WO2012133013A1 - Pièce moulée en couches de résine thermoplastique renforcée de fibres - Google Patents

Pièce moulée en couches de résine thermoplastique renforcée de fibres Download PDF

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Publication number
WO2012133013A1
WO2012133013A1 PCT/JP2012/057102 JP2012057102W WO2012133013A1 WO 2012133013 A1 WO2012133013 A1 WO 2012133013A1 JP 2012057102 W JP2012057102 W JP 2012057102W WO 2012133013 A1 WO2012133013 A1 WO 2012133013A1
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fiber
molded product
fiber reinforced
layer
thickness
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PCT/JP2012/057102
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English (en)
Japanese (ja)
Inventor
葭原　法
辻井　彰司
名合　聡
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東洋紡績株式会社
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Priority to JP2012515840A priority Critical patent/JP5812439B2/ja
Publication of WO2012133013A1 publication Critical patent/WO2012133013A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres

Definitions

  • the present invention is a molded product obtained by compressing and molding a fiber reinforced thermoplastic resin prepreg, and in the cross section in the thickness direction, five or more fiber reinforced layers sandwiched between fiber-free layers are provided.
  • the present invention relates to a fiber reinforcing layer in which fiber orientation in each layer is made uniform and random between layers, thereby increasing bending strength and compressive strength and reducing mechanical property anisotropy.
  • a molded product obtained by compression-molding a fiber reinforced thermoplastic resin has been recently developed for a structural material (for example, see Non-Patent Document 1).
  • the fiber reinforced thermoplastic resin is used as a plate-like or beam-like structural material because it has high strength and rigidity.
  • Fiber reinforced thermoplastic resin shows very high strength and rigidity against the axial tension of the fiber, but for bending deformation and compression deformation, the fiber bends due to deformation and the reinforcing effect is not utilized. , Strength and rigidity are low. Further, there is almost no reinforcing effect by the fibers against tensile deformation in the direction orthogonal to the fiber axis.
  • a molded article using a fiber reinforced thermoplastic resin has extremely large anisotropy in mechanical properties, and improvement of reliability as a structural material has been a problem in practical use.
  • the molded product that has undergone bending deformation consists of a tensile deformation side and a compression deformation side.
  • the reinforcing effect of the fiber is significant on the pulling side, so that it often breaks on the compression side. Therefore, in the case of a composite material that starts fracture from the compression side as in the present invention, improvement in compression strength also leads to improvement in bending strength.
  • the fiber bundle is made into a woven or knitted fabric woven from the machine direction and the transverse direction, then impregnated with resin or impregnated prepreg tape as a woven or knitted fabric, and heated and compressed. Molded to obtain a molded product.
  • preforms made into woven fabrics and knitted fabrics before molding have low resin impregnation properties, many voids between single fibers, and single fibers cannot be sufficiently covered with resin, so there are many defects and high targets.
  • a molded product having physical properties could not be obtained.
  • the fiber shaft is constrained by the texture and hardly flows in the mold at the time of molding, a three-dimensional molded product having a deeply drawn shape or a molded product having ribs or bosses cannot be obtained.
  • the obtained prepreg sheet or sheet-like preform has good fluidity and isotropy, but long single fibers are also easily bent and bent due to bending deformation and compression deformation, and are also easily buckled.
  • the strength and rigidity of the molded product were lower than expected.
  • fiber reinforced products using carbon fibers having a narrow distribution of single fiber cross-sectional areas in the thickness direction due to the manufacturability of carbon fibers are difficult to reflect the high physical properties of single fibers.
  • a pre-molded product having a near-isotropic property with random orientation or orthogonal orientation can be obtained from a prepreg produced using a mat or cloth of reinforcing material.
  • a prepreg in which a reinforcing material mat or a reinforcing cloth is impregnated with a resin is entangled with fibers has low fluidity, and the flow of reinforcing fibers is particularly difficult. It was.
  • the present invention has been made in view of the current state of the prior art described above, and an object of the present invention is a molded product obtained by compression-molding a fiber-reinforced thermoplastic resin prepreg, such as bending strength and compressive strength. It is an object of the present invention to provide a molded article having excellent mechanical properties and low anisotropy of the mechanical properties, and thus maintaining high mechanical properties regardless of the deformation direction and location.
  • the present inventors have intensively studied a molded article having a low mechanical property anisotropy and a high mechanical property reliability regardless of the deformation direction and location. It is found that the above-mentioned object is achieved by providing five or more fiber reinforced layers in which the orientation of the constituent single fibers is substantially uniform, and randomizing the orientation of the constituent single fibers between the respective fiber reinforced layers. It came to.
  • the present invention has the following configurations (1) to (5).
  • (1) A molded article obtained by laminating fiber reinforced thermoplastic resin prepregs and compression molding, and having a thickness of 0.01 to 1.0 mm in a cross section in the thickness direction having a thickness of 1 mm or more.
  • the fiber reinforced thermoplastic resin prepreg is a strip having a thickness of 0.03 to 0.5 mm, a width of 3 to 50 mm, and a length of 10 to 150 mm, and is laminated so that the fiber axis direction is random.
  • a molded product having a small anisotropy in the out-of-plane deformation of the molded product can be obtained by laminating a prepreg obtained by impregnating a nonwoven fabric or a mat of long fibers generally obtained by a papermaking method or a spunbond method.
  • the fibers of the molded product thus obtained generally do not form a bundle, and the cut section of the single fiber in the thickness direction does not show an aggregate of fibers having the same ellipticity. Therefore, they have almost no resistance to bending or buckling of fibers due to microscopic fiber bundles.
  • the molded product of the present invention is designed so that the cross-sections in the thickness direction of the single fibers constituting each layer of the fiber reinforced layer have substantially the same ellipticity, so that a microscopic fiber bundle structure is formed, Extremely high resistance to compression and buckling.
  • a prepreg tape made of glass fibers having a single fiber diameter of 13 to 17 ⁇ m is easy to flow during molding, and fiber bundles are dispersed in a remelted molded product, and the degree of opening is high.
  • the single fiber diameter of the carbon fiber obtained by the firing method is small, generally 9 ⁇ m or less, and usually 7 ⁇ m or less.
  • the single fiber has low bending rigidity and buckling resistance.
  • the effect of the present invention is particularly exhibited in a molded article using such carbon fibers.
  • the molded article of the present invention has a fiber bundle structure microscopically, particularly with carbon fibers having a small fiber diameter, and can greatly improve resistance to bending and buckling.
  • the molded product of the present invention has five or more fiber reinforced layers in the thickness direction, and the cross-sections in the thickness direction of the single fibers constituting each layer of the fiber reinforced layer have an average value of random ellipticity. Therefore, it is possible to provide a molded product having high strength and rigidity and high mechanical property reliability regardless of the deformation direction and the location of the molded product. Therefore, the molded product of the present invention can be set with high strength and rigidity as design quality, and has a high degree of freedom in product design such as thinning.
  • FIG. 1 schematically shows a method of observing a cross section in the thickness direction of a molded product.
  • FIG. 2 shows a schematic diagram of a cross section in the thickness direction of an example of the molded article of the present invention.
  • FIG. 3 shows the major axis and minor axis of an ellipse with a single fiber cross section.
  • FIG. 4 shows a cut-out example (A: X-axis direction, B: Y-axis direction) of a test piece used for a bending test of a molded product.
  • the molded product of the present invention is obtained by laminating fiber reinforced thermoplastic prepregs and compression molding, and is characterized in that there are 5 or more fiber reinforced layers in a thickness direction cross section having a thickness of 1 mm or more.
  • the fiber reinforced layer of the present invention has a thickness of 0.005 to 1.0 mm sandwiched between two layers of a fiber-free thermoplastic resin layer having a thickness of 0.01 to 1.0 mm in the cross section in the thickness direction of the molded product.
  • the fiber-containing thermoplastic resin layer is constituted.
  • Each fiber reinforced layer has a standard deviation of ellipticity (minor axis / major axis) of the cross section in the thickness direction of the constituent single fibers of 0.1 or less, and the orientation of the constituent single fibers is substantially uniform in the fiber reinforced layer.
  • An example of the major axis and minor axis of the ellipticity of the single fiber cross section is shown in FIG.
  • the number of the fiber reinforced layers is 5 layers or more, preferably 8 layers or more, particularly preferably 10 layers or more, in the thickness direction cross section having a thickness of 1 mm or more of the molded product. If it is less than 5 layers, it is difficult to diversify the orientation of the fiber bundle of the fiber reinforced layer, and the strength and elastic modulus are different in the deformation direction, which is not preferable because the reliability of mechanical properties is lowered.
  • the size of each fiber reinforced layer in the cross section in the thickness direction of the molded product depends on the size of the prepreg strip used in the molded product, but generally has a thickness of 0.005 to 1.0 mm, preferably 0.01 to The width is 0.6 mm and the width is 3 to 50 mm, preferably 8 to 40 mm.
  • the thickness of the layer is less than 0.005 mm, the rigidity of the layer is low with respect to bending and compression deformation, and the fiber reinforcement effect may not be sufficiently exhibited. If the thickness exceeds 1.0 mm, The influence of individual layers becomes large, and anisotropy tends to appear. Further, when the width of the layer is less than 3 mm, the influence of the anisotropy of the strip in the surface of the molded product is high, and the anisotropy tends to increase in the molded product. The effect of directionality is strong, and macroscopic anisotropy tends to develop.
  • the size of the fiber reinforced layer is calculated by observing a wide width of the cross section of the molded product to be observed, that is, by increasing the cross section width of the test piece or by observing the cross section of the molded product while sliding.
  • FIG. 2 shows a schematic diagram of a cross section in the thickness direction of an example of the molded article of the present invention.
  • the thickness of the reinforcing fiber layer is determined from the average value of the distances between the fiber-free layers sandwiching the reinforcing fiber layer in the cross section of the molded product.
  • the width of the reinforcing fiber layer is the reinforcing fiber layer of the fiber reinforcing layer in which the average ellipticity of the constituent single fibers in the cross section in the thickness direction is 0.9 to 1.0, preferably 0.95 to 1.0. It is calculated
  • the length of the fiber reinforced layer is determined by the merging of the fiber-free layers sandwiching the reinforced fiber layer with respect to the fiber reinforced layer having an average ellipticity of the constituent single fibers in the cross section in the thickness direction of 0.00001 to 0.1. It is obtained from the average value of the distance between points.
  • the fiber reinforced layer was observed on the basis of the fiber reinforced layer included in the field of view by enlarging 100 times the cross section of 10 to 20 mm in width at an arbitrary portion of the portion having a thickness of 1 mm or more in the molded product. .
  • the size of the fiber reinforced layer depends on the size of the prepreg strip used for production, but the strip is fluidly deformed by molding. In the case of the present invention, the degree of fluid deformation is small, preferably 0.8 to 1,2. If the degree of flow deformation is less than 0.8 or more than 1.2, the fiber bundle state is likely to be disturbed, leading to a decrease in the bending rigidity or buckling of the fiber reinforced layer, possibly resulting in a decrease in the bending strength or compressive strength of the molded product.
  • the degree of flow deformation depends on the pressure method used when stacking strips. When the pressure is gradually increased step by step, the degree of fluid deformation increases and the fiber axis in each fiber reinforced layer is disturbed. As a result, since the distribution of ellipticity in the reinforcing fiber layer becomes wider, it is not preferable to step up the pressure.
  • the molded article of the present invention has a high bending strength reliability, and a bending strength of 730 MPa or more, preferably 800 MPa or more, and 0.85 or more, preferably 0. A bending strength ratio of 90 or higher can be achieved.
  • the fiber axes in each layer of the fiber reinforced layer are substantially in the same direction, and therefore the ellipticity (minor axis / major axis) of the cross section in the thickness direction of the constituent single fibers is substantially the same. That is, the distribution of the ellipticity of the cross section in the thickness direction of the constituent single fiber in each layer of the fiber reinforced layer is narrow, and the standard deviation of the ellipticity is 0.1 or less, preferably 0.08 or less. This standard deviation of ellipticity is a microscopic measure of the degree of fiber orientation. When the standard deviation exceeds 0.1, the fiber axis in each layer of the fiber reinforced layer is disturbed, and is rigid against bending and compressive deformation. Is unfavorable because it decreases.
  • the standard deviation in the fiber reinforced layer with respect to the average value of the ellipticity of the cross section in the thickness direction of the single fiber constituting each layer of the fiber reinforced layer is 0.2 or more, preferably 0.3 or more. It is.
  • the standard deviation of the average ellipticity is a measure of the randomness of the fiber axes between the fiber reinforced layers.
  • the standard deviation is less than 0.2, the deviation in the fiber axis direction of the fiber bundle is increased in the cross section of the molded product, and the molded product. This is not preferable because the strength and elastic modulus of the material change in the deformation direction.
  • the molded product of the present invention comprises a fiber reinforced layer having a mean ellipticity of 0.00001 to 0.3, preferably 0.00001 to 0.2 in the thickness direction cross section of the constituent single fiber in the thickness direction cross section. It is preferable that one or more fiber reinforced layers each having an average ellipticity of a cross section in the thickness direction of the single fiber of 0.7 to 1.0, and preferably 0.8 to 1.0 are present.
  • the fiber reinforced layer having an average ellipticity of 0.00001 to 0.3 is a layer in which the fiber axis of the fiber bundle is oriented in the left-right direction in the cross section in the thickness direction of the molded product.
  • the orientation degree of the fiber axis in the left-right direction is low, and the elastic modulus and strength in the left-right direction tend to be low.
  • the fiber reinforced layer having an average ellipticity of 0.7 to 1.0 is a layer in which the fiber axis of the fiber bundle is oriented in the front-rear direction in the cross section in the thickness direction of the molded product, and does not include this layer.
  • the product has a low degree of orientation of the fiber axis in the front-rear direction and tends to have a low elastic modulus and strength in the front-rear direction.
  • it is preferable that each of the layers in which the fiber bundles are oriented in the substantially orthogonal axis is contained.
  • the layer width is obtained only for the layer having an average ellipticity of 0.9 to 1.0 by cross-sectional observation, and the average value is defined as the layer width.
  • the molded product of the present invention preferably has 100 to 50000, preferably 1000 to 20000 single fibers in each layer of the fiber reinforced layer.
  • the number is less than 100, the fiber bundle is thin, the rigidity of the fiber bundle is low, and the effect of bending strength and strength improvement by the fiber bundle is small.
  • the number exceeds 50,000, the fiber bundle is too thick, the uniformity in the thickness direction and the in-plane direction is lowered, and the weakness of the strength and elastic modulus due to the part of the molded product is easily developed.
  • a plastic resin layer fiber-free resin layer.
  • the thickness of the fiber-free resin layer is less than 0.01 mm, entanglement of fibers between adjacent fiber reinforced layers occurs at the time of molding, fluidity is lowered, and orientation in the fiber axis direction is disturbed.
  • the thickness exceeds 1.0 mm the layer having no fiber reinforcing effect becomes thick, so the layer shearing force of the molded product becomes low and high bending strength cannot be obtained, which is not preferable.
  • the molded product of the present invention has a thickness of 0.03 to 0.5 mm, preferably 0.1 to 0.4 mm, a width of 3 to 50 mm, preferably 5 to 40 mm, and a length of 10 to 150 mm, preferably 25 to 100 mm. It is preferably obtained by laminating a certain strip-like fiber-reinforced thermoplastic resin prepreg so that the fiber axis direction is random and compression molding. If the thickness of the prepreg is less than 0.03 mm, the rigidity of each layer is low, and the bulk of the strip at the time of molding becomes large. On the other hand, when the thickness exceeds 0.5 mm, the number of laminated layers in the thickness direction is reduced, and the diversity of fiber axis orientation is difficult.
  • the width of the prepreg is less than 3 mm, the bulk of the strip becomes large and workability is lowered.
  • the width exceeds 50 mm, the uniformity in the in-plane direction of the molded product is lowered, and a defect point is easily developed.
  • the length of the prepreg is less than 10 mm, the fiber length is shortened and the fiber reinforcing effect is lowered.
  • it exceeds 150 mm fluidity
  • Examples of the reinforcing fiber used in the prepreg of the molded product of the present invention include high elastic modulus fibers that are solid at the processing temperature of the thermoplastic resin used, specifically, glass fibers, carbon fibers, and aramid fibers. Steel fiber, polyphenylene sulfide fiber, kenaf, cotton and the like can be used.
  • the average diameter of the reinforcing fibers is preferably 9 ⁇ m or less, more preferably 8 ⁇ m or less. When the average diameter exceeds 9 ⁇ m, the effect of the present invention is slightly low because the single fiber itself is rigid and is not easily buckled against compression.
  • the effect of the present invention is particularly great when carbon fibers having a high elastic modulus are used as reinforcing fibers.
  • a thin carbon fiber having an elastic modulus of 150 GPa or more, preferably 200 GPa or more is used as the reinforcing fiber, the effect of the present invention is remarkable because it is easily buckled by bending or compressive deformation.
  • the carbon fiber is not particularly limited.
  • a fiber such as polyacrylonitrile fiber or cellulose fiber is treated in air at 200 to 300 ° C. and then calcined in an inert gas at 1000 to 3000 ° C. or more.
  • the single fiber diameter of the carbon fiber is not particularly limited, but is preferably 3 to 9 ⁇ m from the viewpoint of handling in the composite production line process. If it is less than 3 ⁇ m, impregnation and defoaming are difficult, and if it exceeds 9 ⁇ m, the specific surface area becomes small and the reinforcing effect becomes small.
  • the carbon fiber is preferably subjected to a treatment for improving adhesion by wet oxidation with air or nitric acid, dry oxidation, heat cleaning, whiskerizing, or the like. Moreover, it is preferable that the carbon fiber is converged by a sizing agent that softens at 120 ° C. or less from the viewpoint of handling in the work process.
  • the number of converging filaments is not particularly limited, but is preferably 1000 to 30000 filaments, more preferably 5000 to 25000 filaments.
  • the thermoplastic resin used in the prepreg is polypropylene, polyamide 6, polyamide 66, polyamide MXD6, polyamide 12, polyamide 11, polyamide 6T copolymer, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polymethylpentene, syndiotactic. Examples thereof include tic polystyrene, copolymers thereof, and polymer alloys.
  • polypropylene, polyamide 6, polyamide MXD6, and polybutylene terephthalate are preferable from the balance of molding processability and physical properties, and polypropylene, polyamide 6, and polyamide MXD6 are particularly preferable.
  • thermoplastic resin is preferably modified so as to enhance the adhesion to the fiber.
  • polypropylene polymethylpentene or syndiotactic polystyrene having no polar group
  • those modified with an unsaturated acid such as maleic anhydride or itaconic acid or an unsaturated epoxy such as glycidyl methacrylate are preferred. .
  • the thermoplastic resin preferably has a melt flow rate of 30 to 150 g / 10 min at 250 ° C. under a load of 1.2 kg, more preferably 50 to 140 g / 10 min. If it is less than 30g / 10min, the impregnation property to a fiber may be low and the porosity may become high. On the other hand, if it exceeds 150 g / 10 min, the resin and the fiber are easily separated during the melt processing of the composite material.
  • the fiber content of the molded article of the present invention is preferably 35 to 80% by mass, more preferably 45 to 75% by mass, particularly 50 to 70% by mass in order to maintain high bending strength and compressive strength.
  • the molded product of the present invention has a crystal nucleating agent, a mold release agent, a lubricant, an antioxidant, a flame retardant, a light-resistant agent, a weather resistance, for the purpose of improving physical properties, moldability, and durability.
  • An agent or the like can be blended.
  • the manufacturing method of the fiber reinforced thermoplastic resin prepreg used in the present invention is not particularly limited.
  • a thermoplastic resin or a modified thermoplastic resin is premixed at a predetermined ratio and supplied to a hopper of a screw type extruder whose temperature is controlled to be equal to or higher than the melting point of the resin.
  • the molten resin is measured at the number of revolutions of the gear pump and supplied upstream of the impregnation extruder whose temperature is adjusted to the melting point of the resin or higher.
  • roving-like carbon fibers are expanded and supplied upstream of the impregnation extruder.
  • the resin is impregnated and defoamed in the roving fiber by resin pressure in an extruder for impregnation equipped with a slit die having a narrowed opening at the downstream end.
  • the tape-like composite material composed of the reinforcing fibers and the thermoplastic resin discharged from the downstream opening is cooled and wound up. Furthermore, this tape-shaped composite material is cut into a length of 10 mm to 50 mm.
  • a thermoplastic resin, a modified thermoplastic resin, or a reinforcing fiber is supplied to the upstream hopper of a screw type extruder whose temperature is adjusted to be equal to or higher than the melting point of the resin.
  • Roving reinforcing fibers are supplied to the downstream outlet die, and the fiber feed rate and resin discharge rate are adjusted to obtain a strand-like fiber resin coating material having a predetermined fiber content.
  • the strand is cooled and wound into skeins.
  • the strand is cut to a length of 10 mm to 50 mm.
  • the cut tape-like or strand-like prepreg is laminated in a flat direction in a random direction and dispersed.
  • the mold is heated to 20 to 100 ° C. from the melting point of the thermoplastic resin and then compressed, and the mold is cooled to a temperature 10 to 120 ° C. lower than the high temperature crystallization temperature to obtain a sheet-like prepreg in which reinforcing fibers are randomly oriented.
  • the laminated molded product of the present invention can be obtained by compression molding this prepreg.
  • a continuous fiber is impregnated with a thermoplastic resin in advance and drawn to form a prepreg in which the longitudinal axes of the constituent fibers are aligned, and the prepreg is reinforced with fiber. Cut to a length that is sufficient for the effect and to a length that keeps the fiber axis in a straight line in a free state. The cut prepreg is spread and overlapped so that the direction distribution of the fiber axis is random within the surface of the molded product.
  • the number of prepreg layers to be stacked is preferably set to a number exceeding (thickness after molding ⁇ thickness of prepreg).
  • the prepreg is melt-bonded by compression molding by applying pressure and heating in a state in which the fiber bundles of the prepreg spread and stacked are not disturbed and the relative flow is suppressed.
  • the pressure is applied in a state where the surface layer is melted.
  • the laminated molded product of the present invention is, for example, cut a prepreg tape obtained by impregnating a resin into a tape-shaped fiber bundle to a length of 10 to 150 mm, randomly spraying into a cavity, compression molding,
  • the resin-impregnated prepreg strand can be cut to a length of 10 to 150 mm, and a rod-shaped prepreg or a strip of prepreg strand flattened between rollers can be sprayed and compression molded.
  • the laminated molded product of the present invention can also be obtained by laminating and compressing the prepreg tape impregnated with the resin without forming a strip.
  • the reinforcing fiber bundles previously cut to a length of 10 to 150 mm are randomly spread and laminated, and then impregnated with resin and molded.
  • the laminated molded product of the present invention is not only a single product, but also a prepreg sheet using a non-woven fabric, a prepreg sheet using a reinforcing fiber mat, a uniaxially oriented sheet in which prepreg tapes are arranged in the same direction, an orthogonal woven fabric of prepreg tape, and many By combining one or more types selected from shaft fabrics and the like, the required performance for various deformation directions can be satisfied.
  • the laminated molded product of the present invention is formed into a structural material part by, for example, heating and melting a resin by infrared heating or high-frequency heating, supplying the resin to a mold of a compression molding machine, and demolding after shaping cooling. Can be done. Molded parts obtained from the laminated molded article of the present invention are used for parts that require high strength and rigidity, such as automobile frames, two-wheeled vehicle frames, agricultural equipment frames, OA equipment frames, and machine parts. Can do.
  • the obtained smooth surface was magnified 400 times by epi-illumination, and the cross section was linearly traced in the thickness direction and photographed. Thickness 0.005 to 1 sandwiched between two fiber-free thermoplastic resin layers having a thickness of 0.01 to 1.0 mm in the thickness direction, with the single fiber cross-sections having the same ellipticity. The number of layers (m) of the fiber reinforced layer of 0.0 mm was obtained. Thereafter, the photograph was magnified 800 times around the center of each layer and photographed. The short diameter (a) and the long diameter (b) of 100 or more (n) single fiber cross sections are randomly measured for each layer in the obtained photograph as shown in FIG. Diameter / major axis).
  • the test piece created in (1) is adjacent on the line in the thickness direction of the cross section (vertical direction in FIG. 2).
  • a layer having a distance between single fibers of 0.01 mm or more was regarded as a fiber-free resin layer substantially free of single fibers, and the other layers were regarded as fiber reinforced layers containing single fibers.
  • the thickness of each layer of a fiber-free resin layer and the thickness of each layer of a fiber reinforcement layer were measured, respectively, and each average value was calculated
  • a three-point bending test was performed on each test piece at a span length of 120 mm and a crosshead speed of 2 mm / min in accordance with JIS K7171. Compare the bending strength of the test piece (A) cut out in the X-axis direction with the bending strength of the test piece (B) cut out in the Y-axis direction, and divide the lower bending strength by the higher bending strength. The ratio (low strength / high strength) was determined. Also, it was observed whether the starting point of bending fracture was due to tension or compression.
  • Example 1 A roving made of 6000 carbon fibers (Teijin Toho Tenax IMS40) was expanded and opened at a rate of 6 kg / hr and supplied to the die head of the impregnation table.
  • Polyamide 6 resin (T802 manufactured by Toyobo Co., Ltd., melt flow rate 42 g / 10 min under a 1.2 kg load) was put into a hopper of a screw type extruder adjusted to 270 ° C., and the molten resin was fed by a gear pump. 4 kg / hr was weighed and supplied to the die head of the impregnation table.
  • the tape-like prepreg coated with the impregnation was drawn out from a die having a width of 10 mm and a height of 0.2 mm, solidified by air cooling, and wound around a basket (67% by mass of carbon fiber, polyamide) Resin 32% by mass).
  • the obtained prepreg tape was cut to a length of 50 mm, and the obtained strip-shaped prepreg tape was laminated in a random direction in a 300 mm ⁇ 300 mm ⁇ 3 mm flat plate mold and supplied by scattering. After heating the mold to 280 ° C., the pressure was set to 100 kgf / cm 2 , holding and compressing in that state for 5 minutes, the mold was cooled to a low temperature of 120 ° C., and a flat molded product in which reinforcing fibers were randomly oriented was obtained. . Table 1 shows the details of the materials used for the molded product and the evaluation results.
  • Examples 2 to 11 A prepreg was prepared in the same manner as in Example 1 except that the types and blending ratios of the reinforcing fiber and the thermoplastic resin, the shape, thickness, width and cut length of the prepreg were changed as shown in Table 1. A molded product was obtained. Table 1 shows the details of the materials used for the molded product and the evaluation results.
  • Example 12 In the same manner as in Example 1, the reinforcing fiber and the thermoplastic resin were supplied to the impregnation table, and the reinforcing fiber strand impregnated with the thermoplastic resin was pulled out from a 1 mm ⁇ nozzle, air-cooled, and wound around a bag. The obtained strand-shaped prepreg was cut to a length of 50 mm, and the obtained linear rod was laminated in a random direction in a 300 mm ⁇ 300 mm ⁇ 3 mm flat plate mold and supplied by scattering.
  • Comparative Examples 1 to 3 A prepreg was produced in the same manner as in Example 1 except that the types and blending ratios of the reinforcing fiber and the thermoplastic resin, the prepreg shape, the thickness, the width, and the cut length were changed as shown in Table 2. I got a product. Table 2 shows the details of the materials used for the molded products and the evaluation results. As in Comparative Example 1, if the tape width is too narrow, the fiber bundle is disturbed (in-layer ellipticity dispersion is large), the effect of the fiber bundle is small, and the bending strength is low.
  • Comparative Example 2 even if the tape width is too wide, the fiber bundle is disturbed (in-layer ellipticity dispersion is large), the effect of the fiber bundle is small, and the bending strength is low. If the thickness of the tape is too thick as in Comparative Example 3, the number of layers in the cross section in the thickness direction decreases, the fiber orientation in the thickness direction becomes nonuniform, and the anisotropy of the bending strength increases. .
  • Comparative Example 4 A prepreg was produced in the same manner as in Example 12 except that the nozzle diameter of the impregnation base was changed to 2 mm ⁇ to obtain a flat molded product.
  • Table 2 shows the details of the materials used for the molded products and the evaluation results. Since the strand size is as large as 2 mm ⁇ , the number of layers in the thickness direction is reduced, the fiber orientation in the thickness direction is nonuniform, and the anisotropy of bending strength is increased.
  • Comparative Example 5 A glass fiber bundle (GF-R) opened to a width of 15 mm in a direction perpendicular to the fiber axis was impregnated with acid-modified polypropylene (MAH003) in a die to produce a continuous glass fiber reinforced polypropylene having a width of 10 mm. Using a guillotine type cutting machine, this was cut into a length of 20 mm, naturally dropped onto a mold from a position having a height of 1.5 m, and deposited non-directionally.
  • MAH003 acid-modified polypropylene
  • the fiber-reinforced thermoplastic resin flakes made of glass fiber and polypropylene are heat-cooled and molded under conditions of a molding temperature of 220 ° C., a molding pressure of 10 kgf / cm 2 , a molding time of 10 minutes, and a cooling temperature of 120 ° C., and a thickness of 2 mm.
  • a sheet-like molded product was prepared.
  • the weight fraction of glass fibers in the molded product was 75% by weight.
  • Table 2 shows the details of the materials used for the molded products and the evaluation results.
  • the molded product had a low bending strength and a low bending strength ratio. This is presumably because the number of reinforcing fiber layers is small and the rigidity effect that the fibers act as a bundle and the disorder effect due to the high number of layers cannot be obtained.
  • Comparative Example 6 The prepreg tape obtained and manufactured in exactly the same manner as in Example 1 was cut to a length of 50 mm, and the obtained strip-shaped prepreg tape was randomly placed in a 300 mm ⁇ 300 mm ⁇ 3 mm flat plate mold. Laminated and supplied. After heating the mold to 280 ° C., the pressure is increased at a pitch of 10 kgf / cm 2 every 0.5 minutes, and after 5 minutes, the pressure is increased to 100 kgf / cm 2 and held and compressed in that state for 5 minutes. To obtain a flat molded product in which reinforcing fibers are randomly oriented. Table 2 shows the details of the materials used for the molded products and the evaluation results. As is apparent from Table 2, the ellipticity of each fiber reinforced layer is uneven, the standard deviation is large, and the bending strength is greatly reduced as compared with Example 1.
  • MAH003 98.5 parts by mass of polypropylene W101 (manufactured by Sumitomo Chemical), 0.5 parts by mass of dicumyl peroxide (Nippon Oil & Fats Park Mill D) and 2 parts by mass of powdered maleic anhydride (manufactured by Nacalai Tesque) are premixed. Then, the maleic anhydride-modified polypropylene obtained by feeding to the hopper of a twin screw extruder whose temperature is adjusted to 190 ° C. and cooling and solidifying the strand obtained by melt reaction at a screw speed of 80 revolutions / minute in a water bath.
  • the molded products of Examples 1 to 12 have high bending strength in both the X-axis direction and the Y-axis direction, and low bending strength with low anisotropy can be obtained. High reliability.
  • the molded products of Comparative Examples 1 to 6 are inferior in bending strength and higher in anisotropy than the molded products of Examples.
  • the molded article of the present invention has high mechanical property reliability and can be freely designed and utilized for various applications.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

La présente invention a trait à une pièce moulée qui est dotée d'excellentes propriétés mécaniques en ce qui concerne la résistance à la flexion, la résistance à la compression, etc. et qui présente une anisotropie réduite des propriétés mécaniques et dont les propriétés mécaniques sont par conséquent conservées à des niveaux élevés quelle que soit la direction de déformation ou la position. La pièce moulée est obtenue en empilant des pré-imprégnés de résine thermoplastique renforcée de fibres et en moulant par compression l'empilement et est caractérisée en ce que dans une coupe transversale dans la direction de l'épaisseur dotée d'une épaisseur supérieure ou égale à 1 mm, il existe cinq couches renforcées de fibres ou plus, dotées chacune d'une épaisseur de 0,005 à 1,0 mm, prises en sandwich entre deux couches de résine thermoplastique sans fibre, dotées chacune d'une épaisseur de 0,01 à 1,0 mm, en ce que dans chacune des couches renforcées de fibres, les valeurs d'ellipticité (longueur du petit axe/longueur du grand axe) des fibres uniques constituantes, telles que déterminées dans la coupe transversale dans la direction de l'épaisseur, ont un écart type inférieur ou égal à 0,1, et en ce que la valeur moyenne de l'ellipticité des fibres uniques constituantes dans chacune des couches renforcées de fibres, telle que déterminée dans la coupe transversale dans la direction de l'épaisseur, a un écart type supérieur ou égal à 0,2 par rapport à la valeur moyenne des couches renforcées de fibres.
PCT/JP2012/057102 2011-03-29 2012-03-21 Pièce moulée en couches de résine thermoplastique renforcée de fibres WO2012133013A1 (fr)

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JP2014145048A (ja) * 2013-01-30 2014-08-14 Toyobo Co Ltd 炭素繊維強化熱可塑性樹脂プリプレグシートまたは成形品
JP2016011403A (ja) * 2014-06-30 2016-01-21 サンコロナ小田株式会社 一方向性繊維強化テープ状複合材の製造方法、製造装置及び当該テープ状複合材を使用したランダムシートの製造方法
JP2016216654A (ja) * 2015-05-22 2016-12-22 株式会社神戸製鋼所 テープ状プリプレグ及び繊維強化成形体
KR20170024525A (ko) * 2015-08-25 2017-03-07 더 보잉 컴파니 첨삭 가공을 위한 복합재 공급원료 스트립 및 그 형성 방법
WO2018061597A1 (fr) * 2016-09-29 2018-04-05 東レ株式会社 Base en résine thermoplastique renforcée par des fibres et article moulé obtenu à partir de celle-ci
KR101874957B1 (ko) * 2014-08-22 2018-07-05 도요타 지도샤（주） 부품끼리의 결합 구조 및 부품끼리의 결합 방법

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JPH05293919A (ja) * 1992-02-19 1993-11-09 Nippon Steel Corp 炭素繊維強化樹脂複合材料とその製造方法
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Cited By (12)

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Publication number Priority date Publication date Assignee Title
JP2014145048A (ja) * 2013-01-30 2014-08-14 Toyobo Co Ltd 炭素繊維強化熱可塑性樹脂プリプレグシートまたは成形品
JP2016011403A (ja) * 2014-06-30 2016-01-21 サンコロナ小田株式会社 一方向性繊維強化テープ状複合材の製造方法、製造装置及び当該テープ状複合材を使用したランダムシートの製造方法
KR101874957B1 (ko) * 2014-08-22 2018-07-05 도요타 지도샤（주） 부품끼리의 결합 구조 및 부품끼리의 결합 방법
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KR20170024525A (ko) * 2015-08-25 2017-03-07 더 보잉 컴파니 첨삭 가공을 위한 복합재 공급원료 스트립 및 그 형성 방법
JP2017094710A (ja) * 2015-08-25 2017-06-01 ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ 付加製造のための複合原料ストリップ、及びそれを形成する方法
KR102528795B1 (ko) 2015-08-25 2023-05-03 더 보잉 컴파니 첨삭 가공을 위한 복합재 공급원료 스트립 및 그 형성 방법
WO2018061597A1 (fr) * 2016-09-29 2018-04-05 東レ株式会社 Base en résine thermoplastique renforcée par des fibres et article moulé obtenu à partir de celle-ci
JPWO2018061597A1 (ja) * 2016-09-29 2019-07-11 東レ株式会社 繊維強化熱可塑性樹脂基材およびそれを用いた成形品
US10723088B2 (en) 2016-09-29 2020-07-28 Toray Industries, Inc. Fiber-reinforced thermoplastic-resin base and molded article obtained therefrom
JP7033271B2 (ja) 2016-09-29 2022-03-10 東レ株式会社 繊維強化熱可塑性樹脂基材およびそれを用いた成形品

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