JP7196464B2 - Fiber-reinforced thermoplastic resin substrate and molded article using the same - Google Patents

Description

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

A fiber-reinforced thermoplastic resin base material obtained by impregnating continuous reinforcing fibers with a thermoplastic resin has excellent specific strength and specific rigidity, is highly effective in reducing weight, and has high heat resistance and chemical resistance. It is preferably used in various applications such as transportation equipment such as automobiles, sports, and electric/electronic parts. In recent years, due to the increasing demand for weight reduction, metal parts are being replaced with resin parts, and parts are becoming smaller and more modular, mainly for aircraft and automobile applications. Material development is required.

For example, as a composite material for structural materials with excellent moldability and mechanical properties, Patent Document 1 discloses that the inner layer 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 has been proposed which is composed of a matrix resin and reinforcing fibers, and whose surface portion is composed of a thermoplastic resin having a lower melting point. 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 reinforcing fibers. It can exhibit high mechanical properties equivalent to plastic), and the surface layer is composed of low-melting thermoplastic resin, so press molding by stacking prepregs, injection molding with prepreg inserted, injection press molding, etc. , it is said that excellent adhesion between substrates can be obtained.

WO2013-008720

However, in the technique described in Patent Document 1, a thermoplastic resin with a low melting point is used for the surface layer, and although the adhesiveness is improved, the strength between the layers remains unchanged, and there is concern about a decrease in heat resistance.

Therefore, an object of the present invention is to provide a fiber-reinforced thermoplastic resin substrate 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 a thermoplastic resin (A). An object of the present invention is to provide a fiber-reinforced thermoplastic resin base material in which the resin (A) and the thermoplastic resin (B) are strongly bonded together and which has 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 in the reinforcing fibers is made of a thermoplastic resin (B) A surface layer is formed, and at least one of the thermoplastic resin (A) and the thermoplastic resin (B) has a biphase continuous structure with a structural period of 0.001 to 10 μm, or an island phase and sea with a particle size of 0.001 to 10 μm. A fiber-reinforced thermoplastic resin base material that is a polymer alloy that forms a sea-island structure consisting of phases .
[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 the same thermoplastic resin 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), polyethersulfone resin (PES), polyetherimide (PEI), and liquid crystal polymer (LCP). The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [3], which contains a polymer alloy in which at least two or more resins are combined.
[5] The fiber-reinforced thermoplastic resin substrate according to [1] or [2], wherein the thermoplastic resin (A) is a polymer alloy.
[6] Thermoplastic resin (A) and thermoplastic resin (B) are polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyethersulfone resin (PES), polyetherimide (PEI), liquid crystal The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [5], containing a resin selected from polymers (LCP).
[ 7 ] The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [ 6 ], wherein the reinforcing fibers are carbon fibers.
[ 8 ] The fiber-reinforced thermoplastic resin substrate according to any one of [1] to [ 7 ], which has a void fraction of 2% or less .

According to the present invention, a fiber-reinforced thermoplastic resin substrate having excellent mechanical properties, adhesiveness and heat resistance, in which the thermoplastic resin (A) and the thermoplastic resin (B) are strongly integrated, can be obtained.

The present invention will be described in detail below together 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 side of the thermoplastic resin (A) impregnated in the reinforcing fibers is A fiber-reinforced thermoplastic resin base material in which a surface layer made of a thermoplastic resin (B) is formed on the substrate, 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 continuous reinforcing fibers in the fiber-reinforced thermoplastic resin substrate. Examples of the form and arrangement of reinforcing fibers in the present invention include unidirectionally aligned, woven fabric (cloth), knitted fabric, braided cord, tow, and the like. Among them, it is preferable that the reinforcing fibers are arranged in one direction because the mechanical properties in a specific direction can be efficiently improved.

The type of reinforcing fiber is not particularly limited, and examples thereof include carbon fiber, metal fiber, organic fiber, and inorganic fiber. You may use 2 or more types of these. By using carbon fiber as the reinforcing fiber, a fiber-reinforced thermoplastic resin base material having high mechanical properties while being lightweight can be obtained.

Examples of carbon fibers include PAN-based carbon fibers made from polyacrylonitrile (PAN) fibers, pitch-based carbon fibers made from petroleum tar or petroleum pitch, and cellulose-based carbon made from viscose rayon, cellulose acetate, or the like. fibers, vapor-grown carbon fibers made from hydrocarbons, 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 metal fibers include fibers made of metals such as iron, gold, silver, copper, aluminum, brass, and stainless steel.

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

Examples of inorganic fibers include fibers made of inorganic materials such as glass, basalt, silicon carbide, and silicon nitride. Examples of glass fibers include E glass fiber (for electrical use), C glass fiber (for corrosion resistance), S glass fiber, and T glass fiber (high strength and high modulus of elasticity). Basalt fiber is a fibrous material made from mineral basalt, and is a fiber with extremely high heat resistance. Basalt generally contains 9-25% by weight of iron compounds FeO or FeO ₂ and 1-6% by weight of titanium compounds TiO or TiO ₂ ; It is also possible to fiberize by

Since the fiber-reinforced thermoplastic resin substrate according to the present invention is often expected to serve as a reinforcing material, it is desirable to exhibit high mechanical properties. It preferably contains carbon fibers.

In the fiber-reinforced thermoplastic resin base material, the reinforcing fibers are usually configured by arranging one or more reinforcing fiber bundles in which a large number of single fibers are bundled. The total number of reinforcing fiber filaments (number of single fibers) when one or more reinforcing fiber bundles are arranged is preferably 1,000 to 2,000,000. From the viewpoint of productivity, the total number of filaments of the reinforcing fibers is more preferably 1,000 to 1,000,000, still more preferably 1,000 to 600,000, and 1,000 to 300,000. Especially preferred. The upper limit of the total number of filaments of the reinforcing fibers should be determined in consideration of the balance between the dispersibility and the handleability so that the productivity, the dispersibility and the handleability can be maintained satisfactorily.

One reinforcing fiber bundle is preferably configured by bundling 1,000 to 50,000 reinforcing fiber monofilaments having an average diameter of 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, styrenic 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, polyamideimide (PAI) resin, poly Etherimide (PEI) resin, polysulfone (PSU) resin, modified PSU resin, polyethersulfone (PES) resin, polyketone (PK) resin, polyarylene ether ketone (PAEK) resin, polyarylate (PAR) resin, polyethernitrile (PEN) resin, phenolic resin, phenoxy resin, fluorine resin such as polytetrafluoroethylene resin, polystyrene resin, polyolefin resin, polyurethane resin, polyester resin, polyamide resin, polybutadiene resin, polyisoprene Thermoplastic elastomers such as system resins and fluororesins, copolymers, modified products thereof, and resins obtained by blending two or more of these may also be used. Examples of the polyarylene ether ketone resin (PAEK) include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ether ketone ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone ether Ketone ketone (PEKEKK), polyether ether ketone ether ketone (PEEKEK), polyether ether ether ketone (PEEEK), polyether diphenyl ether ketone (PEDEK), copolymers, modified products, and blends of two or more thereof It may be a resin or the like. In particular, polymer alloys are selected from polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyether sulfone resin (PES), polyetherimide (PEI), and liquid crystal polymer (LCP) from the viewpoint of mechanical properties and heat resistance. A 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, a surface layer made of a thermoplastic resin (B) is formed on at least one side of a fiber-reinforced thermoplastic resin substrate in which continuous reinforcing fibers are impregnated with the 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, styrenic 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, polyamideimide (PAI) resin, poly Etherimide (PEI) resin, polysulfone (PSU) resin, modified PSU resin, polyethersulfone (PES) resin, polyketone (PK) resin, polyarylene ether ketone resin (PAEK), polyarylate (PAR) resin, polyethernitrile (PEN) resin, phenolic resin, phenoxy resin, fluorine resin such as polytetrafluoroethylene resin, polystyrene resin, polyolefin resin, polyurethane resin, polyester resin, polyamide resin, polybutadiene resin, polyisoprene Thermoplastic elastomers such as system resins and fluororesins, copolymers, modified products thereof, and resins obtained by blending two or more of these may also be used. Examples of the polyarylene ether ketone resin (PAEK) include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ether ketone ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone ether Ketone ketone (PEKEKK), polyether ether ketone ether ketone (PEEKEK), polyether ether ether ketone (PEEEK), and polyether diphenyl ether ketone (PEDEK), copolymers, modified products, and blends of two or more thereof It may be a resin or the like. In particular, polymer alloys are selected from polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyether sulfone resin (PES), polyetherimide (PEI), liquid crystal polymer (LCP) from the viewpoint of mechanical properties and heat resistance. A 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 base material according to the present invention, either one of the thermoplastic resin (A) and the thermoplastic resin (B) must be a polymer alloy. By using a polymer alloy for either the thermoplastic resin (A) or the thermoplastic resin (B), it is possible to improve impregnability, mechanical properties and adhesiveness. For example, the thermoplastic resin (A) has high mechanical properties, but by using a polymer alloy composed of a high-viscosity thermoplastic resin and a low-viscosity thermoplastic resin, both high mechanical properties and impregnability can be achieved. Further, by using a polymer alloy in which resins having high toughness are combined as the thermoplastic resin (B), the interlaminar strength is improved when the fiber-reinforced thermoplastic resin substrates are laminated. It is preferable that the thermoplastic resin (B) is a polymer alloy, and both the thermoplastic resin (A) and the thermoplastic resin (B) are polymer alloys because impregnability and mechanical properties can be compatible.

In the fiber-reinforced thermoplastic resin substrate according to the present invention, when one of the thermoplastic resin (A) and the thermoplastic resin (B) is a polymer alloy, the other contains the same thermoplastic resin as the polymer alloy. is preferred. By including a thermoplastic resin of the same kind as the polymer alloy, they melt and integrate with each other on the bonding surfaces, thereby enabling strong bonding.

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

In addition, in order to confirm these biphase continuous structures or dispersed structures, it is important to confirm regular periodic structures. For example, in addition to confirming the formation of a biphasic continuous structure by optical microscope observation or transmission electron microscope observation, scattering measurements using a small-angle X-ray scattering device or a light scattering device show that the scattering maximum is Confirmation of appearance is required. The existence of a scattering maximum in this scattering measurement is evidence of a regular phase separation structure with a certain period, and the period Λm (nm) corresponds to the structural period in the case of a biphase continuous structure, and in the case of a dispersed structure Corresponds to the interparticle distance. In addition, the value is calculated by the following formula Λm=(λ/2)/sin(θm/2) using the wavelength λ (nm) of the scattered light in the scattering medium and the scattering angle θm (deg°) giving the scattering maximum. can do.

In addition, even if the structure period in the biphasic continuous structure or the size of the distance between particles in the dispersed structure is within the above range, if there is a partially structurally coarse portion, for example, when receiving an impact, In some cases, the properties of the original polymer alloy cannot be obtained, such as destruction progressing. Therefore, the uniformity of the structural period in the biphase continuous structure of the polymer alloy or the uniformity of the distance between particles in the dispersed structure is important. This uniformity can be evaluated by small-angle X-ray scattering measurement or light scattering measurement of the polymer alloy described above. Small-angle X-ray scattering measurement and light scattering measurement differ in the analyzable phase-separated structure size, so it is necessary to use them appropriately according to the phase-separated structure size of the polymer alloy to be analyzed. Small-angle X-ray scattering measurements and light scattering measurements provide information on the distribution of the structural period in a biphase-continuous structure or the size of the interparticle distance in a dispersed structure. Specifically, the peak position of the scattering maximum in the spectrum obtained by these measurements, that is, the scattering angle θm (deg °) corresponds to the structural period in the biphase continuous structure or the size of the interparticle distance in the dispersed structure, and the peak The spread corresponds to the homogeneity of the structure. In order to obtain excellent physical properties such as mechanical properties, it is preferable that the polymer alloy has a high structural uniformity. characterized by

The fiber-reinforced thermoplastic resin substrate according to the present invention may further contain fillers, various additives, etc., in addition to the above-described thermoplastic resin (A) and thermoplastic resin (B), if necessary. .

As the filler, any one generally used as a filler for resin can be used, and the strength, rigidity, heat resistance, and dimensional stability of the fiber-reinforced thermoplastic resin base material and the molded product using the same can be improved. can be improved. Examples of fillers 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, gypsum fiber, metal fiber, and the like. Fibrous inorganic filler, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, oxide Non-fibrous inorganic fillers such as 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. is mentioned. You may contain 2 or more types of these. These fillers may be hollow. Moreover, 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, an epoxy compound, or the like. As the montmorillonite, organic montmorillonite obtained by cation-exchanging interlayer ions with an organic ammonium salt may be used. If the fibrous filler is composed of discontinuous fibers, it can impart a function without impairing the reinforcing effect of the reinforcing fibers composed of continuous fibers.

Examples of various additives include antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites and substituted products thereof, copper halides, iodine compounds, etc.), weathering agents (resorcinol, salicylate, etc.). , benzotriazole-based, benzophenone-based, hindered amine-based, etc.), release agents and lubricants (fatty alcohols, aliphatic amides, aliphatic bisamides, bi-urea and polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.) , Dyes (nigrosine, aniline black, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic charging Antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (melamine cyanurate, hydroxides such as magnesium hydroxide, aluminum hydroxide, polyphosphoric acid ammonium, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin, or combinations of these brominated flame retardants with antimony trioxide, etc.). You may mix|blend 2 or more types of these.

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

As a method for impregnating the thermoplastic resin (A), for example, a film method of melting a film-like thermoplastic resin and applying pressure to impregnate the reinforcing fiber bundle with the thermoplastic resin, a fibrous thermoplastic resin and reinforcing fibers. A commingling method in which the reinforcing fiber bundle is impregnated with the thermoplastic resin by melting and pressurizing the fibrous thermoplastic resin after blending with the bundle, and the powdered thermoplastic resin is dispersed in the gaps between the fibers in the reinforcing fiber bundle. After that, the powdered thermoplastic resin is melted and pressurized to impregnate the reinforcing fiber bundles with the thermoplastic resin. A drawing method in which the bundle is impregnated with a thermoplastic resin can be mentioned. The drawing method is preferred because it enables the preparation of a wide variety of fiber-reinforced thermoplastic resin base materials such as various thicknesses and fiber volume contents.

Examples of the method for forming the thermoplastic resin (B) include a film method in which a thermoplastic resin in the form of a film or non-woven fabric is laminated on the surface of the fiber-reinforced thermoplastic resin and heated and pressed to adhere to the fiber-reinforced thermoplastic resin; A spray coating method in which the resin is sprayed onto the surface of the fiber-reinforced thermoplastic resin substrate using air, and a T-die is used to extrude the thermoplastic resin onto the surface of the fiber-reinforced thermoplastic resin substrate in a curtain shape to adhere to the substrate surface. A gap coating method in which a fiber-reinforced thermoplastic resin base material is passed through an impregnation die in which the thermoplastic resin is stored, is taken out from a slit-shaped nozzle at the exit of the impregnation die, and the thermoplastic resin is adhered to the surface. can give. The gap coating method is preferred because the resin can adhere uniformly 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 1 to 100 μm. If the thickness is 1 μm or more, the strength of the molded article obtained using the 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 even more preferable, and 50 μm or less is even more preferable.

Further, the fiber-reinforced thermoplastic base material according to the present invention contains 30% by volume or more and 70% by volume or less of reinforcing fibers in 100% by volume of the entire fiber-reinforced thermoplastic resin base material. By containing 30% by volume or more of the reinforcing fiber, the strength of the molded article obtained using the fiber-reinforced thermoplastic resin substrate can be further improved. 40% by volume or more is more preferable, and 50% by volume or more is even more preferable. On the other hand, by containing 70% by volume or less of reinforcing fibers, it is easier to impregnate the reinforcing fibers with the thermoplastic resin. 65% by volume or less is more preferable, and 60% by volume or less is even more preferable.

In addition, the reinforcing fiber volume content Vf of the fiber-reinforced thermoplastic resin substrate is obtained by measuring the mass W0 (g) of the fiber-reinforced thermoplastic resin substrate, and then measuring the fiber-reinforced thermoplastic resin substrate at 500 ° C. in the air. It was heated for 30 minutes to burn off the thermoplastic resin component, 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. By setting the thickness of the thermoplastic resin (B) to 0.01 mm or more, the interlaminar strength can be improved. The thickness of the thermoplastic resin (B) is preferably 0.05 mm or more, more preferably 0.1 mm or more. When the thermoplastic resin (B) has a thickness of 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 with voids remaining inside. In order to improve the mechanical properties of the fiber-reinforced thermoplastic resin substrate, the void content (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 substrate can be expressed without impairing the mechanical properties of the reinforcing fibers. The void ratio is more preferably 1.5% or less, more preferably 1% or less.

The void fraction of the fiber-reinforced thermoplastic resin base material in the present invention was obtained by observing the cross section in the thickness direction of the fiber-reinforced thermoplastic resin base material as follows. A sample in which a fiber-reinforced thermoplastic resin substrate was embedded in 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 satisfactorily. The polished sample was photographed at a magnification of 400 using an ultra-depth color 3D shape measuring microscope VHX-9500 (controller unit)/VHZ-100R (measurement unit) (manufactured by Keyence Corporation). The photographing range was the thickness of the 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 voids were obtained, and the impregnation rate was calculated by Equation (4).
Void ratio (%) = (total area of portions occupied by voids)/(total area of fiber-reinforced thermoplastic resin substrate) x 100 (4)

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

As a method of applying heat and/or pressure, for example, a fiber-reinforced thermoplastic resin substrate laminated in an arbitrary configuration is placed in a mold or on a press plate, and then press molding is performed by closing the mold or press plate and applying pressure. An autoclave molding method in which molding materials laminated in an arbitrary configuration are put into an autoclave and pressurized and heated. A molding material laminated in an arbitrary configuration is wrapped in a film, etc., and the inside is decompressed and pressurized at atmospheric pressure. Wrapping tape method in which a tape is wound while applying tension to a fiber-reinforced thermoplastic resin substrate laminated in an arbitrary configuration and heated in an oven, Fiber-reinforced heat laminated in an arbitrary configuration Examples include an internal pressure molding method in which a plastic resin base material is placed in a mold, and a gas, liquid, or the like is injected into a core placed in the mold and pressurized. In particular, a molding method in which a mold is used to press is preferably used, since the voids in the obtained molded article are few and a molded article having excellent appearance quality can be obtained.

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

There are no particular restrictions on the molding base material or molded article thereof that is integrated with the fiber-reinforced thermoplastic resin substrate or molded article thereof of the present invention. Examples include resin materials or molded articles thereof, metal materials or molded articles thereof, Inorganic materials or molded articles thereof may be mentioned. Among them, the resin material or its molded article or the metal material or its molded article can effectively exhibit the effect of reinforcing the fiber-reinforced thermoplastic resin base material according to the present invention. A resin material or a molded product thereof is preferable in terms of adhesive strength with a fiber-reinforced thermoplastic resin substrate, 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 has moldability and mechanical properties. It is more preferable from the point of High-strength steel, aluminum alloys, titanium alloys, magnesium alloys, and the like can be used as the metal material or its molded product, and the material may be selected according to the properties required for the metal layer, metal member, or metal part.

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

The fiber-reinforced thermoplastic resin base material of the present invention or its molded article can be used for various applications such as aircraft parts, automobile parts, electric/electronic parts, construction parts, various containers, daily necessities, household goods and sanitary goods, taking advantage of its excellent properties. can be used for The fiber-reinforced thermoplastic resin base material or molded article thereof in the present invention is particularly suitable for aircraft engine peripheral parts that require stable mechanical properties, exterior parts for aircraft parts, vehicle skeletons as automobile body parts, and automobile engine peripheral parts. , automobile underhood parts, automobile gear parts, automobile interior parts, automobile exterior parts, intake and exhaust system parts, engine cooling water system parts, automobile electrical parts, and electric/electronic parts.

Specifically, the fiber-reinforced thermoplastic resin base material or molded article thereof in the present invention can be used for aircraft engine peripheral parts such as fan blades, landing gear pods, winglets, spoilers, edges, rudders, elevators, failings, ribs, and the like. Aircraft-related parts, various seats, front bodies, under bodies, various pillars, various members, various frames, various beams, various supports, various rails, automobile body parts such as various hinges, engine covers, air intake pipes, timing belt covers , intake manifolds, filler caps, throttle bodies, cooling fans and other automobile engine peripheral parts, cooling fans, radiator tank tops and bases, cylinder head covers, oil pans, brake pipes, fuel pipe tubes, exhaust system parts, etc. Automotive gear parts such as hood parts, gears, actuators, bearing retainers, bearing cages, chain guides, chain tensioners, shift lever brackets, steering lock brackets, key cylinders, door inner handles, door handle cowls, interior mirror brackets, air conditioner switches, Automotive interior parts such as instrument panels, console boxes, glove boxes, steering wheels, trims, front fenders, rear fenders, fuel lids, door panels, cylinder head covers, door mirror stays, tailgate panels, license garnishes, roof rails, engine mount brackets, rear Automotive exterior parts such as garnishes, rear spoilers, trunk lids, rocker moldings, moldings, lamp housings, front grilles, mudguards, side bumpers, air intake manifolds, intercooler inlets, turbochargers, exhaust pipe covers, inner bushes, bearing retainers, engines Intake and exhaust system parts such as mounts, engine head covers, resonators, and throttle bodies, engine cooling water system parts such as chain covers, thermostat housings, outlet pipes, radiator tanks, alternators, and delivery pipes, connectors and wire harness connectors, motor parts, Automotive electrical components such as lamp sockets, sensor-mounted switches, combination switches, electrical/electronics Parts include, for example, generators, motors, transformers, current transformers, voltage regulators, rectifiers, resistors, inverters, relays, power contacts, switches, circuit breakers, switches, knife switches, multipolar rods, Motor cases, TV housings, notebook computer housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers, handheld mobiles, IC and LED compatible housings, Condenser seat plate, fuse holder, various gears, various cases, electric parts such as cabinets, connectors, connectors for SMT, card connectors, jacks, coils, coil bobbins, sensors, LED lamps, sockets, resistors, relays, relay cases, Reflectors, small switches, power supply parts, coil bobbins, capacitors, variable condenser cases, optical pickup chassis, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power supplies It is preferably used for electronic parts such as modules, Si power modules, SiC power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, transformer members, parabolic antennas, and computer-related parts.

Claims (8)

A fiber-reinforced thermoplastic resin base material in which continuous reinforcing fibers are impregnated with a thermoplastic resin, wherein a surface layer made of a thermoplastic resin (B) is formed on at least one surface of the thermoplastic resin (A) impregnated in the reinforcing fibers. At least one of the thermoplastic resin (A) and the thermoplastic resin (B) has a biphase continuous structure with a structural period of 0.001 to 10 μm, or an island phase and a sea phase with a particle size of 0.001 to 10 μm. A fiber-reinforced thermoplastic resin substrate that is a polymer alloy that forms a sea-island structure . 2. 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 the same thermoplastic resin 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 selected from polyphenylene sulfide resin (PPS), polyarylene ether ketone resin (PAEK), polyethersulfone 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, comprising a polymer alloy in which two or more resins are combined. 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, which contains a resin selected from imide (PEI) and liquid crystal polymer (LCP). The fiber-reinforced thermoplastic resin substrate according to any one of claims 1 to 6 , wherein the reinforcing fibers are carbon fibers. The fiber-reinforced thermoplastic resin substrate according to any one of claims 1 to 7 , which has a void fraction of 2% or less .