WO2011043259A1 - 難燃性樹脂組成物及びそれを用いた絶縁電線、フラットケーブル、成形品 - Google Patents
難燃性樹脂組成物及びそれを用いた絶縁電線、フラットケーブル、成形品 Download PDFInfo
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- WO2011043259A1 WO2011043259A1 PCT/JP2010/067234 JP2010067234W WO2011043259A1 WO 2011043259 A1 WO2011043259 A1 WO 2011043259A1 JP 2010067234 W JP2010067234 W JP 2010067234W WO 2011043259 A1 WO2011043259 A1 WO 2011043259A1
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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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
- C08K5/16—Nitrogen-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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/427—Polyethers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/442—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from aromatic vinyl compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/08—Flat or ribbon cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
Definitions
- the present invention relates to a flame retardant resin composition composed of a non-halogen flame retardant material and having excellent flame retardancy and mechanical properties, and an insulated wire, a flat cable and a molded product using the flame retardant resin composition.
- Exceptional mechanical properties are required for insulating coating layers of insulated wires and insulating layers of flat cables used in the fields of electronic equipment and automobiles.
- the initial maximum tensile strength is required to be 10.4 MPa or more for an insulated wire or flat cable using a plastic such as polyethylene as an insulator. .
- insulated wires and flat cables have applications that require high flame resistance.
- flame retardancy such as a horizontal flame retardancy test and an inclined burn test is defined in the automobile field
- VW-1 test vertical flame test
- a soft polyvinyl chloride composition or a brominated flame retardant for polyolefin resins such as polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer
- a flame retardant resin composition mixed with a halogen flame retardant such as a chlorine flame retardant has been used.
- a flame retardant material containing a halogen element generates a combustion gas harmful to the human body such as hydrogen halide gas during incineration, which is not preferable in terms of environment.
- metal hydroxide flame retardants such as aluminum hydroxide and magnesium hydroxide are blended with polyolefin resins such as polyethylene, ethylene-ethyl acrylate copolymer, and ethylene-vinyl acetate copolymer are practical.
- polyolefin resins such as polyethylene, ethylene-ethyl acrylate copolymer, and ethylene-vinyl acetate copolymer.
- Patent Document 1 it is necessary to add a large amount of metal hydroxide flame retardant in order to obtain the flame retardance sufficient to pass the UL vertical combustion test VW-1 with the metal hydroxide flame retardant. It was difficult to achieve both flame retardancy and mechanical properties because the mechanical properties deteriorated.
- Patent Document 2 describes a non-halogen flame retardant resin composition in which a metal hydroxide and red phosphorus are blended in a polyolefin resin, and an insulated wire using the same as a coating material.
- Patent Document 2 the amount of metal hydroxide added can be reduced by using red phosphorus in combination, and both flame retardancy and mechanical properties can be achieved.
- red phosphorus is undesirable in terms of environment because toxic phosphine is generated during combustion.
- the insulating layer is colored by red phosphorus.
- Organic phosphorus flame retardants such as phosphate esters are also known as phosphorus flame retardants, but their flame retardant effect is not sufficient, and satisfactory flame retardancy cannot be obtained unless added in large amounts. Since phosphoric acid esters have low compatibility with polyolefin-based resins, so-called bleed out occurs in which phosphoric acid esters emerge on the surface of the resin composition when added in a large amount.
- the present inventors use a mixture of polyphenylene ether, thermoplastic styrene elastomer and olefin resin as a base polymer, and add flame retardancy to which an organic phosphorus flame retardant, nitrogen flame retardant, and polyfunctional monomer are added.
- a resin composition and an insulated wire using the resin composition were developed and filed as Japanese Patent Application No. 2008-100755. This insulated wire can achieve both flame retardancy and mechanical properties, and is excellent in heat resistance and heat distortion resistance by crosslinking a resin.
- the heat resistance required for insulated wires varies, and one of the test items is heat resistance with a conductor. Specifically, after leaving the insulating layer and the conductor (metal) in contact with each other for a long time at a high temperature, the flexibility of the insulating layer is evaluated. It has been found that in the insulated wire using the flame retardant resin composition, the required characteristics may not be satisfied when the test conditions are severe. Although the reason is not certain, the phosphate ester and metal contained in the flame retardant resin composition interact with each other to deteriorate the characteristics, and the nitrogen flame retardant is contained in the flame retardant resin composition. The reason is that the flexibility is lowered.
- the present invention provides a flame retardant resin composition that can satisfy both mechanical characteristics and flame retardancy, and can satisfy strict heat resistance characteristics such as heat resistance with a conductor, and an insulated wire and a flat cable using the same. It is an object to provide a molded product.
- the invention described in claim 1 is a flame retardant resin composition containing a thermoplastic resin, a polyfunctional monomer, and an organophosphorus flame retardant, wherein the thermoplastic resin has a carbon-carbon unsaturated bond.
- a resin or a resin having a carbonyl group is contained in an amount of 5% by mass or more based on the whole thermoplastic resin, and the organophosphorus flame retardant opens a phosphinic acid metal salt, a melamine phosphate compound, an ammonium phosphate compound, and cyclophosphazene.
- One or more selected from the group consisting of polyphosphazene compounds obtained by ring polymerization, and the content of the organic phosphorus flame retardant is 5 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin,
- the flame-retardant resin composition has a polyfunctional monomer content of 1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
- organic phosphorus flame retardants in particular, use one or more selected from the group consisting of metal phosphinic acid salts, melamine phosphate compounds, ammonium phosphate compounds, and polyphosphazene compounds obtained by ring-opening polymerization of cyclophosphazene. It is possible to improve flame resistance and heat resistance with a conductor.
- thermoplastic resin Any resin can be selected as the thermoplastic resin. However, if only a resin having low flame retardancy such as polyethylene or polypropylene is used, the flame retardancy becomes insufficient, and therefore a highly flame retardant carbon-carbon unsaturated bond is formed. It is necessary to contain 5% by mass or more of the resin having a carbonyl group or a resin having a carbonyl group.
- the thermoplastic resin is polyphenylene ether resin, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, styrene thermoplastic elastomer, polystyrene resin, nylon, thermoplastic polyamide elastomer, carbon-carbon unsaturated. It is preferable to contain 5% by mass or more of at least one selected from the group consisting of a polyolefin resin having a bond and a polyolefin resin having a carbonyl group. Since these resins have relatively high flame retardancy, the flame retardancy of the flame retardant resin composition can be improved.
- the thermoplastic resin preferably comprises 5 to 80% by mass of a polyphenylene ether resin or polystyrene resin, 20 to 95% by mass of a styrene thermoplastic elastomer, and 0 to 70% by mass of a polyolefin resin (Claim 3).
- Polyphenylene ether resins and polystyrene resins are particularly excellent in flame retardancy.
- Styrenic thermoplastic elastomers are excellent in flexibility and extrusion processability, and have good compatibility with polyphenylene ether resins, so that mechanical properties can be improved.
- Polyolefin resins are excellent in flexibility and can improve mechanical properties and extrusion processability. By mixing these resins in a well-balanced manner, mechanical properties and flame retardancy can be improved.
- the thermoplastic resin contains 50 to 100% by mass of an ethylene- ⁇ olefin copolymer having a carbonyl group, and the ethylene- ⁇ olefin copolymer having a carbonyl group has a comonomer content of 9 to 46% by mass.
- the melt flow rate is preferably 0.3 to 25 g / 10 min.
- the ethylene- ⁇ -olefin copolymer having a carbonyl group is excellent in flame retardancy, and even when used alone, the properties can be balanced, and therefore the resin composition can be easily mixed.
- the melt flow rate (MFR) is a value measured under conditions of 190 ° C. and a load of 2.16 kg in accordance with ASTM D 1238.
- the flame retardant it is preferable to further contain 3 to 100 parts by mass of a nitrogen-based flame retardant with respect to 100 parts by mass of the thermoplastic resin.
- the flame retardancy can be further improved by using the above organic phosphorus flame retardant and nitrogen flame retardant together.
- the nitrogen-based flame retardant melamine cyanurate can be preferably used (Claim 6).
- a phosphoric acid ester is further contained as the organophosphorus flame retardant (claim 7).
- the flame retardancy of the flame retardant resin composition is further improved by using together an organic phosphorus flame retardant having excellent flame retardancy such as a phosphinic acid metal salt and a phosphate ester.
- invention of Claim 8 is an insulated wire which has a coating layer which consists of a flame-retardant resin composition in any one of said.
- the invention according to claim 9 is a flat cable in which a plurality of conductors are arranged in parallel in the insulating coating layer at intervals, wherein the insulating coating layer is the flame retardant resin composition according to any one of the above. It is a flat cable made of objects.
- the invention according to claim 10 is a molded article obtained by injection molding the flame retardant resin composition according to any one of the above.
- the invention according to claim 11 is the insulated wire according to claim 8, which passes the vertical combustion test (VW-1).
- the invention according to claim 12 is the flat cable according to claim 9, which passes the vertical combustion test (VW-1).
- a flame retardant resin composition that can achieve both mechanical properties and flame retardancy and is particularly excellent in heat resistance, and an insulated wire, a flat cable, and a molded product using the flame retardant resin composition.
- Phosphorus flame retardant Various materials constituting the flame retardant resin composition of the present invention will be described.
- an organic phosphorus flame retardant one or more selected from the group consisting of polyphosphazene compounds obtained by ring-opening polymerization of phosphinic acid metal salts, melamine phosphate compounds, ammonium phosphate compounds, and cyclophosphazenes are essential components. To do. Of these, phosphinic acid metal salts are particularly preferred because of their excellent flame retardancy.
- the phosphinic acid metal salt is a compound represented by the following formula (I).
- R1 and R2 are each an alkyl group having 1 to 6 carbon atoms or an aryl group having 12 or less carbon atoms
- M is calcium, aluminum, or zinc
- phosphinic acid metal salt aluminum salt of organic phosphinic acid such as EXOLIT OP1230, EXOLIT OP1240, EXOLIT OP930, EXOLIT OP935 etc. manufactured by Clariant Co., Ltd., or a blend of aluminum phosphinic acid such as EXOLIT OP1312 and melamine polyphosphate You can use things.
- melamine polyphosphate such as MELAPUR200 manufactured by Ciba Specialty Co., Ltd., melamine polyphosphate, melamine phosphate, melamine orthophosphate, melamine pyrophosphate, or the like can be used.
- ammonium phosphate compound ammonium polyphosphate, polyphosphate amide, ammonium polyphosphate amide, polyphosphate carbamic acid and the like can be used.
- polyphosphazene compound obtained by ring-opening polymerization of cyclophosphazene SPR-100, SA-100, SR-100, SRS-100, SPB-100L, etc. manufactured by Otsuka Chemical Co., Ltd. can be used.
- the above organophosphorous flame retardants may be used alone or in combination.
- phosphate esters include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, cresyl 2,6-xylenyl phosphate, 2- Ethylhexyl diphenyl phosphate, 1,3 phenylene bis (diphenyl phosphate), 1,3 phenylene bis (di 2,6 xylenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis diphenyl phosphate, octyl diphenyl Phosphate, diethylene ethyl ester phosphate, dihydroxypropylene butyl ester phosphate, ethylene disodium ester phosphate,
- the content of the organic phosphorus flame retardant is 5 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
- the organophosphorus flame retardant may be used by treating the surface with melamine, melamine cyanurate, fatty acid, or silane coupling agent. Further, instead of pre-treating the surface in advance, an integral blend in which a surface treating agent is added when mixing with the thermoplastic resin may be performed.
- thermoplastic resin polyphenylene ether resin, polyethylene terephthalate, polybutylene terephthalate, thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, styrene thermoplastic elastomer, polystyrene resin, nylon, thermoplastic polyamide Elastomer, polyolefin resin having carbon-carbon unsaturated bond, resin having carbon-carbon unsaturated bond, such as polyolefin resin having carbonyl group, and resin having carbonyl group are 5% by mass or more based on the whole thermoplastic resin. It is necessary to contain.
- Polyphenylene ether is an engineering plastic obtained by oxidative polymerization of 2,6-xylenol synthesized from methanol and phenol.
- various materials are commercially available as modified polyphenylene ether resins in which polyphenylene ether is blended with polystyrene, HIPS, styrene butadiene rubber, or a hydrogenated product thereof.
- the polyphenylene ether resin used in the present invention any of the above-mentioned polyphenylene ether resin alone and polystyrene, HIPS, styrene butadiene rubber, or polyphenylene ether resin obtained by melt blending these hydrogenated products can be used.
- transduced carboxylic acid, such as maleic anhydride can also be blended suitably and used.
- polystyrene-based resin examples include polystyrene obtained by polymerizing styrene and HIPS in which rubber is dispersed, and those obtained by introducing maleic anhydride, an epoxy group, and oxazoline may be appropriately blended and used.
- Styrenic thermoplastic elastomer is a block copolymer of polystyrene block and rubber component block.
- the styrenic thermoplastic elastomer referred to in the present invention is styrene / ethylene butylene / styrene copolymer, styrene / ethylene butylene copolymer, styrene / ethylene butylene / olefin copolymer, styrene / isoprene copolymer, styrene / ethylene.
- styrene / isoprene / styrene copolymers styrene / ethylene / isoprene / styrene copolymers, etc.
- the styrene butadiene rubber include styrene and butadiene copolymers having a styrene content of 30 to 60% by mass, hydrogenated polymers, partially hydrogenated polymers, and the like.
- maleic anhydride modified Or can be exemplified an epoxy-modified product, besides using these alone, it may be used in combination.
- Polyolefin resins include polypropylene (homopolymer, block polymer, random polymer), polypropylene thermoplastic elastomer, reactor-type polypropylene thermoplastic elastomer, dynamically cross-linked polypropylene thermoplastic elastomer, polyethylene (high-density polyethylene, linear) Low density polyethylene, low density polyethylene, ultra low density polyethylene), ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, Ethylene-ethyl methacrylate copolymer, ethylene-propyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-propylene rubber, ethylene acrylic rubber, ethylene-glycidyl methacrylate Ionomer resins, etc., in which intermolecular bonds of sodium, zinc, and other metal ions are used
- ethylene- ⁇ olefin copolymers having a carbonyl group having a comonomer content of 9 to 46% by mass and a melt flow rate of 0.3 to 25 g / 10 min are particularly flame retardant. It is excellent, and the burning time can be shortened. As the comonomer content increases, the flame retardancy improves. However, since the resin price increases as the comonomer content increases, the comonomer content is preferably 9 to 46% by mass considering the balance of flame retardancy and cost.
- Thermoplastic polyurethane elastomer is a polymer in which a polyurethane composed of a condensation polymer of diisocyanate such as tolylene diisocyanate and a short chain diol such as polyethylene glycol is used as a hard segment, and a soft segment comprising a bifunctional polyol is block copolymerized. It is.
- a polyether type using polytetramethylene glycol (PTMG) or the like, an adipate type, a caprolactone type, a polycarbonate type, or the like can be used. Among these, it is preferable to select one having a hardness of 95 or less in JIS A.
- Thermoplastic polyamide elastomers include amorphous hard composed of crystalline hard segments such as 6-nylon, 6,6-nylon, 11-nylon and 12-nylon and polyoxymethylene glycol such as polytetramethylene ether glycol.
- a block copolymerized segment can be used.
- Polyfunctional monomers include monoacrylates, diacrylates, triacrylates, monomethacrylates, dimethacrylates, trimethacrylates, triallyl isocyanurates, triallyl cyanurates, etc.
- Monomers having a carbon-carbon double bond can be used.
- the content of the polyfunctional monomer is 1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin. If it is less than 1 part by mass, the crosslinking effect cannot be obtained, and the heat distortion resistance and heat resistance are lowered. On the other hand, when the amount exceeds 20 parts by mass, the unreacted monomer remains, resulting in poor flame retardancy.
- a ring agent or the like may be added.
- Metal hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, or nitrogen-based flame retardants such as melamine and melamine cyanurate may be added.
- a nitrogen-based flame retardant such as melamine or melamine cyanurate because flame retardancy is further improved.
- the content of the nitrogen-based flame retardant is 3 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
- An organophosphorus flame retardant selected from the group consisting of polyphosphazene compounds obtained by ring-opening polymerization of phosphinic acid metal salts, melamine phosphate compounds, ammonium phosphate compounds, and cyclophosphazenes has a plasticizing effect. Even when a flame retardant is used in combination, flexibility does not decrease.
- the above components are mixed in a predetermined amount and mixed using a known mixer such as a single screw extruder, an open roll mixer, a pressure kneader, a Banbury mixer, a twin screw mixer, etc., and a flame retardant resin composition Can be obtained.
- a known mixer such as a single screw extruder, an open roll mixer, a pressure kneader, a Banbury mixer, a twin screw mixer, etc.
- a flame retardant resin composition Can be obtained.
- the twin screw mixer is preferable in terms of kneading properties and productivity.
- the insulated wire has a coating layer made of the flame retardant resin composition, and the coating layer is formed on the conductor directly or through another layer.
- a known extruder such as a melt extruder can be used.
- the insulating layer is preferably cross-linked by irradiating with ionizing radiation.
- the conductor copper wire, aluminum wire, etc. having excellent conductivity can be used.
- the diameter of the conductor can be appropriately selected according to the intended use, but is preferably 2 mm or less in order to enable wiring in a narrow space. In consideration of ease of handling, the thickness is preferably 0.1 mm or more.
- the conductor may be a single wire or may be a strand of a plurality of strands.
- the thickness of the coating layer can be appropriately selected according to the conductor diameter. In consideration of insulation and flame retardancy, the thickness is preferably 0.1 mm to 2 mm. The thinner the coating layer, the better the flexibility. However, if the coating layer is too thin, flame retardancy cannot be ensured.
- the insulated wire of the present invention is excellent in that it can ensure flame retardancy that passes the VW-1 flame retardancy test even if the thickness of the entire insulating layer is reduced.
- the coating layer is cross-linked by irradiation with ionizing radiation in that the mechanical strength is improved.
- ionizing radiation sources include accelerated electron beams, gamma rays, X-rays, ⁇ rays, ultraviolet rays, and the like. Accelerated electron beams are used from the viewpoint of industrial use, such as ease of use of the radiation source, transmission thickness of ionizing radiation, and speed of crosslinking treatment Is most preferably used.
- the flat cable is a cable in which a plurality of conductors are arranged in parallel at intervals in an insulating coating layer made of the above-mentioned flame retardant resin composition.
- a conductive metal such as copper, tin-plated annealed copper, or nickel-plated annealed copper can be used.
- the conductor preferably has a rectangular shape, and its thickness corresponds to the amount of current used, but is preferably 15 ⁇ m to 200 ⁇ m in view of the flexibility of the flat cable.
- the flat cable may be formed by extruding a flame retardant resin composition into conductors arranged in parallel, or a film of the flame retardant resin composition is formed in advance and arranged in parallel with two films. After sandwiching the conductor, the films may be formed by thermocompression bonding. Moreover, you may coat
- the molded product is obtained by injection molding the flame retardant resin composition.
- the injection-molded molded product is irradiated with ionizing radiation to be crosslinked to improve heat resistance.
- the VW-1 vertical combustion test described in UL standard 1581, 1080 was performed on five samples. When each sample is ignited 15 times 5 times, it digests within 60 seconds, the absorbent cotton laid underneath is not burned by burning fallen objects, and the kraft paper attached to the top of the sample does not burn or burn Things were accepted. If even one of the five samples did not pass, it was rejected. For some samples, the combustion time (time from completion of ignition to extinction) was measured.
- Heat deformation resistance This was performed according to JIS C3005.
- the insulated wire or flat cable was put in a thermostat set at 140 ° C. and preheated for 1 hour. Thereafter, a jig having a diameter of 9.5 mm was pressed against the insulated wire or the flat cable, and a load of 500 g was placed.
- the thickness of the insulating layer after being left in a constant temperature bath at 140 ° C. for 1 hour in a state where a load was applied was measured, and the remaining ratio relative to the thickness before deformation was calculated. If the remaining rate is 50% or more, it is an acceptable level.
- Examples 1 to 19, Comparative Examples 1 to 10 Each material was blended in the proportions shown in Tables 1 to 3, and 0.5 parts of oleic acid amide, pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4) were added to 100 parts of the base polymer. -Hydroxyphenyl) propionate] 3 parts by mass was added and kneaded in a twin screw mixer set at a die temperature of 280 ° C.
- 17 wires of twisted annealed copper wire) were extruded and coated to a thickness of 0.4 mm, and an electron beam with an acceleration voltage of 2 MeV was irradiated with 250 kGy to produce an insulated wire.
- the conductor used was a twist of seven 0.16 mm ⁇ tin-plated annealed copper wires, and the coating thickness (wall thickness) was 0.27 mm.
- the created insulated wires were evaluated for mechanical properties, heat resistance, flame retardancy, heat distortion, and heat resistance with conductor. In addition, mechanical characteristics and heat resistance were evaluated by using only the covering layer obtained by removing the conductor from the prepared insulated wire.
- Examples 20 to 22, Comparative Examples 11 to 18 Using the flame-retardant resin compositions shown in Tables 4 and 5, eight conductors (flat conductors having a thickness of 0.15 mm and a width of 1.2 mm) were arranged in parallel at intervals of 0.8 mm (pitch 2.0 mm). After extrusion coating so that the coating thickness was 0.2 mm on both sides of the conductor, an electron beam with an acceleration voltage of 2 MeV was irradiated with 250 kGy to create a flat cable, and a series of evaluations were performed.
- Examples 23 to 25, Comparative Examples 19 to 21 The flame retardant resin compositions shown in Tables 6 and 7 were extruded on a biaxially stretched polyester film (thickness: 12 ⁇ m) by a T-die extrusion method to a thickness of 30 ⁇ m to prepare a polyester film-bonded tape. 27 pieces of conductor (flat conductor with thickness 0.05mm x width 0.1mm) are arranged in parallel at intervals of 0.2mm (pitch 0.3mm). A series of evaluations were performed after the flat cables were prepared by bonding them using a thermal laminator. The mechanical properties and heat resistance were evaluated by preparing a film of a flame retardant resin composition alone that is not bonded to a polyester film.
- Phosphinic acid metal salt Exolit OP935 manufactured by Clariant Co., Ltd. (OP930 fine particle type)
- Polyphosphazene SPB-100L manufactured by Otsuka Chemical
- Example 1 using polyphenylene ether, styrene thermoplastic elastomer, and ethylene- ⁇ olefin copolymer having a carbonyl group (polyolefin resin) as the thermoplastic resin has a short combustion time of 20 seconds and is particularly flame retardant. Was excellent.
- Example 17 In Examples 1, 10, and 14 to 18 containing 50 parts by mass or more of an ethylene- ⁇ -olefin copolymer having a carbonyl group, the burning time was within 30 seconds and the flame retardancy was excellent.
- the formulation of Example 17 was able to balance the characteristics with only one type of resin.
- mixing is easy and the cost is high. Has the advantage of lowering.
- the content of the organophosphorous flame retardant is 105 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
- the result was inferior in heat resistance, heat deformability, and heat resistance with a conductor.
- the insulated wires of Comparative Examples 2, 3, 4, 9, and 10 and the flat cables of Comparative Examples 12, 13, and 14 had a low content of organophosphorus flame retardant and failed in flame retardancy.
- the insulated wire of Comparative Example 5 and the flat cable of Comparative Example 15 were clear of flame retardancy, but failed due to heat resistance with conductors.
- the insulated wire of Comparative Example 6 and the flat cable of Comparative Example 16 have a low content of less than 5% by mass of a resin having a carbon-carbon unsaturated bond or a resin having a carbonyl group in the thermoplastic resin, and have low flame resistance. It was a failure.
- the insulated wire of Comparative Example 7 and the flat cable of Comparative Example 17 are low in elongation because the content of the polyfunctional monomer is 22 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and more than 20 parts by mass. The flammability was also rejected. Since the insulated wire of Comparative Example 8 and the flat cable of Comparative Example 18 did not contain a polyfunctional monomer, the results were inferior in heat resistance, heat resistance with conductor, and heat deformability.
- the insulated wire of Comparative Example 10 and the flat cables of Comparative Examples 19 and 20 are opened with phosphinic acid metal salts, melamine phosphate compounds, ammonium phosphate compounds, and cyclophosphazenes, which are highly flame retardant organophosphorus flame retardants.
- 17 wires of twisted annealed copper wire were extrusion coated so as to have a thickness of 0.4 mm, and irradiated with an electron beam having an acceleration voltage of 2 MeV to produce an insulated wire.
- the created insulated wires were evaluated for mechanical properties, heat resistance, flame retardancy, heat distortion, and heat resistance with conductor. In addition, mechanical characteristics and heat resistance were evaluated by using only the covering layer obtained by removing the conductor from the prepared insulated wire.
- Examples 29 to 35 satisfied the required characteristics in all the items of mechanical characteristics, flame retardancy, heat resistance, heat deformability, and heat resistance with conductor. Further, Examples 33 to 35 in which the organophosphorus flame retardant and the nitrogen flame retardant were used in combination had a short combustion time of 30 seconds or less and were excellent in flame retardancy.
- Table 10 shows the results of Example 23 using only the organophosphorus flame retardant.
- Examples 37 and 38 using the flame retardant resin composition of Example 32 and Example 33 in which an organophosphorus flame retardant and a nitrogen flame retardant are used in combination have a short combustion time of 30 seconds or less, making it flame retardant. It was excellent.
- the flame retardant resin composition is excellent in mechanical strength (elongation, tensile strength), heat distortion resistance, and heat resistance. Insulated wires, flat cables and molded products can be obtained and used as internal wiring and parts for electronic equipment, OA equipment, consumer electronic equipment such as audio, video, DVD, Blu-ray, vehicles, ships, etc. Is possible.
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Abstract
Description
本発明の難燃性樹脂組成物を構成する各種材料について説明する。有機リン系難燃剤としては、ホスフィン酸金属塩、リン酸メラミン化合物、リン酸アンモニウム化合物、及びシクロホスファゼンを開環重合して得られるポリホスファゼン化合物からなる群から選ばれる1種以上を必須成分とする。このなかでも特にホスフィン酸金属塩が難燃性に優れており好ましい。
(機械的特性)
絶縁電線、フラットケーブルの被覆層について、引張試験(引張速度=500mm/分、標線間距離=20mm)を行い、引張強度(MPa)と引張破断伸び(%)を各3点の試料で測定し、それらの平均値を求めた。引張強さが10.4MPa以上かつ引張破断伸び150%を合格レベルとした。
絶縁電線、フラットケーブルを158℃に設定したギアオーブン内で168時間(7日間)放置した後、機械的特性評価と同様に引張試験を行い、加熱処理前の引張強度、破断伸びとの比較を行った。加熱処理前の引張強度、破断伸びに対する残率75%以上を合格レベルとした。
UL規格1581、1080項に記載のVW-1垂直燃焼試験を5点の試料で行った。各試料に15秒着火を5回繰り返した場合に、60秒以内に消化し、下部に敷いた脱脂綿が燃焼落下物によって類焼せず、かつ試料の上部に取り付けたクラフト紙が燃えたり焦げたりしないものを合格とした。5点の試料中1点でも合格レベルにならなかった場合には不合格とした。また一部の試料については燃焼時間(着火終了から消火までの時間)を測定した。
JIS C3005に準じて行った。絶縁電線又はフラットケーブルを140℃に設定した恒温槽に入れて1時間予熱した。その後、絶縁電線又はフラットケーブルに直径9.5mmの治具を押し当てて500gの荷重を載せた。荷重をかけた状態で140℃の恒温槽内で1時間放置した後の絶縁層の厚みを測定し、変形前の厚みに対する残率を算出した。残率50%以上であれば合格レベルである。
絶縁電線の場合は外径と同径の金属棒に巻き付けたサンプルを、フラットケーブルの場合はZ曲げ(2カ所を180度に折り曲げ)したサンプルを158℃に設定したギアオーブン内で168時間(7日間)放置した後、絶縁層の外観を観察した、クラックや割れなどが発生したものを不合格、外観上特に変化がないものを合格とした。
表1~表3に示す割合で各材料を配合し、さらにベースポリマー100部に対してオレイン酸アミド0.5部、ペンタエリスリトール-テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]3質量部を加えてダイス温度280℃に設定した二軸混合機で混練した。得られた混練物のストランドをペレタイザーでペレット状にした後、溶融押出機(45mmΦ、L/D比=24、圧縮比2.5、フルフライトタイプ)を使用して導体(0.16mmΦの錫メッキ軟銅線を17本撚りしたもの)上に肉厚が0.4mmになるように押出被覆し、加速電圧2MeVの電子線を250kGy照射して絶縁電線を作成した。なお実施例8及び実施例9では、導体は0.16mmΦの錫メッキ軟銅線を7本撚りしたものを使用し、被覆厚み(肉厚)を0.27mmとした。作成した絶縁電線について、機械的特性、耐熱性、難燃性、加熱変形性、導体付き耐熱性を評価した。なお機械的特性及び耐熱性は、作成した絶縁電線から導体を取り除いて被覆層のみとしたものを使用して評価した。
表4、表5に示す難燃性樹脂組成物を使用し、導体(厚み0.15mm×幅1.2mmの平角導体)を0.8mm間隔(ピッチ2.0mm)で8本並列に配置した導体の両面に、被覆厚が0.2mmとなるように押出被覆した後、加速電圧2MeVの電子線を250kGy照射してフラットケーブルを作成し、一連の評価を行った。
表6、表7に示す難燃性樹脂組成物をTダイ押出法で二軸延伸ポリエステルフィルム(厚み12μm)上に、厚みが30μmとなるように押出して、ポリエステルフィルム貼り合わせテープを作成した。導体(厚み0.05mm×幅0.1mmの平角導体)を0.2mm間隔(ピッチ0.3mm)で27本並列に配置した導体の両面にポリエステルフィルム貼り合わせテープを2枚、ポリエステルフィルムが外面となるように配置し、熱ラミネータを用いて貼り合わせてフラットケーブルを作成した後、一連の評価を行った。なお機械的特性及び耐熱性は、ポリエステルフィルムと貼り合わせない難燃性樹脂組成物単独のフィルムを作製して評価した。
(*2)旭化成ケミカルズ(株)製ザイロンX9102
(*3)PSジャパン(株)製HH102
(*4)スチレン-エチレンブチレン-スチレン共重合体:旭化成ケミカルズ(株)製タフテックH1041(スチレン量30wt%)
(*5)スチレン・エチレン・ブチレン・オレフィン結晶ブロックポリマー:JSR株式会社製ダイナロン4600P(スチレン量20wt%)
(*6)エチレン-エチルアクリレート:日本ポリエチレン(株)製レクスパールA1150(15%EA)
(*7)超低密度ポリエチレン:ダウケミカル日本(株)製エンゲージ8150(MFR=0.5@190℃*2.16kg、密度=0.868g/cm3)
(*8)ホスフィン酸金属塩:クラリアント(株)製ExolitOP930
(*9)ポリリン酸メラミン:チバスペシャルティ製Melapur200
(*10)ポリホスファゼン:大塚化学(株)製SPS-100
(*11)縮合リン酸エステル:大八化学工業(株)製PX-200(リン9.0%)
(*12)トリメチロールプロパントリメタクリレート:新中村化学工業(株)製NKエステルTMPT
(*13)ランダム共重合熱可塑性ポリエステルエラストマー:EMSケミー製GriltexD 1652E GF(融点85℃)
(*14)熱可塑性ポリウレタンエラストマー:レザミンPL201(エーテル系)
(*15)熱可塑性ポリアミドエラストマー:アルケマ製Pebax2533(融点134℃)
(*16)エチレン-メチルアクリレート:Dupont製エルバロイAC1125(25%MA、MFR=0.5@190℃*2.16kg、コモノマー含有量25質量%)
(*17)超低密度ポリエチレン:ダウケミカル日本製エンゲージ8150(MFR=0.5@190℃*2.16kg、密度=0.868g/cm3)
(*18)ホスフィン酸金属塩:クラリアント(株)社製Exolit OP935(OP930の微粒タイプ)
(*19)ポリホスファゼン:大塚化学製SPB-100L
(*20)超低密度ポリエチレン:ダウケミカル日本(株)製エンゲージ8411(MFR=18@190℃×2.16kg、密度0.880g・cm3)
(*21)三光(株)製環状有機リン系難燃剤HCA-HQ-HS
(*22)チバスペシャルティ(株)製Melapur MC15
(*23)縮合リン酸エステル:大八化学工業(株)製PX-110(リン7.8%)
(*24)日産化学(株)製MC6000
特に、熱可塑性樹脂としてポリフェニレンエーテル、スチレン系熱可塑性エラストマー、カルボニル基を有するエチレン-αオレフィン共重合体(ポリオレフィン系樹脂)を使用した実施例1は燃焼時間が20秒と短く、特に難燃性が優れていた。またカルボニル基を有するエチレン-αオレフィン共重合体を50質量部以上含有する実施例1、10、14~18はいずれも燃焼時間が30秒以内であり難燃性に優れていた。特に実施例17の配合は1種類の樹脂のみで特性のバランスを取ることが可能であった。混合する樹脂の種類が多い場合は樹脂同士の相溶性を高めるために混合時に剪断応力をかける必要があり混合のコストが上がるが、1種類の樹脂を使用する場合には混合が容易でありコストが下がるという利点がある。
表9に示す割合で各材料を配合し、さらにベースポリマー100部に対してオレイン酸アミド0.5部、ペンタエリスリトール-テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]3質量部を加えてダイス温度280℃に設定した二軸混合機で混練した。得られた混練物のストランドをペレタイザーでペレット状にした後、溶融押出機(45mmΦ、L/D比=24、圧縮比2.5、フルフライトタイプ)を使用して導体(0.16mmΦの錫メッキ軟銅線を17本撚りしたもの)上に肉厚が0.4mmになるように押出被覆し、加速電圧2MeVの電子線を照射して絶縁電線を作成した。作成した絶縁電線について、機械的特性、耐熱性、難燃性、加熱変形性、導体付き耐熱性を評価した。なお機械的特性及び耐熱性は、作成した絶縁電線から導体を取り除いて被覆層のみとしたものを使用して評価した。
表10に示す難燃性樹脂組成物を使用し、導体(厚み0.15mm×幅1.2mmの平角導体)を0.8mm間隔(ピッチ2.0mm)で8本並列に配置した導体の両面に、被覆厚が0.2mmとなるように押出被覆した後、加速電圧2MeVの電子線を250kGy照射してフラットケーブルを作成し、一連の評価を行った。
Claims (12)
- 熱可塑性樹脂、多官能性モノマー、有機リン系難燃剤を含有する難燃性樹脂組成物であって、
前記熱可塑性樹脂は、炭素-炭素不飽和結合を有する樹脂又はカルボニル基を有する樹脂を熱可塑性樹脂全体に対して5質量%以上含有し、
前記有機リン系難燃剤は、ホスフィン酸金属塩、リン酸メラミン化合物、リン酸アンモニウム化合物、及びシクロホスファゼンを開環重合して得られるポリホスファゼン化合物からなる群から選ばれる1種以上であり、
前記有機リン系難燃剤の含有量が前記熱可塑性樹脂100質量部に対して5~100質量部であり、前記多官能性モノマーの含有量が前記熱可塑性樹脂100質量部に対して1~20質量部である、難燃性樹脂組成物。 - 前記熱可塑性樹脂は、ポリフェニレンエーテル系樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、熱可塑性ポリエステルエラストマー、熱可塑性ポリウレタンエラストマー、スチレン系熱可塑性エラストマー、ポリスチレン系樹脂、ナイロン、熱可塑性ポリアミドエラストマー、炭素-炭素不飽和結合を持つポリオレフィン系樹脂、カルボニル基を有するポリオレフィン系樹脂からなる群から選ばれる1種以上を5質量%以上含有する、請求項1に記載の難燃性樹脂組成物。
- 前記熱可塑性樹脂は、ポリフェニレンエーテル系樹脂又はポリスチレン系樹脂5~80質量%、スチレン系熱可塑性エラストマー20~95質量%、ポリオレフィン系樹脂0~70質量%からなる、請求項1又は2に記載の難燃性樹脂組成物。
- 前記熱可塑性樹脂はカルボニル基を有するエチレン-αオレフィン共重合体を50~100質量%含有し、該カルボニル基を有するエチレン-αオレフィン共重合体は、コモノマー含有量が9~46質量%であると共にメルトフローレートが0.3~25g/10分である、請求項1又は2に記載の難燃性樹脂組成物。
- さらに、前記熱可塑性樹脂100質量部に対して、窒素系難燃剤を3~100質量部含有する、請求項1~4のいずれか一項に記載の難燃性樹脂組成物。
- 前記窒素系難燃剤がメラミンシアヌレートである、請求項5に記載の難燃性樹脂組成物。
- 前記有機リン系難燃剤としてさらにリン酸エステルを含有する請求項1~6のいずれか1項に記載の難燃性樹脂組成物。
- 請求項1~7のいずれか1項に記載の難燃性樹脂組成物からなる被覆層を有する絶縁電線。
- 絶縁被覆層内に複数本の導体を間隔をおいて並列に配置したフラットケーブルであって、上記絶縁被覆層が請求項1~7のいずれか1項に記載の難燃性樹脂組成物からなるフラットケーブル。
- 請求項1~7のいずれか1項に記載の難燃性樹脂組成物を射出成形した成形品。
- UL規格で規定される垂直燃焼試験(VW-1)に合格する、請求項8に記載の絶縁電線。
- UL規格で規定される垂直燃焼試験(VW-1)に合格する、請求項9に記載のフラットケーブル。
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US13/500,872 US20120205136A1 (en) | 2009-10-06 | 2010-10-01 | Flame-retardant resin composition, and insulated electric wire, flat cable, and molded article, which are made using same |
SG2012018222A SG179145A1 (en) | 2009-10-06 | 2010-10-01 | Flame-retardant resin composition, and insulated electric wire, flat cable, and molded article, which are made using same |
CN2010800451839A CN102575106A (zh) | 2009-10-06 | 2010-10-01 | 阻燃性树脂组合物、以及使用了该阻燃性树脂组合物的绝缘电线、扁平电缆和模制品 |
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Also Published As
Publication number | Publication date |
---|---|
MY160886A (en) | 2017-03-31 |
SG179145A1 (en) | 2012-04-27 |
CN102575106A (zh) | 2012-07-11 |
EP2471871A4 (en) | 2014-09-17 |
TW201120138A (en) | 2011-06-16 |
KR20120088698A (ko) | 2012-08-08 |
JP2011099084A (ja) | 2011-05-19 |
TWI485199B (zh) | 2015-05-21 |
JP5556183B2 (ja) | 2014-07-23 |
EP2471871A1 (en) | 2012-07-04 |
US20120205136A1 (en) | 2012-08-16 |
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