Flame-resistant polycarbonate ABS moulding materials

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

2002-02-27

2004-06-29

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...

C524S119000, C524S120000, C524S124000, C524S127000

Reexamination Certificate

active

06756433

ABSTRACT:

The present invention relates to polycarbonate-ABS blends provided with phosphonate amines and phosphorus compounds, which blends exhibit excellent flame protection and very good mechanical properties, such as joint line strength or modulus of elasticity, and a good crude shade.
U.S. Pat. No. 4,073,767 and 5,844,028 describe cyclic phosphorus compounds including phoshorinane rings as suitable flameproofing agents for polyurethanes, polycarbonates, polyesters and polyamides. In U.S. Pat. No. 4,397,750, particular cyclic phosphonate esters are described as efficient flameproofing agents for polypropylene and other polyolefins. U.S. Pat. No. 5,276,066 and U.S. Pat. No. 5,844,028 describe particular (1,3,2-dioxaphosphorinanemethane)-amines which are suitable flameproofing agents for polyurethanes, polyesters, styrene polymers, PVC, PVAc or polycarbonate.
U.S. Pat. No. 3,505,431, French-Patent 1 371 139, U.S. Pat. Nos. 3,711,577, 4,054,544 describe acyclic trisphosphonate amines, some of which are halogenated.
EP-A0 640 655 describes moulding compositions of aromatic polycarbonate, styrene-containing copolymers and graft polymers, which moulding compositions can be rendered flame-resistant with monomeric and/or oligomeric phosphorus compounds.
In EP-A 0 363 608, flame-resistant polymer mixtures of aromatic polycarbonate, styrene-containing copolymer or graft copolymer and oligomeric phosphates are described as flameproofing additives. For some applications, such as, for example, mouldings inside casing parts, the dimensional stability of those mixtures under heat is often inadequate.
In U.S. Pat. No. 5,061,745, polymer mixtures of aromatic polycarbonate, ABS graft polymer and/or styrene containing copolymer and monophosphates are described as flameproofing additives. The level of resistance of those mixtures to stress cracking is often inadequate for the production of thin-walled casing parts.
A combination of phosphonate amines and phosphorus compounds is not described either in WO 9740092 or in EP-A 728 811.
The object of the present invention is to provide polycarbonate moulding compositions having improved flame resistance as a result of improved after-burning times and excellent mechanical properties, such as joint line strength, modulus of elasticity, as well as good processability and a good crude shade. That spectrum of properties is required especially in the case of applications in the field of data technology, such as, for example, for casings for monitors, printers, copiers, etc.
It has now been found that compositions containing polycarbonate and phosphonate amines in combination with phosphorus compounds and/or salts of phosphate compounds and, optionally, other blend partners exhibit the desired properties.
Accordingly, the invention provides compositions containing polycarbonate, at least one phosphonate amine of formula (I)
A
3−y
—N—B
y
  (I),
in which
A represents a radical of formula (IIa)
R
1
and R
2
are each independently of the other unsubstituted or substituted C
1
-C
10
-alkyl or unsubstituted or substituted C
6
-C
10
aryl,
R
3
and R
4
are each independently of the other unsubstituted or substituted C
1
-C
10
-alkyl or unsubstituted or substituted C
6
-C
10
-aryl, or
R
3
and R
4
together represent unsubstituted or substituted C
3
-C
10
-alkylene,
y represents the numerical values 0, 1 or 2, and
the substituents B are each independently hydrogen, optionally halogenated C
2
-C
8
-alkyl, unsubstituted or substituted C
6
C
10
-aryl,
and at least one phosphorus compound of formulae (IIa), (IIb), (IIc) and (IId)
wherein
R
1
, R
2
, R
3
and R
4
are each independently of the others 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 each optionally substituted by alkyl, preferably C
1
-C
4
-alkyl, and/or by halogen, preferably chlorine, bromine,
the substituents n are each independently of the others 0 or 1,
k represents from 0 to 30, and
X represents a mono- or poly-nuclear aromatic radical having from 6 to 30 carbon atoms,
wherein
R
1
and R
6
are each independently of the other optionally halogenated C
1
-C
24
-alkyl, or C
5
-C
6
-cycloalkyl, C
6
-C
20
-aryl or C
7
-C
12
-allyl each optionally substituted by halogen and/or by C
1
-C
10
-alkyl,
or
R
5
and R
6
in the case of formula (IId) form an alkyl chain, preferably having up to 6, especially 2 or 3, carbon atoms,
Me represents a metal selected from main group 1 to 3 and subsidiary groups VIII, 1B and 2B of the periodic system,
and q is determined by the valency of the metal ion,
and, optionally, impact strength modifiers.
The composition according to the invention contains preferably from 0.1 to 30 parts by weight, especially from 1 to 25 parts by weight, very especially from 2 to 20 parts by weight, of phosphonate amine and preferably from 0.5 to 20 parts by weight, especially from 1 to 18 parts by weight, more especially from 2 to 15 parts by weight, of phosphorus compound, the indicated amounts being based on the total mixture.
The compositions preferably contain graft polymer and, optionally, vinyl (co)polymer and/or polyalkylene terephthalate as the impact strength modifier.
The invention preferably provides blends containing
A) from 40 to 99 parts by weight, preferably from 60 to 98.5 parts by weight, of aromatic polycarbonate and/or polyester carbonate,
B) from 0.5 to 60 parts by weight, preferably from 1 to 40 parts by weight, especially from 2 to 25 parts by weight, of graft polymer of
B.1) from 5 to 95 wt. %, preferably from 30 to 80 wt. %, of one or more vinyl monomers on
B.2) from 95 to 5 wt %, preferably from 20 to 70 wt. %, of one or more graft bases having a glass transition temperature <10° C., preferably <0° C., especially <−20° C.,
C) from 0 to 45 parts by weight, preferably from 0 to 30 parts by weight, especially from 2 to 25 parts by weight, of at least one thermoplastic polymer selected from the group of the vinyl (co)polymers and polyalkylene terephthalates,
D) from 0.1 to 30 parts by weight, preferably from 1 to 25 parts by weight, especially from 2 to 20 parts by weight, of phosphonate amine of formula (I) described above,
E) from 0.5 to 20 parts by weight, preferably from 1 to 18 parts by weight, especially from 2 to 15 parts by weight, selected from at least one phosphorus compound of formulae (IIa), (IIb), (IIc) and (IId) described above,
F) from 0 to 5 parts by weight, preferably from 0.1 to 3 parts by weight, especially from 0.1 to 1 part by weight, more especially from 0.1 to 0.5 part by weight, of fluorinated polyolefin,
the sum of the parts by weight of the components being 100.
Component
Aromatic polycarbonates and/or aromatic polyester carbonates which are suitable according to the invention as component A are known in the literature or can be prepared by processes which are known in 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, DE-OS 3 832 396; for the preparation of aromatic polyester carbonates see, for example, DE-OS 3 077 934).
The preparation of aromatic polycarbonates is carried out, 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 boundary process, optionally using chain terminators, for example monophenols, and optionally using branching agents having a functionality of three or more, for example triphenols or tetraphenols.
Diphenols for the preparation of aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of formula (III)
wherein
A represents 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, to which there may be condensed other aromatic rings optionally containing hetero atoms.
or a radical of formu

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