Flame-resistant polycarbonate ABS moulding materials

Details Flame-resistant polycarbonate ABS moulding materials Flame-resistant polycarbonate ABS moulding materials

2000-12-21

2003-09-02

Szekely, Peter (Department: 1714)

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

Synthetic resins

Processes of preparing a desired or intentional composition...

C524S117000, C524S119000, C524S127000, C524S140000, C524S145000

Reexamination Certificate

active

06613822

ABSTRACT:

The present invention relates to polycarbonate/ABS moulding compositions with incorporated phosphazenes and phosphorus compounds, which compositions exhibit excellent flameproofing and very good mechanical properties such as weld line strength or notched impact strength.
DE-A 196 16 968 describes polymerisable phosphazene derivatives, a process for the production thereof and the use thereof as curable binders for lacquers, coatings, fillers, surfacing compositions, adhesives, mouldings or films.
WO 97/400 92 describes flameproofed moulding compositions prepared from thermoplastic polymers and unsubstituted phosphazenes (of the type PN
n−x
H
1−y
).
EP-A 728 811 describes a thermoplastic blend consisting of aromatic polycarbonate, graft copolymer, copolymer and phosphazenes which exhibits good flameproofing properties, impact strength and heat resistance.
Neither WO 97400 92 nor EP-A 728 811 describe a combination of phosphazenes and phosphorus compounds.
The object of the present invention is to provide polycarbonate/ABS moulding compositions having excellent flame resistance and weld line strength, excellent mechanical properties such as notched impact strength and stress cracking resistance. This range of properties is required in particular for applications in data processing, such as for example casings for monitors, printers, copiers etc.
It has now been found that PC/ABS moulding compositions which contain phosphazenes in combination with phosphorus compounds and/or salts of phosphate compounds exhibit the desired properties.
The present invention accordingly provides thermoplastic moulding compositions containing
A) 40 to 99, preferably 60 to 98.5 parts by freight of aromatic polycarbonate and/or polyester carbonate
B) 0.5 to 60, preferably 1 to 40, in particular 2 to 25 parts by weight of graft polymer of
B.1) 5 to 95, preferably 30 to 80 wt. % of one or more vinyl monomers on
B.2) 95 to 5, preferably 20 to 70 wt. % of one or more grafting backbones having a glass transition temperature of <10° C., preferably of <0° C., particularly preferably of <−20° C.,
C) 0 to 45, preferably 0 to 30, particularly preferably 2 to 25 parts by weight of at least one thermoplastic polymer selected from the group composing vinyl (co)polymers and polyalkylene terephthalates.
D) 0.1 to 50, preferably 2 to 35, in particular 5 to 25 parts by weight of at least one component selected from the group comprising phosphazenes of the formulae
in which
R is in each case identical or different and denotes amino. C
1
to C
9
alkyl, in each case optionally halogenated, preferably halogenated with fluorine, or C
1
to C
4
alkoxy, C
5
to C
6
cycloalkyl, C
6
to C
20
aryl, preferably phenyl or naphthyl, C
6
to C
20
aryloxy, preferably phenoxy, naphthyloxy, or C
7
to C
12
aralkyl, preferably phenyl-C
1
-C
4
-alkyl, in each case optionally substituted by alkyl, preferably C
1
-C
4
-alkyl, and/or halogen, preferably chlorine and,or bromine
k denotes 0 or a number from 1 to 15, preferably a number from 1 to 10,
E) 0.5 to 20 parts by weight, preferably 1 to 18 parts by weight, particularly preferably 2 to 15 parts by weight selected from at least one phosphorus compound of the general formulae (IIa), (IIb), (IIc) and (IId),
in which
R
1
, R
2
, R
3
and R
4
mutually independently denote C
1
to C
8
alkyl, in each case optionally halogenated, 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, bromine,
n mutually independently mean 0 or 1
N means 0 to 30 and
X means a mono- or polycyclic aromatic residue having 6 to 30 C atoms.
in which
R
5
and R
6
mutually independently mean optionally halogenated C
1
-C
24
alkyl, C
5
-C
6
cycloalkyl, C
6
-C
20
aryl or C
7
-C
12
aralkyl, in each case optionally substituted by halogen and, or C
1
-C
10
alkyl, or
R
5
and R
6
in the case of the formula (IId) form an alkylene chain, preferably having up to 6, in particular 2 or 3 carbon atoms,
Me denotes a metal selected from main groups 1 to 3 and subgroups VIII, 1B and 2B of the periodic system,
and q is determined by the valency of the metal ion,
F 0.05 to 5, preferably 0.1 to 1, particularly preferably 0.1 to 0.5 parts by weight of fluorinated polyolefin.
Component A
Component A aromatic polycarbonates and/or aromatic polyester carbonates which are suitable according to the invention are known from the literature or may be produced using processes known from the literature (c.f. in relation to the production of aromatic polycarbonates, for example Schnell,
Chemistry, & 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, DE-OS 3 832 396; in relation to the production of aromatic polyester carbonates for example DE-OS 3 077 934).
Aromatic polycarbonates are produced for example by reacting diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators, for example monophenols, and optionally using trifunctional or greater than trifunctional branching agents for example triphenols or tetraphenols.
Diphenols for the production of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of the formula (III)
wherein
A means a single bond, C
1
-C
5
alkylene, C
2
-C
5
alkylidene, C
5
-C
6
cycloalkylidene, —O—, —SO—, —CO—, —S—, —SO
2
—, C
6
-C
12
arylene, onto which further aromatic rings optionally containing heteroatoms may be fused.
or a residue of the formula (IV) or (V)
B in each case means C
1
-C
12
alkyl, preferably methyl, halogen, preferably chlorine and/or bromine
x in each case mutually independently mean 0, 1 or 2,
p means 1 or 0 and
R
7
and R
8
mutually independently, individually selectably for each X
1
, mean hydrogen or C
1
-C
6
alkyl, preferably hydrogen, methyl or ethyl,
X
1
means carbon and
m means an integer from 4 to 7, preferably 4 or 5, providing that R
7
and R
8
are simultaneously alkyl on at least one atom X
1
.
Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxy-phenyl)-C
1
-C
5
-alkanes, bis-(hydroxyphenyl)-C
5
-C
6
-cycloalkanes, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones, bis-(hydroxy-phenyl) sulfones and &agr;,&agr;-bis-(hydroxyphenyl)diisopropylbenzenes together with the ring-brominated and/or ring-chlorinated derivatives thereof.
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 together with the 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-hydroxy-phenyl)propane.
2,2-Bis-(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred.
The diphenols may be used individually or as any desired mixtures.
The diphenols are known from the literature or are obtainable using processes known from the literature.
Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert.-butylphenol or 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)-phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkyiphenols having a total of 8 to 20 C atoms in the alkyl substituents, such as 3,5-di-tert.-butylphenol. p-iso-octylphenol, p-tert.-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)phenol. The quantity of chain terminators to be used is generally between 0.5 mol % and 10 mol %, relative to sum of moles of the diphenols used in each

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