WO2020137946A1 - 金属・繊維強化プラスチック複合材料 - Google Patents
金属・繊維強化プラスチック複合材料 Download PDFInfo
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- WO2020137946A1 WO2020137946A1 PCT/JP2019/050298 JP2019050298W WO2020137946A1 WO 2020137946 A1 WO2020137946 A1 WO 2020137946A1 JP 2019050298 W JP2019050298 W JP 2019050298W WO 2020137946 A1 WO2020137946 A1 WO 2020137946A1
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- Prior art keywords
- metal
- reinforced plastic
- resin
- fiber reinforced
- resin composition
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Definitions
- the present invention relates to a metal/fiber reinforced composite material in which a metal member and a fiber reinforced plastic molding material are laminated and integrated, and a manufacturing method thereof.
- Fiber-reinforced plastic material is a lightweight and high-strength material that is widely used for fishing rods, tennis rackets, sports cycles, automobiles, wind power generator blades, and aircraft. Particularly in the automobile industry, active consideration is being made to reduce the weight of the vehicle body and improve fuel efficiency and running performance by adopting a fiber reinforced plastic material.
- FRP is lightweight and high-strength, it is more expensive than conventionally used metal-based materials, and members can only be manufactured in a predetermined shape, or epoxy resin that is a thermosetting resin. As a matrix resin is used, there is a problem that the manufacturing time of the member is long.
- Patent Document 1 discloses a metal/CFRP composite material in which a metal and a carbon fiber reinforced plastic material having a thermoplastic resin as a matrix resin are laminated and integrated as a member for an automobile.
- Patent Document 2 discloses a metal/CFRP composite material in which CFRP using an aluminum alloy and a polyamide resin is firmly integrated.
- Patent Document 1 mentions the use of polypropylene, polyethylene, polyamide and/or a mixture thereof as a matrix resin of a thermoplastic resin, it does not teach the use of a phenoxy resin as a matrix resin.
- Patent Document 2 is characterized in that the surface of the metal is subjected to fine processing using a technique such as microetching so as to have specific parameters, and the metal and the FRP are firmly integrated by being filled with resin. Therefore, only a highly crystalline polyamide or polyphenylene sulphate resin composition is disclosed for that purpose.
- Patent Document 3 a resin composition containing an epoxy compound and a polyamide resin is disclosed in Patent Document 3 and Patent Document 4.
- Patent Document 3 merely discloses a carbon fiber reinforced polyamide resin composition in which 0.1 to 10 parts by weight of an epoxy compound having a molecular weight of 10,000 or less is blended, and moreover, it is an injection molding material and is not compatible with a metal. No compounding is expected.
- Patent Document 4 discloses a polyamide resin composition composed of a nylon 6 resin and a phenoxy resin, it is only studied as a vibration damping material that is mechanically attached to automobile parts and the like, and is bonded to a metal. No consideration is given to power. Further, since it is premised that a molded product made of a resin material alone is mechanically attached around the engine or the like, a metal/FRP composite as a structural material has not been studied.
- An object of the present invention is to provide a metal/fiber reinforced plastic composite material which has good adhesion to a metal member and impregnation of a matrix resin into a reinforced fiber base material, and which has excellent heat resistance, impact resistance and mechanical properties.
- thermoplastic resin composition (B) is A laminate of a metal member and a fiber reinforced plastic, wherein the fiber reinforced plastic comprises a reinforced fiber base material (A) and a thermoplastic resin composition (B), and the thermoplastic resin composition (B) is The phenoxy resin (B-1) and the polyamide resin (B-2) are contained in a mass ratio (B-1)/(B-2) of 80/20 to 20/80, and the reinforced fiber substrate (A)
- the adhesive strength of the thermoplastic resin composition (B) to the monofilament is 40 MPa or more as the interfacial shear strength ( ⁇ ) at 23° C. in the microdroplet method, and the adhesive strength of the metal member and the thermoplastic resin composition (B) is A metal/fiber reinforced plastic composite material having a tensile shear strength at 23° C.
- the metal/fiber reinforced plastic composite material wherein the absolute value of the rate of change in thickness after applying a heat history of 180° C. for 30 minutes to the fiber reinforced plastic is less than 2.0%.
- the metal/fiber-reinforced plastic composite material wherein the polyamide resin (B-2) is a wholly aliphatic polyamide and/or a semi-aliphatic polyamide.
- the above metal/fiber reinforced plastic composite material in which the material of the metal member is steel material, stainless steel, or aluminum.
- the above metal/fiber reinforced plastic composite in which the reinforcing fiber base material contains one or more kinds of fibers selected from the group consisting of carbon fibers, boron fibers, silicon carbide fibers, glass fibers and aramid fibers. material.
- the present invention it is possible to obtain a lightweight metal-fiber reinforced plastic composite material in which the fiber reinforced plastic material and the metal member are firmly bonded to each other, the mechanical properties are very excellent, the moisture absorption is low, and the heat resistance is high.
- the metal/fiber reinforced plastic composite material (also referred to as metal/FRP composite material) of the present invention is a fiber reinforced plastic (FRP) in which a thermoplastic resin composition (B) is impregnated into a reinforced fiber base material (A) as a matrix resin. )
- FRP fiber reinforced plastic
- a composite material in which a material and a metal member are laminated and integrated.
- the matrix resin of the FRP material laminated and integrated with the metal member is a thermoplastic resin containing phenoxy resin (B-1) and polyamide resin (B-2) as essential components. It is a plastic resin composition (B). Since the FRP material of the present invention uses the phenoxy resin (B-1) as a matrix resin, it can be easily pressure-molded by a heating press and the productivity can be greatly improved. Further, since the polyamide resin (B-2) which is an engineering plastic is used as the matrix resin, it has good mechanical properties such as high heat resistance and excellent toughness.
- the reinforcing fiber base material (A) of the FRP material used in the metal/FRP composite material of the present invention includes carbon fiber, glass fiber, ceramic fiber such as boron, alumina, silicon carbide, metal fiber such as stainless steel, aramid, etc.
- a wide variety of organic fibers can be selected. Among these, carbon fibers and glass fibers are preferably used, and it is most preferable to use carbon fibers having high strength and good thermal conductivity.
- the carbon fiber can be either pitch-based or PAN-based, but the pitch-based carbon fiber is not only high in strength but also high in thermal conductivity, and therefore the generated heat can be quickly diffused. It is preferred over PAN systems for applications requiring heat dissipation.
- the form of the reinforcing fiber substrate is not particularly limited, and for example, a unidirectional material, a cloth such as plain weave or twill, a three-dimensional cloth, a chopped strand mat, a tow consisting of several thousand or more filaments, or a non-woven fabric is used. Can be used. These reinforcing fiber bases may be used alone or in combination of two or more.
- the reinforcing fibers have a sizing agent (a sizing agent), a coupling agent, or the like attached to the surface thereof, because the wettability of the matrix resin with the reinforcing fibers and the handleability can be improved.
- the sizing agent include maleic anhydride compounds, urethane compounds, acrylic compounds, epoxy compounds, phenol compounds, and derivatives of these compounds.
- the coupling agent include amino-based, epoxy-based, chloro-based, mercapto-based, and cationic-based silane coupling agents.
- the content of the sizing agent and the coupling agent is 0.1 to 10 parts by weight, and more preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the reinforcing fiber. When the content of the sizing agent and the coupling agent is 0.1 to 10% by weight, the wettability with the matrix resin composition and the handleability are more excellent. It is more preferably 0.5 to 6% by weight.
- the monofilament of the reinforcing fiber substrate (A) has good adhesiveness with the thermoplastic resin composition (B) which is a matrix resin composition of the FRP material.
- the adhesiveness can be evaluated by measuring the interfacial shear strength ( ⁇ ) between the monofilament and the thermoplastic resin composition (B) by the microdroplet method (MD method) (Non-Patent Document 1).
- MD method microdroplet method
- the interfacial shear strength with the reinforcing fiber is preferably 42 MPa or more, more preferably 45 MPa or more.
- the phenoxy resin (B-1), which is one of the essential components of the matrix resin, is a thermoplastic resin obtained from the condensation reaction between a dihydric phenol compound and epihalohydrin or the polyaddition reaction between a dihydric phenol compound and a bifunctional epoxy resin. It is a resin and can be obtained by a conventionally known method in a solution or without a solvent.
- the average molecular weight is usually 10,000 to 200,000 as a mass average molecular weight (Mw), preferably 20,000 to 100,000, and more preferably 30,000 to 80,000. If the Mw is too low, the strength of the molded article will be poor, and if it is too high, the workability and workability will tend to be poor.
- the Mw is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
- the hydroxyl group equivalent (g/eq) of the phenoxy resin is usually 50 to 1000, preferably 50 to 750, and particularly preferably 50 to 500. If the hydroxyl group equivalent is too low, the water absorption rate increases due to an increase in the number of hydroxyl groups, and there is a concern that the mechanical properties will deteriorate. If the hydroxyl group equivalent is too high, the number of hydroxyl groups is small, so that the wettability with the reinforcing fiber base material, especially with the carbon fiber is lowered.
- the glass transition temperature (Tg) of the phenoxy resin is suitably 65°C to 160°C, preferably 70°C to 150°C. If the glass transition temperature is lower than 65°C, the moldability will be improved, but problems such as deterioration of storage stability of powder or pellets due to blocking and stickiness (poor tackiness) during preform will occur. If the temperature is higher than 160° C., the melt viscosity will be high and the moldability and the filling property into the fiber will be poor, and as a result, higher temperature press molding is required.
- the glass transition temperature of the phenoxy resin is a numerical value obtained from the peak value of the second scan, which is measured in the range of 20 to 280° C. under a temperature rising condition of 10° C./min using a differential scanning calorimeter.
- the phenoxy resin is not particularly limited as long as it satisfies the above physical properties, but is a bisphenol A type phenoxy resin (for example, Phenotote YP-50, YP-50S, YP-55U manufactured by Nippon Steel Chemical & Material), bisphenol.
- a bisphenol A type phenoxy resin for example, Phenotote YP-50, YP-50S, YP-55U manufactured by Nippon Steel Chemical & Material
- F-type phenoxy resin for example, Phenototo FX-316 manufactured by Nittetsu Chemical & Material
- copolymerized phenoxy resin of bisphenol A and bisphenol F for example, YP-70 manufactured by Nittetsu Chemical & Material
- special phenoxy resin for example, Nittetsu Chemical &Material's Fenotote YPB-43C, FX293
- a thermoplastic resin called a thermoplastic epoxy resin similar to the phenoxy resin can be used as a substitute for the phenoxy resin, it is preferable to use the phenoxy resin.
- the phenoxy resin is preferably solid at room temperature and has a melt viscosity of 10 to 3000 Pa ⁇ s in any of the temperature ranges of 180 to 350° C.
- the melt viscosity is more than 3000 Pa ⁇ s, the resin is not sufficiently impregnated into the reinforcing fiber base material when it is laminated and composited with the metal member, and when the melt viscosity is less than 10 Pa ⁇ s, the flowability of the resin is low. It becomes excessive, which makes it difficult to control the fiber volume content of the FRP molded body, and the occurrence of blurring due to insufficient resin during molding and the thickness accuracy decrease.
- thermogravimetric measurement it is preferable that the heating weight loss rate when heated to 350° C. is less than 1%. When the heating weight loss rate exceeds 1%, the phenoxy resin is thermally deteriorated during the molding process, which may cause discoloration of the molded body or decrease in mechanical strength.
- the matrix resin of the FRP material used for the metal/FRP composite material of the present invention contains a phenoxy resin (B-1) and a polyamide resin (B-2).
- a phenoxy resin (B-1) and a polyamide resin (B-2) are not compatible with each other, but since they are both polar resins, they have a good compatibility and are therefore formed during heat molding. It is presumed that the resin composition has a strong structure, and therefore the strength of the phenoxy resin (B-1) and the elongation and heat resistance of the polyamide resin (B-2) are reflected without mutual inhibition. .. Further, such improvement in performance can be applied to applications requiring higher heat resistance, such as automobile materials and aerospace materials.
- the polyamide resin (B-2) is a thermoplastic resin whose main chain is formed by repeating amide bonds, and is used for ring-opening polymerization of lactams, co-condensation polymerization of lactams, dehydration condensation of diamine and dicarboxylic acid, etc. can get.
- lactam include ⁇ -caprolactam, undecane lactam, lauryl lactam and the like
- the diamine includes hexamethylene diamine, nonane diamine, aliphatic diamine such as methyl pentadiamine, cyclohexane diamine, methyl cyclohexane diamine, isophoro diamine, norbornane.
- Alicyclic diamines such as dimethylamine and tricyclodecanedimethyldiamine, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′- Aromatic diamines such as diaminodiphenyl sulfone and 4,4′-diaminodiphenyl ether.
- dicarboxylic acid examples include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethyl acid.
- Aliphatic dicarboxylic acids such as succinic acid, azelaic acid, sebacic acid and suberic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4′- Aromatic dicarboxylic acids such as oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid and 4,4'-biphenyldicarboxylic acid.
- the polyamide resin (B-2) is an all-aliphatic polyamide resin (eg, nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, etc.) whose main chain has an aliphatic skeleton and whose main chain is Aromatic semi-aliphatic polyamide resin or semi-aromatic polyamide resin (for example, nylon 6I, nylon 6T, nylon 9T, nylon M5T, nylon MXD6, etc.), and aramid whose main chain is composed only of aromatic skeleton
- Aromatic semi-aliphatic polyamide resin or semi-aromatic polyamide resin for example, nylon 6I, nylon 6T, nylon 9T, nylon M5T, nylon MXD6, etc.
- aramid whose main chain is composed only of aromatic skeleton
- There are known all-aromatic polyamide resins Kevlar, Nomex (Toray DuPont), Twaron, Conex (Teijin).
- any of these can be used as the matrix resin of the FRP material of the metal/FRP composite material of the present invention, but it is preferable to use a wholly aliphatic polyamide resin or a semi-aliphatic (semi-aromatic) polyamide resin. .. More preferred is an all-aliphatic polyamide resin, and most preferred is an all-aliphatic polyamide resin called nylon 6 obtained by ring-opening polymerization of ⁇ -caprolactam.
- the polyamide resin (B-2) preferably has a melting point of 180 to 320° C. and a melt viscosity at 180 to 350° C. of 10 to 3000 Pa ⁇ s or less.
- the melting point is preferably 200 to 310°C.
- the wholly aliphatic and semi-aromatic polyamide resins have relatively low melt viscosities, and the melt viscosities of the matrix resins can be kept low.
- the melt viscosity of the polyamide resin (B-2) exceeds 3000 Pa ⁇ s, the filling property of the matrix resin into the reinforcing fiber base material is deteriorated and defects such as voids are likely to occur. Poor homogeneity of the molded product.
- melt viscosity of the polyamide resin is low to less than 10 Pa ⁇ s, the fluidity becomes excessive, making it difficult to control the fiber volume content of the FRP molded product, and the occurrence of blurring due to resin shortage during molding and deterioration of thickness accuracy. May occur, and the strength of the metal/FRP composite material may be reduced.
- the Mw of the polyamide resin (B-2) is preferably 10,000 or more, more preferably 25,000 or more.
- thermoplastic resin composition of the present invention containing the phenoxy resin (B-1) and the polyamide resin (B-2) is solid at room temperature and has a melt viscosity before it becomes a matrix resin by thermoforming. It is 3000 Pa ⁇ s or less in any of the temperature range of 180 to 350°C.
- the melt viscosity of this thermoplastic resin composition is preferably 10 to 2900 Pa ⁇ s, more preferably 30 to 2800 Pa ⁇ s. If the melt viscosity exceeds 3000 Pa ⁇ s in any of the temperature range of 180 to 350° C., the fluidity of the matrix resin composition at the time of molding is deteriorated, so that the solid resin adhered to the surface is sufficiently contained in the fiber base material.
- the voids do not spread and cause mechanical properties of the molded product to deteriorate. Further, if the melt viscosity is less than 10 Pa ⁇ s, the flowability of the resin becomes excessive, making it difficult to control the fiber volume content of the FRP molded body, and the occurrence of blurring due to insufficient resin during molding and deterioration of thickness accuracy. As a result, the mechanical strength of the molded product decreases. Then, there is a concern that the mechanical properties of the metal/FRP composite material may be deteriorated as a result of these factors.
- the matrix resin of the metal/FRP composite material of the present invention comprises the phenoxy resin (B-1) and the polyamide resin (B-2) at a compounding ratio represented by (B-1)/(B-2). It is a resin composition blended in a ratio of 80/2-0 to 20/80.
- the mass ratio (B-1)/(B-2) is preferably 75/25 to 25/75, more preferably 70/30 to 30/70, and most preferably 70/30 to 50/50. .. If the mass ratio (B-1)/(B-2) exceeds 75/25, the effect of improving the properties such as heat resistance and mechanical strength, which is the effect of blending the polyamide resin, tends to be insufficient.
- the mass ratio (B-1)/(B-2) is less than 25/75, the impregnation property into the reinforcing fiber base material cannot be improved by blending the phenoxy resin, so that the reinforcing fiber base material is impregnated. Becomes difficult.
- the adhesive strength between the metal member of the present invention and the thermoplastic resin composition (B) is such that the tensile shear strength at 23° C. is 7.0 MPa or more.
- the tensile shear strength in the present invention refers to a breaking stress measured according to JIS K 6850, and when the tensile shear strength is 7.0 MPa or more, the adhesion between the metal member and the thermoplastic resin composition is good, Since the metal and the reinforced fiber plastic are firmly bonded to each other when the metal/fiber reinforced plastic composite material is used, the composite material can exhibit high mechanical properties.
- the tensile shear strength is less than 7.0 MPa, the adhesion between the metal and the fiber reinforced plastic is weak, and the interface strength is likely to occur during loading, resulting in a decrease in mechanical strength.
- the tensile shear strength is preferably 7.5 MPa or more.
- the thermoplastic resin composition which is the matrix resin of the FRP material, has an interfacial shear strength of 35 MPa or more with the reinforcing fiber (monofilament) described above, and It is essential that the tensile shear strength satisfies both of 7.0 MPa or more.
- the phenoxy resin (B-1) which is one of the resin materials constituting the thermoplastic resin composition that serves as the matrix resin of the fiber-reinforced plastic molding material of the present invention, has a reinforcing fiber (particularly glass) due to the presence of a hydroxyl group in its side chain. Good compatibility with fibers and carbon fibers). Therefore, even if the thermoplastic resin composition is applied to the surface of the reinforcing fiber base material in a powder state or in a film-like state such as a film, it is very easily penetrated into the fiber bundle of the reinforcing fiber base material. You can Further, since it is an amorphous polymer, it is transparent, and a molded product having a high surface design after molding can be obtained.
- the polyamide resin (B-2) which is another resin material that constitutes the matrix resin, is a crystalline polymer, but has a high melting point and a high melt viscosity. By using it as a powder, the impregnating property into the substrate can be greatly improved.
- polyamide resins generally have high heat resistance and good mechanical strength such as impact resistance.
- the average particle diameter (D50) is preferably in the range of 10 to 150 ⁇ m.
- the fiber-reinforced plastic of the present invention preferably has an absolute value of the thickness change rate of less than 2.0% after a heat history of 180° C. for 30 minutes.
- the thickness change rate (%) in the present invention means the thickness L (mm) of the FRP material at room temperature after the heat history is added, divided by the thickness Lo (mm) of the FRP material at the room temperature before the heat history is added to obtain 100. Is multiplied by (L/Lo ⁇ 100).
- the phenoxy resin (B-1) and the polyamide resin (B-2) are finely pulverized and mixed, and even if they are melted, they are compatible with each other and do not become mixed and integrated. However, since the phenoxy resin has a hydroxyl group and the polyamide resin has a polarity due to an amide bond, it is assumed that the phenoxy resin has a sea-island structure or a co-continuous structure with a certain degree of affinity. The structure of these matrix resins can be arbitrarily adjusted by the blending ratio of the phenoxy resin (B-1) and the polyamide resin (B-2).
- the physical properties of the metal/FRP composite material can be adjusted according to the required performance. It can be adjusted arbitrarily.
- the FRP material of the metal/FRP composite material of the present invention preferably contains a flame retardant and a flame retardant aid.
- the flame retardant is not particularly limited as long as it is solid at room temperature and has no sublimation property.
- these flame retardants include inorganic flame retardants such as calcium hydroxide, organic and inorganic phosphorus flame retardants such as ammonium phosphates and phosphate ester compounds, nitrogen-containing flame retardants such as triazine compounds, and bromination.
- examples thereof include bromine-containing flame retardants such as phenoxy resin. Among them, brominated phenoxy resin and phosphorus-containing phenoxy resin can be used as a flame retardant/matrix resin.
- the blending amount of the flame retardant (and the flame retardant aid) is appropriately selected depending on the kind of the flame retardant and the desired degree of flame retardancy, but is generally 0.01 to 50 parts by weight with respect to 100 parts by weight of the matrix resin. Within the range, it is preferable to mix them in such an amount that the adhesion and impregnation of the matrix resin and the physical properties of the molded product are not impaired.
- the FRP material of the present invention includes a thermoplastic resin other than a phenoxy resin or a polyamide resin or a thermosetting resin, for example, in a range that does not impair the good adhesion of the matrix resin to the reinforcing fiber base material or the physical properties thereof.
- a thermoplastic resin other than a phenoxy resin or a polyamide resin or a thermosetting resin for example, in a range that does not impair the good adhesion of the matrix resin to the reinforcing fiber base material or the physical properties thereof.
- Polyvinylidene chloride resin, natural rubber, synthetic rubber, epoxy compound and the like can be blended.
- the epoxy compound can be used in combination with the phenoxy resin (B-1) to improve the moldability of the FRP material and the impregnation of the matrix resin into the reinforcing fiber base material, and the affinity between the phenoxy resin and the polyamide resin. It is preferably used because it can improve the adhesiveness to a metal member or a reinforcing fiber base material.
- the epoxy compound means a compound having at least one epoxy group in one molecule, is a solid at room temperature, and has a number average molecular weight of 10,000 or less, preferably 1,000 to 10,000, more preferably 5,000 to 10,000. It is desirable that the phenoxy resin is mixed in a proportion of 0.1 to 100 parts by weight with respect to 100 parts by weight.
- examples of such an epoxy compound include a bisphenol type epoxy resin, a phenol novolac type epoxy resin, and a triphenylglycidyl ether type epoxy resin. Among them, a bisphenol A type or a bisphenol F type skeleton having a softening point of 80 A solid epoxy resin having a temperature of not less than 0°C is preferably used.
- the FRP material of the metal/FRP composite material of the present invention includes various inorganic fillers, carbon black, carbon nanotubes, etc. as long as the melt viscosity of the matrix resin composition at 160 to 250° C. does not exceed 3000 Pa ⁇ s.
- the carbon filler, extender pigment, colorant, antioxidant, UV inhibitor, etc. can be added, and when an epoxy compound is added, other additives such as a curing agent and a curing accelerator can also be added.
- the resin composition is a mixture containing a phenoxy resin and a polyamide resin, but may contain other resins and additives as described above, if necessary. However, the solid content that does not melt or dissolve with the resin composition such as the inorganic filler is not treated as a component constituting the resin composition.
- the resin composition contains components other than the phenoxy resin and the polyamide resin, the proportion thereof is 50% by mass or less, preferably 20% by mass or less.
- the resin composition in this case preferably satisfies the melt viscosity as a whole.
- the metal member used in the metal/FRP composite material of the present invention is not particularly limited as long as it can be formed by pressing or the like, but the shape is preferably a thin plate.
- the material include iron, titanium, aluminum, magnesium, copper and alloys thereof.
- alloys include iron-based alloys including stainless steel, Ti-based alloys, Al-based alloys, Mg alloys, and copper alloys such as brass.
- the material of the metal member is preferably a steel material, an iron-based alloy, titanium and aluminum, and more preferably a steel material having a higher elastic modulus than other metal species.
- steel materials include steel materials specified by Japanese Industrial Standards (JIS) and the like, and carbon steel, alloy steel, high-strength steel, etc. used for general structures and machine structures You can Specific examples of such steel materials include cold rolled steel materials, hot rolled steel materials, hot rolled steel sheet materials for automobile structures, hot rolled high tensile steel sheet materials for automobile processing, and the like.
- the steel material may be subjected to any surface treatment.
- the surface treatment is, for example, various plating treatments such as zinc plating and aluminum plating, chemical conversion treatments such as chromate treatment and non-chromate treatment, and physical surface such as sandblasting or chemical surface treatment such as chemical etching. Roughening treatment may be mentioned, but the treatment is not limited thereto. Further, plural kinds of surface treatments may be applied.
- the surface treatment it is preferable that at least a treatment for the purpose of imparting antirust property is performed.
- a primer for the purpose of improving the adhesiveness with the FRP material.
- a silane coupling agent or a triazine thiol derivative is preferable.
- the silane coupling agent include epoxy type silane coupling agents, amino type silane coupling agents, and imidazole silane compounds.
- the triazinethiol derivative include 6-diallylamino-2,4-dithiol-1,3,5-triazine, 6-methoxy-2,4-dithiol-1,3,5-triazine monosodium and 6-propyl-2. , 4-dithiolamino-1,3,5-triazine monosodium and 2,4,6-trithiol-1,3,5-triazine are exemplified.
- the metal/FRP composite material of the present invention can be obtained by a method including the following steps (1) to (3).
- Step (1) the phenoxy resin (B-1) and the polyamide resin (B-2) are mixed at any mass ratio (B-1)/(B-2) within the range of 80/20 to 20/80. It is a step of preparing the thermoplastic resin composition (B) blended in a ratio.
- the compounding method of the phenoxy resin (B-1) and the polyamide resin (B-2) is not particularly limited, and a generally known method can be used.
- both may be finely pulverized to form a powder, which may be mixed using a blender such as a Henschel mixer or a rocking mixer to obtain a resin composition powder, or a kneader or the like may be used to melt-knead both. You can use it.
- components other than the phenoxy resin (B-1) and the polyamide resin (B-2), the above flame retardant and inorganic filler may be mixed at the same time.
- the step (2) is a step of producing a prepreg by attaching the thermoplastic resin composition (B), which is the matrix resin of the FRP material prepared in the previous step, to the reinforcing fiber base material (A).
- the prepreg means a molding material (FRP molding material) for molding the FRP material.
- the method for attaching the thermoplastic resin composition (B) to the reinforcing fiber base material (A) is not particularly limited, and a generally known method can be used.
- a method may be used in which the thermoplastic resin composition (B) obtained in step (1) is formed into a film, and the reinforcing fiber base material (A) is bonded while being heated and pressure-impregnated.
- a method may also be used in which (B) is made into a fine powder, sprayed or deposited on the reinforcing fiber base material (A), and then heated and welded.
- the amount of the thermoplastic resin composition (B) attached to the reinforcing fiber substrate (A) (resin ratio: RC) is 20 to 50%, and preferably 25 to 45%. , And more preferably 25 to 40%.
- RC exceeds 50%, mechanical properties such as tensile and bending elastic modulus of FRP deteriorate, and when it falls below 10%, the resin adhesion amount is extremely small. There is a concern that it will be sufficient and that both thermophysical properties and mechanical properties will deteriorate.
- the reinforcing fiber base material (A) used is subjected to an opening treatment.
- the fiber-opening treatment it becomes easier to impregnate the inside of the reinforced fiber base material with the thermoplastic resin composition during this step (the step of attaching the heat-visible resin composition (B)) and the subsequent molding process. Therefore, higher physical properties of the molded product can be expected.
- the step (3) is a step of obtaining a metal/fiber reinforced plastic composite material by laminating the metal member and the prepreg and heat-molding them together by a hot press or the like.
- a single or a plurality of FRP molding materials may be laminated on at least one surface of the metal member, or a metal member may be laminated on at least one surface of the FRP molding material laminated alone or in a plurality of sheets. good. Also, a plurality of metal members may be inserted into the FRP molding material in which a large number are laminated.
- the compounding/molding method As long as it is heat and pressure molding, various molding methods such as autoclave molding and heat press molding using a metal mold are appropriately selected and performed according to the size and shape of the target FRP molded product. can do. Further, at this time, by using a mold, it is possible to obtain a metal/FRP composite material shaped into an arbitrary three-dimensional shape.
- the molding temperature is, for example, 180 to 350°C, preferably 200°C to 340°C, more preferably 220°C to 340°C.
- the molding temperature exceeds the upper limit temperature, it takes a long time to raise the temperature, the molding time (tact time) becomes long, the productivity is deteriorated, and the resin may be thermally deteriorated by adding excessive heat more than necessary. ..
- the molding temperature is lower than the lower limit temperature, the melt viscosity of the matrix resin becomes high, and in particular, the polyamide resin becomes insufficiently melted, so that the impregnating property of the matrix resin into the reinforcing fiber base becomes poor.
- the molding time is usually 30 to 60 minutes.
- the thicknesses of the fiber reinforced plastic and the metal member are not particularly limited as long as the characteristics required by the application in which the composite material is used are satisfied.
- the fiber reinforced plastic is in the range of about 50 to 5000 ⁇ m, preferably 100 to 2000 ⁇ m.
- the thickness of the metal member is appropriately in the range of, for example, 100 to 5000 ⁇ m, preferably 200 to 2000 ⁇ m.
- ⁇ Metal/FRP composite material can be subjected to post-processing after composite/molding, as a post-process, for drilling for mechanical joining by bolting or riveting with other members.
- the metal member of the present invention is a light-weight material in which the FRP material using the thermoplastic resin composition (B), which is a blend of a phenoxy resin and a polyamide resin in an appropriate mass ratio, as a matrix resin is firmly bonded to the metal member. Since it is a high-strength and high-heat-resistant composite material, and is manufactured by a simple method and at low cost, it is suitable not only as a casing for electric and electronic devices but also as a structural member for applications such as automobile members and aircraft members. Can be used for.
- thermoplastic resin composition (B) As the reinforcing fiber base material (A), a plain weave carbon fiber woven fabric prepared by opening T700 (carbon fiber manufactured by Toray) is used, and the thermoplastic resin composition (B) is statically applied to the carbon fiber woven fabric. Powder coating was performed using an electric coating device (manufactured by Nippon Parkerizing). Then, the prepreg was created by heat-welding at 240° C. for 1 minute in an oven. The RC was adjusted to 30%.
- thermoplastic resin composition (B) Interfacial shear strength with reinforcing fiber
- MPa interfacial shear strength measured by the microdroplet method
- the thermoplastic resin composition (B) used in this test was added to a kneading extrusion molding machine (manufactured by Toyo Seiki Co., Ltd., Labo Plastomill 4C150) which had been preheated to 240° C. in the mixer in the mass ratio of the example.
- the phenoxy resin (B-1) and the polyamide resin (B-2) weighed out were charged, preheated for 1 minute, melt-kneaded for 3 minutes, and allowed to cool.
- the method for measuring the interfacial shear strength (MPa) will be specifically described.
- a composite material interface characteristic evaluation device HM410 manufactured by Toei Sangyo
- HM410 composite material interface characteristic evaluation device
- the obtained sample was set in the device, the drop was sandwiched between device blades, the filament was run on the device at a speed of 2 ⁇ m/s, and the maximum withdrawal load F when the drop was withdrawn from the filament was measured.
- Adhesiveness 2 Tensile shear strength with metal member
- the adhesion between the metal member and the thermoplastic resin composition (B) was evaluated using the tensile shear strength (MPa) of the metal member and the thermoplastic resin composition (B).
- the tensile shear strength was measured by preparing a test piece according to JIS K 6850.
- the thermoplastic resin composition (B) prepared by dry blending in advance is placed on the tip of the metal piece (25 mm ⁇ 100 mm ⁇ thickness 1.6 mm) and in the range of 25 mm ⁇ 12.5 mm, and the metal piece A test piece was prepared by stacking metal pieces of the same size and heating and pressing at 240° C. and 3 MPa for 10 minutes. Shimadzu AGS-X was used for loading.
- Shimadzu AGS-X was used for loading.
- the case where the interface between the metal plate and the FRP material was peeled off was judged as x, and the case where it was not peeled off was judged as o.
- Examples 1 to 13 and Comparative Examples 1 to 6 Various tests were conducted at the resin ratios shown in Table 1 and Table 2.
- the metal member used for the adhesiveness 2 and the bending test is steel SGCC (purchased from the standard test piece).
- the thickness of the metal member used in the bending test is 0.4 mm.
- the metal/fiber reinforced plastic composite material according to the present invention has good adhesiveness to steel materials and good mechanical properties as a composite material.
- the reinforcing fiber base material (A) used is an open carbon fiber woven fabric SA-3203 manufactured by Sakai Ovex Co., Ltd., and the metal member used for the adhesiveness 2 and bending test is SGCC (purchased from the standard test piece).
- the thickness of the metal member used in the bending test is 0.4 mm.
- thermoplastic resin composition (B) and the monofilament of the reinforcing fiber base material (A) are low, the physical properties are inferior, or the resin flows out from the base material when the prepreg is heated and pressed, and the test piece is removed.
- ND could not be created
- Examples 14 to 25, Comparative Examples 13 to 17 Various tests were conducted at the resin ratios shown in Tables 4 and 5.
- the metal member used for the adhesiveness 2 and the bending test is aluminum A1050 (purchased from the standard test piece).
- the thickness of the metal member used in the bending test is 0.5 mm.
- the metal/fiber reinforced plastic composite material of the present invention has good adhesiveness to non-ferrous metals and good mechanical properties as a composite material.
- the metal/fiber reinforced plastic composite material of the present invention is used as a fiber reinforced plastic (FRP) material for housing electronic devices such as notebook PCs and tablets, arms for industrial robots, reinforcing materials for building structures, and sports. It can be used in a wide range of fields such as leisure fields.
- FRP fiber reinforced plastic
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Abstract
Description
また、特許文献2では、アルミニウム合金とポリアミド樹脂を使用したCFRPが強固に一体化された金属・CFRP複合材料が開示されている。
また特許文献2は、金属の表面をマイクロエッチングなどの手法を用いて特定のパラメータを有するように微細加工を行い、そこを樹脂で埋めることによって金属とFRPが強固に一体化させることに特徴があるのであって、そのために高結晶性のポリアミド又はポリフェニレンサルフェイド系樹脂組成物を開示しているにすぎない。
(2)繊維強化プラスチックに対して180℃、30分の熱履歴を加えた後の厚み変化率の絶対値が2.0%未満である上記金属・繊維強化プラスチック複合材料。
(3)ポリアミド樹脂(B-2)が、全脂肪族ポリアミドおよび/または、半脂肪族ポリアミドである上記金属・繊維強化プラスチック複合材料。
(4)金属部材の材質が鉄鋼材料、ステンレス鋼、アルミニウムである上記金属・繊維強化プラスチック複合材料。
(5)強化繊維基材が炭素繊維、ボロン繊維、シリコンカーバイト繊維、ガラス繊維及びアラミド繊維よりなる群の中から選ばれる1種または2種以上の繊維を含むものである上記金属・繊維強化プラスチック複合材料。
本発明の金属・繊維強化プラスチック複合材料(金属・FRP複合材料ともいう。)は、熱可塑性樹脂組成物(B)がマトリックス樹脂として強化繊維基材(A)に含浸された繊維強化プラスチック(FRP)材料と金属部材と積層一体化された複合材料である。
強化繊維100重量部に対し、サイジング剤及びカップリング剤の含有量は、0.1~ 10重量部、より好ましくは0.5~6重量部である。サイジング剤及びカップリング剤の含有量が0.1~10重量%であれば、マトリックス樹脂組成物との濡れ性、取り扱い性がより優れる。より好ましくは0.5~6重量%である。
なお、強化繊維との界面せん断強度については、42MPa以上が好ましく、45MPa以上がより好ましい。
また、フェノキシ樹脂に類似した熱可塑性エポキシ樹脂と呼称される熱可塑性樹脂をフェノキシ樹脂の代替として使用することもできるが、フェノキシ樹脂を用いることが好ましい。
なお、溶融粘度が3000Pa・sを超えると金属部材との積層複合化の際に強化繊維基材への樹脂の含浸が不十分となり、溶融粘度が10Pa・s未満であると樹脂の流れ性が過剰となり、FRP成形体の繊維体積含有量の制御が困難になったり、成形時に樹脂不足によるかすれの発生や厚み精度が低下する。このため、FRP成形物の機械強度が低下し、結果として金属部材との複合体の機械物性も低下してしまう懸念がある。
また、熱重量測定(TG)において、350℃まで加熱した時の加熱重量減少率が1%未満であることが好ましい。加熱重量減少率が1%以上を超えると成形加工の際にフェノキシ樹脂が熱劣化することにより、成形体の変色や機械強度が低下する恐れがある。
ラクタムとしては、ε‐カプロラクタム、ウンデカンラクタム、ラウリルラクタム等が挙げられ、前記ジアミンとしては、ヘキサメチレンジアミン、ノナンジアミン、メチルペンタジアミンなどの脂肪族ジアミン、シクロヘキサンジアミン、メチルシクロヘキサンジアミン、イソホロジアミン、ノルボルナンジメチルアミン、トリシクロデカンジメチルジアミン等の脂環族ジアミン、p-フェニレンジアミン、m-フェニレンジアミン、p-キシリレンジアミン、m-キシリレンジアミン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルスルホン、4,4’-ジアミノジフェニルエーテル等の芳香族ジアミンなどである。また、前記ジカルボン酸としては、マロン酸、ジメチルマロン酸、コハク酸、グルタル酸、アジピン酸、2-メチルアジピン酸、トリメチルアジピン酸、ピメリン酸、2,2-ジメチルグルタル酸、3,3-ジエチルコハク酸、アゼライン酸、セバシン酸、スベリン酸等の脂肪族ジカルボン酸、1,3-シクロペンタンジカルボン酸、1,4-シクロヘキサンジカルボン酸等の脂環族ジカルボン酸、テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸、2,7-ナフタレンジカルボン酸、1,4-ナフタレンジカルボン酸、1,4-フェニレンジオキシジ酢酸、1,3-フェニレンジオキシジ酢酸、ジフェン酸、4,4’-オキシジ安息香酸、ジフェニルメタン-4,4’-ジカルボン酸、ジフェニルスルホン-4,4’-ジカルボン酸、4,4’-ビフェニルジカルボン酸等の芳香族ジカルボン酸などである。
本発明の金属・FRP複合材料のFRP材料のマトリックス樹脂には、これらのいずれも使用することができるが、全脂肪族ポリアミド樹脂又は半脂肪族(半芳香族)ポリアミド樹脂を使用することが好ましい。より好ましくは全脂肪族ポリアミド樹脂であり、最も好ましくは、ε‐カプロラクタムを開環重合して得られるナイロン6と呼称される全脂肪族ポリアミド樹脂である。
なお、ポリアミド樹脂(B-2)の溶融粘度が3000Pa・sを超えると、マトリックス樹脂の強化繊維基材への充填性が劣り、ボイドなどの欠陥が発生しやすくなるので、得られる繊維強化プラスチック成形物の均質性に劣る。一方、10Pa・s未満までポリアミド樹脂の溶融粘度が低いと流動性が過剰となり、FRP成形体の繊維体積含有量の制御が困難になったり、成形時に樹脂不足によるかすれの発生や厚み精度の低下を招き、金属・FRP複合材料の強度を低下させてしまう恐れがある。
このようなエポキシ化合物として、ビスフェノール型エポキシ樹脂やフェノールノボラック型エポキシ樹脂、トリフェニルグリシジルエーテル型エポキシ樹脂などが例示されるが、なかでもビスフェノールA型またはビスフェノールF型の骨格であり、軟化点が80℃以上である固形エポキシ樹脂が好ましく使用される。
樹脂組成物にフェノキシ樹脂とポリアミド樹脂以外の成分を含む場合は、その割合は50質量%以下、好ましくは20質量%以下がよい。この場合の樹脂組成物は、全体として上記溶融粘度を満足することがよい。
(1)熱可塑性樹脂組成物(B)を調整する工程;
(2)熱可塑性樹脂組成物(B)を強化繊維基材(A)に付着させ、プリプレグを製造する工程;
(3)金属部材とプリプレグを積層し、熱プレス機などにより一括して加熱成形することによって金属・繊維強化プラスチック複合材料を得る工程。
なお、金属・FRP複合体を得るための工程については、前記工程(1)~(3)がこの順番で全て含まれていればよく、(1)~(3)以外の工程が中間やその前後にあっても構わない。以下、その詳細を説明する。
工程(1)はフェノキシ樹脂(B-1)とポリアミド樹脂(B-2)を、その質量比( B-1)/(B-2)が80/20~20/80の範囲内の任意の割合で配合された熱可塑性樹脂組成物(B)を用意する工程である。
工程(2)は、前工程で用意したFRP材料のマトリックス樹脂となる熱可塑性樹脂組成物(B)を強化繊維基材(A)に付着させ、プリプレグを製造する工程である。なお、プリプレグとは、FRP材料を成形するための成形材料(FRP成形材料)を指す。
工程(3)は、金属部材とプリプレグを積層し、熱プレス機などにより一括して加熱成形することによって金属・繊維強化プラスチック複合材料を得る工程である。
また、このときに金型を使用することによって、任意の3次元形状に賦形された金属・FRP複合材料を得ることも可能である。
成形温度は、例えば180~350℃、好ましくは200℃~340℃、より好ましくは220℃~340℃である。成形温度が上限温度を超えると、昇温に時間がかかり、成形時間(タクトタイム)が長くなり生産性が悪くなるほか、必要以上の過剰な熱を加えることによって樹脂が熱劣化する恐れがある。一方、成形温度が下限温度を下回るとマトリックス樹脂の溶融粘度が高くなるほか、特にポリアミド樹脂の溶融が不十分となるため、強化繊維基材へのマトリックス樹脂の含浸性が悪くなる。成形時間については、通常30~60分で行うことができる。
フェノキシ樹脂(B-1)としてYP50S(日鉄ケミカル&マテリアル製)、およびポリアミド樹脂(B-2)としてCM1017(東レ製、ポリアミド6(PA6))、1300S(旭化成製、ポリアミド66(PA66))、6002(三菱エンジニアリングプラスチック製、ポリアミドMXD6(PAMXD6))、N1000A(クラレ製、ポリアミド9T(PA9T))を凍結粉砕、分級して平均粒子径D50が60μmである粉体を準備した。これを、各種の質量比に量り取り、ヘンシェルミキサーを用いてドライブレンドすることで熱可塑性樹脂組成物(B)を調整した。
強化繊維基材(A)として、T700(東レ製炭素繊維)を開繊して作成した平織りの炭素繊維織物を使用し、炭素繊維織物に対して、前記熱可塑性樹脂組成物(B)を静電塗装装置(日本パーカライジング製)を用いて、粉体塗装を行った。その後、オーブンで240℃、1分間加熱溶着させることでプリプレグを作成した。なお、RCは30%となるように調整した。
マイクロドロップレット法により測定した界面せん断強度(MPa)を用いて、強化繊維基材(A)のモノフィラメントに対する熱可塑性樹脂組成物(B)の接着性を評価した。
本試験で使用する熱可塑性樹脂組成物(B)は、予めミキサー内を240℃に予備加熱しておいた混錬押出成形機(東洋精機製、ラボプラストミル4C150)に、例の質量比に量り取ったフェノキシ樹脂(B-1)およびポリアミド樹脂(B-2)を投入した後、1分間の予熱、3分間の溶融混練を行い、放冷したものを用いた。
界面せん断強度(MPa)の測定方法を具体的に記載する。測定には、複合材料界面特性評価装置(東栄産業製、HM410)を使用した。まず、強化繊維基材(A)よりモノフィラメントを取り出し、試料ホルダーにセットする。この試料ホルダーと、熱可塑性樹脂組成物(B)をセットし、装置内で溶融させ、フィラメント上に樹脂を付着させることでフィラメント上にドロップを形成させ、測定用の試料を得た。得られた試料を装置にセットし、ドロップを装置ブレードで挟み、フィラメントを装置上で2μm/sの速度で走行させ、フィラメントからドロップを引き抜く際の最大引き抜き荷重Fを測定した。次式により界面せん断強度τを算出した。なお、1試料につき10~20個程度のドロップの界面せん断強度τを測定し、その平均値を求めた。
界面せん断強度τ(MPa)=F/πdl
(F:最大引き抜き荷重、d:フィラメント直径、l:引抜方向のドロップ径)
プリプレグを所定の枚数積層し、250℃、3MPaで5分間熱プレスし、加圧状態を維持したまま50℃まで冷却することで、試験片を得た。プリプレグの積層枚数は試験片の厚みが1.0mmとなるように調整した。また、試験片は25mm×25mmにカットした。
本試験片の初期厚みLo(mm)をデジタルノギスで測定後、120℃のオーブンで30分間熱履歴を加えた。冷却後の試験片厚みL(mm)をデジタルノギスで測定した。次式により、厚み変化率(%)を算出し、その絶対値が2.0%未満の場合は「耐熱性○」、2.0~2.5%の場合は「耐熱性△」、3.0%以上の場合を「耐熱性×」と判断した。
厚み変化率(%)=L/Lo×100
金属部材と熱可塑性樹脂組成物(B)の引張せん断強度(MPa)を用いて、金属部材と熱可塑性樹脂組成物(B)の接着性を評価した。
引張せん断強度は、JIS K 6850に準拠した試験片を作成し測定した。金属片(25mm×100mm×厚み1.6mm)の先端、25mm×12.5mmの範囲に、予めドライブレンドすることで作成した熱可塑性樹脂組成物(B)を乗せ、その上から前記金属片と同サイズの金属片を重ね、240℃、3MPaで10分間加熱プレスすることで試験片を作成した。荷重載荷は、島津製作所製AGS-Xを使用した。
JIS K 7074を参考に、得られた金属・FRP複合材料の機械物性(曲げ強度及び曲げ弾性率)を測定した。
まず、成形後の厚みが約0.4mmとなるのに必要な枚数のプリプレグを2セット準備した。次に、準備したプリプレグの1セット分をまず積層し、その上に厚みが0.4mmの金属板を1枚積層し、前記金属板の上にプリプレグの残りの1セット分を更に積層し、これを250℃、3MPaで5分間熱プレスし、加圧状態を維持したまま50℃まで冷却することで複合材料を成形した(全体の厚み1.2mm)。これを10mm×80mmにカットすることで曲げ試験片を作成した。荷重載荷は、島津製作所製AGS-Xを使用した。
また、載荷試験終了後の試験片について、金属板とFRP材料が界面剥離したものを×、剥離しなかったものを○と判断した。
表1、表2に記載の樹脂比率にて、各種試験を行った。接着性2及び曲げ試験に使用した金属部材は、鉄鋼SGCC(スタンダードテストピースより購入)である。曲げ試験に使用した金属部材の厚みは 0.4mmである。
表3に記載の樹脂比率にて、各種試験を行った。使用した強化繊維基材(A)はサカイオーベックス社製の開繊炭素繊維織物SA-3203であり、接着性2及び曲げ試験に使用した金属部材はSGCC(スタンダードテストピースより購入)である。曲げ試験に使用した金属部材の厚みは0.4mmである。
表4、表5に記載の樹脂比率にて、各種試験を行った。接着性2及び曲げ試験に使用した金属部材は、アルミニウムA1050(スタンダードテストピースより購入)である。曲げ試験に使用した金属部材の厚みは0.5mmである。
Claims (5)
- 金属部材と繊維強化プラスチックの積層体であって、
前記繊維強化プラスチックが、強化繊維基材(A)と熱可塑性樹脂組成物(B)から成り、
熱可塑性樹脂組成物(B)はフェノキシ樹脂(B-1)とポリアミド樹脂(B-2)を質量比(B-1)/(B-2)が80/20~20/80の割合で含み、
強化繊維基材(A)のモノフィラメントに対する熱可塑性樹脂組成物(B)の接着強度が、マイクロドロップレット法における23℃における界面せん断強度で40MPa以上であり、
かつ、金属部材と熱可塑性樹脂組成物(B)の接着強度が、23℃における引張せん断強度で7.0MPa以上、
であることを特徴とする金属・繊維強化プラスチック複合材料。 - 180℃、30分の熱履歴を加えた後の常温における強化繊維プラスチックの厚み変化率の絶対値が2.0%未満である請求項1に記載の金属・繊維強化プラスチック複合材料。
- ポリアミド樹脂(B-2)が、全脂肪族ポリアミドおよび/または半脂肪族ポリアミドであることを特徴とする請求項1または2に記載の金属・繊維強化プラスチック複合材料。
- 金属部材の材質が鉄鋼材料、アルミニウムである請求項1~3のいずれか一項に記載の金属・繊維強化プラスチック複合材料。
- 強化繊維基材が炭素繊維、ボロン繊維、シリコンカーバイト繊維、ガラス繊維及びアラミド繊維よりなる群の中から選ばれる1種または2種以上の繊維を含むものである請求項1~4のいずれか一項に記載の金属・繊維強化プラスチック複合材料。
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EP19905148.3A EP3904074A4 (en) | 2018-12-27 | 2019-12-23 | METAL FIBER REINFORCED PLASTIC COMPOSITE |
US17/418,076 US20220097345A1 (en) | 2018-12-27 | 2019-12-23 | Metal-fiber reinforced plastic composite material |
CN201980086023.XA CN113226737A (zh) | 2018-12-27 | 2019-12-23 | 金属纤维强化塑料复合材料 |
KR1020217023506A KR20210107797A (ko) | 2018-12-27 | 2019-12-23 | 금속·섬유 강화 플라스틱 복합 재료 |
JP2020563240A JPWO2020137946A1 (ja) | 2018-12-27 | 2019-12-23 | 金属・繊維強化プラスチック複合材料 |
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EP (1) | EP3904074A4 (ja) |
JP (1) | JPWO2020137946A1 (ja) |
KR (1) | KR20210107797A (ja) |
CN (1) | CN113226737A (ja) |
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EP3904457A4 (en) * | 2018-12-28 | 2022-08-31 | NIPPON STEEL Chemical & Material Co., Ltd. | COMPOSITION OF HIGHLY HEAT RESISTANT THERMOPLASTIC RESIN AND MOLDED ARTICLE MADE THEREOF |
CN113140660A (zh) * | 2020-01-20 | 2021-07-20 | 光宝光电(常州)有限公司 | 封装结构与封装结构的制作方法 |
WO2024017899A1 (en) * | 2022-07-22 | 2024-01-25 | Solvay Specialty Polymers Usa, Llc | Thermoplastic composite materials |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0411654A (ja) * | 1990-04-27 | 1992-01-16 | Toyoda Gosei Co Ltd | ポリアミド樹脂組成物 |
JPH0411654B2 (ja) | 1982-09-17 | 1992-03-02 | Toyota Jido Shotsuki Seisakusho Kk | |
JP2010260974A (ja) * | 2009-05-08 | 2010-11-18 | Hitachi Chem Co Ltd | 絶縁性樹脂組成物、プリプレグ、金属箔張積層板、プリント配線板及び多層配線板 |
WO2012002434A1 (ja) * | 2010-07-01 | 2012-01-05 | 住友ベークライト株式会社 | プリプレグ、配線板および半導体装置 |
JP2015129271A (ja) | 2013-12-05 | 2015-07-16 | 東レ株式会社 | 炭素繊維強化ポリアミド樹脂組成物およびそれを成形してなる成形品 |
JP2016060051A (ja) | 2014-09-16 | 2016-04-25 | 合資会社アンドーコーポレーション | 金属とfrtpの複合体の製造方法とその複合体 |
JP2018039247A (ja) * | 2016-09-06 | 2018-03-15 | 大成プラス株式会社 | Cfrtpと金属の複合体 |
JP2019150990A (ja) * | 2018-03-01 | 2019-09-12 | 日本製鉄株式会社 | 金属―熱可塑性繊維強化樹脂材料複合部材の加工方法、金属―熱可塑性繊維強化樹脂材料複合部材及び自動車用部品。 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102011015071A1 (de) | 2011-03-24 | 2012-09-27 | Thyssenkrupp Steel Europe Ag | Verbundwerkstoff und Strukturbauteil für ein Kraftfahrzeug |
JP5898391B1 (ja) * | 2014-07-28 | 2016-04-06 | 東邦テナックス株式会社 | プリプレグおよび繊維強化複合材料 |
BR112018071036A2 (pt) * | 2016-04-13 | 2019-02-12 | Teijin Limited | material compósito reforçado com fibra de pré-impregnado e fibras de reforço de superfície modificada |
JP6953438B2 (ja) * | 2016-12-28 | 2021-10-27 | 日鉄ケミカル&マテリアル株式会社 | 金属−繊維強化樹脂材料複合体、その製造方法及び接着シート |
TW201903013A (zh) * | 2017-03-31 | 2019-01-16 | 日商新日鐵住金化學股份有限公司 | 金屬-纖維強化樹脂材料複合體及其製造方法 |
-
2019
- 2019-12-23 EP EP19905148.3A patent/EP3904074A4/en not_active Withdrawn
- 2019-12-23 US US17/418,076 patent/US20220097345A1/en not_active Abandoned
- 2019-12-23 KR KR1020217023506A patent/KR20210107797A/ko unknown
- 2019-12-23 CN CN201980086023.XA patent/CN113226737A/zh active Pending
- 2019-12-23 WO PCT/JP2019/050298 patent/WO2020137946A1/ja unknown
- 2019-12-23 JP JP2020563240A patent/JPWO2020137946A1/ja not_active Ceased
- 2019-12-25 TW TW108147595A patent/TW202035138A/zh unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0411654B2 (ja) | 1982-09-17 | 1992-03-02 | Toyota Jido Shotsuki Seisakusho Kk | |
JPH0411654A (ja) * | 1990-04-27 | 1992-01-16 | Toyoda Gosei Co Ltd | ポリアミド樹脂組成物 |
JP2010260974A (ja) * | 2009-05-08 | 2010-11-18 | Hitachi Chem Co Ltd | 絶縁性樹脂組成物、プリプレグ、金属箔張積層板、プリント配線板及び多層配線板 |
WO2012002434A1 (ja) * | 2010-07-01 | 2012-01-05 | 住友ベークライト株式会社 | プリプレグ、配線板および半導体装置 |
JP2015129271A (ja) | 2013-12-05 | 2015-07-16 | 東レ株式会社 | 炭素繊維強化ポリアミド樹脂組成物およびそれを成形してなる成形品 |
JP2016060051A (ja) | 2014-09-16 | 2016-04-25 | 合資会社アンドーコーポレーション | 金属とfrtpの複合体の製造方法とその複合体 |
JP2018039247A (ja) * | 2016-09-06 | 2018-03-15 | 大成プラス株式会社 | Cfrtpと金属の複合体 |
JP2019150990A (ja) * | 2018-03-01 | 2019-09-12 | 日本製鉄株式会社 | 金属―熱可塑性繊維強化樹脂材料複合部材の加工方法、金属―熱可塑性繊維強化樹脂材料複合部材及び自動車用部品。 |
Non-Patent Citations (2)
Title |
---|
REINFORCED PLASTICS, vol. 59, 2013, pages 330 |
See also references of EP3904074A4 |
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US20220097345A1 (en) | 2022-03-31 |
KR20210107797A (ko) | 2021-09-01 |
EP3904074A1 (en) | 2021-11-03 |
TW202035138A (zh) | 2020-10-01 |
EP3904074A4 (en) | 2022-09-14 |
CN113226737A (zh) | 2021-08-06 |
JPWO2020137946A1 (ja) | 2021-11-11 |
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