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WO2022158383A1 - Composition de résine de polyamide ignifuge et article moulé la comprenant - Google Patents

Composition de résine de polyamide ignifuge et article moulé la comprenant 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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WIPO (PCT)
Prior art keywords
mass
polyamide resin
polyamide
parts
flame
Prior art date
Application number
PCT/JP2022/001087
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English (en)
Japanese (ja)
Inventor
和樹 岩村
信宏 吉村
誠 玉津島
亮 梅木
Original Assignee
東洋紡株式会社
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Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to JP2022576644A priority Critical patent/JPWO2022158383A1/ja
Priority to CN202280009842.6A priority patent/CN116724079A/zh
Publication of WO2022158383A1 publication Critical patent/WO2022158383A1/fr

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Classifications

    • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir une composition de résine de polyamide ignifuge présentant une faible fuite de retardateur de flamme et présentant une résistance à la décoloration thermique, une aptitude au moulage, un ajustement par pression de pièces, etc., exceptionnels tout en présentant une ininflammabilité au niveau de la norme UL 94V-0 sur une large plage d'épaisseur. La solution selon l'invention porte sur une composition de résine de polyamide ignifuge caractérisée en ce qu'elle contient une résine de polyamide (A) et du cyanurate de mélamine (B); en ce qu'elle contient de 90 à 98 parties en masse de résine de polyamide (A) et de 2 à 10 parties en masse de cyanurate de mélamine (B) par rapport à un total de 100 parties en masse des composants (A) et (B); en ce quelle est telle que la proportion d'une résine de polyamide 66 (A1) dans la résine de polyamide (A) est de 55 à 85 % en masse, et la proportion d'une résine de polyamide 6 (A2) dans la résine de polyamide (A) est de 15 à 45 % en masse; et en ce qu'elle contient de 0,01 à 1 partie en masse d'un antioxydant à base de phosphore (C), de 0,01 à 1 partie en masse d'un antioxydant à base de phénol encombré (D) et de 0,1 à 1 partie en masse d'un lubrifiant (E) à base de sel métallique d'acide gras C22 ou inférieur par rapport à un total de 100 parties en masse des composants (A) et (B).
PCT/JP2022/001087 2021-01-22 2022-01-14 Composition de résine de polyamide ignifuge et article moulé la comprenant WO2022158383A1 (fr)

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JP2022576644A JPWO2022158383A1 (fr) 2021-01-22 2022-01-14
CN202280009842.6A CN116724079A (zh) 2021-01-22 2022-01-14 阻燃性聚酰胺树脂组合物及其成形品

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62195043A (ja) * 1986-02-21 1987-08-27 Mitsubishi Chem Ind Ltd 難燃性ポリアミド樹脂組成物
CN108795037A (zh) * 2018-06-21 2018-11-13 广东聚石化学股份有限公司 一种用于紧固件的抗紫外无卤阻燃尼龙组合物及其制备方法
WO2021044880A1 (fr) * 2019-09-02 2021-03-11 東洋紡株式会社 Composition de résine de polyamide ignifuge et article moulé la comprenant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62195043A (ja) * 1986-02-21 1987-08-27 Mitsubishi Chem Ind Ltd 難燃性ポリアミド樹脂組成物
CN108795037A (zh) * 2018-06-21 2018-11-13 广东聚石化学股份有限公司 一种用于紧固件的抗紫外无卤阻燃尼龙组合物及其制备方法
WO2021044880A1 (fr) * 2019-09-02 2021-03-11 東洋紡株式会社 Composition de résine de polyamide ignifuge et article moulé la comprenant

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CN116724079A (zh) 2023-09-08
TW202237744A (zh) 2022-10-01

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