WO2023181645A1 - 繊維強化樹脂構造体および繊維強化樹脂構造体の製造方法 - Google Patents
繊維強化樹脂構造体および繊維強化樹脂構造体の製造方法 Download PDFInfo
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- WO2023181645A1 WO2023181645A1 PCT/JP2023/003030 JP2023003030W WO2023181645A1 WO 2023181645 A1 WO2023181645 A1 WO 2023181645A1 JP 2023003030 W JP2023003030 W JP 2023003030W WO 2023181645 A1 WO2023181645 A1 WO 2023181645A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/003—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
- B29C70/0035—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties comprising two or more matrix materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
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- B29D24/00—Producing articles with hollow walls
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C43/32—Component parts, details or accessories; Auxiliary operations
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- B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
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- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
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- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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- C08J2381/02—Polythioethers; Polythioether-ethers
Definitions
- the present invention relates to a fiber-reinforced resin structure produced using a base material in which reinforcing fibers are impregnated with a thermoplastic resin, and a method for manufacturing the fiber-reinforced resin structure.
- Patent Document 1 and Patent Document 2 disclose a sandwich structure in which a porous structure is used as a core material and a skin layer is arranged on the surface.
- Patent Document 1 describes that the core material and the skin layer are formed from a mat made of reinforcing fibers and a sheet-like intermediate base material made of a thermoplastic resin. Further, it is described that a porous structure is formed by molding because the sheet-like intermediate base material used for the core material has heat-expandability.
- the thermoplastic resins of the core material and the skin material are made to flow simultaneously to form an anchoring structure at the interface, It claims to have the effect of increasing the bonding strength between the core material and the skin material.
- Patent Document 2 describes that the core material is a composite of randomly dispersed discontinuous fibers bonded with a thermoplastic resin, and the skin layer is a composite of continuous reinforcing fibers impregnated with a thermoplastic resin. ing. It is also described that the core material expands upon heating to form a porous structure.
- the core material and the thermoplastic resin forming the skin layer are compatible with each other, and by melting the core material and the thermoplastic resin of the skin layer at the same time and making them compatible, the core material and the skin layer do not separate. , it says that it will be joined.
- the present invention has been made in view of the above problems, and its purpose is to maintain good surface quality in a fiber-reinforced resin structure that is lightweight and has excellent mechanical properties.
- a fiber-reinforced resin structure in which a void body (I) made of reinforcing fibers (A1) and a thermoplastic resin (B1) and a skin layer (II) made of reinforcing fibers (A2) and a thermoplastic resin (B2) are integrated. Therefore, the melting point Tc (°C) of the thermoplastic resin (B1) and the melting point Ts (°C) of the thermoplastic resin (B2) are both 230°C or higher, and the difference between Tc (°C) and Ts (°C) is Ts - Tc Or a fiber reinforced resin structure in which Tc-Ts is 20°C or higher.
- [Aspect 1] A fiber-reinforced resin structure in which a void body (I) made of reinforcing fibers (A1) and a thermoplastic resin (B1) and a skin layer (II) made of reinforcing fibers (A2) and a thermoplastic resin (B2) are integrated. Therefore, the melting point Tc (°C) of the thermoplastic resin (B1) and the melting point Ts (°C) of the thermoplastic resin (B2) are both 230°C or higher, and the difference between Tc (°C) and Ts (°C) is Ts - Tc A fiber-reinforced resin structure whose temperature is 20°C or higher.
- the present inventors have discovered that the above problem can be solved by defining the relationship between the melting points of the thermoplastic resin used for the void body (I) and the thermoplastic resin used for the skin layer (II), and have arrived at the present invention. did.
- the present invention will be explained in detail below.
- the fiber-reinforced resin structure (hereinafter sometimes simply referred to as "structure") of the present invention comprises a void body (I) consisting of reinforcing fibers (A1) and a thermoplastic resin (B1), and reinforcing fibers (A2). and a skin layer (II) made of a thermoplastic resin (B2) are integrated into a structure. That is, the void body (I) contains reinforcing fibers (A1) and a thermoplastic resin (B1), and the skin layer (II) contains reinforcing fibers (A2) and a thermoplastic resin (B2).
- the skin layer (II) may be present on at least one surface of the void body (I), but it may be a so-called sandwich structure in which the skin layer (II) is present on both surfaces of the void body (I).
- sandwich structure By forming a sandwich structure, the elastic modulus and strength of the fiber-reinforced resin structure can be further increased, and the symmetrical structure can reduce the occurrence of warpage due to heat shrinkage during molding.
- the void body (I) has voids.
- FIG. 1 is a schematic diagram showing a fiber-reinforced resin structure in one embodiment of the present invention.
- FIG. 1(b) is a schematic cross-sectional view showing a partial structure of the void body (I).
- the voids in the present invention typically refer to reinforcing fibers formed by reinforcing fibers (A1) coated with thermoplastic resin (B1) serving as columnar supports that overlap or intersect. It refers to a space in which neither (A1) nor thermoplastic resin (B1) exists.
- the thermoplastic resin (B1) accompanying the heating is heated.
- the orientation angle in the thickness direction of the reinforcing fibers (A1) is preferably 1° or more from the viewpoint of expansion coefficient, and more preferably 3° or more.
- the void body (I) has a porosity of 10 volume % or more and 90 volume % or less. It is preferable that the porosity is 10% by volume or more, since the density of the void body (I) becomes low and lightness can be satisfied. On the other hand, when the porosity is 90% by volume or less, the thickness of the thermoplastic resin (B1) coated around the reinforcing fibers (A1) is sufficient, so the reinforcement in the void body (I) This is preferable because the fibers (A1) can be sufficiently reinforced with each other and the mechanical properties are improved.
- the reinforcing fibers (A1) used in the void body (I) are typically discontinuous fibers.
- the discontinuous fiber in the present invention is preferably a reinforcing fiber having a fiber length of 1 mm or more and 15 mm or less. Since the reinforcing fibers (A1) are discontinuous fibers, voids can be easily formed by raising as described above. When the fiber length of the reinforcing fiber (A1) is less than 1 mm, voids may not be formed efficiently, which is not preferable.
- a method for measuring the fiber length of reinforcing fibers for example, there is a method of directly extracting reinforcing fibers from a group of reinforcing fibers and measuring them by microscopic observation.
- the resin is dissolved from the reinforcing fiber group using a solvent that dissolves only the resin contained therein, and the remaining reinforcing fibers are filtered out and measured by microscopic observation ( If there is no solvent to dissolve the resin, there are methods such as burning off only the resin at a temperature range where the reinforcing fibers do not lose weight due to oxidation, separating the reinforcing fibers, and measuring them by microscopic observation (burning off method). .
- the reinforcing fibers (A1) are preferably substantially monofilament-like and randomly dispersed in the void body (I).
- substantially monofilament-like refers to the presence of reinforcing fibers in fine strands of less than 500 single filaments. More preferably, it is dispersed in the form of a monofilament, that is, as a single thread.
- the number of reinforcing fibers (A1) present as a fiber bundle is reduced, so the weak portions at the ends of the reinforcing fibers (A1) can be minimized, and in addition to excellent reinforcing efficiency and reliability.
- isotropy is also imparted. By randomly distributing them, further isotropy can be imparted.
- the reinforcing fibers (A2) used in the skin layer (II) are not particularly limited, but are preferably continuous fibers.
- the continuous fibers are reinforcing fibers that are continuous in at least one direction with a length of 100 mm or more.
- Examples of forms made of continuous fibers include fiber fabrics made of reinforcing fiber bundles made of a large number of continuous fibers, and unidirectional continuous fibers in which a large number of continuous fibers are arranged in one direction.
- unidirectional continuous fibers are preferred from the viewpoint of enhancing the reinforcing effect of the molded body, and when the molded body is to have a complex shape, a fibrous fabric with excellent shapeability is preferred.
- reinforcing fibers (A1) and reinforcing fibers (A2) there are no particular restrictions on the types of reinforcing fibers (A1) and reinforcing fibers (A2), and examples include metal fibers such as aluminum fibers, brass fibers, and stainless steel fibers, polyacrylonitrile (PAN)-based carbon fibers, rayon-based carbon fibers, and lignin.
- metal fibers such as aluminum fibers, brass fibers, and stainless steel fibers, polyacrylonitrile (PAN)-based carbon fibers, rayon-based carbon fibers, and lignin.
- PAN polyacrylonitrile
- carbon fibers such as pitch-based carbon fibers and pitch-based carbon fibers (including graphite fibers), insulating fibers such as glass fibers, aramid fibers, polyparaphenylenebenzoxazole (PBO) fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, Examples include organic fibers such as nylon fibers and polyethylene fibers, and inorganic fibers such as silicon carbide fibers and silicon nitride fibers. Moreover, these fibers may be surface-treated. Surface treatments include treatment with a coupling agent, treatment with a sizing agent, treatment with a binding agent, treatment with an additive, and the like, in addition to treatment with a metal that is a conductor. Moreover, these reinforcing fibers may be used alone or in combination of two or more types.
- carbon fibers such as PAN-based carbon fibers, pitch-based carbon fibers, and rayon-based carbon fibers, which have excellent specific strength and specific stiffness, are preferably used from the viewpoint of weight reduction effects, and have excellent mechanical properties such as strength and elastic modulus.
- PAN-based carbon fibers are particularly preferably used.
- glass fiber is preferably used, and in particular, from the viewpoint of a balance between mechanical properties and economic efficiency, it is preferable to use carbon fiber and glass fiber in combination.
- aramid fibers are preferably used, and in particular, it is preferable to use carbon fibers and aramid fibers in combination from the viewpoint of the balance between mechanical properties and shock absorbing properties. Furthermore, from the viewpoint of increasing the conductivity of the resulting molded product, reinforcing fibers coated with metals such as nickel, copper, and ytterbium can also be used.
- the carbon fibers may also be recycled carbon fibers obtained by recycling carbon fiber reinforced plastics containing carbon fibers and matrix resin.
- the matrix resin is removed by a treatment method such as an ordinary pressure dissolution method, a subcritical decomposition method, a supercritical decomposition method, an electrolytic method, a thermal decomposition method, a superheated steam method, or the like.
- the reinforcing fiber (A1) contained in the void body (I) preferably has a tensile modulus of 200 GPa or more and 1000 GPa or less, more preferably 220 GPa or more and 500 GPa or less, from the viewpoint of the rigidity of the fiber reinforced resin structure. can be used. If the tensile modulus of the reinforcing fiber is smaller than 200 GPa, the stiffness of the fiber reinforced resin structure may be inferior, and if it is larger than 1000 GPa, it is necessary to increase the crystallinity of the reinforcing fiber, and such reinforcement The fibers are difficult to manufacture.
- the tensile modulus of the discontinuous reinforcing fibers is within the above range in terms of the rigidity of the fiber reinforced resin structure and the manufacturability of the reinforcing fibers. Note that the tensile modulus of the reinforcing fibers can be measured by a strand tensile test described in JIS R7601-1986.
- the melting point Tc of the thermoplastic resin (B1) and the melting point Ts of the thermoplastic resin (B2) are both 230° C. or higher.
- crystalline thermoplastic resins having such a melting point include polyamide (PA), polyphenylene sulfide (PPS), polyetherketone (PEK), polyetheretherketone (PEEK), and polyetherketoneketone (PEKK). ) and other polyaryletherketones (PAEK).
- the glass transition temperature of the thermoplastic resin (B1) and the thermoplastic resin (B2) is 120°C or higher, and as a thermoplastic resin having such a glass transition temperature, polyarylether Copolymers of ketones or polyaryletherketones are preferred, and compounds selected from polyetheretherketones and polyetherketoneketones are more preferred.
- the melting point of either one of Tc and Ts is preferably 270°C or higher and 330°C or lower.
- thermoplastic resin with a high melting point When using a thermoplastic resin with a high melting point, molding is often performed at a temperature near the melting point of the thermoplastic resin from the viewpoint of the temperature raising ability of a molding die. Therefore, molding under high pressure is often necessary in a state of high melt viscosity, and if the entire molded product flows, the surface quality tends to be poor.
- the void body (I) and the skin layer (II) can flow separately, the effect of improving the surface quality can be significantly obtained when using a resin with a high melting point. Furthermore, by using a thermoplastic resin with a high melting point, the resulting structure can be used better at high temperatures.
- thermoplastic resins (B1) and thermoplastic resins (B2) may contain impact resistance improvers such as elastomers or rubber components, other fillers, and additives within a range that does not impair the purpose of the present invention. It's okay.
- fillers and additives include inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, and color inhibitors. , a heat stabilizer, a mold release agent, an antistatic agent, a plasticizer, a lubricant, a colorant, a pigment, a dye, a foaming agent, an antifoaming agent, or a coupling agent.
- the difference between Tc (°C) and Ts (°C) is 20°C or more.
- a fiber-reinforced resin structure that satisfies this requirement can be molded by solidifying either the void (I) or the skin layer (II) and softening the other during manufacturing, so that the entire structure does not flow. Therefore, it is possible to manufacture a structure with an excellent surface appearance.
- the melting point of the thermoplastic resin in the present invention the melting point measured in accordance with JIS K7120 (1987) is used. The melting point of a resin varies depending on the additives and molecular weight distribution, so it cannot be uniformly defined.
- suitable combinations of resin types to achieve a design that satisfies the above melting point relationship include polyamide and polyphenylene sulfide, and polyamide and polyamide.
- suitable combinations of resin types to achieve a design that satisfies the above melting point relationship include polyamide and polyphenylene sulfide, and polyamide and polyamide.
- Examples include ether ketone ketone, polyamide and polyether ether ketone, polyphenylene sulfide and polyether ketone ketone, polyphenylene sulfide and polyether ether ketone, and polyether ketone ketone and polyether ether ketone.
- thermoplastic resin (B1) and thermoplastic resin (B2) By using such a combination of thermoplastic resin (B1) and thermoplastic resin (B2), either the void body (I) or the skin layer (II) is solidified, and the other is melted or softened. Only the parts that are melted or softened can be molded. Therefore, in the structure of the present invention, the surface quality of the skin layer (II) is good even without post-processing after molding, and the surface quality of the skin layer (II) is good as measured in accordance with JIS B 0601 (2001). It becomes possible to suppress the average surface roughness Ra to 10 ⁇ m or less. From the viewpoint of surface quality, the average surface roughness is more preferably 5 ⁇ m or less, and even more preferably 1 ⁇ m or less.
- thermoplastic resin (B1) in the void body (I) and the thermoplastic resin (B1) in the skin layer (II) are molded.
- B2) is preferably not mutually compatible but forms an interface.
- the thickness of the void body (I) and the skin layer (II) when the thickness of the void body (I) is Hc and the thickness of the skin layer (II) is Hs, it is preferable that Hc/Hs is 5 or more. By increasing the ratio of voids (I) in the fiber-reinforced resin structure, a lightweight molded body can be obtained.
- the melting point Tc of the thermoplastic resin (B1) constituting the void body (I) is 20° C. higher than the melting point Ts of the thermoplastic resin (B2) constituting the skin layer (II). If Ts-Tc ⁇ 20 (°C), as shown in Figure 2, which shows the changes in molding temperature and molding pressure, - Precursor (i) of void body (I) containing nonwoven fabric of reinforcing fiber (A1) and thermoplastic resin (B1) - The first step of laminating prepregs made of reinforcing fibers (A2) and thermoplastic resin (B2) and placing them in a mold; The thermoplastic resin (B1) and the thermoplastic resin (B2) are both melted by heating to a temperature higher than Ts, and the precursor (i) of the void body (I) and the skin layer (II) are bonded and shaped.
- the second step A third step of lowering the temperature to a temperature higher than Tc and lower than Ts to solidify the epidermal layer (II); A fourth step of expanding the precursor (i) of the void body (I) by releasing the pressure while maintaining the temperature higher than Tc and lower than Ts; A fifth step of lowering the temperature to a temperature lower than Tc and solidifying the void body (I);
- the fiber reinforced resin structure of the present invention can be manufactured by the manufacturing method having the following.
- the expanding thermoplastic resin (B1) It is possible to suppress deterioration of surface quality such as scratching of the epidermal layer (II) due to the flow of the liquid.
- the precursor of the void body (I) may be a laminate of sheets made of a nonwoven fabric of reinforcing fibers (A1) and a thermoplastic resin (B1), or a nonwoven fabric of reinforcing fibers (A1) and a thermoplastic resin (B1). Any substrate impregnated with can be used.
- a laminate of sheets made of a nonwoven fabric of reinforcing fibers (A1) and a thermoplastic resin (B1) is used as a precursor of the void body (I)
- any step before the fourth step preferably the third step. After the step, it is preferable to carry out an impregnation operation in which the reinforcing fibers (A1) are impregnated with the thermoplastic resin (B1) by pressurization.
- the fiber reinforced resin structure of the present invention can be manufactured by the manufacturing method having the following.
- the fifth step it is preferable to apply a pressure lower than the compressive strength of the solidified void body (I) so that the structure of the void body (I) is not destroyed.
- a pressure lower than the compressive strength of the solidified void body (I) so that the structure of the void body (I) is not destroyed.
- the melting point Tc of the thermoplastic resin (B1) constituting the void body (I) is 20° C. or more higher than the melting point Ts of the thermoplastic resin (B2) constituting the skin layer (II) (Tc - Ts ⁇ 20 (°C))
- the void body (I) and the skin layer (II) are laminated, and as shown in Figure 4, the molding temperature and molding pressure are lower than Tc and higher than Ts in the autoclave.
- the fiber-reinforced resin structure of the present invention can be manufactured by a manufacturing method that involves heating and pressurizing at a temperature. Since the void body (I) does not melt, the surface can be smoothed in a state where the skin layer (II) can stably flow, and deterioration of surface quality such as scratches can be suppressed.
- FIG. 5 is a schematic diagram showing an embodiment of a fiber-reinforced resin structure in which the skin layer (II) has a bent portion.
- the structure consisting of the skin layer (II) 2 and the void body (I) 1 is a plate-like body having a constant thickness, and the plate-like body is shaped into a bent shape by two bending parts. It is shaped.
- the epidermal layer (II) has two bent portions 3 bent at approximately 90° to follow the bent shape.
- the bent portion in the present invention is a shape having a curved surface, and includes, for example, a shape in which the cross-sectional shape of the molded body is part of a circle or an ellipse. Since molding pressure tends to concentrate at the bent portion, scratches and scratches are likely to occur on the surface of the skin layer, and the effect of the present invention in preventing scratches and scratches from occurring on the surface of the skin layer is more pronounced.
- thermoplastic resin B1, B2
- the melting point and glass transition temperature of the thermoplastic resin (B1) and thermoplastic resin (B2) impregnated into the fiber reinforced resin structure were evaluated as follows. The melting point and glass transition temperature were measured in accordance with the "Method for Measuring Plastic Transition Temperature" specified in JIS K7121 (1987).
- the sheet or nonwoven fabric used for producing the fiber-reinforced resin structure was dried for 24 hours or more in a vacuum dryer controlled at a furnace temperature of 50° C., and then cut into pieces to prepare samples.
- the melting point of this sample was determined according to the above standard using a differential scanning calorimeter (DSC 200F3 Maia, manufactured by NETZSCH).
- Average surface roughness Ra of epidermal layer (II) Using a surface roughness meter, the cutoff value and reference length were selected based on JIS-B-0601 (2001), and the surface roughness Ra of the bent portion in the epidermal layer was determined.
- Carbon fiber A polymer containing polyacrylonitrile as a main component was spun and fired to obtain continuous carbon fibers with a total number of 12,000 filaments. Further, the continuous carbon fibers were subjected to electrolytic surface treatment and dried in heated air at 120° C. to obtain reinforcing fibers I. The characteristics of this carbon fiber were as shown below. Density: 1.80g/ cm3 Single fiber diameter: 7 ⁇ m Tensile strength: 4.9GPa Tensile modulus: 230 GPa.
- the reinforcing fibers were cut into 6 mm pieces using a cartridge cutter to obtain chopped reinforcing fibers.
- 40 liters of a dispersion medium with a concentration of 0.1% by weight consisting of water and a surfactant (manufactured by Nacalai Tesque Co., Ltd., polyoxyethylene lauryl ether (trade name)) was prepared, and the dispersion medium was introduced into a paper-making apparatus.
- the papermaking device consists of an upper papermaking tank (capacity 30 liters) equipped with a rotor-equipped agitator and a lower water storage tank (capacity 10 liters), with a porous support provided between the papermaking tank and the water tank. .
- the dispersion medium was stirred using a stirrer until microbubbles of air were generated. Thereafter, the chopped reinforcing fibers whose weight had been adjusted so as to have a desired basis weight were put into a dispersion medium in which air microbubbles were dispersed and stirred, thereby obtaining a slurry in which the reinforcing fibers were dispersed. Next, the slurry was sucked from the water storage layer and dehydrated through a porous support to obtain a reinforced fiber paper product. The paper product was dried in a hot air dryer at 150° C. for 2 hours to obtain a reinforced fiber mat.
- PA66 sheet A sheet with a basis weight of 100 g/m 2 was prepared using nylon 66 resin (manufactured by Toray Industries, Inc., "Amilan” (registered trademark) CM3006).
- PPS sheet A sheet with a basis weight of 100 g/m 2 was prepared using polyphenylene sulfide resin (“TORELINA” (registered trademark) M2888, manufactured by Toray Industries, Inc.).
- PEKK sheet ( ⁇ ) A sheet with a basis weight of 100 g/m 2 was prepared using polyetherketoneketone resin (manufactured by Arkema Corporation, "Kepstan” (registered trademark) 6003).
- PEKK sheet ( ⁇ ) A sheet with a basis weight of 100 g/m 2 was prepared using polyetherketoneketone resin (manufactured by Arkema Corporation, "Kepstan” (registered trademark) 8003).
- PEEK sheet A sheet having a basis weight of 100 g/m 2 was prepared using polyether ether ketone resin ("PEEK” 381G, manufactured by Victrex Japan Co., Ltd.).
- PA66 prepreg Opened carbon fibers were aligned in parallel and arranged in one direction at a density of 1.4 fibers/cm to form a sheet-like reinforcing fiber group. A PA66 sheet was laminated on the reinforcing fiber group and impregnated with a press machine heated to 280° C. while applying a surface pressure of 10 MPa to obtain a PPS prepreg.
- PPS prepreg Opened carbon fibers were aligned in parallel and arranged in one direction at a density of 1.4 fibers/cm to form a sheet-like reinforcing fiber group. A PPS sheet was laminated on the reinforcing fiber group and impregnated with a press machine heated to 300° C. while applying a surface pressure of 10 MPa to obtain a PPS prepreg.
- PEKK prepreg ( ⁇ ) Opened carbon fibers were aligned in parallel and arranged in one direction at a density of 1.4 fibers/cm to form a sheet-like reinforcing fiber group.
- a PEKK sheet ( ⁇ ) was laminated on the reinforcing fiber group and impregnated with a press machine heated to 330° C. while applying a surface pressure of 10 MPa to obtain a PEKK prepreg ( ⁇ ).
- PEKK prepreg ( ⁇ ) Opened carbon fibers were aligned in parallel and arranged in one direction at a density of 1.4 fibers/cm to form a sheet-like reinforcing fiber group.
- a PEKK sheet ( ⁇ ) was laminated on the reinforcing fiber group and impregnated with a press machine heated to 380° C. while applying a surface pressure of 10 MPa to obtain a PEKK prepreg ( ⁇ ).
- PEEK prepreg Opened carbon fibers were aligned in parallel and arranged in one direction at a density of 1.4 fibers/cm to form a sheet-like reinforcing fiber group. A PEEK sheet was laminated on the reinforcing fiber group and impregnated with a press machine heated to 360° C. while applying a surface pressure of 10 MPa to obtain a PEEK prepreg.
- FIG. 6(a) is a schematic diagram of a press molding die having a curved surface portion
- FIG. 6(b) is an overview diagram of a fiber-reinforced resin structure having a shape P obtained using the die.
- the dimensions of the mold are 300 mm long x 200 mm wide, and the average surface roughness of the mold surface is 0.2 ⁇ m.
- Example 2 When Tc-Ts ⁇ 20 (°C)
- a 6 mm mat was used as the reinforcing fiber (A1)
- a PPS sheet was used as the thermoplastic resin (B1)
- a PA66 prepreg was used as the skin layer (II).
- a fiber reinforced resin structure was obtained by passing through the following press molding conditions. (1st step) Laminating in the order of [skin layer (II) / reinforcing fiber (A1) / thermoplastic resin (B1) / reinforcing fiber (A1) / thermoplastic resin (B1) / reinforcing fiber (A1)], A laminated precursor is produced. The laminated precursor is placed in a press mold cavity preheated to 300° C., and the mold is closed.
- Example 3 When Ts-Tc ⁇ 20 (°C)
- a 6 mm mat was used as the reinforcing fiber (A1)
- a PPS sheet was used as the thermoplastic resin (B1)
- a PEKK prepreg was used as the skin layer (II).
- a fiber reinforced resin structure was obtained by passing through the following press molding conditions. (1st step) [Skin layer (II)/thermoplastic resin (B1)/reinforced fiber (A1)/thermoplastic resin (B1)/reinforced fiber (A1)/thermoplastic resin (B1)] is laminated in this order. , to produce a laminated precursor. The laminated precursor is placed in a press mold cavity preheated to 330° C., and the mold is closed.
- Example 4 When Ts-Tc ⁇ 20 (°C)
- a 6 mm mat was used as the reinforcing fiber (A1)
- a PEKK sheet was used as the thermoplastic resin (B1)
- a PEEK prepreg was used as the skin layer (II).
- a fiber reinforced resin structure was obtained by passing through the following press molding conditions. (1st step) [Skin layer (II)/thermoplastic resin (B1)/reinforced fiber (A1)/thermoplastic resin (B1)/reinforced fiber (A1)/thermoplastic resin (B1)] is laminated in this order. , to produce a laminated precursor. The laminated precursor is placed in a press mold cavity preheated to 380° C., and the mold is closed.
- Example 5 When Tc-Ts ⁇ 20 (°C)
- a 6 mm mat was used as the reinforcing fiber (A1)
- a PEEK sheet was used as the thermoplastic resin (B1)
- a PEKK prepreg was used as the skin layer (II).
- a fiber reinforced resin structure was obtained by passing through the following press molding conditions. (1st step) Laminating in the order of [skin layer (II) / reinforcing fiber (A1) / thermoplastic resin (B1) / reinforcing fiber (A1) / thermoplastic resin (B1) / reinforcing fiber (A1)], A laminated precursor is produced. The laminated precursor is placed in a press mold cavity preheated to 380° C., and the mold is closed.
- Example 6 Tc-Ts ⁇ 20°C
- a fiber reinforced resin structure was produced in the same manner as in Example 5.
- the surface of the taken out fiber-reinforced resin structure on the void side is cut by about 0.4 mm so that the ratio Hc/Hs of the thickness Hc of the void to the thickness Hs of the skin layer is 3.
- Table 1 shows the properties of the obtained fiber reinforced resin structure.
- Example 7 When Ts-Tc ⁇ 20 (°C) A fiber-reinforced resin structure was produced in the same manner as in Example 1, except that a metal spacer was inserted so that the expansion ratio when obtaining the fiber-reinforced resin structure was 1.05 times. Table 1 shows the properties of the obtained fiber reinforced resin structure.
- Example 8 When Ts-Tc ⁇ 20 (°C)
- a fiber-reinforced resin structure was produced in the same manner as in Example 1, except that a metal spacer was inserted so that the expansion ratio when obtaining the fiber-reinforced resin structure was 20 times.
- Table 1 shows the obtained fiber reinforced resin structure.
- Example 10 When Ts-Tc ⁇ 20 (°C)
- a fiber-reinforced resin structure was produced in the same manner as in Example 4, except that the layers were laminated in the order shown in Example 4 to produce a laminated precursor.
- Table 1 shows the obtained fiber reinforced resin structure.
- Example 11 A fiber-reinforced resin structure was produced in the same manner as in Example 1, except that a press molding die having a cavity for forming a bent portion was used.
- FIG. 7(a) is a schematic diagram of the press molding die used
- FIG. 7(b) shows the shape Q of the fiber-reinforced resin structure obtained using the die.
- the dimensions of the mold are as follows: flat parts measuring 300 mm long x 200 mm wide, with a bent part having a radius of curvature of 12 mm, and the average surface roughness of the mold surface is 0.2 ⁇ m. Table 1 shows the obtained fiber reinforced resin structure. Here, the surface roughness was measured at the bent portion.
- Example 12 A 6 mm mat was used as the reinforcing fiber (A1), a PEEK sheet was used as the thermoplastic resin (B1), and a PEKK prepreg was used as the skin layer (II).
- a fiber-reinforced resin structure was obtained under the following molding conditions.
- First step [Reinforcing fiber (A1)/Thermoplastic resin (B1)/Reinforcing fiber (A1)/Thermoplastic resin (B1)/Reinforcing fiber (A1)] is laminated in this order to produce a laminated precursor. .
- the laminated precursor is placed in a press mold cavity preheated to 380° C., and the mold is closed.
- a 6 mm mat was used as the reinforcing fiber (A1)
- a PPS sheet was used as the thermoplastic resin (B1)
- a PPS prepreg was used as the skin layer (II).
- a fiber reinforced resin structure was obtained by passing through the following press molding conditions. (1st step) [Skin layer (II)/thermoplastic resin (B1)/reinforced fiber (A1)/thermoplastic resin (B1)/reinforced fiber (A1)/thermoplastic resin (B1)] is laminated in this order. , to produce a laminated precursor. The laminated precursor is placed in a press mold cavity preheated to 300° C., and the mold is closed.
- a 6 mm mat was used as the reinforcing fiber (A1)
- a PEEK sheet was used as the thermoplastic resin (B1)
- a PEKK prepreg was used as the skin layer (II).
- a fiber reinforced resin structure was obtained by passing through the following press molding conditions. (1st step) [Skin layer (II)/thermoplastic resin (B1)/reinforced fiber (A1)/thermoplastic resin (B1)/reinforced fiber (A1)/thermoplastic resin (B1)] is laminated in this order. , to produce a laminated precursor. The laminated precursor is placed in a press mold cavity preheated to 380° C., and the mold is closed.
- FIG. 7(a) is a schematic diagram of the press molding die used
- FIG. 7(b) shows the shape Q of the fiber-reinforced resin structure obtained using the die.
- the dimensions of the mold are as follows: flat parts measuring 300 mm long x 200 mm wide, with a bent part having a radius of curvature of 12 mm, and the average surface roughness of the mold surface is 0.2 ⁇ m.
- Table 1 shows the obtained fiber reinforced resin structure. Here, the surface roughness was measured at the bent portion.
- any of the examples since there was a difference of 20°C or more in the melting points of the thermoplastic resins used for the void body and the skin layer, it was possible to shape only one of the skin layer or the void body in a molten state. . As a result, since the skin layer did not flow due to the expansion of the precursor of the void body, it was possible to obtain a fiber-reinforced resin structure having good surface quality with a surface roughness of 10 ⁇ m or less at the bent portion.
- Example 4 a thermoplastic resin whose glass transition temperature of the void body is 120°C or higher is used, and in continuous use at high temperatures, the fiber reinforced resin structures of Examples 4 and 5 are It is clear that this structure is superior to fiber reinforced resin structures No. 1 and 2.
- Example 6 the density was increased as a result of making the thickness of the void body smaller than the thickness of the skin layer, suggesting that the specific strength could be improved by changing the thickness configuration.
- Example 7 and 8 the precursor of the void body was expanded and shaped with the skin layer solidified, so fiber-reinforced resin structures with good appearance quality were obtained, but the porosity was It was suggested that the specific gravity and bending strength could be improved.
- Example 9 since the skin layer was laminated on both sides of the void body, it was possible to obtain a fiber-reinforced resin structure having further excellent bending strength and good surface quality.
- Example 11 the shape was formed into a shape having a bent part, but since the precursor of the void body could be expanded and shaped with the skin layer solidified, flow of the skin layer occurred due to load concentration on the bent part. It was possible to obtain a fiber-reinforced resin structure having good surface quality with a surface roughness of 10 ⁇ m or less at the bent portion.
- Example 12 the laminate of the void body and the skin layer was molded in an autoclave, but since the skin layer was shaped while the void body was solidified, it had a good surface quality with a surface roughness of 10 ⁇ m or less. A fiber reinforced resin structure could be obtained.
- Comparative Example 1 the melting points of the thermoplastic resin used for the void body and the thermoplastic resin used for the skin layer were the same, so the void body and the skin layer flowed simultaneously during shaping, and the surface of the skin layer The roughness was 10 ⁇ m or more, indicating that the surface quality of the fiber-reinforced resin structure was insufficient.
- Comparative Example 2 the difference in the melting points of the thermoplastic resins was 15° C., so the effect of the present invention was not fully exhibited, and the surface roughness was greater than 10 ⁇ m.
- Comparative Example 3 the difference in the melting points of the thermoplastic resins was 15°C, so the effect of the present invention was not fully exhibited, and the load was concentrated on the bent part, and the surface roughness was even greater than that of Comparative Example 2. It became.
- Voids Epidermal layer b.
- Cross section of void body 3.
- Reinforced fiber (A1) Air gap 5.
- Thermoplastic resin (B1) Bent portion 7.
- Lower mold Fiber-reinforced resin molded body shape
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Abstract
Description
強化繊維(A1)と熱可塑性樹脂(B1)からなる空隙体(I)と、強化繊維(A2)と熱可塑性樹脂(B2)からなる表皮層(II)が一体化した繊維強化樹脂構造体であって、熱可塑性樹脂(B1)の融点Tc(℃)と熱可塑性樹脂(B2)の融点Ts(℃)がともに230℃以上であり、Tc(℃)とTs(℃)の差Ts-TcまたはTc-Tsが20℃以上である、繊維強化樹脂構造体。
[態様1]
強化繊維(A1)と熱可塑性樹脂(B1)からなる空隙体(I)と、強化繊維(A2)と熱可塑性樹脂(B2)からなる表皮層(II)が一体化した繊維強化樹脂構造体であって、熱可塑性樹脂(B1)の融点Tc(℃)と熱可塑性樹脂(B2)の融点Ts(℃)がともに230℃以上であり、Tc(℃)とTs(℃)の差Ts-Tcが20℃以上である、繊維強化樹脂構造体。
強化繊維(A1)と熱可塑性樹脂(B1)からなる空隙体(I)と、強化繊維(A2)と熱可塑性樹脂(B2)からなる表皮層(II)が一体化した繊維強化樹脂構造体であって、熱可塑性樹脂(B1)の融点Tc(℃)と熱可塑性樹脂(B2)の融点Ts(℃)がともに230℃以上であり、Tc(℃)とTs(℃)の差Tc-Tsが20℃以上である、繊維強化樹脂構造体。
・強化繊維(A1)の不織布と熱可塑性樹脂(B1)を含む空隙体(I)の前駆体(i)
・強化繊維(A2)および熱可塑性樹脂(B2)からなるプリプレグ
を積層して成形金型に配置する第1ステップ;
Tsよりも高い温度に加熱して熱可塑性樹脂(B1)および熱可塑性樹脂(B2)をともに溶融し、空隙体(I)の前駆体(i)および表皮層(II)を接合するとともに賦形する第2ステップ;
Tcより高く、Tsより低い温度にまで降温し、表皮層(II)を固化する第3ステップ;
Tcより高く、Tsより低い温度を維持したまま、圧力を開放して空隙体(I)の前駆体(i)を膨張させる第4ステップ;
Tcより低い温度にまで降温し、空隙体(I)を固化させる第5ステップ;
を有する製造方法により、本発明の繊維強化樹脂構造体を製造することができる。このような方法によれば、第3ステップで既に表皮層(II)が硬化した状態で、第4ステップにおいて空隙体(I)の前駆体が膨張するため、膨張中の熱可塑性樹脂(B1)の流動よる表皮層(II)のカスレ等の表面品位の低下を抑制することができる。
Tcよりも高い温度に加熱して熱可塑性樹脂(B1)および熱可塑性樹脂(B2)をともに溶融し、空隙体(I)の前駆体(i)および表皮層(II)を接合する第2ステップ;
Tcよりも高い温度を維持したまま、圧力を解放し、空隙体(I)の前駆体(i)を膨張させる第3ステップ;
Tsより高く、Tcより低い温度にまで降温し、膨張した空隙体(I)を固化させる第4ステップ;
Tsより高く、Tcより低い温度を維持したまま、圧力を加えて表皮層(II)を流動させる第5ステップ;
Tsより低い温度にまで降温し、表皮層(II)を固化させる第6ステップ;
を有する製造方法により、本発明の繊維強化樹脂構造体を製造することができる。なお第5ステップにおいては固化した空隙体(I)の圧縮強度未満の圧力を加えることが、空隙体(I)の構造が破壊されないため好ましい。このような方法によれば、第3ステップにおいて空隙体(I)を膨張させた時点では、表皮層(II)の表面は空隙体(I)の膨張によって引きずられて粗い状態であるが、後に、第5ステップにおいて表皮層(II)を流動させる際に空隙体(I)が流動しないため、表皮層(II)が安定して流動できる状態で表面を平滑化することができ、カスレ等の表面品位の低下を抑制することができる。
(1)熱可塑性樹脂(B1、B2)の融点
繊維強化樹脂構造体に含浸される熱可塑性樹脂(B1)および熱可塑性樹脂(B2)の融点およびガラス転移温度を次のように評価した。JIS K7121(1987)に規定される「プラスチックの転移温度測定方法」に準拠して融点およびガラス転移温度を測定した。繊維強化樹脂構造体の作製に用いたシートないし不織布を、炉内温度50℃で制御された真空乾燥機中で24時間以上乾燥させた後、細かく裁断して試料を準備した。この試料について、示差走査熱量測定装置(NETZSCH社製、DSC 200F3 Maia)を用いて、前記規格による融点を得た。
繊維強化樹脂構造体の平面部から縦10mm、横10mmに試験片を切り出し、断面を走査型電子顕微鏡(SEM)((株)日立ハイテクノロジーズ製S-4800型)により観察し、構造体の表面から、等間隔に10箇所を1000倍の倍率で撮影した。それぞれの画像について、画像内の空隙の面積を求めた。さらに、空隙の面積を画像全体の面積で除算することにより空隙率を算出した。構造体の空隙の体積含有率は、5枚の試験片でそれぞれ10箇所ずつ撮影した合計50箇所の空隙率から算術平均により求めた。
繊維強化樹脂構造体の平面部から縦10mm、横10mmに試験片を切り出し、断面を走査型電子顕微鏡(SEM)((株)日立ハイテクノロジーズ製S-4800型)により観察し、樹脂界面の観察と厚みの測定を行った。厚みはランダムに選んだ点5か所における厚みの算術平均により求めた。
繊維強化樹脂構造体の平面部から縦10mm、横100mmに試験片を切り出し、JIS K7017(1999)に準拠して4点曲げ試験を実施し、曲げ強度を測定した。
表面粗さ計を用いて、JIS-B-0601(2001)に基づき、カットオフ値および基準長さを選定し、表皮層における屈曲部の表面粗さRaを求めた。
[炭素繊維]
ポリアクリロニトリルを主成分とする重合体から紡糸、焼成処理を行い、総フィラメント数12000 本の連続炭素繊維を得た。さらに該連続炭素繊維を電解表面処理し、120℃の加熱空気中で乾燥して強化繊維Iを得た。この炭素繊維の特性は次に示す通りであった。
密度:1.80g/cm3
単繊維径:7μm
引張強度:4.9GPa
引張弾性率:230GPa。
強化繊維をカートリッジカッターで6mmにカットし、チョップド強化繊維を得た。水と界面活性剤(ナカライテスク(株)製、ポリオキシエチレンラウリルエーテル(商品名))からなる濃度0.1重量%の分散媒を40リットル作製し、斯かる分散媒を抄造装置に投入した。抄造装置は、回転翼付き攪拌機を備えた上部の抄造槽(容量30リットル)と、下部の貯水槽(容量10リットル)からなり、抄造槽と貯水槽の間には多孔支持体を設けてある。まず、かかる分散媒を攪拌機にて空気の微小気泡が発生するまで撹拌した。その後、所望の目付となるように、重量を調整したチョップド強化繊維を、空気の微小気泡が分散した分散媒中に投入して攪拌することにより、強化繊維が分散したスラリーを得た。次いで、貯水層からスラリーを吸引し、多孔支持体を介して脱水して強化繊維抄造体とした。前記抄造体を熱風乾燥機にて150℃、2時間の条件下で乾燥させ、強化繊維マットを得た。
ナイロン66樹脂(東レ(株)製、“アミラン”(登録商標)CM3006)を用いて、目付100g/m2のシートを作製した。
ポリフェニレンサルファイド樹脂(東レ(株)製、“トレリナ”(登録商標)M2888)を用いて、目付100g/m2のシートを作製した。
ポリエーテルケトンケトン樹脂(アルケマ(株)製、“Kepstan”(登録商標)6003)を用いて、目付100g/m2のシートを作製した。
ポリエーテルケトンケトン樹脂(アルケマ(株)製、“Kepstan”(登録商標)8003)を用いて、目付100g/m2のシートを作製した。
ポリエーテルエーテルケトン樹脂(ヴィクトレックスジャパン(株)製、“PEEK”381G)を用いて、目付100g/m2のシートを作製した。
開繊加工を施した炭素繊維を平行に引き揃え、1.4本/cmの密度で一方向に配列してシート状の強化繊維群を形成した。前記強化繊維群の上にPA66シートを積層し、280℃に加熱されたプレス機にて10MPaの面圧を付与しながら含浸させ、PPSプリプレグを得た。
開繊加工を施した炭素繊維を平行に引き揃え、1.4本/cmの密度で一方向に配列してシート状の強化繊維群を形成した。前記強化繊維群の上にPPSシートを積層し、300℃に加熱されたプレス機にて10MPaの面圧を付与しながら含浸させ、PPSプリプレグを得た。
開繊加工を施した炭素繊維を平行に引き揃え、1.4本/cmの密度で一方向に配列してシート状の強化繊維群を形成した。前記強化繊維群の上にPEKKシート(α)を積層し、330℃に加熱されたプレス機にて10MPaの面圧を付与しながら含浸させ、PEKKプリプレグ(α)を得た。
開繊加工を施した炭素繊維を平行に引き揃え、1.4本/cmの密度で一方向に配列してシート状の強化繊維群を形成した。前記強化繊維群の上にPEKKシート(β)を積層し、380℃に加熱されたプレス機にて10MPaの面圧を付与しながら含浸させ、PEKKプリプレグ(β)を得た。
開繊加工を施した炭素繊維を平行に引き揃え、1.4本/cmの密度で一方向に配列してシート状の強化繊維群を形成した。前記強化繊維群の上にPEEKシートを積層し、360℃に加熱されたプレス機にて10MPaの面圧を付与しながら含浸させ、PEEKプリプレグを得た。
強化繊維(A1)として6mmマット、熱可塑性樹脂(B1)としてPA66シート、表皮層(II)としてPPSプリプレグを用いた。以下の成形条件を経ることにより繊維強化樹脂構造体を得た。図6(a)は用いた曲面部を有するプレス成形用金型の模式図であり、図6(b)は当該金型を用いて得られる形状Pの繊維強化樹脂構造体の概観図である。前記金型の寸法は縦300mm×横200mmの平面部が付き合わされたものであり、金型表面の平均表面粗さは0.2μmである。
(第1ステップ)[表皮層(II)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)]の順番に積層し、積層前駆体を作製する。前記積層前駆体を、300℃に予熱した屈曲部を有するプレス成形用金型キャビティ内に配置して金型を閉じる。
(第2ステップ)次いで、120秒間保持する。
(第3ステップ)280℃に冷却し、5MPaの圧力を付与してさらに60秒間保持する。
(第4ステップ)前記金型キャビティを解放し、その末端に金属スペーサーを挿入し、繊維強化樹脂構造体を得る際の膨張倍率が3倍となるように調整する。
(第5ステップ)その後、再度前記金型キャビティを締結し、圧力を保持した状態でキャビティ温度を50℃まで冷却した後、金型を開いて繊維強化樹脂構造体を取り出す。
得られた繊維強化樹脂構造体の特性を表1に示す。
強化繊維(A1)として6mmマット、熱可塑性樹脂(B1)としてPPSシート、表皮層(II)としてPA66プリプレグを用いた。以下のプレス成形条件を経ることにより繊維強化樹脂構造体を得た。
(第1ステップ)[表皮層(II)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)]の順番に積層し、積層前駆体を作製する。前記積層前駆体を、300℃に予熱したプレス成形用金型キャビティ内に配置して金型を閉じる。
(第2ステップ)次いで、120秒間保持した後、300℃のまま、10MPaの圧力を付与してさらに60秒間保持する。
(第3ステップ)金型キャビティを解放し、その末端に金属スペーサーを挿入し、繊維強化樹脂構造体を得る際の膨張倍率が3倍となるように調整する。
(第4ステップ)その後、再度金型キャビティを締結し、圧力を保持した状態でキャビティ温度を280℃まで冷却する。
(第5ステップ)その後、0.5MPaの圧力を付与して、0.2mm繊維強化樹脂構造体を押し込む。
(第6ステップ)50℃まで冷却した後、金型を開いて繊維強化樹脂構造体を取り出す。
得られた繊維強化樹脂構造体の特性を表1に示す。
強化繊維(A1)として6mmマット、熱可塑性樹脂(B1)としてPPSシート、表皮層(II)としてPEKKプリプレグを用いた。以下のプレス成形条件を経ることにより繊維強化樹脂構造体を得た。
(第1ステップ)[表皮層(II)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)]の順番に積層し、積層前駆体を作製する。前記積層前駆体を、330℃に予熱したプレス成形用金型キャビティ内に配置して金型を閉じる。
(第2ステップ)次いで、120秒間保持する。
(第3ステップ)300℃に冷却し、8MPaの圧力を付与してさらに60秒間保持する。
(第4ステップ)金型キャビティを解放し、その末端に金属スペーサーを挿入し、繊維強化樹脂構造体を得る際の膨張倍率が3倍となるように調整する。
(第5ステップ)その後、再度金型キャビティを締結し、圧力を保持した状態でキャビティ温度を50℃まで冷却した後、金型を開いて繊維強化樹脂構造体を取り出す。
得られた繊維強化樹脂構造体の特性を表1に示す。
強化繊維(A1)として6mmマット、熱可塑性樹脂(B1)としてPEKKシート、表皮層(II)としてPEEKプリプレグを用いた。以下のプレス成形条件を経ることにより繊維強化樹脂構造体を得た。
(第1ステップ)[表皮層(II)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)]の順番に積層し、積層前駆体を作製する。前記積層前駆体を、380℃に予熱したプレス成形用金型キャビティ内に配置して金型を閉じる。
(第2ステップ)次いで、120秒間保持する。
(第3ステップ)330℃に冷却し、10MPaの圧力を付与してさらに60秒間保持する。
(第4ステップ)金型キャビティを解放し、その末端に金属スペーサーを挿入し、繊維強化樹脂構造体を得る際の膨張倍率が3倍となるように調整する。
(第5ステップ)その後、再度金型キャビティを締結し、圧力を保持した状態でキャビティ温度を50℃まで冷却した後、金型を開いて繊維強化樹脂構造体を取り出す。
得られた繊維強化樹脂構造体の特性を表1に示す。
強化繊維(A1)として6mmマット、熱可塑性樹脂(B1)としてPEEKシート、表皮層(II)としてPEKKプリプレグを用いた。以下のプレス成形条件を経ることにより繊維強化樹脂構造体を得た。
(第1ステップ)[表皮層(II)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)]の順番に積層し、積層前駆体を作製する。前記積層前駆体を、380℃に予熱したプレス成形用金型キャビティ内に配置して金型を閉じる。
(第2ステップ)次いで、120秒間保持した後、380℃のまま、10MPaの圧力を付与してさらに60秒間保持する。
(第3ステップ)金型キャビティを解放し、その末端に金属スペーサーを挿入し、繊維強化樹脂構造体を得る際の膨張倍率が3倍となるように調整する。
(第4ステップ)その後、再度金型キャビティを締結し、圧力を保持した状態でキャビティ温度を330℃まで冷却する。
(第5ステップ)その後、0.5MPaの圧力を付与して、0.2mm繊維強化樹脂構造体を押し込む。
(第6ステップ)50℃まで冷却した後、金型を開いて繊維強化樹脂構造体を取り出す。
得られた繊維強化樹脂構造体の特性を表1に示す。
実施例5と同様に繊維強化樹脂構造体を作製した。
繊維強化樹脂構造体を得る際の膨張倍率が1.05倍となるように金属スペーサーを挿入すること以外は実施例1と同様に繊維強化樹脂構造体を作製した。得られた繊維強化樹脂構造体の特性を表1に示す。
繊維強化樹脂構造体を得る際の膨張倍率が20倍となるように金属スペーサーを挿入すること以外は実施例1と同様に繊維強化樹脂構造体を作製した。得られた繊維強化樹脂構造体を表1に示す。
第1ステップにて[表皮層(II)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/表皮層(II)]の順番に積層し、積層前駆体を作製した以外は実施例1と同様に繊維強化樹脂構造体を作製した。得られた繊維強化樹脂構造体を表1に示す。
第1ステップにて[表皮層(II)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/表皮層(II)]の順番に積層し、積層前駆体を作製した以外は実施例4と同様に繊維強化樹脂構造体を作製した。得られた繊維強化樹脂構造体を表1に示す。
プレス成形用金型に屈曲部を形成するキャビティ有する金型を用いたこと以外は実施例1と同様に繊維強化樹脂構造体を作製した。図7(a)は用いたプレス成形用金型の模式図であり、図7(b)に当該金型を用いて得られる繊維強化樹脂構造体の形状Qを示す。前記金型の寸法は縦300mm×横200mmの平面部が付き合わされた曲率半径12mmの屈曲部を有するものであり、金型表面の平均表面粗さは0.2μmである。得られた繊維強化樹脂構造体を表1に示す。ここで表面粗さは屈曲部において測定を行った。
強化繊維(A1)として6mmマット、熱可塑性樹脂(B1)としてPEEKシート、表皮層(II)としてPEKKプリプレグを用いた。以下の成形条件を経ることにより繊維強化樹脂構造体を得た。
(第1ステップ)[強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)]の順番に積層し、積層前駆体を作製する。前記積層前駆体を、380℃に予熱したプレス成形用金型キャビティ内に配置して金型を閉じる。
(第2ステップ)次いで、120秒間保持した後、380℃のまま、10MPaの圧力を付与してさらに60秒間保持する。
(第3ステップ)金型キャビティを解放し、その末端に金属スペーサーを挿入し、繊維強化樹脂構造体を得る際の膨張倍率が3倍となるように調整する。
(第4ステップ)その後、0.5MPaの圧力を付与して、0.2mm繊維強化樹脂構造体を押し込む。
(第5ステップ)50℃まで冷却した後、金型を開いて空隙体(I)を取り出す。
(第6ステップ)[空隙体(I)/表皮層(II)]の順番に積層し、オートクレーブ内にて330℃で加熱加圧する。
(第7ステップ)50℃まで冷却した後、金型を開いて繊維強化樹脂構造体を取り出す。
得られた繊維強化樹脂構造体の特性を表1に示す。
強化繊維(A1)として6mmマット、熱可塑性樹脂(B1)としてPPSシート、表皮層(II)としてPPSプリプレグを用いた。以下のプレス成形条件を経ることにより繊維強化樹脂構造体を得た。
(第1ステップ)[表皮層(II)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)]の順番に積層し、積層前駆体を作製する。前記積層前駆体を、300℃に予熱したプレス成形用金型キャビティ内に配置して金型を閉じる。
(第2ステップ)次いで、120秒間保持した後、300℃のまま、8MPaの圧力を付与してさらに60秒間保持する。
(第3ステップ)金型キャビティを解放し、その末端に金属スペーサーを挿入し、繊維強化樹脂構造体を得る際の膨張倍率が3倍となるように調整する。
(第4ステップ)その後、再度金型キャビティを締結し、圧力を保持した状態でキャビティ温度を50℃まで冷却する。金型を開いて繊維強化樹脂構造体を取り出す。
得られた繊維強化樹脂構造体の特性を表1に示す。
強化繊維(A1)として6mmマット、熱可塑性樹脂(B1)としてPEEKシート、表皮層(II)としてPEKKプリプレグ(β)を用いた。以下のプレス成形条件を経ることにより繊維強化樹脂構造体を得た。
(第1ステップ)[表皮層(II)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)/強化繊維(A1)/熱可塑性樹脂(B1)]の順番に積層し、積層前駆体を作製する。前記積層前駆体を、380℃に予熱したプレス成形用金型キャビティ内に配置して金型を閉じる。
(第2ステップ)次いで、120秒間保持した後、380℃のまま、10MPaの圧力を付与してさらに60秒間保持する。
(第3ステップ)350℃に冷却し、10MPaの圧力を付与してさらに60秒間保持する。
(第4ステップ)金型キャビティを解放し、その末端に金属スペーサーを挿入し、繊維強化樹脂構造体を得る際の膨張倍率が3倍となるように調整する。
(第5ステップ)その後、再度金型キャビティを締結し、圧力を保持した状態でキャビティ温度を50℃まで冷却した後金型を開いて繊維強化樹脂構造体を取り出す。
得られた繊維強化樹脂構造体の特性を表1に示す。
プレス成形用金型に屈曲部を形成するキャビティ有する金型を用いたこと以外は比較例2と同様に繊維強化樹脂構造体を作製した。図7(a)は用いたプレス成形用金型の模式図であり、図7(b)に当該金型を用いて得られる繊維強化樹脂構造体の形状Qを示す。前記金型の寸法は縦300mm×横200mmの平面部が付き合わされた曲率半径12mmの屈曲部を有するものであり、金型表面の平均表面粗さは0.2μmである。得られた繊維強化樹脂構造体を表1に示す。ここで表面粗さは屈曲部において測定を行った。
2. 表皮層
b. 空隙体の断面
3. 強化繊維(A1)
4. 空隙
5. 熱可塑性樹脂(B1)
6. 屈曲部
7. 上型
8. 下型
9. 繊維強化樹脂成形体形状
Claims (18)
- 強化繊維(A1)と熱可塑性樹脂(B1)からなる空隙体(I)と、強化繊維(A2)と熱可塑性樹脂(B2)からなる表皮層(II)が一体化した繊維強化樹脂構造体であって、熱可塑性樹脂(B1)の融点Tc(℃)と熱可塑性樹脂(B2)の融点Ts(℃)がともに230℃以上であり、Tc(℃)とTs(℃)の差Ts-TcまたはTc-Tsが20℃以上である、繊維強化樹脂構造体。
- JIS B 0601(2001)に準拠して測定される前記表皮層(II)の平均表面粗さRaが10μm以下である、請求項1に記載の繊維強化樹脂構造体。
- 前記熱可塑性樹脂(B1)および熱可塑性樹脂(B2)のガラス転移温度が120℃以上である、請求項1に記載の繊維強化樹脂構造体。
- 前記融点 Tc(℃)と融点 Ts(℃)のいずれか一方が270℃以上、330℃以下の範囲である、請求項1に記載の繊維強化樹脂構造体。
- 前記熱可塑性樹脂(B1)および熱可塑性樹脂(B2)がともにポリアリールエーテルケトンまたはポリアリールエーテルケトン共重合体である、請求項1に記載の繊維強化樹脂構造体。
- 表皮層(II)を構成する熱可塑性樹脂(B2)と空隙体(I)を構成する熱可塑性樹脂(B1)が境界面を持つ、請求項の1に記載の繊維強化樹脂構造体。
- 前記空隙体(I)の厚みHcと前記表皮層(II)の厚みHsの比Hc/Hsが5以上である、請求項1に記載の繊維強化樹脂構造体。
- 前記空隙体(I)の空隙率が10体積%以上90体積%以下である、請求項1に記載の繊維強化樹脂構造体。
- 前記強化繊維(A1)が繊維長1mm以上15mm以下の不連続繊維である、請求項1に記載の繊維強化樹脂構造体。
- 前記強化繊維(A1)が略モノフィラメント状、且つランダムに分散している、請求項1に記載の繊維強化樹脂構造体。
- 前記強化繊維(A1)と強化繊維(A2)がともに炭素繊維である、請求項1に記載の繊維強化樹脂構造体。
- 前記強化繊維(A2)が一方向連続繊維である、請求項に1に記載の繊維強化樹脂構造体。
- 空隙体(I)の両面に表皮層(II)を配置したサンドイッチ構造を有する、請求項1に記載の繊維強化樹脂構造体。
- 前記表皮層(II)が少なくとも一つの屈曲部を有する、請求項1に記載の繊維強化樹脂構造体。
- 請求項1に記載の繊維強化樹脂構造体からなる、航空機、人工衛星、UAM(Urban air mobility)、およびドローンからなる群より選択される航空部材。
- 強化繊維(A1)と熱可塑性樹脂(B1)からなる空隙体(I)と、強化繊維(A2)と熱可塑性樹脂(B2)からなる表皮層(II)が一体化した繊維強化樹脂構造体であって、熱可塑性樹脂(B1)の融点Tc(℃)と熱可塑性樹脂(B2)の融点Ts(℃)がともに230℃以上であり、Tc(℃)とTs(℃)の差Ts-Tcが20(℃)以上である繊維強化樹脂構造体の製造方法であって、
強化繊維(A1)の不織布と熱可塑性樹脂(B1)を含む空隙体(I)の前駆体(i)
強化繊維(A2)および熱可塑性樹脂(B2)からなるプリプレグ
を積層して成形金型に配置する第1ステップ;
Tsよりも高い温度に加熱して熱可塑性樹脂(B1)および熱可塑性樹脂(B2)をともに溶融し、空隙体(I)の前駆体(i)および表皮層(II)を接合するとともに賦形する第2ステップ;
Tcより高く、Tsより低い温度にまで降温し、表皮層(II)を固化する第3ステップ;
Tcより高く、Tsより低い温度を維持したまま、圧力を開放して空隙体(I)の前駆体(i)を膨張させる第4ステップ;
Tcより低い温度にまで降温し、空隙体(I)を固化させる第5ステップ;
をこの順に有する繊維強化樹脂構造体の製造方法。 - 強化繊維(A1)と熱可塑性樹脂(B1)からなる空隙体(I)と、強化繊維(A2)と熱可塑性樹脂(B2)からなる表皮層(II)が一体化した繊維強化樹脂構造体であって、熱可塑性樹脂(B1)の融点Tc(℃)と熱可塑性樹脂(B2)の融点Ts(℃)がともに230℃以上であり、Tc(℃)とTs(℃)の差Tc-Tsが20(℃)以上である繊維強化樹脂構造体の製造方法であって、
強化繊維(A1)の不織布と熱可塑性樹脂(B1)を含む空隙体(I)の前駆体(i)
強化繊維(A2)および熱可塑性樹脂(B2)からなるプリプレグ
を積層して成形金型に配置する第1ステップ;
Tcよりも高い温度に加熱して熱可塑性樹脂(B1)および熱可塑性樹脂(B2)をともに溶融し、空隙体(I)の前駆体(i)および表皮層(II)を接合する第2ステップ;
Tcよりも高い温度を維持したまま、圧力を解放し、空隙体(I)の前駆体(i)を膨張させる第3ステップ;
Tsより高く、Tcより低い温度にまで降温し、膨張した空隙体(I)を固化させる第4ステップ;
Tsより高く、Tcより低い温度を維持したまま、圧力を加えて表皮層(II)を流動させる第5ステップ;
Tcより低い温度にまで降温し、表皮層(II)を固化させる第6ステップ;
をこの順に有する繊維強化樹脂構造体の製造方法。 - 強化繊維(A1)と熱可塑性樹脂(B1)からなる空隙体(I)と、強化繊維(A2)と熱可塑性樹脂(B2)からなる表皮層(II)が一体化した繊維強化樹脂構造体であって、熱可塑性樹脂(B1)の融点Tc(℃)と熱可塑性樹脂(B2)の融点Ts(℃)がともに230℃以上であり、
Tc(℃)とTs(℃)の差Tc-Tsが20(℃)以上である繊維強化樹脂構造体の製造方法であって、
強化繊維(A1)と熱可塑性樹脂(B1)を含む空隙体(I)
強化繊維(A2)および熱可塑性樹脂(B2)からなるプリプレグ
を積層してオートクレーブ内に配置する工程を有するとともに、
成形温度が熱可塑性樹脂(B1)の融点Tcを超えることがない、繊維強化樹脂構造体の製造方法。
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| JP7715311B1 (ja) * | 2024-02-06 | 2025-07-30 | 東レ株式会社 | 繊維強化樹脂構造体 |
| WO2025169854A1 (ja) * | 2024-02-06 | 2025-08-14 | 東レ株式会社 | 繊維強化樹脂構造体 |
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| WO2014162873A1 (ja) | 2013-04-02 | 2014-10-09 | 東レ株式会社 | サンドイッチ積層体、サンドイッチ構造体とそれを用いた一体化成形品およびそれらの製造方法 |
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