Flame-resistant polycarbonate ABS moulding material

Details Flame-resistant polycarbonate ABS moulding material Flame-resistant polycarbonate ABS moulding material

2001-05-16

2003-07-22

Sanders, Kriellion A. (Department: 1714)

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

Synthetic resins

Processes of preparing a desired or intentional composition...

C524S125000, C524S127000, C524S139000, C524S140000, C524S141000, C524S142000, C524S144000, C524S145000

Reexamination Certificate

active

06596794

ABSTRACT:

The present invention relates to polycarbonate-ABS moulding compositions which have been given a flame-resistant treatment with phosphorus compounds and have an excellent profile of mechanical properties, in particular a significantly improved elongation at break, an outstanding modulus of elasticity in tension and excellent processing properties.
EP-A-0 363 608 describes polymer mixtures of aromatic polycarbonate, styrene-containing copolymer or graft copolymer and oligomeric phosphates as flameproofing additives. The profile of mechanical properties and the processing properties of these mixtures are often inadequate for particular intended purposes.
EP-A-0 704 488 describes moulding compositions of aromatic polycarbonate, styrene-containing copolymers and graft polymers with a specific graft base in particular ratios of amounts. These moulding compositions have a very good notched impact strength and can optionally be given a flame-resistant treatment with phosphorus compounds. The profile of properties is inadequate for the production of shaped articles of increased elasticity requirements and the required processing properties.
U.S. Pat. No. 5,061,745 describes moulding compositions of aromatic polycarbonate, graft polymer and monophosphates. The volatility of the monophosphates can cause severe impairment of the processing properties.
EP-A 755 977 describes moulding compositions of aromatic polycarbonate, ABS graft polymers with a rubber content of <25% and oligomeric phosphates. To obtain good stress cracking properties, the phosphate contents should not exceed 8 wt. %. It is furthermore stated that bulk ABS and mixtures of graft polymer of high rubber content and SAN resin have similar mechanical and rheological properties. To achieve adequate flameproofing, the amount of flameproofing agent employed of max. 8 wt. % may be too low.
The object of the present invention is to provide flame-resistant polycarbonate ABS moulding compositions which combine excellent mechanical properties, such as weld seam strength and elongation at break, with excellent processing properties (few surface defects, flowability, low contents of volatile components). This profile of properties corresponds to the trend towards ever thinner and therefore more lightweight components of housings.
It has now been found that PC/ABS moulding compositions which comprise phosphorus compounds according to component D (see below) and graft polymer obtainable by bulk polymerization can be processed to shaped articles having a very good profile of mechanical properties.
The present invention therefore provides flame-resistant thermoplastic moulding compositions based on polycarbonate and/or polyester-carbonate comprising graft polymer prepared by means of bulk, solution or bulk-suspension polymerization processes and, as flameproofing agents, phosphorus-containing compounds. The phosphorus compounds of the general formula (I) mentioned below as component D are employed as the phosphorus-containing compounds.
The present invention preferably provides flame-resistant thermoplastic moulding compositions comprising
A. 40 to 99, preferably 60 to 98.5 parts by wt. aromatic polycarbonate and/or polyester-carbonate,
B. 0.5 to 60, preferably 1 to 40, in particular 2 to 25 parts by wt. graft polymer, prepared by means of bulk, solution or bulk-suspension polymerization processes, of
B.1 50 to 99, preferably 65 to 98 wt. % of one or more vinyl monomers on
B.2 50 to 1, preferably 35 to 2 wt. % of one or more graft bases having a glass transition temperature of <10° C., preferably <0° C., particularly preferably <−10° C.,
C. 0 to 45, preferably 0 to 30, particularly preferably 2 to 25 parts by wt. thermoplastic vinyl (co)polymer and/or polyalkylene terephthalate
D. 0.5 to 20 parts by wt., preferably 1 to 18 parts by wt., particularly preferably 2 to 17 parts by wt. phosphorus compound of the general formula (I)
 wherein
R
1
, R
2
, R
3
and R
4
independently of one another each denote optionally halogenated C
1
- to C
8
-alkyl, or C
5
- to C
6
-cycloalkyl, C
6
- to C
20
-aryl or C
7
- to C
12
-aralkyl, in each case optionally substituted by alkyl, preferably C
1
-C
4
-alkyl, and/or halogen, preferably chlorine or bromine,
n independently of one another denote 0 or 1
N denotes 0 to 30 and
X denotes a mono or polynuclear aromatic radical having 6 to 30 C atoms,
E. 0.05 to 5 parts by wt., preferably 0.1 to 1 part by wt., particularly preferably 0.1 to 0.5 part by wt. fluorinated polyolefin.
Component A
Aromatic polycarbonates and/or aromatic polyester-carbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, and DE-OS 3 832 396; for the preparation of aromatic polyester-carbonates e.g. DE-OS 3 077 934).
Aromatic polycarbonates are prepared e.g. by reaction of diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase boundary process, optionally using chain stoppers, for example monophenols, and optionally using branching agents which are trifunctional or more than trifunctional, for example triphenols or tetraphenols.
Diphenols for the preparation of the aromatic polycarbonates and/or aromatic polyester-carbonates are preferably those of the formula (II)
wherein
A is a single bond, C
1
-C
5
-alkylene, C
2
-C
5
-alkylidene, C
5
-C
6
-cycloalkylidene, —O—, —SO—, —CO—, —S—, SO
2
— or C
6
-C
12
-arylene, to which further aromatic rings optionally containing heteroatoms can be fused,
or a radical of the formula (III) or (IV)
B in each case is hydrogen, C
1
-C
12
-alkyl, preferably methyl, or halogen, preferably chlorine and/or bromine,
x in each case independently of one another is 0, 1 or 2,
p is 1 or 0 and
R
5
and R
6
can be chosen individually for each X
1
and independently of one another denote hydrogen or C
1
-C
6
-alkyl, preferably hydrogen, methyl or ethyl,
X
1
denotes carbon and
m denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X
1
, R
5
and R
6
are simultaneously alkyl.
Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C
1
-C
5
-alkanes, bis-(hydroxyphenyl)-C
5
-C
6
-cycloalkanes, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones and &agr;,&agr;-bis-(hydroxyphenyl)-diisopropyl-benzenes and derivatives thereof brominated on the nucleus and/or chlorinated on the nucleus.
Particularly preferred diphenols are 4,4′-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfone and di- and tetrabrominated or -chlorinated derivatives thereof, such as, for example, 2,2-bis(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularly preferred.
The diphenols can be employed individually or as any desired mixtures.
The diphenols are known from the literature or obtainable by processes known from the literature.
Examples of chain stoppers which are suitable for the preparation of the thermoplastic, aromatic polycarbonates are phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, and also long-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)-phenol according to DE-OS 2 842 005, or monoalkylphenols or dialkylphenols having a total of 8 to 20 C atoms in the alkyl substituents, such as 3,5-di-tert-butyl-phenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2

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