral
  • ELM120 and ELM100 above, manufactured by Sumitomo Chemical Co., Ltd.
  • jER registered trademark
  • 630 manufactured by Mitsubishi Chemical Corporation
  • Araldite registered trademark
  • the epoxy resin composition used in the present invention includes an epoxy resin other than the constituent element [A] and the constituent element [B] as long as it does not significantly reduce heat resistance and mechanical properties.
  • an epoxy resin include a monoepoxy compound having only one epoxy group in one molecule.
  • the constituent element [C] used in the present invention refers to a material having a curing action of an epoxy resin, and is selected from amine compounds, acid anhydride compounds, phenol compounds, etc. that are usually used as a curing agent for epoxy resins.
  • the Such curing agents include diaminodiphenylsulfone, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetraethylenepentamine, dimethylbenzylamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Examples thereof include maleic anhydride and tetrahydrophthalic anhydride.
  • 3,3'-diaminodiphenylsulfone and 4,4'-diaminodiphenylsulfone which are excellent in mechanical properties such as heat resistance and elastic modulus, and can obtain a cured product having a small linear expansion coefficient, should be used.
  • These curing agents may be used alone or in combination of two or more.
  • the curing agent can be used in either liquid or solid form.
  • the content of the component [C] is 10 to 100 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin including the component [A] and the component [B]. It is preferable from the viewpoint of ensuring, more preferably 25 to 100 parts by mass. From the viewpoint of satisfying mechanical properties such as sufficient curing speed when molding the prepreg, heat resistance and elongation of the molded product, and elastic modulus, the ratio of the amount of active hydrogen of the curing agent to the amount of epoxy groups in the epoxy resin composition is A stoichiometric amount of 0.5 to 1.5 equivalents is preferred. From the viewpoint of obtaining heat resistance, the amount is more preferably 0.8 to 1.2 equivalents, still more preferably 0.9 to 1.1 equivalents.
  • the amount of volatile components contained in the prepreg of the present invention needs to be 0.8% by mass or less when the mass of the prepreg is 100% by mass.
  • the amount of volatile components contained in the prepreg is calculated by the following method. First, a unidirectional prepreg is cut into 100 mm ⁇ 100 mm to obtain a test piece. After weighing this test piece (W1), the test piece placed on the aluminum plate is kept in a constant temperature bath set at 150 ° C. for 20 minutes. After allowing the test piece to cool to room temperature in a desiccator, it is weighed (W2) and the volatile content (W) is calculated from the following equation.
  • W (mass%) (W1-W2) ⁇ 100 / W1
  • the flame retardancy of the prepreg can be evaluated by a combustion test according to the ISO 5660 method using a corn calorimeter.
  • flame retardant evaluation include an average value of calorific value due to combustion per unit area (also referred to as average heat generation rate, AHRR; unit: kW / m 2 ), maximum calorific value due to combustion per unit area ( Maximum calorific value, also described as PHRR (unit: kW / m 2 ), total calorific value by combustion (also described as total calorific value, THR, unit: MJ / m 2 ), etc. Represents high flame retardancy.
  • thermoplastic resin soluble in the epoxy resin composition in order to control the tackiness of the resulting prepreg, to control the flowability of the resin when impregnating the epoxy resin composition into the reinforcing fiber, and to impart toughness to the resulting fiber-reinforced composite material, As [D], a thermoplastic resin soluble in the epoxy resin composition can be blended.
  • a thermoplastic resin in the epoxy resin composition By including a thermoplastic resin in the epoxy resin composition, the brittleness of the epoxy resin composition can be covered with the high toughness of the thermoplastic resin compared to the case where the epoxy resin composition or the thermoplastic resin is used alone, The molding difficulty of the thermoplastic resin can be covered with the epoxy resin composition, and a well-balanced base resin can be obtained.
  • thermoplastic resin that is soluble in the epoxy resin composition it is possible to obtain a fiber-reinforced composite material in which high toughness is obtained while avoiding a decrease in heat resistance of the fiber-reinforced composite material, and interlayer toughness is greatly improved. Can do.
  • thermoplastic resin is soluble in the epoxy resin composition. That is, when evaluating the change in viscosity when the epoxy resin composition to which the thermoplastic resin powder is added is held at a temperature lower than the glass transition temperature of the thermoplastic resin for several hours, for example, 2 hours, the initial viscosity is obtained. On the other hand, when an increase in viscosity of 10% or more is observed, it may be determined that the thermoplastic resin is soluble in the epoxy resin composition.
  • the thermoplastic resin may cause phase separation in the process of curing the prepreg, but the fiber reinforcement obtained by curing From the viewpoint of increasing the solvent resistance of the composite material, it is more preferable not to perform phase separation during the curing process. Further, from the viewpoint of improving the mechanical properties, solvent resistance, and the like of the obtained fiber-reinforced composite material, it is more preferable to dissolve and mix the thermoplastic resin in the epoxy resin composition in advance. It becomes easy to disperse
  • Such component [D] is selected from the group consisting of a carbon-carbon bond, an amide bond, an imide bond, an ester bond, an ether bond, a carbonate bond, a urethane bond, a thioether bond, a sulfone bond, and a carbonyl bond in the main chain.
  • a thermoplastic resin having a bonded bond is preferable.
  • the component [D] may have a partially crosslinked structure as long as it has thermoplasticity, and may be a crystalline resin or an amorphous resin. .
  • the component [D] is preferably contained in an amount of 1 to 40 parts by weight, more preferably 1 to 35 parts by weight, and still more preferably 2 to 2 parts by weight with respect to 100 parts by weight of the total epoxy resin in the epoxy resin composition. 30 parts by weight, most preferably 5 to 25 parts by weight.
  • the component [D] is contained in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the total amount of epoxy resins in the epoxy resin composition, a prepreg excellent in processability and handleability can be obtained.
  • the weight average molecular weight of the component [D] is preferably in the range of 4000 to 40000, more preferably 10,000 to 40000, and further preferably 15000 to 30000.
  • the average molecular weight of the component [D] is in the range of 4000 to 40000, a prepreg excellent in processability and handleability can be obtained.
  • the glass transition temperature of the constituent element [D] is at least 150 ° C. or more and 170 ° C. or more from the viewpoint that it is difficult to cause thermal deformation when used as a molded body. Is preferred.
  • the constituent element [D] include polycarbonate, polysulfone, polyetherimide, and polyethersulfone.
  • a hydroxyl group, a carboxyl group, an amino group, a thiol group, an acid anhydride or the like can react with the cationic polymerizable compound and is preferably used.
  • the component [D] having a hydroxyl group include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, and phenoxy resins.
  • Examples of commercially available products of polysulfone include “UDEL (registered trademark)” P-1700, “UDEL (registered trademark)” P-3500, “Virantage (registered trademark)” VW-30500RP (manufactured by Solvay Advanced Polymers) and the like. Can be mentioned.
  • polyetherimides examples include “Ultem (registered trademark)” 1000, “Ultem (registered trademark)” 1010, “Ultem (registered trademark)” 1040 (manufactured by SABIC Japan LLC), and the like.
  • polyethersulfone products include “Sumika Excel (registered trademark)” PES3600P, “Sumika Excel (registered trademark)” PES5003P, “Sumika Excel (registered trademark)” PES5200P, “Sumika Excel (registered trademark)” PES7600P (and above) , Manufactured by Sumitomo Chemical Co., Ltd.), “Ultrason (registered trademark)” E2020P SR, “Ultrason (registered trademark)” E2021SR (above, manufactured by BASF), “Virantage (registered trademark)” VW-10700RP (Solvay Advanced Polymers) Etc.).
  • a copolymer oligomer of polyethersulfone and polyetherethersulfone as described in JP-T-2004-506789 can be mentioned.
  • the oligomer refers to a polymer having a relatively low molecular weight in which about 10 to 100 finite number of monomers are bonded.
  • the epoxy resin composition used in the present invention includes components other than the constituent element [A], the constituent element [B], the constituent element [C], and the constituent element [D] as long as the object of the present invention is not impaired. May be included. Examples thereof include inorganic particles and organic particles as exemplified below, and curing accelerators, flame retardants, viscosity modifiers, light stabilizers, and the like.
  • thermoplastic resin particles particles mainly composed of a thermoplastic resin can be blended.
  • polyamide is most preferable.
  • polyamides polyamide 12, polyamide 6, polyamide 11, polyamide 66, polyamide 6/12 copolymer, and epoxy described in Example 1 of JP-A-1-104624 are used.
  • Polyamide semi-IPNed with a compound gives particularly good adhesive strength with an epoxy resin.
  • IPN is an abbreviation for interpenetrating polymer network, and is a kind of polymer blend.
  • the blend component polymer is a cross-linked polymer, and the different cross-linked polymers are partially or wholly entangled with each other to form a multi-network structure.
  • Semi-IPN is a structure in which a heavy network structure is formed by a bridge polymer and a linear polymer.
  • Semi-IPN thermoplastic resin particles can be obtained by, for example, reprecipitation after dissolving a thermoplastic resin and a thermosetting resin in a common solvent and mixing them uniformly. By using particles comprising an epoxy resin and semi-IPN polyamide, excellent heat resistance and impact resistance can be imparted to the prepreg.
  • thermoplastic resin particles may be spherical particles, non-spherical particles, or porous particles, but the spherical shape is superior in viscoelasticity because it does not deteriorate the flow characteristics of the resin, and there is no origin of stress concentration. This is a preferred embodiment in terms of giving high impact resistance.
  • Commercially available polyamide particles include SP-500, SP-10, TR-1, TR-2, 842P-48, 842P-80 (above, manufactured by Toray Industries, Inc.), “Orgasol (registered trademark)” 1002D. , 2001UD, 2001EXD, 2002D, 3202D, 3501D, 3502D, (manufactured by Arkema Co., Ltd.) and the like can be used. These polyamide particles may be used alone or in combination.
  • an inorganic filler such as a coupling agent, thermosetting resin particles, silica gel, carbon black, clay, carbon nanotubes, graphene, carbon particles, and metal powder is used as long as the effects of the present invention are not hindered. Etc. can be blended.
  • the physical properties of a fiber reinforced composite material have a strong correlation with the physical properties of the cured resin obtained by curing the matrix resin. Therefore, the physical properties of the cured resin are good when evaluating the physical properties of the fiber reinforced composite material.
  • Can be an indicator For example, it is known that the higher the elastic modulus of the cured resin, the higher the compressive strength of the corresponding fiber-reinforced composite material. It is known that it is difficult to become the starting point of destruction.
  • the cured resin is usually obtained by heating at 100 to 200 ° C. for 1 to 8 hours, depending on the type of curing agent and the coexisting epoxy.
  • molding may be carried out by providing two or more stages of holding temperatures.
  • phase separation structure is preferably a so-called sea-island structure or a bicontinuous structure.
  • component insoluble in the composition [B] such as crosslinked particles and inorganic particles in the composition, the above is preferably achieved with components other than the insoluble components.
  • the prepreg of the present invention is a composite material in which the epoxy resin composition is impregnated in a fiber material (referred to as a reinforced fiber in the composite material industry), and a fiber-reinforced composite material is obtained by curing this.
  • Examples of the reinforcing fiber used in the present invention include glass fiber, carbon fiber, graphite fiber, aramid fiber, boron fiber, alumina fiber, and silicon carbide fiber. Two or more kinds of these reinforcing fibers may be mixed and used, but it is preferable to use carbon fibers or graphite fibers in order to obtain a molded product that is lighter and more durable. In particular, in applications where there is a high demand for reducing the weight and strength of materials, carbon fibers are preferably used because of their excellent specific modulus and specific strength.
  • the carbon fiber preferably used in the present invention can be any type of carbon fiber depending on the application, but is a carbon fiber having a tensile modulus of at least 230 GPa from the viewpoint of impact resistance and weight reduction. It is preferable. From the viewpoint of strength, a carbon fiber having a tensile strength of preferably 4.4 to 6.5 GPa is preferably used because a composite material having high rigidity and mechanical strength can be obtained. Also, the tensile elongation is an important factor, and it is preferable that the carbon fiber is a high strength and high elongation carbon fiber of 1.7 to 2.3%. Therefore, the carbon fiber having the characteristics that the tensile modulus is at least 230 GPa, the tensile strength is at least 4.4 GPa, and the tensile elongation is at least 1.7% or more is most suitable.
  • Carbon fibers include “Torayca (registered trademark)” T700G-24K, “Torayca (registered trademark)” T300-3K, and “Torayca (registered trademark)” T700S-12K (Toray Industries, Inc.) (Manufactured by Co., Ltd.), “Torayca (registered trademark)” T800G-24K, “Torayca (registered trademark)” T800S-24K, and the like of 294 MPa.
  • the form and arrangement of the carbon fibers can be appropriately selected from long fibers and woven fabrics arranged in one direction.
  • It is preferably in the form of continuous fibers such as long fibers (fiber bundles) or woven fabrics arranged in one direction.
  • the term “long fiber” as used herein means a fiber strand having an average length of 10 mm or more.
  • it is desirable to use a long fiber or its woven fabric from the viewpoint of mechanical properties.
  • the carbon fiber bundle used in the present invention does not cause damage to the carbon fiber bundle at the time of twisting or impregnation treatment of the resin composition, and from the viewpoint of sufficiently impregnating the carbon fiber bundle with the resin composition, the single fiber fineness is It is preferably 0.2 to 2.0 dtex, more preferably 0.4 to 1.8 dtex.
  • the carbon fiber bundle used in the present invention has a number of filaments in the range of 2500 to 50000 from the viewpoint that the fiber arrangement does not meander and the resin is easily impregnated during prepreg production or molding. Preferably there is.
  • the number of filaments is more preferably in the range of 2800 to 40000.
  • the prepreg of the present invention is preferably prepared by a hot melt method because it easily adjusts the volatile matter.
  • the hot melt method is a method in which a reinforcing fiber is impregnated by reducing the viscosity by heating without using a solvent.
  • a method of directly impregnating a reinforcing fiber with a matrix resin whose viscosity has been reduced by heating, or a release paper sheet with a resin film once coated with a matrix resin on a release paper or the like is first prepared. There is a method in which the reinforcing fibers are overlapped from both sides or one side and heated and pressed to impregnate the reinforcing fibers with the matrix resin.
  • the basis weight of the reinforcing fiber is preferably 100 to 1000 g / m 2 .
  • the reinforcing fiber basis weight is less than 100 g / m 2, it is necessary to increase the number of laminated layers in order to obtain a predetermined thickness when molding the fiber reinforced composite material, and the laminating operation may be complicated.
  • the prepreg drapability tends to deteriorate.
  • the preferred fiber mass content is 40 to 90% by mass, more preferably 50 to 80% by mass. When the fiber mass content is in this range, it is preferable to suppress the generation of voids in the molded body and express the excellent mechanical properties of the reinforcing fiber.
  • it depends on the molding process it is also preferable from the viewpoint of obtaining a uniform molded body by controlling the curing heat generation of the resin when molding a large member.
  • the form of the prepreg of the present invention may be either a unidirectional prepreg or a woven prepreg.
  • the fiber-reinforced composite material of the present invention can be obtained by laminating the prepreg of the present invention in a predetermined form and then curing the resin by heating. It is preferable to apply pressure during molding from the viewpoint of suppressing voids and obtaining a uniform cured body.
  • a method for applying heat and pressure 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.
  • the glass transition temperature of the fiber reinforced composite material molded by the above method is preferably in the range of 100 to 250 ° C. from the viewpoint of the passability of the molded material after-treatment process. Particularly for aircraft applications, a temperature range of 170 to 250 ° C. is preferable because it can be used for high temperature members.
  • the glass transition temperature here is an intersection temperature value between a tangent in a glass state and a tangent in a transition state of a storage elastic modulus G ′ curve obtained by a dynamic viscoelasticity measuring apparatus.
  • the prepreg and the fiber-reinforced composite material of the present invention will be described more specifically with reference to examples.
  • Reinforcing fiber, resin raw material and resin cured product, prepreg, method for producing fiber reinforced composite material, flame retardancy of resin cured product, bending elastic modulus, bending deflection, volatile content contained in prepreg, fiber reinforcement The evaluation method of the glass transition temperature of the composite material is shown below.
  • the production environment and evaluation of the prepregs of the examples are performed in an atmosphere at a temperature of 25 ° C. ⁇ 2 ° C. and a relative humidity of 50% unless otherwise specified.
  • the mixture was gradually added at 50 to 55 ° C. and left to stir for 3 hours. After completion of the reaction, 150 g of methyl isobutyl ketone was added to the system, and further washed with 75 g of distilled water until the pH of the aqueous layer became neutral. Next, after washing twice with 80 g of distilled water, methyl isobutyl ketone was distilled off under reduced pressure to obtain the desired compound silsesquioxane (SQ-A). The weight average molecular weight of silsesquioxane (SQ-A) was 5,500.
  • silsesquioxane (ladder-type silsesquioxane in which 75% of the substituent R contains an epoxy ring structure)
  • a reaction vessel equipped with a stirrer and a thermometer 150 g of methyl isobutyl ketone, water
  • tetramethylammonium oxide tetramethylammonium hydroxide 28.6 mmol
  • 36.7 g of distilled water 32.7 g (218.0 mmol) of ethyltrimethoxysilane, ⁇ -glycidoxy 154.8 g (655.0 mmol) of propyltrimethoxysilane was gradually added at 50 to 55 ° C.
  • silsesquioxane (ladder-type silsesquioxane in which 60% of the substituent R contains an epoxy ring structure)
  • a reaction vessel equipped with a stirrer and a thermometer 150 g of methyl isobutyl ketone, water
  • tetramethylammonium oxide tetramethylammonium hydroxide 22.6 mmol
  • 29.0 g of distilled water 54.7 g (276.0 mmol) of phenyltrimethoxysilane, ⁇ -glycidoxy 97.8 g (414.0 mmol) of propyltrimethoxysilane was gradually added at 50 to 55 ° C.
  • silsesquioxane (ladder-type silsesquioxane in which 50% of the substituent R contains an epoxy ring structure)
  • a reaction vessel equipped with a stirrer and a thermometer 150 g of methyl isobutyl ketone, water
  • tetramethylammonium oxide tetramethylammonium hydroxide 20.0 mmol
  • 26.0 g of distilled water 46.4 g (309.0 mmol) of ethyltrimethoxysilane, ⁇ -glycidoxy 73.0 g (309.0 mmol) of propyltrimethoxysilane was gradually added at 50 to 55 ° C.
  • silsesquioxane (SQ-D) had a weight average molecular weight of 5,800.
  • a reaction vessel equipped with a thermometer, a stirrer and a back-flow cooler was charged with 150 g (1.1 mol) of methyltrimethoxysilane, 65 g of deionized water, 100 g of toluene, 200 g of n-propyl acetate and 2 g of concentrated hydrochloric acid at room temperature. Thereafter, the mixture was left stirring at 50 ° C. for 1 hour. Thereafter, the pH was adjusted to 8.0 with aqueous ammonia, and then the backflow cooler was replaced with a forward flow cooler. Next, the temperature is raised from 50 ° C. to 120 ° C.
  • Curing agent> -4,4'-diaminodiphenyl sulfone (Seika Cure S, manufactured by Wakayama Seika Kogyo Co., Ltd.).
  • a test piece of 10 cm ⁇ 10 cm ⁇ 1 mm was cut out from the cured epoxy resin, and flame retardancy was evaluated according to ISO 5660 using a cone calorimeter C3 (manufactured by Toyo Seiki).
  • the heater temperature was 750 ° C.
  • the heater radiation amount was 50 kW / m 2
  • the test time was 2 minutes.
  • a bending test is performed under the conditions of a crosshead speed of 2.5 mm / min, a span length of 40 mm, an indenter diameter of 10 mm, and a fulcrum diameter of 4 mm. The amount was measured.
  • the epoxy resin composition prepared in (1) was applied onto release paper using a knife coater to produce a resin film.
  • two resin films are stacked on both sides of the carbon fiber on a carbon fiber “Torayca (registered trademark)” T800G-24K manufactured by Toray Industries, Ltd., which is arranged in one direction in a sheet shape, at a temperature of 100 ° C. and an atmospheric pressure of 1
  • the resin was impregnated into the carbon fiber while being heated and pressurized at atmospheric pressure to obtain a unidirectional prepreg having a carbon fiber basis weight of 190 g / m 2 and a matrix resin content of 35.5% by mass.
  • W (mass%) (W1-W2) ⁇ 100 / W1 (6) Definition of 0 ° of fiber reinforced composite material As described in JIS K7017 (1999), the axis when the fiber direction of the unidirectional fiber reinforced composite material is defined as the axial direction and the axial direction is defined as the 0 ° axis. The orthogonal direction is defined as 90 °.
  • the intersection temperature value of the tangent in the glass state and the tangent in the transition state was defined as the glass transition temperature (° C.).
  • the measurement was performed at a heating rate of 5 ° C./min and a frequency of 1 Hz.
  • Example 1 As shown in Table 1, 10 parts by mass of silsesquioxane (SQ-A) as component [A], and 60 parts by mass of tetraglycidyldiaminodiphenylmethane (“SUMI Epoxy (registered trademark)” ELM434) as component [B] , 30 parts by mass of bisphenol A type epoxy resin (“jER (registered trademark)” 825), 45 parts by mass of 3,3′-diaminodiphenylsulfone as component [C], and polyethersulfone (D) as component [D]
  • the epoxy resin composition was prepared using 7 parts by weight of “SUMICA EXCEL (registered trademark)” PES5003P. According to the above (1) to (7), flame retardancy evaluation, mechanical evaluation, and prepreg of the cured resin The amount of volatile components contained in the fiber and the glass transition temperature of the fiber reinforced composite material were measured. The results are shown in Table 1.
  • Examples 2 to 14, Comparative Examples 1 to 5 Implemented except that the types and blending ratios (parts by mass) of the component [A], component [B], component [C] and component [D] used were changed as shown in Tables 1 to 3
  • the epoxy resin composition was prepared in the same manner as in Example 1, and the flame retardancy evaluation, mechanical property evaluation, volatile content contained in the prepreg, and the glass transition temperature of the fiber reinforced composite material were measured. The results are shown in Tables 1 to 3.
  • the resin varnish was impregnated into a sheet of carbon fibers arranged in one direction and dried by heating to prepare a prepreg, and the amount of volatile components contained in the prepreg was evaluated according to the above (5).
  • the results are shown in Table 3.
  • the obtained unidirectional prepreg was cut into a predetermined size, and six sheets were laminated in one direction, and then a vacuum bag was formed and cured using an autoclave at a temperature of 180 ° C. and a pressure of 6 kg / cm 2 for 2 hours. To obtain a unidirectional fiber reinforced composite material.
  • the component [A] is contained in the epoxy resin composition, and the total amount of the epoxy resin in the epoxy resin composition is 100 parts by mass.
  • the element [A] is contained in an amount of 1 to 40 parts by mass and the epoxy group structure is contained in 50 to 100% of the substituent R of the constituent element [A]
  • the resulting fiber-reinforced composite material is flame retardant and heat resistant. And it was found to be excellent in mechanical properties.
  • Comparative Example 1 when the ladder-type silsesquioxane was not contained, the heat resistance and flame retardancy of the fiber-reinforced composite material tended to decrease. Further, as shown in Comparative Examples 2 and 3, when the content of the constituent element [A] was larger than 40 parts by mass, although the heat resistance and flame retardancy were sufficient, the mechanical properties were lowered. Furthermore, as shown in Comparative Example 4, when the amount of substituents containing an epoxy ring is less than 50% of all substituents even if it contains ladder-type silseoxane, the resin viscosity is high and a resin plate of good quality is obtained. Cann't get. As shown in Comparative Example 5, when a non-ladder silsesquioxane was blended in the epoxy resin composition, the bending deflection amount tended to decrease.
  • Example 1 Comparative Example 6
  • the amount of volatile components contained in the prepreg tended to be high.
  • the fiber reinforced composite material obtained by curing the prepreg laminate of Comparative Example 6 had many voids and cracks, and it was difficult to evaluate the mechanical properties. It has been found that the prepreg of the present invention that can be produced without using a solvent can suppress the volume shrinkage at the time of curing the prepreg laminate and the generation of voids and cracks in the molded product due to the residual solvent.
  • a prepreg and a fiber reinforced composite material having high flame retardancy and heat resistance, and excellent mechanical properties.
  • aircraft primary structural materials such as main wings and fuselage , Tail beams, floor beams, flaps, ailerons, cowls, fairings, interior materials, and other secondary structural materials, rocket motor cases and satellite structural materials.
  • structural materials for moving bodies such as automobiles, ships, and railway vehicles, drive shafts, leaf springs, windmill blades, various turbines, pressure vessels, flywheels, paper rollers, roofing materials, cables, reinforcement bars
  • suitable for civil engineering and building material applications such as repair and reinforcement materials.
  • it is suitably used for golf shafts, fishing rods, tennis, badminton and squash rackets, hockey sticks, and ski pole applications.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

Le but de la présente invention concerne un préimprégné qui présente une résistance élevée à la flamme et une résistance élevée à la chaleur sans utiliser de solvant et pour lequel un silsesquioxane de type échelle présentant d'excellentes caractéristiques mécaniques est introduit dans une résine de matrice ; et un matériau composite renforcé par des fibres. A cet effet, la présente invention concerne un préimprégné formé par imprégnation des fibres de renforcement par une composition de résine époxy qui comprend au moins les constituants [A], [B] et [C], la composition de résine époxy comprenant 1 à 40 parties en masse de [A] par rapport à un total de 100 parties en masse d'une résine époxy et la quantité de substances volatiles contenues dans le préimprégné étant inférieure ou égale à 0,8 % en masse. [A] Un silsesquioxane de type échelle présentant une structure spécifique. [B] Une résine époxy présentant deux groupes époxy ou plus par molécule. [C] Un agent de durcissement.
PCT/JP2017/042434 2017-01-10 2017-11-27 Préimprégné et matériau composite renforcé par des fibres Ceased WO2018131300A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN112143169A (zh) * 2020-06-30 2020-12-29 西北工业大学 高硅氧纤维增强的反应型倍半硅氧烷改性的杂化酚醛复合材料及制备方法
JP2021001245A (ja) * 2019-06-20 2021-01-07 三菱ケミカル株式会社 繊維強化エポキシ樹脂複合材及び繊維強化プラスチック
CN115093674A (zh) * 2022-06-10 2022-09-23 佛山萤鹤新材料有限公司 用于led封装的改性环氧树脂及其制备方法
EP4108713A1 (fr) * 2021-06-23 2022-12-28 Toray Advanced Composites Préimprégné à faible teneur en composants volatils
CN117462763A (zh) * 2023-12-27 2024-01-30 中国科学院空间应用工程与技术中心 氮化硅纤维增强聚醚醚酮复合材料、制备方法及应用

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WO2004072150A1 (fr) * 2003-02-12 2004-08-26 Nippon Kayaku Kabushiki Kaisha Compose de silicium contenant un groupe epoxy et composition de resine thermodurcissable
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JP2007002192A (ja) * 2005-06-27 2007-01-11 Nippon Kayaku Co Ltd 半導体装置用アンダーフィル材
JP2011057736A (ja) * 2009-09-07 2011-03-24 Toho Tenax Co Ltd エポキシ樹脂組成物及びそれを用いたプリプレグ
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JPH04161435A (ja) * 1990-10-24 1992-06-04 Kansai Paint Co Ltd ガラス繊維質用硬化性シリコン樹脂組成物及びその硬化物
JPH06240024A (ja) * 1992-03-30 1994-08-30 Toray Ind Inc プリプレグおよび複合材料
JP2000191807A (ja) * 1998-12-24 2000-07-11 Mitsubishi Rayon Co Ltd トウプリプレグおよびその製造方法
JP2001288333A (ja) * 2000-04-05 2001-10-16 Hitachi Ltd エポキシ樹脂複合材料及びそれを用いた装置
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WO2004072150A1 (fr) * 2003-02-12 2004-08-26 Nippon Kayaku Kabushiki Kaisha Compose de silicium contenant un groupe epoxy et composition de resine thermodurcissable
JP2004256609A (ja) * 2003-02-25 2004-09-16 Nippon Kayaku Co Ltd エポキシ基を有するケイ素化合物、その製造方法及び熱硬化性樹脂組成物
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JP2007002192A (ja) * 2005-06-27 2007-01-11 Nippon Kayaku Co Ltd 半導体装置用アンダーフィル材
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JP2014043542A (ja) * 2012-07-31 2014-03-13 Toray Ind Inc プリプレグおよび炭素繊維強化複合材料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021001245A (ja) * 2019-06-20 2021-01-07 三菱ケミカル株式会社 繊維強化エポキシ樹脂複合材及び繊維強化プラスチック
CN112143169A (zh) * 2020-06-30 2020-12-29 西北工业大学 高硅氧纤维增强的反应型倍半硅氧烷改性的杂化酚醛复合材料及制备方法
EP4108713A1 (fr) * 2021-06-23 2022-12-28 Toray Advanced Composites Préimprégné à faible teneur en composants volatils
WO2022268712A1 (fr) * 2021-06-23 2022-12-29 Toray Advanced Composites Préimprégné à faible teneur en volatile
CN115093674A (zh) * 2022-06-10 2022-09-23 佛山萤鹤新材料有限公司 用于led封装的改性环氧树脂及其制备方法
CN117462763A (zh) * 2023-12-27 2024-01-30 中国科学院空间应用工程与技术中心 氮化硅纤维增强聚醚醚酮复合材料、制备方法及应用

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