WO2016136540A1 - プリプレグおよび繊維強化複合材料 - Google Patents
プリプレグおよび繊維強化複合材料 Download PDFInfo
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- WO2016136540A1 WO2016136540A1 PCT/JP2016/054503 JP2016054503W WO2016136540A1 WO 2016136540 A1 WO2016136540 A1 WO 2016136540A1 JP 2016054503 W JP2016054503 W JP 2016054503W WO 2016136540 A1 WO2016136540 A1 WO 2016136540A1
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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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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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
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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
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Definitions
- the present invention relates to a prepreg from which a fiber reinforced composite material having excellent interlaminar fracture toughness and heat resistance can be obtained, and a fiber reinforced composite material using the prepreg.
- the fiber reinforced composite material obtained by impregnating a reinforced fiber base material with a resin is used in a wide range of applications as a material having both light weight and mechanical properties.
- carbon fiber reinforced composite material with carbon fiber base material impregnated with thermosetting resin is excellent in specific strength, specific rigidity, and heat resistance, and is used for aircraft structural members, wind power blades, automobile members, electronic devices.
- the demand is increasing year by year.
- thermosetting resin having excellent impregnation and heat resistance
- an epoxy resin a phenol resin, a melanin resin, a bismaleimide resin, an unsaturated polyester resin, or the like is used.
- epoxy resins are widely used because they are excellent in heat resistance and moldability, and have high mechanical properties when made into a carbon fiber composite material.
- a fiber reinforced composite material As a method for producing a fiber reinforced composite material, various methods are applied depending on the form of the product and the required physical properties. However, a sheet-like intermediate material (prepreg with carbon fiber impregnated with a thermosetting resin as a matrix resin) is used. ) Is the most common method. A fiber reinforced composite material having high specific strength, specific rigidity, and heat resistance can be produced by laminating a plurality of prepregs in an arbitrary direction and curing the resin by heating.
- carbon fiber composite materials have been studied in order to increase the strength and rigidity (elastic modulus) of the matrix resin after curing in order to make the best use of the high mechanical properties of carbon fibers.
- the high-rigidity matrix resin has low toughness, cracks may occur in the matrix resin due to external forces such as impact, and there has been a problem in safety and durability in actual use.
- composite materials in which prepregs are laminated have a problem of deterioration of mechanical properties due to interlayer fracture, and various methods for improving interlayer fracture toughness have been studied. Among them, many methods have been proposed in which a material different from the matrix resin is dispersed between layers to absorb the fracture energy generated by stress loading.
- Patent Document 1 For example, a technique for dispersing polyamide particles in a matrix resin has been proposed (Patent Document 1). However, since polyamide has a property that its mechanical properties are lowered by moisture absorption, there is a problem that the mechanical properties of the fiber-reinforced composite material change with time. In addition, techniques for improving interlaminar fracture toughness in shear mode (mode II) by dispersing silicone particles and urethane particles in a matrix resin have been proposed (Patent Documents 2 and 3). However, if the amount of polymer particles added is increased in order to obtain a sufficient effect for improving the interlaminar fracture toughness, problems such as a decrease in specific strength / specific rigidity and a decrease in prepreg handling properties, which are the characteristics of fiber reinforced composite materials, occur.
- An object of the present invention is to provide a fiber-reinforced composite material that improves interlaminar fracture toughness and also has high heat resistance.
- the present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a resin composition having a specific composition in a prepreg obtained by impregnating a reinforcing fiber with a resin component, and the present invention has been completed.
- a prepreg comprising a reinforcing fiber (A) and a resin composition (E), wherein the resin composition (E) satisfies the following requirements (i) to (ii):
- the ultra high molecular weight olefin polymer constituting the particles has an intrinsic viscosity [ ⁇ ] measured in a 135 ° C. decalin solvent of 5 to 50 dl / g.
- the average particle diameter d50 is 3 to 200 ⁇ m.
- the ultra high molecular weight olefin polymer constituting the ultra high molecular weight olefin polymer or a particle (D) composed of a crosslinked product thereof is ultra high molecular weight polyethylene.
- thermosetting resin (B) is an epoxy resin
- curing agent (C) is an epoxy curing agent
- a fiber-reinforced composite material obtained by curing the prepreg according to any one of [1] to [6].
- the present invention it is possible to provide a prepreg from which a fiber-reinforced composite material having excellent interlaminar fracture toughness and heat resistance is obtained, and a fiber-reinforced composite material using the prepreg.
- Examples of the reinforcing fiber (A) used in the present invention include glass fiber, carbon fiber, aramid fiber, and boron fiber. Two or more kinds of these fibers may be mixed and used. Among these, carbon fibers having light weight and high mechanical properties are preferable.
- the form of the reinforcing fiber (A) is not particularly limited, and examples thereof include continuous fibers arranged in one direction, single tow, roving, woven fabric, mat, knit, braid, nonwoven fabric, and paper.
- a composite material using continuous fibers arranged in one direction and a form in which the fibers are woven are suitable for expressing high mechanical properties.
- the resin composition (E) used in the present invention contains a thermosetting resin (B) and a curing agent (C), and is composed of particles composed of an ultrahigh molecular weight olefin polymer or a crosslinked product thereof (hereinafter referred to as “ultra-high”). Also referred to as “molecular weight olefin polymer particles”.) (D) is 0.1 to 10% by mass, preferably 0.3 to 8% by mass, more preferably 0.5 to 6% by mass, particularly preferably 0.5. Comprising 4% by weight.
- the content of the ultrahigh molecular weight olefin polymer particles (D) is preferably not less than the above lower limit value in terms of improving the interlaminar fracture toughness of the obtained fiber reinforced composite material, and it is not more than the above upper limit value. It is preferable in the mechanical properties such as strength and elastic modulus of the reinforced composite material and heat resistance.
- the ultrahigh molecular weight olefin polymer means a homopolymer such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or a small amount of ethylene and a small amount satisfying the following specific requirements.
- Copolymers with other ⁇ -olefins such as propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene, but are preferably ethylene-based polymers, particularly preferably Is a homopolymer of ethylene.
- the ultra high molecular weight olefin polymer particles (D) may be a crosslinked product of the ultra high molecular weight olefin polymer.
- the ultrahigh molecular weight olefin polymer constituting the ultrahigh molecular weight olefin polymer particle (D) (when the ultrahigh molecular weight olefin polymer particle (D) is a cross-linked product of ultrahigh molecular weight olefin polymer) Is an ultra-high molecular weight olefin polymer before crosslinking), and the intrinsic viscosity [ ⁇ ] measured in a 135 ° C. decalin solvent is 5 to 50 dl / g, preferably 10 to 40 dl / g, more preferably 10 to 30 dl. / G.
- the ultra-high molecular weight olefin polymer particles (D) have high impact resistance and are difficult to flow even in the temperature range above the melting point. It is preferable because a high effect can be expected.
- the prepreg manufacturing process generally includes heating and pressurizing processes, and the intrinsic viscosity [ ⁇ ] is preferably 5 dl / g or more from the viewpoint of maintaining the shape.
- the average particle diameter d50 of the ultrahigh molecular weight olefin polymer particles (D) is a value at which the integrated value of the particle shape distribution is 50% by mass by measurement of the weight-based particle size distribution by the Coulter counter method.
- d50 is in the range of 3 to 200 ⁇ m, preferably 3 to 100 ⁇ m, more preferably 3 to 50 ⁇ m.
- the average particle size is less than or equal to the above upper limit in that an effect of preventing crack growth due to impact or the like can be obtained with a small addition amount.
- the ultrahigh molecular weight olefin polymer particles (D) have a narrow particle size distribution in that the ultra high molecular weight olefin polymer particles (D) are uniformly dispersed in the resin composition (E). .
- the average particle diameter d50 is in the range of 3 to 50 ⁇ m, it is preferable that the following requirement (ii) -2 is further satisfied.
- the average particle diameter d50 of the ultra high molecular weight olefin polymer particles (D) is in the range of 3 to 50 ⁇ m, and the particles having a particle diameter of 40 ⁇ m or less are 50% by mass or more of the ultra high molecular weight olefin polymer particles (D). Be.
- the proportion of particles having a particle size of 40 ⁇ m or less is 50% by mass or more, more preferably 90% by mass or more, and further preferably It is 95 mass% or more.
- the ratio of particles having a particle diameter of 40 ⁇ m or less being 50% by mass or more means that the abundance of coarse particles is small.
- the ultrahigh molecular weight olefin polymer particles (D) are dispersed in a thermosetting resin, the added substance (particles) will contribute to the improvement of impact resistance efficiently. It is considered preferable.
- the ultra high molecular weight olefin polymer particles (D) further satisfy one or more of the following requirements in addition to the above requirements.
- the aspect ratio is 1.0 to 1.4.
- the aspect ratio is measured by image analysis of ultra high molecular weight olefin polymer particles (D).
- the aspect ratio is represented by the ratio of the length and width of the smallest rectangle (the circumscribed rectangle) when the figure on which the particle is projected is surrounded by a rectangle, and the particle projection figure is closer to a perfect circle as it approaches 1. This indicates that the particle itself is close to a true sphere.
- the aspect ratio is measured for several thousand particles, and the cumulative value of 50% is adopted as the aspect ratio of the entire high molecular weight olefin polymer particles (D).
- the lower limit value of the aspect ratio is 1.0, as is clear from the definition of the aspect ratio described above. Since the numerical value indicates the most preferable case, there is no point in setting the lower limit value. If set, it is 1.1, preferably 1.05, more preferably 1.0. On the other hand, a preferable upper limit is 1.4, preferably 1.3, and more preferably 1.2.
- Ultra high molecular weight olefin polymer constituting the particle (D) (when the ultra high molecular weight olefin polymer particle (D) is a crosslinked product of ultra high molecular weight olefin polymer,
- the melting point (Tm) of the molecular weight olefin polymer) measured by a differential scanning calorimeter (DSC) is 125 to 145 ° C. Specific measurement methods are described in the Examples section.
- the melting point is not less than the above lower limit, the shape is easily maintained even after the heating step in the production of the resin composition, prepreg, and fiber reinforced composite material, which is preferable in improving the interlaminar fracture toughness of the obtained fiber reinforced composite material.
- the production method of the ultrahigh molecular weight olefin polymer particles (D) is not particularly limited.
- the particles comprising the ultrahigh molecular weight olefin polymer are For example, it can be produced by the method disclosed in the following document. (1) International Publication No. 2006/054696 (2) International Publication No. 2010/074073 (3) Japanese Patent Laid-Open No. 60-163935 (4) International Publication No. 2008/013144 (5) International Publication No.
- the ultra high molecular weight olefin polymer particles (D) may be a crosslinked body.
- a method of treating the ultra high molecular weight olefin polymer with an organic oxide There are a method of irradiating a high molecular weight olefin polymer with a radiation, a method of treating an ultrahigh molecular weight olefin polymer with a silane, and the like. These changes in particle shape due to cross-linking are usually not recognized. Therefore, the ultrahigh molecular weight olefin polymer to be crosslinked usually has a particle shape.
- the irradiation amount is usually 50 to 700 kGy, preferably 100 to 500 kGy.
- the crosslinking reaction of the ultrahigh molecular weight olefin polymer proceeds efficiently, which is preferable.
- the irradiation dose is less than or equal to the above upper limit, deterioration of the ultrahigh molecular weight olefin polymer is suppressed, and when the irradiation dose is greater than or equal to the lower limit, the crosslinking of the polymer chain proceeds at a sufficient speed. preferable.
- the physical properties defined by the requirements of the ultrahigh molecular weight olefin polymer particles (D) can be adjusted as follows.
- the intrinsic viscosity [ ⁇ ] can be adjusted by the temperature of the polymerization system during the polymerization reaction, and can also be adjusted by the presence of hydrogen in the polymerization system.
- the average particle diameter d50 is adjusted by the type of catalyst used for the production of the ultrahigh molecular weight olefin polymer particles (D). More specifically, according to the disclosure of the above documents (1) and (2), polymer particles having an average particle diameter of several ⁇ m to 10 ⁇ m, that is, near the lower limit can be obtained. In accordance with the disclosure in the literature (3), polymer particles having a controlled average size in the range of about 10 to 100 ⁇ m can be obtained. Furthermore, in accordance with the disclosures of the above references (4) and (5), polymer particles having an average particle diameter of about 100 ⁇ m to several hundred ⁇ m, that is, near the upper limit can be obtained. It can also be adjusted by selecting those satisfying the requirement (ii) from commercially available ultrahigh molecular weight olefin polymer particles.
- coarse particles can be removed by sieving a polymer obtained by polymerization or a commercially available product. In some cases, the average particle diameter can be adjusted.
- the opening of the sieve can be selected according to the purpose.
- fusing point is adjusted with the kind of olefin which comprises ultra high molecular weight olefin type polymer particle (D).
- olefin which comprises ultra high molecular weight olefin type polymer particle (D).
- D ultra high molecular weight olefin type polymer particle
- fusing point is adjusted with the kind of olefin which comprises ultra high molecular weight olefin type polymer particle (D).
- it is a copolymer
- it can be adjusted by the composition.
- the melting point of the resulting polymer decreases as the proportion of ⁇ -olefin copolymerized with ethylene increases.
- An aspect ratio can be adjusted with the kind of catalyst used for manufacture of ultra high molecular weight olefin polymer particle (D). As the shape of the catalyst is closer to a true sphere, that is, the aspect ratio is smaller, the aspect ratio of the resulting ultrahigh molecular weight olefin polymer particles (D) tends to be smaller.
- thermosetting resin (B) As the thermosetting resin (B) used in the present invention, a resin that is cured by external energy such as heat, light, and electron beam to form a three-dimensional cured product at least partially is preferably used.
- the thermosetting resin include an epoxy resin, a modified epoxy resin, a phenol resin, a melanin resin, a bismaleimide resin, an unsaturated polyester resin, a vinyl ester resin, and a benzoxazine resin.
- a modified epoxy resin is preferably used.
- the epoxy resin any conventionally known epoxy resin can be used and is not particularly limited.
- bisphenol type epoxy resin such as bisphenol type epoxy resin, alcohol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, diphenylfluorene type epoxy resin, hydrophthalic acid type epoxy resin, dimer acid type epoxy resin, Bifunctional epoxy resins such as alicyclic epoxy resins, glycidyl ether type epoxy resins such as tetrakis (glycidyloxyphenyl) ethane, tris (glycidyloxyphenyl) methane, glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, naphthalene Type epoxy resin, novolac type epoxy resin phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc., phenol type epoxy resin, etc. Polyfunctional epoxy resins. Furthermore, various modified epoxy resins such as urethane-modified epoxy resin and rubber-modified epoxy resin can also
- thermosetting resin (B) a known curing agent that cures the thermosetting resin (B) is used.
- an epoxy resin curing agent a compound having an active group capable of reacting with an epoxy group is used.
- aliphatic polyamines such as tetramethylguanidine, thiourea addition amine, methylhexahydrophthalic anhydride, carboxylic acid hydrazide, carboxylic acid amide, polymercaptan and Lewis acid complexes such as boron trifluoride ethylamine complex, etc.
- these curing agents may be used alone or in combination.
- an aromatic polyamine as a curing agent, a cured epoxy resin with good heat resistance can be obtained.
- diaminodiphenyl sulfone or a derivative thereof, or various isomers thereof are curing agents suitable for obtaining a cured epoxy resin having good heat resistance.
- a combination of dicyandiamide and a urea compound such as 3,4-dichlorophenyl-1,1-dimethylurea or imidazoles as a curing agent
- high heat resistance and water resistance can be obtained while curing at a relatively low temperature.
- a cured product having a lower water absorption than the amine compound curing is obtained.
- a latent product of these curing agents for example, a microencapsulated product, the storage stability of the prepreg, in particular, tackiness and draping properties hardly change even when left at room temperature.
- the preferable addition amount of the curing agent (C) varies depending on the types of the thermosetting resin (B) and the curing agent (C), and can be appropriately set with reference to the addition amount in the conventional prepreg.
- the curing agent is generally stoichiometrically 0.7 to 1.3, preferably 0.1 to 1 epoxy equivalent.
- the addition of 8 to 1.2 is preferable from the viewpoints of mechanical properties and heat resistance of the fiber-reinforced composite material.
- the resin composition (E) used in the present invention has a thermosetting property other than the thermosetting resin (B), the curing agent (C), and the ultrahigh molecular weight olefin polymer, as long as the effects of the present invention are not impaired.
- a resin or a thermoplastic resin may be included.
- the content of the thermosetting resin and the thermoplastic resin in the resin composition (E) is usually 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less.
- the resin composition (E) may further contain various additives such as a curing accelerator, a reactive diluent, a filler, an anti-aging agent, a flame retardant, and a pigment as necessary.
- various additives such as a curing accelerator, a reactive diluent, a filler, an anti-aging agent, a flame retardant, and a pigment as necessary.
- the content of various additives in the resin composition (E) is usually 10% by mass or less, preferably 5% by mass or less.
- the method for producing the resin composition (E) is not particularly limited, and any conventionally known method may be used.
- the thermosetting resin (B) is an epoxy resin
- the kneading temperature applied during the production of the resin composition (E) can be in the range of 10 to 200 ° C. When it exceeds 200 ° C., thermal deterioration of the epoxy resin or partial curing reaction starts, and the storage stability of the resulting resin composition (E) and the prepreg using the resin composition (E) may be lowered. If it is lower than 10 ° C., the viscosity of the resin composition (E) is high, and it may be difficult to knead substantially.
- the temperature is preferably 20 to 180 ° C, more preferably 30 to 170 ° C.
- a conventionally known apparatus can be used. Examples thereof include a roll mill, a planetary mixer, a kneader, an extruder, a Banbury mixer, a mixing vessel provided with a stirring blade, and a horizontal mixing vessel.
- the kneading of each component can be performed in the air or in an inert gas atmosphere.
- an atmosphere in which temperature and humidity are controlled is preferable.
- a low humidity atmosphere such as a temperature controlled at a constant temperature of 30 ° C. or lower or a relative humidity of 50% RH or lower.
- each component may be performed in a single stage, or may be performed in multiple stages by sequentially adding each component. Moreover, when adding sequentially, it can add in arbitrary orders, but it is preferable to add a hardening
- the prepreg in the present invention can be produced by impregnating the reinforcing fiber (A) with the resin composition (E) obtained as described above.
- the method for producing the prepreg of the present invention is not particularly limited, and can be produced using any conventionally known method.
- the hot melt method in which the resin composition (E) obtained above is coated on a release paper on a thin film, and the resin film obtained by peeling is impregnated into a sheet-like reinforcing fiber (A).
- a solvent method may be mentioned in which the resin composition (E) is varnished with a solvent and the reinforced varnish (A) is impregnated with the varnish.
- the hot melt method is preferable from the viewpoint of handling properties and mechanical properties of the obtained fiber-reinforced composite material.
- the preferred range of the content of the reinforcing fiber (A) in the obtained prepreg differs depending on the type and form of the reinforcing fiber (A) and the composition of the resin composition (E), but generally it is 10 to 80% by volume.
- the reinforcing fiber (A) is preferably included.
- the fiber-reinforced composite material of the present invention is obtained by curing the prepreg of the present invention.
- the prepreg can be used as a single layer or laminated, it is generally used by laminating. That is, the prepreg of the present invention is appropriately cut and then laminated as necessary, and is heated and pressurized with an autoclave, a hot press or the like to be thermally cured and formed into a desired shape.
- the thermosetting conditions are determined by the thermosetting resin and the curing agent used.
- the method for stacking the prepreg is not particularly specified, and may be selected depending on the product design and the like. For example, pseudo-isotropic, unidirectional, ⁇ 45 ° stacking or the like is used. However, when two or more layers are stacked in the same direction, it is desirable from the viewpoint of reinforcing efficiency that the same kind of carbon fibers are stacked so as not to overlap.
- Examples of the shape of the molded body include a flat plate, a cylindrical shape, and the like, and a three-dimensional shape obtained by lamination molding of a prepreg.
- the orientation angle and thickness of the fiber may be determined according to the required performance of the obtained fiber-reinforced composite material.
- the intrinsic viscosity [ ⁇ ] was measured in decalin at a temperature of 135 ° C. by dissolving ultrahigh molecular weight olefin polymer particles in decalin.
- the average particle diameter d50 was measured by a Coulter counter (Multisizer 3 type, manufactured by Beckman). An aperture tube having pores with a pore size of 200 ⁇ m was attached to a Coulter counter, and the particle size distribution was measured for 2 mg of sample to obtain a particle size distribution curve. This curve was analyzed by a conventional method to determine the average particle size d50 and the proportion of particles having a particle size of 40 ⁇ m or less.
- the melting point (Tm) was measured by DSC. Using a DSC (DSC220C, manufactured by Seiko Instruments Inc.), a sample of about 5 mg was put in an aluminum pan for measurement, and the temperature was raised to 200 ° C. to melt the sample, and then cooled to 30 ° C. at ⁇ 10 ° C./min. The melting point (Tm) was calculated from the peak apex of the crystal melting peak when the temperature was raised at ° C / min.
- ⁇ Tensile strength and tensile modulus of composite material The tensile strength and tensile modulus were measured by a tensile test. An aluminum tab having a length of 50 mm was attached to both ends of a test piece having a width of 20 mm and a length of 200 mm. A Tensilon universal testing machine (RTC-1350A, manufactured by Orientec Co., Ltd.) was used and the test speed was 1 mm / min.
- ⁇ Bending strength and flexural modulus of composite material The bending strength and the bending elastic modulus were measured by a three-point bending test described in JIS K7074. A test piece having a width of 15 mm and a length of 100 mm was prepared, and an Instron universal testing machine (Type 55R4026, manufactured by Instron) was used at a test speed of 5 mm / min.
- the mode II interlaminar fracture toughness value was measured by ENF (End Notched Flexure) test. An initial crack having an initial crack length of 40 mm was introduced into a test piece having a width of 25 mm, a length of 140 mm, and a thickness of 3 mm. Using an Instron universal testing machine (Type55R4026, manufactured by Instron), an interlaminar fracture toughness value was determined by a three-point bending test. The test speed was 0.5 mm / min.
- the resin raw materials, prepregs and fiber reinforced composite materials used in the examples are prepared as follows, and the physical property measurement results are 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.
- Examples 1 to 4, Comparative Example 1 An epoxy resin (trade name: jER828, manufactured by Mitsubishi Chemical Corporation) as a thermosetting resin that is a base material of the matrix resin, and a modified aromatic amine (trade name: jER Cure W, manufactured by Mitsubishi Chemical Corporation) as a curing agent. Using. The blending amount was jER cure W: 25 parts by mass with respect to jER828: 100 parts by mass. These were mixed to prepare a mixture.
- jER cure W 25 parts by mass with respect to jER828: 100 parts by mass.
- an ultra high molecular weight olefin polymer having an intrinsic viscosity [ ⁇ ] of 14 dl / g, an average particle diameter d50 of 30 ⁇ m, a ratio of particles having a particle diameter of 40 ⁇ m or less is 70% by mass, an aspect ratio is 1.2, a melting point
- ultra-high molecular weight polyethylene fine particles having a temperature of 136 ° C. (trade name: Mipperon XM220, manufactured by Mitsui Chemicals, Inc.) are irradiated with an electron beam of 200 kGy, the concentrations shown in Table 1 (the amount of the resin composition obtained is 100 mass%) And stirred and mixed for 24 hours under conditions of 600 rpm and 100 ° C.
- the ultrahigh molecular weight olefin polymer after crosslinking by electron beam irradiation had a melting point of 136 ° C. and was partially insoluble in 135 ° C. decalin.
- the average particle size d50, the proportion of particles having a particle size of 40 ⁇ m or less, and the aspect ratio were unchanged from those before electron beam irradiation.
- a 12-layer laminated prepreg was produced by the hand lay-up method using the resin composition and a plain weave of carbon fiber (trade name: Torayca cloth manufactured by Toray Industries, Inc.).
- a flat plate sample was prepared by curing the laminated prepreg under conditions of 100 ° C. for 2 hours and then 175 ° C. for 4 hours while applying a pressure of 4 kPa.
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Abstract
Description
[1]強化繊維(A)および樹脂組成物(E)を含むプリプレグであって、前記樹脂組成物(E)が、下記要件(i)~(ii)を満たす超高分子量オレフィン系重合体またはその架橋体からなる粒子(D)を0.1~10質量%含み、かつ熱硬化性樹脂(B)および硬化剤(C)を含むプリプレグ。
(i)該粒子を構成する超高分子量オレフィン系重合体の135℃デカリン溶媒中で測定した極限粘度[η]が5~50dl/gである。
(ii)平均粒子径d50が3~200μmである。
(iii)アスペクト比が1.0~1.4である。
(iv)該粒子を構成する超高分子量オレフィン系重合体の示差走査熱量計(DSC)で測定した融点(Tm)が125~145℃である。
本発明で用いられる強化繊維(A)としては、例えばガラス繊維、炭素繊維、アラミド繊維、ボロン繊維などが挙げられる。これらの繊維を2種類以上混合して用いても構わない。中でも軽量かつ高い力学物性を有する炭素繊維が好ましい。
本発明で用いられる樹脂組成物(E)は、熱硬化性樹脂(B)および硬化剤(C)を含み、また、超高分子量オレフィン系重合体またはその架橋体からなる粒子(以下「超高分子量オレフィン系重合体粒子」ともいう。)(D)を0.1~10質量%、好ましくは0.3~8質量%、より好ましくは0.5~6質量%、特に好ましくは0.5~4質量%含んでなる。
本発明において超高分子量オレフィン系重合体とは、下記特定の要件を満たす、ポリエチレン、ポリプロピレン、ポリ-1-ブテン、ポリ-4-メチル-1-ペンテンなどの単独重合体や、エチレンと少量の他のα-オレフィン、たとえば、プロピレン、1-ブテン、1-ヘキセン、1-オクテンおよび4-メチル-1-ペンテンなどとの共重合体であるが、好ましくはエチレン系のポリマーであり、特に好ましくはエチレンの単独重合体である。また、超高分子量オレフィン系重合体粒子(D)は前記超高分子量オレフィン系重合体の架橋体であってもよい。
前記超高分子量オレフィン系重合体粒子(D)を構成する超高分子量オレフィン系重合体(前記超高分子量オレフィン系重合体粒子(D)が超高分子量オレフィン系重合体の架橋体である場合には、架橋前の超高分子量オレフィン系重合体)の135℃デカリン溶媒中で測定した極限粘度[η]は5~50dl/gであり、好ましくは10~40dl/g、より好ましくは10~30dl/gの範囲である。
前記超高分子量オレフィン系重合体粒子(D)の平均粒子径d50は、コールターカウンター法による重量基準粒度分布の測定によって、粒形分布の積算値が50質量%となる値であり、平均粒子径d50は3~200μm、好ましくは3~100μm、さらに好ましくは3~50μmの範囲である。
超高分子量オレフィン系重合体粒子(D)の平均粒子径d50が3~50μmの範囲にあり、かつ、粒子径40μm以下の粒子が超高分子量オレフィン系重合体粒子(D)の50質量%以上であること。
アスペクト比が1.0~1.4であること。アスペクト比は、超高分子量オレフィン系重合体粒子(D)の画像解析によって測定される。アスペクト比は、粒子を投影した図形を長方形で囲んだ時の最小長方形(外接長方形)の長さと幅の比で表され、1に近づくほど粒子投影図形が真円に近いということになり、当該粒子自体が真球に近いことを示すものである。本発明においては、数千個の粒子についてアスペクト比を計測し、累積50%の値を高分子量オレフィン系重合体粒子(D)全体のアスペクト比として採用する。
前記粒子(D)を構成する超高分子量オレフィン系重合体(前記超高分子量オレフィン系重合体粒子(D)が超高分子量オレフィン系重合体の架橋体である場合には、架橋前の超高分子量オレフィン系重合体)の示差走査熱量計(DSC)により測定した融点(Tm)が125~145℃であること。具体的な測定方法は実施例の項に記載する。融点が上記下限値以上であると、樹脂組成物、プレプリグおよび繊維強化複合材料の作製における加熱工程を経ても形状を保ちやすく、得られる繊維強化複合材料の層間破壊靭性の向上において好ましい。
本発明において超高分子量オレフィン系重合体粒子(D)の製造方法は特に限定は無いが、前記超高分子量オレフィン系重合体粒子(D)のうち前記超高分子量オレフィン系重合体からなる粒子は、例えば、以下の文献に開示された方法により製造することができる。
(1)国際公開第2006/054696号
(2)国際公開第2010/074073号
(3)特開昭60-163935号公報
(4)国際公開第2008/013144号
(5)国際公開第2009/011231号
また、前記超高分子量オレフィン系重合体粒子(D)は前述の通り、架橋体であってもよく、架橋には、超高分子量オレフィン系重合体を有機化酸化物により処理する方法、超高分子量オレフィン系重合体に放射線を照射する方法、および超高分子量オレフィン系重合体をシラン処理する方法などがある。これらの架橋による粒子形状の変化は通常認められない。よって架橋される超高分子量オレフィン系重合体は、通常粒子形状を有している。例えば、超高分子量オレフィン系重合体に放射線を照射することによって、分子鎖の切断と架橋が生じ、その結果、分子鎖が架橋点で結び合わされる。放射線としては、α線、β線、γ線、電子線、イオンなどがあり、いずれも使用可能であるが、電子線あるいはγ線が適している。架橋することにより、高温下での変形がさらに抑制され、粒子形状を維持する効果が期待できるため好ましい。
なお、放射線を照射する方法では、照射量は通常50~700kGy、好ましくは100~500kGyである。照射線量が上記範囲内にある場合、超高分子量オレフィン系重合体の架橋反応が効率よく進行し好ましい。照射線量が上記上限値以下であることで、超高分子量オレフィン系重合体の劣化が抑制され、また、照射線量が下限値以上であることで、ポリマー鎖の架橋が十分な速度で進む点で好ましい。
極限粘度[η]は、重合反応時における重合系の温度により調節可能であり、また、重合系に水素を存在させることによっても調節可能である。
平均粒子径d50は、超高分子量オレフィン系重合体粒子(D)の製造に用いる触媒の種類によって調節される。より具体的に例を示すと、上記の文献(1)、(2)の開示に従って、平均粒子径が数μm~10μm付近の、すなわち下限値付近の重合体粒子を得ることができ、上記の文献(3)の開示に従って、平均粒子径を10~100μm程度の範囲において大きさをコントロールした重合体粒子を得ることができる。またさらに、上記の文献(4)、(5)の開示に従って、平均粒子径が100μm程度から数百μm程度、すなわち上限値付近の重合体粒子を得ることができる。また、市販品の超高分子量オレフィン系重合体粒子の中から、この要件(ii)を満たすものを選択することによっても調節可能である。
融点は、超高分子量オレフィン系重合体粒子(D)を構成するオレフィンの種類によって調整される。共重合体である場合は、その組成によって調整可能である。例えばエチレン・α-オレフィン共重合体であれば、エチレンと共重合するα-オレフィンの比率が大きくなるほど、得られる重合体の融点は低くなる。
アスペクト比は、超高分子量オレフィン系重合体粒子(D)の製造に用いる触媒の種類によって調整可能である。触媒の形状がより真球に近く、すなわちアスペクト比が小さいほど、得られる超高分子量オレフィン系重合体粒子(D)のアスペクト比が小さくなる傾向である。
本発明で用いられる熱硬化性樹脂(B)としては、熱、光、電子線などの外部からのエネルギーにより硬化して、少なくとも部分的に三次元硬化物を形成する樹脂が好ましく用いられる。熱硬化性樹脂の具体例としては、エポキシ樹脂、変性エポキシ樹脂、フェノール樹脂、メラニン樹脂、ビスマレイミド樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、ベンゾオキサジン樹脂などがあげられるが、特に、エポキシ樹脂、変性エポキシ樹脂が好ましく用いられる。エポキシ樹脂としては、従来公知のいずれのエポキシ樹脂でも用いることができ、特に限定されるものではない。具体的には、ビスフェノール型エポキシ樹脂、アルコール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ジフェニルフルオレン型エポキシ樹脂、ヒドロフタル酸型エポキシ樹脂、ダイマー酸型エポキシ樹脂、脂環型エポキシ樹脂などの2官能エポキシ樹脂、テトラキス(グリシジルオキシフェニル)エタン、トリス(グリシジルオキシフェニル)メタンのようなグリシジルエーテル型エポキシ樹脂、テトラグリシジルジアミノジフェニルメタンのようなグリシジルアミン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ノボラック型エポキシ樹脂であるフェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂など、また、フェノール型エポキシ樹脂などの多官能エポキシ樹脂等が挙げられる。更に、ウレタン変性エポキシ樹脂、ゴム変性エポキシ樹脂などの各種変性エポキシ樹脂も用いることができる。また、これらの混合物も用いることができる。
硬化剤(C)としては、熱硬化性樹脂(B)を硬化させる公知の硬化剤が用いられる。例えば、エポキシ樹脂の硬化剤としては、エポキシ基と反応し得る活性基を有する化合物が用いられる。具体的には、例えば、脂肪族ポリアミン、芳香族ポリアミン、ポリアミド樹脂、二級および三級アミン類、アミノ安息香酸エステル類、各種酸無水物、フェノールノボラック樹脂、クレゾールノボラック樹脂、ポリフェノール化合物、イミダゾール誘導体、テトラメチルグアニジン、チオ尿素付加アミン、メチルヘキサヒドロフタル酸無水物のようなカルボン酸無水物、カルボン酸ヒドラジド、カルボン酸アミド、ポリメルカプタンおよび三フッ化ホウ素エチルアミン錯体のようなルイス酸錯体などが挙げられる。また、これらの硬化剤は、単独で使用しても複数を併用してもよい。
本発明で用いられる樹脂組成物(E)には、本発明の効果を損なわない範囲で、熱硬化性樹脂(B)、硬化剤(C)および超高分子量オレフィン系重合体以外の熱硬化性樹脂、熱可塑性樹脂を含んでも構わない。当該熱硬化性樹脂および熱可塑性樹脂の樹脂組成物(E)における含有量は、通常30質量%以下、好ましくは20質量%以下、より好ましくは10質量%以下である。
前記樹脂組成物(E)の製造方法は、特に限定されるものではなく、従来公知のいずれの方法を用いてもよい。例えば、熱硬化性樹脂(B)がエポキシ樹脂である場合、樹脂組成物(E)の製造時に適用される混練温度としては、10~200℃の範囲が例示できる。200℃を超えるとエポキシ樹脂の熱劣化や、部分的な硬化反応が開始し、得られる樹脂組成物(E)並びにそれを用いたプリプレグの保存安定性が低下する場合がある。10℃より低いと樹脂組成物(E)の粘度が高く、実質的に混練が困難となる場合がある。好ましくは20~180℃であり、更に好ましくは30~170℃の範囲である。
次に、プリプレグの製造方法について説明する。
本発明におけるプリプレグは、上記の如くして得られる樹脂組成物(E)を、強化繊維(A)に含浸させることにより製造できる。
本発明のプリプレグを硬化させることにより本発明の繊維強化複合材料が得られる。プリプレグは、単層で、あるいは積層して用いることができるが、一般的には積層して用いられる。すなわち、本発明のプリプレグを適宜切断後、必要に応じて積層し、オートクレーブ、ホットプレス等で加熱、加圧して熱硬化させるとともに、所望の形状に成形する。熱硬化条件は、用いる熱硬化性樹脂と硬化剤によって決定される。
極限粘度[η]は、超高分子量オレフィン系重合体粒子をデカリンに溶解させ、温度135℃のデカリン中で測定した。
[η]=lim(ηsp/C) (C→0)
平均粒子径d50は、コールターカウンター(マルチサイザー3型、ベックマン社製)によって測定した。孔径200μmの細孔を有するアパチャーチューブをコールターカウンターに装着し、サンプル2mgについて粒度分布を測定し、粒度分布曲線を得た。この曲線を定法で解析して平均粒子径d50と、粒子径40μm以下の粒子の割合を求めた。
粒度・形状分布測定器(PITA-2、株式会社セイシン企業製)を用い、3300個の粒子について画像解析によってアスペクト比を計測し、累積50%の値を超高分子量オレフィン系重合体粒子(D)のアスペクト比と決定した。
融点(Tm)は、DSCにより測定した。DSC(DSC220C、セイコーインスツルメンツ社製)を用い、測定用アルミパンに約5mgの試料をつめ、200℃まで昇温し試料を融解させた後、-10℃/分で30℃まで冷却し、10℃/分で昇温した時の結晶溶融ピークのピーク頂点から融点(Tm)を算出した。
引張強度および引張弾性率は、引張試験により測定した。幅20mm、長さ200mmの試験片の両端に長さ50mmのアルミ製タブを装着した。テンシロン万能試験機(RTC-1350A、オリエンテック社製)を用い、試験速度1mm/分で行った。
曲げ強度および曲げ弾性率は、JIS K7074に記載の3点曲げ試験により測定した。幅15mm、長さ100mmの試験片を用意し、インストロン万能試験機(Type55R4026、インストロン社製)を用い、試験速度5mm/分で行った。
モードII層間破壊靭性値は、ENF(End Notched Flexure)試験により測定した。幅25mm、長さ140mm、厚み3mmの試験片に、初期き裂長さ40mmの初期き裂を導入した。インストロン万能試験機(Type55R4026、インストロン社製)を用い、三点曲げ試験により層間破壊靭性値を求めた。試験速度は0.5mm/分とした。
マトリックス樹脂の母材となる熱硬化性樹脂として、エポキシ樹脂(商品名:jER828、三菱化学株式会社製)、硬化剤として変性芳香族アミン(商品名:jERキュアW、三菱化学株式会社製)を用いた。配合量はjER828:100質量部に対して、jERキュアW:25質量部とした。これらを混合して混合物を調製した。
Claims (7)
- 強化繊維(A)および樹脂組成物(E)を含むプリプレグであって、前記樹脂組成物(E)が、下記要件(i)~(ii)を満たす超高分子量オレフィン系重合体またはその架橋体からなる粒子(D)を0.1~10質量%含み、かつ熱硬化性樹脂(B)および硬化剤(C)を含むプリプレグ。
(i)該粒子を構成する超高分子量オレフィン系重合体の135℃デカリン溶媒中で測定した極限粘度[η]が5~50dl/gである。
(ii)平均粒子径d50が3~200μmである。 - 前記超高分子量オレフィン系重合体またはその架橋体からなる粒子(D)がさらに下記要件(iii)を満たす請求項1に記載のプリプレグ。
(iii)アスペクト比が1.0~1.4である。 - 前記超高分子量オレフィン系重合体またはその架橋体からなる粒子(D)がさらに下記要件(iv)を満たす請求項1または2に記載のプリプレグ。
(iv)該粒子を構成する超高分子量オレフィン系重合体の示差走査熱量計(DSC)で測定した融点(Tm)が125~145℃である。 - 前記強化繊維(A)が炭素繊維である請求項1~3のいずれか一項に記載のプリプレグ。
- 前記超高分子量オレフィン系重合体またはその架橋体からなる粒子(D)を構成する超高分子量オレフィン系重合体が超高分子量ポリエチレンである請求項1~4のいずれか一項に記載のプレプリグ。
- 前記熱硬化性樹脂(B)がエポキシ樹脂であり、前記硬化剤(C)がエポキシ硬化剤である請求項1~5のいずれか一項に記載のプリプレグ。
- 請求項1~6のいずれか一項に記載のプリプレグを硬化させてなる繊維強化複合材料。
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PCT/JP2016/054503 WO2016136540A1 (ja) | 2015-02-26 | 2016-02-17 | プリプレグおよび繊維強化複合材料 |
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US (1) | US20180030226A1 (ja) |
EP (1) | EP3263634B1 (ja) |
JP (1) | JP6514764B2 (ja) |
KR (1) | KR102037650B1 (ja) |
CN (1) | CN107207750B (ja) |
WO (1) | WO2016136540A1 (ja) |
Cited By (3)
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WO2018105682A1 (ja) | 2016-12-09 | 2018-06-14 | 三井化学株式会社 | グラフトコポリマー含有固形物およびその用途 |
WO2020100999A1 (ja) * | 2018-11-14 | 2020-05-22 | 株式会社ブリヂストン | 強化繊維複合樹脂の製造方法 |
WO2020158233A1 (ja) * | 2019-01-29 | 2020-08-06 | 日信工業株式会社 | 多層シート及び多層シートの製造方法 |
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JP2011057907A (ja) | 2009-09-12 | 2011-03-24 | Toho Tenax Co Ltd | 熱硬化性樹脂組成物とそれを用いたプリプレグ |
JP2012193322A (ja) | 2011-03-18 | 2012-10-11 | Toray Ind Inc | プリプレグ、および炭素繊維強化複合材料 |
JP5912922B2 (ja) | 2012-06-29 | 2016-04-27 | Jxエネルギー株式会社 | 繊維強化複合材料 |
JP5947262B2 (ja) * | 2013-07-22 | 2016-07-06 | 株式会社ユニバーサルエンターテインメント | 遊技機 |
CN105452373B (zh) * | 2013-08-07 | 2017-02-22 | 东丽株式会社 | 环氧树脂组合物、预浸料坯及纤维增强复合材料 |
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2016
- 2016-02-17 US US15/553,840 patent/US20180030226A1/en not_active Abandoned
- 2016-02-17 EP EP16755287.6A patent/EP3263634B1/en active Active
- 2016-02-17 WO PCT/JP2016/054503 patent/WO2016136540A1/ja active Application Filing
- 2016-02-17 KR KR1020177024617A patent/KR102037650B1/ko active IP Right Grant
- 2016-02-17 CN CN201680010444.0A patent/CN107207750B/zh active Active
- 2016-02-17 JP JP2017502287A patent/JP6514764B2/ja active Active
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JPS6295325A (ja) * | 1985-10-21 | 1987-05-01 | Shin Kobe Electric Mach Co Ltd | 積層板の製造法 |
JPS63162732A (ja) * | 1986-12-25 | 1988-07-06 | Toray Ind Inc | プリプレグ |
JPH09216958A (ja) * | 1996-02-08 | 1997-08-19 | Nippon Oil Co Ltd | プリプレグ |
JPH09291200A (ja) * | 1996-04-25 | 1997-11-11 | Sumitomo Metal Ind Ltd | リジッドプリント配線板に適した樹脂組成物 |
JP2003012818A (ja) * | 2001-06-28 | 2003-01-15 | Bando Chem Ind Ltd | ベルト用帆布及びそれを用いた伝動ベルト並びに高負荷伝動用vベルト |
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WO2018105682A1 (ja) | 2016-12-09 | 2018-06-14 | 三井化学株式会社 | グラフトコポリマー含有固形物およびその用途 |
KR20190078617A (ko) | 2016-12-09 | 2019-07-04 | 미쓰이 가가쿠 가부시키가이샤 | 그래프트 코폴리머 함유 고형물 및 그의 용도 |
WO2020100999A1 (ja) * | 2018-11-14 | 2020-05-22 | 株式会社ブリヂストン | 強化繊維複合樹脂の製造方法 |
WO2020158233A1 (ja) * | 2019-01-29 | 2020-08-06 | 日信工業株式会社 | 多層シート及び多層シートの製造方法 |
Also Published As
Publication number | Publication date |
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EP3263634B1 (en) | 2020-06-24 |
JPWO2016136540A1 (ja) | 2017-12-07 |
KR102037650B1 (ko) | 2019-10-29 |
CN107207750B (zh) | 2020-06-02 |
CN107207750A (zh) | 2017-09-26 |
JP6514764B2 (ja) | 2019-05-15 |
KR20170110674A (ko) | 2017-10-11 |
EP3263634A4 (en) | 2018-10-03 |
EP3263634A1 (en) | 2018-01-03 |
US20180030226A1 (en) | 2018-02-01 |
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