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CN-116790120-B - Polyamide composition, method for producing same, and molded article

CN116790120BCN 116790120 BCN116790120 BCN 116790120BCN-116790120-B

Abstract

The present invention relates to a polyamide composition, a method for producing the same, and a molded article. The invention provides a polyamide composition which contains halogen-free flame retardant and has excellent flame retardance and long-term heat resistance, and a method for producing the same. A polyamide composition comprising (A) a polyamide, (B) a phosphorus-containing flame retardant and (C) a styrene copolymer, wherein the content of the (C) styrene copolymer is 0.1 mass% or more and 7.0 mass% or less relative to the total mass of the (A) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer. The method for producing the polyamide composition is a method for producing the polyamide composition, wherein raw material components comprising the (A) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer are melt kneaded.

Inventors

  • Watarai Masashi
  • NAGASE KOICHI
  • IEDA SHINJI

Assignees

  • 旭化成株式会社

Dates

Publication Date
20260505
Application Date
20200519
Priority Date
20190521

Claims (12)

  1. 1. A polyamide composition comprising: (A) Polyamide(s), (B) Phosphorus-containing flame retardants (C) A styrene copolymer, wherein, The content of the (C) styrene copolymer is 0.1 mass% or more and 7.0 mass% or less relative to the total mass of the (A) polyamide, the (B) phosphorus-containing flame retardant and the (C) styrene copolymer, The polyamide (A) comprises an aliphatic polyamide (A1) and a semiaromatic polyamide (A2), the semiaromatic polyamide (A2) comprises a diamine unit and a dicarboxylic acid unit, The (A2) semiaromatic polyamide contains 75 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.
  2. 2. The polyamide composition according to claim 1, wherein the (A2) semiaromatic polyamide contains 100 mol% of isophthalic acid units among all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.
  3. 3. The polyamide composition according to claim 1 or 2, wherein the (C) styrene copolymer contains acrylonitrile units and styrene units.
  4. 4. The polyamide composition according to claim 1 or 2, wherein the (C) styrene copolymer contains acrylonitrile units and styrene units, and The content of the acrylonitrile unit is 30 mass% or more relative to the total mass of the constituent units of the (C) styrene copolymer.
  5. 5. The polyamide composition according to claim 1 or 2, wherein the phosphorus-containing flame retardant (B) comprises at least one phosphinate selected from the group consisting of phosphinates represented by the following general formula (1), diphosphinates represented by the following general formula (2) and condensates thereof, In the general formula (1), R 11 and R 12 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, M n11+ is a metal ion having a valence of n11, M is an element belonging to group IIA or group VA of the periodic Table, a transition element or aluminum, n11 is 2 or 3, and when n11 is 2 or 3, a plurality of R 11 and a plurality of R 12 which are present are each the same or different; In the general formula (2), R 21 and R 22 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, Y 21 is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms, M ' x m21+ is a metal ion having a valence of M21, M ' is an element belonging to group IIA or group VA of the periodic table, a transition element or aluminum, n21 is an integer of 1 to 3, n21 is an integer of 2 or 3, a plurality of R 21 , a plurality of R 22 and a plurality of Y 21 which are present are each the same or different, M21 is 2 or 3, x is 1 or 2, a plurality of M ' which are present are the same or different when x is 2, and n21, x and M21 are integers satisfying a relation of 2×n21=m21×x.
  6. 6. The polyamide composition according to claim 1 or 2, wherein the content of the phosphorus-containing flame retardant is 0.1 mass% or more and 30 mass% or less relative to the total mass of the polyamide (a), the phosphorus-containing flame retardant (B) and the styrene copolymer (C).
  7. 7. The polyamide composition according to claim 1 or 2, wherein the polyamide composition has a tan δ peak temperature of 90 ℃ or higher.
  8. 8. The polyamide composition according to claim 1 or 2, wherein the polyamide composition has a weight average molecular weight of 10000 or more and 50000 or less.
  9. 9. Polyamide composition according to claim 1 or 2, wherein the polyamide composition further comprises at least one (D) filler material.
  10. 10. A molded article obtained by molding the polyamide composition according to any one of claims 1 to 9.
  11. 11. A process for producing the polyamide composition according to any one of claims 1 to 9, wherein, The raw material components comprising the polyamide (A), the phosphorus-containing flame retardant (B) and the styrene copolymer (C) are melt-kneaded.
  12. 12. A method in which a styrene copolymer is added as a flame retardant aid to a resin composition containing a polyamide and a phosphorus-containing flame retardant, The content of the styrene copolymer is 0.1 mass% or more and 7.0 mass% or less relative to the total mass of the polyamide, the phosphorus-containing flame retardant and the styrene copolymer, The polyamide comprises (A1) an aliphatic polyamide and (A2) a semiaromatic polyamide, the (A2) semiaromatic polyamide comprising diamine units and dicarboxylic acid units, The (A2) semiaromatic polyamide contains 75 mol% or more of isophthalic acid units in all dicarboxylic acid units constituting the (A2) semiaromatic polyamide.

Description

Polyamide composition, method for producing same, and molded article The application relates to a division application of Chinese patent application with the application date of 2020, 5-month and 19 and the application number of 202010423271.3. Technical Field The present invention relates to a polyamide composition, a method for producing the same, and a molded article Background The aliphatic polyamide-based composition has excellent characteristic properties and is therefore used for manufacturing molded articles in a very large number of applications. In particular, polyamide compositions having flame retardant properties are necessary for the components in the electrical and electronic industry in order to ensure adequate fire resistance. Polyamides are often flame retardant treated by the addition of halogen compounds. Recently, however, various regulations have been formulated such that products containing halogen compounds are not used in electric and electronic parts according to regulations of hazardous substances such as RoHS (hazardous substances restriction directive) and PoHS (specific hazardous substances are forbidden in consumer products). Accordingly, various halogen-free flame retardants for polyamides have been developed. Examples of the halogen-free flame retardant include phosphorus compounds. Patent document 1 discloses the use of calcium and aluminum salts of phosphinic acid or diphosphinic acid as flame retardants for polyamides. Test pieces having a sample thickness of 1.2mm, which were produced from a polyamide composition containing these halogen-free flame retardants and reinforced with 30 mass% of glass fibers relative to the total mass of the composition, reached a flammability classification V-0 based on UL 94. In order to achieve the flammability classification V-0 of UL94, patent document 2 discloses that aluminum phosphinate is required in an amount of much more than 20 mass% relative to the total mass of the composition in a glass fiber reinforced polyamide composition containing polyamide 6 as a main component, and that aluminum phosphinate is required in an amount of more than 30 mass% in a glass fiber reinforced polyamide composition containing polyamide 66 as a main component. It can be seen that in order to achieve the flammability classification V-0 using the phosphinic flame retardant, a large amount of the phosphinic flame retardant must be added, thereby adversely affecting the mechanical properties, which is problematic. Accordingly, patent document 3 discloses a polyamide composition containing phosphinate as a flame retardant, which is based on a mixture of aliphatic polyamide and semiaromatic polyamide. It is reported that the addition of the semiaromatic polyamide can reduce the amount of the flame retardant used and improve the tensile elongation. In addition, patent document 4 discloses a polyamide composition using phosphinate as a flame retardant and based on a mixture of polyamide containing aromatic polyamide and polyphenylene sulfide. It is reported that by adding polyphenylene sulfide excellent in flame retardancy to a polyamide containing an aromatic polyamide, the amount of the flame retardant used can be reduced, and the amount of outgas emissions from the flame retardant can be reduced. Prior art literature Patent literature Patent document 1 Japanese patent No. 3947261 Patent document 2 Japanese patent No. 4698789 Patent document 3 Japanese patent No. 4614959 Patent document 4 Japanese patent application laid-open No. 2009-270107 Patent document 5 Japanese patent laid-open publication No. 2005-179362 Patent document 6 European patent application publication 699708 Patent document 7 Japanese patent laid-open No. 08-073720 Disclosure of Invention Problems to be solved by the invention However, the polyamide composition described in patent document 3 has room for improvement in long-term heat resistance and the like required for automobiles and various electric parts, although the tensile elongation at break is improved by reducing the amount of the flame retardant used. In addition, although the polyamide composition described in patent document 4 has reduced the amount of flame retardant used and reduced outgas by adding polyphenylene sulfide, there is a concern that it is difficult to maintain the flammability classification V-0 based on UL94 when the proportion of aliphatic polyamide relative to aromatic polyamide is increased. It can be seen that in the prior art, a polyamide composition using a halogen-free flame retardant and having both flame retardancy and long-term heat resistance is not known. The present invention has been made in view of the above circumstances, and provides a polyamide composition which contains a halogen-free flame retardant and has excellent flame retardancy and long-term heat resistance, a method for producing the same, and a molded article comprising the polyamide composition. In addition, the invention provides a