Polycarbonate molding materials exhibiting improved...

Details Polycarbonate molding materials exhibiting improved... Polycarbonate molding materials exhibiting improved...

2001-06-01

2003-07-22

Niland, Patrick D. (Department: 1714)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

At least one aryl ring which is part of a fused or bridged...

C524S537000

Reexamination Certificate

active

06596800

ABSTRACT:

The present invention relates to polycarbonate moulding compositions which comprise zinc compounds and have improved mechanical properties and an improved crude shade.
Thermoplastic moulding compositions, in particular those which comprise homo- and/or copolymers of one or more ethylenically unsaturated monomers, polycarbonates and polyesters, are known from a large number of publications. This particularly applies to the use of ABS polymers. Reference is made to the following documents merely by way of example: DE-A 19 616, WO97/40092, EP-A 728 811, EP-A 315 868 (=U.S. Pat. No. 4,937,285), EP-A 0 174 493 (U.S. Pat. No. 4,983,658), U.S. Pat. No. 5,030,675, JA 5 920 240, EP-A 0 363 608 (=U.S. Pat. No. 204,394), EP-A 0 767 204, EP-A 0 611 798, WO 96/27600 and EP-A 0 754.
The thermoplastic moulding compositions described in this prior art are still in need of improvement in their mechanical properties. This particularly applies to the use of these moulding compositions in safety-relevant components, e.g. in the motor vehicle industry, where high requirements are imposed on elongation at break, ESC properties and heat distortion point. The crude shade of the known moulding compositions furthermore also requires improvement.
EP-A 761 746 describes moulding compositions which are based on polycarbonate and optionally other thermoplastics and comprise very fine-particled inorganic powders and flameproofing agents. Zinc oxide is mentioned amongst others. 0.1 to 100 nm is mentioned as the average particle diameter.
Surprisingly, it has now been found that polycarbonate moulding compositions have an improved crude shade and improved mechanical properties if zinc compounds of a particular size are added to them. The invention accordingly provides moulding compositions comprising thermoplastic polycarbonate and 0.01 to 30 parts by weight per 100 parts by weight (polycarbonate) of zinc compounds having an average particle diameter of 1 nm to 20 &mgr;m, preferably 1 nm to 10 &mgr;m.
The invention also provides thermoplastic moulding compositions comprising
A. 40 to 99 parts by wt., preferably 50 to 95 parts by wt., particularly preferably 60 to 90 parts by wt. of an aromatic polycarbonate,
B. 0 to 50, preferably 1 to 40 parts by wt. of a vinyl (co)polymer of at least one monomer chosen from the series consisting of styrene, &agr;-methylstyrene, styrenes substituted on the nucleus, C
1
-C
8
-alkyl methacrylates and C
1
-C
8
-alkyl acrylates with at least one monomer from the series consisting of acrylonitrile, methacrylonitrile, C
1
-C
8
-alkyl methacrylates, C
1
-C
8
-alkyl acrylates, maleic anhydride and N-substituted maleimides,
C. 0.5 to 60 parts by wt., preferably 1 to 40 parts by wt., particularly preferably 2 to 30 parts by wt. of a graft copolymer comprising at least two monomers from the group consisting of mono- or polyunsaturated olefins, such as e.g. ethylene, propylene, chloroprene, butadiene and isoprene, vinyl acetate, styrene, &agr;-methylstyrene, styrenes substituted on the nucleus, vinyl cyanides, such as e.g. acrylonitrile and methacrylonitrile, maleic anhydride and N-substituted maleimides,
D. 0.01 to 30 parts by wt., preferably 0.01 to 20 parts by wt., particularly preferably 0.01 to 10 parts by wt., especially preferably 0.1 to 5 parts by wt. of zinc compounds having an average particle diameter of 1 nm to 20 &mgr;m, preferably 1 nm to 10 &mgr;m, zinc oxide having average particle diameters of ≦100 nm being excluded.
The moulding compositions according to the invention can furthermore comprise as additives (component E): conventional flameproofing agents, very fine-particled inorganic compounds or fluorinated polyolefins and mixtures thereof. The flameproofing agents and very fine-particled inorganic compounds are in general each used in an amount of 0.1 to 25, preferably 2 to 15 parts by wt. The fluorinated polyolefins are in general employed in an amount of 0.01 to 5, preferably 0.05 to 2 parts by wt.
The sum of all the parts by weight of A+B+C+D+E gives 100.
Component A
Thermoplastic aromatic polycarbonates according to component A which are suitable according to the invention are those based on diphenols of the formula (I)
wherein
A is a single bond, C
1
-C
5
-alkylene, C
2
-C
5
-alkylidene, C
5
-C
6
-cycloalkylidene, —S— or —SO
2
—,
B is chlorine or bromine,
q is 0, 1 or 2 and
p is 1 or 0,
or alkyl-substituted dihydroxyphenylcycloalkanes of the formula (II)
wherein
R
7
and R
8
independently of one another each denote hydrogen, halogen, preferably chlorine or bromine, C
1
-C
8
-alkyl, C
5
-C
6
-cycloalkyl, C
6
-C
10
-aryl, preferably phenyl, and C
7
-C
12
-aralkyl, preferably phenyl-C
1
-C
4
-alkyl, in particular benzyl,
m denotes an integer of 4, 5, 6 or 7, preferably 4 or 5,
R
9
and R
10
can be chosen individually for each Z and independently of one another denote hydrogen or C
1
-C
6
-alkyl, and
Z denotes carbon, with the proviso that on at least one atom Z R
9
and R
10
simultaneously denote alkyl.
Suitable diphenols of the formula (I) are e.g. hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
Preferred diphenols of the formula (I) are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane.
Preferred diphenols of the formula (II) are 1,1-bis-(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 1,1-bis-(4-hydroxyphenyl)-2,4,4-trimethyl-cyclopentane.
Polycarbonates which are suitable according to the invention are both homopolycarbonates and copolycarbonates.
Component A can also be a mixture of the thermoplastic polycarbonates defined above.
Polycarbonates can be prepared in a known manner from diphenols with phosgene by the phase boundary process or with phosgene by the process in a homogeneous phase, the so-called pyridine process, it being possible for the molecular weight to be adjusted in a known manner by a corresponding amount of known chain stoppers.
Suitable chain stoppers are e.g. phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, and also long-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)-phenol, in accordance with DE-OS 28 42 005, or monoalkylphenols or dialkylphenols having a total of 8 to 20 C atoms in the alkyl substituents, in accordance with German Patent Application P 3506472.2, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethyl-heptyl)-phenol and 4-(3,5-dimethyl-heptyl)-phenol.
The amount of chain stoppers is in general between 0.5 and 10 mol %, based on the sum of the particular diphenols of the formulae (I) and/or (II) employed.
Polycarbonates A which are suitable according to the invention have average molecular weights ({overscore (M)}
w
, weight-average, measured e.g. by ultracentrifugation or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.
Polycarbonates A which are suitable according to the invention can be branched in a known manner, and in particular preferably by incorporation of 0.05 to 2 mol %, based on the sum of the diphenols employed, of compounds which are trifunctional or more than trifunctional, e.g. those having three or more than three phenolic groups.
Preferred polycarbonates are, in addition to bisphenol A homopolycarbonate, the copolycarbonates of bisphenol A with up to 15 mol %, based on the molar sum of diphenols, of 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and the copolycarbonates of bisphenol A with up to 60 mol %, based on the molar sum of diphenols, of 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
Polycarbonate A can be replaced in part or completely by aromatic polyester carbonates. The aromatic polycarbonates of component A can also contain polysiloxane blocks. The preparation thereof is described, for example, in DE-OS

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