Reinforced polyamide moulding materials

• US 9,221,974 B2
• Filed: 11/08/2006
• Issued: 12/29/2015
• Est. Priority Date: 11/18/2005
• Status: Active Grant

• Current Assignee: Ems-Chemie AG (Emesta Holding AG)
• Original Assignee: Ems-Chemie AG (Emesta Holding AG)
• Inventors: Rexin, Ornulf, Linster, Jean-Jacques, Hewel, Manfred
• Primary Examiner(s): Ahvazi, Bijan
• Assistant Examiner(s): Miller, David L
• Application Number:
  US11/594,249
• Publication Number:
  US 20070123632A1
• Time in Patent Office: 3,338 Days
• Field of Search: 524/1, 524/494, 524/500, 524/397, 524/447, 524/449, 524/451, 524/496, 524/606
• US Class Current: 1/1
• CPC Class Codes: C08G 69/26 derived from polyamines and polycarboxylic acids
• CPC Class Codes: C08K 7/14 Glass
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2666/20 Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/02 Polyamides derived from omega-amino carboxylic acids or from lactams thereof C08L77/10 takes precedence
• CPC Class Codes: C08L 77/06 Polyamides derived from polyamines and polycarboxylic acids C08L77/10 takes precedence
• CPC Class Codes: C08L 77/10 Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids

Abstract

The present invention relates to reinforced polyamide molding materials which can be prepared from a polyamide blend and, for example, by compounding with cut fibers or continuous filaments on twin-screw extruders and have mechanical properties which are usually not compatible with one another, namely a combination of exceptionally high rigidity and strength and at the same time good toughness. Furthermore, a high heat distortion temperature (HDT) is achieved according to the invention.

The thermoplastic polyamide molding materials according to the invention are suitable for the production of moldings or other semifinished products or finished articles, which can be produced, for example, by extrusion, injection molding, direct methods or direct compounding, in which the compounded polyamide molding material is processed directly by injection molding, or other deformation techniques.

Claims

1. High rigid and simultaneously tough, reinforced polyamide moulding material, characterized by:

heat distortion temperature values HDT/A (1.8 MPa) (measured according to ISO

     75) of more than 242°

C., and HDT/C (8 MPa) of more than 150°

C., consisting of

(1) a polyamide matrix consisting of a blend of the following components;

(A) polyamide 66,

(B) copolyamide, composed of

(b₁) 50 to 80 parts by weight of units which are derived from terephthalic acid (T) in combination with hexamethylenediamine (6) in approximately equimolar ratio,

(b₂) 50 to 20 parts by weight of units which are derived from isophthalic acid (I) in combination with hexamethylenediamine in approximately equimolar ratio,

wherein the copolyamide has a relative viscosity (RV), measured in 0.5% m-cresol solution, of between 1.4 and 1.8;

the parts by weight of the components (b₁) and (b₂) together giving 100 parts by weight,

and (2) a filler component containing a mixture of;

(C) glass fibres and

(D) carbon fibres,

the percentages by weight of the components (A) to (D) together giving 100% and the components (A), (B), (C), and (D) fulfilling the following conditions;

(A)+(B);

20 to 39% by weight,

weight ratio (A)/(B);

50/50 to 95/5,

(C)+(D);

61 to 80% by weight,

weight ratio (C)/(D);

80/20 to 95/5,

the polyamide moulding material optionally containing (3) at least one additive (E) in addition to the components (A) to (D), and the amount thereof being additive to the sum of the components (A) to (D);

wherein the optional additive (E) is selected from the group consisting of inorganic stabilizers, organic stabilizers, lubricants, dyes, metallic pigments, metal spangles, metal-coated particles, halogen-containing flameproofing agents, halogen-free flameproofing agents, impact modifiers, antistatic agents, conductivity additives, demoulding agents, optical brighteners, natural sheet silicates, synthetic sheet silicates and mixtures thereof.

2. Polyamide moulding material according to claim 1, characterized by ultimate tensile strength of more than 230 MPa (measured on standard test specimens according to ISO 527) and optionally elongation at break of more than 1.4% (measured on standard test specimens according to ISO 527).

3. Polyamide moulding material according to claim 1, characterized by a total fibre content of 66 to 74% by weight, a tensile modulus of elasticity of more than 25 500 MPa, and optionally an elongation at break of at least 1.5%.

4. Polyamide moulding material according to claim 1, characterized by a total fibre content of 66 to 74% by weight and an elongation at break of at least 1.7%.

5. Polyamide moulding material according to claim 1, characterized by a tensile modulus of elasticity of more than 18 000 MPa, and optionally an elongation at break of at least 2.0%.

6. Polyamide moulding material according to claim 1, characterized by an elongation at break of at least 2.3%.

7. Polyamide moulding material according to claim 1, in which the copolyamide is copolyamide 6T/6I and has a relative viscosity (RV), measured in 0.5% m-cresol solution, of between 1.48 and 1.7.

8. Polyamide moulding material according to claim 1, in which the glass fibres have a diameter of 5 to 20 μ

m.

9. Polyamide moulding material according to claim 1, characterized in that said antistatic agents are present and comprise carbon black and/or carbon nanotubes in amounts of up to 10% by weight.

10. Process for the preparation of the polyamide moulding material according to claim 1, comprising compounding the molding material at a set extruder barrel temperature 280°

C. to 320°

C., the polymeric components first being melted and cut fibres or continuous filaments then being introduced.

11. Process for the preparation of the polyamide moulding material according to claim 1, characterized in that for the fabrication of long fibre-reinforced rod-granulate by pultrusion, an endless fibre strand is completely impregnated with the polymer melt, subsequently cooled down and cut, so that long fibre-reinforced rod-granulate is obtained.

12. Process for the preparation of the polyamide moulding material according to claim 1, characterized in that initially a compound in granulate form is made from the components (A) and/or (B) and the fillers (C) and/or (D) and optionally the additive (E), and these granulates are subsequently admixed, in which still other amounts of granulate of component (A) and/or (B) are added optionally, and the granulate is further processed.

13. Long fibre-reinforced rod-shaped pellets obtained by pultrusation method according to claim 11, which has a granulate length of 4 to 25 mm.

14. A method comprising molding the moulding material of claim 1 having an ultimate tensile strength of above 230 MPa (measured at norm test specimens according to ISO 527), elongation at break of above 1.5% (measured at norm test specimens according to ISO 527), thermal deformation resistance value HDT/A (1.8 MPa) (measured according to ISO 75) of above 242°

C., HDT/C (8 MPa) (measured according to ISO

     75) of above 165°

C., for the fabrication of shaped articles and/or hollow parts.

15. Production of shaped articles and/or hollow parts from the polyamide moulding material according to claim 1, by extrusion, injection moulding, pressing or direct compounding.

16. A shaped article, obtained from the polyamide moulding materials according to claim 1.

17. The reinforced polyamide moulding material of claim 1 having the heat distortion temperature values HDTA (1.8 MPa) of at least 245°

C. and HDT/C (8 MPa) more than 170°

C. wherein

in said (B) there are 50-70 parts by weight, relative to the weight of (B), of units (b₁) which are derived from terephthalic acid (T) and 50-30 parts by weight, relative to the weight of (B), of units (b₂) which are derived from isophthalic acid (I).

18. The polyamide moulding material of claim 1 wherein (C)+(D) is 61-75% by weight.

19. The polyamide moulding material of claim 1 wherein (C)+(D) is 64-75% by weight.

20. The polyamide moulding material of claim 1 wherein (C)+(D) is 66-75% by weight.

21. The polyamide moulding material according to claim 3 wherein the tensile modulus of elasticity is more than 28,000 MPa.

22. The polyamide moulding material of claim 4 wherein the elongation at break is at least 1.8%.

23. The polyamide moulding material according to claim 4 wherein the tensile modulus of elasticity is more than 20,000 MPa.

24. The polyamide moulding material of claim 6 wherein the elongation at break is at least 2.5%.

25. The polyamide moulding material of claim 9 wherein the glass fibres have a diameter of 5-10 μ

m.

26. Polyamide moulding material according to claim 8, wherein the glass fibers are E-glass fibres.

27. Long fibre-reinforced rod-shaped pellets according to claim 13, which has a granulate length of 5 to 12 mm.

28. Polyamide moulding material according to claim 8, in which the glass fibres have a cross-section being round, oval or rectangular.