Polyamide compositions

Abstract

The present invention relates to flame retardant polyamide-based compositions or moulding materials and to articles of manufacture of the electricals or electronics industries producible therefrom, in particular charging components, containing at least one polyamide, aluminium oxide, magnesium hydroxide and at least one organic epoxide.

Claims

1. A composition or moulding material containing a) at least one polyamide, b) aluminium oxide, c) magnesium hydroxide and d) at least one organic, halogen-free, epoxidized compound.

2. The composition or moulding material according to claim 1 wherein per 100 parts by mass of the component a) the component b) is employed in amounts in the range from 20 to 300 parts by mass.

3. The composition or moulding material according to claim 1 wherein per 100 parts by mass of the component a) the component b) is employed in amounts in the range from 70 to 120 parts by mass.

4. The composition or moulding material according to claim 1, wherein per 100 parts by mass of the component a) the component c) is employed in amounts in the range from 20 to 350 parts by mass.

5. The composition or moulding material according to claim 1, wherein per 100 parts by mass of the component a) the component c) is employed in amounts in the range from 120 to 210 parts by mass.

6. The composition or moulding material according to claim 1, wherein per 100 parts by mass of the component a) the component d) is employed in amounts in the range from 0.1 to 25 parts by mass.

7. The composition or moulding material according to claim 1, wherein per 100 parts by mass of the component a) the component d) is employed in amounts in the range from 2 to 10 parts by mass.

8. The composition or moulding material according to claim 1, wherein component d) comprises two epoxy groups per molecule.

9. The composition or moulding material according to claim 8, wherein at least one epoxy group is terminal.

10. The composition or moulding material according to claim 8, wherein component d) is polyglycidyl ether or poly(beta-methylglycidyl) ether.

11. The composition or moulding material according to claim 8, wherein the epoxidized compound is an oligomeric reaction product of bisphenol A with epichlorohydrin having an epoxy index according to ISO 3001 in the range from 450 to 750 grams per equivalent.

12. The composition or moulding material according to claim 8, wherein the epoxidized compound contains in any desired combination and frequency the epoxy-containing unit ##STR00006## and the unit ##STR00007## and/or the unit ##STR00008## wherein R.sup.9, R.sup.19 independently of one another represent H or C.sub.1-C.sub.6-alkyl, R.sup.11 represents C.sub.1-C.sub.8-alkyl, X and Y each represent integers in the range from 0 to 20, with the proviso that either X or Y is 1 at least once, Z represents an integer in the range from 2 to 20 and R* represents H or C.sub.1-C.sub.8-alkyl, wherein the units designated X, Y, Z may occur repeatedly and in any desired sequence.

13. The composition or moulding material according to claim 8, wherein the epoxidized compound is a compound of formula (II) ##STR00009## wherein R.sup.9, R.sup.19 independently of one another represent H or C.sub.1-C.sub.8-alkyl, R.sup.11 represents C.sub.1-C.sub.8-alkyl, X and Y each represent integers in the range from 0 to 20, with the proviso that either X or Y is 1 at least once, Z represents an integer in the range from 2 to 20 and R* represents H or C.sub.1-C.sub.8—alkyl, wherein the units designated X, Y, Z may occur repeatedly and in any desired sequence.

14. The composition or moulding material according to claim 8, wherein the epoxidized compound is an oligomeric reaction product of bisphenol A with epichlorohydrin of formula (III) ##STR00010## wherein a represents an integer in the range from 0 to 12, wherein a represents the average number of repeating units.

15. The composition or moulding material according to claim 1, wherein the component a) is selected from semicrystalline polyamides which have a melting enthalpy in the range from 4 to 25 J/g measured by the DSC method according to ISO 11357 in the 2.sup.nd heating and integration of the melting peak.

16. The composition or moulding material according to claim 1, wherein the component a) is polyamide 6 or polyamide 66 or a copolyamide of polyamide 6 or polyamide 66.

17. An article of manufacture of the electricals or electronics industries based on a composition or moulding material according to claim 1.

18. The article according to claim 17 wherein the article is a charging component.

19. The article according to claim 18 wherein the article is a charging component for electromobility.

20. The article according to claim 19, wherein the charging component is a battery charging component for charging electrical batteries.

21. The article according to claim 18, wherein the charging component is a charging cable plug, a charging inlet or a component of a charging inlet.

22. The article according to claim 21, wherein the charging component is a pin holder of a charging inlet.

23. A process for producing an article of manufacture of the electricals or electronics industries, comprising processing a composition containing a) at least one polyamide, b) aluminium oxide, c) magnesium hydroxide and d) at least one organic, halogen-free, epoxidized compound, into moulding materials by mixing, extruding in a water bath, cooling until pelletizable, pelletizing and injection moulding.

24. The process according to claim 23, wherein the article of manufacture is a charging component.

25. The process according to claim 24, wherein the article of manufacture is a battery charging component.

26. The process according to claim 24, wherein the article of manufacture is a charging cable plug, a charging inlet or a component of a charging inlet.

Description

EXAMPLES

[0225] The components listed in table 1 were mixed in a ZSK 26 Compounder twin-screw extruder from Coperion Werner & Pfleiderer (Stuttgart, Germany) at a temperature of about 290° C., extruded into a water bath, cooled until pelletizable and pelletized. The pelletized material was dried to constant weight at 70° C. in a vacuum drying cabinet.

[0226] The pelletized material was then processed on an Arburg A470 injection moulding machine at melt temperatures between 280° C. and 300° C. and mould temperatures in the range from 80° C. to 100° C. to afford test pieces having dimensions of 125 mm.Math.13 mm.Math.0.75 mm for the tests according to UL94, test pieces having dimensions of 60 mm.Math.45 mm.Math.2.0 mm for producing the test specimens for the thermal conductivity measurement and test specimens having dimensions of 80 mm.Math.10 mm.Math.4 mm for the mechanical tests.

[0227] Flame resistance was determined according to the UL94V method (Underwriters Laboratories Inc. Standard of Safety, “Test for Flammability of Plastic Materials for Parts in Devices and Appliances”, p. 14 to p. 18 Northbrook 1998).

[0228] Flexural strength and edge fibre elongation were obtained from flexural tests in accordance with ISO178-A on test specimens having dimensions of 80 mm.Math.10 mm.Math.4 mm.

[0229] Impact strength was obtained by the IZOD method according to ISO180-1U on test specimens having dimensions of 80 mm.Math.10 mm.Math.4 mm.

[0230] Thermal conductivity was measured according to the laser flash method according to EN821-2 using a Netzsch LFA447 Nanoflash® instrument. Measurement of thermal conductivity perpendicular to the flow direction of the test specimen (through plane) was effected on test specimens having dimensions of 12.5 mm.Math.12.5 mm.Math.2 mm, with the light pulse incident on the side having dimensions of 12.5 mm.Math.12.5 mm. The respective test specimens were previously milled from a test piece having dimensions of 60 mm.Math.45 mm.Math.2.0 mm.

[0231] Measurement of thermal conductivity in the flow direction of the test specimen (in plane) was effected on 6 test specimens arranged close together in rows and having dimensions of 12.5 mm.Math.2 mm.Math.2 mm which were each milled from a test piece having dimensions of 60 mm.Math.45 mm.Math.2.0 mm, then rotated about the longitudinal axis by 90° and finally reassembled such that the light pulse was in turn incident on a resulting surface of about 12 mm.Math.12.5 mm.

[0232] The quotient of the thermal conductivity perpendicular to the flow direction (through plane) and the thermal conductivity in the flow direction (in plane) served as a measure of the isotropy of the thermal conductivity. At completely isotropic thermal conductivity this assumes a value of 1.

[0233] Materials Used:

[0234] Component a/1: polyamide 6 (Durethan® B24, from Lanxess Deutschland GmbH, Cologne, Germany)

[0235] Component b/1: aluminium oxide (Martoxid® TM4250, Martinswerk GmbH, Bergheim, Germany)

[0236] Component c/1: magnesium hydroxide (Magnifin® SHIV, Martinswerk GmbH, Bergheim, Germany)

[0237] Component d/1: 2,2-bis(4-hydroxyphenyl)propane-epichlorohydrin copolymer [CAS-No. 25068-38-6](Araldite® GT7071 from Huntsman Advanced Materials, Everberg, Belgium)

[0238] Employed as component e) were further additives customary for use in polyamides such as nucleating agents (for example based on talc [CAS No. 14807-96-6]) and/or heat stabilizers such as 1,6-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionylamino]hexane [CAS No. 23128-74-7](Irganox® 1098, BASF, Ludwigshafen, Germany) and/or demoulding agents such as ethylene-bis-stearylamide [CAS No. 110-30-5] (Loxiol® EBS from Emery Oleochemicals GmbH, Düsseldorf, Germany). The type and amount of the further additives employed as component e) in each case correspond in the examples and comparative examples.

[0239] The compositions reported in table 1 were processed as described hereinabove.

TABLE-US-00001 TABLE 1 Component Ex. 1 Comp. 1 a/1 [parts by 100 100 mass] b/1 [parts by 167 161 mass] c/1 [parts by 91 87 mass] d/1 [parts by 3.6 mass] e [parts by 1.5 1.4 mass] UL94 (0.75 mm) Class V-0 V-2 IZOD impact strength [kJ/m.sup.2] 30 27 Thermal conductivity [through plane] [W/mK] 1.2 1.3 Thermal conductivity [in plane] [W/mK] 1.7 1.6 Isotropy of thermal conductivity 0.7 0.8 Flexural strength [MPa] >160 >160 Edge fibre elongation [%] >1.7 >1.7

[0240] Tab. 1 shows that while both Ex. 1 and Comp. 1 exhibited the mechanical performance required according to the problem addressed by the invention with an edge fibre elongation above 1.5% and a flexural strength above 150 MPa and also a thermal conductivity of at least 1 W/mK with sufficient isotropy, the required flammability classification of UL94 V-0 at a wall thickness of 0.75 mm was additionally achieved only in the case of the inventive composition in Ex. 1.

[0241] Furthermore, the samples based on a composition according to example 1 showed significant advantages in impact strength.