WO2022158383A1 - Flame-retardant polyamide resin composition and molded article comprising same - Google Patents

Flame-retardant polyamide resin composition and molded article comprising same Download PDF

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Publication number
WO2022158383A1
WO2022158383A1 PCT/JP2022/001087 JP2022001087W WO2022158383A1 WO 2022158383 A1 WO2022158383 A1 WO 2022158383A1 JP 2022001087 W JP2022001087 W JP 2022001087W WO 2022158383 A1 WO2022158383 A1 WO 2022158383A1
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mass
polyamide resin
polyamide
parts
flame
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PCT/JP2022/001087
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French (fr)
Japanese (ja)
Inventor
和樹 岩村
信宏 吉村
誠 玉津島
亮 梅木
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東洋紡株式会社
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Priority to CN202280009842.6A priority Critical patent/CN116724079A/en
Priority to JP2022576644A priority patent/JPWO2022158383A1/ja
Publication of WO2022158383A1 publication Critical patent/WO2022158383A1/en

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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a non-halogen flame-retardant polyamide resin composition. More specifically, it relates to a halogen-free, flame-retardant polyamide resin composition having high flame retardancy, good snap-fitting properties, and excellent resistance to heat discoloration.
  • Polyamide resins are used in various fields such as electric/electronic parts and automobile parts, taking advantage of their excellent mechanical properties, electrical properties, chemical resistance, and the like.
  • melamine cyanurate is used as a flame retardant when non-reinforced and non-halogen flame retardants are required to impart flame retardancy (for example, Patent Documents 1 and 2).
  • melamine cyanurate has poor dispersibility in polyamide resins, and when the amount is increased, the mechanical properties of polyamide resins are reduced, bleeding occurs, and thermal decomposition causes melamine and cyanuric acid to decompose and sublimate easily.
  • the melamine and cyanuric acid have drawbacks, such as generation of silver on the surface of the molded product during molding and contamination of the mold surface.
  • the present invention is a flame-retardant polyamide resin that has UL94V-0 level flame retardancy over a wide range of thicknesses, less bleeding of flame retardants, excellent heat discoloration resistance, moldability, and snap-fitting of parts.
  • a composition is provided.
  • the present inventors have completed the present invention as a result of intensive research to solve the above problems.
  • the present invention has the following configurations. - Contains polyamide resin (A) and melamine cyanurate (B), and 90 to 98 parts by mass of polyamide resin (A) and melamine cyanurate ( B) contained at a rate of 2 to 10 parts by mass, phosphorus antioxidant (C) 0.01 to 1 part by mass, hindered phenol antioxidant (D) 0.01 to 1 part by mass, and carbon number 22 or less fatty acid metal salt-based lubricant (E) in a proportion of 0.1 to 1 part by mass, the polyamide resin (A) is 55 to 85 mass% of polyamide 66 resin (A1), polyamide 6 resin (A2) A flame-retardant polyamide resin composition containing 15 to 45% by mass.
  • the flame-retardant polyamide resin composition of the present invention not only has excellent heat discoloration resistance and moldability, but also does not significantly impair breaking strength and toughness, and has UL94V-0 level flame retardancy over a wide range of thickness. .
  • Polyamide resin (A) The polyamide resin (A) in the present invention is not particularly limited as long as it is a polymer having an amide bond (--NHCO--) in its main chain.
  • Polyamide resin (A) is preferably crystalline, for example, polyamide 6 (PA6), polyamide 66 (PA66), polyamide 46 (PA46), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 610 (PA610 ), polyamide 612 (PA612), polymetaxylylene adipamide (PAMXD6), hexamethylenediamine-terephthalic acid polymer (PA6T), hexamethylenediamine-terephthalic acid and adipic acid polymer (PA6T/66), hexamethylenediamine - terephthalic acid and ⁇ -caprolactam copolymer (PA6T/6), trimethylhexamethylenediamine-terephthalic acid polymer (PATMD-T), meta
  • the blending amount (content) of the polyamide resin (A) is 90 to 98 parts by mass when the total of the polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass.
  • the blending amount (content) of the polyamide resin (A) is preferably 92 to 96 parts by mass, more preferably 93 to 95 parts by mass.
  • the blending amount of each component becomes the content as it is.
  • the polyamide resin (A) in the present invention is preferably a mixture of polyamide 66 resin (A1) and polyamide 6 resin (A2) in terms of excellent moldability, melt fluidity and flame retardancy.
  • Examples of the polyamide 66 resin (A1) in the present invention include polyamide 66 resins obtained by polycondensation of adipic acid and hexamethylenediamine as raw materials.
  • the relative viscosity of the polyamide 66 resin (A-1) is preferably 2.2 to 3.5 as measured according to JIS K6810 at a concentration of 1% in 98% sulfuric acid at a temperature of 25°C. If the relative viscosity is less than 2.2, the mechanical properties tend to deteriorate, and if it exceeds 3.5, the melt fluidity tends to be insufficient.
  • the relative viscosity of the polyamide 66 resin (A1) is more preferably 2.3-3.0.
  • Polyamide 66 resin (A1) may be adjusted to a preferable relative viscosity range by mixing polyamide 66 resins having different relative viscosities.
  • the terminal amino group concentration of the polyamide 66 resin (A1) is not particularly limited, it is preferably 50 to 90 eq/ton, more preferably 60 to 80 eq/ton in terms of heat discoloration resistance.
  • the blending amount of the polyamide 66 resin (A1) is preferably 55 to 85 parts by mass based on 100 parts by mass of the polyamide resin (A). When the amount of the polyamide 66 resin (A1) exceeds 85 parts by mass, the hinge property (snap-fitting property) is deteriorated.
  • the blending amount of the polyamide 66 resin (A1) is more preferably 60 to 80 parts by mass from the viewpoint of the balance between the snap fit property and the moldability.
  • the polyamide 6 resin (A2) in the present invention is a polyamide 6 resin obtained by polycondensation using ⁇ -caprolactam as a raw material.
  • the relative viscosity of the polyamide 6 resin (A2) is preferably 1.5 to 4.0 as measured according to JIS K6810 at a concentration of 1% in 98% sulfuric acid at a temperature of 25°C. If the relative viscosity is less than 1.5, the mechanical properties tend to deteriorate, and if it exceeds 3.6, flame retardancy and fluidity tend to be impaired.
  • the relative viscosity of the polyamide 6 resin (A2) is more preferably 1.8-3.6.
  • the polyamide 6 resin (A-2) may be adjusted to a preferable relative viscosity range by mixing polyamide 6 resins having different relative viscosities.
  • the terminal amino group concentration of the polyamide 6 resin (A2) is not particularly limited, it is preferably 50 to 90 eq/ton, more preferably 60 to 80 eq/ton in terms of heat discoloration resistance.
  • the blending amount of the polyamide 6 resin (A2) is preferably 15 to 45 parts by mass based on 100 parts by mass of the polyamide resin (A). If the amount of the polyamide 6 resin (A2) is less than 15 parts by mass, the hinge properties (snap fit properties) tend to deteriorate, and if it exceeds 45 parts by mass, the moldability tends to deteriorate.
  • the blending amount of the polyamide 6 resin (A2) is more preferably 20 to 40 parts by mass from the viewpoint of the balance between snap-fitting properties and moldability.
  • An amorphous polyamide resin (A3) can also be blended in order to improve the appearance of the molded product.
  • Amorphous polyamide resins include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane (CA), 4,4'-diaminodicyclohexylmethane (PACM), metaxylylenediamine (MXD), trimethylhexamethylene.
  • Diamines such as diamine (TMD), isophoronediamine (IA), 4,4'-diaminodicyclohexylpropane (PACP), hexamethylenediamine, and dicarboxylic acids such as terphthalic acid, isophthalic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid
  • dicarboxylic acids such as terphthalic acid, isophthalic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid
  • Polymers, copolymers or blends obtained by polycondensation from acids and lactams such as caprolactam and lauryllactam can be exemplified.
  • the amount of the amorphous polyamide resin (A3) to be blended is more preferably 0 to 15 parts by mass from the viewpoint of the balance between snap-fitting properties and moldability.
  • Melamine cyanurate (B) in the present invention is preferably an equimolar reaction product of cyanuric acid and melamine. Moreover, some of the amino groups or hydroxyl groups in the 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 the mixture with stirring at 90 to 100° C., and filtering the resulting precipitate. Although the obtained solid can be used as it is, it is preferable to use it after pulverizing it, if necessary.
  • the particle size is not particularly limited, the average particle size is preferably 0.5 to 20 ⁇ m, more preferably 1 to 15 ⁇ m, from the viewpoint of flame retardancy and toughness.
  • the blending amount (content) of melamine cyanurate (B) is 2 to 10 parts by mass when the total of polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass. It is 2 parts by mass or more from the viewpoint of flame retardancy, and 10 parts by mass or less from the viewpoint of snap fit and bleeding. It is more preferably 3 to 9 parts by mass, still more preferably 4 to 8 parts by mass.
  • the phosphorus-based antioxidant (C) in the present invention may be either an inorganic compound or an organic compound, and is not particularly limited.
  • Preferred phosphorus compounds include inorganic phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, triphenylphosphite, Phyte, Trioctadecylphosphite, Tridecylphosphite, Triisodecylphosphite, Trinonylphenylphosphite, Diphenylisodecylphosphite, Diphenylalkylphosphite, Phenyldialkylphosphite, Tris(nonylphenyl)phosphite, Trilauryl Phosphite,
  • a phosphite compound is preferable as the phosphorus-based antioxidant (C).
  • the phosphite compounds compounds having a pentaerythritol diphosphite skeleton are preferred.
  • compounds having a pentaerythritol diphosphite skeleton are preferred.
  • bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (“ADEKASTAB PEP-36”, molecular weight 633)
  • bis(2,4-di-tert-butyl phenyl) pentaerythritol diphosphite (“ADEKASTAB PEP-24G”, molecular weight 604)
  • distearylpentaerythritol diphosphite (“ADEKASTAB PEP-8”, molecular weight 733)
  • bis(nonylphenyl) pentaerythritol diphosphite (“ Adekastab
  • the amount (content) of the phosphorus-based antioxidant (C) is 0.01 to 1 part by mass when the total of the polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass.
  • the content of the phosphorus antioxidant (C) is preferably 0.1 to 0.5 parts by mass.
  • the hindered phenol-based antioxidant (D) in the present invention includes N,N'-hexamethylene-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, bis(3 , 3-bis-(4′-hydroxy-3′-tert-butylphenyl)butanoic acid) glycol ester, 2,1′-thioethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate "SONGNOX2450", molecular weight 633), etc., and mixtures of two or more of these can also be used.
  • the amount (content) of the hindered phenol-based antioxidant (D) is 0.01 to 1 part by mass when the total of the polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass.
  • the content of the hindered phenol-based antioxidant (D) is preferably 0.1 to 0.5 parts by mass.
  • fatty acid metal salt-based lubricant having 22 or less carbon atoms examples include metal salts of fatty acids such as stearic acid, palmitic acid and behenic acid.
  • a fatty acid metal salt-based lubricant with a carbon number of 22 or less not only is the releasability improved, but the temperature at which fatty acid-derived combustion gas starts to be generated during combustion and the generation of non-combustible gas generated by the decomposition of melamine cyanurate. Since the temperatures are close to each other, ignition of combustible gas can be prevented, so flame retardancy tends to be exhibited even better.
  • a metal salt of an aliphatic carboxylic acid having 18 or less carbon atoms is more preferable, and an alkali metal or alkaline earth metal salt such as stearic acid or palmitic acid is more preferable from the viewpoint of achieving both releasability and flame retardancy.
  • Alkali metals or alkaline earth metals include, for example, lithium, sodium, magnesium, calcium salts and the like.
  • the alkali metal or alkaline earth metal salt of stearic acid has the same starting temperature for generating combustible gas derived from fatty acid by decomposition of fatty acid metal salt and non-combustible gas generated by decomposition of melamine cyanurate during combustion, so it is flame retardant by addition. It is optimal because it can improve the releasability without causing a decrease in the
  • the blending amount (content) of the fatty acid metal salt-based lubricant (E) is 0.1 to 1 part by mass when the total of the polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass. If the amount exceeds 1 part by mass, the flame retardancy may deteriorate.
  • the amount of the fatty acid metal salt-based lubricant (E) to be blended is preferably 0.2 to 0.8 parts by mass.
  • the total of the components (A), (B), (C), (D), and (E) described above preferably accounts for 80% by mass or more, More preferably, it accounts for 90% by mass or more, and even more preferably 95% by mass or more.
  • Suitable molded parts obtained using the flame-retardant polyamide resin composition of the present invention specifically include connectors, coil bobbins, breakers, electromagnetic switches and holders used in fields such as electric/electronic parts and automobile parts. Molded parts such as plugs, sockets, switches, cases, covers, etc. More specifically, parts that require heat discoloration resistance and snap fit properties such as ferrite core covers, ESC locks, cable ties, and electrical wiring protection members. is.
  • the method for producing the flame-retardant polyamide resin composition of the present invention is not particularly limited, and a general single-screw extruder, twin-screw extruder, pressure kneader, or the like can be used as a kneading device.
  • a twin-screw extruder is particularly preferred.
  • the above (A), (B), (C), (D), and (E) and, depending on the application, pigments and the like are mixed and fed into a twin-screw extruder.
  • a polyamide-based resin composition having excellent toughness and flame retardancy can be produced by uniformly kneading with a twin-screw extruder.
  • the kneading temperature of the twin-screw extruder is preferably 220 to 300° C., and the kneading time is preferably about 2 to 15 minutes.
  • A2-2: Polyamide 6 (RV 3.6) ZISAMIDE TP6603 (manufactured by Shusei), melting point 225°C
  • B melamine cyanurate (B); B: MC6000 (manufactured by Nissan Chemical Co., Ltd.)
  • C ADEKA STAB PEP-36 (manufactured by ADEKA Corporation)
  • E fatty acid metal salt-based lubricant
  • E1 Magnesium stearate NP-1500S (manufactured by Tannan Chemical Industry Co., Ltd.) other release agents
  • E2 Calcium montanate CS-8-CP (manufactured by Nitto Kasei Kogyo Co., Ltd.)
  • E3 Fatty acid ester Recolb WE-40 (manufactured by Clariant Japan Co., Ltd.)
  • each raw material was weighed in the blending ratio of the polyamide resin composition shown in Table 1, mixed in a tumbler, and charged into a twin-screw extruder.
  • the set temperature of the twin-screw extruder was 250° C. to 300° C., and the kneading time was 5 to 10 minutes.
  • the obtained pellets were molded into various evaluation samples using an injection molding machine.
  • the cylinder temperature of the injection molding machine was 250°C to 280°C, and the mold temperature was 80°C.
  • Table 1 shows the evaluation results.
  • Relative viscosity of polyamide resin [RV] (98% sulfuric acid solution method) Using an Ubbelohde viscometer, measurement was performed at 25° C. with a 98 mass % sulfuric acid solution and a polyamide resin concentration of 1 g/dl.
  • Melting Point of Polyamide Resin Measurement was performed using a differential scanning calorimeter EXSTAR 6000 (Seiko Instruments Inc.) at a heating rate of 20° C./min, and the peak top temperature of the endothermic peak was determined as the melting point. 3.
  • Snap fit property (tensile strength, tensile elongation): Measured according to ISO527 to determine tensile strength (tensile strength) and tensile elongation (tensile breaking strain). 4. Flammability: Measured according to UL94, Vertical Burning Test. V-0 represents the highest flame retardancy. 5. Bleeding property: A molded product of 100 mm x 100 mm with a thickness of 2 mm was left at rest for 96 hours in a constant temperature and humidity bath set at 80 ° C. and 95% RH at least twice, and then returned to room temperature and precipitates were present on the surface. It was confirmed visually with a stereoscopic microscope. 6.
  • Thermal discoloration The color difference ( ⁇ E) between the pellets after being left in the oven for 8 hours at a temperature of 120° C. and the pellets before treatment was calculated. 7. Moldability: Using a mold equipped with a mold release force measuring device, molding was performed under the above molding temperature conditions, and the mold release force was measured from the 31st shot to the 35th shot to obtain the mold release resistance value.
  • the tensile strength is equivalent to that of general polyamide 6, 66 resin, the tensile elongation is 5% or more, there is no breakage even after the tensile yield point is exceeded, and there is no significant embrittlement. It is expected that a good snap-fit property will be obtained.
  • Examples 1 to 12 achieved UL94 V-0 evaluation, demonstrating high flame retardancy over a wide range of thicknesses. It can be seen that it has In terms of heat discoloration, Examples 1 to 12 had ⁇ E of 20 or less after 8 hours at 120° C., indicating that discoloration in a heat environment is suppressed.
  • the molded article has a resistance value of 1 MPa or less when released from the mold, and the composition has an extremely low possibility of deformation and adhesion of the molded article during release even if continuously molded.
  • Comparative Examples 1 to 7 partially satisfy the characteristics, Comparative Example 1 was evaluated as UL94 V-2 in terms of flame retardancy at thicknesses of 0.4, 0.8, 1.6, and 3.0 mm. It is not preferable because the flame retardancy is greatly lowered. Comparative Example 2 has a tensile elongation of 3%, and embrittlement cannot be suppressed, which is not preferable. In Comparative Example 3, the flame retardancy at thicknesses of 0.4, 0.8, 1.6, and 3.0 mm was rated V-2, and the tensile elongation was 3%, which was sufficient. It is difficult to say that both the flame retardancy and the snap-fit property are compatible, which is not preferable.
  • Comparative Examples 4, 5, and 7 are evaluated as UL94 V-2 in terms of flame retardancy at thicknesses of 0.8, 1.6, and 3.0 mm, and it cannot be said that flame retardancy is high in a wide range of thicknesses. I don't like it because it's too hot.
  • the mold release resistance which is an index of moldability, exceeded 1 MPa, and it cannot be said that the moldability is good (good mold release), which is also undesirable in this respect.
  • Comparative Example 6 in addition to the UL94 V-2 evaluation for flame retardancy at thicknesses of 0.8, 1.6, and 3.0 mm, the tensile elongation is 3%, which is sufficient. It is difficult to say that both flame retardancy and snap-fitting are achieved, which is undesirable.
  • the flame-retardant polyamide resin composition of the present invention has a wide range of product thicknesses and is suitable for molded products that have a hinge portion. and excellent snap-fitting properties, it can be suitably used for electric/electronic parts, automobile parts, etc. where both high flame retardancy and snap-fitting properties are desired.

Abstract

[Problem] To provide a flame-retardant polyamide resin composition having little bleed-out of flame retardant and exceptional thermal discoloration resistance, moldability, snap fit of parts, etc., while having flame retardancy at the UL 94V-0 level over a wide range of thickness. [Solution] A flame-retardant polyamide resin composition characterized by: containing a polyamide resin (A) and melamine cyanurate (B); containing 90-98 parts by mass of the polyamide resin (A) and 2-10 parts by mass of the melamine cyanurate (B) relative to a total of 100 parts by mass of the components (A) and (B); being such that the proportion of a polyamide 66 resin (A1) in the polyamide resin (A) is 55-85 mass%, and the proportion of a polyamide 6 resin (A2) in the polyamide resin (A) is 15-45 mass%; and containing 0.01-1 part by mass of a phosphorus-based antioxidant (C), 0.01-1 part by mass of a hindered-phenol-based antioxidant (D), and 0.1-1 part by mass of a C22 or lower fatty acid metal-salt-based lubricant (E) relative to a total of 100 parts by mass of the components (A) and (B).

Description

難燃性ポリアミド樹脂組成物及びそれからなる成形品Flame-retardant polyamide resin composition and molded article made of same
　本発明は非ハロゲン系の難燃性ポリアミド樹脂組成物に関する。詳しくは高い難燃性と良好なスナップフィット性を有し、かつ耐熱変色性に優れた非ハロゲン系の難燃性ポリアミド樹脂組成物に関するものである。 The present invention relates to a non-halogen flame-retardant polyamide resin composition. More specifically, it relates to a halogen-free, flame-retardant polyamide resin composition having high flame retardancy, good snap-fitting properties, and excellent resistance to heat discoloration.
　ポリアミド樹脂は、機械的特性、電気特性、耐薬品性などに優れることを利用して、電気・電子部品、自動車部品などの各種分野で使用されている。これらの分野において、非強化系でかつ非ハロゲン系難燃剤による難燃性付与が要求される場合、難燃剤としてメラミンシアヌレートが用いられている（例えば、特許文献１、２）。
　しかしながら、メラミンシアヌレートは、ポリアミド樹脂に対する分散性が悪く、配合量が多くなるとポリアミド樹脂の機械的特性が低下する、ブリードする、熱分解によりメラミンとシアヌル酸とに分解し昇華しやすく、昇華したメラミン及びシアヌル酸の影響で成形加工時に成形品表面にシルバーの発生や、金型表面を汚染しやすい、などの欠点を有している。 Polyamide resins are used in various fields such as electric/electronic parts and automobile parts, taking advantage of their excellent mechanical properties, electrical properties, chemical resistance, and the like. In these fields, melamine cyanurate is used as a flame retardant when non-reinforced and non-halogen flame retardants are required to impart flame retardancy (for example, Patent Documents 1 and 2).
However, melamine cyanurate has poor dispersibility in polyamide resins, and when the amount is increased, the mechanical properties of polyamide resins are reduced, bleeding occurs, and thermal decomposition causes melamine and cyanuric acid to decompose and sublimate easily. The melamine and cyanuric acid have drawbacks, such as generation of silver on the surface of the molded product during molding and contamination of the mold surface.
　近年、電気・電子部品、自動車部品などに対する各種の要求レベルが高くなり、難燃性は様々な厚みにおいてＵＬ９４ Ｖ－０のレベルが要求されるともに、難燃剤のブリードがなく、耐熱変色性、成形性、さらには部品のスナップフィット性など、より高いレベルが望まれるようになっている。 In recent years, the level of various requirements for electrical and electronic parts, automobile parts, etc. has increased, and flame retardancy is required to meet the UL94 V-0 level in various thicknesses. A higher level of formability, snap-fitting of parts, etc. is now desired.
特公昭５８－２５３７９号公報Japanese Patent Publication No. 58-25379 特公昭５８－３５５４１号公報Japanese Patent Publication No. 58-35541
　本発明は、ＵＬ９４Ｖ－０レベルの難燃性を幅広い厚みの範囲で有しながら、難燃剤のブリードが少なく、耐熱変色性、成形性、部品のスナップフィット性などにも優れる難燃性ポリアミド樹脂組成物を提供しようとするものである。 The present invention is a flame-retardant polyamide resin that has UL94V-0 level flame retardancy over a wide range of thicknesses, less bleeding of flame retardants, excellent heat discoloration resistance, moldability, and snap-fitting of parts. A composition is provided.
　本発明者等は、上記課題を解決する為に鋭意研究をした結果、本発明を完成するに至った。 The present inventors have completed the present invention as a result of intensive research to solve the above problems.
　すなわち本発明は、以下の構成を有するものである。
　　　　・　ポリアミド樹脂（Ａ）及びメラミンシアヌレート（Ｂ）を含有し、前記成分（Ａ）及び（Ｂ）の合計１００質量部に対して、ポリアミド樹脂（Ａ）９０～９８質量部及びメラミンシアヌレート（Ｂ）２～１０質量部の割合で含有し、リン系酸化防止剤（Ｃ）０．０１～１質量部、ヒンダードフェノール系酸化防止剤（Ｄ）０．０１～１質量部、及び炭素数２２以下の脂肪酸金属塩系潤滑剤（Ｅ）０.１～1質量部の割合で含有し、前記ポリアミド樹脂（Ａ）はポリアミド６６樹脂（Ａ１）５５～８５質量％、ポリアミド６樹脂（Ａ２）１５～４５質量％を含有する難燃性ポリアミド樹脂組成物。
［２］　前記脂肪酸金属塩系潤滑剤（Ｅ）が、ステアリン酸の金属塩である［１］に記載の難燃性ポリアミド樹脂組成物。
［３］　［１］～［２］のいずれかに記載の難燃性ポリアミド樹脂組成物からなる成形品。
［４］　前記成形品が、フェライトコアカバー、エスシーロック、結束バンド、電気配線保護部材のいずれかである［３］に記載の成形品。 That is, the present invention has the following configurations.
- Contains polyamide resin (A) and melamine cyanurate (B), and 90 to 98 parts by mass of polyamide resin (A) and melamine cyanurate ( B) contained at a rate of 2 to 10 parts by mass, phosphorus antioxidant (C) 0.01 to 1 part by mass, hindered phenol antioxidant (D) 0.01 to 1 part by mass, and carbon number 22 or less fatty acid metal salt-based lubricant (E) in a proportion of 0.1 to 1 part by mass, the polyamide resin (A) is 55 to 85 mass% of polyamide 66 resin (A1), polyamide 6 resin (A2) A flame-retardant polyamide resin composition containing 15 to 45% by mass.
[2] The flame-retardant polyamide resin composition according to [1], wherein the fatty acid metal salt-based lubricant (E) is a metal salt of stearic acid.
[3] A molded article made of the flame-retardant polyamide resin composition according to any one of [1] to [2].
[4] The molded article according to [3], which is any one of a ferrite core cover, an ESC lock, a binding band, and an electrical wiring protection member.
　本発明の難燃性ポリアミド樹脂組成物は、耐熱変色性、成形性に優れるのみならず、破断強さ、じん性を大きく損なわず、ＵＬ９４Ｖ－０レベルの難燃性を幅広い厚みの範囲で有する。 The flame-retardant polyamide resin composition of the present invention not only has excellent heat discoloration resistance and moldability, but also does not significantly impair breaking strength and toughness, and has UL94V-0 level flame retardancy over a wide range of thickness. .
　以下に本発明を具体的に説明する。
［ポリアミド樹脂（Ａ）］
　本発明におけるポリアミド樹脂（Ａ）としては、主鎖中にアミド結合（－ＮＨＣＯ－）を有する重合体であれば特に限定されない。ポリアミド樹脂（Ａ）は、結晶性であることが好ましく、例えばポリアミド６（ＰＡ６）、ポリアミド６６（ＰＡ６６）、ポリアミド４６（ＰＡ４６）、ポリアミド１１（ＰＡ１１）、ポリアミド１２（ＰＡ１２）、ポリアミド６１０（ＰＡ６１０）、ポリアミド６１２（ＰＡ６１２）、ポリメタキシリレンアジパミド（ＰＡＭＸＤ６）、ヘキサメチレンジアミン－テレフタル酸重合体（ＰＡ６Ｔ）、ヘキサメチレンジアミン－テレフタル酸およびアジピン酸重合体（ＰＡ６Ｔ／６６）、ヘキサメチレンジアミン－テレフタル酸およびεカプロラクタム共重合体（ＰＡ６Ｔ／６）、トリメチルヘキサメチレンジアミン－テレフタル酸重合体（ＰＡＴＭＤ－Ｔ）、メタキシリレンジアミンとアジピン酸およびイソフタル酸共重合体（ＰＡＭＸＤ６／ＭＸＤＩ）、トリヘキサメチレンジアミンとテレフタル酸およびε－カプロラクタム共重合体（ＰＡＴＭＤＴ／６）、ジアミノジシクロヘキシレンメタンとイソフタル酸およびラウリルラクタム共重合体等の結晶性ポリアミド樹脂、もしくはこれらのブレンド物等を例示することが出来るが、これらに限定されるものではない。 The present invention will be specifically described below.
[Polyamide resin (A)]
The polyamide resin (A) in the present invention is not particularly limited as long as it is a polymer having an amide bond (--NHCO--) in its main chain. Polyamide resin (A) is preferably crystalline, for example, polyamide 6 (PA6), polyamide 66 (PA66), polyamide 46 (PA46), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 610 (PA610 ), polyamide 612 (PA612), polymetaxylylene adipamide (PAMXD6), hexamethylenediamine-terephthalic acid polymer (PA6T), hexamethylenediamine-terephthalic acid and adipic acid polymer (PA6T/66), hexamethylenediamine - terephthalic acid and ε-caprolactam copolymer (PA6T/6), trimethylhexamethylenediamine-terephthalic acid polymer (PATMD-T), meta-xylylenediamine and adipic and isophthalic acid copolymer (PAMXD6/MXDI), tri Examples include crystalline polyamide resins such as hexamethylenediamine, terephthalic acid and ε-caprolactam copolymer (PATMDT/6), diaminodicyclohexylenemethane, isophthalic acid and lauryllactam copolymer, or blends thereof. are possible, but not limited to these.
　ポリアミド樹脂（Ａ）の配合量（含有量）は、ポリアミド樹脂（Ａ）及びメラミンシアヌレート（Ｂ）の合計１００質量部としたとき、９０～９８質量部である。ポリアミド樹脂（Ａ）の配合量がこの範囲にあることで、難燃剤のブリード抑制、かつ高い難燃性の保持を組成物に与えることができる。ポリアミド樹脂（Ａ）の配合量（含有量）は、９２～９６質量部が好ましく、９３～９５質量部がより好ましい。本発明の難燃ポリアミド樹脂組成物においては、各成分の配合量がそのまま含有量となる。 The blending amount (content) of the polyamide resin (A) is 90 to 98 parts by mass when the total of the polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass. When the blending amount of the polyamide resin (A) is within this range, the composition can be provided with suppression of bleeding of the flame retardant and retention of high flame retardancy. The blending amount (content) of the polyamide resin (A) is preferably 92 to 96 parts by mass, more preferably 93 to 95 parts by mass. In the flame-retardant polyamide resin composition of the present invention, the blending amount of each component becomes the content as it is.
　成形性、溶融流動性、難燃性に優れるなどの点で、本発明におけるポリアミド樹脂（Ａ）は、ポリアミド６６樹脂（Ａ１）とポリアミド６樹脂（Ａ２）との混合物が好ましい態様である。 The polyamide resin (A) in the present invention is preferably a mixture of polyamide 66 resin (A1) and polyamide 6 resin (A2) in terms of excellent moldability, melt fluidity and flame retardancy.
　本発明におけるポリアミド６６樹脂（Ａ１）としては、アジピン酸とヘキサメチレンジアミンを原料とし、これらの重縮合によって得られるポリアミド６６樹脂が挙げられる。ポリアミド６６樹脂（Ａ－１）の相対粘度は、ＪＩＳ　Ｋ６８１０に従って、９８％硫酸中濃度１％、温度２５℃で測定した値で、好ましくは２．２～３．５である。相対粘度が２．２未満であると機械的性質が低下しやすく、３．５を越えると溶融流動性が不足しやすい。ポリアミド６６樹脂（Ａ１）の相対粘度は、より好ましくは２．３～３．０である。なお、ポリアミド６６樹脂（Ａ１）は異なる相対粘度を有するポリアミド６６樹脂を混合して好ましい相対粘度の範囲に調整してもよい。 Examples of the polyamide 66 resin (A1) in the present invention include polyamide 66 resins obtained by polycondensation of adipic acid and hexamethylenediamine as raw materials. The relative viscosity of the polyamide 66 resin (A-1) is preferably 2.2 to 3.5 as measured according to JIS K6810 at a concentration of 1% in 98% sulfuric acid at a temperature of 25°C. If the relative viscosity is less than 2.2, the mechanical properties tend to deteriorate, and if it exceeds 3.5, the melt fluidity tends to be insufficient. The relative viscosity of the polyamide 66 resin (A1) is more preferably 2.3-3.0. Polyamide 66 resin (A1) may be adjusted to a preferable relative viscosity range by mixing polyamide 66 resins having different relative viscosities.
　ポリアミド６６樹脂（Ａ１）の末端アミノ基濃度は、特に限定されないが、５０～９０ｅｑ／ｔｏｎであることが好ましく、６０～８０ｅｑ／ｔｏｎであることが、耐熱変色性の点でより好ましい。 Although the terminal amino group concentration of the polyamide 66 resin (A1) is not particularly limited, it is preferably 50 to 90 eq/ton, more preferably 60 to 80 eq/ton in terms of heat discoloration resistance.
　ポリアミド６６樹脂（Ａ１）の配合量は、ポリアミド樹脂（Ａ）１００質量部としたとき、５５～８５質量部であることが好ましい。ポリアミド６６樹脂（Ａ１）の配合量が８５質量部を越えるとヒンジ性（スナップフィット性）が低下し、５０質量部未満であると成形加工性が低下しやすい。ポリアミド６６樹脂（Ａ１）の配合量は、スナップフィット性と成形加工性のバランスの点より、６０～８０質量部がより好ましい。 The blending amount of the polyamide 66 resin (A1) is preferably 55 to 85 parts by mass based on 100 parts by mass of the polyamide resin (A). When the amount of the polyamide 66 resin (A1) exceeds 85 parts by mass, the hinge property (snap-fitting property) is deteriorated. The blending amount of the polyamide 66 resin (A1) is more preferably 60 to 80 parts by mass from the viewpoint of the balance between the snap fit property and the moldability.
　本発明におけるポリアミド６樹脂（Ａ２）としては、ε－カプロラクタムを原料とし、重縮合によって得られるポリアミド６樹脂である。ポリアミド６樹脂（Ａ２）の相対粘度は、ＪＩＳ Ｋ６８１０に従って、９８％硫酸中濃度１％、温度２５℃で測定した値で、好ましくは１．５～４．０である。相対粘度が１．５未満であると機械的性質が低下しやすく、３．６を越えると難燃性や流動性を損ないやすい。ポリアミド６樹脂（Ａ２）の相対粘度は、より好ましくは１．８～３．６である。なお、ポリアミド６樹脂（Ａ－２）は異なる相対粘度を有するポリアミド６樹脂を混合して好ましい相対粘度の範囲に調整してもよい。 The polyamide 6 resin (A2) in the present invention is a polyamide 6 resin obtained by polycondensation using ε-caprolactam as a raw material. The relative viscosity of the polyamide 6 resin (A2) is preferably 1.5 to 4.0 as measured according to JIS K6810 at a concentration of 1% in 98% sulfuric acid at a temperature of 25°C. If the relative viscosity is less than 1.5, the mechanical properties tend to deteriorate, and if it exceeds 3.6, flame retardancy and fluidity tend to be impaired. The relative viscosity of the polyamide 6 resin (A2) is more preferably 1.8-3.6. The polyamide 6 resin (A-2) may be adjusted to a preferable relative viscosity range by mixing polyamide 6 resins having different relative viscosities.
　ポリアミド６樹脂（Ａ２）の末端アミノ基濃度は、特に限定されないが、５０～９０ｅｑ／ｔｏｎであることが好ましく、６０～８０ｅｑ／ｔｏｎであることが、耐熱変色性の点でより好ましい。 Although the terminal amino group concentration of the polyamide 6 resin (A2) is not particularly limited, it is preferably 50 to 90 eq/ton, more preferably 60 to 80 eq/ton in terms of heat discoloration resistance.
　ポリアミド６樹脂（Ａ２）の配合量は、ポリアミド樹脂（Ａ）１００質量部としたとき、１５～４５質量部であることが好ましい。ポリアミド６樹脂（Ａ２）の配合量が１５質量部未満であるとヒンジ性（スナップフィット性）が低下しやすく、４５質量部を越えると成形加工性が低下しやすい。ポリアミド６樹脂（Ａ２）の配合量は、スナップフィット性と成形加工性のバランスの点より、２０～４０質量部がより好ましい。 The blending amount of the polyamide 6 resin (A2) is preferably 15 to 45 parts by mass based on 100 parts by mass of the polyamide resin (A). If the amount of the polyamide 6 resin (A2) is less than 15 parts by mass, the hinge properties (snap fit properties) tend to deteriorate, and if it exceeds 45 parts by mass, the moldability tends to deteriorate. The blending amount of the polyamide 6 resin (A2) is more preferably 20 to 40 parts by mass from the viewpoint of the balance between snap-fitting properties and moldability.
　成形品の外観を向上させるために、非晶性ポリアミド樹脂（Ａ３）を配合することもできる。
　非晶性ポリアミド樹脂としては、４，４'－ジアミノ-３，３'－ジメチルジシクロヘキシルメタン（ＣＡ）、４，４’－ジアミノジシクロヘキシルメタン（ＰＡＣＭ）、メタキシリレンジアミン（ＭＸＤ）、トリメチルヘキサメチレンジアミン（ＴＭＤ）、イソフォロンジアミン（ＩＡ）、４，４’－ジアミノジシクロヘキシルプロパン（ＰＡＣＰ）、ヘキサメチレンジアミン等のジアミンと、テルフタル酸、イソフタル酸、アジピン酸、セバシン酸、ドデカンジカルボン酸等のジカルボン酸およびカプロラクタム、ラウリルラクタム等のラクタム類から重縮合して得られる重合体または共重合体もしくはブレンド物等を例示することができる。非晶性ポリアミド樹脂（Ａ３）の配合量は、スナップフィット性と成形加工性のバランスの点より、０～１５質量部がより好ましい。 An amorphous polyamide resin (A3) can also be blended in order to improve the appearance of the molded product.
Amorphous polyamide resins include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane (CA), 4,4'-diaminodicyclohexylmethane (PACM), metaxylylenediamine (MXD), trimethylhexamethylene. Diamines such as diamine (TMD), isophoronediamine (IA), 4,4'-diaminodicyclohexylpropane (PACP), hexamethylenediamine, and dicarboxylic acids such as terphthalic acid, isophthalic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid Polymers, copolymers or blends obtained by polycondensation from acids and lactams such as caprolactam and lauryllactam can be exemplified. The amount of the amorphous polyamide resin (A3) to be blended is more preferably 0 to 15 parts by mass from the viewpoint of the balance between snap-fitting properties and moldability.
［メラミンシアヌレート（Ｂ）］
　本発明におけるメラミンシアヌレート（Ｂ）としては、シアヌル酸とメラミンとの等モル反応物が好ましく挙げられる。また、メラミンシアヌレート中のアミノ基又は水酸基の一部が、他の置換基で置換されていても良い。メラミンシアヌレートは、例えば、シアヌル酸の水溶液とメラミンの水溶液とを混合し、９０～１００℃の撹拌下で反応させて、生成した沈殿をろ過することによって得ることができる。得られた固体はそのままでも使用できるが、必要に応じて粉砕して使用することが好ましい。粒子径として特に制限はないが、難燃性と靱性の観点から、好ましくは平均粒子径が０．５～２０μｍであり、より好ましくは１～１５μｍである。 [Melamine cyanurate (B)]
Melamine cyanurate (B) in the present invention is preferably an equimolar reaction product of cyanuric acid and melamine. Moreover, some of the amino groups or hydroxyl groups in the 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 the mixture with stirring at 90 to 100° C., and filtering the resulting precipitate. Although the obtained solid can be used as it is, it is preferable to use it after pulverizing it, if necessary. Although the particle size is not particularly limited, the average particle size is preferably 0.5 to 20 μm, more preferably 1 to 15 μm, from the viewpoint of flame retardancy and toughness.
　メラミンシアヌレート（Ｂ）の配合量（含有量）は、ポリアミド樹脂（Ａ）及びメラミンシアヌレート（Ｂ）の合計１００質量部としたとき、２～１０質量部である。難燃性の観点から２質量部以上であり、スナップフィット性とブリードの観点から１０質量部以下である。より好ましくは３～９質量部であり、さらに好ましくは４～８質量部である。 The blending amount (content) of melamine cyanurate (B) is 2 to 10 parts by mass when the total of polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass. It is 2 parts by mass or more from the viewpoint of flame retardancy, and 10 parts by mass or less from the viewpoint of snap fit and bleeding. It is more preferably 3 to 9 parts by mass, still more preferably 4 to 8 parts by mass.
［リン系酸化防止剤（Ｃ）］
　本発明におけるリン系酸化防止剤（Ｃ）としては、無機化合物でも有機化合物でもよく、特に制限はない。好ましいリン系化合物としては、リン酸一ナトリウム、リン酸二ナトリウム、リン酸三ナトリウム、亜リン酸ナトリウム、亜リン酸カルシウム、亜リン酸マグネシウム、亜リン酸マンガン、などの無機リン酸塩、トリフェニルホスファイト、トリオクタデシルホスファイト、トリデシルホスファイト、トリイソデシルホスファイト、トリノニルフェニルホスファイト、ジフェニルイソデシルホスファイト、ジフェニルアルキルホスファイト、フェニルジアルキルホスファイト、トリス（ノニルフェニル）ホスファイト、トリラウリルホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、ジイソデシルペンタエリスリトールジホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、ジイソデシルオキシペンタエリスリトールジホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６－トリス（ｔｅｒｔ－ブチルフェニル））ペンタエリスリトールジホスファイト、トリステアリルソルビトールトリホスファイト、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）－４，４’－ビフェニレンジホスホナイト、６－イソオクチルオキシ－２，４，８，１０－テトラ－ｔｅｒｔ－ブチル－１２Ｈ－ジベンゾ［ｄ，ｇ］－１，３，２－ジオキサホスホシン、６－フルオロ－２，４，８，１０－テトラ－ｔｅｒｔ－ブチル－１２－メチル－ジベンゾ［ｄ，ｇ］－１，３，２－ジオキサホスホシン、ビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）メチルホスファイト及びビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）エチルホスファイトなどが挙げられ、耐熱変色性を高めるために配合される。 [Phosphorus-based antioxidant (C)]
The phosphorus-based antioxidant (C) in the present invention may be either an inorganic compound or an organic compound, and is not particularly limited. Preferred phosphorus compounds include inorganic phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, triphenylphosphite, Phyte, Trioctadecylphosphite, Tridecylphosphite, Triisodecylphosphite, Trinonylphenylphosphite, Diphenylisodecylphosphite, Diphenylalkylphosphite, Phenyldialkylphosphite, Tris(nonylphenyl)phosphite, Trilauryl Phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite Phosphites, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ) pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl))pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4 ,4′-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphosine, 6 -fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphosine, bis(2,4-di-tert-butyl -6-methylphenyl)methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite and the like, which are blended to enhance resistance to heat discoloration.
　リン系酸化防止剤（Ｃ）としては、ホスファイト化合物が好ましい。ホスファイト化合物のなかでも、ペンタエリスリトールジホスファイト骨格を有する化合物が好ましい。具体的には、ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト（「アデカスタブＰＥＰ－３６」、分子量６３３）、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト（「アデカスタブＰＥＰ－２４Ｇ」、分子量６０４）、ジステアリルペンタエリスリトールジホスファイト（「アデカスタブＰＥＰ－８」、分子量７３３）、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト（「アデカスタブＰＥＰ－４Ｃ」、分子量６３３）などのペンタエリスリトールジホスファイト骨格を有し、分子量が６００～８００程度のものが、難燃性を低下させることなく、離型性をより向上させることができ、かつスナップフィット性にも好適な点で特に好ましい。 A phosphite compound is preferable as the phosphorus-based antioxidant (C). Among the phosphite compounds, compounds having a pentaerythritol diphosphite skeleton are preferred. Specifically, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (“ADEKASTAB PEP-36”, molecular weight 633), bis(2,4-di-tert-butyl phenyl) pentaerythritol diphosphite (“ADEKASTAB PEP-24G”, molecular weight 604), distearylpentaerythritol diphosphite (“ADEKASTAB PEP-8”, molecular weight 733), bis(nonylphenyl) pentaerythritol diphosphite (“ Adekastab PEP-4C", molecular weight 633), which has a pentaerythritol diphosphite skeleton and a molecular weight of about 600 to 800, can further improve releasability without reducing flame retardancy. and snap-fitting properties.
　リン系酸化防止剤（Ｃ）の配合量（含有量）は、ポリアミド樹脂（Ａ）及びメラミンシアヌレート（Ｂ）の合計１００質量部としたとき、０．０１～１質量部である。リン系酸化防止剤（Ｃ）の配合量がこの範囲にあることで、押出加工時の変色を抑制し、かつリン由来のラジカルによる二次的な酸化劣化を誘発することを防ぐことができる。リン系酸化防止剤（Ｃ）の配合量は、０．１～０．５質量部が好ましい。 The amount (content) of the phosphorus-based antioxidant (C) is 0.01 to 1 part by mass when the total of the polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass. When the amount of the phosphorus-based antioxidant (C) is within this range, it is possible to suppress discoloration during extrusion processing and prevent secondary oxidative deterioration due to phosphorus-derived radicals. The content of the phosphorus antioxidant (C) is preferably 0.1 to 0.5 parts by mass.
［ヒンダードフェノール系酸化防止剤（Ｄ）］
　本発明におけるヒンダードフェノール系酸化防止剤（Ｄ）としては、Ｎ，Ｎ’－ヘキサメチレン－ビス－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオンアミド、ビス（３，３－ビス－（４’－ヒドロキシ－３’－ｔｅｒｔ－ブチルフェニル）ブタン酸）グリコールエステル、２，１’－チオエチルビス（３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、４，４’－ブチリデン－ビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、トリエチレングリコール－３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオネート「ＳＯＮＧＮＯＸ２４５０」、分子量６３３）などが挙げられ、これらの二つ以上の混合物も用いることができる。 [Hindered phenolic antioxidant (D)]
The hindered phenol-based antioxidant (D) in the present invention includes N,N'-hexamethylene-bis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, bis(3 , 3-bis-(4′-hydroxy-3′-tert-butylphenyl)butanoic acid) glycol ester, 2,1′-thioethylbis(3-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate "SONGNOX2450", molecular weight 633), etc., and mixtures of two or more of these can also be used.
　ヒンダードフェノール系酸化防止剤（Ｄ）の配合量（含有量）は、ポリアミド樹脂（Ａ）及びメラミンシアヌレート（Ｂ）の合計１００質量部としたとき、０．０１～１質量部である。ヒンダードフェノール系酸化防止剤（Ｄ）の配合量がこの範囲にあることで、ポリアミド組成物の配位結合に応じた適切な処方量で経時的な酸化劣化を防止することができる。ヒンダードフェノール系酸化防止剤（Ｄ）の配合量は、０．１～０．５質量部が好ましい。 The amount (content) of the hindered phenol-based antioxidant (D) is 0.01 to 1 part by mass when the total of the polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass. When the amount of the hindered phenol-based antioxidant (D) is within this range, oxidative deterioration over time can be prevented with an appropriate amount according to the coordination bonds of the polyamide composition. The content of the hindered phenol-based antioxidant (D) is preferably 0.1 to 0.5 parts by mass.
［炭素数２２以下の脂肪酸金属塩系潤滑剤（Ｅ）］
　本発明における炭素数２２以下の脂肪酸金属塩系潤滑剤（Ｅ）としては、ステアリン酸、パルミチン酸、ベヘン酸等の脂肪酸の金属塩が挙げられる。炭素数２２以下の脂肪酸金属塩系潤滑剤を用いることで、離形性を向上させるだけでなく、燃焼時に脂肪酸由来の燃焼ガスの発生開始温度とメラミンシアヌレートの分解で生じる不燃ガスの発生開始温度が近いため、可燃ガスへの引火を妨げることができるため、難燃性をさらに良好に発揮できる傾向にある。 [Fatty acid metal salt-based lubricant having 22 or less carbon atoms (E)]
Examples of the fatty acid metal salt-based lubricant (E) having 22 or less carbon atoms in the present invention include metal salts of fatty acids such as stearic acid, palmitic acid and behenic acid. By using a fatty acid metal salt-based lubricant with a carbon number of 22 or less, not only is the releasability improved, but the temperature at which fatty acid-derived combustion gas starts to be generated during combustion and the generation of non-combustible gas generated by the decomposition of melamine cyanurate. Since the temperatures are close to each other, ignition of combustible gas can be prevented, so flame retardancy tends to be exhibited even better.
炭素数１８以下の脂肪族カルボン酸の金属塩がより好ましく、ステアリン酸、パルミチン酸などのアルカリ金属またはアルカリ土類金属塩は離形性と難燃性の両立する点でより好ましい。アルカリ金属またはアルカリ土類金属としては、例えば、リチウム、ナトリウム、マグネシウム、カルシウム塩などが挙げられる。特にステアリン酸のアルカリ金属またはアルカリ土類金属塩は燃焼時に脂肪酸金属塩の分解による脂肪酸由来の可燃ガスとメラミンシアヌレートの分解で生じる不燃ガスの発生開始温度が同一のため、添加による難燃性の低下を生じさせることなく離形性を向上させることができるため最適である。 A metal salt of an aliphatic carboxylic acid having 18 or less carbon atoms is more preferable, and an alkali metal or alkaline earth metal salt such as stearic acid or palmitic acid is more preferable from the viewpoint of achieving both releasability and flame retardancy. Alkali metals or alkaline earth metals include, for example, lithium, sodium, magnesium, calcium salts and the like. In particular, the alkali metal or alkaline earth metal salt of stearic acid has the same starting temperature for generating combustible gas derived from fatty acid by decomposition of fatty acid metal salt and non-combustible gas generated by decomposition of melamine cyanurate during combustion, so it is flame retardant by addition. It is optimal because it can improve the releasability without causing a decrease in the
　脂肪酸金属塩系潤滑剤（Ｅ）の配合量（含有量）は、ポリアミド樹脂（Ａ）及びメラミンシアヌレート（Ｂ）の合計１００質量部としたとき、０.1～１質量部である。１質量部を超えると難燃性が低下することがある。脂肪酸金属塩系潤滑剤（Ｅ）の配合量は、０．２～０．８質量部が好ましい。 The blending amount (content) of the fatty acid metal salt-based lubricant (E) is 0.1 to 1 part by mass when the total of the polyamide resin (A) and melamine cyanurate (B) is 100 parts by mass. If the amount exceeds 1 part by mass, the flame retardancy may deteriorate. The amount of the fatty acid metal salt-based lubricant (E) to be blended is preferably 0.2 to 0.8 parts by mass.
［その他の成分］
　本発明の難燃性ポリアミド樹脂組成物には、本発明の目的を損なわない範囲で、上述した（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、（Ｅ）の他に、他の成分、例えば顔料、染料等の着色剤や、熱安定剤、耐候性改良剤、核剤、可塑剤、離型剤、帯電防止剤等の添加剤、他の樹脂ポリマー等を添加することができる。本発明の難燃性ポリアミド樹脂組成物には、上述した（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、及び（Ｅ）成分の合計で、８０質量％以上を占めることが好ましく、９０質量％以上を占めることがより好ましく、９５質量％以上を占めることが更に好ましい。 [Other ingredients]
In addition to (A), (B), (C), (D) and (E) described above, other Components such as colorants such as pigments and dyes, additives such as heat stabilizers, weather resistance improvers, nucleating agents, plasticizers, release agents and antistatic agents, and other resin polymers can be added. . In the flame-retardant polyamide resin composition of the present invention, the total of the components (A), (B), (C), (D), and (E) described above preferably accounts for 80% by mass or more, More preferably, it accounts for 90% by mass or more, and even more preferably 95% by mass or more.
　本発明の難燃ポリアミド樹脂組成物を用いて得られる好適な成形部品としては、具体的には、電気・電子部品、自動車部品などの分野で用いられるコネクター、コイルボビン、ブレーカー、電磁開閉器、ホルダー、プラグ、ソケット、スイッチ、ケース、カバーなどの成形部品であり、より具体的には、フェライトコアカバー、エスシーロック、結束バンド、電気配線保護部材など、耐熱変色性、スナップフィット性が求められる部品である。 Suitable molded parts obtained using the flame-retardant polyamide resin composition of the present invention specifically include connectors, coil bobbins, breakers, electromagnetic switches and holders used in fields such as electric/electronic parts and automobile parts. Molded parts such as plugs, sockets, switches, cases, covers, etc. More specifically, parts that require heat discoloration resistance and snap fit properties such as ferrite core covers, ESC locks, cable ties, and electrical wiring protection members. is.
　本発明の難燃ポリアミド樹脂組成物の製造方法は、特に限定されるものではなく、混練装置として一般の単軸押出機や二軸押出機、加圧ニーダー等が使用できるが、本発明においては二軸押出機が特に好ましい。一実施様態としては、前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、（Ｅ）および用途によっては顔料等を混合し、二軸押出機に投入する。二軸押出機によって均一に混練することにより強靭性と難燃性に優れたポリアミド系樹脂組成物を製造することができる。二軸押出機の混練温度は２２０～３００℃で混練時間は２～１５分程度が好ましい。 The method for producing the flame-retardant polyamide resin composition of the present invention is not particularly limited, and a general single-screw extruder, twin-screw extruder, pressure kneader, or the like can be used as a kneading device. A twin-screw extruder is particularly preferred. In one embodiment, the above (A), (B), (C), (D), and (E) and, depending on the application, pigments and the like are mixed and fed into a twin-screw extruder. A polyamide-based resin composition having excellent toughness and flame retardancy can be produced by uniformly kneading with a twin-screw extruder. The kneading temperature of the twin-screw extruder is preferably 220 to 300° C., and the kneading time is preferably about 2 to 15 minutes.
　以下に実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例により何ら制限されるものではない。 Although the present invention will be described in more detail below with reference to examples, the present invention is not limited by these examples.
　各成分は下記のものを用いた。
ポリアミド樹脂（Ａ）；
Ａ１-１：ポリアミド６６（ＲＶ＝２．８）　Ｖｙｄｙｎｅ　２１Z（Ａｓｃｅｎｄ社製）、融点２６５℃
Ａ１-２：ポリアミド６６（ＲＶ＝２．４）　ＥＰＲ２４ （上海神馬塑料科技術有限公司製）、融点２６５℃
Ａ２－１：ポリアミド６（ＲＶ＝２．０）　　M２０００（MEIDA社製）、融点２２５℃
Ａ２－２：ポリアミド６（ＲＶ＝３．６）　ＺＩＳＡＭＩＤＥ　ＴＰ６６０３（集盛社製）、融点２２５℃ The following components were used for each component.
polyamide resin (A);
A1-1: Polyamide 66 (RV = 2.8) Vydyne 21Z (manufactured by Ascend), melting point 265°C
A1-2: Polyamide 66 (RV = 2.4) EPR24 (manufactured by Shanghai Jinma Plastic Technology Co., Ltd.), melting point 265°C
A2-1: Polyamide 6 (RV = 2.0) M2000 (manufactured by MEIDA), melting point 225 ° C.
A2-2: Polyamide 6 (RV = 3.6) ZISAMIDE TP6603 (manufactured by Shusei), melting point 225°C
メラミンシアヌレート（Ｂ）；
Ｂ：ＭＣ６０００（日産化学株式会社製） melamine cyanurate (B);
B: MC6000 (manufactured by Nissan Chemical Co., Ltd.)
リン系酸化防止剤（Ｃ）；
Ｃ：アデカスタブＰＥＰ－３６（ＡＤＥＫＡ株式会社製） phosphorus antioxidant (C);
C: ADEKA STAB PEP-36 (manufactured by ADEKA Corporation)
ヒンダードフェノール系酸化防止剤（Ｄ）；
Ｄ：ＳＯＮＧＮＯＸ２４５０（ソンウォンインターナショナルジャパン社製） Hindered phenolic antioxidant (D);
D: SONGNOX2450 (manufactured by Songwon International Japan)
脂肪酸金属塩系潤滑剤（Ｅ）；
Ｅ１：ステアリン酸マグネシウム　N.P.－１５００S（淡南化学工業株式会社製）
その他の離型剤；
Ｅ２：モンタン酸カルシウム　ＣＳ－８－ＣＰ（日東化成工業株式会社製）
Ｅ３：脂肪酸エステル　リコルブ　ＷＥ－４０（クラリアントジャパン株式会社製） fatty acid metal salt-based lubricant (E);
E1: Magnesium stearate NP-1500S (manufactured by Tannan Chemical Industry Co., Ltd.)
other release agents;
E2: Calcium montanate CS-8-CP (manufactured by Nitto Kasei Kogyo Co., Ltd.)
E3: Fatty acid ester Recolb WE-40 (manufactured by Clariant Japan Co., Ltd.)
［実施例１～１２、比較例１～７］
　評価サンプルの製造は、表１に示したポリアミド樹脂組成物の配合割合に各原料を計量し、タンブラーで混合した後、二軸押出機に投入した。二軸押出機の設定温度は２５０℃～３００℃、混錬時間は５～１０分とした。得られたペレットは、射出成形機で各種の評価サンプルを成形した。射出成形機のシリンダー温度は、２５０℃～２８０℃、金型温度は８０℃とした。 [Examples 1 to 12, Comparative Examples 1 to 7]
In the production of the evaluation samples, each raw material was weighed in the blending ratio of the polyamide resin composition shown in Table 1, mixed in a tumbler, and charged into a twin-screw extruder. The set temperature of the twin-screw extruder was 250° C. to 300° C., and the kneading time was 5 to 10 minutes. The obtained pellets were molded into various evaluation samples using an injection molding machine. The cylinder temperature of the injection molding machine was 250°C to 280°C, and the mold temperature was 80°C.
　各種の評価方法は以下の通りである。評価結果を表１示した。
１．ポリアミド樹脂の相対粘度［ＲＶ］（９８％硫酸溶液法）
　ウベローデ粘度管を用い、２５℃において９８質量％硫酸溶液で、ポリアミド樹脂濃度１ｇ／ｄｌで測定した。
２．ポリアミド樹脂の融点
　示差走査熱量計　セイコーインスツルメンツ株式会社　ＥＸＳＴＡＲ　６０００を用いて、昇温速度２０℃／分で測定し、吸熱ピークのピークトップ温度を融点として求めた。
３．スナップフィット性（引張強度、引張伸度）：ＩＳＯ５２７に準じて測定し、引張強度（引張強さ）および引張伸度（引張破壊ひずみ）を求めた。
４．燃焼性：ＵＬ９４、垂直燃焼試験に準じて測定した。Ｖ－０が、最も難燃性が高いことを表す。
５．ブリード性：厚み２ｍｍの１００ｍｍ×１００ｍｍの成形品を温度８０℃、９５％ＲＨに設定した恒温恒湿槽に９６時間静置を少なくとも２回以上繰り返し、その後室温に戻して表面に析出物が存在するか、実体顕微鏡にて目視で確認した。
６．熱変色性：温度１２０℃、オーブン内放置時間８ｈｒ後のペレットと処理前ペレットとの色差（ΔＥ）を算出した。
７．成形性：離型力測定装置を取り付けた金型を用いて上記成形温度条件で成形を行い、３１ショット目から３５ショットまでの離型力を測定して離型抵抗値を求めた。 Various evaluation methods are as follows. Table 1 shows the evaluation results.
1. Relative viscosity of polyamide resin [RV] (98% sulfuric acid solution method)
Using an Ubbelohde viscometer, measurement was performed at 25° C. with a 98 mass % sulfuric acid solution and a polyamide resin concentration of 1 g/dl.
2. Melting Point of Polyamide Resin Measurement was performed using a differential scanning calorimeter EXSTAR 6000 (Seiko Instruments Inc.) at a heating rate of 20° C./min, and the peak top temperature of the endothermic peak was determined as the melting point.
3. Snap fit property (tensile strength, tensile elongation): Measured according to ISO527 to determine tensile strength (tensile strength) and tensile elongation (tensile breaking strain).
4. Flammability: Measured according to UL94, Vertical Burning Test. V-0 represents the highest flame retardancy.
5. Bleeding property: A molded product of 100 mm x 100 mm with a thickness of 2 mm was left at rest for 96 hours in a constant temperature and humidity bath set at 80 ° C. and 95% RH at least twice, and then returned to room temperature and precipitates were present on the surface. It was confirmed visually with a stereoscopic microscope.
6. Thermal discoloration: The color difference (ΔE) between the pellets after being left in the oven for 8 hours at a temperature of 120° C. and the pellets before treatment was calculated.
7. Moldability: Using a mold equipped with a mold release force measuring device, molding was performed under the above molding temperature conditions, and the mold release force was measured from the 31st shot to the 35th shot to obtain the mold release resistance value.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～１２は、引張強度は一般的なポリアミド６、６６樹脂と同等であり、引張伸度も５％以上であり、引張降伏点を超えても破断はなく、大きく脆化していないため良好なスナップフィット性が得られることが期待される。０．４、０．８、１．６、３．０ｍｍの厚みにおける難燃性においても、実施例１～１２はUL９４　Ｖ－０評価を実現しており、幅広い厚みで難燃性の高さを有していることがわかる。熱変色性においても、実施例１～１２は１２０℃、８ｈｒ後のΔＥは２０以下であり、熱環境下での変色が抑制されていることがわかる。成形性においても、成形品の離型時の抵抗値が１ＭＰａ以下であり、連続成形をしても離型中に成形品が変形し、癒着する可能性が極めて少ない組成物となっている。 In Examples 1 to 12, the tensile strength is equivalent to that of general polyamide 6, 66 resin, the tensile elongation is 5% or more, there is no breakage even after the tensile yield point is exceeded, and there is no significant embrittlement. It is expected that a good snap-fit property will be obtained. In terms of flame retardancy at thicknesses of 0.4, 0.8, 1.6, and 3.0 mm, Examples 1 to 12 achieved UL94 V-0 evaluation, demonstrating high flame retardancy over a wide range of thicknesses. It can be seen that it has In terms of heat discoloration, Examples 1 to 12 had ΔE of 20 or less after 8 hours at 120° C., indicating that discoloration in a heat environment is suppressed. In terms of moldability, the molded article has a resistance value of 1 MPa or less when released from the mold, and the composition has an extremely low possibility of deformation and adhesion of the molded article during release even if continuously molded.
　一方、比較例１～７は部分的には特性を満たすものの、比較例１は０．４、０．８、１．６、３．０ｍｍの厚みにおける難燃性においてUL９４　Ｖ－２評価となっており大きく難燃性が低下しており好ましくない。比較例２は引張伸度が３％となっており、脆化を抑制できておらず、好ましくない。比較例３は０．４、０．８、１．６、３．０ｍｍの厚みにおける難燃性がＶ－２評価となっているのに加えて、引張伸度が３％となっており十分な難燃性とスナップフィット性を両立しているとは言い難く好ましくない。比較例４、５、７は０．８、１．６、３．０ｍｍの厚みにおける難燃性においてUL９４　Ｖ－２評価となっており、幅広い領域の厚みで難燃性が高いとは言いがたいため好ましくない。加えて比較例７は、成型性の指標となる離型抵抗値が1MPaを超えており、成形性が良好(良好な離型性)とは言えず、この点においても好ましくない。最後に比較例６は０．８、１．６、３．０ｍｍの厚みにおける難燃性においてUL９４　Ｖ－２評価となっているのに加えて、引張伸度が３％となっており十分な難燃性とスナップフィット性を両立しているとは言い難く好ましくない。 On the other hand, although Comparative Examples 1 to 7 partially satisfy the characteristics, Comparative Example 1 was evaluated as UL94 V-2 in terms of flame retardancy at thicknesses of 0.4, 0.8, 1.6, and 3.0 mm. It is not preferable because the flame retardancy is greatly lowered. Comparative Example 2 has a tensile elongation of 3%, and embrittlement cannot be suppressed, which is not preferable. In Comparative Example 3, the flame retardancy at thicknesses of 0.4, 0.8, 1.6, and 3.0 mm was rated V-2, and the tensile elongation was 3%, which was sufficient. It is difficult to say that both the flame retardancy and the snap-fit property are compatible, which is not preferable. Comparative Examples 4, 5, and 7 are evaluated as UL94 V-2 in terms of flame retardancy at thicknesses of 0.8, 1.6, and 3.0 mm, and it cannot be said that flame retardancy is high in a wide range of thicknesses. I don't like it because it's too hot. In addition, in Comparative Example 7, the mold release resistance, which is an index of moldability, exceeded 1 MPa, and it cannot be said that the moldability is good (good mold release), which is also undesirable in this respect. Finally, in Comparative Example 6, in addition to the UL94 V-2 evaluation for flame retardancy at thicknesses of 0.8, 1.6, and 3.0 mm, the tensile elongation is 3%, which is sufficient. It is difficult to say that both flame retardancy and snap-fitting are achieved, which is undesirable.
　本発明の難燃性ポリアミド樹脂組成物は、幅広い製品厚みを有し、かつヒンジ部を有するような成形品に好適で、得られた成形品は、幅広い製品厚みでの難燃性の高さを有していて、かつスナップフィット性にも優れるため、高い難燃性とスナップフィット性の両立が望まれる電気・電子部品、自動車部品などに好適に用いることができる。 The flame-retardant polyamide resin composition of the present invention has a wide range of product thicknesses and is suitable for molded products that have a hinge portion. and excellent snap-fitting properties, it can be suitably used for electric/electronic parts, automobile parts, etc. where both high flame retardancy and snap-fitting properties are desired.

Claims (4)

  1. 　ポリアミド樹脂（Ａ）及びメラミンシアヌレート（Ｂ）を含有し、前記成分（Ａ）及び（Ｂ）の合計１００質量部に対して、ポリアミド樹脂（Ａ）９０～９８質量部、メラミンシアヌレート（Ｂ）２～１０質量部、リン系酸化防止剤（Ｃ）０．０１～１質量部、ヒンダードフェノール系酸化防止剤（Ｄ）０．０１～１質量部、及び炭素数２２以下の脂肪酸金属塩系潤滑剤（Ｅ）０.１～1質量部の割合で含有し、前記ポリアミド樹脂（Ａ）はポリアミド６６樹脂（Ａ１）５５～８５質量％、ポリアミド６樹脂（Ａ２）１５～４５質量％を含有する難燃性ポリアミド樹脂組成物。 Polyamide resin (A) and melamine cyanurate (B) are contained, and 90 to 98 parts by mass of polyamide resin (A) and melamine cyanurate (B ) 2 to 10 parts by mass, phosphorus antioxidant (C) 0.01 to 1 part by mass, hindered phenol antioxidant (D) 0.01 to 1 part by mass, and fatty acid metal salt having 22 or less carbon atoms System lubricant (E) is contained in a proportion of 0.1 to 1 part by mass, and the polyamide resin (A) contains 55 to 85% by mass of polyamide 66 resin (A1) and 15 to 45% by mass of polyamide 6 resin (A2). flame-retardant polyamide resin composition containing;
  2. 　前記脂肪酸金属塩系潤滑剤（Ｅ）が、ステアリン酸の金属塩である請求項１に記載の難燃性ポリアミド樹脂組成物。 The flame-retardant polyamide resin composition according to claim 1, wherein the fatty acid metal salt-based lubricant (E) is a metal salt of stearic acid.
  3. 　請求項１～２のいずれかに記載の難燃性ポリアミド樹脂組成物からなる成形品。 A molded article made of the flame-retardant polyamide resin composition according to any one of claims 1 and 2.
  4. 　前記成形品が、フェライトコアカバー、エスシーロック、結束バンド、電気配線保護部材のいずれかである請求項３に記載の成形品。 　The molded article according to claim 3, wherein the molded article is any one of a ferrite core cover, an ESC lock, a binding band, and an electrical wiring protection member.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62195043A (en) * 1986-02-21 1987-08-27 Mitsubishi Chem Ind Ltd Flame-retardant polyamide resin composition
CN108795037A (en) * 2018-06-21 2018-11-13 广东聚石化学股份有限公司 A kind of uvioresistant halogen-free reinforced nylon composition and preparation method thereof for fastener
WO2021044880A1 (en) * 2019-09-02 2021-03-11 東洋紡株式会社 Flame-retardant polyamide resin composition and molded article comprising same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62195043A (en) * 1986-02-21 1987-08-27 Mitsubishi Chem Ind Ltd Flame-retardant polyamide resin composition
CN108795037A (en) * 2018-06-21 2018-11-13 广东聚石化学股份有限公司 A kind of uvioresistant halogen-free reinforced nylon composition and preparation method thereof for fastener
WO2021044880A1 (en) * 2019-09-02 2021-03-11 東洋紡株式会社 Flame-retardant polyamide resin composition and molded article comprising same

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