WO2020071421A1 - 樹脂成形体 - Google Patents
樹脂成形体Info
- Publication number
- WO2020071421A1 WO2020071421A1 PCT/JP2019/038898 JP2019038898W WO2020071421A1 WO 2020071421 A1 WO2020071421 A1 WO 2020071421A1 JP 2019038898 W JP2019038898 W JP 2019038898W WO 2020071421 A1 WO2020071421 A1 WO 2020071421A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin molded
- resin
- mass
- component
- molded body
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/041—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with metal fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
- H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
- H01M50/222—Inorganic material
- H01M50/224—Metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
- H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
- H01M50/227—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
- H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
- H01M50/229—Composite material consisting of a mixture of organic and inorganic materials
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
- H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/249—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for aircraft or vehicles, e.g. cars or trains
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/249928—Fiber embedded in a ceramic, glass, or carbon matrix
- Y10T428/249929—Fibers are aligned substantially parallel
Definitions
- the present invention relates to a resin molded article that can be used as a battery module housing component or a peripheral component of a battery-type electric transport device such as an electric vehicle or an electric motorcycle.
- a rechargeable energy storage system such as a battery mounted on a battery-powered electric transport device such as an electric vehicle (EV) or a plug-in hybrid vehicle (PHV) includes a conventional vehicle-mounted component.
- EV electric vehicle
- PSV plug-in hybrid vehicle
- Higher flame retardancy and self-extinguishing properties than resin parts for automobiles are required. For example, it is necessary to satisfy laws and regulations on electrical safety such as European ECE-R100.
- Japanese Patent Application Laid-Open No. 2014-133808 describes a resin molded product relating to a charger connector for an electric vehicle, a holder for a battery capacitor, a housing for a battery capacitor, and a housing for a charging stand for an electric vehicle. In addition, it has tracking resistance for ensuring safety against ignition of an electric load.
- the flame retardant uses a halogen-based flame retardant.
- An object of the present invention is to provide, in one aspect, a resin molded body having flame retardancy that satisfies a criterion for being mountable on a battery-type electric transport device, further having good mechanical strength, and having electromagnetic wave shielding properties. I do.
- the present invention provides, in one embodiment, a resin molded product obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, and (C) a metal fiber, Component (A) wherein the resin molded product contains (B) 15 to 30% by mass of a flame retardant, (C) 2.5 to 7.5% by mass of a metal fiber, and the balance is 100% by mass in total.
- the resin molded product has a combustion test result determined by UL94 V test method of V-0 or V-1 in a test piece having a thickness of 1.5 mm, and satisfies the following requirements (I) to (IV). I will provide a.
- the resin molded body has a thickness of 1.5 to 8.0 mm.
- the resin molded article extinguishes itself within 5 minutes after the end of the combustion test according to the following combustion test E method.
- the resin molded body has no holes in the molded body after the combustion test according to the following combustion test E method.
- the resin molded body has a value in which the electromagnetic wave shielding property by the KEC method electric field exceeds 30 dB in a frequency range of 1 to 100 MHz.
- Combustion test E method A flat plate (150 ⁇ 150 ⁇ 2.0 mm) made of the above molded product is used. Using a flame having a length of 200 mm, an indirect flame is applied from above the flat plate to the center of the flat plate for 130 seconds. The distance from the flame contact position of the flat plate to the burner opening was 150 mm.
- the present invention is a resin molded product obtained from a resin composition containing (A) a thermoplastic resin, (B) a flame retardant, (C) a metal fiber, and (D) a glass fiber.
- the resin molded product contains (B) 15 to 30% by mass of a flame retardant, (C) 2.5 to 7.5% by mass of a metal fiber, and (D) 5 to 50% by mass of a glass fiber, and the remainder.
- the resin molded product has a combustion test result determined by UL94 V test method of V-0 or V-1 in a test piece having a thickness of 1.5 mm, and satisfies the following requirements (I) to (IV). I will provide a.
- the resin molded body has a thickness of 1.5 to 8.0 mm.
- the resin molded article extinguishes itself within 5 minutes after the end of the combustion test according to the following combustion test E method.
- the resin molded body has no holes in the molded body after the combustion test according to the following combustion test E method.
- the resin molded body has a value in which the electromagnetic wave shielding property by the KEC method electric field exceeds 30 dB in a frequency range of 1 to 100 MHz.
- Combustion test E method A flat plate (150 ⁇ 150 ⁇ 2.0 mm) made of the above molded product is used. Using a flame having a length of 200 mm, an indirect flame is applied from above the flat plate to the center of the flat plate for 130 seconds. The distance from the flame contact position of the flat plate to the burner opening was 150 mm.
- the present invention provides (A) a thermoplastic resin, (B) a flame retardant, (C) a metal fiber, (D) a glass fiber, and (E) magnesium bicarbonate, zinc oxide, and titanium oxide.
- a resin molded article obtained from a resin composition containing at least one carbonization accelerator selected from magnesium oxide and silicon oxide, In the molded product, (B) 15 to 30% by mass of a flame retardant, (C) 2.5 to 7.5% by mass of metal fiber, (D) 5 to 50% by mass of glass fiber, and (E) carbonized Component (A) containing 0.7 to 5.0% by mass of an accelerator, with the balance being 100% by mass in total.
- the resin molded product has a burning test result determined by a UL94 V test method of V-0 or V-1 in a test piece having a thickness of 1.5 mm, and satisfies the following requirements (I) to (IV): I will provide a.
- the resin molded body has a thickness of 1.5 to 8.0 mm.
- the resin molded article extinguishes itself within 5 minutes after the end of the combustion test according to the following combustion test E method.
- III The resin molded body has no holes in the molded body after the combustion test according to the following combustion test E method.
- the resin molded body has a value in which the electromagnetic wave shielding property by the KEC method electric field exceeds 30 dB in a frequency range of 1 to 100 MHz.
- Combustion test E method A flat plate (150 ⁇ 150 ⁇ 2.0 mm) made of the above molded product is used. Using a flame having a length of 200 mm, an indirect flame is applied from above the flat plate to the center of the flat plate for 130 seconds. The distance from the flame contact position of the flat plate to the burner opening was 150 mm.
- the resin molded article according to the example of the present invention has not only the self-extinguishing property showing the fire convergence performance in the event of a fire accident, but also the flame retardancy that satisfies the criteria (e.g., ECE-R100) that can be mounted on battery-powered electric transport equipment. In addition, it has good mechanical strength and high electromagnetic wave shielding properties.
- thermoplastic resin As the thermoplastic resin of the component (A), for example, a polyolefin-based resin may be used. Some examples include polyethylene based resins (such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE, ULDPE)), polypropylene based resins, methyl ⁇ -C2-20 chain olefin resins such as pentene resins, cyclic olefin resins and the like can be used. These polyolefin resins may be used alone or in combination of two or more. In one embodiment of the present invention, a polypropylene resin is particularly preferably used.
- polyethylene based resins such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE, ULDPE)
- polypropylene based resins methyl ⁇ -C2-20 chain olefin resins such as pen
- the polypropylene resin may be a homopolymer of propylene or a copolymer of propylene and another copolymerizable monomer.
- copolymerizable monomers include olefin-based monomers (eg, ⁇ -C2-20 chain olefins such as ethylene, 1-butene, isobutene, 1-pentene, and 4-methyl-1-pentene).
- polypropylene resin in addition to homopolypropylene which is a homopolymer, as a copolymer, for example, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene And propylene- ⁇ 2-20 chain olefin copolymers having a propylene content of 80% by mass or more, such as -ethylene-butene-1 copolymers (random copolymers, block copolymers, etc.).
- a copolymer for example, propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene And propylene- ⁇ 2-20 chain olefin copolymers having a propylene content of 80% by mass or more, such as -ethylene-butene-1 copolymers (random copolymers, block copolymers, etc.).
- polypropylene-based resins in a preferred embodiment of the present invention, homopolypropylene and propylene- ⁇ 2 to 6-chain olefin copolymers (random copolymers, block copolymers, etc.) are used. In one embodiment, it is a homopolypropylene or a propylene-ethylene copolymer (random copolymer, block copolymer). These polypropylene resins may be used alone or in combination of two or more.
- the flame retardant of the component (B) is a phosphorus-based flame retardant from the viewpoint of self-extinguishing properties after a combustion test and suppression of pore opening of a molded article. It may be B-1) an organic phosphoric acid compound or (B-2) an organic phosphate compound, or a mixture thereof, and does not contain a halogen atom.
- Examples of the organic phosphoric acid compound include phosphoric acid, melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, melamine phosphate and the like. Among these, melamine polyphosphate is preferable, and melamine pyrophosphate is preferable. Particularly preferred.
- organic phosphate compound examples include piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate, and the like.
- piperazine polyphosphate is used.
- it is piperazine pyrophosphate.
- the mass ratio of the component (B-1) to the component (B-2) is preferably one aspect of the present invention. 1:99 to 99: 1, in another preferred embodiment of the invention from 10:90 to 90:10, and in yet another preferred embodiment of the invention from 30:70 to 70:30.
- the mass ratio is in the range of 1:99 to 99: 1, the flame retardant effect is good.
- component (B) commercially available products include ADK STAB FP-2100JC, FP-2200S, and FP-2500S manufactured by ADEKA Corporation.
- the component (B) has a mean particle size of 40 ⁇ m or less in a preferred embodiment of the present invention, and can have a mean particle size of 10 ⁇ m or less in another preferred embodiment of the present invention from the viewpoint of flame retardancy.
- the average particle size is 40 ⁇ m or less, the dispersibility of the component (A) in the thermoplastic resin is good, high flame retardancy can be obtained, and the mechanical strength of the resin molded product is also good.
- the flame retardant of the component (B) may contain a conventionally known flame retardant aid, a foaming agent, another non-halogen flame retardant, or the like, if necessary, as long as the object of the present invention is not impaired.
- the flame retardant of the component (B) may contain a carbonization accelerator corresponding to the component (E) described below.
- the flame retardant aid may be selected from condensates of pentaerythritol dimer or more and esters thereof in a preferred embodiment of the present invention, and pentaerythritol and esters thereof in another preferred embodiment of the present invention. It may be one or more selected from dipentaerythritol and its ester, and tripentaerythritol and its ester.
- the flame retardant aid contains the above-mentioned condensate of pentaerythritol or the like as a main component (in a preferred embodiment of the present invention, 80% by mass or more), and the remainder can contain other flame retardant aids.
- flame-retardant aids include, for example, polyols such as pentaerythritol, cellulose, maltose, glucose, arabinose, ethylene glycol, propylene glycol, polyethylene glycol, ethylene-vinyl alcohol copolymer; or these polyol components and carboxylic acid.
- polyols such as pentaerythritol, cellulose, maltose, glucose, arabinose, ethylene glycol, propylene glycol, polyethylene glycol, ethylene-vinyl alcohol copolymer; or these polyol components and carboxylic acid.
- isocyanuric acid tris (2-hydroxy Triazine derivatives such as ethyl) isocyanuric acid, tris (hydroxymethyl) isocyanuric acid, tris (3-hydroxypropyl) isocyanurate and tris (4-hydroxyphenyl) isocyanurate.
- the blowing agent is melamine, a melamine formaldehyde resin, a methylamine melamine having 4 to 9 carbon atoms, a melamine derivative such as melamine cyanurate, urea, thiourea, (thio) urea-formaldehyde resin.
- urea derivatives having 2 to 5 carbon atoms such as methylol (thio) urea, guanamines such as benzoguanamine, phenylguanamine, acetoguanamine, succinylguanamine, reaction products of guanamines with formaldehyde, dicyandiamide, guanidine and guanidine sulfamate and the like. And those selected from the nitrogen-containing compounds described above.
- phosphate ester flame retardants include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o- or p-phenylphenyl) phosphate, trinaphthyl phosphate, cresyldiphenyl Phosphate, xylenyldiphenylphosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenylphosphate, o-phenylphenyldicresylphosphate, tris (2,6-dimethylphenyl) phosphate, tetraphenyl-m-
- fatty acid / aromatic phosphate examples include diphenyl (2-ethylhexyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, Mention may be made of orthophosphates such as ethyl pyrocatechol phosphate and mixtures thereof.
- the flame retardant auxiliary may be used alone or in combination in the flame retardant of the component (B).
- Addition of a flame retardant aid can reduce the amount of the flame retardant, or can provide flame retardancy that cannot be obtained with the flame retardant alone, so use it appropriately according to the type and application of the resin in which the flame retardant is blended. be able to.
- the particle size, melting point, viscosity and the like of the flame retardant auxiliary can be selected so as to be excellent in the flame retarding effect and the powder characteristics.
- the compounding amount of the flame retardant auxiliary is, for example, 10 to 60 parts by mass based on 100 parts by mass of the total content of (B-1) and (B-2). In another preferred embodiment of the present invention, the amount is 15 to 50 parts by mass, and in still another preferred embodiment of the present invention, the amount is 15 to 45 parts by mass.
- the molded article has good mechanical strength, does not have stickiness on the surface, and further has a strong carbonized layer acting to improve the flame retardancy, thereby improving the flame retardancy.
- the resin composition may contain a resin mixture containing the flame retardant of the component (B), and the resin composition contains the flame retardant of the component (B) in the resin mixture.
- the content ratio of the total content of -1) and (B-2) is 50 to 80% by mass in a preferred embodiment of the present invention, and 55 to 75% by mass in another preferred embodiment of the present invention. In still another preferred embodiment of the present invention, the content is 60 to 70% by mass.
- the resin mixture may contain the thermoplastic resin as the component (A) as the balance of the content. Furthermore, the resin mixture may contain a conventionally known antioxidant and a lubricant, if necessary, as long as the object of the present invention is not impaired.
- the thermoplastic resin as the component (A) is specifically a polypropylene resin. In another preferred embodiment of the present invention, a homopolypropylene or a propylene-ethylene copolymer (random copolymer) is used. Unified, block copolymer).
- antioxidants examples include phosphorus-based antioxidants, sulfur-based antioxidants, and phenol-based antioxidants (for example, phosphite-based antioxidants and thioether-based antioxidants) which are known as antioxidants for resins. JP-A 7-76640, paragraphs 0015 to 0025, and allyl phosphites and alkyl phosphites such as tris (2,4-di-t-butylphenyl) phosphite and tris isodecyl phosphite. And amine-based antioxidants. Examples of commercially available products include “Irganox1010” manufactured by BASF Japan Co., Ltd. and “ADK STAB PEP36” manufactured by ADEKA Corporation.
- lubricant examples include conventionally known lubricants, for example, lipids, waxes, silicone resins, and the like, for example, those selected from those described in paragraphs 0068 to 0073 of JP-A-2009-167270. Can be mentioned.
- lubricants for example, lipids, waxes, silicone resins, and the like, for example, those selected from those described in paragraphs 0068 to 0073 of JP-A-2009-167270.
- Alflow H-50S manufactured by NOF Corporation can be exemplified.
- the component (C) is selected from, for example, stainless steel (SUS) fiber, copper fiber, silver fiber, gold fiber, aluminum fiber, and brass fiber as the metal fiber. In one preferred embodiment of the present invention, it may be a stainless steel fiber.
- the component (C) melts the resin component containing the thermoplastic resin of the component (A) into the metal fiber bundle in which the metal fibers are bundled in the length direction, and becomes necessary. Accordingly, a resin-attached metal fiber bundle obtained by attaching the component (B) of the flame retardant in a dispersed state and then integrating the resultant into a predetermined length may be used.
- the fiber diameter of the metal fiber of the component (C) is 5 to 20 ⁇ m in a preferred embodiment of the present invention, 7 to 16 ⁇ m in another preferred embodiment of the present invention, and in still another preferred embodiment of the present invention. It is 10 to 13 ⁇ m, and it may be a long fiber or a short fiber.
- the metal fiber of the component (C) when the metal fiber of the component (C) is in the form of the resin-attached metal woven fiber bundle, the metal fiber in the resin-attached metal woven fiber bundle is the component (C), and the resin component is (A) It is included in the component.
- the resin-metal-attached fiber bundle referred to here is impregnated (impregnated) with the resin up to the central portion of the metal fiber bundle depending on the attached state, so that the fiber between the central portions of the fiber bundle is formed.
- Resin-filled metal fiber bundle hereinafter referred to as “resin-impregnated metal fiber bundle”
- resin-reinforced fiber bundle only surface covered with resin (“resin surface-coated metal fiber bundle”);
- metal surface-coated metal fiber bundle The surface of the fiber bundle is covered with resin, the resin is impregnated only in the vicinity of the surface, and the resin does not penetrate to the center)
- metal fiber bundle partially impregnated with resin "resin-impregnated metal fiber bundle partially impregnated with resin”.
- the resin-attached metal fiber bundle can be manufactured by a well-known manufacturing method described in paragraph No. 0043 of Japanese Patent No. 5959183, for example.
- the number of metal fibers in the metal fiber bundle can be adjusted, for example, from the range of 100 to 30,000.
- the content of the metal fibers in the resin-attached metal fiber bundle is 20 to 70% by mass in a preferable aspect of the present invention based on 100% by mass of the resin-attached metal fiber bundle. In another preferred embodiment of the present invention, it is 30 to 60% by mass, and in still another preferred embodiment of the present invention, it is 40 to 50% by mass.
- the balance may be a resin component containing the thermoplastic resin of the component (A), and the thermoplastic resin of the component (A) is a polypropylene resin in a preferred embodiment of the present invention, and is another preferred embodiment of the present invention. Are homopolypropylene and propylene-ethylene copolymers (random copolymers and block copolymers).
- the resin component containing the thermoplastic resin as the component (A) may contain a resin additive such as a stabilizer, but does not contain a flame retardant such as the component (B).
- the length of the resin-attached metal fiber bundle (that is, the length of the metal fiber of the component (C)) is 1 to 15 mm in a preferred embodiment of the present invention. Is 2 to 10 mm in one preferred embodiment of the present invention, 3 to 7 mm in still another preferred embodiment of the present invention, and 5 to 7 mm in still another preferred embodiment of the present invention.
- the diameter of the resin-attached metal fiber bundle is not particularly limited, but can be, for example, in the range of 0.5 to 5 mm.
- the resin composition can contain glass fiber as the component (D).
- the component (D) may be a resin mixture containing glass fibers, and the content ratio of glass fibers in 100% by mass of the resin mixture is 10 to 70% by mass in a preferred embodiment of the present invention. In another preferred embodiment of the present invention, the content is 20 to 65% by mass, and in still another preferred embodiment of the present invention, the content is 30 to 60% by mass.
- the balance may be a resin component containing the thermoplastic resin of the component (A), and the thermoplastic resin of the component (A) is a polypropylene resin in a preferred embodiment of the present invention, and is a polypropylene resin in another preferred embodiment of the present invention. Homopolypropylene and propylene-ethylene copolymer (random copolymer, block copolymer).
- the glass fiber of the component (D) is a resin mixture containing the component (A)
- the glass fiber in the resin mixture is the component (C)
- the resin component is included in the component (A).
- the fiber diameter of the glass fiber of the component (D) is 9 to 20 ⁇ m in a preferred embodiment of the present invention, 10 to 17 ⁇ m in another preferred embodiment of the present invention, and in still another preferred embodiment of the present invention. It is 13 to 17 ⁇ m, and it may be a long fiber or a short fiber.
- the glass fiber of the component (D) is a long fiber
- a resin component containing the thermoplastic resin of the component (A) is melted in a glass fiber bundle bundled in a state where the glass fibers are aligned in the longitudinal direction.
- a resin-attached glass long fiber bundle obtained by cutting into a predetermined length after being adhered and integrated with each other may be used.
- the resin component containing the thermoplastic resin as the component (A) may contain a resin additive such as a stabilizer, but does not contain a flame retardant such as the component (B).
- the glass fiber of the component (D) is in the form of a resin-attached glass long fiber bundle
- the glass fiber in the resin-attached glass long fiber bundle is the component (D), and the resin component is included in the component (A). .
- the resin-attached glass long fiber bundle referred to here is “resin-impregnated glass long fiber bundle” that is distinguished by the adhesion state, as in the case described in the above [(C) Metal fiber]; Bundle ";” a bundle of glass long fibers impregnated with resin ", and” a bundle of long fibers of glass impregnated with resin "may be preferably used.
- the number of glass fibers in the glass long fiber bundle is adjusted, for example, in the range of 500 to 10000, and is manufactured in accordance with the “method of manufacturing resin-attached metal fiber bundle” described in [(C) Metal Fiber]. can do.
- the length of the resin-attached glass long fiber bundle (that is, the length of the glass fiber of the component (D)) is 5 to 50 mm in a preferred embodiment of the present invention. In another preferred embodiment, it is 7 to 25 mm, and in still another preferred embodiment of the present invention, it is 9 to 15 mm.
- the diameter of the resin-attached fiber bundle is not particularly limited, but may be, for example, in the range of 0.5 to 5 mm.
- the glass fiber of the component (D) is a short fiber
- the glass fiber is a short glass fiber having a length range of 1 to 4 mm. In one embodiment, it is a short glass fiber of 2-3 mm.
- the short glass fiber may be, for example, a chopped strand or the like, or may be a surface-treated fiber.
- the glass fiber of the component (D) when the glass fiber of the component (D) is a short fiber, a resin mixture in which the glass short fiber is dispersed in a resin component containing a thermoplastic resin of the component (A) is used.
- the resin component may include a resin additive such as a stabilizer and a flame retardant of the component (B).
- the above long fiber (resin-attached glass long fiber bundle) and short glass fiber can be used in combination.
- the component (D) may be short glass fibers from the viewpoint of electromagnetic wave shielding.
- short glass fibers the electromagnetic wave shielding properties of the molded article containing the resin composition of the present invention can be enhanced without hindering contact between metal fibers.
- examples of the carbonization promoter include organometallic complex compounds such as ferrocene, cobalt hydroxide, magnesium hydroxide, metal hydroxides such as aluminum hydroxide, magnesium borate, and magnesium magnesium borate.
- the carbonization accelerator is at least one selected from, for example, magnesium bicarbonate, zinc oxide, titanium oxide, magnesium oxide and silicon oxide. In another preferred embodiment of is zinc oxide. Optionally, it may further contain any of the other carbonization promoters described above.
- the resin composition may contain carbon black.
- the carbon black include known furnace black, channel black, acetylene black, and Ketjen black.
- the carbon black contained in the resin composition of the present invention may be a resin mixture (master batch) containing carbon black, and the content of carbon black in 100% by mass of the resin mixture is a preferable embodiment of the present invention. In another preferred embodiment of the present invention, the content is 0.01 to 30% by mass.
- the remainder may be a resin component containing the thermoplastic resin of the component (A), and specific examples of the thermoplastic resin of the component (A) include, for example, polypropylene-based resins, polyethylene-based resins, and mixtures thereof. Good.
- the resin composition contains a heat stabilizer, a lubricant, a light stabilizer, an antioxidant, a colorant, a release agent, and the like as long as the object of the present invention can be solved. Can be.
- the resin composition is prepared, for example, using a mixer such as a tumbler mixer, a Henschel mixer, a ribbon mixer, a kneader, and the like except for the components (C) and (D). May be. Furthermore, after pre-mixing with the mixer, kneading with an extruder such as a single-screw or twin-screw extruder together with the components (C) and (D) to prepare pellets, kneading with a heating roll or a Banbury mixer, etc. A method of preparing by melt-kneading with a machine can be applied.
- a mixer such as a tumbler mixer, a Henschel mixer, a ribbon mixer, a kneader, and the like except for the components (C) and (D). May be.
- an extruder such as a single-screw or twin-screw extruder together with the components (C) and (D) to prepare pellets, k
- the resin molded article of the first exemplary embodiment is a molded article obtained from a resin composition containing the above components (A) to (C) (but not the components (D) and (E)),
- the component (A) contains 15 to 30% by mass of a flame retardant (B), 2.5 to 7.5% by mass of a metal fiber (C), and the total is 100% by mass.
- the resin molded product has a combustion test result determined by UL94 V test method of V-0 or V-1 in a test piece having a thickness of 1.5 mm, and satisfies the following requirements (I) to (IV). is there.
- the resin molded body has a thickness of 1.5 to 8.0 mm.
- the resin molded article extinguishes itself within 5 minutes after the end of the combustion test according to the following combustion test E method.
- the resin molded body has no holes in the molded body after the combustion test according to the following combustion test E method.
- the resin molded body has a value in which the electromagnetic wave shielding property by the KEC method electric field exceeds 30 dB in a frequency range of 1 to 100 MHz.
- Combustion test E method A flat plate (150 ⁇ 150 ⁇ 2.0 mm) made of the above molded product is used. Using a flame having a length of 200 mm, an indirect flame is applied from above the flat plate to the center of the flat plate for 130 seconds. The distance from the flame contact position of the flat plate to the burner opening was 150 mm.
- the resin molded body in a 1.5 mm-thick test piece, has a combustion test determination result of V-0 or V-1 by a UL94 V test method. V-0.
- the size and shape of the resin molded body can be appropriately adjusted according to the use within a range satisfying the following requirement (I).
- the resin molded body has a thickness of 1.5 to 8.0 mm, in one preferred embodiment of the present invention it is 2.0 to 6.0 mm, and in another preferred embodiment of the present invention, it has a thickness of 2 to 6.0 mm. 0.0 to 4.0 mm (requirement (I)).
- the resin molded article has self-extinguishing properties that extinguishes the fire within 2 minutes after the end of the combustion test by the combustion test E method without externally applying a fire-extinguishing treatment (requirement (II)).
- Self-extinguishing refers to the property of burning in a flame when brought into contact with a flame, but extinguishing the flame within a certain time if the flame is kept away.
- the self-extinguishing property can be obtained within 2 minutes after the end of the combustion test by any one or more of the following combustion tests A to D. Good.
- the method A is the mildest combustion condition, and then the combustion conditions are relatively strict in the order of the method B and the method C.
- the methods D and E are This is a severe test for combustion conditions.
- Combustion test A method: A flat plate (150 ⁇ 150 ⁇ 2.0 mm) made of the above molded product is used. Using a 20 mm flame in UL94, indirectly flame from below the plate to the center of the plate for 130 seconds. The distance from the flame contact position of the flat plate to the burner opening was 10 mm.
- Combustion test B method A flat plate (150 ⁇ 150 ⁇ 2.0 mm) made of the above molded product is used. Using a 38 mm flame in UL94, indirectly flame from below the plate to the center of the plate for 130 seconds. The distance from the flame contact position of the flat plate to the burner opening was 20 mm.
- Combustion test C method A flat plate (150 ⁇ 150 ⁇ 2.0 mm) made of the above molded product is used. Using a 125 mm flame in UL94, indirectly flame from below the plate to the center of the plate for 130 seconds. The distance from the flame contact position of the flat plate to the burner opening was 100 mm.
- Combustion test D method A flat plate (150 ⁇ 150 ⁇ 2.0 mm) made of the above-mentioned molded body is used. Using a 125 mm flame in UL94, indirectly flame from below the plate to the center of the plate for 130 seconds. The distance from the flame contact position of the flat plate to the burner opening was 40 mm.
- the various combustion test methods are based on the self-flammability test in European ECE-R100, and the resin molded article of the present invention having self-extinguishing properties in the various combustion test methods may satisfy the requirements of European ECE-R100. it can.
- the ignition portion of the molded article is not melted by the combustion heat, and the hole is not opened ( There are no openings (Requirement (III)).
- the term “open hole” as used herein refers to a hole that opens from the surface of the ignited molded body in the thickness direction of the molded body, and has a maximum diameter of 3 mm or less, or a hole or dent that does not penetrate. Is not included.
- the molded body after the combustion test by any one or more of the above-mentioned combustion tests A to D has no opening.
- the resin molded article of the second exemplary embodiment is a molded resin article obtained from the resin composition containing the components (A) to (D) (but not the component (E)).
- the molded article contains (B) 15 to 30% by mass of a flame retardant, (C) 2.5 to 7.5% by mass of a metal fiber, and (D) 5 to 50% by mass of a glass fiber, and the remainder is a total.
- the component (A) is defined as 100% by mass, and the resin molded product has a combustion test determination result of UL94 V test method of V-0 or V-1 in a test piece having a thickness of 1.5 mm. It meets the requirements of (IV).
- the resin molded article of the third exemplary embodiment is a molded resin molded article obtained from the resin composition containing the above-mentioned components (A) to (E). 15 to 30% by mass of the flame retardant, 2.5 to 7.5% by mass of the metal fiber (C), 5 to 50% by mass of the glass fiber (D), and 0.7 to 5.0% of the (E) carbonization accelerator.
- the component (A) contains 100% by mass, and the balance is 100% by mass.
- the resin molded product has a combustion test determination result of UL94mmV test method of V-0 or V -1, which satisfies the above requirements (I) to (IV).
- the second embodiment and the third embodiment satisfy the following requirements (V) and (VI) in addition to the above requirements (I) to (IV) in another exemplary embodiment. May be.
- Cone calorimeter exothermic test A flat molded product having a size of 100 mm x 100 mm and a thickness of 2.0 mm excluding the heated surface and covered with aluminum foil (12 ⁇ m thick) in accordance with ISO 5660-1 was used as a sample. The heating is performed at a radiation heat intensity of 50 kW / m 2 for 5 minutes.
- a cone calorimeter C4 manufactured by Toyo Seiki Seisaku-sho, Ltd.
- the requirement (V) is, in a preferred embodiment of the present invention, 8 MJ / m 2 or less after a lapse of 130 sec from the start of heating. In another preferred embodiment of the present invention, the requirement (V) is 7 MJ / m 2 after a lapse of 130 sec from the start of heating. 0.5 MJ / m 2 or less.
- the “opening” of requirement (VI) is an opening that penetrates in the thickness direction of the aluminum foil, and does not include a hole having a maximum diameter of 3 mm or less, a hole that does not penetrate, a dent, and the like.
- the surface excluding the heated surface of the sample is covered with aluminum foil, so heat is mainly transmitted to the coated portion on the opposite side of the heated surface, and the melting point of aluminum is approximately When the temperature exceeds 660 ° C., the aluminum foil is melted to form holes.
- the resin molded body is a KEC electric field in a frequency range of 1 to 100 MHz, measured using a flat plate (150 mm long, 150 mm wide, 2.0 mm thick) made of the molded body. Shows a value exceeding 30 dB due to the electromagnetic wave shielding property (Requirement (IV)).
- the method described in the embodiment can be applied.
- the resin molded product may have (B), (C), and (D) components within the following ranges with respect to each content of the molded product.
- a resin mixture (compound) such as a master batch (MB), containing a resin component containing at least one of the components (B), (C) and (D) and the thermoplastic resin (A). It may be what was.
- the resin molded article containing the components (A) to (C) (but not the components (D) and (E)) contains 15 to 30% by mass of the flame retardant as the component (B).
- the content is 17 to 28% by mass, in another preferred embodiment of the present invention, 18.5 to 25% by mass, and in still another preferred embodiment of the present invention, 19 to 25% by mass.
- the resin molded product contains 2.5 to 7.5% by mass of a metal fiber as the component (C).
- the resin molded product has a content of 2.5 to 7.0% by mass.
- the resin molded article containing the components (A) to (D) (but not the component (E)) contains 15 to 30% by mass of the flame retardant as the component (B). In one preferred embodiment, the content is 17 to 28% by mass, in another preferred embodiment of the present invention, 18.5 to 25% by mass, and in still another preferred embodiment of the present invention, 19 to 25% by mass. In another embodiment, the resin molded product contains 2.5 to 7.5% by mass of a metal fiber as the component (C). In a preferred embodiment of the present invention, the resin molded product has a content of 2.5 to 7.0% by mass.
- the resin molded product contains 5 to 50% by mass of glass fiber as the component (D), and in a preferred embodiment of the present invention, contains 10 to 45% by mass. In a preferred embodiment, the content is 20 to 40% by mass. The balance of the remaining component (A) is 100% by mass.
- the resin molded article containing the components (A) to (E) contains 15 to 30% by mass of the flame retardant as the component (B), and in a preferred embodiment of the present invention, 17 to 28% by mass. %, 18.5 to 25% by mass in another preferred embodiment of the present invention, and 19 to 25% by mass in still another preferred embodiment of the present invention.
- the resin molded product contains 2.5 to 7.5% by mass of a metal fiber as the component (C).
- the resin molded product has a content of 2.5 to 7.0% by mass. In another preferred embodiment of the invention, from 2.5 to 6.0% by weight, in another preferred embodiment of the invention, from 3.0 to 5.0% by weight, in another preferred embodiment of the invention, 3.0.
- the resin molded product contains 5 to 50% by mass of glass fiber as the component (D), and in a preferred embodiment of the present invention, contains 10 to 45% by mass. In a preferred embodiment, the content is 20 to 40% by mass. In still another embodiment, the resin molded product contains the carbonization accelerator as the component (E) in an amount of from 0.7 to 5.0% by mass, and in one preferred embodiment of the present invention, from 0.7 to 4.0% by mass. %, And in another preferred embodiment of the present invention, the content is 0.8 to 3.5% by mass. The balance of the remaining component (A) is 100% by mass.
- the compounding amount of the carbonization accelerator may be 1 to 30 parts by mass with respect to 100 parts by mass of the total content of (B-1) and (B-2). In another preferred embodiment of the present invention, the amount may be 0.5 to 10 parts by mass, and in still another preferred embodiment of the present invention, the amount may be 0.5 to 6 parts by mass. In a preferred embodiment, the amount may be 2 to 5 parts by mass.
- the content is within the above range, the flame retardant effect is good, the extrusion at the time of molding is stable, the mechanical properties of the molded body are good, and the flame retardancy is good.
- the glass fibers of component (D) and the carbonization promoter of component (E) are, in a preferred aspect of the present invention, (E) in the total amount of components (D) and (E).
- the content ratio of the component [(E) / ((D) + (E)) ⁇ 100] is 2 to 13% by mass, and in another preferred embodiment of the present invention, it is 2.5 to 10% by mass.
- the content ratio of the component (E) in the total amount of the polyolefin resin of the component (A), the phosphorus-based flame retardant of the component (B), and the carbonization accelerator of the component (E) [( E) / ((A) + (B) + (E)) ⁇ 100] in one preferred embodiment of the present invention, 1 to 8% by mass, and in another preferred embodiment of the present invention, 1 to 6% by mass. In still another preferred embodiment of the present invention, the content is 3.1 to 6% by mass.
- the resin molded article containing the components (A) to (D) and carbon black (but not the component (E)) contains 15 to 30% by mass of the flame retardant as the component (B).
- the content is 17 to 28% by mass, in another preferred embodiment of the present invention, 18.5 to 25% by mass, and in still another preferred embodiment of the present invention, 19 to 25% by mass.
- the resin molded product contains 2.5 to 7.5% by mass of a metal fiber as the component (C).
- the resin molded product has a content of 2.5 to 7.0% by mass.
- the resin molded article contains 0 to 50% by mass of a glass fiber as the component (D), and in a preferred embodiment of the present invention, contains 5 to 45% by mass.
- the content is 10 to 40% by mass, and in still another preferred embodiment of the present invention, the content is 20 to 40% by mass.
- the resin molded article contains 0.03 to 3% by mass of carbon black, and in a preferred embodiment of the present invention, contains 0.1 to 1% by mass. In the embodiment, the content is 0.2 to 0.7% by mass. The balance of the remaining component (A) is 100% by mass.
- the resin molding is obtained from the following formula (B) / [(A) + (B)] ⁇ 100 with respect to the total content of the components (A) and (B) (B)
- the content ratio (% by mass) of the component is 18 to 40% by mass in one preferred embodiment of the present invention, and 20 to 38% by mass in another preferred embodiment of the present invention.
- the content is 23 to 35% by mass, and in still another preferred embodiment of the present invention, the content is 28 to 30% by mass.
- the resin molded article has the following formula (B) / [(A) + (C) + (D) based on the total content of the components (A), (C), and (D). ]
- the content ratio (% by mass) of the component (B) determined from ⁇ 100 is 23 to 40% by mass in a preferred embodiment of the present invention, and 23 to 30% by mass in another preferred embodiment of the present invention. In still another preferred embodiment of the present invention, the content is 23 to 25% by mass.
- a resin molded article is formed using the resin composition by a known technique, for example, injection molding, extrusion molding, vacuum molding, irregular molding, foam molding, injection press, press. It can be formed into various molded products by molding, blow molding, gas injection molding, or the like. For example, from the viewpoint that the advantages of the present invention as described above can be more enjoyed, various molded articles can be formed by injection molding.
- the following polyolefin resins (A1) to (A6) were used.
- Component (C) resin-impregnated stainless steel long fiber bundle prepared according to Production Example 12
- Component (D) chopped glass fiber (ECS03T-480, manufactured by Nippon Electric Glass Co., Ltd.), average fiber diameter 13 ⁇ m, average length 3 mm
- (E) component zinc oxide, zinc oxide II, manufactured by Sakai Chemical Industry Co., Ltd.
- the measuring method of the evaluation items was as follows. (1) MFR (g / 10min) The measurement was performed at a temperature of 230 ° C. and a load of 2.16 kg in accordance with ISO 1133. (2) Tensile strength (MPa) It was measured according to ISO527. (3) Flexural strength (MPa) It measured according to ISO178. (4) Flexural modulus (MPa) It measured according to ISO178. (5) Charpy impact strength (kJ / m 2 ) The notched Charpy impact strength was measured according to ISO179 / 1eA.
- Electromagnetic shielding Using the molded product (length 150 mm, width 150 mm, thickness 2.0 mm), the electromagnetic wave shielding property in a frequency range of 1 to 100 MHz was evaluated in accordance with the KEC method (electric field).
- a resin molded article of the present invention self-extinguished within 2 minutes after the end of the combustion test by the above-mentioned combustion test E using a flat molded article having a size of 150 mm x 150 mm and a thickness of 2.0 mm as a sample. Were evaluated as "(self-extinguishing)" and those not self-extinguishing within 2 minutes as "(self-extinguishing) no".
- Total calorific value According to ISO 5660-1, a flat molded product having a size of 100 mm x 100 mm and a thickness of 2.0 mm was used as a sample, and a total calorific value was measured using a cone calorimeter C4 (manufactured by Toyo Seiki Seisaku-sho, Ltd.) as a test device. Was measured. Heating was performed at a radiation heat intensity of 50 kW / m 2 for 5 minutes. The surface excluding the heated surface of the sample was covered with an aluminum foil (thickness: 12 ⁇ m). Table 4 shows the total calorific value [MJ / m 2 ] after the elapse of 130 seconds from the start of heating and the results of the presence or absence (visual observation) of holes in the aluminum foil.
- Table 1 shows a resin mixture containing the thermoplastic resin (A), the flame retardant (B), the zinc oxide (E), carbon black (masterbatch), and other additives shown in Table 1.
- the mixture is supplied from a hopper of a twin-screw extruder (“TEX30 ⁇ ”, manufactured by Japan Steel Works, 230 ° C.), and the chopped glass fiber and the chopped carbon fiber of the component (D) are further fed from a side feeder.
- the mixture was supplied, melt-kneaded and shaped to obtain a resin mixture (pellets having a diameter of 3.0 mm and a length of 3.0 mm) shown in Table 1.
- Production Example 11 (Production of resin mixture containing phosphorus-based flame retardant (B-1)) (A7) After dry blending 30 parts by mass of the component, 0.20 parts by mass of the stabilizer 1, 0.20 parts by mass of the stabilizer 2 and 2.50 parts by mass of the lubricant, a twin-screw extruder (Japan Co., Ltd.) It was supplied from a hopper of “TEX30 ⁇ ” manufactured by Steel Works, 230 ° C.). Further, 70 parts by mass of the component (B-1) was supplied from a side feeder, melt-kneaded and shaped to obtain a resin mixture containing the phosphorus-based flame retardant (B-1) shown in Table 2 (diameter 3.0 mm ⁇ length). 3.0 mm pellets).
- Production Example 12 Production of resin impregnated stainless steel fiber bundle
- a blend of 50: 0.25: 0.25 (parts by mass) was melted and supplied, and was impregnated into a stainless fiber bundle to obtain a resin-impregnated stainless long fiber bundle. Then, it is shaped with a shaping nozzle at the crosshead die outlet (3.5 mm in diameter), shaped with a shaping roll, cut into 7 mm with a pelletizer, and impregnated with a resin containing 50% by mass of stainless fiber (C).
- a fiber bundle (pellet) was obtained. When the resin-impregnated fiber bundle thus obtained was cut and confirmed, it was found that the stainless fibers were substantially parallel to the length direction and the resin was impregnated to the center.
- Example 3 (A) The resin mixture containing the flame retardant (B) of Production Example 11 and the resin-impregnated metal long fiber bundle of Production Example 12 were mixed in a tumbler in the composition shown in Table 2, and then the same production method as in Example 1 was performed. Thus, a resin molded body was obtained.
- Comparative Example 1 The fiber-containing polypropylene-based flame-retardant compound of Production Example 1 and the resin-impregnated fiber bundle of Production Example 12 were mixed by a tumbler with the composition shown in Table 2, and a resin molded product was obtained by the same production method as in Example 1.
- Comparative Examples 2 to 8 The fiber-containing polypropylene-based flame-retardant compounds of Production Examples 1 to 7 were charged into an injection molding machine (FANUC ROBOSHOT ⁇ -S150iA, FANUC CORPORATION, mold 50 ° C, molding temperature 220 ° C). I got Table 2 also shows the evaluation results of Examples 1 to 3 and Comparative Examples 1 to 8.
- Example 1 a resin molded product having high mechanical strength in addition to high self-extinguishing properties, flame retardancy, and electromagnetic wave shielding properties was obtained.
- a resin molded product having a lighter weight, that is, a lower density than Examples 1 and 2 containing glass fibers and having self-extinguishing properties, flame retardancy, and electromagnetic wave shielding properties equivalent to Examples 1 and 2 was obtained. Obtained.
- the resin molded article according to the example of the present invention has flame retardancy and self-extinguishing properties that meet the standards for fire resistance test such as ECE-R100, it can be used for electric vehicles, electric shuttle buses, electric trucks, electric motorcycles, electric wheelchairs, electric stands. All or part of the battery module housing of a battery-type electric transport device such as a riding motorcycle or the like, particularly a battery module of an electric transport device using a fixed battery to which the battery cannot be attached / detached, peripheral parts (such as fastening parts), and an electric vehicle Battery charger connector, battery capacitor holder, battery capacitor housing, or electric vehicle charging stand housing.
- a battery-type electric transport device such as a riding motorcycle or the like, particularly a battery module of an electric transport device using a fixed battery to which the battery cannot be attached / detached, peripheral parts (such as fastening parts), and an electric vehicle Battery charger connector, battery capacitor holder, battery capacitor housing, or electric vehicle charging stand housing.
- the resin molded article according to the example of the present invention has an electromagnetic wave shielding property, it is possible to prevent unnecessary radio waves generated from the above-mentioned housing or components from becoming noise to the vehicle-mounted radio. Furthermore, the resin molded article according to the example of the present invention can be used for housings of electric / electronic devices other than vehicles.
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Abstract
Description
前記樹脂成形体中、(B)難燃剤を15~30質量%、および(C)金属繊維を2.5~7.5質量%含有し、残部が合計で100質量%とする(A)成分であり、
前記樹脂成形体は、UL94 V試験法による燃焼試験判定結果が1.5mm厚みの試験片においてV-0またはV-1であり、下記(I)~(IV)の要件を満たす、樹脂成形体を提供する。
(I)前記樹脂成形体の厚みが1.5~8.0mmであること。
(II)前記樹脂成形体が、下記燃焼試験E法による燃焼試験終了後5分以内に自己消火すること。
(III)前記樹脂成形体が、下記燃焼試験E法による燃焼試験後の成形体に開孔がないこと。
(IV)前記樹脂成形体が、周波数範囲1~100MHzにおいてKEC法電界による電磁波シールド性が30dBを超える値であること。
燃焼試験E法:前記成形体からなる平板(150×150×2.0mm)を使用する。200mm長さの炎を使用し、前記平板の上方から、前記平板の中心に対して130秒間接炎する。前記平板の接炎位置からバーナー口までの距離は150mm。
前記樹脂成形体中、(B)難燃剤を15~30質量%、(C)金属繊維を2.5~7.5質量%、および(D)ガラス繊維を5~50質量%含有し、残部が合計で100質量%とする(A)成分であり、
前記樹脂成形体は、UL94 V試験法による燃焼試験判定結果が1.5mm厚みの試験片においてV-0またはV-1であり、下記(I)~(IV)の要件を満たす、樹脂成形体を提供する。
(I)前記樹脂成形体の厚みが1.5~8.0mmであること。
(II)前記樹脂成形体が、下記燃焼試験E法による燃焼試験終了後5分以内に自己消火すること。
(III)前記樹脂成形体が、下記燃焼試験E法による燃焼試験後の成形体に開孔がないこと。
(IV)前記樹脂成形体が、周波数範囲1~100MHzにおいてKEC法電界による電磁波シールド性が30dBを超える値であること。
燃焼試験E法:前記成形体からなる平板(150×150×2.0mm)を使用する。200mm長さの炎を使用し、前記平板の上方から、前記平板の中心に対して130秒間接炎する。前記平板の接炎位置からバーナー口までの距離は150mm。
前記成形体中、(B)難燃剤を15~30質量%、(C)金属繊維を2.5~7.5質量%、(D)ガラス繊維を5~50質量%、および(E)炭化促進剤を0.7~5.0質量%含有し、残部が合計で100質量%とする(A)成分であり、
前記樹脂成形体は、UL94 V試験法による燃焼試験判定結果が1.5mm厚みの試験片においてV-0またはV-1であり、下記(I)~(IV)の要件を満たす、樹脂成形体を提供する。
(I)前記樹脂成形体の厚みが1.5~8.0mmであること。
(II)前記樹脂成形体が、下記燃焼試験E法による燃焼試験終了後5分以内に自己消火すること。
(III)前記樹脂成形体が、下記燃焼試験E法による燃焼試験後の成形体に開孔がないこと。
(IV)前記樹脂成形体が、周波数範囲1~100MHzにおいてKEC法電界による電磁波シールド性が30dBを超える値であること。
燃焼試験E法:前記成形体からなる平板(150×150×2.0mm)を使用する。200mm長さの炎を使用し、前記平板の上方から、前記平板の中心に対して130秒間接炎する。前記平板の接炎位置からバーナー口までの距離は150mm。
以下、本発明の実施態様による樹脂成形体で使用する樹脂組成物の幾つかの例を説明する。
[(A)熱可塑性樹脂]
(A)成分の熱可塑性樹脂としては、例えばポリオレフィン系樹脂が使用されてよい。幾つかの例では、ポリエチレン系樹脂(高密度ポリエチレン(HDPE)、低密度ポリエチレン(LDPE)、直鎖低密度ポリエチレン(LLDPE)、超低密度ポリエチレン(VLDPE,ULDPE)など)、ポリプロピレン系樹脂、メチルペンテン系樹脂などのα-C2~20鎖状オレフィン系樹脂、環状オレフィン系樹脂などが使用できる。これらのポリオレフィン樹脂は、単独で使用してもよく、又は二種以上組み合わせて使用してもよい。本発明の1つの実施態様では、特に、ポリプロピレン系樹脂が好適に使用される。
(B)成分の難燃剤は、本発明の好ましい一態様では燃焼試験後の自己消火性や成形体の開孔抑制の点からリン系難燃剤であり、本発明の別の好ましい一態様では(B-1)有機リン酸化合物または(B-2)有機リン酸塩化合物であってよく、それらの混合物であってもよく、ハロゲン原子は含まない。
(C)成分は、金属繊維として、本発明の好ましい一態様では例えばステンレス(SUS)繊維、銅繊維、銀繊維、金繊維、アルミニウム繊維、および黄銅繊維から選ばれるものであり、本発明の別の好ましい一態様ではステンレス繊維であってよい。
さらに、例えば剛性向上および強度向上(引張強度、曲げ強度、衝撃強度)の点から、樹脂組成物は(D)成分であるガラス繊維を含有することができる。
本発明の実施形態によれば、炭化促進剤としては、例えばフェロセンなどの有機金属錯体化合物、水酸化コバルト、水酸化マグネシウム、水酸化アルミニウムなどの金属水酸化物、硼酸マグネシウム、硼酸カルシウムマグネシウムなどの硼酸アルカリ土類金属塩、硼酸マンガン、硼酸亜鉛、メタ硼酸亜鉛、三酸化アンチモン、アルミナ三水和物、重炭酸マグネシウム、酸化アルミニウム、酸化マグネシウム、酸化ケイ素、酸化ジルコニウム、酸化バナジウム、酸化モリブデン、酸化ニッケル、酸化マンガン、酸化チタン、酸化ケイ素、酸化コバルト、酸化亜鉛などの金属酸化物類、ゼオライトなどのアルミノケイ酸塩、シリカチタニアなどの珪酸塩型固体酸、リン酸カルシウム、リン酸マグネシウム、リン酸アルミニウム、リン酸亜鉛などの金属リン酸塩、ハイドロタルサイト、カオリナイト、セリサイト、パイロフィライト、ベントナイト、タルクなどの粘土鉱物類を挙げることができる。
幾つかの実施形態において、樹脂組成物には、本発明の課題を解決できる範囲内で、熱安定剤、滑剤、光安定剤、酸化防止剤、着色剤、および離型剤などを含有することができる。
以下、本発明の幾つかの実施形態による樹脂成形体を説明する。
例示的な第1実施形態の樹脂成形体は、上記(A)~(C)成分を含む((D)成分と(E)成分は含まない)樹脂組成物から得られる成形体であって、前記樹脂成形体中、(B)難燃剤を15~30質量%、(C)金属繊維を2.5~7.5質量%含有し、残部が合計で100質量%とする(A)成分であり、前記樹脂成形体は、UL94 V試験法による燃焼試験判定結果が1.5mm厚みの試験片においてV-0またはV-1であり、下記(I)~(IV)の要件を満たすものである。
(I)前記樹脂成形体の厚みが1.5~8.0mmであること。
(II)前記樹脂成形体が、下記燃焼試験E法による燃焼試験終了後5分以内に自己消火すること。
(III)前記樹脂成形体が、下記燃焼試験E法による燃焼試験後の成形体に開孔がないこと。
(IV)前記樹脂成形体が、周波数範囲1~100MHzにおいてKEC法電界による電磁波シールド性が30dBを超える値であること。
燃焼試験E法:前記成形体からなる平板(150×150×2.0mm)を使用する。200mm長さの炎を使用し、前記平板の上方から、前記平板の中心に対して130秒間接炎する。前記平板の接炎位置からバーナー口までの距離は150mm。
UL94における125mm炎を使用し、前記平板下方から、前記平板の中心に対して130秒間接炎する。前記平板の接炎位置からバーナー口までの距離は100mm。
・(A1)ホモポリプロピレン、MFR(メルトフローレート)7、製品名「PM600A」、サンアロマー株式会社製
・(A3)高流動性ホモポリプロピレン、MFR70、製品名「PMB02A」、サンアロマー株式会社製
・(A5)高流動性プロピレン-エチレンブロック共重合体、MFR60、製品名「PMB60A」、サンアロマー株式会社製
・(A6)無水マレイン酸変性ポリプロピレン、MFR10(190℃×0.325kg)、製品名「OREVAC CA100」、アルケマ株式会社製
・(A7)プロピレン-エチレンランダム共重合体、MFR25、製品名「PM921V」、サンアロマー株式会社製
・(B-1)リン系難燃剤、製品名「FP-2500S」、株式会社ADEKA製
・(B-2)リン系難燃剤、製品名「FP-2100JC」、株式会社ADEKA製
・製造例11にしたがって調製したリン系難燃剤(B-1)を含む樹脂混合物
・チョップドカーボン繊維(HT C413、帝人株式会社製)、繊維の平均径7μm、平均長さ6mm
・カーボンブラックマスターバッチ(以下、CBMB)、製品名「EPP-K-22771」、ポリコール工業株式会社製(カーボンブラック30質量%含有、残部はポリプロピレンとポリエチレンの混合物)
・安定剤1、製品名「Irganox1010」、BASFジャパン株式会社製
・安定剤2、製品名「アデカスタブPEP36」、(株)ADEKA製
・滑剤、製品名「アルフローH-50S」、日油株式会社製(エチレンビスステアリン酸アミド)
(1)MFR(g/10min)
ISO1133に準拠して温度230℃および荷重2.16kgで測定した。
(2)引張強さ(MPa)
ISO527に準拠して測定した。
(3)曲げ強度(MPa)
ISO178に準拠して測定した。
(4)曲げ弾性率(MPa)
ISO178に準拠して測定した。
(5)シャルピー衝撃強度(kJ/m2)
ISO179/1eAに準拠して、ノッチ付きシャルピー衝撃強さを測定した。
UL94のバー型試験片(125mm×13mm×1.5mm)の20mm炎垂直燃焼試験(V試験)にて、実施例および比較例の樹脂組成物から作製した厚さ1.5mmの試験片にて試験した。
成形体(縦150mm、横150mm、厚み2.0mm)を用い、KEC法(電界)に準拠して周波数範囲1~100MHzにおける電磁波シールド性を評価した。
成形体として大きさ150mm×150mm、厚み2.0mmの平板状成形品を試料に用い、上記の燃焼試験E法による燃焼試験終了後2分以内に、本発明の樹脂成形体が自己消火したものを「(自己消火性)有り」、2分以内には自己消火しなかったものを「(自己消火性)無し」と評価した。
ISO5660-1に準拠し、大きさ100mm×100mm、厚み2.0mmの平板状成形品を試料とし、試験装置としてコーンカロリーメータC4((株)東洋精機製作所製)を使用して、総発熱量を測定した。輻射熱強度は50kW/m2にて、5分間加熱を行った。試料の加熱面を除いた面はアルミニウム箔(厚さ12μm)で被覆した。加熱開始から130sec経過後の総発熱量[MJ/m2]とアルミニウム箔の開孔の有無(目視観察)の結果を表4に示す。
表1に示す(A)成分の熱可塑性樹脂、(B)成分の難燃剤、(E)成分の酸化亜鉛、カーボンブラック(マスターバッチ)およびその他の添加剤を含む樹脂混合物を、表1に示す配合でタンブラーにて混合後、二軸押出機((株)日本製鋼所製「TEX30α」、230℃)のホッパーから供給し、さらに(D)成分のチョップドガラス繊維およびチョップドカーボン繊維をサイドフィーダーから供給して、溶融混練および賦形して、表1に示す樹脂混合物(直径3.0mm×長さ3.0mmのペレット)を得た。
(A7)成分30質量部、安定剤1を0.20質量部、安定剤2を0.20質量部、および滑剤2.50質量部をドライブレンドした後、二軸押出機((株)日本製鋼所製「TEX30α」、230℃)のホッパーから供給した。さらに(B-1)成分70質量部はサイドフィーダーから供給して、溶融混練および賦形して、表2に示すリン系難燃剤(B-1)を含む樹脂混合物(直径3.0mm×長さ3.0mmのペレット)を得た。
(C)成分であるステンレス繊維束(約7000本の繊維の束)をクロスヘッドダイに通して、(A5)成分:(A6)成分:安定剤1:安定剤2=48.0:1.50:0.25:0.25(質量部)のブレンド物を溶融させて供給し、ステンレス繊維束に含浸させ、樹脂含浸ステンレス長繊維束を得た。その後、クロスヘッドダイ出口の賦形ノズルで賦形し(直径3.5mm)、整形ロールで形を整えた後、ペレタイザーにより7mmに切断し、ステンレス繊維(C)50質量%を含有する樹脂含浸繊維束(ペレット)を得た。このようにして得た樹脂含浸繊維束を切断して確認したところ、ステンレス繊維が長さ方向にほぼ平行になっており、中心部まで樹脂が含浸されていた。
製造例1の繊維含有ポリプロピレン系難燃コンパウンドおよび製造例12の樹脂含浸繊維束を、表2に示す配合でタンブラーにて混合後、射出成形機(ファナック(株)製FANUC ROBOSHOTα-S150iA、金型50℃、成形温度220℃)に投入して、樹脂成形体を得た。
(A)成分、製造例11の難燃剤(B)を含む樹脂混合物、製造例12の樹脂含浸金属長繊維束を、表2に示す配合でタンブラーにて混合後、実施例1同様の製造方法によって樹脂成形体を得た。
製造例1の繊維含有ポリプロピレン系難燃コンパウンドおよび製造例12の樹脂含浸繊維束を、表2に示す配合でタンブラーにて混合後、実施例1と同様の製造方法によって樹脂成形体を得た。
製造例1~7の繊維含有ポリプロピレン系難燃コンパウンドを射出成形機射出成形機(ファナック(株)製FANUC ROBOSHOT α-S150iA、金型50℃、成形温度220℃)に投入して、樹脂成形体を得た。実施例1~3および比較例1~8の評価結果を表2に併せて示す。
表1に示す製造例8~10の繊維含有ポリプロピレン系難燃コンパウンドおよび製造例12の樹脂含浸繊維束を、表3に示す配合でタンブラーにて混合後、射出成形機(ファナック(株)製FANUC ROBOSHOTα-S150iA、金型50℃、成形温度220℃)に投入して、樹脂成形体を得た。評価結果を表3に併せて示す。
Claims (8)
- (A)熱可塑性樹脂、(B)難燃剤、および(C)金属繊維を含む樹脂組成物から得られる樹脂成形体であって、
前記樹脂成形体中、(B)難燃剤を15~30質量%、および(C)金属繊維を2.5~7.5質量%含有し、残部が合計で100質量%とする(A)成分であり、
前記樹脂成形体は、UL94 V試験法による燃焼試験判定結果が1.5mm厚みの試験片においてV-0またはV-1であり、下記(I)~(IV)の要件を満たす、樹脂成形体。
(I)前記樹脂成形体の厚みが1.5~8.0mmであること。
(II)前記樹脂成形体が、下記燃焼試験E法による燃焼試験終了後5分以内に自己消火すること。
(III)前記樹脂成形体が、下記燃焼試験E法による燃焼試験後の成形体に開孔がないこと。
(IV)前記樹脂成形体が、周波数範囲1~100MHzにおいてKEC法電界による電磁波シールド性が30dBを超える値であること。
燃焼試験E法:前記成形体からなる平板(150×150×2.0mm)を使用する。200mm長さの炎を使用し、前記平板の上方から、前記平板の中心に対して130秒間接炎する。前記平板の接炎位置からバーナー口までの距離は150mm。 - (A)熱可塑性樹脂、(B)難燃剤、(C)金属繊維、および(D)ガラス繊維を含む樹脂組成物から得られる樹脂成形体であって、
前記樹脂成形体中、(B)難燃剤を15~30質量%、(C)金属繊維を2.5~7.5質量%、および(D)ガラス繊維を5~50質量%含有し、残部が合計で100質量%とする(A)成分であり、
前記樹脂成形体は、UL94 V試験法による燃焼試験判定結果が1.5mm厚みの試験片においてV-0またはV-1であり、下記(I)~(IV)の要件を満たす、樹脂成形体。
(I)前記樹脂成形体の厚みが1.5~8.0mmであること。
(II)前記樹脂成形体が、下記燃焼試験E法による燃焼試験終了後5分以内に自己消火すること。
(III)前記樹脂成形体が、下記燃焼試験E法による燃焼試験後の成形体に開孔がないこと。
(IV)前記樹脂成形体が、周波数範囲1~100MHzにおいてKEC法電界による電磁波シールド性が30dBを超える値であること。
燃焼試験E法:前記成形体からなる平板(150×150×2.0mm)を使用する。200mm長さの炎を使用し、前記平板の上方から、前記平板の中心に対して130秒間接炎する。前記平板の接炎位置からバーナー口までの距離は150mm。 - (A)熱可塑性樹脂、(B)難燃剤、(C)金属繊維、(D)ガラス繊維、および(E)重炭酸マグネシウム、酸化亜鉛、酸化チタン、酸化マグネシウムおよび酸化ケイ素から選ばれる少なくとも1つの炭化促進剤を含む樹脂組成物から得られる樹脂成形体であって、
前記成形体中、(B)難燃剤を15~30質量%、(C)金属繊維を2.5~7.5質量%、(D)ガラス繊維を5~50質量%、および(E)炭化促進剤を0.7~5.0質量%含有し、残部が合計で100質量%とする(A)成分であり、
前記樹脂成形体は、UL94 V試験法による燃焼試験判定結果が1.5mm厚みの試験片においてV-0またはV-1であり、下記(I)~(IV)の要件を満たす、樹脂成形体。
(I)前記樹脂成形体の厚みが1.5~8.0mmであること。
(II)前記樹脂成形体が、下記燃焼試験E法による燃焼試験終了後5分以内に自己消火すること。
(III)前記樹脂成形体が、下記燃焼試験E法による燃焼試験後の成形体に開孔がないこと。
(IV)前記樹脂成形体が、周波数範囲1~100MHzにおいてKEC法電界による電磁波シールド性が30dBを超える値であること。
燃焼試験E法:前記成形体からなる平板(150×150×2.0mm)を使用する。200mm長さの炎を使用し、前記平板の上方から、前記平板の中心に対して130秒間接炎する。前記平板の接炎位置からバーナー口までの距離は150mm。 - さらに下記(V)、および(VI)の要件を満たす、請求項2または3記載の樹脂成形体。
(V)下記方法のコーンカロリーメータ発熱性試験により測定される総発熱量が、加熱開始から130sec経過後において8MJ/m2以下であること。
(VI)下記方法のコーンカロリーメータ発熱性試験による総発熱量測定の際、加熱開始から5min経過後において前記自己消火性樹脂成形体を被覆するアルミニウム箔に開孔がないこと。
コーンカロリーメータ発熱性試験:ISO5660-1に準拠し、大きさ100mm×100mm、厚み2.0mmの平板状成形品の加熱面を除いた面をアルミニウム箔(厚さ12μm)で覆ったものを試料とし、輻射熱強度は50kW/m2にて、5分間加熱を行う。 - (C)成分の金属繊維または(D)成分のガラス繊維が、金属繊維またはガラス繊維を長さ方向に揃えた状態で束ねた金属繊維束またはガラス繊維束に(A)成分の熱可塑性脂が溶融状態で付着されて一体化されたものが1~15mmの長さに切断された樹脂付着長繊維束の形態のものである、請求項1~4のいずれか1項記載の樹脂成形体。
- (B)成分がリン系難燃剤である、請求項1~5のいずれか1項記載の樹脂成形体。
- (A)成分がポリプロピレン系樹脂である、請求項1~5のいずれか1項記載の樹脂成形体。
- 車両用バッテリーモジュールの筐体部品またはその周辺部品である、請求項1~7のいずれか1項記載の樹脂成形体。
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