|Title of Invention||
"COLORED COMPOSITIONS BASED ON POLYALKYLENE TEREPTHALATE / POLYCARBONATE BLENDS"
|Abstract||The present invention relates to the composition, wherein the composition is characterized by its color homogeneity consisting of components selected from A,B,C,D,E and F, as herein described in the specification.|
|Full Text|| The present invention relates to a colored compositions based on polyalkylene terepthalate/polycarbonate blends
The present invention relates to coloured compositions based on polyalkylene terephthalate/polycarbonate blends modified with impact resistance, and moulding compositions, semi-finished products and moulded parts manufactured from them, which are used either un-lacquered or coated only with a transparent clear lacquer for example for external automotive applications.
Moulding compositions modified with impact resistance, which contain partially crystalline polyesters, amorphous polycarbonates and graft copolymers are known. Such moulding compositions are used for example in the automotive sector for moulded parts such as bumpers, mudguards, radiator grilles, panels, rear panels, sills, spoilers, door handles, tank covers, coatings, horizontal components such as bonnets or roof elements, door modules or similar. The preconditions for use in automotive applications are high resistance to thermoforming, high flowability in the melt, good lacquer adhesion, high resistance to chemicals, high rigidity, high dimensional stability and high low-temperature toughness.
Moulded parts of polyalkylene terephthalate/polycarbonate blends modified with impact resistance are normally lacquered with a colouring lacquer, known as the base lacquer. Before the base lacquer, the moulded parts can optionally also be coated with primer and/or filler. A transparent clear lacquer can also optionally be applied to the base lacquer. These systems are referred to below as top coat lacquered systems. In the top coat lacquered system, the natural colour of the moulding composition itself is immaterial as it is coloured by the base lacquer.
As an alternative to top coat lacquer systems, there are systems that are referred to below as penetration-dyed systems. In penetration-dyed systems, the colour of the moulded part in the application is determined by the natural colour of the moulded part itself, which means that penetration-dyed systems are not lacquered with a primer, filler or colouring base lacquer. However, the penetration-dyed systems may
optionally be coated with a transparent clear lacquer. The advantage of penetration-dyed systems lies in the cost savings, as the work processes of priming with primer and/or fillers and the lacquering with a colouring base lacquer and the associated drying are not required.
In penetration-dyed systems, however, there is no covering base lacquer to provide a UV blocking function. At best, a UV clear lacquer can block the majority of the damaging UV radiation from penetration-dyed systems. Moulding compositions that are based on penetration-dyed systems must nevertheless have high UV stability, which means that impact resistance modifiers based on rubbers containing conjugated dienes, such as for example butadiene in ABS- or MBS rubbers, cannot be used.
Weather-resistant PC/polyester blends therefore use, for example, acrylate rubbers, as disclosed in DE-A1 3302124.
EP-Bl 0 787 769 discloses the use of PC/polyester blends containing a combination of AES and acrylate rubbers to obtain moulding compositions with improved weather-resistance and good toughness.
However in penetration-dyed systems, in addition to weather-resistance, the ability to be homogeneously coloured is of very great importance. It is precisely when using PC/polyester blends modified with impact resistance containing acrylate impact resistance modifiers for injection moulded parts, that undesirable inhomogeneity of colour occurs, in which regularly-recurring less-deeply-coloured areas, which appear optically lighter, together with more-deeply-coloured areas, which appear optically darker or more intensely-coloured, are formed vertically to the direction of flow during the injection moulding process. These are known as tiger stripes. For moulded parts that are visible to the user in their final application such as for example the external bodywork of a motor vehicle - such as e.g. mudguards, bumpers, tailgate, panel, spoiler, air intake grille, bonnet, car roof -,
motor vehicle interior, casing for electrical equipment, casing for electronic
equipment, these tiger stripe effects are unacceptable.
The object was to develop homogeneously-coloured polyalkylene terephthalate/
polycarbonate moulding compositions modified with impact resistance for
applications in so-called penetration-dyed systems. Penetration-dyed systems place
increased demands on homogeneous colouring of the moulding compositions or
moulded parts, as the colouring of the moulding composition is at the same time for
the appearance of the colour of the finished moulded part in the application.
Practical experience shows, that materials used for automotive applications may
have large variations in the listed properties, depending on the actual area of use.
However, the ability to be coloured homogeneously is the decisive factor for
applications in penetration-dyed systems. This ability to be coloured homogeneously
is a key criterion for the use of the material in penetration-dyed systems, in addition
to the material properties already mentioned, such as for example the stiffness of the
material, resistance to thermoforming and low-temperature impact resistance.
Surprisingly, it was found that coloured polyalkylene terephthalate/polycarbonate
blends modified with impact resistance by means of impact resistance modifiers
based on graft copolymer compositions based on acrylonitrile/ethylene propylene
rubbers/styrene (AES) can be produced, that result in moulded parts with very
homogeneous colouring. The moulding compositions according to the invention are
also characterised by high resistance to thermoforming, high flowability in the melt,
good lacquer adhesion, high resistance to chemicals, high rigidity, high dimensional
stability and high low-temperature toughness. As AES rubbers contain no doublebond
groups, they are also UV-stable.
The invention provides compositions containing
A) 40 to 80, preferably 10 to 60, particularly preferably 12 to 40, in particular
19 to 29 wt.% of at least one polyalkylene terephthalate, preferably a
polyethylene terephthalate or a polybutylene terephthalate, particularly
preferably a polyethylene terephthalate,
B) 10 to 90, preferably 20 to 80, particularly preferably 25 to 55, in particular
30 to 50 wt.% of at least one aromatic polycarbonate,
C) 1.5 to 30, preferably 3 to 25, particularly preferably 6 to 20, in particular 8 to
17 wt.% of at least one AES graft polymer,
D) 0 to 54, preferably 3 to 34, particularly preferably 6 to 25, in particular 8 to
21 wt.% of at least one mineral filler in particle form,
E) 0.01 to 10 wt.%, preferably 0.05 to 6 wt.% particularly preferably 0.1 to
3 wt.% of conventional colouring agents,
F) 0 to 10 wt.%, preferably 0.05 to 3 wt.% particularly preferably 0.1 to
0.9 wt.% of other conventional additives.
According to the invention, the compositions contain as component A one or a
mixture of two or more different polyalkylene terephthalates. Polyalkylene
terephthalates according to the invention are polyalkylene terephthalates, which are
derived from terephthalic acid (or its reactive derivatives) and alkane diols, for
example based on ethylene glycol, propylene glycol or butane diol. According to the
invention, preferably polybutylene terephthalate, polytrimethylene terephthalate
and/or polyethylene terephthalate, particularly preferably polybutylene terephthalate
and/or polyethylene terephthalate, most preferably polyethylene terephthalate are
used as component A.
Polyalkylene terephthalates according to the invention are reaction products of
aromatic dicarboxylic acid or its reactive derivatives (e.g. dimethyl esters or
anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these
Preferred polyalkylene terephthalates can be produced from terephthalic acid (or its
reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to I O C atoms by
known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Karl-Hanser-Verlag,
Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol.%, in
relation to the dicarboxylic acid, of terephthalic acid groups and at least 80,
preferably at least 90 mol.%, in relation to the diol component, of ethylene glycoland/
or propane diol-1,3- and/or butane diol-1,4 groups.
The preferred polyalkylene terephthalates may contain, in addition to terephthalic
acid groups, up to 20 mol.% of groups of other aromatic dicarboxylic acids having 8
to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, such as groups
of phthalic acid, isophthalic acid, naphthaline-2,6-dicarboxylic acid, 4,4'-diphenyl
dicarboxylic acid, succinic-, adipic-, sebacic acid, azelaic acid, cyclohexane diacetic
acid, cyclohexane dicarboxylic acid.
The preferred polyalkylene terephthalates may contain, in addition to ethylene- or
propane diol-1,3- or butane diol-l,4-glycol groups, up to 20 mol.% of other aliphatic
diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms, e.g.
groups of propane diol-1,3, 2-ethyl propane diol-1,3, neopentyl glycol, pentane diol-
1,5, hexane diol-1,6, cyclohexane-dimethanol-1,4, 3-methyl pentane diol-2,4 2-
methyl pentane diol-2,4, 2,2,4-trimethyl pentane diol-1,3, and -1,6,2-ethyl hexane
diol-1,3, 2,2-diethyl propane diol-1,3, hexane diol-2,5, 1,4-di-((8-hydroxy-ethoxy)-
benzene, 2,2-bis-(4-hydroxy-cyclohexyl)-propane, 2,4-dihydroxy-l,l,3,3-
tetramethyl cyclobutane, 2,2-bis-(3-(8-hydroxy-ethoxy-phenyl)-propane and 2,2-bis-
(4-hydroxy-propoxy-phenyl)-propane (DE-A 24 07 674, 24 07 776, 27 15 932).
The polyalkylene terephthalates may be branched by incorporating relatively small
quantities of 3- or 4-valent alcohols or 3- or 4-basic carboxylic acids, as disclosed
e.g. in DE-A 19 00 270 and US-A 3 692 744. Examples of preferred branching
agents are trimesic acid, trimellitic acid, trimethylol ethane and -propane and
It is advisable to use no more than 1 mol.% of the branching agent in relation to the
Polyalkylene terephthalates, which have been produced solely from terephthalic acid
and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and/or
propane diol-1,3 and/or butane diol-1,4 (polyethylene- and polybutylene
terephthalate) and mixtures of these polyalkylene terephthalates, are preferred in
Preferred polyalkylene terephthalates are also copolyesters, which are produced
from at least two of the above-mentioned acid components and/or from at least two
of the above-mentioned alcohol components, particularly preferred copolyesters are
poly-(ethylene glycol/butane diol-l,4)-terephthalates.
The polyalkylene terephthalates generally have an intrinsic viscosity of ca 0.4 to 1.5,
preferably 0.5 to 1.3, measured in each case in phenol/o-dichloro benzene
The polyesters manufactured according to the invention are preferably also used in
mixture with other polyesters and/or other polymers. Mixtures of polyalkylene
terephthalates with other polyesters are particularly preferred, mixtures of
polybutylene terephthalate with polyethylene terephthalate are most particularly
Conventional additives such as e.g. mould-release agents, stabilisers, and/or flowing
agents can be admixed in the melt or applied to the surface.
According to the invention, the compositions according to the invention contain as
component B a polycarbonate or a mixture of polycarbonates.
Preferred polycarbonates are those homopolycarbonates and copolycarbonates based
on bisphenols of the general formula (I),
in which Z is a divalent organic group having 6 to 30 C atoms, which contains one
or more aromatic groups.
Bisphenols of formula (la) are preferred
means a single bond, Ci-C5-alkylene, C2-C5-alkylidene, C5-C6-
cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, Ce-Cia-arylene, on to which
other aromatic rings optionally containing heteroatoms may be condensed,
or a group of formula (II) or (III)
B is in each case Ci-Cu-alkyl, preferably methyl, halogen, preferably, chlorine
x is in each case, independently of the other, 0, 1 or 2,
p is 1 or 0, and
R1 and R2 may be selected individually for each X1, independently of each other, as
hydrogen or Ci-Ce-alkyl, preferably hydrogen, methyl or ethyl,
X1 means carbon and
m means an integer from 4 to 7, preferably 4 or 5, with the proviso that, on at
lest one atom X1, R1 and R2 are simultaneously alkyl.
Examples of bisphenols according to the general formula (I) are bisphenols, which
belong to the following groups: dihydroxy diphenyls, bis-(hydroxyphenyl)-alkanes,
bis-(hydroxyphenyl)-cycloalkanes, indane bisphenols, bis-(hydroxyphenyl)-sulfides,
bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-
sulfones, bis-(hydroxyphenyl)-sulfoxides and a,a'-bis-(hydroxyphenyl)-diisopropyl
Derivatives of the stated bisphenols, which are accessible for example by alkylation
or halogenation on the aromatic rings of the stated bisphenols, are examples of
bisphenols according to the general formula (I).
Examples of bisphenols according to the general formula (I) are, in particular, the
following compounds: hydroquinone, resorcinol, 4,4'-dihydroxy diphenyl, bis-(4
hydroxyphenyl)sulfide, bis-(4-hydroxyphenyl)sulfone, bis-(3,5-dimethyl-4-hydroxyphenyl)-
methane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 1,1 -bis-(3,5-
dimethyl-4-hydroxyphenyl)-p/m-diisopropyl benzene, l,l-bis-(4-hydroxyphenyl)-lphenyl-
ethane, 1 ,l-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, l,l-bis-(4-
hydroxyphenyi)-3-methyl cyclohexane, l,l-bis-(4-hydroxyphenyl)-3,3-dimethyl
cyclohexane, 1,1-bis-(4-hydroxyphenyl)-4-methyl cyclohexane, l,l-bis-(4-
cyclohexane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3-methyl-4-
hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-bis-
(4-hydroxyphenyl)-propane (i.e. bisphenol A), 2,2-bis-(3-chloro-4-hydroxyphenyl)-
propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 2,4-bis-(4-
hydroxyphenyl)-2-methyl butane, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methyl
butane, o,a'~bis-(4-hydroxyphenyl)-o-diisopropyl benzene, o,a'-bis-(4-
hydroxyphenyl)-m-diisopropyl benzene (i.e. bisphenol M), a,a'-bis-(4-
hydroxyphenyl)-p-diisopropyl benzene and indane bisphenol.
Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol
A, the homopolycarbonate based on l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethyl
cyclohexane and the copolycarbonate based on the two monomers bisphenol A and
The bisphenols disclosed according to the general formula (I) can be produced by
known processes, e.g. from the corresponding phenols and ketones.
The stated bisphenols and processes for producing them are disclosed for example in
the monograph H. Schnell "Chemistry and Physics of Polycarbonates", Polymer
Reviews, Volume 9, p. 77-98, Interscience Publishers, New York, London, Sydney,
1964 and in US-A 3 028 635, in US-A 3 062 781, in US-A 2 999 835, in US-A 3
148 172, in US-A 2 991 273, in US-A 3 271 367, in US-A 4 982 014, in US-A 2 999
846, in DE-A 1 570 703, in DE-A 2 063 050, in DE-A 2 036 052, in DE-A 2 211
956, in DE-A 3 832 396, and in FR-A 1 561 518 as well as in the Japanese laid open
specifications with the application numbers JP-A 62039 1986, JP-A 62040 1986 and
JP-A 105550 1986.
l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethyl cyclohexane and its production are
disclosed e.g. in US-A 4 982 014.
Indane bisphenols and their production are disclosed for example in US-A 3 288
864, in JP-A 60 035 150 and in US-A 4 334 106. Indane bisphenols may be
produced, for example, from isopropenyl phenol or its derivatives or from dimers of
isopropenyl phenol or its derivatives in the presence of a Friedel-Craft-Catalyst in
Polycarbonates can also be produced by known processes. Suitable processes for the
production of polycarbonates are, for example, production from bisphenols with
phosgene by the phase interface process or from bisphenols with phosgene by the
homogeneous phase process, the so-called pyridine process, or from bisphenols with
carbonic acid esters by the melt transesterification process. These production
processes are disclosed e.g. in H. Schnell, "Chemistry and Physics of
Polycarbonates", Polymer Reviews, Volume 9, p. 31-76, Interscience Publishers,
New York, London, Sydney, 1964. The stated production processes are also
disclosed in D. Freitag, U. Grigo, P. R. Miiller, H. Nouvertne "Polycarbonates" in
Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition,
1988, pages 648 to 718 and in U. Grigo, K. Kircher and P.R. Mttller
"Polycarbonate" in Becker, Braun, Kunststoff-Handbuch, Volume 3/1,
Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich,
Vienna 1992, pages 117 to 299 and in D. C. Prevorsek, B. T. Debona and Y. Kesten,
Corporate Research Center, Allied Chemical Corporation, Morristown, New Jersey
07960, "Synthesis of Poly(ester carbonate) Copolymers" in Journal of Polymer
Science, Polymer Chemistry Edition, Vol. 9, 75-90 (1980).
The melt transesterification process is disclosed in particular in H. Schnell
"Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, p. 44 to
51, Interscience Publishers, New York, London, Sydney, 1964 and also in DE-A 1
031 512, in US-A 3 022 272, in US-A 5 340 905 and in US-A 5 399 659.
When producing polycarbonate, raw materials and auxiliary substances with a low
level of impurities are preferably used. In particular for production by the melt
transesterification process, the bisphenols used and the carbonic acid derivatives
used should be as free as possible from alkali ions and earth alkali ions. Such pure
raw materials can be obtained, for example, by re-crystallising, washing or distilling
the carbonic acid derivatives, for example carbonic acid esters, and the bisphenols.
The polycarbonates suitable according to the invention preferably have a weight
average of the molar masses (Mw), which can be determined e.g. by
ultracentrifugation or light scattering measurement, of 10 000 to 200 000 g/mol.
Particularly preferably, they have a weight average of the molar masses of 12 000 to
80 000 g/mol, in particular of 20 000 to 35 000 g/mol.
The average molar mass of the polycarbonates according to the invention can be set,
for example, in the known way by a corresponding quantity of chain stoppers. The
chain stoppers can be used individually, or as a mixture of different chain stoppers.
Suitable chain stoppers are both monophenols and monocarboxylic acids. Suitable
monophenols are e.g. phenol, p-chlorophenol, p-tert.-butyl phenol, cumyl phenol or
2,4,6-tribromophenol, and also long-chain alkyl phenols, such as e.g. 4-(l,l,3,3-
tetramethylbutyl)-phenol or monoalkyl phenols or dialkyl phenols having a total of 8
to 20 C atoms in the alkyl substituents such as e.g. 3,5-di-tert.-butyl phenol, p-tertoctyl
phenol, p-dodecyl phenol, 2-(3,5-diemthyl-heptyl)-phenol or 4-(3,5-dimethylheptyl)-
phenol. Suitable monocarboxylic acids are benzoic acids, alkyl benzoic
acids and halogen benzoic acids.
Preferred chain stoppers are phenol, p-tert.-butyl phenol, 4-(l,l,3,3-tetramethyl
butyl)-phenol and cumyl phenol.
The quantity of chain stoppers is preferably 0.25 to 10 mol.% in relation to the total
of the bisphenols used in each case.
The polycarbonates suitable according to the invention can be branched in the
known way, and preferably by incorporating trifunctional or more-than-trifunctional
branching agents. Suitable branching agents are e.g. those having three or more than
three phenolic groups or those having three or more than three carboxylic acid
Suitable branching agents are for example phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-
1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1 -tris-(4-hydroxyphenyl)-ethane, tri-(4-
hydroxyphenyl)-phenyl methane, 2,2-bis-[4,4,-bis-(4-hydroxyphenyl)-cyclohexyl]-
propane, 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol, 2,6-bis-(2-hydroxy-5 '-
methyl-benzyl)-4-methyl phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-
propane, hexa-(4-(4-hydroxyphenyl-isopropyl)-phenyl)-terephthalic acid ester, tetra-
methane and l,4-bis-(4',4"-dihydroxy triphenyl)-methyl benzene and also 2,4-
dihydroxybenzoic acid ester, trimesic acid, cyanuric chloride, 3,3-bis(-3-methyl-4-
hydroxyphenyl)-2-oxo-2,3-dihydro indol, trimesic acid trichloride and a,o:',Q!"-tris-
(4-hydroxyphenol)-l ,3,5-triisopropyl benzene.
Preferred branching agents are l,l,l-tris-(4-hydroxyphenyi)-ethane and 3,3-bis-(3-
The quantity of the branching agents optionally to be used is preferably 0.05 mol%
to 2 mol% in relation to mols of bisphenols used.
When producing the polycarbonate by the phase interface process for example, the
branching agents can be provided with the bisphenols and the chain stoppers in the
aqueous alkaline phase, or they may be added dissolved in an organic solvent
together with the carbonic acid derivatives. When using the transesterification
process, the branching agents are preferably dosed in together with the dihydroxy
aromatics or bisphenols.
Preferred catalysts to be used for the production of polycarbonate by the melt
transesterification process are the ammonium salts and phosphonium salts known
from the literature (see for example US-A 3 442 864, JP-A-14742/72, US-A 5 399
Copolycarbonates may also be used. Copolycarbonates according to the invention
are, in particular, polydiorganosiloxane-polycarbonate block copolymers of which
the weight average of the molar masses M w is preferably 10 000 to 200 000 g/mol,
in particular 20 000 to 80 000 g/mol (determined by gel chromatography after prior
calibration by light scattering measurement or ultracentrifugation). The content of
aromatic carbonate structural elements in the polydiorganosiloxane-polycarbonate
block copolymers is preferably 75 to 97.5 wt.%, in particular 85 to 97 wt.%. The
content of polydiorganosiloxane structural elements in the polydiorganosiloxanepolycarbonate
block copolymers is preferably 25 to 2.5 wt.%, in particular 15 to
3 wt.%. The polydiorganosiloxane -polycarbonate block copolymers may be
produced, for example, on the basis of o,w-bishydroxy aryloxy terminal groupcontaining
polydiorganosiloxanes with an average degree of polymerisation of
preferably Pn = 5 to 100, in particular Pn = 20 to 80.
The polydiorganosiloxane-polycarbonate block copolymers may also be a mixture
of polydiorganosiloxane-polycarbonate block copolymers with conventional
polysiloxane-free, thermoplastic polycarbonates, the total content of
polydiorganosiloxane structural elements in this mixture being preferably 2.5 to
Such polydiorganosiloxane-polycarbonate block copolymers are characterised in
that they contain in the polymer chain on the one hand aromatic carbonate structural
elements (I) and on the other hand aryloxy terminal group-containing
Ar are the same or different difunctional aromatic groups and
R and R1 are the same or different and mean linear alkyl, branched alkyl, alkenyl,
halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated
aryl, preferably methyl, and
n means the average degree of polymerisation of preferably 5 to 100, in
particular 20 to 80.
Alkyl in the above formula (2) is preferably Ci-C2o-alkyl, alkenyl in the above
formula (2) is preferably C2-C6-alkenyl; aryl in the above formula (2) is preferably
Ce-Cu-aryl. Halogenated in the above formula means partially or fully chlorinated,
brominated or fluorinated.
Examples of alkyls, alkenyls, aryls, halogenated alkyls and halogenated aryls are
methyl, ethyl, propyl, n-butyl, tert.-butyl, vinyl, phenyl, naphthyl, chloromethyl,
perfluorobutyl, perfluorooctyl and chlorophenyl.
Such polydiorganosiloxane-polycarbonate block copolymers and their production
are disclosed for example in US-A 3 189 662, US-A 3 821 325 and US-A 3 832 419.
Preferred polydiorganosiloxane-polycarbonate block copolymers may be produced
e.g. by reacting a,w-bishydroxy aryloxy terminal group-containing
polydiorganosiloxanes together with other bisphenols, optionally also using
branching agents in the conventional quantities, e.g. by the two phase interface
process (as disclosed for example in H. Schnell "Chemistry and Physics of
Polycarbonates", Polymer Reviews, Volume 9, p. 31-76, Interscience Publishers,
New York, London, Sydney, 1964). The o,w-bishydroxy aryloxy terminal groupcontaining
polydiorganosiloxanes used for this synthesis and their production are
disclosed for example in US-A 3 419 634.
The polycarbonates may contain conventional additives such as e.g. mould release
agents, admixed in the melt or applied to the surface. The polycarbonates used
preferably already contain mould release agents before compounding with the other
components of the moulding compositions according to the invention.
According to the invention, one or a mixture of two or more graft copolymers are
used as component C), which are obtained by copolymerisation of a mixture of
styrene and acrylonitrile on a base of an ethylene-propylene-copolymer (EPM) or an
ethylene-propylene-unconjugated diene-copolymer (EPDM), and are designated
The graft polymers used according to the invention in the compositions are those
containing EP(D)M rubbers as the grafting base. The glass transition temperature of
such rubbers can be 0 to -60°C, they have only a small number of double bonds, for
example less than 20 per 1000 carbon atoms. Copolymers or terpolymers containing
at least one ethylene and propylene and preferably having only a small number of
double bonds, for example, are used, for which see EP-A 163 411 and 244 857. (Mr
Braig, that is the core of the invention, please describe briefly in application and
provide precise quotation) The latter were produced by polymerising at least
30 wt.% ethylene, at least about 30 wt.% oolefin, such as e.g. propylene, 1-butene,
octene, hexene and optionally 0.5 to 15 wt.% of an unconjugated diolefinic
component. In general diolefins having at least five carbon atoms such as 5-
ethylidene norbornene, dicyclo pentadiene, 2,2,1-dicyclo pentadiene and 1,4-
hexadiene are used as the ter component. Polyalkylene amers such as polypentamer,
polyoctenamer, polydodecanamer or mixtures of these are also suitable. Finally,
partially hydrogenated polybutadiene rubbers in which at least 70% of the residual
double bonds are hydrogenated, are also possible. In general, EP(D)M rubbers have
a Mooney viscosity (ML1-4(100°C) of 25 to 120. They can be obtained
commercially. Furthermore, polyolefin elastomers or ethene/octene polyolefins
similar to those offered under the commercial name Engage, may be used. Vinyl
aromatics and/or core-substituted vinyl aromatics and vinyl cyanides and/or
(meth)acrylic acid-(Ci-Cg)-alkyl esters are grafted on.
Graft polymers of
Cl) 5 to 95 wt.%, preferably 10 to 80 wt.%, in particular 20 to 50 wt.%, of at
least one vinyl monomer on
C2) 95 to 5 wt.%, preferably 90 to 20, in particular 80 to 20 wt.% of one or more
grafting bases having glass transition temperatures of the rubber component
of are preferred.
The grafting base C2) generally has an average particle size (dso value) of 0.05 to
5 um, preferably 0.10 to 2 um, in particular 0.15 to 1 um.
Monomers Cl) are preferably mixtures
Cl.l) of 50 to 99, preferably 60 to 80 parts by weight vinyl aromatics and/or coresubstituted
vinyl aromatics such as styrene, a-methyl styrene, p-methyl
styrene, p-chlorostyrene and/or methacrylic acid-(C]-Cg)-alkyl ester, such as
methyl methacrylate and ethyl methacrylate and
C1.2) 1 to 50, preferably 40 to 20 parts by weight vinyl cyanides (unsaturated
nitriles such as acrylonitrile and methacrylonitrile) and/or (meth)acrylic acid
~(C|-C8)-alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl
acrylate and/or derivatives, such as anhydrides and imides of unsaturated
carboxylic acids, for example maleic acid anhydride and N-phenyl
Particularly preferred monomers Cl.l) are selected from at least one of the
monomers styrene, a-methyl styrene, methyl methacrylate, particularly preferred
monomers C2.2) are selected from at least one of the monomers acrylonitrile, maleic
acid anhydride and methyl methacrylate.
The graft polymer based on EP(D)M can be produced for example by producing a
solution of the EP(D)M elastomer in the monomer mixture and optionally inert
solutions and carrying out the grafting reaction at higher temperatures using radical
starters such as azo compounds or peroxides. The processes of DE-AS 23 02 014
and DE-A 25 33 991 are mentioned by way of example. It is possible to carry out
the process in a suspension as in US-A 4 202 948 or in mass.
AES rubbers, as disclosed in EP-A1 0 502 237 are preferred in particular. Such AES
rubbers can be obtained for example under the name Blendex WX 270 from Ube
Cycon Ltd, Tokyo, Japan or Royaltuf 374 from Uniroyal, Great Britain or AES 665
from Techno Polymers Tokyo, Japan.
The thermoplastic moulding compositions contain, as component D), a filler or
reinforcing material or a mixture of two or more different fillers and/or reinforcing
materials, for example based on talc, mica, silicate, quartz, titanium dioxide,
wollastonite, kaolin, amorphous silicas, magnesium carbonate, chalk, feldspar,
barium sulfate, glass beads and/or filling materials in fibre form and/or reinforcing
materials based on carbon fibres and/or glass fibres. Mineral fillers in particle form
based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin,
amorphous silicas, magnesium carbonate, chalk, feldspar, barium sulfate and/or
glass fibres are preferred. Mineral fillers in particle form based on talc, wollastonite
and/or glass fibres are preferred in particular according to the invention. Fillers
based on talc are most preferred.
Particularly for applications, in which isotropy in dimensional stability and high
thermal dimensional stability are required, such as for example automotive
applications for external bodywork parts, mineral fillers are preferred, in particular
talc, wollastonite or kaolin.
Acicular mineral fillers are also preferred in particular. Acicular mineral fillers
according to the invention are understood to mean mineral fillers with a highlydistinctive
acicular character. Examples are acicular wollastonites. The mineral
preferably has a length : diameter ratio of 2:1 to 35:1, particularly preferably of 3:1
to 19:1, most preferably of 4:1 to 12:1. The average particle size of the acicular
minerals according to the invention is preferably less than 20um, particularly
preferably less than 15urn, in particular less than lOum and most preferably less
than Sum measured with a CILAS GRANULOMETER.
Mineral fillers based on talc are most preferred as Component D). Mineral fillers
based on talc according to the invention include all particle-form fillers, which the
person skilled in the art connects with talc or talcum. All particle-form fillers, which
are offered commercially and which contain, in their product description as
characterising features, the terms talc or talcum may also be used.
Mineral fillers which have a talc content according to DIN 55920 greater than
50wt.%, preferably greater than 80 wt.%, particularly preferably greater than
95 wt.% and in particular greater than 98 wt.% in relation to the total quantity of
filler are preferred.
The mineral fillers based on talc can also be surface-treated. They can, for example,
be equipped with a bonding agent system e.g. based on silane.
The mineral fillers based on talc according to the invention preferably have an upper
particle- or grain size d97 of less than 50um, preferably less than 10, particularly
preferably less than 6, in particular les than 2.Sum. A value less than 10, preferably
less than 6, particularly preferably less than 2 and in particular less than 1 um is
preferably selected as the average grain size d50. The d97 and d50 values of the
fillers D are measured by SEDIGRAPH D 5 000 sedimentation analysis or by
DIN 66 165 sieve analysis.
The average aspect ratio (diameter to thickness) of the particle-form fillers based on
talc is preferably in the range of 1 to 100, particularly preferably 2 to 25 and in
particular 5 to 25, determined on electron-microscopic images of ultra-thin sections
of the finished products and measurement of a representative quantity (ca 50 of the
The filler and/or reinforcing material can optionally be surface modified, for
example with a bonding agent or bonding agent system e.g. based on silane.
However, pre-treatment is not necessarily required. Particularly when using glass
fibres, polymer dispersions, film-formers, branching agents and/or glass fibre
processing auxiliary substances can be used in addition to silanes.
Glass fibres are also preferred in particular according to the invention, which
generally have a fibre diameter of 7 to 18, preferably 9 to 15 urn, which can be
added as continuous fibres or as cut or ground glass fibres, and the fibres can be
equipped with a suitable sizing system and a bonding agent or bonding agent system
e.g. based on silane.
Common silane compounds for pre-treatment have, for example, the general formula
in which the substituents have the following meaning:
o / NH2-JIO-, H2C~S
q an integer from 2 to 10, preferably 3 to 4
r an integer from 1 to 5, preferably 1 to 2
k an integer from 1 to 3, preferably 1.
Preferred silane compounds are aminopropyl trimethoxy silane, aminobutyl
trimethoxy silane, aminopropyl triethoxy silane, aminobutyl triethoxysilane and the
corresponding si lanes, which contain a glycidyl group as substituent X.
The silane compounds are generally used in quantities of 0.05 to, preferably 0.5 to
1.5 and in particular 0.8 to 1 wt.% in relation to the mineral filler for surface coating.
The fillers in particle form may have a smaller d97 or d50 value in the moulding
composition or moulded body than the filler originally used as a result of processing
to produce the moulding composition or moulded body. The glass fibres may have
shorter length distributions in the moulding composition or moulded body than those
originally used as a result of processing to produce the moulding composition or
The particle diameter of the finished product can be determined for example by
making electron-microscopic images of thin sections of the polymer mixture and
using at least 25, preferably at least 50 filler particles for the evaluation.
According to the invention, the compositions may contain, as component E),
conventional colouring agents and/or pigments such as e.g. titanium dioxide,
ultramarine blue, iron oxide, carbon black, phthalocyanine, quinacridone, perylene,
nigrosin and anthraquinone and derivatives of these. The colouring agents and/or
pigments can be added without solvent or as master batches for example in
component A), component B), component C), polyethylene, polypropylene, waxes
The compositions according to the invention may also contain, as component F),
conventional additives, in general up to 15, which are added preferably in a quantity
of 0.01 to 10, particularly preferably 0.05 to 5, in particular 0.1 to 3 wt.% in relation
to the total weight of the moulding compositions.
All conventional additives such as e.g. stabilisers (for example UV stabilisers,
thermostabilisers), anti-statics, flow auxiliary substances, mould release agents, fireprotection
additives, emulsifiers, nucleating agents, plasticisers, mould lubricants,
pH-reducing additives (e.g. compounds containing carboxyl groups), additives to
increase conductivity, dyes and pigments may be used. These and other suitable
additives are disclosed for example in Gachter, Muller, Kunststoff-Additive, 3rd
Edition, Hanser-Verlag, Munich, Vienna, 1989. The additives can be used alone or
in mixture or in the form of masterbatches. The additives can be admixed and/or
applied to the surface.
Sterically hindered phenols and/or phosphites, hydroquinones, aromatic secondary
amines such as diphenyl amines, substituted resorcinols, salicylates, benzotriazols
and benzophenones, as well as variously-substituted representatives of these groups
and mixtures thereof, for example, can be used as stabilisers.
Sodiurn phenyl phosphinate, aluminium oxide, silicon dioxide and preferably
talcum, and the nucleating agents described earlier can be used e.g. as nucleating
Ester waxes, pentaerythritol tetrastearate (PETS), long-chain fatty acids (e.g. stearic
acid or behenic acid), their salts (e.g. Ca or Zn stearate) and amide derivatives (e.g.
ethylene-bis-stearyl amide) or montan waxes (mixtures of straight-chain, saturated
carboxylic acids with chain lengths of 28 to 32 C atoms) and also low-molecular
polyethylene- or polypropylene waxes, can be used as mould lubricants and mould
Phthalic acid dioctyl esters, phthalic acid dibenzyl esters, phthalic acid butyl benzyl
esters, hydrocarbon oils, N-(n-butyl)benzene sulfonamide, for example, can be used
To obtain conductive moulding compositions, carbon blacks, conductive carbon
blacks, carbon fibrils, nanoscale graphite fibres (nanotubes), graphite, conductive
polymers, metal fibres and other conventional additives can be added to increase
Commercial organic halogen compounds containing synergists or commercial
organic nitrogen compounds or organic/inorganic phosphorus compounds can be
used individually or in mixture as flame retardants. Mineral flame retarding
additives such as magnesium hydroxide or Ca-Mg-carbonate hydrate (e.g. DE-A 4
236 122) can also be used. The following are given as examples of halogencontaining,
in particular brominated and chlorinated, compounds: ethylene-1,2-
bistetrabromo phthalimide, epoxidated tetrabromo bisphenol A resin, tetrabromo
bisphenol A oligocarbonate, tetrachloro bisphenol A oligocarbonate, pentabromo
polyacrylate, brominated polystyrene. The phosphorus compounds according to
WO-A 98/17720 (PCT/EP/05705) are suitable as organic phosphorus compounds,
e.g. triphenyl phosphate (TPP), resorcinol-bis-(diphenyl phosphate) including
oligomers and also bisphenol A-bis-diphenyl phosphate including oligomers (cf. e.g.
EP-A 363 608 and EP-A 640 655), melamine phosphate, melamine pyrophosphate,
melamine polyphosphate and mixtures of these. Melamine and melamine cyanurate
are possible in particular as nitrogen compounds. Antimony compounds, in
particular antimony trioxide and antimony pentoxide, zinc compounds, tin
compound such as e.g. tin stannate and borate, for example, are suitable as
synergists. Carbon formers and tetrafluoroethylene polymers may be added. The
flame retardants, optionally containing a synergist, such as antimony compounds
and anti-dripping agents, are generally used up to a quantity of 30, preferably
20 wt.% (in relation to the total composition).
Reinforcing materials e.g. in the form of glass fibres can also be added as additives.
The invention also provides a process for the production of the compositions, the use
of the compositions according to the invention for the production of semi-finished
products and moulded parts and the semi-finished products and moulded parts
produced from them.
The compositions according to the invention are produced by mixing the
components using processes known per se. It may be advantageous to pre-mix
individual components. Components A to D and other components are preferably
mixed at temperatures of 220 to 330°C by kneading, extruding or rolling the
The compositions according to the invention may be processed by the conventional
processes to form semi-finished products or moulded parts of all kinds. Examples of
processing methods are extrusion and injection moulding. Examples of semifinished
products are films and sheets.
Because of their great homogeneity of colour, the moulded parts are suitable for
applications that are visible and optically significant. The moulded parts may be
used according to the invention un-lacquered or coated with a transparent clear
lacquer system. The moulded parts may be small or large and may be used for
external or internal applications. Large moulded parts are preferably produced for
vehicle construction, in particular in the automobile sector. External bodywork parts
in particular can be manufactured from the moulding compositions according to the
invention, such as e.g. mudguards, tail gates, bonnets, bumpers, loading areas,
covers for loading areas, car roofs, air intake grilles, spoilers or other bodywork
Moulded parts or semi-finished products made of the moulding compositions
according to the invention may also be found in composites with other materials
such as e.g. metal or plastic. The moulding compositions according to the invention
or the moulded parts/semi-finished products made from the moulding compositions
according to the invention can be used by means of the conventional techniques for
connecting and joining several components or parts such as e.g. coextrusion, film
back spraying, spray coating of union ends, gluing, welding, screwing or clamping
in composite structures with other materials or themselves for the production of
finished parts such as e.g. external bodywork parts.
The moulding compositions according to the invention can also be used for
numerous other applications. Examples are the use in electrics and electronics and in
the building industry. In the stated applications, moulded parts made of the
moulding compositions according to the invention can be used for example as lamp
covers, safety screens, as a case material for electronic devices, as a case material
for domestic appliances, as sheets for the production of covers.
The compositions according to the invention are characterised by very good
homogeneity of colour. In addition they fulfil the strict requirements for processing
stability, flowability of the melt, toughness, low-temperature toughness, stiffness,
resistance to thermoforming, thermal expansion, surface quality, lacquerability,
resistance to chemicals and resistance to fuels.
Polyethylene terephthalate type Al: this is polyethylene terephthalate with an
intrinsic viscosity IV of 0.74 cmVg and an isothermal crystallisation time at 215°C
of ca4.2 minutes.
The intrinsic viscosity is measured in phenol/0-dichlorobenzene (1:1 parts by
weight) at 25°C.
The isothermal crystallisation time of PET is measured by the DSC method
(differential scanning calorimetry) with a PERKIN ELMER DSC 7 Differential
Scanning Calorimeter (weighed portion ca 10 mg, perforated Al pan) with the
following temperature programme:
1. Heating up from 30°C to 290°C at 40°C/min,
2. 5 min. isothermal at 290°C
3. Cooling from 290°C to 215°C at 160°C/min,
4. 30 min isothermal at 215°C (crystallisation temperature).
The evaluation software is PE Thermal Analysis 4.00.
Linear polycarbonate (Makrolon 2805 from Bayer AG, Leverkusen, Germany)
based on bisphenol A with a viscosity Tjrel. of ca 1.29 (measuring conditions: 5 g
polycarbonate per litre methylene chloride, 25°C) and a molecular weight Mw of ca
29 000 g/mol (determined by GPC methods against polycarbonate standard).
The AES graft polymer used is Blendex WX 270 from Ube Cycon Ltd., Tokyo,
Acrylate rubber 1
The acrylate graft polymer used as a reference is Paraloid EXL 2300 from Rohm
und Haas Deutschland GmbH, Frankfurt.
Acrylate rubber 2
The acrylate graft polymer used as a reference is Paraloid EXL 3361 from Rohm
und Haas Deutschland GmbH, Frankfurt.
Acrylate rubber 3
The acrylate graft polymer used as a reference is Paraloid EXL 2314 from Rohm
und Haas Deutschland GmbH, Frankfurt.
A 50% carbon black masterbatch in polyethylene with the name RuB Plasblack PM
3798 (commercial product of Cabot) was used as a colouring agent.
A mixture of conventional stabilisers, nucleating agents and mould release agents
was used as the additive for Component F.
Compounding was carried out on a twin shaft extruder of the type ZSK32 (Werner
und Pfleiderer) at composition temperatures of 250 to 290°C.
The test bodies were injection moulded on an Arburg 320-210-500 injection
moulding machine at composition temperatures of 260 to 280°C and mould
temperatures of 70 to 90°C.
The moulding compositions according to the invention were tested according to the
Vicat B: resistance to thermoforming to DIN ISO 306/B 120 in silicon oil.
Izod impact resistance: resistance to ISO 180 method 1 U at -23°C
Izod notched impact resistance: resistance to ISO 180 method 1 A at 23°C
Tensile modulus: stiffness to DIN/EN/ISO 527-2/1 A.
Elongation at break: extensibility to DIN/EN/ISO 527-2/1 A.
MVR: flowability to DIN/ISO 1133 at 280°C and 2.16 kg.
Homogeneity of colour: Determination of the homogeneity of colour of the surface
by visual inspection.
"+" means homogeneous colouring without the formation of stripes of lesser colour
intensity vertical to the direction of flow
"o" means largely homogeneous colouring with slight formation of stripes of lesser
colour intensity vertical to the direction of flow
"-" means inhomogeneous colouring with marked formation of stripes vertical to the
direction of flow.
Homogeneity of colour was determined on 150x105x1.6 mm sheets, which were
produced at a composition temperature of 270°C, a mould temperature of 80°C and
a fill speed of 50 mm/s through a film feed on one 105 mm side.
As can be seen from Table 1, the moulding compositions according to the invention
have very good homogeneity of colour and at the same time good mechanical
properties. In comparison with the reference examples Ref. 1 and Ref. 3, which have
poorer homogeneity of colour, the toughness of Ref. 1 and Ref. 3 was exceeded by
Example 2 even with a reduced content of AES rubber.
The composition and properties of the thermoplastic moulding compositions
according to the invention can be seen in (Table Removed)
1. Composition characterized by its color homogeneity consisting of
A) 4 to 80 wt. % of at least one polyalkylene terephthalate;
B) 10 to 90 wt. % of at least one aromatic polycarbonate based on bisphenol A;
C) 1.5 to 30 wt. % of at least one AES graft polymer;
D) 0 to 54 wt. % of at least one mineral filler in particle form of the kind such as herein described;
E) 0.01 to 10 wt.% of at least one colouring material selected from
the group consisting of titanium dioxide, ultramarine blue, iron
oxide, carbon black, phthalocyanine, quinacridone, perylene,
nigrosin and anthraquinone;
F) 0 to 10 wt.% of at least one other additive selected from the
group consisting of stablisers, anti-statics, flow auxiliary
substances, mould release agents, fire-protection additives,
emulsifiers, nucleating agents, plasticisers, mould lubricants,
pH-reducing additives, additives to increase conductivity, dyes
2. Composition as claimed in claim 1, wherein C is composed of graft
C1) 5 to 95 wt.%, preferably 10 to 80 wt.%, in particular 20 to 50 wt.% of at least one vinyl monomer;
C2) 95 to 5 wt.%, preferably 90 to 20, in particular 80 to 20 wt. % of one or more grafting bases having glass transition temperatures of the rubber component
3. Composition as claimed in one or more of the preceding claims, wherein polyethylene terephthalate is used as component A.
4. A molded article comprising the composition as claimed in claim 1.
|Indian Patent Application Number||2767/DELNP/2005|
|PG Journal Number||08/2009|
|Date of Filing||22-Jun-2005|
|Name of Patentee||BAYER MATERIALSCIENCE AG|
|Applicant Address||51368 LEVERKUSEN, GERMANY.|
|PCT International Classification Number||C08L 69/00|
|PCT International Application Number||PCT/EP2003/014886|
|PCT International Filing date||2003-12-24|