Metal-glass fiber reinforced thermoplastic resin composite materials

Abstract

The present invention provides a metal-glass fiber reinforced thermoplastic resin composite material. The metal-glass fiber reinforced thermoplastic resin composite material can have excellent bonding strength and heat cycle resistance between the metal material and the glass fiber reinforced thermoplastic resin material. The metal-glass fiber reinforced thermoplastic resin composite material of the present invention comprises a metal material and a glass fiber reinforced thermoplastic resin material located on at least one surface of the metal material, characterized in that the glass fiber contained in the glass fiber reinforced thermoplastic resin material has a Vickers hardness H in the range of 700 to 800HV0.2 and an elastic modulus M in the range of 70.0 to 110.0GPa, and the Vickers hardness H and the elastic modulus M satisfy the following formula (1): 849.5≤M 3 / H≤940.5…(1).

Description

Technical Field

[0001] The invention relates to a metal-glass fiber reinforced thermoplastic resin composite material. Background Art

[0002] Glass fiber has been widely used in various applications for its ability to increase the strength of resin materials. Among glass fiber reinforced resin materials, the most commonly used is E-glass fiber, which has an elastic modulus of 76.0 GPa and a Vickers hardness of 740 HV0.2.

[0003] In recent years, the use of glass fiber reinforced resin materials has expanded to include metal replacement materials. In particular, for components requiring high mechanical strength, researchers are studying the use of composite materials formed by integrating metal materials with glass fiber reinforced thermoplastic resin materials, namely metal-glass fiber reinforced thermoplastic resin composite materials (for example, see Patent Documents 1 and 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2018 / 139034

[0007] Patent Document 2: Japanese Patent Application Laid-Open No. 2013-107273 Summary of the Invention

[0008] Problems to be solved by the invention

[0009] However, in the conventional metal-glass fiber reinforced thermoplastic resin composite materials, submicron-level interfacial delamination is easily generated at the interface between the metal material and the glass fiber reinforced thermoplastic resin material as the thermoplastic resin expands and contracts, resulting in a disadvantageous problem of low heat cycle resistance, which constitutes an indicator of the bonding strength between the metal material and the glass fiber reinforced thermoplastic resin material, especially the bonding strength when repeatedly subjected to temperature changes.

[0010] An object of the present invention is to solve the above-mentioned problems and provide a metal-glass fiber reinforced thermoplastic resin composite material having excellent bonding strength and heat cycle resistance between a metal material and a glass fiber reinforced thermoplastic resin material.

[0011] Means for solving problems

[0012] In order to achieve the above-mentioned object, the metal-glass fiber reinforced thermoplastic resin composite material of the present invention is a metal-glass fiber reinforced thermoplastic resin composite material comprising a metal material and a glass fiber reinforced thermoplastic resin material located on at least one surface of the metal material, characterized in that the glass fiber contained in the glass fiber reinforced thermoplastic resin material has a Vickers hardness H in the range of 700 to 800 HV0.2 and an elastic modulus M in the range of 70.0 to 110.0 GPa, and the Vickers hardness H and the elastic modulus M satisfy the following formula (1).

[0013] 849.5≤M 3 / H≤940.5…(1)

[0014] The glass fiber contained in the glass fiber reinforced thermoplastic resin material of the present invention has a Vickers hardness H within the above range and an elastic modulus M within the above range. The above Vickers hardness H and the above elastic modulus M satisfy the conditions of the above formula (1). Therefore, the metal material and the glass fiber reinforced thermoplastic resin material of the metal-glass fiber reinforced thermoplastic resin composite material of the present invention have excellent bonding strength and heat cycle resistance.

[0015] Here, "excellent bonding strength between the metal material and the glass fiber reinforced thermoplastic resin material in the metal-glass fiber reinforced thermoplastic resin composite material" means that the bonding strength between the metal material and the glass fiber reinforced thermoplastic resin material in the metal-glass fiber reinforced thermoplastic resin composite material, as measured by the method described below, is improved by 10.0% or more relative to a benchmark bonding strength, where the benchmark bonding strength is the bonding strength between the metal material and the glass fiber reinforced thermoplastic resin material in the metal-glass fiber reinforced thermoplastic resin composite material obtained under identical conditions except for the use of E-glass fiber. Furthermore, "excellent heat cycle resistance between the metal material and the glass fiber reinforced thermoplastic resin material in the metal-glass fiber reinforced thermoplastic resin composite material" means that the metal-glass fiber reinforced thermoplastic resin composite material does not suffer from interface failure after 100 cycles of the low-temperature resistance test described below.

[0016] The Vickers hardness H and elastic modulus M of the glass fiber contained in the glass fiber reinforced thermoplastic resin material can be measured by the following methods.

[0017] (Vickers hardness H)

[0018] First, the glass fiber reinforced thermoplastic resin material is separated from the metal-glass fiber reinforced thermoplastic resin composite material using a cutter, etc. Then, the glass fiber reinforced thermoplastic resin material is heated in a muffle furnace at 300 to 650° C. for about 0.5 to 24 hours to decompose organic matter.

[0019] Next, the remaining glass fibers were placed in a platinum crucible and held in an electric furnace at 1600°C for 6 hours, while being stirred to melt the glass fibers, thereby producing a homogeneous molten glass. The platinum crucible containing the molten glass was then removed from the furnace and cooled. After removing the molten glass from the platinum crucible, it was heated at a strain removal temperature (660-750°C) for 2 hours to remove strain from the glass, and then cooled to room temperature (20-25°C) over 8 hours to produce a glass block.

[0020] The resulting glass block is then processed into a test piece with a width of 3 mm, a length of 80 mm, and a thickness of 1 mm using a cutting machine, such as a diamond tool and a grinder. Next, a Vickers hardness (HV 0.2) is measured at at least five locations on the surface of the resulting test piece using a Vickers hardness tester (Mitutoyo Co., Ltd., trade name: HM-220) under a load of 0.2 kgf and a loading time of 15 seconds. The Vickers hardness (H) of the glass fiber can be determined by averaging the measured values.

[0021] (Elastic modulus M)

[0022] First, molten glass is obtained in exactly the same manner as the above-mentioned method for measuring Vickers hardness H. Next, the obtained molten glass is poured onto a carbon plate to produce glass chips. The resulting glass chips are then placed into a small cylindrical platinum bushing with a circular nozzle chip at the bottom of the container. The bushing is heated to a predetermined temperature such that the viscosity of the introduced glass chips reaches 1000±150 poise, thereby melting the glass chips and obtaining molten glass.

[0023] The molten glass ejected from the nozzle of the platinum sheath is wound at a predetermined speed using a winder so that the glass fiber diameter is 13±2 μm. The molten glass is then stretched and cooled to solidify, thereby producing a glass fiber having a true circular cross-section. A single fiber (monofilament) is selected between the nozzle of the platinum sheath and the winder, and the monofilament is selected in a state where degradation due to contact and friction is minimized.

[0024] Next, the resulting monofilament was arranged along its long side and bonded to the backing paper, wherein the backing paper had two gripping portions and two auxiliary portions, so that the line connecting the center points of the short sides of the backing paper overlapped and the line connecting the center points of the short sides of the backing paper was bonded to the backing paper to prepare a monofilament test piece. The diameter of the resulting monofilament was then measured using a scanning electron microscope (manufactured by Hitachi, Ltd., trade name: S-3400), and the cross-sectional area of ​​the monofilament was calculated based on the obtained diameter.

[0025] Next, the two pinches of the backing paper were placed on the upper and lower pinches of a tensile testing machine (manufactured by A&D Co., Ltd., trade name: Tabletop Material Testing Machine STB-1225S) with a pinch spacing of 50 mm. The two auxiliary sections of the backing paper were cut away, leaving the pinches connected only by the monofilament. A tensile test was then conducted at a crosshead speed of 5 mm / min. The stresses corresponding to strains ε1 = 0.0005 and ε2 = 0.0025 between the two locations were designated as σ1 and σ2, respectively. The difference in stress (σ2 - σ1) was divided by the difference in strain (ε2 - ε1) to calculate the tensile modulus. Excluding monofilament test pieces that became delaminated during the measurement, the tensile modulus values ​​for n = 15 were averaged to determine the glass fiber modulus M.

[0026] It should be noted that the above-mentioned backing paper has a short side of 25 mm and a long side of 75 mm. In addition, in the center of the interior of the backing paper, there is a cut-out portion with a short side of 15 mm and a long side of 50 mm. The short side and long side of the above-mentioned backing paper are parallel to the short side and long side of the above-mentioned cut-out portion, respectively. A gripping portion of a gripping tool of a tensile testing machine is provided between the short side of the above-mentioned cut-out portion and the short side of the above-mentioned backing paper. In addition, an auxiliary portion for connecting the above-mentioned two gripping portions and supporting them is provided between the long side of the above-mentioned cut-out portion and the long side of the above-mentioned backing paper.

[0027] In addition, in the metal-glass fiber reinforced thermoplastic resin composite material of the present invention, the glass content of the glass fiber reinforced thermoplastic resin material is preferably in the range of 10.0 to 60.0 mass %, which can more reliably ensure that the metal material and the glass fiber reinforced thermoplastic resin material have excellent bonding strength and heat cycle resistance.

[0028] In addition, in the metal-glass fiber reinforced thermoplastic resin composite material of the present invention, in order to ensure excellent bonding strength and heat cycle resistance between the metal material and the glass fiber reinforced thermoplastic resin material, the thermoplastic resin contained in the above-mentioned glass fiber reinforced thermoplastic resin material is preferably a thermoplastic resin selected from the group consisting of polyphenylene sulfide, polyamide, polybutylene terephthalate, and polyaryletherketone, and the above-mentioned metal material is preferably aluminum, aluminum alloy or stainless steel. DETAILED DESCRIPTION

[0029] Next, embodiments of the present invention will be described in more detail.

[0030] The metal-glass fiber reinforced thermoplastic resin composite material of this embodiment is a metal-glass fiber reinforced thermoplastic resin composite material comprising a metal material and a glass fiber reinforced thermoplastic resin material located on at least one surface of the metal material. The glass fiber contained in the glass fiber reinforced thermoplastic resin material has a Vickers hardness H in the range of 700 to 800 HV0.2 and an elastic modulus M in the range of 70.0 to 110.0 GPa. The Vickers hardness H and the elastic modulus M satisfy the following formula (1).

[0031] 849.5≤M 3 / H≤940.5…(1)

[0032] In the metal-glass fiber reinforced thermoplastic resin composite material of this embodiment, the glass fiber contained in the glass fiber reinforced thermoplastic resin material has a Vickers hardness H within the above range and an elastic modulus M within the above range, and the above Vickers hardness H and the above elastic modulus M satisfy the conditions of the above formula (1). As a result, the metal material and the glass fiber reinforced thermoplastic resin material can have excellent bonding strength and heat cycle resistance.

[0033] In the metal-glass fiber-reinforced thermoplastic resin composite material of the present embodiment, if the Vickers hardness H of the glass fibers contained in the glass fiber-reinforced thermoplastic resin material is less than 700 HV0.2, good metal bonding strength and thermal cycle resistance cannot be ensured. If the Vickers hardness H exceeds 800 HV0.2, sufficient productivity cannot be ensured, and glass fiber products cannot be produced. Furthermore, in the metal-glass fiber-reinforced thermoplastic resin composite material of the present invention, if the elastic modulus M of the glass fibers contained in the glass fiber-reinforced thermoplastic resin material is less than 70.0 GPa, excellent metal bonding strength and thermal cycle resistance cannot be ensured. If the elastic modulus M exceeds 110.0 GPa, sufficient productivity cannot be ensured, and glass fiber products cannot be produced.

[0034] In the metal-glass fiber reinforced thermoplastic resin composite material of this embodiment, the Vickers hardness H of the glass fiber contained in the glass fiber reinforced thermoplastic resin material is preferably in the range of 750 to 790 HV0.2, and more preferably in the range of 760 to 780 HV0.2.

[0035] In the metal-glass fiber reinforced thermoplastic resin composite material of this embodiment, the elastic modulus M of the glass fiber contained in the above-mentioned glass fiber reinforced thermoplastic resin material is preferably in the range of 80.0 to 95.0 GPa, the elastic modulus M is more preferably in the range of 85.0 to 90.0 GPa, and the elastic modulus M is further preferably in the range of 86.0 to 89.0 GPa.

[0036] Furthermore, in the metal-glass fiber reinforced thermoplastic resin composite material of the present invention, even if the Vickers hardness H and elastic modulus M of the glass fiber contained in the glass fiber reinforced thermoplastic resin material are within the above ranges, when the value of the above formula (1) is less than 849.5 or exceeds 940.5, sufficient bonding strength and heat cycle resistance cannot be achieved between the metal material and the glass fiber reinforced thermoplastic resin material.

[0037] In the metal-glass fiber reinforced thermoplastic resin composite material of the present invention, the Vickers hardness H and elastic modulus M of the glass fiber contained in the glass fiber reinforced thermoplastic resin material preferably satisfy the following formula (2), and more preferably satisfy the following formula (3).

[0038] 865.0≤M 3 / H≤935.0…(2)

[0039] 880.0≤M 3 / H≤920.0…(3)

[0040] As a preferred form of the glass fiber contained in the glass fiber reinforced thermoplastic resin material of this embodiment before molding, the following chopped strands can be mentioned: glass filaments constituting the glass fiber are preferably 1 to 20,000, more preferably 50 to 10,000, and even more preferably 1,000 to 8,000 (number of strands in a bundle) cut into glass fibers having a length of preferably 1.0 to 100.0 mm, more preferably 1.2 to 51.0 mm, even more preferably 1.5 to 30.0 mm, particularly preferably 2.0 to 15.0 mm, and most preferably 2.3 to 7.8 mm. Here, glass fiber is also referred to as a glass fiber bundle or glass strand. In addition, as forms that the glass fibers contained in the glass fiber reinforced thermoplastic resin material of this embodiment can adopt before molding processing, in addition to chopped strands, there can also be mentioned: for example, coarse yarns in which the number of glass filaments constituting the glass fibers is in the range of 10 to 30,000 without being cut; and cut fibers in which the number of glass filaments constituting the glass fibers is in the range of 1 to 20,000, which are crushed into cut fibers in the range of 0.001 to 0.900 mm in length using a known method such as a ball mill or a Henschel mixer.

[0041] The glass fibers included in the glass fiber reinforced thermoplastic resin material of this embodiment may be coated with an organic material for the purpose of improving the adhesion between the glass fibers and the resin, improving the uniform dispersion of the glass fibers in a mixture of the glass fibers and the resin or an inorganic material, etc. Examples of such organic materials include polyurethane resins, epoxy resins, vinyl acetate resins, acrylic resins, modified polypropylene, especially carboxylic acid-modified polypropylene, copolymers of (poly)carboxylic acids, especially maleic acid, and unsaturated monomers, and silane coupling agents.

[0042] Furthermore, the glass fibers included in the glass fiber-reinforced thermoplastic resin material of this embodiment may be coated with, in addition to being coated with the resin or silane coupling agent, a composition including a lubricant, a surfactant, etc. The composition coats the glass fibers at a ratio of 0.1 to 2.0% by mass, based on the mass of the glass fibers not coated with the composition.

[0043] Here, examples of the silane coupling agent include aminosilane, chlorosilane, epoxysilane, mercaptosilane, vinylsilane, acrylsilane, and cationic silane. These compounds may be used alone or in combination of two or more.

[0044] Examples of the aminosilane include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-N′-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane.

[0045] Examples of the chlorosilane include γ-chloropropyltrimethoxysilane and the like.

[0046] Examples of epoxysilane include γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0047] Examples of the mercaptosilane include γ-mercaptotrimethoxysilane and the like.

[0048] Examples of the vinylsilane include vinyltrimethoxysilane and N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane.

[0049] Examples of acrylic silane include γ-methacryloxypropyltrimethoxysilane and the like.

[0050] Examples of the cationic silane include N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and N-phenyl-3-aminopropyltrimethoxysilane hydrochloride.

[0051] Examples of lubricants include modified silicone oils, animal oils and their hydrogenates, vegetable oils and their hydrogenates, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids and higher saturated alcohols, polyethyleneimine, polyalkylpolyamine alkyl linolenic acid derivatives, fatty acid amides, and quaternary ammonium salts. These lubricants may be used alone or in combination of two or more.

[0052] Examples of animal oils include beef tallow and the like.

[0053] Examples of the vegetable oil include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.

[0054] Examples of animal waxes include beeswax and lanolin.

[0055] Examples of the vegetable wax include candelilla wax and carnauba wax.

[0056] Examples of the mineral wax include paraffin wax and montan wax.

[0057] Examples of the condensation product of a higher saturated fatty acid and a higher saturated alcohol include stearic acid esters such as lauryl stearate.

[0058] Examples of the fatty acid amide include dehydration condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid.

[0059] Examples of the quaternary ammonium salt include alkyltrimethylammonium salts such as lauryltrimethylammonium chloride.

[0060] Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more.

[0061] Examples of the nonionic surfactant include ethylene oxide propylene oxide alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene-polyoxypropylene-block copolymers, alkyl polyoxyethylene-polyoxypropylene-block copolymer ethers, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid monoesters, polyoxyethylene fatty acid diesters, polyoxyethylene sorbitan fatty acid esters, glycerol fatty acid ester ethylene oxide adducts, polyoxyethylene stearyl ethers, hydrogenated castor oil ethylene oxide adducts, alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, glycerol fatty acid esters, polyglycerol fatty acid esters, pentaerythritol fatty acid esters, sorbitol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyol alkyl ethers, fatty acid alkanolamides, acetylene glycols, ethylene oxide adducts of acetylene glycols, and ethylene oxide adducts of acetylene alcohols.

[0062] Examples of the cationic surfactant include alkyldimethylbenzylammonium chloride, alkyltrimethylammonium chloride, alkyldimethylethylammonium ethylsulfate, higher alkylamine acetates, higher alkylamine hydrochlorides, ethylene oxide adducts of higher alkylamines, condensates of higher fatty acids and polyalkylene polyamines, salts of esters of higher fatty acids and alkanolamines, salts of higher fatty acid amides, imidazoline-type cationic surfactants, and alkylpyridinium salts.

[0063] Examples of the anionic surfactant include higher alcohol sulfates, higher alkyl ether sulfates, α-olefin sulfates, alkylbenzenesulfonates, α-olefinsulfonates, reaction products of fatty acid halides and N-methyltaurine, dialkyl sulfosuccinates, higher alcohol phosphates, and phosphates of higher alcohol ethylene oxide adducts.

[0064] Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as alkylaminopropionic acid alkali metal salts, betaine-type amphoteric surfactants such as alkyldimethylbetaine, and imidazoline-type amphoteric surfactants.

[0065] It should be noted that glass fiber is usually formed by bundling multiple glass filaments. However, in the glass fiber reinforced thermoplastic resin material, the above-mentioned bundling is released due to the molding process, and the glass fibers are dispersed in the glass fiber reinforced thermoplastic resin material.

[0066] In the metal-glass fiber-reinforced thermoplastic resin composite material of this embodiment, the glass content of the glass fiber-reinforced thermoplastic resin material is preferably in the range of 10.0 to 60.0 mass%. In the metal-glass fiber-reinforced thermoplastic resin composite material of this embodiment, if the glass content of the glass fiber-reinforced thermoplastic resin material is less than 10.0 mass%, the elastic modulus and strength, which are the mechanical properties of the glass fiber-reinforced thermoplastic resin material, become insufficient, thereby insufficiently reinforcing the metal-glass fiber-reinforced thermoplastic resin composite material. If the glass content of the glass fiber-reinforced thermoplastic resin material exceeds 60.0 mass%, the surface properties of the glass fiber-reinforced thermoplastic resin material deteriorate, making it difficult to achieve sufficient adhesion with the resin-glass fiber-reinforced thermoplastic resin material.

[0067] In the metal-glass fiber reinforced thermoplastic resin composite material of this embodiment, the glass content of the glass fiber reinforced thermoplastic resin material is more preferably 20.0 to 55.0 mass %, further preferably 30.0 to 50.0 mass %, and particularly preferably 30.0 to 40.0 mass %.

[0068] In the metal-glass fiber reinforced thermoplastic resin composite material of this embodiment, the glass content of the above-mentioned glass fiber reinforced thermoplastic resin material can be calculated as follows: the glass fiber reinforced resin material is separated from the metal-glass fiber reinforced thermoplastic resin composite material, and the glass content of the separated glass fiber reinforced resin material is calculated according to JIS K 7052:1999.

[0069] In the metal-glass fiber reinforced thermoplastic resin composite material of this embodiment, the above-mentioned metal material is preferably aluminum, aluminum alloy or stainless steel. As the above-mentioned aluminum, for example, A1050 and A1100 in the Japanese Industrial Standard (JIS) can be cited. As the above-mentioned aluminum alloy, for example, A1200, A2017, A2024, A3003, A3004, A4032, A5005, A5052, A5083, A6061, A6063, A7075 in the Japanese Industrial Standard can be cited. In addition, as the above-mentioned stainless steel, for example, SUS301, SUS304, SUS316, SUS316L in the Japanese Industrial Standard can be cited. In order to greatly improve the bonding strength, the above-mentioned metal material is more preferably stainless steel.

[0070] In the metal-glass fiber reinforced thermoplastic resin composite material of this embodiment, preferably, the entire or a portion of the surface of the metal material in contact with the glass fiber reinforced thermoplastic resin material is roughened by a known method to have irregularities.

[0071] In addition, in the metal-glass fiber reinforced thermoplastic resin composite material of the present embodiment, examples of the thermoplastic resin contained in the glass fiber reinforced thermoplastic resin material include polyethylene, polypropylene, polystyrene, styrene / maleic anhydride resin, styrene / maleimide resin, polyacrylonitrile, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin, chlorinated polyethylene / acrylonitrile / styrene (ACS) resin, acrylonitrile / ethylene / styrene (AES) resin, acrylonitrile / styrene / methyl acrylate (ASA) resin, styrene / acrylonitrile (SAN) resin, methacrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), Polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycarbonate, polyarylene sulfide, polyethersulfone (PES), polyphenylsulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryletherketone, liquid crystal polymer (LCP), fluororesin, polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyamideimide (PAI), polyaminobismaleimide (PABM), thermoplastic polyimide (TPI), polyethylene naphthalate (PEN), ethylene / vinyl acetate (EVA) resin, ionomer (IO) resin, polybutadiene, styrene / butadiene resin, polybutene, polymethylpentene, olefin / vinyl alcohol resin, cyclic olefin resin, cellulose resin, polylactic acid, etc.

[0072] Specifically, examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high molecular weight polyethylene.

[0073] Examples of the polypropylene include isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, and mixtures thereof.

[0074] Examples of the polystyrene include general-purpose polystyrene (GPPS) which is atactic polystyrene having an atactic structure, high impact polystyrene (HIPS) obtained by adding rubber to GPPS, and syndiotactic polystyrene having a syndiotactic structure.

[0075] Examples of the methacrylic resin include polymers obtained by polymerizing one of the following components alone or two or more of the following components: acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and fatty acid vinyl esters.

[0076] Examples of polyvinyl chloride include vinyl chloride homopolymers polymerized by conventionally known methods such as emulsion polymerization, suspension polymerization, microsuspension polymerization, and bulk polymerization, copolymers of vinyl chloride monomers and copolymerizable monomers, and graft copolymers in which vinyl chloride monomers are grafted onto polymers.

[0077] Examples of the polyamide include copolymers obtained by combining one or more of the following components, or mixtures thereof: polycaprolactam (polyamide 6), polyhexamethylene adipamide (polyamide 66), polybutylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 410), polyheptamethylene adipamide (polyamide 56), polypentamethylene sebacamide (polyamide 510), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecanoamide (polyamide 610), and polyoctane diamide (polyamide 611). 2), polydecanediamine adipamide (polyamide 106), polydecanediamine adipamide (polyamide 1010), polydecanediamine dodecane (polyamide 1012), polyundecanamide (polyamide 11), polyundecanamide adipamide (polyamide 116), polydodecaneamide (polyamide 12), polyphenylene adipamide (polyamide XD6), polyphenylene adipamide (polyamide XD10), polym-phenylene adipamide (polyamide MXD6), polyp-phenylene adipamide (polyamide P XD6), polybutylene terephthalamide (polyamide 4T), polypentamethylene terephthalamide (polyamide 5T), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polynonamethylene terephthalamide (polyamide 9T), polydecane terephthalamide (polyamide 10T), polyundecanediamine terephthalamide (polyamide 11T), polydodecane terephthalamide (polyamide 12T), polybutylene isophthalamide (polyamide 4I), polybis(3 The present invention also includes a copolymer or a mixture thereof of one or more of the following components: poly(3-methyl-4-aminohexyl)methane terephthalamide (polyamide PACMT), polybis(3-methyl-4-aminohexyl)methane isophthalamide (polyamide PACMI), polybis(3-methyl-4-aminohexyl)methane dodecanedioamide (polyamide PACM12), and polybis(3-methyl-4-aminohexyl)methane tetradecanedioamide (polyamide PACM14). Due to their low water absorption and excellent dimensional accuracy, the polyamide is preferably a long-chain polyamide having an average number of carbon atoms per nitrogen atom of more than 9 and no more than 30, such as polyamide 11, polyamide 12, polyamide 1010, and polyamide 1012.

[0078] Examples of the polyacetal include homopolymers having oxymethylene units as main repeating units and copolymers mainly composed of oxymethylene units and containing oxyalkylene units having 2 to 8 adjacent carbon atoms in the main chain.

[0079] Examples of polyethylene terephthalate include polymers obtained by polycondensing terephthalic acid or a derivative thereof with ethylene glycol.

[0080] Examples of the polybutylene terephthalate include polymers obtained by polycondensing terephthalic acid or a derivative thereof with 1,4-butanediol.

[0081] Examples of the polytrimethylene terephthalate include polymers obtained by polycondensing terephthalic acid or a derivative thereof with 1,3-propylene glycol.

[0082] Examples of the polycarbonate include polymers obtained by an ester exchange method in which a dihydroxydiaryl compound is reacted with a carbonate such as diphenyl carbonate in a molten state, and polymers obtained by a phosgene method in which a dihydroxydiaryl compound is reacted with phosgene.

[0083] Examples of the polyarylene sulfide include linear polyphenylene sulfide, cross-linked polyphenylene sulfide whose molecular weight is increased by a curing reaction after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.

[0084] Examples of the polyphenylene ether include poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2-phenyl-1,4-phenylene ether), and poly(2-phenyl-2-methyl-6-phenyl-1,4-phenylene ether). 4-phenylene ether), poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), and the like.

[0085] Examples of modified polyphenylene ethers include polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polystyrene, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene copolymers, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / maleic anhydride copolymers, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and polyamides, polymer alloys of poly(2,6-dimethyl-1,4-phenylene) ether and styrene / butadiene / acrylonitrile copolymers, substances in which functional groups such as amino groups, epoxy groups, carboxyl groups, and styryl groups are introduced into the polymer chain terminals of the above polyphenylene ethers, substances in which functional groups such as amino groups, epoxy groups, carboxyl groups, and styryl groups are introduced into the side chains of the polymer chains of the above polyphenylene ethers, and the like.

[0086] Examples of the polyaryletherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK). From the viewpoints of market availability and cost, the polyaryletherketone is preferably polyetheretherketone.

[0087] Examples of liquid crystal polymers (LCPs) include (co)polymers composed of one or more structural units selected from aromatic hydroxycarbonyl units, aromatic dihydroxy units, aromatic dicarbonyl units, aliphatic dihydroxy units, aliphatic dicarbonyl units, etc., which are thermotropic liquid crystal polyesters.

[0088] Examples of the fluororesin include polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene / chlorotrifluoroethylene resin (ECTFE).

[0089] Examples of the ionomer (IO) resin include copolymers of olefins or styrene and unsaturated carboxylic acids, and polymers in which a portion of the carboxyl groups is neutralized with metal ions.

[0090] Examples of the olefin / vinyl alcohol resin include ethylene / vinyl alcohol copolymers, propylene / vinyl alcohol copolymers, ethylene / vinyl acetate copolymer saponification products, and propylene / vinyl acetate copolymer saponification products.

[0091] Examples of the cyclic olefin resin include monocyclic compounds such as cyclohexene, polycyclic compounds such as tetracyclopentadiene, and polymers of cyclic olefin monomers.

[0092] Examples of the polylactic acid include poly-L-lactic acid which is an L-isomer homopolymer, poly-D-lactic acid which is a D-isomer homopolymer, and stereocomplex polylactic acid which is a mixture thereof.

[0093] Examples of the cellulose resin include methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, cellulose acetate, cellulose propionate, and cellulose butyrate.

[0094] In the metal-glass fiber-reinforced thermoplastic resin composite material of this embodiment, the thermoplastic resin contained in the glass fiber-reinforced thermoplastic resin material is preferably a thermoplastic resin selected from the group consisting of polyphenylene sulfide, polyamide, polybutylene terephthalate, and polyaryletherketone from the perspectives of mechanical properties, heat resistance, dielectric properties, chemical resistance, and productivity (molding temperature and fluidity). From the perspective of ease of use, the thermoplastic resin is preferably a thermoplastic resin selected from the group consisting of polyphenylene sulfide, polyamide, and polybutylene terephthalate. From the perspective of improved bonding strength, the thermoplastic resin is more preferably polybutylene terephthalate or polyphenylene sulfide, and particularly preferably polyphenylene sulfide. Furthermore, from the perspective of significantly improved bonding strength and high bonding strength, the thermoplastic resin is particularly preferably polybutylene terephthalate.

[0095] In the metal-glass fiber-reinforced thermoplastic resin composite material of this embodiment, the glass fiber-reinforced thermoplastic resin material may also contain ingredients other than the glass fiber and the thermoplastic resin, within the scope that does not hinder the purpose of the present invention. Examples of such ingredients include: reinforcing fibers other than the glass fibers, such as carbon fibers and metal fibers; fillers other than the glass fibers, such as glass powder, talc, and mica; flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, flow improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments, and the like. Furthermore, in the metal-glass fiber-reinforced thermoplastic resin composite material of this embodiment, the glass fiber-reinforced thermoplastic resin material may contain a total of 0 to 40% by mass of the above ingredients relative to the total amount of the glass fiber-reinforced thermoplastic resin material.

[0096] The metal-glass fiber reinforced thermoplastic resin composite material of this embodiment can be obtained, for example, by placing the above-mentioned metal material in a mold of an injection molding machine, adding resin pellets having a specified glass content obtained by kneading the above-mentioned glass fiber and the above-mentioned thermoplastic resin using a biaxial kneader into the injection molding machine, and performing insert molding to obtain the metal-glass fiber reinforced thermoplastic resin composite material.

[0097] In the metal-glass fiber-reinforced thermoplastic resin composite material of this embodiment, the glass fiber-reinforced thermoplastic resin material may be located on, for example, the upper surface, lower surface, or both surfaces of the thin plate-shaped metal material. Furthermore, the glass fiber-reinforced thermoplastic resin composite material may be disposed in contact with the entire surface of each surface of the metal material, or may be disposed in contact with only a portion of each surface of the metal material.

[0098] Examples of uses for the metal-glass fiber reinforced thermoplastic resin composite material of this embodiment include: accessories such as housings and frames of portable electronic devices represented by smartphones, automotive electrical components such as battery tray covers, sensors, and coil bobbins, accessories for electronic and electrical equipment other than portable electronic devices, and electrical connection terminal accessories.

[0099] Next, examples of the present invention and comparative examples are shown.

[0100] Example

[0101] (Example 1 and Comparative Examples 1 to 4)

[0102] Resin pellets having a glass content of 40.0% by mass were prepared by kneading glass fibers (chopped strands) having the Vickers hardness H and glass fiber elastic modulus shown in Table 1, a fiber diameter of 9 μm, and a cut length of 3 mm, with polyphenylene sulfide (trade name: FORTRON KPSW-203A, manufactured by KUREHA Co., Ltd., referred to as "PPS" in the table) using a twin-screw kneader (manufactured by Shibaura Machine Co., Ltd., trade name: TEM-26SS) at a screw speed of 100 rpm to produce the resin pellets. It should be noted that the glass fiber used in Comparative Example 1 was E-glass fiber.

[0103] Next, a test piece made of aluminum (JIS A1050, indicated as "Al" in the table) with a long side of 35 mm, a short side of 13 mm, and a thickness of 2 mm was roughened using #200 sandpaper and then immersed in ethanol to clean the surface, thereby obtaining a surface-roughened aluminum test piece.

[0104] Next, the resulting surface-roughened aluminum test piece was placed in the mold of an injection molding machine (NEX80, manufactured by Nissei Plastics Co., Ltd.). The resin pellets were then placed into the hopper of the injection molding machine heated to 310°C and insert molded. This yielded the metal-glass fiber-reinforced thermoplastic resin composite materials of Example 1 and Comparative Examples 1 to 4.

[0105] The bonding strength and heat cycle resistance of the metal-glass fiber reinforced thermoplastic resin composite materials of Example 1 and Comparative Examples 1 to 4 obtained above were measured or evaluated by the following methods.

[0106] [Metal-Glass Fiber Reinforced Thermoplastic Resin Bond Strength]

[0107] The metal-glass fiber-reinforced thermoplastic resin composite was stretched at a rate of 5 mm / min using a tensile testing machine (Shimadzu Corporation, trade name: Autograph AG-5000B) to measure its breaking strength. The bond strength was calculated by dividing the breaking strength by the bonded area.

[0108] [Heat cycle resistance of metal-glass fiber reinforced thermoplastic resin materials]

[0109] The heat cycle resistance test consisted of a cycle consisting of a metal-glass fiber-reinforced thermoplastic resin composite material, which was left at -25°C for 1 hour, then heated to 150°C, left at 150°C for 30 minutes, and then cooled to -25°C. The test evaluated the presence or absence of interface failure. After 100 cycles, if interface failure occurred, the test was rated "×"; if no interface failure occurred, the test was rated "○."

[0110] (Table 1)

[0111]

[0112] (Example 2 and Comparative Examples 5 to 8)

[0113] The metal-glass fiber-reinforced thermoplastic resin composite materials of Example 2 and Comparative Examples 5 to 8 were obtained in the same manner as in Example 1 and Comparative Examples 1 to 4, except that a stainless steel test piece (JIS SUS304, indicated as "SUS" in the table) with a long side of 35 mm, a short side of 13 mm, and a thickness of 2 mm was used instead of the aluminum test piece. It should be noted that the glass fiber used in Comparative Example 5 was E-glass fiber.

[0114] The bonding strength and heat cycle resistance of the metal-glass fiber reinforced thermoplastic resin composite materials of Example 2 and Comparative Examples 5 to 8 obtained above were measured or evaluated in exactly the same manner as in Example 1. The results are shown in Table 2.

[0115] (Table 2)

[0116]

[0117] (Example 3 and Comparative Examples 9 to 12)

[0118] Metal-glass fiber-reinforced thermoplastic resin composite materials of Example 3 and Comparative Examples 9 to 12 were obtained in the same manner as in Example 1 and Comparative Examples 1 to 4, except that polyamide (manufactured by Ube Industries, Ltd., trade name: UBE 1015B, indicated as "PA" in the tables) was used instead of polyphenylene sulfide. It should be noted that the glass fiber used in Comparative Example 9 was E-glass fiber.

[0119] The bonding strength and heat cycle resistance of the metal-glass fiber reinforced thermoplastic resin composite materials of Example 3 and Comparative Examples 9 to 12 obtained above were measured or evaluated in exactly the same manner as in Example 1. The results are shown in Table 3.

[0120] (Table 3)

[0121]

[0122] (Example 4 and Comparative Examples 13 to 16)

[0123] Metal-glass fiber-reinforced thermoplastic resin composite materials of Example 4 and Comparative Examples 13 to 16 were obtained in the same manner as in Example 2 and Comparative Examples 5 to 8, except that polyamide (manufactured by Ube Industries, Ltd., trade name: UBE 1015B) was used instead of polyphenylene sulfide. It should be noted that the glass fiber used in Comparative Example 13 was E-glass fiber.

[0124] The bonding strength and heat cycle resistance of the metal-glass fiber reinforced thermoplastic resin composite materials of Example 4 and Comparative Examples 13 to 16 obtained above were measured or evaluated in exactly the same manner as in Example 1. The results are shown in Table 4.

[0125] (Table 4)

[0126]

[0127] (Example 5 and Comparative Examples 17 to 20)

[0128] Metal-glass fiber-reinforced thermoplastic resin composite materials of Example 5 and Comparative Examples 17 to 20 were obtained in the same manner as in Example 1 and Comparative Examples 1 to 4, except that polybutylene terephthalate (manufactured by Polyplastics Corporation, trade name: DURANEX 2000, indicated as "PBT" in the tables) was used instead of polyphenylene sulfide. The glass fiber used in Comparative Example 17 was E-glass fiber.

[0129] The bonding strength and heat cycle resistance of the metal-glass fiber reinforced thermoplastic resin composite materials of Example 5 and Comparative Examples 17 to 20 obtained above were measured or evaluated in exactly the same manner as in Example 1. The results are shown in Table 5.

[0130] (Table 5)

[0131]

[0132] (Example 6 and Comparative Examples 21 to 24)

[0133] Metal-glass fiber-reinforced thermoplastic resin composite materials of Example 6 and Comparative Examples 21 to 24 were obtained in the same manner as in Example 2 and Comparative Examples 5 to 8, except that polybutylene terephthalate (manufactured by Polyplastics Corporation, trade name: DURANEX 2000) was used instead of polyphenylene sulfide. The glass fiber used in Comparative Example 21 was E-glass fiber.

[0134] The bonding strength and heat cycle resistance of the metal-glass fiber reinforced thermoplastic resin composite materials of Example 6 and Comparative Examples 21 to 24 obtained above were measured or evaluated in exactly the same manner as in Example 1. The results are shown in Table 6.

[0135] (Table 6)

[0136]

[0137] (Example 7 and Comparative Examples 25 to 28)

[0138] Metal-glass fiber-reinforced thermoplastic resin composite materials of Example 7 and Comparative Examples 25 to 28 were obtained in the same manner as in Example 5 and Comparative Examples 17 to 20, except that resin particles having a glass content of 20% by mass were used. It should be noted that the glass fiber used in Comparative Example 25 was E-glass fiber.

[0139] The bonding strength and heat cycle resistance of the metal-glass fiber reinforced thermoplastic resin composite materials of Example 7 and Comparative Examples 25 to 28 obtained above were measured or evaluated in exactly the same manner as in Example 1. The results are shown in Table 7.

[0140] (Table 7)

[0141]

[0142] As apparent from Tables 1 to 6, the metal-glass fiber reinforced thermoplastic resin composite material can have excellent bonding strength and excellent heat cycle resistance between the metal material and the glass fiber reinforced thermoplastic resin material. The metal-glass fiber reinforced thermoplastic resin composite material includes a metal material and a glass fiber reinforced thermoplastic resin material located on at least one surface of the metal material. The glass fiber contained in the glass fiber reinforced thermoplastic resin material has a Vickers hardness H in the range of 700 to 800 HV0.2 and an elastic modulus M in the range of 70.0 to 110.0 GPa. The Vickers hardness H and the elastic modulus M satisfy the above formula (1).

[0143] In addition, as is apparent from Table 7, the metal-glass fiber reinforced thermoplastic resin composite material can have excellent bonding strength and excellent heat cycle resistance between the metal material and the glass fiber reinforced thermoplastic resin material. The metal-glass fiber reinforced thermoplastic resin composite material includes a metal material and a glass fiber reinforced thermoplastic resin material located on at least one surface of the metal material. The glass fiber contained in the glass fiber reinforced thermoplastic resin material has a Vickers hardness H in the range of 700 to 800 HV0.2, an elastic modulus M in the range of 70.0 to 110.0 GPa, and a glass content of 20 mass%. The Vickers hardness H and the elastic modulus M satisfy the above formula (1).

Claims

1. A metal-glass fiber reinforced thermoplastic resin composite material comprising a metal material and a glass fiber reinforced thermoplastic resin material located on at least one surface of the metal material. The metal-glass fiber reinforced thermoplastic resin composite material is characterized in that the glass fiber contained in the glass fiber reinforced thermoplastic resin material has a Vickers hardness H in the range of 700 to 800 HV0.2 and an elastic modulus M in the range of 70.0 to 110.0 GPa. The glass fibers are dispersed in the glass fiber reinforced thermoplastic resin material in the form of glass filaments. The Vickers hardness H and the elastic modulus M satisfy the following formula (1): 849.5≤M 3 / H≤940.5…(1)。 2. The metal-glass fiber reinforced thermoplastic resin composite material according to claim 1, characterized in that: The glass content of the glass fiber reinforced thermoplastic resin material is in the range of 10.0 to 60.0% by mass.

3. The metal-glass fiber reinforced thermoplastic resin composite material according to claim 1, characterized in that: The thermoplastic resin contained in the glass fiber reinforced thermoplastic resin material is a thermoplastic resin selected from the group consisting of polyphenylene sulfide, polyamide, polybutylene terephthalate, and polyaryletherketone.

4. The metal-glass fiber reinforced thermoplastic resin composite material according to any one of claims 1 to 3, characterized in that: The metal material is aluminum, aluminum alloy or stainless steel.

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