WO2022044539A1 - Composition de résine de polyamide et article moulé obtenu par moulage de cette dernière - Google Patents

Composition de résine de polyamide et article moulé obtenu par moulage de cette dernière Download PDF

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WO2022044539A1
WO2022044539A1 PCT/JP2021/024902 JP2021024902W WO2022044539A1 WO 2022044539 A1 WO2022044539 A1 WO 2022044539A1 JP 2021024902 W JP2021024902 W JP 2021024902W WO 2022044539 A1 WO2022044539 A1 WO 2022044539A1
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weight
flame retardant
polyamide resin
parts
resin composition
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PCT/JP2021/024902
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English (en)
Japanese (ja)
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森山正幸
吉川元晴
秋田大
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東レ株式会社
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Priority to CN202180044102.1A priority Critical patent/CN115916899A/zh
Priority to JP2021541123A priority patent/JPWO2022044539A1/ja
Publication of WO2022044539A1 publication Critical patent/WO2022044539A1/fr

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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
    • 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
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention is a polyamide resin composition having excellent rigidity and toughness during water absorption, excellent glow wire characteristics, flame retardancy, and electrical characteristics, and capable of reducing resin discoloration and mold stains during continuous molding, and molding thereof. It is related to a molded product.
  • plastic materials are widely used for power supply peripheral members of electrical and electronic parts such as connectors.
  • polyamide resins are widely used for power supply peripheral members because they are excellent in moldability, mechanical properties, heat resistance, flame retardancy, and electrical properties, and various resins are used according to the resin properties and required needs. High functionality and high performance have been achieved by prescription.
  • the comparative tracking index (Comparative Tracking Index (CTI)) is 250 V or more with a thickness of 3 mm.
  • Patent Document 1 describes a polyamide resin composition containing a halogen-based flame retardant using ethylene-bis (pentabromobenzene), which has a particularly high bromine content among halogen-based flame retardants. Proposed. Further, in Patent Document 2, a polyamide resin containing a halogen-based flame retardant in combination with ethylene-bis (pentabromobenzene) and a triazine-based flame retardant which is a non-halogen flame retardant as a flame retardant imparting tracking resistance. Compositions have been proposed.
  • Patent Document 1 flame retardancy V-0 (0.8 mm thickness) is achieved, but CTI is 225 V.
  • Ethylene-bis (pentabromobenzene) is a monomer-type flame retardant, has poor heat resistance, and is a resin for molded products in continuous molding at a cylinder temperature of 260 ° C or higher, which is the general molding temperature for nylon resins. There was a problem that mold stains frequently occurred due to discoloration and generation of gas.
  • Patent Document 2 by combining ethylene-bis (pentabromobenzene) with a triazine-based flame retardant, which is a non-halogen flame retardant as a flame retardant that imparts tracking resistance, in a region where a large amount of triazine-based flame retardant is blended.
  • Flame retardant V-0 (0.8 mm thickness), GW-IT 775 ° C (3 mm thickness), CTI 400 V or higher.
  • the effect of improving the flame retardancy and glow wire property of the triazine-based flame retardant is not so high as compared with the halogen-based flame retardant, a large amount of compounding is required and the toughness becomes poor.
  • the flame retardancy did not reach V-0, and the problems of resin discoloration and mold stain during continuous molding remained.
  • the present invention has an excellent balance of flame retardancy, glow wire characteristics, tracking resistance, rigidity and toughness, and can reduce resin discoloration and mold stains during continuous molding. It is an object to provide a composition.
  • the present invention has the following configuration.
  • it can be a molded product made of the above-mentioned polyamide resin composition.
  • the polyamide resin composition of the present invention comprises a polyamide resin (A), a flame retardant (B) containing 75% by weight or more and 90% by weight or less of bromine in one molecule, a flame retardant aid (C), and an average particle size of 0. It is composed of a triazine-based flame retardant (D) of 1 to 20 ⁇ m.
  • the polyamide resin (A) constituting the polyamide resin composition according to the present invention is a polyamide obtained by polycondensation of a three-membered ring or more lactam, a polymerizable ⁇ -amino acid, or a dibasic acid and a diamine. .. Specifically, polymers such as ⁇ -caprolactam, aminocaproic acid, enantractum, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, ⁇ -pyrrolidone, ⁇ -piperidone, tetramethylenediamine, pentamethylene.
  • Diamine Hexamethylenediamine, Nonamethylenediamine, Undecamethylenediamine, Dodecamethylenediamine, Metaxylylenediamine, Paraxylylenediamine, 2-Methylpentamethylenediamine, 2,2,4- / 2,4,4-trimethyl Hexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylsik Hexamethylenediamine, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, etc.
  • Fat group alicyclic group, aromatic diamine, adipic acid, spellic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid.
  • an aliphatic, alicyclic, or aromatic dicarboxylic acid such as acid, 5-sodiumsulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and cyclohexanedicarboxylic acid. Examples thereof include the obtained polymer or a copolymer thereof.
  • These polyamide resins may be those whose ends are sealed with a carboxylic acid or an amine also for controlling the molecular weight.
  • polyamide 4 polyamide 6, polyamide 7, polyamide 8, polyamide 11, polyamide 12, polyamide 46, polyamide 56, polyamide 66, polyamide 69, polyamide 410, polyamide 510, polyamide 610, polyamide 611, polyamide. 612, Polyamide 66 / 6T copolymer, Polyamide 6/66 copolymer, Polyamide 6/12 copolymer, Polyamide 6 / 6T copolymer, Polyamide 6T / 6I copolymer, Polyamide MXD6, etc. It may be a mixture of the kinds of polyamide resins.
  • Preferred polyamide resins include polyamide 6, polyamide 6/66 copolymer, polyamide 66, and mixtures thereof from the viewpoints of flame retardancy, rigidity / toughness, and moldability, and polyamide 66 is particularly preferable.
  • Examples of the flame retardant (B) containing 75% by weight or more and 90% by weight or less of bromine in one molecule constituting the polyamide resin composition according to the present invention include ethylene-bis (pentabromobenzene) and decabromodiphenyloxide. Examples thereof include tetradecabromodihydroxybenzene.
  • ethylene-bis (pentabromobenzene) is preferable from the viewpoint of the balance between toughness, flame retardancy, glow wire characteristics, and tracking resistance.
  • one molecule contains 80% by weight or more and 85% by weight or less of bromine.
  • the blending amount of the flame retardant (B) containing 75% by weight or more and 90% by weight or less of bromine in one molecule is in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the polyamide resin (A).
  • the blending amount of the flame retardant (B) is preferably 8.1 to 30 parts by weight, more preferably 10 to 18 parts by weight.
  • Examples of the flame-retardant aid (C) constituting the polyamide resin composition according to the present invention include antimony compounds such as antimony trioxide and antimony pentoxide, boric acid metal salts such as zinc borate, and tin acid metal salts such as zinc tintate. Can be mentioned. In particular, antimony trioxide and zinc borate are preferable, and antimony trioxide is most preferable, from the viewpoint of imparting flame retardancy and glow wire characteristics.
  • the blending amount of the flame retardant aid (C) is 1 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin (A). When the blending amount of the flame retardant aid (C) is less than 1 part by weight, the flame retardancy and the glow wire characteristics are deteriorated. When the blending amount of the flame retardant aid (C) exceeds 10 parts by weight, the toughness is lowered.
  • the blending amount of the flame retardant aid (C) is preferably 1 to 9 parts by weight, more preferably 3 to 6 parts by weight.
  • the triazine-based flame retardant (D) constituting the flame-retardant polyamide resin composition according to the present invention includes (i) a compound represented by the following general formula (1) or (2), (ii) melamines, and (Iii) Examples thereof include equimolar reactants of (i) and (ii).
  • R 1 to R 6 each represent a hydrogen atom or an alkyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 to 5, and more preferably 1 to 3.).
  • Specific examples of the compound represented by the above general formula (1) include cyanuric acid, trimethyl cyanurate, triethyl cyanurate, tri (n-propyl) cyanurate, methyl cyanurate, diethyl cyanurate and the like.
  • Specific examples of the compound represented by the general formula (2) include isocyanuric acid, trimethylisocyanurate, triethylisocyanurate, tri (n-propyl) isocyanurate, diethylisocyanurate, methylisocyanurate and the like. ..
  • melamines examples include melamine, melamine derivatives, compounds having a structure similar to melamine, and condensates of melamine.
  • Specific examples of melamines include melamine, ammelide, ammeline, formoguanamine, guanylmelamine, cyanomelamine, arylguanamine, melam, melem, and melon.
  • an equimolar reaction product of cyanuric acid and melamine is preferably mentioned. Further, some of the amino groups or hydroxyl groups in melamine cyanurate may be substituted with other substituents.
  • Melamine cyanurate can be obtained, for example, by mixing an aqueous solution of cyanuric acid and an aqueous solution of melamine, reacting them under stirring at a temperature of 90 to 100 ° C., and filtering the produced precipitate.
  • Melamine cyanurate is a white solid and is preferably used after being pulverized into a fine powder. Of course, a solid commercial product can be used as it is, or it can be pulverized and used.
  • Melamine cyanurate is most preferable from the viewpoint of imparting rigidity, toughness, flame retardancy, glow wire characteristics, and tracking resistance in a well-balanced manner, and reducing resin discoloration and mold stains during continuous molding.
  • the average particle size of the triazine-based flame retardant (D) is 0.1 to 20 ⁇ m.
  • the triazine-based flame retardant (D) exhibits flame retardancy by combining the endothermic reaction of the sublimation heat and decomposition heat of (D) with the oxygen dilution and blocking effect of the generated nitrogen-based gas.
  • the mechanism is not clear by using the above-mentioned triazine-based flame retardant (D) having an average particle size.
  • the dispersibility of (D) in the polyamide resin composition is good, an efficient endothermic effect is exhibited, and the decomposition of (B) due to shear heat generation during melt kneading and injection molding can be significantly suppressed. Conceivable.
  • the average particle size of the triazine-based flame retardant (D) is less than 0.1 ⁇ m, it becomes difficult to supply the triazine-based flame retardant (D) to the kneader during melt-kneading.
  • the average particle size of the triazine-based flame retardant (D) exceeds 20 ⁇ m, the toughness and flame retardancy are lowered, and the resin burn and mold stain during continuous molding become remarkable.
  • Triazine-based flame retardant (D) By setting the average particle size to 0.1 to 20 ⁇ m, toughness and flame retardancy are highly exhibited, and it is difficult to contain bromine in 75% by weight% 90% by weight or less in one molecule. By efficiently suppressing the decomposition of the flame retardant (B), it is possible to suppress resin discoloration and mold stains during continuous molding.
  • the average particle size of the triazine-based flame retardant (D) is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the average particle size is a numerical average calculated from the values measured using a laser diffraction type particle size distribution meter LMS-24 (manufactured by Seishin Co., Ltd.) in accordance with JIS K 5600-9-3 (2006). Particle size.
  • the triazine-based flame retardant (D) has the same particle size as the raw material before melting and mixing and the particle size in the polyamide resin composition.
  • the blending amount of the triazine-based flame retardant (D) is 1 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin (A). If the blending amount of the triazine-based flame retardant (D) is less than 1 part by weight, the flame retardancy and glow wire characteristics are deteriorated, and resin discoloration and mold stains become remarkable during continuous molding. If the blending amount of the triazine-based flame retardant (D) exceeds 10 parts by weight, the toughness is greatly reduced, which leads to breakage in the thin-walled molded product.
  • the blending amount of the triazine-based flame retardant (D) is preferably 1 to 6.9 parts by weight, more preferably 4 to 6.5 parts by weight.
  • the polyamide resin composition of the present invention contains 8.1 to 30 parts by weight of the flame retardant (B) and 1 to 6.9 parts of the triazine flame retardant (D) containing 75% by weight or 90% by weight or more of bromine in one molecule.
  • the UL-94 flame retardant standard is preferably V-0.
  • hydrotalcite used in the present invention refers to magnesium, aluminum, hydroxyoxide, carbonate, and hydrate as naturally occurring minerals in a narrow sense, and has a composition similar to that of hydrotalcite as a mineral in a broad sense. It shall also include synthetic products of metal oxides. It is preferable to use calcined hydrotalcite represented by the following general formula (3). (Mg 1-X Al X ) O 1 + 0.5X (3) However, in the formula, 0 ⁇ x ⁇ 0.4
  • the calcined hydrotalcite represented by the formula (3) is a so-called magnesium oxide-based solid solution in which aluminum oxide (Al 2 O 3 ) is solid-dissolved in magnesium oxide (MgO), and is, for example, the following general formula (4).
  • An- indicates an n- valent anion
  • x, m and n are positive numbers satisfying the range of 0 ⁇ x ⁇ 0.4, 0 ⁇ m ⁇ 1, 1 ⁇ n ⁇ 4, respectively.
  • the anions An - of the hydrotalcite of the formula (4) include F-, Cl- , Br-, I- , OH- , HCO 2- , CH 3 COO- , HCOO- , CO 3 2- , SO 4 2 -Etc ., but not limited to these.
  • the blending amount of the hydrotalcite of the present invention is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.5 parts by weight, based on 100 parts by weight of the polyamide resin component. From the viewpoint of the balance between mechanical properties and flame retardancy, it is more preferably 0.5 to 4.0 parts by weight. If it is less than 0.1 part by weight, the trapping of the halogen compound becomes insufficient and the desired mold stain suppressing effect cannot be obtained. If it exceeds 5.0 parts by weight, the mechanical properties such as strength and toughness are deteriorated. Flame retardancy and glow wire characteristics tend to deteriorate. It was
  • the polyamide resin composition of the present invention comprises a polyamide resin (A), a flame retardant (B) containing 75% by weight or more and 90% by weight or less of bromine in one molecule, and a flame retardant aid (flame retardant aid), as long as the characteristics are not impaired.
  • A a polyamide resin
  • B flame retardant
  • B flame retardant aid
  • C a triazine-based flame retardant
  • E hydrotalcite
  • thermoplastic resin other than the component (A) may be contained as another component.
  • thermoplastic resin include polyamide resins other than the polyamide resin (A), polyester resins, polyphenylene sulfide resins, polyphenylene oxide resins, polycarbonate resins, polylactic acid resins, polyacetal resins, polysulfone resins, tetrafluoropolyethylene resins, and polyetherimides.
  • polyamideimide resin polyimide resin
  • polyether sulfone resin polyether ketone resin
  • polythioether ketone resin polyether ether ketone resin
  • polyolefin resin such as polyethylene resin and polypropylene resin
  • styrene resin such as polystyrene resin and ABS resin.
  • Polyalkylene oxide resin polybutadiene, polyisoprene, styrene / butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile / butadiene copolymers, butadiene / isoprene copolymers, etc.
  • ethylene / propylene random copolymers and block copolymers ethylene / butene random copolymers and block copolymers, ethylene / ⁇ -olefin copolymers, ethylene / acrylic acid esters, ethylene / Ethylene / unsaturated carboxylic acid ester copolymers such as methacrylic acid esters, acrylic acid esters / butadiene copolymers such as butyl acrylate / butadiene copolymers, and ethylene / fatty acid vinyl copolymers such as ethylene / vinyl acetate copolymers.
  • Polymers such as ethylene / propylene / non-conjugated diene ternary copolymers such as ethylene / propylene / etilidennorbornene copolymers, ethylene / propylene / hexadiene copolymers, butylene / isoprene copolymers, chlorinated polyethylene, polyamide elastomers, Examples thereof include thermoplastic elastomers such as polyester elastomers.
  • thermoplastic resin when such a thermoplastic resin is used, the content thereof is not limited, but is preferably 0.1 part by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the polyamide resin (A).
  • an ultraviolet absorber an antioxidant, a heat stabilizer, a crystal nucleating agent, an antioxidant, a weathering agent, a mold release agent, a lubricant, an antistatic agent, etc.
  • an ultraviolet absorber an antioxidant, a heat stabilizer, a crystal nucleating agent, an antioxidant, a weathering agent, a mold release agent, a lubricant, an antistatic agent, etc.
  • One or more kinds of ordinary additives such as colorants containing dyes and pigments can be added.
  • additives examples include ultraviolet absorbers such as benzotriazole-based, phenol-based, and phosphorus-based, antioxidants such as copper-based, hindered phenol-based, phosphorus-based, and sulfur-based, heat stabilizers, and aromatic carboxylic acids.
  • organic nucleating agents such as aromatic amide compounds
  • crystal nucleating agents including talc, boron nitride, and other inorganic nucleating agents such as silicate metal salts, resorcinol-based, salicylate-based
  • Weather resistant agents such as benzotriazole, benzophenone, and hinder
  • -Sluices such as octyl oxybenzoate and wax, alkyl sulfate type anionic type, quaternary ammonium salt type cationic type, non-ionic type such as polyoxyethylene sorbitan monostearate, betaine type amphoteric antistatic agent and the like can be mentioned. It is also possible to use two or more kinds of such additives.
  • the content thereof is not particularly limited, but is preferably 0.01 parts by weight or more and less than 5 parts by weight with respect to 100 parts by weight of the polyamide resin (A).
  • the method for producing the polyamide resin composition of the present invention comprises a polyamide resin (A), a flame retardant (B) containing 75% by weight or more and 90% by weight or less of bromine in one molecule, a flame retardant aid (C), and average particles.
  • a flame retardant B
  • C flame retardant aid
  • D triazine-based flame retardant
  • melt-kneading by a twin-screw extruder is usually preferably used from the viewpoint of productivity and kneadability.
  • melt-kneading method using a twin-screw extruder include a polyamide resin (A), a flame retardant (B) containing 75% by weight or more and 90% by weight or less of bromine in one molecule, and a flame retardant aid (C).
  • a triazine flame retardant (D) having an average particle size of 0.1 to 20 ⁇ m, and if necessary, components other than (A), (B), (C), and (D), and the cylinder temperature.
  • the mixing order of the raw materials is not particularly limited, and all the raw materials are melt-kneaded by the above method, some raw materials are melt-kneaded by the above method, and the remaining raw materials are melt-kneaded, or some of them. Any method may be used, such as a method of mixing the remaining raw materials using a side feeder while the raw materials are melt-kneaded.
  • the screw configuration preferably has 1 to 5 kneading zones, and the ratio (%) of the total length of the kneading zones to the total length of the screw is calculated by (total length of the kneading zones) ⁇ (total length of the screw).
  • ⁇ 100 it is preferably 5 to 40%.
  • a method of removing the gas generated by exposing to a vacuum state in the middle of the extruder is also preferably used.
  • the resin composition extruded after melt-kneading is usually taken up in the form of strands and processed into pellets by a pelletizer.
  • the method for producing the resin of the present invention is not particularly limited, but there is no problem as long as it is a normal processing method for a thermoplastic resin, and an injection molding method having high dimensional accuracy of the product and excellent productivity is usually preferably used. ..
  • the polyamide resin composition of the present invention can be molded by any method.
  • the molding method include extrusion molding, injection molding, hollow molding, calender molding, compression molding, vacuum molding, foam molding, blow molding, rotary molding and the like.
  • the molding shape include a box shape, a plate shape, a fibrous shape, an uneven shape, a strand shape, a film or sheet shape, a pipe shape, a hollow shape, a box shape, a claw shape, and the like.
  • the obtained molded products can be applied to various uses such as electrical and electronic parts, automobile parts, vehicle-related parts, building material-related parts, general / industrial machine parts, sports goods, household goods, household / office goods, and furniture parts. Above all, high flame retardancy, glow wire characteristics, and tracking resistance are required for power supply peripheral members of unmanned operating equipment in which a current exceeding 0.2 A flows, including connectors, and fitting of molded products and insertion / removal of terminals are required.
  • the polyamide resin composition of the present invention is preferably applicable because the product is required to have large strain, high rigidity, and high toughness.
  • the unmanned driving device refers to a device that is automatically operated in the absence of an operator, or a device that is operated in a state where an operator is not nearby for a long time (several hours or more) such as at night.
  • Such equipment has a high risk of fire or explosion when heat is generated due to some abnormality, and glow wire characteristics are required.
  • the polyamide resin composition of the present invention and a molded product obtained by molding the same have high glow wire characteristics. Specifically, in the test compliant with IEC60695-2-13, the glow wire ignition temperature for the material is 775 ° C or higher at a thickness of 3 mm, and in the test compliant with IEC60695-2-11, the glow wire for the final product. It means that the temperature is 750 ° C or higher.
  • the glow wire ignition temperature is called GW-IT (Glow Wire Ignition Temperature) and is a test performed on a material. A wire heated to a desired temperature is pushed into a resin molded product having a specified thickness. It is the lowest temperature at which ignition for 5 seconds or more is confirmed.
  • the GW-IT is preferably 800 ° C. or higher with a thickness of 3 mm.
  • the glow wire temperature for the final product is called GWT (Glow-wire Temperature), which is the lowest temperature at which a wire heated to a desired temperature is pressed against the final product and combustion for 2 seconds or longer is confirmed. Yes, it is required to pass 750 ° C.
  • GWT Low-wire Temperature
  • Glow wire ignition temperature The pellets obtained in Examples and Comparative Examples were injection molded by an injection molding machine NEX1000 manufactured by Nissei Plastic Industry Co., Ltd. under the conditions of a cylinder temperature of 280 ° C and a mold surface temperature of 80 ° C. A test piece was prepared. Using the obtained test piece, the glow wire ignition temperature (GW-IT) was measured according to IEC60695-2-13.
  • CTI test Comparative tracking index test
  • the pellets obtained in Examples and Comparative Examples were injection molded by an injection molding machine NEX1000 manufactured by Nissei Plastic Industry Co., Ltd. under the conditions of a cylinder temperature of 280 ° C and a mold surface temperature of 80 ° C.
  • a test piece was prepared.
  • the resulting test piece was used to determine CTI according to IEC60112.
  • CTI shows resistance to tracking at a voltage of 25V increments between 100V and 600V when the surface of a solid electrical insulating material is wet-contaminated with an electric field applied, and the higher the value, the better.
  • the CTI is preferably 250 V or higher.
  • the ranks of CTI are as follows. 600V or higher: Rank 0 400V or more and less than 600V: Rank 1 250V or more and less than 400V: Rank 2 175V or more and less than 250V: Rank 3 100V or more and less than 175V: Rank 4
  • the raw materials of the resin compositions used in Examples and Comparative Examples are as follows.
  • A-2 Polyamide 6/66 copolymer (66 components 5% by weight) having a viscosity number of 135 ml / g measured in accordance with JIS K 6933 (2013).
  • (D-1) Melamine cyanurate with an average particle size of 14 ⁇ m measured using a laser diffraction type particle size distribution meter LMS-24 (manufactured by Seishin Co., Ltd.) according to JIS K5600-9-3.
  • (D-2) Melamine cyanurate with an average particle size of 4 ⁇ m measured using a laser diffraction type particle size distribution meter LMS-24 (manufactured by Seishin Co., Ltd.) according to JIS K5600-9-3.
  • (D-3) Melamine cyanurate with an average particle size of 2 ⁇ m measured using a laser diffraction type particle size distribution meter LMS-24 (manufactured by Seishin Co., Ltd.) according to JIS K5600-9-3.
  • (G-1) Melamine cyanurate having an average particle size of 40 ⁇ m measured according to JIS K5600-9-3.
  • Examples 1 to 7, Comparative Examples 1 to 10 Each raw material was charged from the raw material supply port upstream of the twin-screw extruder with the composition shown in Tables 1 to 3 and melt-kneaded, and the extruded strands were pelletized to obtain a pellet-shaped resin composition.
  • a MAX46 manufactured by Nippon Placon Co., Ltd. was used as a twin-screw extruder, and melt kneading was performed at a cylinder temperature of 270 ° C., a screw rotation speed of 270 rpm, and a discharge rate of 70 kg / hr.
  • the pellets of the obtained resin composition were vacuum dried at 80 ° C. for 12 hours or more, and then various characteristics were examined by the above evaluation method. The results are shown in Tables 1 to 3.
  • Example 8 by blending hydrotalcite (E), mold stains were further suppressed as compared with Example 1, and mold stains were not observed even after 1000 shot molding.
  • Comparative Example 1 since melamine cyanurate having an average particle diameter larger than 20 ⁇ m is used, the toughness and glow wire characteristics are poor as compared with Example 1, and resin discoloration and mold stains during continuous molding are also suppressed. could not.

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Abstract

La présente invention concerne une composition de résine présentant un excellent équilibre entre l'effet retardateur de flamme, les caractéristiques de fil incandescent, la résistance au cheminement, la rigidité et la ténacité, qui est susceptible de réduire la brûlure de la résine et la contamination du moule pendant un moulage continu.　L'invention porte sur une composition de résine de polyamide obtenue par mélange de 1 à 30 parties en poids d'un retardateur de flamme (B) contenant 75 à 90 % en poids de brome dans une molécule unique, 1 à 10 parties en poids d'un auxiliaire de retardateur de flamme (C) et 1 à 10 parties en poids d'un retardateur de flamme (D) à base de triazine pour 100 parties en poids de la résine de polyamide (A), la granulométrie moyenne de (D) étant de 0,1 à 20 μm.
PCT/JP2021/024902 2020-08-25 2021-07-01 Composition de résine de polyamide et article moulé obtenu par moulage de cette dernière WO2022044539A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001207053A (ja) * 1999-01-06 2001-07-31 Sankyo Organic Chem Co Ltd 難燃化ポリアミド系樹脂組成物
JP2005200636A (ja) * 2003-12-18 2005-07-28 Mitsubishi Engineering Plastics Corp 難燃性ポリアミド樹脂組成物
JP2007126555A (ja) * 2005-11-04 2007-05-24 Toray Ind Inc レーザーマーキング用難燃性ポリアミド樹脂組成物
WO2008143096A1 (fr) * 2007-05-17 2008-11-27 Mitsubishi Engineering-Plastics Corporation Composition de résine polyamide ignifuge
JP2010163472A (ja) * 2009-01-13 2010-07-29 Mitsubishi Engineering Plastics Corp 電離放射線照射用難燃性ポリアミド樹脂組成物
CN103319885A (zh) * 2013-07-23 2013-09-25 广东顺德顺炎新材料有限公司 高灼热丝、高cti值阻燃非增强尼龙及制备方法
CN109401303A (zh) * 2018-10-31 2019-03-01 中山市华邦塑料有限公司 高灼热丝起燃温度的增强阻燃尼龙组合物及其制备方法
JP2019175584A (ja) * 2018-03-27 2019-10-10 東レ株式会社 コネクターおよび樹脂組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5688201B2 (ja) * 2008-05-15 2015-03-25 三菱エンジニアリングプラスチックス株式会社 電気安全性に優れた難燃性ポリアミド樹脂組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001207053A (ja) * 1999-01-06 2001-07-31 Sankyo Organic Chem Co Ltd 難燃化ポリアミド系樹脂組成物
JP2005200636A (ja) * 2003-12-18 2005-07-28 Mitsubishi Engineering Plastics Corp 難燃性ポリアミド樹脂組成物
JP2007126555A (ja) * 2005-11-04 2007-05-24 Toray Ind Inc レーザーマーキング用難燃性ポリアミド樹脂組成物
WO2008143096A1 (fr) * 2007-05-17 2008-11-27 Mitsubishi Engineering-Plastics Corporation Composition de résine polyamide ignifuge
JP2010163472A (ja) * 2009-01-13 2010-07-29 Mitsubishi Engineering Plastics Corp 電離放射線照射用難燃性ポリアミド樹脂組成物
CN103319885A (zh) * 2013-07-23 2013-09-25 广东顺德顺炎新材料有限公司 高灼热丝、高cti值阻燃非增强尼龙及制备方法
JP2019175584A (ja) * 2018-03-27 2019-10-10 東レ株式会社 コネクターおよび樹脂組成物
CN109401303A (zh) * 2018-10-31 2019-03-01 中山市华邦塑料有限公司 高灼热丝起燃温度的增强阻燃尼龙组合物及其制备方法

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