GLASS FIBER REINFORCED THERMOPLASTIC COMPOSITIONS WITH GOOD MECHANICAL PROPERTIES

Abstract

The invention relates to compositions for the production of thermoplastic moulding materials, where the compositions comprise the following constituents: A) at least one polymer selected from the group consisting of aromatic polycarbonate, aromatic polyester carbonate and polyester, B) at least one anhydride-functionalized ethylene--olefin-copolymer or anhydride-functionalized ethylene--olefin terpolymer with a weight-average molar mass M.sub.w determined by high-temperature gel permeation chromatography using ortho-dichlorobenzene as solvent against polystyrene standards of 50000 to 500000 g/mol, C) at least one rubber-modified graft polymer, D) glass fibers,
and also to a process for the production of the moulding materials, to the moulding materials themselves, to the use of the compositions or moulding materials for the production of mouldings, and to the mouldings themselves.

Claims

1. A compositions for the production of thermoplastic moulding materials comprising: A) at least one polymer selected from the group consisting of aromatic polycarbonate, aromatic polyester carbonate and polyester, B) at least one anhydride-functionalized ethylene--olefin-copolymer or anhydride-functionalized ethylene--olefin terpolymer with a weight-average molar mass Mw determined by high-temperature gel permeation chromatography using ortho-dichlorobenzene as solvent against polystyrene standards of 50000 to 500000 g/mol, C) at least one rubber-modified graft polymer, and D) glass fibers.

2. The composition of claim 1, wherein component B has from 2 to 40 mol % of -olefin units and from 60 to 98 mol % of ethylene units, based on the entirety of -olefin and ethylene.

3. The composition of claim 1, wherein the anhydride content of component B is from 0.1 to 3.0% by weight.

4. The composition of claim 1, wherein component B is a maleic-anhydride-functionalized copolymer of ethylene and 1-octene.

5. The composition of claim 1, wherein component C is at least one graft polymer of C.1 5 to 95% by weight of at least one vinyl monomer on C.2 5 to 95% by weight of a one or more elastomeric graft bases with glass transition temperatures below 10 C., wherein the glass transition temperature is determined by means of differential scanning calorimetry according to standard DIN EN 61006 at a heating rate of 10 K/min. with definition of the glass transition temperature as the mid-point temperature.

6. The composition of claim 5, wherein component C.2 is selected from the group consisting of diene rubbers, styrene-butadiene block copolymer rubbers, acrylate rubbers, silicone rubbers, silicone/acrylate composite rubbers and ethylene/propylene/diene rubbers.

7. The composition of claim 6, wherein component C has a core-shell structure and component C.2 is selected from the group consisting of diene rubbers, acrylate rubber and silicone/acrylate composite rubbers.

8. The composition of claim 1, wherein as component D cut glass fibers are used with a sizing selected from the group consisting of epoxy sizing, polyurethane sizing and siloxane sizing.

9. The composition of claim 1, wherein the glass fibers according to component D have diameters from 5 to 25 m.

10. The composition of claim 1, wherein the weight ratio of component B to component C is at least 1:1.

11. The composition of claim 1, comprising: from 40 to 95% by weight of component A, from 0.1 to 10% by weight of component B, from 0.1 to 10% by weight of component C, from 2 to 40% by weight of component D and further comprising from 0 to 10% by weight of other polymeric constituents or polymer additives as component E.

12. A process for the production of moulding materials comprising: (i) heating the composition of claim 1 via introduction of thermal or mechanical energy, to melt at least component A), and to disperse all of the components or dissolve the components in one another, and (ii) solidifying the melt resulting from step (i) by cooling and (iii) optionally pelletizing, where the steps (ii) and (iii) can be carried out in any desired order.

13. A moulding material obtained by the process of claim 12.

14. (canceled)

15. A moulded article comprising the composition of claim 1.

16. A moulded article comprising the moulding material according to claim 13.

Description

EXAMPLES

[0143] Components Used:

[0144] Component A:

[0145] A1: Linear polycarbonate based on bisphenol A with weight-average molar mass M.sub.W of 28 000 g/mol determined by gel permeation chromatography in methylene chloride with polycarbonate as standard.

[0146] Component B:

[0147] B1: Maleic-anhydride-functionalized ethylene-1-octene copolymer with MAH content of 0.8% by weight and with an ethylene:1-octene ratio of 87:13 mol %, and with weight-average molar mass M.sub.W of 200 000 g/mol (Paraloid EXL 3808 D, producer Dow Chemical).

[0148] B2: Maleic-anhydride-functionalized ethylene-1-octene copolymer with MAH content of 0.4% by weight and with an ethylene:1-octene ratio of 83:17 mol %, and with weight-average molar mass M.sub.W of 322 000 g/mol (Paraloid EXL 3815, producer Dow Chemical).

[0149] Component C:

[0150] C1: Impact modifier with core-shell structure and with a butadiene rubber as elastomeric graft base (rubber core) (Kane ACE M732, producer Kaneka).

[0151] C2: Impact modifier with core-shell structure and with a silicone-acrylate composite rubber as elastomeric graft base (Metablen S2001, producer Mitsubishi Rayon)

[0152] C3: Impact modifier with core-shell structure and with an acrylate rubber as elastomeric graft base (Paraloid EXL 2300, producer Dow Chemical).

[0153] Component D:

[0154] D1: cut glass fiber with an epoxy sizing based on bisphenol A, an average fiber diameter of 11 m and an average fiber length of 4.5 mm (CS 7968, producer Lanxess)

[0155] D2: cut glass fiber with a polyurethane sizing, an average fiber diameter of 14 m and an average fiber length of 4.5 mm (CS 7942, producer Lanxess)

[0156] Component E:

[0157] E1: Heat stabilizer, Irganox B900 (mixture of 80% Irgafos 168 (tris(2,4-di-tert-butylphenyl) phosphite) and 20% of Irganox 1076 (2,6-di-tert-butyl-4-(octadecanoxycarbonylethyl)phenol); BASF (Ludwigshafen, Germany).

[0158] E2: Demoulding agent, pentaerythritol tetrastearate

[0159] Production and Testing of the Moulding Materials of the Invention

[0160] The components were mixed in a ZSK-25 twin-screw extruder from Werner & Pfleiderer at a melt temperature of 300 C. The mouldings were produced at a melt temperature of 300 C. and a mould temperature of 80 C. in an Arburg 270 E injection-moulding machine.

[0161] Strain at break was determined with a tensile test at 23 C. according to ISO 527 (1996 version)

[0162] The impact penetration test to measure maximum force and puncture energy (multi-axial ductility) is carried out at 23 C. on test specimens of dimensions 60 mm60 mm2 mm in accordance with ISO 6603-2 (2000 version, but without visual inspection of the test specimens).

TABLE-US-00001 TABLE 1 Compositions and properties thereof Component (part by weight) V1 2 3 4 V5 A1 74.35 74.35 74.35 74.35 74.35 B1 5.00 1.50 2.50 3.50 B2 C1 3.50 2.50 1.50 5.00 C2 C3 D1 20.00 20.00 20.00 20.00 20.00 E1 0.25 0.25 0.25 0.25 0.25 E2 0.40 0.40 0.40 0.40 0.40 Properties Unit Dart penetration test Maximum Force N 2018 2821 2762 2245 1414 Puncture Energy J 11.7 13.9 13.8 12.0 11.4 Tensile test Strain at break % 12.4 14.0 13.7 14.6 3.1

TABLE-US-00002 TABLE 2 Compositions and properties thereof Component (% by weight) V6 7 8 V5 A1 74.35 74.35 74.35 74.35 B1 B2 5.00 2.50 3.50 C1 2.50 1.50 5.00 C2 C3 D1 20.00 20.00 20.00 20.00 E1 0.25 0.25 0.25 0.25 E2 0.40 0.40 0.40 0.40 Properties Unit Dart penetration test Maximum Force N 2007 2349 2625 1414 Puncture Energy J 10.3 12.5 13.0 11.4 Tensile test Strain at break % 14.5 19.4 18.0 3.1

TABLE-US-00003 TABLE 3 Compositions and properties thereof Component (% by weight) V1 9 V10 A1 74.35 74.35 74.35 B1 5.00 2.50 B2 C1 C2 2.50 5.00 C3 D1 20.00 20.00 20.00 E1 0.25 0.25 0.25 E2 0.40 0.40 0.40 Properties Unit Dart penetration test Maximum Force N 2018 2273 974 Puncture Energy J 11.7 12.0 6.8 Tensile test Strain at break % 12.4 14.2 2.8

TABLE-US-00004 TABLE 4 Compositions and properties thereof Component (part by weight) V1 11 V12 V6 13 A1 74.35 74.35 74.35 74.35 74.35 B1 5.00 2.50 B2 5.00 2.50 C1 C2 C3 2.50 5.00 2.50 D1 20.00 20.00 20.00 20.00 20.00 E1 0.25 0.25 0.25 0.25 0.25 E2 0.40 0.40 0.40 0.40 0.40 Properties Unit Dart penetration test Maximum Force N 2018 2348 1094 2007 2387 Puncture Energy J 11.7 12.0 7.0 10.3 11.0 Tensile test Strain at break % 12.4 15.4 3.0 14.5 18.1

TABLE-US-00005 TABLE 5 Compositions and properties thereof Component (part by weight) V14 15 16 V17 A1 74.35 74.35 74.35 74.35 B1 5.00 2.50 3.50 B2 C1 2.50 1.50 5.00 C2 C3 D2 20.00 20.00 20.00 20.00 E1 0.25 0.25 0.25 0.25 E2 0.40 0.40 0.40 0.40 Properties Unit Dart penetration test Maximum Force N 1881 2269 2232 886 Puncture Energy J 10.3 11.6 12.5 5.5 Tensile test Strain at break % 12.6 13.0 14.7 2.6

[0163] The examples in Table 1 show that the compositions according to the invention (2, 3 and 4) with a mixture of components B and C provide better performance with regard to maximum force, puncture energy, strain at break than the compositions containing only component B (V1) or only component C (V5). The same synergistic effect is observed when component B is adapted with regard to molecular weight, ethylene:1-octene ratio and content of maleic anhydride (table 2, compositions 7 and 8 compared to V6 and V5). Also when the graft base of component C is changed to acrylate rubber or silicone/acrylate composite rubber, the benefits of combining components B and C remain (tables 3 and 4). Finally as apparent from table 5, also with a different glass fiber grade the synergistic property combination when using components B and C is observed.