JP2020029534A - Fiber-reinforced thermoplastic resin base material and molded article using the same - Google Patents

Abstract

To provide a fiber-reinforced thermoplastic resin base material which strongly bonds a thermoplastic resin (A) and a thermoplastic resin (B), and has high mechanical characteristics, adhesion and heat resistance.SOLUTION: There are provided: a fiber-reinforced thermoplastic resin base material in which continuous reinforcement fibers are impregnated with a thermoplastic resin, in which a surface layer formed of a thermoplastic resin (B) is formed on at least one surface of a thermoplastic resin (A) impregnating the reinforcement fibers, and at least one of the thermoplastic resin (A) and the thermoplastic resin (B) is a polymer alloy; and a molded article of the fiber-reinforced thermoplastic resin base material.SELECTED DRAWING: None

Description

  The present invention relates to a fiber-reinforced thermoplastic resin substrate and a molded article using the same.

  Fiber reinforced thermoplastic resin base material made by impregnating thermoplastic resin into continuous reinforcing fiber is excellent in specific strength, specific rigidity, high weight reduction effect, heat resistance, chemical resistance, aircraft, It is preferably used for various applications such as transportation equipment such as automobiles, sports, and electric / electronic parts. In recent years, with increasing demand for weight reduction, metal parts are being replaced with resin parts, and downsizing and modularization of parts are being promoted, especially for aircraft and automobile applications, so that they are more excellent in moldability and mechanical properties. Material development is required.

  For example, as a composite material for a structural material having excellent moldability and mechanical properties, Patent Literature 1 discloses that the inner layer portion of a prepreg is made of a thermoplastic resin having a linear or branched polymer structure and a higher melting point. A thermoplastic resin prepreg composed of a matrix resin and a reinforcing fiber and having a surface portion made of a thermoplastic resin having a lower melting point has been proposed. In this thermoplastic resin prepreg, the inner layer portion of the prepreg is composed of a thermoplastic resin having a linear or branched polymer structure and a higher melting point and a reinforcing fiber. Plastics) can exhibit the same high mechanical properties, and the surface layer is made of a low-melting thermoplastic resin. Therefore, press molding in which prepregs are overlapped and laminated, injection molding with prepregs inserted, injection press molding, etc. It is said that excellent adhesiveness between the substrates is obtained.

WO2013-008720 gazette

  However, in the technology described in Patent Literature 1, a thermoplastic resin having a low melting point is used for the surface layer, and although the adhesiveness is improved, the strength between the layers does not change and there is a concern that the heat resistance may be reduced.

  Therefore, an object of the present invention is to provide a fiber-reinforced thermoplastic resin base material in which a thermoplastic resin (B) is formed on the surface of a fiber-reinforced thermoplastic resin in which continuous reinforcing fibers are impregnated with the thermoplastic resin (A). It is an object of the present invention to provide a fiber-reinforced thermoplastic resin base material in which a resin (A) and a thermoplastic resin (B) are firmly bonded to each other and have high mechanical properties, adhesiveness, and heat resistance.

In order to solve the above problems, the present invention mainly has the following configurations.
[1] A fiber-reinforced thermoplastic resin substrate in which continuous reinforcing fibers are impregnated with a thermoplastic resin, wherein at least one surface of the thermoplastic resin (A) impregnated with the reinforcing fibers is made of a thermoplastic resin (B). A fiber-reinforced thermoplastic resin base material having a surface layer formed thereon, wherein at least one of the thermoplastic resin (A) and the thermoplastic resin (B) is a polymer alloy.
[2] The fiber-reinforced thermoplastic according to [1], wherein one of the thermoplastic resin (A) and the thermoplastic resin (B) is a polymer alloy and the other contains a thermoplastic resin of the same type as the polymer alloy. Resin base material.
[3] The fiber-reinforced thermoplastic resin substrate according to [1] or [2], wherein the thermoplastic resin (B) is a polymer alloy.
[4] The thermoplastic resin (B) is selected from polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyether sulfone resin (PES), polyetherimide (PEI), and liquid crystal polymer (LCP) The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [3], comprising a polymer alloy obtained by combining at least two or more resins.
[5] The fiber-reinforced thermoplastic resin substrate according to [1] or [2], wherein the thermoplastic resin (A) is a polymer alloy.
[6] The thermoplastic resin (A) and the thermoplastic resin (B) are polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyether sulfone resin (PES), polyetherimide (PEI), liquid crystal The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [5], including a resin selected from a polymer (LCP).
[7] The polymer alloy contains a biphasic continuous structure having a structural period of 0.001 to 10 μm, or the polymer alloy contains a polymer alloy forming a sea-island structure composed of an island phase having a particle diameter of 0.001 to 10 μm and a sea phase. The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [6].
[8] The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [7], wherein the reinforcing fibers are carbon fibers.
[9] The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [8], wherein the void ratio is 2% or less.
[10] A molded article comprising the fiber-reinforced thermoplastic resin substrate according to any one of [1] to [9].
[11] The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [9] or the molded article according to [10], and a metal material or a molded article thereof, or a resin material or a molded article thereof. A composite molded product that is integrated.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin (A) and the thermoplastic resin (B) are firmly integrated, and the fiber reinforced thermoplastic resin base material excellent in high mechanical characteristics, adhesiveness, and heat resistance is obtained.

  Hereinafter, the present invention will be described in detail with embodiments.

  The fiber-reinforced thermoplastic resin substrate according to the present invention is a fiber-reinforced thermoplastic resin substrate in which continuous reinforcing fibers are impregnated with a thermoplastic resin, and at least one surface of the thermoplastic resin (A) in which the reinforcing fibers are impregnated. Is a fiber reinforced thermoplastic resin substrate in which a surface layer made of a thermoplastic resin (B) is formed, and at least one of the thermoplastic resin (A) and the thermoplastic resin (B) is a polymer alloy.

  In the present invention, the continuous reinforcing fibers refer to those in which the reinforcing fibers are not interrupted in the fiber-reinforced thermoplastic thermoplastic resin base material. The form and arrangement of the reinforcing fibers in the present invention include, for example, ones aligned in one direction, woven fabric (cloth), knit, braid, tow, and the like. Above all, it is preferable that the reinforcing fibers are arranged in one direction because the mechanical properties in a specific direction can be efficiently enhanced.

  The type of the reinforcing fiber is not particularly limited, and examples thereof include a carbon fiber, a metal fiber, an organic fiber, and an inorganic fiber. Two or more of these may be used. By using carbon fibers for the reinforcing fibers, a fiber-reinforced thermoplastic thermoplastic resin base material having high mechanical properties while being lightweight can be obtained.

  Examples of the carbon fiber include PAN-based carbon fiber made from polyacrylonitrile (PAN) fiber, pitch-based carbon fiber made from petroleum tar and oil pitch, and cellulosic carbon made from viscose rayon and cellulose acetate. Vapor-grown carbon fibers made from fibers, hydrocarbons and the like, and graphitized fibers thereof. Among these carbon fibers, PAN-based carbon fibers are preferably used because they have an excellent balance between strength and elastic modulus.

  Examples of the metal fiber include fibers made of metal such as iron, gold, silver, copper, aluminum, brass, and stainless steel.

  Examples of the organic fibers include fibers made of organic materials such as aramid, polybenzoxazole (PBO), polyphenylene sulfide, polyester, polyamide, and polyethylene. Examples of the aramid fiber include a para-aramid fiber excellent in strength and elastic modulus and a meta-aramid fiber excellent in flame retardancy and long-term heat resistance. Examples of the para-aramid fiber include polyparaphenylene terephthalamide fiber and copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber, and examples of the meta-aramid fiber include polymetaphenylene isophthalamide fiber. Is mentioned. As the aramid fiber, a para-aramid fiber having a higher elastic modulus than a meta-aramid fiber is preferably used.

Examples of the inorganic fibers include fibers made of inorganic materials such as glass, basalt, silicon carbide, and silicon nitride. Examples of the glass fiber include E glass fiber (for electric use), C glass fiber (for corrosion resistance), S glass fiber, and T glass fiber (high strength and high elastic modulus). Basalt fiber is a fiber made of basalt, which is a mineral, and has extremely high heat resistance. Basalt, generally the FeO or FeO ₂ which is a compound of iron 9-25% by weight, although the TiO or TiO ₂ which is a compound of titanium containing 1-6 wt%, increase of these components in the molten state It is also possible to make the fibers.

  Since the fiber-reinforced thermoplastic resin base material according to the present invention is often expected to serve as a reinforcing material, it is desirable to express high mechanical properties, and in order to express high mechanical properties, as a reinforcing fiber, It is preferable to include carbon fibers.

  In the fiber-reinforced thermoplastic resin base material, the reinforcing fiber is usually formed by arranging one or more reinforcing fiber bundles in which many single fibers are bundled. When one or a plurality of reinforcing fiber bundles are arranged, the total number of reinforcing fiber filaments (the number of single fibers) is preferably 1,000 to 2,000,000. From the viewpoint of productivity, the total number of reinforcing fibers is preferably 1,000 to 1,000,000, more preferably 1,000 to 600,000, and 1,000 to 300,000. Particularly preferred. The upper limit of the total number of filaments of the reinforcing fibers may be determined in consideration of the balance between the dispersibility and the handleability so as to maintain good productivity, dispersibility, and handleability.

  One reinforcing fiber bundle is formed by bundling 1,000 to 50,000 single fibers of reinforcing fibers having an average diameter of preferably 5 to 10 μm.

  Examples of the thermoplastic resin (A) used in the present invention include polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, polyethylene naphthalate (PEN) resin, and liquid crystal polyester. Polyester such as resin, polyolefin such as polyethylene (PE) resin, polypropylene (PP) resin, polybutylene resin, styrene resin, polyoxymethylene (POM) resin, polyamide (PA) resin, polycarbonate (PC) Resin, polymethylene methacrylate (PMMA) resin, polyvinyl chloride (PVC) resin, polyphenylene sulfide (PPS) resin, polyphenylene ether (PPE) resin, modified PPE resin, polyimide (PI) resin, polyamide Amide (PAI) resin, polyetherimide (PEI) resin, polysulfone (PSU) resin, modified PSU resin, polyethersulfone (PES) resin, polyketone (PK) resin, polyarylene ether ketone (PAEK) resin, polyarylate ( PAR) resin, polyether nitrile (PEN) resin, phenolic resin, fluorinated resin such as phenoxy resin, polytetrafluoroethylene resin, and further polystyrene resin, polyolefin resin, polyurethane resin, polyester resin, polyamide resin And thermoplastic elastomers such as polybutadiene-based resin, polyisoprene-based resin and fluorine-based resin, and copolymers and modified products thereof, and resins blended with two or more kinds. Examples of the polyarylene ether ketone resin (PAEK) include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone (PEKK), and polyether ketone ether. Ketone ketone (PEKEKK), polyether ether ketone ether ketone (PEEKEK), polyether ether ether ketone (PEEEK), polyether diphenyl ether ketone (PEDEK), and copolymers, modified products, and blends of two or more thereof Resin or the like may be used. In particular, from the viewpoint of mechanical properties and heat resistance, the polymer alloy is made of polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyether sulfone resin (PES), polyetherimide (PEI), liquid crystal polymer (LCP) The selected resin is preferable, and a polymer alloy obtained by combining two or more of the above resins is more preferable.

  The fiber-reinforced thermoplastic resin substrate according to the present invention forms a surface layer made of a thermoplastic resin (B) on at least one surface of a fiber-reinforced thermoplastic resin substrate in which continuous thermoplastic fibers are impregnated with the above-described thermoplastic resin. It is important to.

  Examples of the thermoplastic resin (B) used in the present invention include polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polytrimethylene terephthalate (PTT) resin, polyethylene naphthalate (PEN) resin, and liquid crystal polyester. Polyester such as resin, polyolefin such as polyethylene (PE) resin, polypropylene (PP) resin, polybutylene resin, styrene resin, polyoxymethylene (POM) resin, polyamide (PA) resin, polycarbonate (PC) Resin, polymethylene methacrylate (PMMA) resin, polyvinyl chloride (PVC) resin, polyphenylene sulfide (PPS) resin, polyphenylene ether (PPE) resin, modified PPE resin, polyimide (PI) resin, polyamide Amide (PAI) resin, polyetherimide (PEI) resin, polysulfone (PSU) resin, modified PSU resin, polyethersulfone (PES) resin, polyketone (PK) resin, polyarylene ether ketone resin (PAEK), polyarylate ( PAR) resin, polyether nitrile (PEN) resin, phenolic resin, fluorinated resin such as phenoxy resin, polytetrafluoroethylene resin, and further polystyrene resin, polyolefin resin, polyurethane resin, polyester resin, polyamide resin And thermoplastic elastomers such as polybutadiene-based resin, polyisoprene-based resin and fluorine-based resin, and copolymers and modified products thereof, and resins blended with two or more kinds. Examples of the polyarylene ether ketone resin (PAEK) include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone (PEKK), and polyether ketone ether. Ketone ketone (PEKEKK), polyether ether ketone ether ketone (PEEKEK), polyether ether ether ketone (PEEEK), polyether diphenyl ether ketone (PEDEK), and copolymers, modified products, and blends of two or more thereof Resin or the like may be used. In particular, from the viewpoint of mechanical properties and heat resistance, the polymer alloy is made of polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyether sulfone resin (PES), polyetherimide (PEI), liquid crystal polymer (LCP) The selected resin is preferable, and a polymer alloy obtained by combining two or more of the above resins is more preferable.

  In the fiber-reinforced thermoplastic resin substrate according to the present invention, one of the thermoplastic resin (A) and the thermoplastic resin (B) needs to be a polymer alloy. By using one of the thermoplastic resin (A) and the thermoplastic resin (B) as a polymer alloy, impregnation, mechanical properties, and adhesion can be improved. For example, when the thermoplastic resin (A) is a polymer alloy having high mechanical properties but a high-viscosity thermoplastic resin and a low-viscosity thermoplastic resin, both high mechanical properties and impregnation can be achieved. Further, by forming the thermoplastic resin (B) into a polymer alloy in which a resin having high toughness is combined, the interlayer strength when the fiber-reinforced thermoplastic resin base material is laminated is improved. The thermoplastic resin (B) is preferably a polymer alloy, and both the thermoplastic resin (A) and the thermoplastic resin (B) are more preferably a polymer alloy, since both impregnation and mechanical properties can be achieved.

  When one of the thermoplastic resin (A) and the thermoplastic resin (B) is a polymer alloy, the other contains a thermoplastic resin of the same type as the polymer alloy. Is preferred. By containing a thermoplastic resin of the same type as the polymer alloy, the adhesive is melted and integrated with each other at the bonding surface, so that strong bonding can be achieved.

  The polymer alloy constituting the thermoplastic resin (A) or the thermoplastic resin (B) of the present invention has a biphasic continuous structure having a structural period of 0.001 to 10 μm in a fiber-reinforced thermoplastic resin base material. Alternatively, it is preferable that the polymer alloy forms a sea-island structure including an island phase having a particle diameter of 0.001 to 10 μm and a sea phase. High mechanical properties and heat resistance can be achieved by controlling the structure to a biphasic continuous structure in the range of 0.001 μm to 10 μm or a sea-island structure composed of an island phase and a sea phase in a particle size range of 0.001 to 1 μm. It is more preferable to form a biphasic continuous structure in the range of 0.01 μm to 5 μm or a sea-island structure composed of an island phase and a sea phase having a particle size in the range of 0.01 to 5 μm. The phase continuity structure or the range of the particle diameter of 0.05 to 1 μm is more preferable.

Further, in order to confirm these two-phase continuous structure or dispersed structure, it is important to confirm a regular periodic structure. This means that, for example, in addition to confirming that a biphasic continuous structure is formed by optical microscopy or transmission electron microscopy, the scattering maxima in scattering measurements performed using a small-angle X-ray scattering device or light scattering device Confirmation of appearance is necessary. The existence of a scattering maximum in this scattering measurement is a proof that a regular phase-separated structure having a certain period is present. The period Δm (nm) corresponds to the structural period in the case of a biphasic continuous structure, and in the case of a dispersed structure Corresponds to the distance between particles. The value is calculated from the following equation using the wavelength λ (nm) of the scattered light in the scatterer and the scattering angle θm (deg °) that gives the maximum scattering, according to the following equation: Δm = (λ / 2) / sin (θm / 2) can do.

  In addition, even if the size of the inter-particle distance in the structural period or the dispersed structure in the biphasic continuous structure is in the above range, if there is a partially structurally coarse part, for example, when there is an impact, there is a starting point In some cases, the original properties of the polymer alloy cannot be obtained, for example, the fracture proceeds. Therefore, the uniformity of the structural period in the biphasic continuous structure of the polymer alloy or the uniformity of the interparticle distance in the dispersed structure is important. This uniformity can be evaluated by the above-mentioned small angle X-ray scattering measurement or light scattering measurement of the polymer alloy. In the small-angle X-ray scattering measurement and the light scattering measurement, the size of the phase separation structure that can be analyzed is different. Therefore, it is necessary to appropriately use the phase separation structure size according to the size of the phase separation structure of the polymer alloy to be analyzed. The small-angle X-ray scattering measurement and light scattering measurement provide information on the distribution of the structure period in the biphasic continuous structure or the size of the interparticle distance in the dispersed structure. Specifically, the peak position of the scattering maximum in the spectrum obtained by those measurements, that is, the scattering angle θm (deg °) corresponds to the structure period in the biphasic continuous structure or the size of the distance between particles in the dispersed structure. The way of spreading corresponds to the uniformity of the structure. In order to obtain excellent physical properties such as mechanical properties, it is preferable that the structural uniformity is high. In the polymer alloy of the present invention, the scattering spectrum obtained by small-angle X-ray scattering measurement or light scattering measurement has a maximum value. It is characterized by.

  The fiber-reinforced thermoplastic resin base material according to the present invention may further contain a filler, various additives, and the like, if necessary, in the thermoplastic resin (A) and the thermoplastic resin (B). .

  As the filler, any one generally used as a resin filler can be used, and the strength, rigidity, heat resistance, and dimensional stability of a fiber-reinforced thermoplastic thermoplastic resin base material and a molded product using the same can be further improved. Can be improved. Examples of the filler include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber, metal fiber, and the like. Fibrous inorganic filler, wollastenite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, oxide Iron, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, silica, etc. Such as fibrous inorganic filler and the like. Two or more of these may be contained. These fillers may be hollow. Further, it may be treated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound. Further, as the montmorillonite, an organized montmorillonite obtained by cation-exchanging interlayer ions with an organic ammonium salt may be used. In addition, if the fibrous filler is made of discontinuous fibers, the function can be provided without impairing the reinforcing effect of the reinforcing fibers made of continuous fibers.

  Examples of the various additives include antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites and their substitutes, copper halides, iodine compounds, etc.), weathering agents (resorcinols, salicylates) Benzotriazoles, benzophenones, hindered amines, etc.), release agents and lubricants (aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.) , Dyes (eg, nigrosine, aniline black), plasticizers (eg, octyl p-oxybenzoate, N-butylbenzenesulfonamide), antistatic agents (eg, alkyl sulfate-type anionic antistatic agents, and quaternary ammonium salt-type cationic charges). Inhibitor, polyoxyethylene Nonionic antistatic agents such as bitane monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (melamine cyanurate, hydroxides such as magnesium hydroxide and aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, Brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin, or a combination of these brominated flame retardants with antimony trioxide). Two or more of these may be blended.

  The fiber-reinforced thermoplastic resin substrate according to the present invention can be obtained by impregnating continuous reinforcing fibers with the thermoplastic resin (A) and forming a surface layer made of the thermoplastic resin (B).

  Examples of the method of impregnating the thermoplastic resin (A) include, for example, a film method in which a thermoplastic resin in a film form is melted and pressurized to impregnate the thermoplastic resin into a reinforcing fiber bundle, a fibrous thermoplastic resin and a reinforcing fiber. After blending with the bundle, the fibrous thermoplastic resin is melted, and the commingle method of impregnating the reinforcing fiber bundle with the thermoplastic resin by applying pressure, the powdery thermoplastic resin is dispersed in the gaps between the fibers in the reinforcing fiber bundle After that, the powdered thermoplastic resin is melted, and the powder method in which the reinforcing fiber bundle is impregnated with the thermoplastic resin by pressing, the reinforcing fiber bundle is immersed in the melted thermoplastic resin, and the reinforcing fiber is pressed. A drawing method in which a bundle is impregnated with a thermoplastic resin is exemplified. The drawing method is preferable because various types of fiber-reinforced thermoplastic resin base materials having various thicknesses and fiber volume contents can be produced.

  As a method for forming the thermoplastic resin (B), for example, a film method in which a thermoplastic resin in the form of a film or nonwoven fabric is laminated on the surface of the fiber-reinforced thermoplastic resin, and heated and pressed to adhere to the fiber-reinforced thermoplastic resin, Spray coating method, in which the air-blown resin is sprayed onto the surface of the fiber-reinforced thermoplastic resin substrate using air, the thermoplastic resin is extruded in the form of a curtain from the T-die onto the surface of the fiber-reinforced thermoplastic resin substrate and adhered to the substrate surface The gap coating method, in which the fiber-reinforced thermoplastic resin base material is passed through the impregnated die in which the thermoplastic resin is stored, is taken out from the slit-shaped nozzle at the exit of the impregnated die, and the thermoplastic resin is adhered to the surface. can give. The gap coating method is preferable because the resin can be uniformly attached and the coating can be performed at a low pressure without disturbing the alignment of the fibers.

  The thickness of the fiber-reinforced thermoplastic resin substrate according to the present invention is preferably from 1 to 100 μm. When the thickness is 1 μm or more, the strength of a molded product obtained by using the fiber-reinforced fiber-reinforced thermoplastic resin base material can be improved. 10 μm or more is more preferable. On the other hand, if the thickness is 100 μm or less, it is easier to impregnate the reinforcing fibers with the thermoplastic resin base material. 70 μm or less is more preferable, 60 μm or less is further preferable, and 50 μm or less is further preferable.

  The fiber-reinforced thermoplastic substrate according to the present invention contains 30% by volume or more and 70% by volume or less of the reinforcing fibers in 100% by volume of the entire fiber-reinforced thermoplastic resin substrate. By containing the reinforcing fiber in an amount of 30% by volume or more, the strength of a molded product obtained by using the fiber-reinforced thermoplastic resin base material can be further improved. 40 volume% or more is more preferable, and 50 volume% or more is still more preferable. On the other hand, when the reinforcing fibers are contained at 70% by volume or less, the reinforcing fibers can be more easily impregnated with the thermoplastic resin. 65 volume% or less is more preferable, and 60 volume% or less is further preferable.

The reinforcing fiber volume content Vf of the fiber-reinforced thermoplastic resin substrate is measured by measuring the mass W0 (g) of the fiber-reinforced thermoplastic resin substrate, and then placing the fiber-reinforced thermoplastic resin substrate in air at 500 ° C. The thermoplastic resin component was burned off by heating for 30 minutes, and the mass W1 (g) of the remaining reinforcing fibers was measured and calculated by the formula (3).
Vf (% by volume) = (W1 / ρf) / {W1 / ρf + (W0−W1) / ρ1} × 100 (3)
ρf: density of reinforcing fiber (g / cm ³ )
ρr: density of thermoplastic resin (g / cm ³ )

  The thickness of the thermoplastic resin (B) forming the surface of the fiber-reinforced thermoplastic resin substrate according to the present invention is preferably in the range of 0.01 mm to 0.3 mm. When the thickness of the thermoplastic resin (B) is 0.01 mm or more, the interlayer strength can be improved. The thickness of the thermoplastic resin (B) is preferably at least 0.05 mm, more preferably at least 0.1 mm. When the thickness of the thermoplastic resin (B) is 0.3 mm or less, the mechanical properties of the fiber-reinforced thermoplastic resin substrate impregnated with the thermoplastic resin (A) are not impaired. The thickness of the thermoplastic resin (B) is preferably 0.25 mm or less, more preferably 0.2 mm or less.

  The fiber-reinforced thermoplastic resin substrate according to the present invention may be completely impregnated with the thermoplastic resin (A), or may be in a semi-impregnated state in which voids remain inside. In order to enhance the mechanical properties of the fiber-reinforced thermoplastic resin substrate, the content of voids (void ratio) in the fiber-reinforced thermoplastic resin substrate is preferably 2% or less. When the void ratio is 2% or less, the mechanical properties of the fiber-reinforced thermoplastic resin base material can be exhibited without impairing the mechanical properties of the reinforcing fibers. The void fraction is more preferably 1.5% or less, and still more preferably 1% or less.

The void ratio of the fiber-reinforced thermoplastic resin substrate in the present invention was determined by observing a cross section in the thickness direction of the fiber-reinforced thermoplastic resin substrate as follows. A sample in which a fiber-reinforced thermoplastic resin substrate was embedded with an epoxy resin was prepared, and the sample was polished until a cross section in the thickness direction of the fiber-reinforced thermoplastic resin substrate could be observed well. The polished sample was photographed at a magnification of 400 times using an ultra-depth color 3D shape measurement microscope VHX-9500 (controller unit) / VHZ-100R (measurement unit) (manufactured by Keyence Corporation). The photographing range was a range of thickness of fiber-reinforced thermoplastic resin substrate × width of 500 μm. In the photographed image, the cross-sectional area of the base material and the area of the void (void) were determined, and the impregnation rate was calculated by equation (4).
Void rate (%) = (total area of site occupied by voids) / (total area of fiber-reinforced thermoplastic resin base material) × 100 (4)

  In the present invention, a molded article is obtained by laminating one or more sheets of the fiber-reinforced thermoplastic resin substrate according to the present invention in an optional configuration and then applying heat and / or pressure as necessary. .

  As a method for applying heat and / or pressure, for example, after forming a fiber-reinforced thermoplastic resin base material laminated in an arbitrary configuration in a mold or on a press plate, press molding in which the mold or the press plate is closed and pressed. The autoclave molding method in which the molding material laminated in an arbitrary configuration is put into an autoclave and pressurized and heated, the molding material laminated in an arbitrary configuration is wrapped in a film or the like, and the inside is depressurized and pressurized at atmospheric pressure. Bag-forming method of heating in an oven while heating, wrapping tape method of winding a tape while applying tension to a fiber-reinforced thermoplastic resin base material laminated in any configuration and heating in an oven, fiber-reinforced heat laminated in any configuration An internal pressure molding method in which a plastic resin base material is placed in a mold, and a gas or liquid is injected into a core also placed in the mold and pressurized.In particular, a molding method in which pressing is performed using a mold is preferably used, since a molded article obtained is small in voids and a molded article having excellent appearance quality can be obtained.

  The fiber-reinforced thermoplastic resin substrate of the present invention or a molded product thereof is excellent in productivity such as insert molding, integrated molding such as outsert molding, correction treatment by heating, heat welding, vibration welding, and ultrasonic welding. Integration using a bonding method or an adhesive can be performed, and a composite can be obtained.

  There is no particular limitation on the molding substrate or its molded product integrated with the fiber-reinforced thermoplastic resin substrate of the present invention or its molded product, for example, a resin material or its molded product, a metal material or its molded product, An inorganic material or a molded product thereof can be used. Among them, the resin material, the molded product thereof, the metal material, or the molded product thereof can effectively exert the reinforcing effect of the fiber-reinforced thermoplastic resin substrate according to the present invention. A resin material or a molded product thereof is preferable in terms of adhesive strength to a fiber-reinforced thermoplastic resin base material, and a fiber-reinforced resin obtained by impregnating a matrix resin into a reinforcing fiber mat having a fiber length of 5 to 100 mm is used for forming and mechanical properties. Is more preferred from the viewpoint of As the metal material or its molded product, high-tensile steel, an aluminum alloy, a titanium alloy, a magnesium alloy, or the like can be used, and may be selected according to the characteristics required for the metal layer, the metal member, and the metal component.

  The matrix resin of the molding material or the molded product thereof integrated with the fiber-reinforced thermoplastic resin substrate of the present invention may be the same kind of resin as the fiber-reinforced thermoplastic resin substrate or the molded product thereof, or may be of a different type. It may be a resin. In order to further increase the adhesive strength, it is preferable that the resins are of the same type. In the case of different kinds of resins, it is more preferable to provide a resin layer at the interface.

  The fiber-reinforced thermoplastic resin substrate of the present invention or a molded article thereof is used for various purposes such as aircraft parts, automobile parts, electric / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods, by utilizing its excellent properties. Can be used for The fiber-reinforced thermoplastic resin base material or the molded product thereof according to the present invention is used especially for aircraft engine peripheral parts requiring stable mechanical properties, exterior parts of aircraft parts, vehicle frames as automobile body parts, and automobile engine peripheral parts. It is particularly preferably used for automobile underhood parts, automobile gear parts, automobile interior parts, automobile exterior parts, intake / exhaust system parts, engine cooling water system parts, automobile electric parts, and electric / electronic parts.

Specifically, the fiber-reinforced thermoplastic resin base material or the molded product thereof according to the present invention includes aircraft engine peripheral parts such as fan blades, landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, ribs and the like. Aircraft related parts, various seats, front body, underbody, various pillars, various members, various frames, various beams, various supports, various rails, various kinds of automobile body parts such as hinges, engine covers, air intake pipes, timing belt covers , Intake manifold, Filler cap, Throttle body, Automotive engine peripheral parts such as cooling fan, Cooling fan, Radiator tank top and base, Cylinder head cover, Oil pan, Brake Automotive underhood parts such as pipes, fuel piping tubes, exhaust gas system parts, etc., automotive gear parts such as gears, actuators, bearing retainers, bearing cages, chain guides, chain tensioners, shift lever brackets, steering lock brackets, key cylinders, doors Automobile interior parts such as inner handle, door handle cowl, interior mirror bracket, air conditioner switch, instrument panel, console box, glove box, steering wheel, trim, front fender, rear fender, fuel lid, door panel, cylinder head cover, door mirror stay, Tailgate panel, license garnish, roof rail, engine mount bracket, rear garnish , Rear spoiler, trunk lid, rocker molding, molding, lamp housing, front grille, mudguard, side bumper, etc., automotive exterior parts, air intake manifold, intercooler inlet, turbocharger, exhaust pipe cover, inner bush, bearing retainer, engine mount Intake and exhaust system parts such as engine head covers, resonators, and throttle bodies, chain cover, thermostat housing, outlet pipes, radiator tanks, alternators, delivery pipes and other engine cooling water parts, connectors and wire harness connectors, motor parts, lamps Automotive electrical components such as sockets, sensor-mounted switches, and combination switches, and electrical and electronic Components include, for example, generators, motors, transformers, current transformers, voltage regulators, rectifiers, resistors, inverters, relays, power contacts, switches, breakers, switches, knife switches, multi-pole rods, Motor case, TV housing, notebook PC housing and internal parts, CRT display housing and internal parts, printer housing and internal parts, mobile terminal housing and internal parts such as mobile phones, mobile personal computers, handheld mobiles, IC and LED compatible housings, Electrical parts such as condenser seat plate, fuse holder, various gears, various cases, cabinets, connectors, SMT compatible connectors, card connectors, jacks, coils, coil bobbins, sensors, LED lamps, sockets, resistors, relays, relays Sources, reflectors, small switches, power supplies, coil bobbins, capacitors, variable condenser cases, optical pickup chassis, oscillators, various terminal boards, transformers, plugs, printed boards, tuners, speakers, microphones, headphones, small motors, magnetic heads It is preferably used for electronic parts such as bases, power modules, Si power modules and SiC power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, transformer members, parabolic antennas, computer-related parts, and the like.

Claims (11)

  A fiber-reinforced thermoplastic resin substrate in which continuous reinforcing fibers are impregnated with a thermoplastic resin, wherein a surface layer made of the thermoplastic resin (B) is formed on at least one surface of the thermoplastic resin (A) impregnated with the reinforcing fibers. A fiber-reinforced thermoplastic resin base material wherein at least one of the thermoplastic resin (A) and the thermoplastic resin (B) is a polymer alloy.   The fiber-reinforced thermoplastic resin substrate according to claim 1, wherein one of the thermoplastic resin (A) and the thermoplastic resin (B) is a polymer alloy, and the other contains a thermoplastic resin of the same type as the polymer alloy. .   The fiber-reinforced thermoplastic resin substrate according to claim 1 or 2, wherein the thermoplastic resin (B) is a polymer alloy.   The thermoplastic resin (B) is at least one selected from polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyether sulfone resin (PES), polyetherimide resin (PEI), and liquid crystal polymer (LCP). The fiber-reinforced thermoplastic resin substrate according to any one of claims 1 to 3, further comprising a polymer alloy obtained by combining two or more resins.   The fiber reinforced thermoplastic resin substrate according to claim 1 or 2, wherein the thermoplastic resin (A) is a polymer alloy.   The thermoplastic resin (A) and the thermoplastic resin (B) are polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyether ketone ketone resin (PEKK), polyether sulfone resin (PES), polyether The fiber-reinforced thermoplastic resin substrate according to any one of claims 1 to 5, further comprising a resin selected from imide (PEI) and liquid crystal polymer (LCP).   The polymer alloy comprises a biphasic continuous structure having a structural period of 0.001 to 10 μm, or the polymer alloy contains a polymer alloy forming a sea-island structure composed of an island phase and a sea phase having a particle diameter of 0.001 to 10 μm. 7. The fiber-reinforced thermoplastic resin substrate according to any one of 1 to 6.   The fiber-reinforced thermoplastic resin substrate according to any one of claims 1 to 7, wherein the reinforcing fibers are carbon fibers.   The fiber-reinforced thermoplastic resin substrate according to any one of claims 1 to 8, wherein a void ratio is 2% or less.   A molded article comprising the fiber-reinforced thermoplastic resin substrate according to any one of claims 1 to 9. A composite obtained by integrating the fiber-reinforced thermoplastic resin substrate according to any one of claims 1 to 9 or the molded product according to claim 10 with a metal material or a molded product thereof, or a resin material or a molded product thereof. Molding.