Source: http://www.patentsencyclopedia.com/app/20130018137
Timestamp: 2016-07-29 12:05:06
Document Index: 730275342

Matched Legal Cases: ['Application No.\n10196932', 'in fine', 'art 1977', 'art 18', 'art 18', 'art 21', 'art 18', 'art 18', 'art 18', 'art 21', 'art 18', 'art\n18', 'art 21', 'arts 14', 'art 18', 'art 8', 'art 15', 'art 15', 'art 15', 'art 15', 'art 15', 'art 15', 'art 15']

PROCESS FOR IMPROVING CARBON BLACK DISPERSIONAANM SEIDEL; AndreasAACI DormagenAACO DEAAGP SEIDEL; Andreas Dormagen DEAANM THIEM; Hans-JuergenAACI DormagenAACO DEAAGP THIEM; Hans-Juergen Dormagen DEAANM RUDOLF; ReinerAACI LagenfeldAACO DEAAGP RUDOLF; Reiner Lagenfeld DEAANM REICHENAUER; JoergAACI KrefeldAACO DEAAGP REICHENAUER; Joerg Krefeld DEAANM ECKEL; ThomasAACI DormagenAACO DEAAGP ECKEL; Thomas Dormagen DE - Patent application
Patent application title: PROCESS FOR IMPROVING CARBON BLACK DISPERSIONAANM SEIDEL; AndreasAACI DormagenAACO DEAAGP SEIDEL; Andreas Dormagen DEAANM THIEM; Hans-JuergenAACI DormagenAACO DEAAGP THIEM; Hans-Juergen Dormagen DEAANM RUDOLF; ReinerAACI LagenfeldAACO DEAAGP RUDOLF; Reiner Lagenfeld DEAANM REICHENAUER; JoergAACI KrefeldAACO DEAAGP REICHENAUER; Joerg Krefeld DEAANM ECKEL; ThomasAACI DormagenAACO DEAAGP ECKEL; Thomas Dormagen DE
Andreas Seidel (Dormagen, DE)
Hans-Jüergen Thiem (Dormagen, DE)
Reiner Rudolf (Lagenfeld, DE)
Joerg Reichenauer (Krefeld, DE)
Thomas Eckel (Dormagen, DE)
Patent application number: 20130018137
A masterbatch comprising pigment and demoulding agent is provided. The
demoulding agent is selected from the group comprising low molecular
weight polyolefin oils, low molecular weight polyolefin waxes, montan
waxes and aliphatic or aromatic carboxylic acid esters of fatty acids
and/or fatty alcohols, wherein the pigment content of the masterbatch is
from 3 to 70 wt. %, based on the total weight of the masterbatch. The
masterbatch is suitable for preparation of a polymer composition having
improved pigment dispersion.Claims:
1. A masterbatch for colouring a polymer composition comprising at least
one pigment and at least one demoulding agent, wherein the demoulding
agent is at least one selected from the group consisting of low molecular
waxes and aliphatic or aromatic carboxylic acid esters of fatty acids and
fatty alcohols, wherein the content of pigment in the masterbatch is from
3 to 70 wt. %, based on the total weight of the masterbatch.
2. The masterbatch according to claim 1, wherein the demoulding agent is
an aliphatic or aromatic carboxylic acid ester of fatty acids and/or
fatty alcohols or a mixture of a plurality of aliphatic or aromatic
carboxylic acid esters of fatty acids and/or fatty alcohols.
3. The masterbatch according to claim 1, wherein the demoulding agent is
selected from the group consisting of pentaerythritol tetrastearate,
glycerol monostearate and stearyl stearate.
4. The masterbatch according to claim 1, wherein the pigment is a
carbon-based pigment.
5. The masterbatch according to claim 4, wherein the pigment is carbon
6. The masterbatch according to claim 1, wherein the content of the
pigment is from 40 to 60 wt. %, based on the total weight of the
7. A process for preparing a masterbatch according to claim 1,
comprising: a) metering said demoulding agent and said pigment into a
shear and mixing unit, b) melt-mixing the pigment in the demoulding agent
and dispersing the pigment in the demoulding agent to form a melt
mixture, c) optionally filtering the melt mixture, d) forming melt
strands, e) cooling and granulating the melt strands, and f) when using
underwater or water-ring granulation in step e), drying granules.
8. The process according to claim 7, wherein the shear and mixing unit is
a single-shaft extruder, multi-shaft extruder, internal mixer, co-kneader
or a shear roller device.
9. The process according to claim 7, wherein the granulating is carried
out by underwater granulation or hot-face water-ring granulation.
10. The masterbatch according to claim 1 which is capable of being used
in the preparation of coloured polymer compositions having improved
11. The masterbatch according to claim 10, wherein the polymer
composition is a polycarbonate composition comprising a) from 1 to 99.96
wt. % of at least one thermoplastic polymer (a), b) from 0.02 to 10 wt. %
of at least one pigment component (b), c) from 0.02 to 10 wt. % of at
least one demoulding agent (c), d) from 0 to 70 wt. % of one or more
thermoplastic polyesters (d), e) from 0 to 50 wt. % of one or more
elastomers (e) other than component f, f) from 0 to 70 wt. % of one or
more optionally rubber-modified vinyl (co)polymers (f), and g) from 0 to
40 wt. % one or more further additives.
12. A process for preparing a coloured polymer composition by
melt-mixing, wherein pigment and demoulding agent are used in compounding
in the form of a masterbatch, according to claim 1.
13. A process according to claim 12, wherein the composition is a
polycarbonate composition comprising a) from 1 to 99.96 wt. % of at least
one thermoplastic polymer (a), b) from 0.02 to 10 wt. % of at least one
pigment component (b), c) from 0.02 to 10 wt. % of at least one
demoulding agent (c), d) from 0 to 70 wt. % of one or more thermoplastic
polyesters (d), e) from 0 to 50 wt. % of one or more elastomers (e) other
than component f, f) from 0 to 70 wt. % of one or more optionally
rubber-modified vinyl (co)polymers (f), and g) from 0 to 40 wt. % one or
more further additives.
14. A polymer composition prepared by a process according to claim 12,
comprising a) from 1 to 99.96 wt. % of at least one thermoplastic polymer
(a), b) from 0.02 to 10 wt. % of at least one pigment component (b), c)
from 0.02 to 10 wt. % of at least one demoulding agent (c), d) from 0 to
70 wt. % of one or more thermoplastic polyesters (d), e) from 0 to 50 wt.
% of one or more elastomers (e) other than component f, f) from 0 to 70
wt. % of one or more optionally rubber-modified vinyl (co)polymers (f),
and g) from 0 to 40 wt. % one or more further additives.
15. A moulded article comprising a polymer composition according to claim
14, wherein the number of surface defects of said modulated article is at
least 20% lower as compared with a moulded article of a moulding
composition prepared by a compounding process using a pigment component b
16. A masterbatch of claim 1 wherein said pigment is not in powder form.
17. A masterbatch of claim 1 wherein said pigment is in the form of a
pigment concentrate.
18. A polycarbonate moulding composition that has been prepared and
colored using a masterbatch of claim 1, and wherein said pigment
comprises carbon black.
19. A composition of claim 18, wherein said masterbatch comprises a
concentrate of carbon black in said demoulding agent and said demoulding
agent is optionally pentaerythritol tetrastearate.Description:
[0001] This application claims priority to European Patent Application No.
10196932.7, filed Dec. 23, 2010, the content of which is incorporated
[0003] The invention provides pigment-containing polycarbonate compounds
having improved dispersion of the pigment particles in the polymer
matrix, and a process for the preparation of these compounds. Carbon
black is preferably used as the pigment, "carbon black" in the present
invention representing all particulate pure carbon substrates and carbon
compounds, for example colour carbon blacks, conductivity carbon blacks,
carbon nanotubes, graphite. The pigment-containing polycarbonate
compounds can contain further polymers, such as, for example, elastomers
or graft polymers, or further thermoplastics, such as, for example,
[0004] The present invention relates further to the use of pigment
masterbatches containing the pigment and a demoulding agent which is to
be added to the polycarbonate composition.
[0005] The present invention relates further to a process for the
preparation of such polycarbonate compounds having improved dispersion of
the pigment particles in the polymer matrix, in which, in the compounding
of the polycarbonate composition, a masterbatch of the pigment in fatty
acid esters based on aliphatic alcohols or polyols is used. The invention
further provides the preparation of such pigment masterbatches in fatty
[0007] A technical problem when incorporating pigments, and carbon black
particles in particular, into thermoplastic polymer compositions is that
of dispersing the pigment particles completely and uniformly in the
polymer matrix. Incompletely dispersed pigment particles form pigment
agglomerates which apart from colour inhomogeneities and inadequate depth
of colour also result in particular in defects which have an adverse
effect on the mechanical properties of the polymer compositions, such as
their strength and ultimate elongation, and also on the surface
properties of the materials. Larger pigment agglomerates lead, for
example, to faults and defects on the surface of such compositions such
as pitting, streakiness and, ultimately, to an undesirable reduction in
the degree of gloss. In a composite with other materials, such surface
defects can additionally also adversely affect the composite adhesion
properties (for example lacquer adhesion).
[0008] Carbon-based pigments--such as, for example, carbon blacks,
graphites, fullerenes, graphenes, activated charcoals and carbon
nanotubes, which are used in many commercial fields of application, for
example for black colouration, for increasing the electrical or thermal
conductivity of the composition, for mechanical strengthening or also for
binding and reducing the volatility of low molecular weight organic
compounds such as residual monomers or odour-bearing substances are
distinguished by particularly strong interparticle binding forces and
therefore have a particularly high tendency to form agglomerates, which
can be broken up again only with difficulty on incorporation into
[0009] Various methods are known from the prior art for improving the
dispersion of such pigments in thermoplastic polymer compositions. For
example, pigment dispersion can be improved by increasing the specific
energy input by means of shear during the incorporation of the pigments
into the polymer melt in conventional compounding units such as
twin-screw extruders or internal kneaders.
[0010] However, the energy input which can be used for pigment dispersion
is technically limited in the case of polymer melts, in particular those
having a low viscosity, that is to say high melt flowability, as is
required for good thermoplastic processability in most fields of
application. In other cases, the energy input is limited by the thermal
loading capacity of the polymer melt into which the pigment is to be
incorporated. High specific energy inputs naturally lead to high process
temperatures which, depending on the polymer, can lead to undesirable
damage, ageing or even decomposition of the polymer.
[0011] A further method is the use of a highly concentrated masterbatch of
the pigment in a polymer matrix, but the technically achievable
concentration of the pigment in the polymer matrix is not high enough for
an economic application without the use of further additives/processing
aids. Furthermore, good pigment dispersion in the end product can be
achieved with this method only if the pigments are already well dispersed
in the masterbatch, which is only insufficiently ensured when using
polymer matrices, in particular in polycarbonate.
[0012] A further possibility for improving the dispersion of pigments
consists in using dispersing aids, which reduce the intermolecular
interactions between the individual pigment particles or pigment
aggregates within a pigment agglomerate and thereby facilitate the
breaking up of the agglomerates during the preparation of the compounds.
The disadvantage of the use of such dispersing aids, which have no other
necessary action in the composition, is that they remain in the polymer
composition that is produced and, as a result, may possibly adversely
affect the application-related properties of the target products.
[0013] For example, such dispersing aids in multiphase compositions
(blends) of different polymers (such as, for example, impact-modified
polymers) can adversely affect the phase compatibility of the different
polymer components by accumulating at the phase boundaries and thereby
adversely affect the mechanical properties of the blend composition.
Likewise, these additives can catalyse undesirable ageing processes in
certain polymer systems, for example hydrolytic decomposition reactions
in polycondensation polymers.
[0014] The preparation of pigment concentrates in wax-like compounds is
already known from U.S. Pat. No. 4,484,952, wherein the preparation of
carbon black concentrates in PETS (pentaerythritol tetrastearate) is also
described. However, the shear forces which occur under the stirring,
spraying or centrifugation conditions mentioned in U.S. Pat. No.
4,484,952 for mixing the pigments with the carrier are too small to
achieve sufficiently fine separation and uniform distribution of the
pigments in the carrier material in the case of highly agglomerated
pigments. However, this is a necessary requirement for subsequent uniform
dispersion of the pigments in a polymer matrix with the aid of such
pigment concentrates. Moreover, U.S. Pat. No. 4,484,952 gives no
indication of the quality of the pigment dispersion which can be achieved
in thermoplastics with carbon black concentrates so prepared, in
particular the dispersion of the carbon black which can be achieved in
polycarbonate compositions. Furthermore, there is no information in U.S.
Pat. No. 4,484,952 regarding the process parameters used in the
preparation of the pigment concentrates and the energy input as well as
the mixing unit used, which have a critical influence on the quality of
[0015] The preparation of pigment and, in particular, carbon black
concentrates in wax-like compounds is also known from U.S. Pat. No.
4,310,483. However, this is likewise a concentrate form in which only a
low energy input for the separation of agglomerated pigments and their
uniform distribution in the matrix material occurs. The preparation
process is in fact aimed at improving the metering properties of the
described pigment concentrates, dust formation being largely avoided and
a more advantageous metering form being achieved by wetting of the
pigments. The amount of pigment in the described carbon black
concentrates far exceeds the amount of granulating aid used. Regarding
the quality of the pigment dispersion in thermoplastics using such
pigment concentrates, it is stated in U.S. Pat. No. 4,310,483 that it is
equally as good as in the case of the metering of pure powder without the
use of granulating aids, but an improvement in the dispersion is not
[0016] WO 2002/092702 relates to the coating of carbon black pellets by
spraying with wax-like compounds, accordingly, for example, also with
PETS, in order to improve the metering properties of carbon black
products by the coating.
[0017] The preparation of carbon black-containing polycarbonate moulding
compositions using carbon black masterbatches is described in EP 578 245
A2. However, the masterbatches here are masterbatches in polyethylenes.
Polyethylenes lead to disadvantageous property changes in polycarbonate
moulding compositions, for example in respect of the low-temperature
strength of the moulding compositions, and are therefore to be avoided.
[0018] US 2009/0057621 A1 describes the melt-mixing of carbon-containing
thermoplastic masterbatches with thermoplastics without isolation of the
masterbatch but with simultaneous continuous metering into a second
thermoplastic melt, wherein the thermoplastic can also be polycarbonate.
Such a process is technically too complex and inflexible, however.
[0019] In order to overcome disadvantages associated with the
above-mentioned art, it was, therefore, an object of the present
invention to provide a novel process for improved dispersion of pigments,
in particular carbon black, in polycarbonate compounds.
[0020] In addition, when using pigment concentrates, no foreign substances
that do not have a necessary action in the composition are to be
introduced into the polycarbonate compounds.
[0021] Furthermore, a pigment concentrate in isolated form is to be
provided, which concentrate is suitable for incorporation into and for
the preparation of polycarbonate compounds having improved pigment
[0022] It was a further object of the invention, by the use of a pigment
concentrate, to achieve better dispersion of pigments in a polymer matrix
than is possible by metering the pure pigment in powder form in a single
compounding step, it still being possible to carry out the preparation
process under standard conditions in conventional mixing units such as,
for example, in single- or multi-shaft extruders, kneaders or internal
[0023] Surprisingly, it has been found that pigments, in particular carbon
blacks, in substances which are used as demoulding agents for
polycarbonate moulding compositions, in a preferred embodiment in
aliphatic fatty acid esters, can, under defined conditions, be both
homogenously distributed and very well dispersed in the melt of the fatty
acid esters using mechanical shear, and that a carbon black concentrate
so prepared, after cooling, can be formed into pellets and used in a
subsequent compounding process as a masterbatch for colouring
thermoplastic compositions, in particular also for colouring
polycarbonate compositions. In principle, various types of demoulding
agents and various, in particular carbon-containing, pigments are
suitable for the preparation of such masterbatches.
[0024] FIG. 1 shows a structure of a co-kneader.
[0025] FIG. 2 shows a structure of a co-kneader without a retaining ring.
[0026] FIG. 3 shows a structure of a co-kneader with a metering hopper.
[0027] FIG. 4 shows a structure of an extruder with a length-to-diameter
ratio of 44.
[0028] FIG. 5 shows a structure of an extruder with a length-to-diameter
ratio of 36.
[0029] FIG. 6 shows a structure of an extruder with an injection valve.
[0030] FIG. 7 shows a structure of an extruder with a length-to-diameter
ratio of 48.
[0031] FIG. 8 shows a structure of an extruder with a length-to-diameter
ratio of 31.5.
[0032] FIG. 9 shows a structure of an extruder with a length-to-diameter
ratio of 40.
[0033] FIG. 10 shows a graph.
[0034] FIG. 11 shows a diagram of the process parameters of an extruder
denoting notched impact strength at an ambient temperatures of
[0035] FIG. 12 shows a diagram of the process parameters of an extruder
[0036] Objects of the present invention can be achieved, for example, by
the compositions, the process and the use as disclosed hereinbelow and
described in the claims, the preferred embodiments according to the
invention generally being described hereinbelow with carbon black as the
preferred pigment by way of example, but this does not imply any
fundamental limitation to carbon black as the pigment.
[0037] Concentrates of suitable carbon black types in demoulding agents
containing fatty acid esters were prepared, which concentrates can
preferably be granulated at room temperature. The demoulding agent that
is preferably used for the preparation of such carbon black masterbatches
is pentaerythritol tetrastearate (PETS). However, other fatty acid
esters, preferably those which are solid at room temperature (20°
C.), can likewise be used for the preparation of carbon black
masterbatches according to the invention. The carbon black masterbatches
according to the invention can be prepared in conventional compounding
units in the melt of the fatty acid esters with the application of
sufficiently high shear energy for the adequate separation of any
agglomerated carbon black particles.
[0038] It has further been found that polycarbonate moulding compositions
which have been prepared and coloured using the carbon black
masterbatches according to the invention by compounding in a single
compounding step in conventional mixing units such as, for example,
single- or multi-shaft extruders, kneaders or internal mixers under
standard conditions, exhibit substantially improved dispersion of the
carbon black particles in the polycarbonate matrix after thermoplastic
processing to moulded articles. The polycarbonate moulding compositions
can contain further thermoplastics or particulate elastomeric polymers,
as well as conventional fillers and polymer additives.
[0039] Accordingly, the invention provides, in particular, a process for
the preparation of carbon black-containing polycarbonate moulding
compositions, wherein the carbon black is present in finely dispersed
form in the form of a masterbatch in a substance which is used as
demoulding agent in the formulation of the polycarbonate moulding
compositions and accordingly exhibits a necessary action in the
composition, and is introduced into the polycarbonate moulding
composition by melt compounding. The carbon black masterbatch is
preferably in the form of a pellet, as described above, and is used and
metered as such in the compounding process. As an alternative, however,
such a carbon black masterbatch, because of the low melt viscosity at the
relatively low melting points, can also be fed into the compounding unit
in liquid or pasty form with the aid of melt metering pumps.
[0040] Suitable mixing units for the preparation of the carbon black
masterbatch are single- or multi-shaft extruders or kneaders, such as,
for example, Buss co-kneaders or internal mixers or shear rollers, and
any mixing units with which a sufficiently high shear energy can be
introduced into the melt of carbon black and demoulding agent in order to
finely separate any solid carbon black agglomerates and distribute them
uniformly in the demoulding agent.
[0041] The starting components carbon black and demoulding agent are fed
to the compounding unit either separately or in the form of a powder or
grain or granule mixture and are intimately mixed in the melt at a
heating temperature of the housing of from 25° C. to 200°
C., preferably from 30° C. to 130° C.
[0042] The masterbatches so obtained, depending on their carbon black
content and the demoulding agent used, preferably have a solid
consistency at room temperature. For metering in the form of a solid, the
carbon black masterbatches are formed into melt strands, optionally
filtered in the melt through a fine-mesh sieve (10-100 μm mesh size,
preferably 20-50 μm) in order to retain incompletely separated carbon
black agglomerates, and then cooled to temperatures below 40° C.,
preferably below 30° C., and subsequently granulated.
[0043] Suitable granulating devices for the preparation of sufficiently
finely divided granules/pellets of the carbon black masterbatch which can
readily be metered in the subsequent compounding of the polycarbonate
moulding compositions are underwater or hot-face water-ring granulators.
The granules or pellets so obtained have a maximum length of preferably 8
mm, particularly preferably not more than 5 mm, and a minimum length of
preferably 0.5 mm, particularly preferably not less than 1 mm, the length
defining the axis in the direction of the greatest extent of a body.
[0044] In an alternative embodiment, the masterbatch is used in the form
of a powder having a maximum diameter smaller than 0.5 mm and not less
than 0.1 mm.
[0045] The amount of carbon black or pigment in the masterbatch can vary
within relatively wide limits from 3 wt. % to 70 wt. %, based on the
masterbatch; the carbon black content is preferably from wt. % to 70 wt.
%, more preferably from 35 wt. % to 65 wt. %, particularly preferably
from 40 to 60 wt. %.
[0046] The nature of the pigment used and in particular also of the carbon
black used can vary very greatly, the term "carbon black" also including
chemical species such as carbon nanotubes, graphite, conductivity carbon
black and colour carbon black, as well as carbon blacks obtained by very
different production processes. Colour carbon blacks and conductivity
carbon blacks are particularly preferred, and colour carbon blacks are
most particularly preferred. These carbon blacks can optionally also be
used together with other organic or inorganic pigments either in the
carbon black masterbatch or in the compounding of the polycarbonate
moulding composition. Carbon nanotubes (CNTs) are preferably not used in
[0047] The nature of the demoulding agent used can likewise vary greatly,
there preferably being used compounds such as low molecular weight
polyolefin oils or waxes, hydrogenated oils, montanic acid or fatty acid
esters, which preferably have a solid consistency at room temperature.
Further preferred demoulding agents are aliphatic montanic or fatty acid
esters, such as, for example, glycerol stearates or palmitates or
pentaerythritol stearates. Pentaerythritol tetrastearate (PETS) is
[0048] These carbon black masterbatches prepared according to the
invention are intimately mixed with polymers, preferably with
polycarbonate and optionally further components of the polymer,
preferably polycarbonate, moulding composition in conventional
melt-mixing units, such as, for example, in single- or multi-shaft
extruders or in kneaders, in the melt under conventional conditions, and
the mixture is extruded and granulated. They can be metered at a suitable
location into the solids feed region of the extruder or into the polymer
melt, either separately in the form of granules or pellets via
proportioning weighers or lateral feed devices or alternatively at
elevated temperature in the form of a melt by means of metering pumps.
The masterbatches in the form of granules or pellets can also be combined
with other particulate compounds to give a premixture and then fed
together into the solids feed region of the extruder or into the polymer
melt in the extruder via metering hoppers or lateral feed devices. The
compounding unit is preferably a twin-shaft extruder, particularly
preferably a twin-shaft extruder having co-rotating shafts, the
twin-shaft extruder having a length/diameter ratio of the screw shaft of
preferably from 20 to 44, particularly preferably from 28 to 40. Such a
twin-shaft extruder comprises a melting and mixing zone or a combined
melting and mixing zone (this "melting and mixing zone" is also referred
to hereinbelow as the "kneading and melting zone") and optionally a
degassing zone in which an absolute pressure pabs of preferably not
more than 800 mbar, more preferably not more than 500 mbar, particularly
preferably not more than 200 mbar, is set. The mean residence time of the
mixture composition in the extruder is preferably limited to not more
than 120 s, particularly preferably not more than 80 s, particularly
preferably not more than 60 s. In a preferred embodiment, the temperature
of the melt of the polymer or of the polymer alloy at the extruder outlet
is from 200° C. to 400° C.
[0049] The invention accordingly also provides pigment-containing polymer
moulding compositions, in a preferred embodiment polycarbonate moulding
compositions, having improved pigment dispersion, which moulding
compositions are prepared by the process according to the invention, that
is to say using a pigment-demoulding agent concentrate according to the
invention containing [0050] a) from 1 to 99.96 wt. %, preferably from
40 to 99.9 wt. %, more preferably from 50 to 99.8 wt. %, particularly
preferably from 50 to 75 wt. %, of at least one thermoplastic polymer
(a), [0051] b) from 0.02 to 10 wt. %, preferably from 0.05 to 5 wt. %,
more preferably from 0.1 to 3 wt. %, particularly preferably from 0.1 to
1.5 wt. %, of at least one pigment component (b), in a preferred
embodiment of a carbon-based pigment, in a particularly preferred
embodiment carbon black, [0052] c) from 0.02 to 10 wt. %, preferably from
0.05 to 5 wt. %, more preferably from 0.1 to 3 wt. %, particularly
preferably from 0.1 to 1.5 wt. %, of at least one demoulding agent (c),
[0053] d) from 0 to 70 wt. %, preferably from 0 to 60 wt. %, more
preferably from 2 to 60 wt. %, particularly preferably from 20 to 60 wt.
%, of one or more thermoplastic polyesters (d), [0054] e) from 0 to 50
wt. %, preferably from 0 to 40 wt. %, more preferably from 1 to 30 wt. %,
particularly preferably from 2 to 20 wt. %, of one or more elastomers (e)
other than component [0055] f) from 0 to 70 wt. %, preferably from 0 to
60 wt. %, more preferably from 1 to 50 wt. %, particularly preferably
from 3 to 40 wt. %, of one or more optionally rubber-modified vinyl
(co)polymers (f), and [0056] g) from 0 to 40 wt. %, preferably from 0 to
30 wt. %, more preferably from 0.1 to 20 wt. %, particularly preferably
from 0.2 to 10 wt. %, of further additives.
[0057] Components b and c can be used in the preparation of the
pigment-containing polymer moulding compositions according to the
invention either wholly or only partially in the form of a masterbatch of
components b and c. In a preferred embodiment, carbon-based pigments
according to component b are used in the preparation of the
invention solely in the form of a masterbatch of components b and c, it
being possible, however, for a portion of component c in this preferred
embodiment also to be used in the form of the pure component in the
preparation of the pigment-containing polymer moulding compositions
according to the invention. In a particularly preferred embodiment,
components b and c are used in the preparation of the pigment-containing
polymer moulding compositions according to the invention solely in the
form of a masterbatch of components b and c.
[0058] Moulded articles which have been produced by thermoplastic
processing, for example by injection moulding, from these pigment/carbon
black-containing polymer/polycarbonate moulding compositions prepared
according to the invention exhibit a markedly more homogeneous moulding
surface with markedly fewer optical imperfections, that is to say surface
defects, and markedly improved strength, in particular improved notched
impact strength, as compared with polymer/polycarbonate moulding
compositions of the same composition which have been prepared by direct
compounding, for example from powder mixtures or by compounding using
thermoplastic-based pigment/carbon black masterbatches.
[0059] In a preferred embodiment, the number of surface defects (pitting,
craters, pinholes, etc.) on moulded articles produced by the injection
moulding process from the polymer/polycarbonate compositions according to
the invention is reduced by at least 20%, particularly preferably by 20
to 95 percent, as compared with moulded articles of the moulding
compositions having the same composition which have been prepared by a
different process, in particular by a one-step compounding process using
pigment component b in powder form.
[0060] The surface defects of injection-moulded articles produced on
injection moulding tools with a high-gloss finish (ISO N1) can be
identified and quantified by optical analysis methods, all imperfections
having a mean diameter of at least 10 min being used in determining the
number of surface defects. The number of surface defects was determined
by observing the moulding surfaces under a reflected light
microscope--e.g. Zeiss Axioplan 2 motorised--through an object lens with
2.5× magnification in a bright field, with illumination by means of
a halogen 100 light source. The number of defects in a surface region
measuring 4 cm×4 cm was determined by scanning the area in a
meandering manner. The determination was assisted by a camera--e.g.
Axiocam IRC--with image evaluation software--e.g. KS 300 Zeiss.
[0061] According to analysis by Raman spectroscopy, the surface defects
thus determined optically on mouldings of polymer/polycarbonate moulding
compositions having the above-mentioned compositions represent
agglomerates and aggregates of pigments, in particular carbon black
particles, optionally together with elastomer particles of components E
and/or F, which are inadequately separated in the melt compounding of the
components in the extruder. Such surface defects are clearly visible by
reflected light microscopy of suitable sections of the material samples.
Such surface defects usually have mean diameters of from about 10 μm
to about 300 μm.
[0062] In the preparation according to the invention of the pigment/carbon
black-containing polymer/polycarbonate moulding compositions, further
process-related measures can be taken which further assist in improving
the dispersion of the pigment/carbon black in the polymer matrix. For
example, during the compounding of the pigment/carbon black-containing
polymer/polycarbonate moulding compositions in the melt, water can be
added in amounts of from 0.2 to 10 wt. %, based on the moulding
composition, and removed again via a degassing nozzle of the extruder, as
described in DE 10 2009 009680 and EP 10001490.1. Likewise, compounding
of the pigment/carbon black-containing polymer/polycarbonate moulding
compositions can be carried out on extruders having enlarged gap widths
between the screw crest and the housing wall, as described in EP
1016954.7. All these measures bring about improvements in the dispersion
of the pigment/carbon black in the polymer/polycarbonate moulding
compositions both on their own and in combination with one another.
[0063] There can be used as thermoplastic polymers a in the compositions
according to the invention, for example, polyolefins (such as
polyethylene and polypropylene), vinyl (co)polymers such as polyvinyl
chloride, styrene (co)polymers (e.g. styrene-acrylonitrile copolymers,
acrylonitrile-butadiene-styrene copolymers, polyacrylates,
polyacrylonitrile), polyvinyl acetate, thermoplastic polyurethanes,
polyacetals (such as polyoxymethylene and polyphenylene ether),
polyamides, polyimides, polycarbonates, polyesters, polyester carbonates,
polysulfones, polyarylates, polyaryl ethers, polyphenylene ethers,
polyarylsulfones, polyaryl sulfides, polyether sulfones, polyphenylene
sulfide, polyether ketones, polyamide imides, polyether imides and
polyester imides.
[0064] In a preferred embodiment there is used as the thermoplastic
polymer a in the compositions according to the invention at least one
representative selected from the group of the aromatic polycarbonates and
aromatic polyester carbonates.
[0065] Aromatic polycarbonates and/or aromatic polyester carbonates
according to component a that are suitable according to the invention are
known in the literature or can be prepared by processes 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-A 2 232 877, BE-A 2 703 376,
DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; for the preparation of
aromatic polyester carbonates see e.g. BE-A 3 007 934). The preparation
of aromatic polycarbonates is carried out, for example, by reaction of
diphenols with carbonic acid halides, preferably phosgene, and/or with
aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid
dihalides, according to the interfacial process, optionally using chain
terminators, for example monophenols, and optionally using branching
agents having a functionality of three or more than three, for example
triphenols or tetraphenols. Preparation by a melt polymerisation process
by reaction of diphenols with, for example, diphenyl carbonate is also
[0066] Diphenols for the preparation of the aromatic polycarbonates and/or
aromatic polyester carbonates are preferably those of formula (I)
wherein A is a single bond, C1- to C5-alkylene, C2- to
C5-alkylidene, C5- to C6-cycloalkylidene, --O--, --SO--,
--CO--, --S--, --SO2--, C6- to C12-arylene, to which
further aromatic rings optionally containing heteroatoms can be fused,
[0067] or a radical of formula (II) or (III)
[0067] B is in each case C1- to C12-alkyl, preferably methyl,
halogen, preferably chlorine and/or bromine, x each independently of the
other is 0, 1 or 2, p is 1 or 0, and R5 and R6 can be chosen
individually for each X1 and each independently of the other is
hydrogen or C1- to C6-alkyl, preferably hydrogen, methyl or
ethyl, X1 is carbon and m is an integer from 4 to 7, preferably 4 or
5, with the proviso that on at least one atom X1, R5 and
R6 are simultaneously alkyl.
[0068] Preferred diphenols are hydroquinone, resorcinol,
dihydroxydiphenols, bis-(hydroxyphenyl)-C1-C5-alkanes,
bis-(hydroxyphenyl)-C5-C6-cycloalkanes,
bis-(hydroxyphenyl)ethers, bis-(hydroxy-phenyl) sulfoxides,
bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl)-sulfones and
α,α-bis-(hydroxyphenyl)-diisopropyl-benzenes, and derivatives
thereof brominated and/or chlorinated on the ring.
[0069] Particularly preferred diphenols are 4,4'-dihydroxydiphenyl,
bisphenol A, 2,4-bis(4-hydroxy-phenyl)-2-methylbutane,
4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenylsulfone and di- and
tetra-brominated or chlorinated derivatives thereof, such as, for
example, 2,2-bis(3-chloro-4-hydroxy-phenyl)-propane,
2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or
2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularly
[0070] The diphenols can be used on their own or in the form of arbitrary
mixtures. The diphenols are known in the literature or are obtainable
according to processes known in the literature.
[0071] Chain terminators suitable for the preparation of thermoplastic
aromatic polycarbonates are, for example, phenol, p-chlorophenol,
p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chained
alkylphenols, such as 4-[2-(2,4,4-trimethylpentyl)]-phenol,
4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or
monoalkylphenol or dialkylphenols having a total of from 8 to 20 carbon
atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol,
p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol and
2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The
amount of chain terminators to be used is generally from 0.5 mol % to 10
mol %, based on the molar sum of the diphenols used in a particular case.
[0072] The thermoplastic aromatic polycarbonates have mean weight-average
molecular weights (Mw, measured by GPC (gel permeation
chromatography with polycarbonate standard in dichloromethane) of from
10,000 to 200,000 g/mol, preferably from 15,000 to 80,000 g/mol,
particularly preferably from 24,000 to 32,000 g/mol.
[0073] The thermoplastic aromatic polycarbonates can be branched in a
known manner, preferably by the incorporation of from 0.05 to 2.0 mol %,
based on the sum of the diphenols used, of compounds having a
functionality of three or more than three, for example those having three
or more phenolic groups. Preference is given to linear polycarbonates,
more preferably based on bisphenol A.
[0074] Both homopolycarbonates and copolycarbonates are suitable. For the
preparation of copolycarbonates of component a according to the invention
it is also possible to use from 1 to 25 wt. %, preferably from 2.5 to 25
wt. %, based on the total amount of diphenols to be used, of
polydiorganosiloxanes having hydroxyaryloxy end groups. These are known
(U.S. Pat. No. 3,419,634) and can be prepared according to processes
known in the literature. Polydiorganosiloxane-containing copolycarbonates
are likewise suitable; the preparation of copolycarbonates containing
polydiorganosiloxanes is described, for example, in DE-A 3 334 782.
[0075] Preferred polycarbonates in addition to the bisphenol A
homopolycarbonates are the copolycarbonates of bisphenol A with up to 15
mol %, based on the molar sums of diphenols, of diphenols other than
those mentioned as being preferred or particularly preferred, in
particular 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.
[0076] Aromatic dicarboxylic acid dihalides for the preparation of
aromatic polyester carbonates are preferably the diacid dichlorides of
isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic
acid and naphthalene-2,6-dicarboxylic acid.
[0077] Mixtures of the diacid dichlorides of isophthalic acid and
terephthalic acid in a ratio of from 1:20 to 20:1 are particularly
[0078] In the preparation of polyester carbonates, a carbonic acid halide,
preferably phosgene, is additionally used concomitantly as bifunctional
[0079] Suitable chain terminators for the preparation of the aromatic
polyester carbonates, in addition to the monophenols already mentioned,
are also the chlorocarbonic acid esters thereof and the acid chlorides of
aromatic monocarboxylic acids, which can optionally be substituted by
C1- to C22-alkyl groups or by halogen atoms, as well as
aliphatic C2- to C22-monocarboxylic acid chlorides.
[0080] The amount of chain terminators is in each case from 0.1 to 10 mol
%, based in the case of phenolic chain terminators on moles of diphenol
and in the case of monocarboxylic acid chloride chain terminators on
moles of dicarboxylic acid dichloride.
[0081] In the preparation of aromatic polyester carbonates, one or more
aromatic hydroxycarboxylic acids can additionally be used.
[0082] The aromatic polyester carbonates can be both linear and branched
in known manner (see in this connection DE-A 2 940 024 and DE-A 3 007
934), linear polyester carbonates being preferred.
[0083] There can be used as branching agents, for example, carboxylic acid
chlorides, such as trimesic acid trichloride, cyanuric acid trichloride,
3,3'-,4,4'-benzophenone-tetracarboxylic acid tetrachloride,
1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic
acid tetrachloride, in amounts of from 0.01 to 1.0 mol % (based on
dicarboxylic acid dichlorides used), or phenols having a functionality of
three or more, such as phloroglucinol,
1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane,
2,2-bis[4,4-bis(4-hydroxy-phenyl)-cyclohexyl]-propane,
2,4-bis(4-hydroxyphenyl-isopropyl)-phenol,
2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol,
tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane,
1,4-bis[4,4'-dihydroxytriphenyl)-methyl]-benzene, in amounts of from 0.01
to 1.0 mol %, based on diphenols used. Phenolic branching agents can be
placed in a vessel with the diphenols; acid chloride branching agents can
be introduced together with the acid dichlorides.
[0084] The content of carbonate structural units in the thermoplastic
aromatic polyester carbonates can vary as desired. The content of
carbonate groups is preferably up to 100 mol %, in particular up to 80
mol %, particularly preferably up to 50 mol %, based on the sum of ester
groups and carbonate groups. Both the esters and the carbonates contained
in the aromatic polyester carbonates can be present in the
polycondensation product in the form of blocks or distributed randomly.
[0085] The thermoplastic aromatic polycarbonates and polyester carbonates
can be used on their own or in an arbitrary mixture.
[0086] Components a which are particularly preferably used according to
the invention are polycarbonates, with bisphenol A homopolycarbonates
[0087] There are used as component b in principle any desired inorganic or
organic, natural or synthetically prepared pigments. A pigment is
understood as being a colour-giving substance which is insoluble in the
application medium (here the thermoplastic polymer according to component
a). Examples of such pigments are titanium dioxide, carbon black, bismuth
pigments, metal oxides, metal hydroxides, metal sulfides, iron cyan blue,
ultramarine, cadmium pigments, chromate pigments, azo pigments as well as
polycyclic pigments.
[0088] There are preferably used as component b those pigments which have
strong interparticle binding forces (van der Waals forces), because these
are particularly difficult to disperse.
[0089] Component b is particularly preferably at least one carbon-based
pigment selected from the group consisting of carbon black, graphite,
fullerene, graphene, activated charcoal and carbon nanotubes (CNTs).
[0090] There are suitable as carbon nanotubes both those having a
single-layer wall (single-walled carbon nanotubes=SWCNTs) and those
having a multi-layer wall (multi-walled carbon nanotubes=MWCNTs).
[0091] Carbon nanotubes (CNTs) are preferably understood as being
cylindrical carbon tubes having a carbon content of >95%, which tubes
do not contain any amorphous carbon. The carbon nanotubes preferably have
an outside diameter of from 3 to 80 nm, particularly preferably from 5 to
20 nm. The mean value of the outside diameter is preferably from 13 to 16
nm. The length of the cylindrical carbon nanotubes is preferably from 0.1
to 20 μm, particularly preferably from 1 to 10 μm. The carbon
nanotubes preferably consist of from 2 to 50, particularly preferably
from 3 to 15, graphitic layers (also referred to as "walls"), which have
a smallest inside diameter of from 2 to 6 nm. These carbon nanotubes are
also referred to as "carbon fibrils" or "hollow carbon fibres", for
[0092] The production of the CNTs used according to the invention is
generally known (see e.g. U.S. Pat. No. 5,643,502 and DE-A 10 2006 017
695); they are preferably produced by the process disclosed in DE-A 10
2006 017 695, particularly preferably by the process disclosed in Example
3 of DE-A 10 2006 017 695.
[0093] In an alternative embodiment, carbon-based pigments according to
component b are preferably not used in the form of carbon nanotubes, but
carbon-based pigments with the exception of CNTs, preferably carbon
black, particularly preferably colour carbon black, are employed as
[0094] Carbon black is a black pulverulent solid which, depending on the
quality and use, consists substantially of carbon. The carbon content of
carbon black is generally from 80.0 to 99.9 wt. %. In the case of carbon
blacks which have not been subjected to oxidative after-treatment, the
carbon content is preferably from 96.0 to 95.5 wt. %. By extraction of
the carbon black with organic solvents, for example with toluene, traces
of organic impurities on the carbon black can be removed and the carbon
content can thereby be increased to more than 99.9 wt. %. In the case of
carbon blacks which have undergone oxidative after-treatment, the oxygen
content can be up to 30 wt. %, preferably up to wt. %, in particular from
5 to 15 wt. %.
[0095] Carbon black consists of mostly spherical primary particles having
a size of preferably from 10 to 500 nm. These primary particles have
grown together to form chain-like or branched aggregates. The aggregates
are generally the smallest unit of the carbon black which can be
separated in a dispersing process. Many of these aggregates in turn
combine by intermolecular (van der Waals) forces to form agglomerates. By
varying the production conditions, both the size of the primary particles
and the aggregation (structure) thereof can purposively be adjusted. The
person skilled in the art understands structure as being the type of
three-dimensional arrangement of the primary particles in an aggregate. A
"high structure" refers to carbon blacks with highly branched and
crosslinked aggregate structures; in the case of largely linear aggregate
structures, that is to say aggregate structures with little branching and
crosslinking, on the other hand, the term "low structure" is used.
[0096] The oil adsorption number measured according to ISO 4656 with
dibutyl phthalate (DBP) is generally given as a measure of the structure
of a carbon black. A high oil absorption number is indicative of a high
[0097] The primary particle size of a carbon black can be determined, for
example, by means of scanning electron microscopy. However, the BET
surface area of the carbon black, determined according to ISO 4652 with
nitrogen adsorption, is also used as a measure of the primary particle
size of a carbon black. A high BET surface area is indicative of a small
[0098] The dispersibility of the agglomerates of a carbon black depends on
the primary particle size and the structure of the aggregates, the
dispersibility of the carbon black generally decreasing as the primary
particle size and the structure decrease.
[0099] As a commercial product, industrial carbon black is produced by
incomplete combustion or pyrolysis of hydrocarbons. Processes for the
production of industrial carbon black are known in the literature. Known
processes for the production of industrial carbon blacks are in
particular the furnace, gas black, flame black, acetylene black and
thermal black processes.
[0100] The particle size distribution of the primary particles and the
size and structure of the primary particle aggregates determine the
properties such as depth of colour, ground shade and conductivity of the
carbon black. Conductive carbon blacks generally have small primary
particles and highly branched aggregates. Colour carbon blacks are
generally carbon blacks with very small primary particles and are often
subjected to subsequent oxidation after production by one of the
above-mentioned processes. The oxidic groups thereby attached to the
carbon black surface are intended to increase the compatibility with the
resins into which the carbon blacks are to be introduced and dispersed.
[0101] Colour carbon blacks are preferably used as component b. In a
preferred embodiment they have a mean primary particle size, determined
by scanning electron microscopy, of from 10 to 100 nm, more preferably
from 10 to 50 nm, particularly preferably from 10 to 30 nm, in particular
from 10 to 20 nm. The particularly finely divided colour carbon blacks
are therefore particularly preferred in the process according to the
invention because the depth of colour and UV resistance which can be
achieved with a particular amount of carbon black increases as the
primary particle size decreases but, on the other hand, their
dispersibility also decreases, for which reason such very finely divided
carbon blacks in particular are in need of improvement in respect of
their dispersibility.
[0102] The colour carbon blacks which are preferably used as component b
have a BET surface area, determined according to ISO 4652 by nitrogen
adsorption, of preferably at least 20 m2/g, more preferably of at
least 50 m2/g, particularly preferably of at least 100 m2/g, in
particular of at least 150 m2/g.
[0103] Colour carbon blacks which are preferably used as component b are
additionally characterised by an oil adsorption number, measured
according to ISO 4656 with dibutyl phthalate (DBP), of preferably from 10
to 200 ml/100 g, more preferably from 30 to 150 ml/100 g, particularly
preferably from 40 to 120 ml/100 g, in particular from 40 to 80 ml/100 g.
The colour carbon blacks with a low oil adsorption number generally
achieve a better depth of colour and are preferred in that regard but, on
the other hand, they are generally more difficult to disperse, for which
reason such carbon blacks in particular are in need of improvement in
respect of their dispersibility.
[0104] The carbon blacks which are used as component b can and are
preferably used in pellet or pearl form. Pearl formation or pelletisation
is carried out by processes known in the literature and serves on the one
hand to increase the bulk density and improve the metering (flow)
properties but, on the other hand, is also carried out for occupational
health reasons. The pellets or pearls are preferably so adjusted in terms
of their hardness that they withstand transport and feeding processes
during metering largely undamaged but break up into agglomerates again
completely under the action of high mechanical shear forces as occur, for
example, in conventional powder mixing devices and/or compounding units.
[0105] Component c
[0106] Demoulding agents which can be used according to the invention are
compounds having softening temperatures of preferably below 120°
C., particularly preferably from 20° C. to 100° C., most
particularly preferably from 40° C. to 80° C., such as, for
example, low molecular weight polyolefin oils or waxes, montan waxes,
aliphatic or aromatic carboxylic acid esters based on fatty acids and/or
fatty alcohols. Demoulding agents which are preferred according to the
invention are aliphatic carboxylic acid esters. These are esters of
aliphatic long-chained carboxylic acids with mono- or di-valent aliphatic
and/or aromatic, preferably aliphatic, hydroxy compounds.
[0107] Aliphatic carboxylic acid esters which are particularly preferably
used are or contain compounds of the general formula (IV):
(R2--CO--O)o--R3--(OH)p where o=1 to 4 and p=0 to 3
wherein R2 is an aliphatic saturated or unsaturated, linear, cyclic
or branched alkyl radical and R3 is an alkylene radical of a mono-
to tetra-hydric aliphatic alcohol of the formula R3--(OH)o+p.
In the compounds of formula (IV), the o radicals R2 in the same
molecule can also have different structures.
[0108] Particularly preferred for R2 are C1-C30-,
particularly preferably C4-C28-, most particularly preferably
C12-C24-alkyl radicals. C1-C30-Alkyl represents, for
example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,
neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl,
1-methylpentyl, 2-methylpropyl, 3-methylpentyl, 4-methylpentyl,
1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,
2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,
2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl or 1-ethyl-2-methylpropyl,
n-heptyl and n-octyl, pinacyl, adamantyl, the isomeric menthyls, n-nonyl,
n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
[0109] Particularly preferred for R3 are C1-C30-,
particularly preferably C1-C18-alkylene radicals. Alkylene
represents a straight-chained, cyclic, branched or unbranched alkylene
radical. C1-C18-Alkylene represents, for example, methylene,
ethylene, n-propylene, isopropylene, n-butylene, n-pentylene, n-hexylene,
n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene,
n-tridecylene, n-tetradecylene, n-hexadecylene or n-octadecylene.
[0110] In the case of esters of polyhydric alcohols, free, non-esterified
OH groups can also be present. Aliphatic carboxylic acid esters which are
suitable according to the invention are, for example and preferably,
glycerol monostearate (GMS), palmityl palmitate and stearyl stearate.
Mixtures of different carboxylic acid esters of formula (IV) can also be
used. Carboxylic acid esters which are preferably used are additionally
mono- or poly-esters of pentaerythritol, glycerol, trimethylolpropane,
propanediol, stearyl alcohol, cetyl alcohol or myristyl alcohol with
myristic, palmitic, stearic or montanic acid and mixtures thereof.
Pentaerythritol tetrastearate, glycerol monostearate, stearyl stearate
and propanediol distearate, or mixtures thereof, are particularly
[0111] A particularly preferred demoulding agent according to the
invention is pentaerythritol tetrastearate and glycerol monostearate, in
particular pentaerythritol tetrastearate.
[0112] Thermoplastic polyesters according to component d which can be used
according to the invention are polyalkylene terephthalates, which can be
prepared by methods known in the literature (see e.g.
Kunststoff-Handbuch, Volume VIII, p, 695 ff, Carl-Hanser-Verlag, Munich
[0113] In a preferred embodiment, the polyalkylene terephthalates are
reaction products of aromatic dicarboxylic acids or reactive derivatives
thereof, such as dimethyl esters or anhydrides, and aliphatic,
cycloaliphatic or araliphatic diols, as well as mixtures of these
[0114] Particularly preferred polyalkylene terephthalates contain at least
80 wt. %, preferably at least 90 wt. %, based on the dicarboxylic acid
component, terephthalic acid radicals and at least 80 wt. %, preferably
at least 90 mol %, based on the diol component, ethylene glycol and/or
1,4-butanediol radicals.
[0115] Particular preference is given to polyalkylene terephthalates which
have been prepared solely from terephthalic acid and reactive derivatives
thereof (e.g. dialkyl esters thereof) and ethylene glycol and/or
1,4-butanediol, and mixtures of these polyalkylene terephthalates.
Polyalkylene terephthalates which are particularly preferably used
according to the invention are polybutylene terephthalate (PBT) and
[0116] There can be used according to the invention as component e any
elastomers other than component f which have a glass transition
temperature <10° C., preferably <0° C., particularly
preferably <-20° C.
[0117] There are preferably used as component e, for example,
thermoplastic elastomers such as, for example, olefin-based thermoplastic
elastomers (TPO), polyurethane-based thermoplastic elastomers (TPU), and
thermoplastic styrene block copolymers (TPS).
[0118] Unless expressly described otherwise in the present invention, the
glass transition temperature is determined for all components by means of
differential scanning calorimetry (DSC) according to DIN EN 61006 at a
heating rate of 10 K/min with determination of the Tg as the mid-point
temperature (tangent method).
[0119] Rubber-modified vinyl (co)polymers which can be used according to
the invention as component fare one or more graft polymers of [0120] f.1
from 5 to 95 wt. %, preferably from 10 to 90 wt. %, particularly
preferably from 30 to 60 wt. %, of at least one vinyl monomer on [0121]
f.2 from 95 to 5 wt. %, preferably from 90 to 10 wt. %, particularly
preferably from 70 to 40 wt. %, of one or more graft bases having glass
transition temperatures <10° C., preferably <0° C.,
particularly preferably <-20° C.
[0122] The graft base f.2 generally has a mean particle size (d50 value)
of from 0.05 to 10.00 μm, preferably from 0.10 to 5.00 μm, more
preferably from 0.15 to 1.00 μm and particularly preferably from 0.2
to 0.5 μm.
[0123] The mean particle size d50 is the diameter above and below which in
each case 50 wt. % of the particles lie. It can be determined by means of
ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z.
Polymere 250 (1972), 782-1796).
[0124] Monomers f.1 are preferably mixtures of [0125] f.1.1 from 50 to 99
parts by weight of vinyl aromatic compounds and/or vinyl aromatic
compounds substituted on the ring (such as styrene,
α-methylstyrene, p-methylstyrene, p-chlorostyrene) and/or
(meth)acrylic acid (C1-C8)-alkyl esters, such as methyl methacrylate,
ethyl methacrylate, and [0126] f.1.2 from 1 to 50 parts by weight of
vinyl cyanides (unsaturated nitriles such as acrylonitrile and
methacrylonitrile) and/or (meth)acrylic acid (C1-C8)-alkyl esters, such
as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, and/or
derivatives (such as anhydrides and imides) of unsaturated carboxylic
acids, for example maleic anhydride.
[0127] Preferred monomers f.1.1 are selected from at least one of the
monomers styrene, α-methylstyrene and methyl methacrylate,
preferred monomers f.1.2 are selected from at least one of the monomers
acrylonitrile, maleic anhydride and methyl methacrylate. Particularly
preferred monomers are f.1.1 styrene and f.1.2 acrylonitrile.
[0128] Graft bases f.2 suitable for the graft polymers according to
component f are, for example, diene rubbers, EP(D)M rubbers, that is to
say those based on ethylene/propylene and optionally diene, acrylate,
polyurethane, silicone, chloroprene, ethylene/vinyl acetate and
acrylate-silicone composite rubbers.
[0129] Preferred graft bases f.2 are diene rubbers, for example based on
butadiene and isoprene, or mixtures of diene rubbers or copolymers of
diene rubbers or mixtures thereof with further copolymerisable monomers
(e.g. according to f.1.1 and f.1.2), with the proviso that the glass
transition temperature of component f.2 is below <10° C.,
preferably <0° C., particularly preferably <-10° C.
[0130] The gel content of the graft base f.2 is at least 30 wt. %,
preferably at least 40 wt. %, particularly preferably at least 70 wt. %
(measured in toluene).
[0131] The gel content of the graft base f.2 is determined at 25°
C. in a suitable solvent (M. Hoffmann, H. Kromer, R. Kuhn,
Polymeranalytik I und II, Georg Thieme-Verlag, Stuttgart 1977).
[0132] Particularly preferred rubber-modified vinyl (co)polymers according
to component f are, for example, ABS polymers (emulsion, mass and
suspension ABS), as are described, for example, in DE-OS 2 035 390 (=U.S.
Pat. No. 3,644,574) or in DE-OS 2 248 242 (=GB-PS 1 409 275) or in
Ullmanns, Enzyklopadie der Technischen Chemie, Vol. 19 (1980), p. 280 ff.
[0133] The graft copolymers according to component f are prepared by
radical polymerisation, for example by emulsion, suspension, solution or
mass polymerisation, preferably by emulsion or mass polymerisation,
particularly preferably by emulsion polymerisation.
[0134] Particularly suitable graft rubbers are also ABS polymers which are
prepared by the emulsion polymerisation process by redox initiation with
an initiator system comprising organic hydroperoxide and ascorbic acid
according to U.S. Pat. No. 4,937,285.
[0135] Because it is known that, in the graft reaction, the graft monomers
are not necessarily grafted onto the graft base completely,
rubber-modified graft polymers according to component f are also
understood according to the invention as being those products which are
obtained by (co)polymerisation of the graft monomers f.1 in the presence
of the graft base f.2 and which also form during working up.
[0136] Acrylate rubbers suitable as the graft base f.2 are preferably
polymers of acrylic acid alkyl esters, optionally with up to 40 wt. %,
based on f.2, of other polymerisable, ethylenically unsaturated monomers.
The preferred polymerisable acrylic acid esters include C1- to C8-alkyl
esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl
esters; haloalkyl esters, preferably halo-C1-C8-alkyl esters, such as
chloroethyl acrylate, as well as mixtures of these monomers.
[0137] For crosslinking, monomers having more than one polymerisable
double bond can be copolymerised. Preferred examples of crosslinking
monomers are esters of unsaturated monocarboxylic acids having from 3 to
8 carbon atoms and unsaturated monohydric alcohols having from 3 to 12
carbon atoms or saturated polyols having from 2 to 4 OH groups and from 2
to 20 carbon atoms, such as ethylene glycol dimethacrylate, allyl
methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl
and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and
tri-vinylbenzenes; but also triallyl phosphate and diallyl phthalate.
Preferred crosslinking monomers are allyl methacrylate, ethylene glycol
dimethacrylate, diallyl phthalate, and heterocyclic compounds which
contain at least three ethylenically unsaturated groups. Particularly
preferred crosslinking monomers are the cyclic monomers triallyl
cyanurate, triallyl isocyanurate, triacryloyl-hexahydro-s-triazine,
triallyl benzenes. The amount of crosslinked monomers is preferably from
0.02 to 5.00 wt. %, in particular from 0.05 to 2.00 wt. %, based on the
graft base B.2. In the case of cyclic crosslinking monomers having at
least three ethylenically unsaturated groups, it is advantageous to limit
the amount to less than 1 wt. % of the graft base f.2.
[0138] Preferred "other" polymerisable, ethylenically unsaturated monomers
which can optionally be used in addition to the acrylic acid esters for
the preparation of acrylate rubbers suitable as the graft base f.2 are,
for example, acrylonitrile, styrene, α-methylstyrene, acrylamides,
vinyl C1-C6-alkyl ethers, methyl methacrylate, butadiene. Preferred
acrylate rubbers as the graft base f.2 are emulsion polymers having a gel
content of at least 60 wt. %.
[0139] Further suitable graft bases according to f.2 are silicone rubbers
having graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3
704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
[0140] Rubber-free vinyl (co)polymers which can be used according to the
invention as component f are, for example and preferably, homo- and/or
co-polymers of at least one monomer from the group of the vinyl aromatic
compounds, vinyl cyanides (unsaturated nitriles), (meth)acrylic acid
(C1-C8)-alkyl esters, unsaturated carboxylic acids, as well as
[0141] Particularly suitable are (co)polymers of from 50 to 99 parts by
weight, preferably from 60 to 80 parts by weight, in particular from 70
to 80 parts by weight, in each case based on the (co)polymer, of at least
one monomer selected from the group of the vinyl aromatic compounds (such
as, for example, styrene, α-methylstyrene), vinyl aromatic
compounds substituted on the ring (such as, for example, p-methylstyrene,
p-chlorostyrene) and (meth)acrylic acid (C1-C8)-alkyl esters (such as,
for example, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate),
and from 1 to 50 parts by weight, preferably from 20 to 40 parts by
weight, in particular from 20 to 30 parts by weight, in each case based
on the (co)polymer, of at least one monomer selected from the group of
the vinyl cyanides (such as, for example, unsaturated nitriles such as
acrylonitrile and methacrylonitrile), (meth)acrylic acid (C1-C8)-alkyl
esters (such as, for example, methyl methacrylate, n-butyl acrylate,
tert-butyl acrylate), unsaturated carboxylic acids and derivatives of
unsaturated carboxylic acids (for example maleic anhydride and
N-phenyl-maleimide). The copolymer of styrene and acrylonitrile is
[0142] Such vinyl (co)polymers are known and can be prepared by radical
polymerisation, in particular by emulsion, suspension, solution or mass
[0143] In an embodiment which is particularly preferred according to the
invention, the vinyl (co)polymers have a weight-average molar mass
Mw (determined by gel chromatography in dichloromethane with
polystyrene calibration) of from 50,000 to 250,000 g/mol, particularly
preferably from 70,000 to 180,000 g/mol.
[0144] Additives according to component g which can be used according to
the invention are, for example, flameproofing agents (for example halogen
compounds or phosphorus compounds such as monomeric or oligomeric organic
phosphoric acid esters, phosphazenes or phosphonate amines, in particular
bisphenol A diphosphate, resorcinol diphosphate and triphenyl phosphate),
flameproofing synergists (for example nano-scale metal oxides),
smoke-inhibiting additives (for example boric acid or borates),
antidripping agents (for example compounds of the substance classes of
the fluorinated polyolefins, of the silicones as well as aramid fibres),
antistatics (for example block copolymers of ethylene oxide and propylene
oxide, other polyethers or polyhydroxy ethers, polyether amides,
polyester amides or sulfonic acid salts), conductivity additives other
than the definition of component b, stabilisers (for example UV/light
stabilisers, heat stabilisers, antioxidants, transesterification
inhibitors, hydrolytic stabilisers), additives having antibacterial
action (for example silver or silver salts), additives improving scratch
resistance (for example silicone oils or hard fillers such as (hollow)
ceramics beads), IR absorbers, optical brightening agents, fluorescent
additives, fillers and reinforcing substances other than the definition
of component b (for example talc, optionally ground glass fibres,
(hollow) glass or ceramics beads, mica, kaolin, CaCO3 and glass
flakes), colourings, ground thermoplastic polymers and Bronstedt-acidic
compounds as base acceptors, or mixtures of a plurality of the mentioned
[0145] The polymer mixtures prepared according to the invention are
preferably used in the production of injection-moulded articles or of
extrudates in which particular demands are made as regards the
homogeneity and freedom from defects of the surfaces.
[0146] Examples of moulded articles according to the invention are
profiles, films, casing parts of any kind, in particular casing parts for
computers, laptops, mobile telephones, television surrounds; for office
equipment such as monitors, printers, copiers; for sheets, tubes,
conduits for electrical installations, windows, doors and profiles for
the construction sector, interior fitting and external applications; in
the field of electrical engineering, for example for switches and
sockets. The moulded articles according to the invention can also be used
for interior fittings for passenger vehicles, railway vehicles, ships,
aircraft, buses and other motor vehicles, as well as for automotive
bodywork parts. Further moulded articles are food and drinks packaging
and structural components which are galvanised or metallised after
[0147] a1
[0148] Linear polycarbonate based on bisphenol A having a weight-average
molecular weight Mw of 17,000 g/mol (determined by GPC in methylene
chloride at 25° C. with polycarbonate calibration).
[0149] Linear polycarbonate based on bisphenol A having a weight-average
molecular weight Mw of 25,000 g/mol (determined by GPC in methylene
[0150] Linear polycarbonate based on bisphenol A having a weight-average
molecular weight Mw of 28,000 g/mol (determined by GPC in methylene
[0151] Linear polycarbonate based on bisphenol A having a weight-average
molecular weight Mw of 30,000 g/mol (determined by GPC in methylene
[0152] Linear polycarbonate based on bisphenol A having a weight-average
molecular weight Mw of 36,000 g/mol (determined by GPC in methylene
chloride at 25° C. with polycarbonate calibration)
[0153] Linear copolycarbonate of bisphenol A and
1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane in a mixing ratio of
70 wt. %:30 wt. % having a melt viscosity measured according to ISO 11433
at a temperature of 340° C. and a shear rate of 1000 s-1 of
[0154] Linear polycarbonate of bisphenol A and
30 wt. %:70 wt. % having a melt viscosity measured according to ISO 11433
320 Pas.
[0155] Component a2 ground to powder
[0156] Linear polycarbonate based on bisphenol A having a weight-average
molecular weight Mw of 32,000 g/mol (determined by GPC in methylene
chloride at 25° C. with polycarbonate calibration), ground to
[0157] Black Pearls 800 (Cabot Corporation, Leuven, Belgium): pearled
pigment carbon black having a mean primary particle size determined by
scanning electron microscopy of 17 nm, a BET surface area determined
according to ISO 4652 by nitrogen adsorption of 210 m2/g and an oil
adsorption number measured according to ISO 4656 with dibutyl phthalate
(DBP) of 65 ml/100 g.
[0158] Printex 85 (Evonik Degussa GmbH, Frankfurt/Main, Germany): pigment
carbon black having a mean primary particle size determined by scanning
electron microscopy of 16 nm, a BET surface area determined according to
ISO 4652 by nitrogen adsorption of 200 m2/g and an oil adsorption
number measured according to ISO 4656 with dibutyl phthalate (DBP) of 48
ml/100 g.
[0159] Chromium rutile pigment
b4 Iron oxide pigment c1
[0160] Pentaerythritol tetrastearate (PETS)
[0161] Glycerol monostearate (GMS)
[0162] Stearyl stearate
[0163] LDPE wax (low-density polyethylene wax)
[0164] Linear polyethylene terephthalate having an intrinsic viscosity of
0.665 measured in phenol/o-dichlorobenzene (1:1 parts by weight) at
[0165] Linear polybutylene terephthalate having a melt volume flow rate of
45 cm2/10 min at 250° C. and 2.16 kg load
[0166] Emulsion ABS granules with an A:B:S weight ratio of 20:24:56
[0167] Mass ABS granules with an A:B:S weight ratio of 25:10:65
[0168] Graft polymer consisting of 28 wt. % styrene-acrylonitrile
copolymer with a ratio of styrene to acrylonitrile of 71 to 29 parts by
weight as shell on 72 wt. % of a particulate graft base as core
consisting of 46 parts by weight, based on the graft base, of silicone
rubber and 54 parts by weight, based on the graft base, of butyl acrylate
rubber, prepared by the emulsion polymerisation process.
[0169] Emulsions ABS graft in powder form with an A:B:S weight ratio of
[0170] Emulsions ABS graft in powder form with an A:B:S weight ratio of
7:75:18
[0171] Polymethyl methacrylate (PMMA)-grafted silicone-butyl acrylate
composite rubber graft in powder form, prepared by emulsion
polymerisation, consisting of a graft shell of 10 wt. %, based on the
graft, of polymethyl methacrylate and 90 wt. %, based on the graft, of
particulate silicone-butyl acrylate composite rubber base with a silicone
content, based on the silicone-butyl acrylate composite rubber base, of
30 wt. % and a butyl acrylate content, based on the silicone-butyl
acrylate composite rubber base, of 70 wt. %.
[0172] Styrene-acrylonitrile copolymer (SAN) with an A:S weight ratio of
[0173] Bisphenol A-based oligophosphate
q=degree of oligomerisation g2
[0174] Polytetrafluoroethylene (PTFE) concentrate consisting of 50 wt. %
styrene-acrylonitrile (SAN) copolymer and 50 wt. % PTFE
[0175] Stabilisers
[0176] Talc with a d50 of 1.2 μm.
[0177] Water
A) Carbon Black Masterbatches
[0178] The carbon black/demoulding agent masterbatches 1 to 14 listed in
table 1 under component B were prepared as described below.
A.1) Mixing Units Used
[0179] A type MDK/E 46 co-kneader from Buss was used. FIG. 1 shows the
structure in principle. The mixture components were metered into the feed
hopper 1 of the Buss co-kneader 2. The mixture components were there
taken into the co-kneader 2 by the screw (not shown) located on the
inside and were conveyed axially. In the region of the retaining ring 3,
accumulation of the mixture components took place, as well as melting of
the demoulding agent, intimate mixing of the mixture components and
dispersion of the carbon black. In the region of the retaining ring 4,
accumulation of the melt mixture took place, as well as further mixing of
the mixture components and dispersion of the carbon black. In the regions
between the feed hopper 1 and the retaining ring 3, the retaining ring 3
and the retaining ring 4 and the retaining ring 4 and the single-shaft
extruder 5 flange-mounted on the co-kneader 2, the kneading blades were
so arranged on the screw shaft that the melt mixture was conveyed axially
in the direction of the single-shaft extruder 5. In the single-shaft
extruder 5, the melt mixture was conveyed through the single-shaft screw
(not shown) and degassed at the degassing opening 6. At the end of the
single-shaft extruder 5 there is a spray head (not shown) having a nozzle
plate with 8 holes, each of which has a diameter of 2.5 mm. The melt
strands emerging from the nozzle plate were then granulated by means of a
hot-face water-ring granulating system (not shown) known to the person
skilled in the art to form granules having a length of up to 5 mm and
were cooled. The water adhering to the granules was then removed by means
of a vibro screen (not shown) and subsequent drying in a fluidised bed
dryer (not shown).
Test Arrangement 2
[0180] As arrangement 1 but without retaining ring 3 (see FIG. 2), so that
the energy input of the co-kneader in test arrangement 2 is lower as
compared with test arrangement 1.
Test Arrangement 3
[0181] As arrangement 1 but with an additional metering hopper 7
downstream of retaining ring 3 (see FIG. 3), so that the carbon black is
added in two portions in two steps via metering hoppers 1 and 7.
Test Arrangement 4
[0182] An Evolum HT32 twin-screw extruder from Clextral with a housing
inside diameter of 32 mm, a ratio of screw outside diameter to screw
inside diameter of 1.55 and a length-to-diameter ratio of 44 was used.
The twin-screw extruder has a housing consisting of 11 parts, in which
two co-rotating, intermeshing shafts (not shown) are arranged.
[0183] The structure of the extruder used is shown in principle in FIG. 4.
[0184] Metering of a portion of the pulverulent carbon black and of the
pulverulent demoulding agent was carried out by means of differential
proportioning weighers (not shown) via the feed hopper 8 into the main
intake of the extruder in housing 9 (intake housing).
[0185] In the region of housings 9 to 11 there is a feed zone in which the
mixture constituents are taken into the extruder in the solid state and
conveyed further.
[0186] In the region of housing 12 there is a plastification zone, which
consists of various conveying double- and triple-threaded kneading blocks
of different widths and a return element at the end of the zone.
[0187] In the region of housings 13 and 14 there is a mixing zone, which
consists of various mixing, kneading and feed elements.
[0188] In housing 15, the remaining portion of the pulverulent carbon
black is metered into the extruder via a lateral feed device.
[0189] In the region of housings 16 and 17 there is a further mixing zone
which consists of various mixing, kneading and feed elements.
[0190] In housing part 18 (degassing housing) there is the degassing
opening 20, which is connected to a suction device (not shown).
[0191] In housing 19 (discharge housing) there the pressure build-up zone,
which is followed by a spray head (not shown) having a nozzle plate with
6 holes, each of which has a diameter of 3.2 mm.
Test Arrangement 5
[0192] A type MDK/E 100 co-kneader from Buss was used. The structure
corresponded in principle to the structure of test arrangement 3.
Test Arrangement 6
[0193] A shear roller unit was used, as is described, for example, in EP
0707037 B1.
A.2) Preparation of Masterbatches B1-B16
[0194] Carbon black/demoulding agent masterbatches B1 to B4 were prepared
using the test arrangements, process parameters and formulations
[0195] The specific mechanical energy input (SME) indicated in Table 2 was
determined according to equation 1.
SME = 2 π M n m . 60000 Equation 1
SME: specific mechanical energy input in kWh/kg M: torque in Nm n: speed
in l/min {dot over (m)}: throughput in kg/h
[0196] Carbon black/demoulding agent masterbatch B5 was prepared using
test arrangement 5 from 58% b1 and 42% c1.
[0197] Carbon black/demoulding agent masterbatches B6 and B7 were prepared
using test arrangement 6 from 50% b1 and 50% c1 (B6) and 65% b1 and 35%
c1 (B7).
[0198] Carbon black/demoulding agent masterbatches B8 to B14 were prepared
indicated in Table 3. The specific mechanical energy input (SME)
indicated in Table 3 was calculated according to equation 1.
[0199] The carbon black/polycarbonate masterbatch B15 was supplied by
Color System S.p.a. Carbon black/polycarbonate masterbatch consisting of
15 wt. % b1 and 85 wt. % of a bisphenol A-based polycarbonate having a
relative solution viscosity of 1.28 (measured in methylene chloride at
[0200] The carbon black/polyethylene masterbatch B16 was supplied by Cabot
(trade name: Plasblak PE6130). Carbon black/polyethylene masterbatch
containing 50 wt. % carbon black.
B) PC Moulding Compositions
B.1) Mixing Units Used
Test Arrangement 7
[0201] An Evolum HT32 twin-screw extruder from Clextral having a housing
inside diameter of 1.55 and a length-to-diameter ratio of 36 was used.
The twin-screw extruder has a housing consisting of 9 parts, in which two
co-rotating, intermeshing shafts (not shown) are arranged.
[0202] The structure of the extruder used is shown in principle in FIG. 5
[0203] Metering of all the components was carried out by means of
differential proportioning weighers (not shown) via the feed hopper 8a
into the main intake of the extruder in housing 9a (intake housing).
[0204] In the region of housings 9a to 13a there is a feed zone in which
the mixture constituents are taken into the extruder in the solid state
and conveyed further.
[0205] In the region of housings 14a and 16a there is a plastification
zone, which consists of various conveying double- and triple-threaded
kneading blocks of different widths and a return element at the end of
[0206] In the region of housings 16a and 18a there is a mixing zone which
consists of various mixing and feed elements.
[0207] In housing part 18a (degassing housing) there is the degassing
opening 20a, which is connected to a suction device (not shown).
[0208] In housing 19a (discharge housing) there is the pressure build-up
zone, which is followed by a spray head (not shown) having a nozzle plate
with 6 holes, each of which has a diameter of 3.2 mm.
Test Arrangement 8
[0209] As test arrangement 7 but with an injection valve 22 arranged at
the end of housing part 21, via which the liquid additive 1 is metered in
formulations 20 and 21 (FIG. 6).
Test Arrangement 9
[0210] A ZSK 25 WLE twin-screw extruder from Coperion Werner & Pfleiderer
having a housing inside diameter of 25.2 mm, a ratio of screw outside
diameter to screw inside diameter of 1.50 and a length-to-diameter ratio
of 48 was used. The twin-screw extruder has a housing consisting of 13
parts, in which two co-rotating, intermeshing shafts (not shown) are
arranged. The structure of the extruder used is shown in principle in
FIG. 7. Metering of all the components was carried out by means of
differential proportioning weighers (not shown) via the feed hopper 8c
into the main intake of the extruder in housing 9c (intake housing). In
the region of housings 9c to 12c there is a feed zone in which the
conveyed further. In the region of housings 13c and 23 (intermediate
plate) there is a plastification zone, which consists of various
conveying double- and triple-threaded kneading blocks of different widths
and a return element at the end of the zone. In the region of housings
14c to 17c there are two mixing zones, which consist of various mixing
and feed elements. In housing part 18c there is the degassing opening
20c, which is connected to a suction device (not shown). In housing 19c
(discharge housing) there is the pressure build-up zone, which is
followed by a spray head (not shown) having a nozzle plate with 2 holes,
each of which has a diameter of 4.5 mm.
Test Arrangement 10
[0211] A ZSK 133Sc twin-screw extruder from Coperion Werner & Pfleiderer
having a housing inside diameter of 134.4 mm, a ratio of screw outside
diameter to screw inside diameter of 1.55 and a length-to-diameter ratio
of 31.5 was used. The twin-screw extruder has a housing consisting of 10
FIG. 8. Metering of all the components was carried out by means of
differential proportioning weighers (not shown) via the feed hopper 8d
into the main intake of the extruder in housing 9d (intake housing). In
the region of housings 9d to 11d there is a feed zone in which the
conveyed further. In the region of housings 12d, 23a and 13d there is a
plastification zone, which consists of various conveying double- and
triple-threaded kneading blocks of different widths and a return element
at the end of the zone. In the region of housings 14d, 24a and 18d there
is a mixing zone which consists of various mixing and feed elements. In
housing part 18d (degassing housing) there is the degassing opening 20d,
which is connected to a suction device (not shown). In housing 19d
followed by a spray head (not shown) having a nozzle plate with 60 holes,
Test Arrangement 11
[0212] A ZSK 92Mc twin-screw extruder from Coperion Werner & Pfleiderer
having a housing inside diameter of 92.8 mm, a ratio of screw outside
of 40 was used. The twin-screw extruder has a housing consisting of 10
FIG. 9. Metering of all the components was carried out by means of
differential proportioning weighers (not shown) via the feed hopper 8e
into the main intake of the extruder in housing 9e (intake housing). In
the region of housings 9e to 13e there is a feed zone in which the
conveyed further. In the region of housings 13e and 14e there is a
at the end of the zone. In housing part 18e (degassing housing) there is
the degassing opening 20e, which is connected to a suction device (not
shown). In housing part 21a there is an injection valve 22a, via which
PETSLoxiolPS613,5Spezial is added in liquid form. In the region of
housings 21a and 26 there is a mixing zone which consists of various
mixing and feed elements. In housing 19e (discharge housing) there is the
pressure build-up zone, which is followed by a spray head (not shown)
having a nozzle plate with 60 holes, each of which has a diameter of 4.5
B.2) Preparation of the PC Moulding Compositions
[0213] The process parameters used in the examples for the preparation of
PC moulding compositions are shown in Table 4. The specific mechanical
energy input (SME) indicated in Table 4 was determined according to
[0214] The PC moulding composition granules prepared in the examples were
processed by an injection moulding process to sheets with a glossy
surface having a size of 150 mm×105 mm×3.2 mm and to test
specimens having a size of 80 mm×10 mm×4 mm for the Izod
notched impact test according to ISO 180/1A.
[0215] The sheets with a glossy surface were produced on a type FM160
injection moulding machine from Klocknrer. This injection moulding
machine has a cylinder diameter of 45 mm. To that end, the PC moulding
composition granules were predried at 110° C. within a period of 4
hours. Processing by injection moulding was carried out under the
conditions characteristic for polycarbonates or polycarbonate/ABS blends
or polycarbonate/PET blends. An injection moulding tool with a gloss
finish (ISO N1) was used for the production of the sheets.
[0216] The number of surface defects on the sheets with a glossy surface
was measured as described hereinbefore. 3 plates were measured in each
case, and the arithmetic mean was determined from the results.
[0217] The Izod notched impact strength of the compound prepared was
determined according to ISO 180/1A on the test specimens for the notched
impact test. To that end, in each case 10 test specimens were tested, and
the arithmetic mean was determined from these results.
[0218] An elastomer-containing polycarbonate blend having a melt volume
flow rate (MVR) of 27 cm3/10 min (measured according to ISO 1133 at
260° C. and 5 kg) was prepared according to formulation 1 (Table
1) using test arrangement 7. Carbon black powder according to Table 1 was
added as the carbon black component.
[0219] For the preparation of the compound, a premix was first prepared
from components b (carbon black component), c (demoulding agent) and g
(additives) and also a9 given in Table 1 in the mentioned amounts, Mixing
of the premix was carried out in a container mixer from Mixaco (type CM30
with Z tool) for 4.5 minutes at a speed of 300 l/min and a degree of
filling of the mixer of 80%.
[0220] The premix and the remaining mixture constituents listed in Table 1
where then metered separately from one another, in each case by means of
a differential proportioning weigher (not shown), via the feed hopper 8a
into the main intake into housing 9a of the extruder.
[0221] In the plastification zone and the mixing zone in the region of
housings 14a, 16a and 18a, the meltable mixture constituents were melted,
all the mixture constituents were dispersed and the melt mixture was
homogenised, the melt being degassed in the penultimate housing part 18a.
[0222] The melt strands emerging from the nozzle plate were cooled in a
water bath and then granulated by means of a strand granulator.
[0223] The process parameters of the extruder and the number, measured as
described above, of surface defects, based on one square centimetre, and
the measured notched impact strength according to ISO 180/1A are listed
in Table 4 under Example 1.
[0224] An elastomer-containing polycarbonate blend having a melt volume
flow rate (MVR) of 27 cm-1/10 min (measured according to ISO 1133 at
260° C. and 5 kg) was prepared according to formulation 4 (see
Table 1) using test arrangement 7. Carbon black/demoulding agent
masterbatch granules according to Table 1, which were prepared as
described under A.2, were added as the carbon black component.
[0225] For the preparation of the compound, a premix was first prepared
from components b (carbon black component), f (elastomer) and g
(additives) given in Table 1 in the mentioned amounts. Preparation of the
premix and compounding of the moulding composition were carried out as
[0226] The process parameters of the extruder and the number, measured as
in Table 4 under Example 2.
[0227] A comparison of Example 2 according to the invention with
Comparison Example 1 shows that, when the carbon black/demoulding agent
masterbatch is used, the number of surface defects is markedly smaller
and the notched impact strength at 23° C. and at 0° C. is
markedly higher than when the carbon black powder is used. Both these
findings indicate better dispersion of the carbon black when the carbon
black/demoulding agent masterbatch is used, even though the specific
mechanical energy input (SME) has remained almost the same.
[0228] An elastomer-containing polycarbonate blend having a melt volume
flow rate (MVR) of 18 cm3/O-min (measured according to ISO 1133 at
260° C. and 5 kg) was prepared according to formulation 18 (see
Table 1) using test arrangement 7. Carbon black powder according to Table
1 was added as the carbon black component.
[0229] For the preparation of the compound, a premix was first prepared
(additives) and also f4 given in Table 1 in the mentioned amounts.
Preparation of the premix and compounding of the moulding composition
[0230] The process parameters of the extruder and the number, measured as
described above, of surface defects, based on one square centimetre, are
listed in Table 4 under Example 3.
[0231] An elastomer-containing polycarbonate blend having a melt volume
flow rate (MVR) of 18 cm3/10 min (measured according to ISO 1133 at
260° C. and 5 kg) was prepared according to formulation 19 (see
[0232] For the preparation of the compound, a premix was first prepared
from components b (carbon black component) and g (additives) and also f4
given in Table 1 in the mentioned amounts. Preparation of the premix and
compounding of the moulding composition were carried out as described in
[0233] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 4.
[0234] A comparison of Example 4 according to the invention with
Comparison Example 3 shows that, when the carbon black/demoulding agent
than when the carbon black powder is used. Both these findings indicate
better dispersion of the carbon black when the carbon black/demoulding
agent masterbatch is used, even though the specific mechanical energy
input (SME) has remained the same. A comparison of Examples 1 to 4 shows
that, in the case of elastomer-containing polycarbonate blends with
markedly different melt volume flow rates too, the number of surface
defects when the carbon black/demoulding agent masterbatch is used is
markedly smaller than when the carbon black powder is used.
[0235] A flame-protected elastomer-containing polycarbonate blend was
prepared according to formulation 20 (see Table 1) using test arrangement
8. Carbon black powder according to Table 1 was added as the carbon black
[0236] For the preparation of the compound, a premix was first prepared
from components b (carbon black component), c (demoulding agent), g2, g3
and also f4 given in Table 1 in the mentioned amounts. Mixing of the
premix was carried out in a container mixer from Mixaco (type CM30 with Z
tool) for 4.5 minutes at a speed of 300 l/min and a degree of filling of
the mixer of 80%.
[0237] The premix and the remaining mixture constituents listed in Table 1
were then metered separately from one another, in each case by means of a
differential proportioning weigher (not shown), via the feed hopper 8b
into the main intake into housing 9b of the extruder.
[0238] In the plastification zone and the mixing zone in the region of
housings 12b and 13b, the meltable mixture constituents were melted, the
mixture constituents metered into the main intake were dispersed and the
melt mixture was homogenised. The melt was then degassed in housing part
18b. In housing part 21, liquid g1 (flameproofing agent) was added via an
injection valve 22 and intimately mixed with the melt in the subsequent
mixing zone in housing parts 14b and 19b.
[0239] The melt strands emerging from the nozzle plate were cooled in a
[0240] The process parameters of the extruder and the number, measured as
in Table 4 under Example 5.
[0241] A flame-protected elastomer-containing polycarbonate blend was
prepared according to formulation 21 (see Table 1) using test arrangement
8. Carbon black/demoulding agent masterbatch granules according to Table
1, which were prepared as described under A.2, were added as the carbon
[0242] For the preparation of the compound, a premix was first prepared
from components b (carbon black component), g2, g3 and also f4 given in
Table 1 in the mentioned amounts. Preparation of the premix and
[0243] The process parameters of the extruder and the number, measured as
in Table 4 under Example 6.
[0244] A comparison of Example 6 according to the invention with
Comparison Example 5 shows that, when the carbon black/demoulding agent
and the notched impact strength at 23° C. is higher than when the
carbon black powder is used. Both these findings indicate better
dispersion of the carbon black when the carbon black/demoulding agent
masterbatch is used, even though the specific mechanical energy input
(SME) has remained almost the same. A comparison of Examples 5 and 6 with
Examples 1 to 4 shows that, even when a liquid flameproofing agent is
added to an elastomer-containing polycarbonate blend, the number of
surface defects is markedly smaller when the carbon black/demoulding
agent masterbatch is used than when the carbon black powder is used.
[0245] A polycarbonate compound having a melt volume flow rate (MVR) of
9.5 cm3/10 min (measured according to ISO 1133 at 300° C. and
1.2 kg) was prepared according to formulation 22 (see Table 1) using test
arrangement 7. Carbon black powder according to Table 1 was added as the
carbon black component.
[0246] For the preparation of the compound, a premix was first prepared
from components b (carbon black component), c (demoulding agent) and also
a9 given in Table 1 in the mentioned amounts. Preparation of the premix
and compounding of the moulding composition were carried out as described
[0247] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 7.
[0248] A polycarbonate compound having a melt volume flow rate (MVR) of
1.2 kg) was prepared according to formulation 23 (see Table 1) using test
arrangement 7. Carbon black/demoulding agent masterbatch granules
according to Table 1, which were prepared as described under A.2, were
[0249] For the preparation of the compound, a premix was first prepared
[0250] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 8.
[0251] A comparison of Example 8 according to the invention with
Comparison Example 7 shows that, when the carbon black/demoulding agent
masterbatch is used, the number of surface defects is smaller than when
the carbon black powder is used. Both these findings indicate better
(SME) has remained almost the same.
[0252] A polycarbonate compound having a melt volume flow rate (MVR) of 5
cm3/10 min (measured according to ISO 1133 at 300° C. and 1.2
kg) was prepared according to formulation 24 (see Table 1) using test
[0253] For the preparation of the compound, a premix was first prepared
[0254] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 9.
[0255] A polycarbonate compound having a melt volume flow rate (MVR) of 5
kg) was prepared according to formulation 25 (see Table 1) using test
[0256] For the preparation of the compound, a premix was first prepared
[0257] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 10.
[0258] A comparison of Example 10 according to the invention with
Comparison Example 9 shows that, when the carbon black/demoulding agent
(SME) has remained the same.
[0259] A high-temperature-resistant polycarbonate compound (Vicat
softening temperature 203° C. measured according to ISO 306 at 50
N; 120° C./h) having a melt volume flow rate (MVR) of 8
cm3/10 min (measured according to ISO 1133 at 330° C. and
2.16 kg) was prepared according to formulation 28 (see Table 1) using
test arrangement 7. Carbon black powder according to Table 1 was added as
the carbon black component.
[0260] For the preparation of the compound, a premix was first prepared
[0261] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 11.
[0262] A high-temperature-resistant polycarbonate compound (Vicat
kg) was prepared according to formulation 29 (see Table 1) using test
[0263] For the preparation of the compound, a premix was first prepared
[0264] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 12.
[0265] A comparison of Example 12 according to the invention with
Comparison Example 11 shows that, when the carbon black/demoulding agent
input (SME) has remained the same.
[0266] A high-temperature-resistant polycarbonate compound (Vicat
softening temperature 184° C. measured according to ISO 306 at 50
N; 120° C./h) having a melt volume flow rate (MVR) of 10
2.16 kg) was prepared according to formulation 30 (see Table 1) using
[0267] For the preparation of the compound, a premix was first prepared
from components b (carbon black component) and a9 given in Table 1 in the
mentioned amounts. Preparation of the premix and compounding of the
moulding composition were carried out as described in Example 1.
[0268] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 13.
[0269] A high-temperature-resistant polycarbonate compound (Vicat
N; 120° C./h) having a melt volume flow rate (MVR) of cm3/10
min (measured according to ISO 1133 at 300° C. and 1.2 kg) was
prepared according to formulation 31 (see Table 1) using test arrangement
7. Carbon black/demoulding agent masterbatch granules according to Table
[0270] For the preparation of the compound, a premix was first prepared
[0271] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 14.
[0272] A comparison of Example 14 according to the invention with
Comparison Example 13 shows that, when the carbon black/demoulding agent
input (SME) has remained almost the same.
[0273] A comparison of Examples 7 to 14 shows that, in the case of
polycarbonate compounds with markedly different melt volume flow rates
and Vicat softening temperatures too, the number of surface defects is
markedly smaller when the carbon black/demoulding agent masterbatch is
used than when the carbon black powder is used.
[0274] A comparison of Examples 7 to 14 with Examples 1 to 4 shows that,
even in the case of pure polycarbonate compounds without the addition of
elastomer-containing components, the number of surface defects is
[0275] An elastomer-containing polycarbonate blend having a melt volume
flow rate (MVR) of 17 cm3/10 min (measured according to ISO 1133 at
260° C. and 5 kg) was prepared according to formulation 35 (Table
1) using test arrangement 9. Carbon black powder according to Table 1 was
[0276] For the preparation of the compound, a premix was first prepared
from components b (carbon black component), c (demoulding agent), g
(additives) and f6 given in Table 1 in the mentioned amounts. Mixing of
the premix was carried out in a container mixer from Mixaco (type CM30
[0277] The premix and the remaining mixture constituents listed in Table 1
differential proportioning weigher (not shown), via the feed hopper 8c
into the main intake into housing 9c of the extruder.
[0278] In the plastification zone in the region of housings 12c and 13c,
the meltable mixture constituents were melted and all the mixture
constituents were dispersed. In the mixing zone in the region of housings
24, 16c, 25 and 17c, the melt mixture was intimately mixed and
homogenised. The melt was degassed in the penultimate housing part 18c.
[0279] The melt strands emerging from the nozzle plate were cooled in a
[0280] The process parameters of the extruder are listed in Table 4 under
Example 15. The notched impact strength at different ambient
temperatures, measured according to ISO 180/1A, is shown in diagrams FIG.
11 for an injection moulding material temperature of 260° C. and
FIG. 12 for an injection moulding material temperature of 300° C.
Each measuring point in the diagrams represents the mean value of 10
measurements. The number pairs additionally given at the measuring points
indicate the number of ductile fractured or brittle fractured test
specimens. "10/0" means, for example, that all 10 test specimens tested
are ductile fractured.
[0281] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 36 (see
Table 1) using test arrangement 9. Carbon black/demoulding agent
masterbatch granules according to Table 1 which were prepared as
[0282] For the preparation of the compound, a premix was first prepared
from components b (carbon black component), g (additives) and f6 given in
[0283] The process parameters of the extruder are listed in Table 4 under
Example 16. The notched impact strength at different ambient
[0284] A comparison of Example 16 according to the invention with
Comparison Example 15 shows that, when the carbon black/demoulding agent
masterbatch is used, the notched impact strength is markedly higher and
the transition from ductile to brittle fracture behaviour occurs at lower
temperatures than when the carbon black powder is used. This indicates
[0285] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 17 (see
Table 1) using test arrangement 7. B16 (carbon black/polyethylene
masterbatch Plasblak PE6130 (50% carbon black) from Cabot) according to
Table 1 was added as the carbon black component.
[0286] For the preparation of the compound, a premix was first prepared
(additives) and f3 given in Table 1 in the mentioned amounts. Preparation
of the premix and compounding of the moulding composition were carried
out as described in Example 1.
[0287] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 17.
[0288] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 16 (see
Table 1) using test arrangement 7. The carbon black/polycarbonate
masterbatch B15 (PC Black 91024 (15% carbon black) from Color Systems)
according to Table 1 was added as the carbon black component.
[0289] For the preparation of the compound, a premix was first prepared
(additives) and also a9 given in Table 1 in the mentioned amounts.
[0290] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 18.
[0291] An elastomer-containing polycarbonate blend having a melt volume
[0292] For the preparation of the compound, a premix was first prepared
from components b (carbon black component), g (additives) and f3 given in
[0293] The process parameters of the extruder and the number; measured as
listed in Table 4 under Example 19.
[0294] A comparison of Example 19 according to the invention with
Comparison Examples 17 and 18 shows that, when the carbon
black/demoulding agent masterbatch is used, the number of surface defects
is markedly smaller than when masterbatches based on polyethylene (B16)
or polycarbonate (B15) are used. Both these findings indicate better
[0295] An elastomer- and polyester-containing polycarbonate blend having a
melt volume flow rate (MVR) of 12 cm3/10 min (measured according to
ISO 1133 at 260° C. and 5 kg) was prepared according to
formulation 32 (Table 1) using test arrangement 10. Carbon black powder
[0296] For the preparation of the compound, a premix was first prepared
(additives) and also a8 given in Table 1 in the mentioned amounts. Mixing
of the premix was carried out in a container mixer from Mixaco (type
CM1000 with MB tool) for 4.5 minutes at a speed of 425 l/min and a degree
of filling of the mixer of 80%.
[0297] The premix and the remaining mixture constituents listed in Table 1
differential proportioning weigher (not shown), via the feed hopper 8d
into the main intake into housing 9d of the extruder.
[0298] In the plastification zone in the region of housings 12d, 23a and
13d, the meltable mixture constituents were melted and all the mixture
14d, 24a and 18d, the mixture constituents were intimately mixed and the
melt mixture was homogenised. The melt mixture was degassed in the
penultimate housing part 8d.
[0299] The melt strands emerging from the nozzle plate were cooled in a
[0300] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 20.
[0301] An elastomer- and polyester-containing polycarbonate blend having a
formulation 33 (Table 1) using test arrangement 10. B86 (carbon
black/polyethylene masterbatch Plasblak PE6130 (50% carbon black) from
Cabot) according to Table 1 was added as the carbon black component.
[0302] For the preparation of the compound, a premix was first prepared
(additives) and also a8 given in Table 1 in the mentioned amounts.
were carried out as described in Example 20.
[0303] The process parameters of the extruder as well as the number,
measured as described above, of surface defects, based on one square
centimetre, are listed in Table 4 under Example 21.
[0304] An elastomer-containing polycarbonate blend having a melt volume
flow rate (MVR) of 12 cm3/10 min (measured according to ISO 1133 at
260° C. and 5 kg) was prepared according to formulation 34 (see
Table 1) using test arrangement 10. Carbon black/demoulding agent
[0305] For the preparation of the compound, a premix was first prepared
[0306] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 22.
[0307] A comparison of Example 22 according to the invention with
Comparison Examples 20 and 21 shows that, for elastomer- and
polyester-containing polycarbonate blends too, the number of surface
defects is markedly smaller when the carbon black/demoulding agent
masterbatch is used than when carbon black powder and a carbon
black/polyethylene masterbatch according to the prior art are used. Both
these findings indicate better dispersion of the carbon black when the
carbon black/demoulding agent masterbatch is used, even though the
specific mechanical energy input (SME) has remained almost the same.
[0308] At the same time it is shown that, even with an extruder having a
larger screw outside diameter (133 mm), the number of surface defects is
used than when carbon black powder or carbon black masterbatch according
to the prior art is used.
[0309] A polycarbonate compound having a melt volume flow rate (MVR) of 19
kg) was prepared according to formulation 26 (see Table 1) using test
arrangement 11. Carbon black powder according to Table 1 was added as the
[0310] For the preparation of the compound, a premix was first prepared
CM1000 with MB tool). Components b, g and a8 were first introduced into
the mixing container and mixed for 2 minutes at a speed of 250 l/min and
a degree of filling of the mixer of 80%. Component c was then added to
the premixed components in the mixing container and mixed for 1.5 minutes
at a speed of 350 l/min.
[0311] The premix and the remaining mixture constituents listed in Table 1
differential proportioning weigher (not shown), via the feed hopper 8e
into the main intake into housing 9e of the extruder.
[0312] In the plastification zone and the mixing zone in the region of
housings 13e and 14e, the meltable mixture constituents were melted and
all the mixture constituents were dispersed. In housing 18e, the melt was
degassed. In housing 21a, liquid g1 (flameproofing agent) was injected
into the melt via an injection nozzle 22a and intimately mixed with the
melt in the subsequent mixing zone in the region of housings 21a, 26 and
19e, and the melt mixture was homogenised.
[0313] The melt strands emerging from the nozzle plate were cooled in a
[0314] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 23.
[0315] A polycarbonate compound having a melt volume flow rate (MVR) of 19
cm3/10 min (measured according to ISO 1133 at 30° C. and 1.2
kg) was prepared according to formulation 27 (see Table 1) using test
arrangement 11. Carbon black/demoulding agent masterbatch granules
[0316] For the preparation of the compound, a premix was first prepared
a8 given in Table 1 in the mentioned amounts. Mixing of the premix was
carried out in a container mixer from Mixaco (type CM1000 with MB tool).
Components b, g and a8 were first introduced into the mixing container
and mixed for 2 minutes at a speed of 250 l/min and a degree of filling
of the mixer of 80%. Component c was then added to the premixed
components in the mixing container and mixed for 1.5 minutes at a speed
of 350 l/min.
[0317] Compounding of the moulding composition was carried out as
described in Example 23.
[0318] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 24.
[0319] A comparison of Example 24 according to the invention with
Comparison Example 23 shows that, when the carbon black/demoulding agent
input (SME) was higher in Example 23 than in Example 24.
[0320] At the same time it is shown that, for a polycarbonate compound
too, in an extruder having a larger screw outside diameter (92 mm), the
number of surface defects is markedly smaller when the carbon
black/demoulding agent masterbatch is used than when carbon black powder
[0321] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 10 (see
masterbatch granules containing 40 wt. % carbon black according to Table
[0322] For the preparation of the compound, a premix was first prepared
[0323] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 25.
[0324] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 12 (see
masterbatch granules containing 45 wt. % carbon black according to Table
[0325] The procedure in the preparation of the polycarbonate blend
corresponded to that of Example 25.
[0326] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 26.
[0327] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 9 (see
masterbatch granules containing 50 wt. % carbon black according to Table
[0328] The procedure in the preparation of the polycarbonate blend
[0329] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 27.
[0330] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 6 (see
masterbatch granules containing 58 wt. % carbon black according to Table
[0331] The procedure in the preparation of the polycarbonate blend
[0332] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 28.
[0333] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 11 (see
masterbatch granules containing 60 wt. % carbon black according to Table
[0334] The procedure in the preparation of the polycarbonate blend
[0335] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 29.
[0336] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 8 (see
masterbatch granules containing 65 wt. % carbon black according to Table
[0337] The procedure in the preparation of the polycarbonate blend
[0338] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 30.
[0339] A comparison of Examples 25 to 30 according to the invention with
Comparison Example 1 shows that, even when carbon black/demoulding agent
masterbatches having carbon black contents varying from 40 wt. % to 65
wt. % are used, the number of surface defects is markedly lower than when
carbon black powder is used. With a carbon black content of 65 wt. % in
the masterbatch (Example 30), however, the number of surface defects is
higher than with 40 wt. % to 60 wt. %, so that 65 wt. % represents the
upper carbon black concentration for good dispersion.
[0340] In tests with carbon black concentrations less than 40 wt. %, it
was not possible to form a strand because the carbon black-demoulding
agent composition had too low a viscosity and was tacky. In the tests,
therefore, a carbon black concentration of 40 wt. % represented the lower
carbon black concentration which could still be processed without
[0341] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 7 (see
[0342] For the preparation of the compound, a premix was first prepared
[0343] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 31.
[0344] A comparison of Examples 2, 27 and 31 according to the invention
with Comparison Example 1 shows that, when carbon black/demoulding agent
masterbatches produced either using a co-kneader or using a twin-screw
extruder or using shear rollers are used, the number of surface defects
is markedly smaller than when carbon black powder is used.
[0345] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 13 (see
Table 1) using test arrangement 7. For the preparation of the compound, a
premix was first prepared from components b (carbon black component), g
[0346] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 32.
[0347] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 14 (see
Table 1) using test arrangement 7. The procedure in the preparation of
the polycarbonate blend corresponded to that of Example 32.
[0348] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 33.
[0349] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 15 (see
[0350] The process parameters of the extruder and the number, measured as
listed in Table 4 under Example 34.
[0351] A comparison of Examples 27, 32, 33 and 34 according to the
invention with Comparison Example 1 shows that, with c1 or c3 or c4 in
the carbon black/demoulding agent masterbatch, when the carbon
black/demoulding agent masterbatch so prepared is used, the number of
surface defects is markedly smaller than with carbon black powder.
Although with c2 in the carbon black/demoulding agent masterbatch, the
number of surface defects is larger when the carbon black/demoulding
agent masterbatch so prepared is used than with c1, c3 or c4, it is still
markedly smaller than with carbon black powder.
[0352] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 5 (see
[0353] The process parameters of the extruder and the number, measured as
in Table 4 under Example 35.
[0354] A comparison of Examples 2 and 35 according to the invention with
Comparison Example 1 shows that, with both b2 and b1 as carbon black in
surface defects is markedly smaller and the notched impact strength at
23° C. and at 0° C. is markedly higher than with carbon
[0355] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 3 (see
[0356] For the preparation of the compound, a premix was first prepared
[0357] The process parameters of the extruder and the number, measured as
in Table 4 under Example 36.
[0358] An elastomer-containing polycarbonate blend having a melt volume
260° C. and 5 kg) was prepared according to formulation 2 (see
[0359] For the preparation of the compound, a premix was first prepared
[0360] The process parameters of the extruder and the number, measured as
in Table 4 under Example 37.
[0361] A comparison of Examples 2, 36 and 37 according to the invention
with Comparison Example 1 shows that, when the carbon black/demoulding
agent masterbatches prepared in a co-kneader with different process
parameters and test arrangements are used, the number of surface defects
is markedly smaller and the notched impact strength at 23° C. and
at 0° C. is markedly higher than when the carbon black powder is
95 1 2 3 4 5 6 7 8
all amounts in wt % Comp. Invention Invention Invention Invention
a1 14.14
a2 42.1 73.3 73.3 73.3 73.3 73.34 73.3 73.3
a9 16.9
B1 1.49
B2 1.49
B3 1.49
B4 1.49
B5 1.29
B6 1.49
B7 1.15
b1 0.75
c1 0.73 0.16 0.34
f3 6.89 6.8 6.8 6.8 6.8 6.8 6.8 6.8
f7 17.6 17.52 17.52 17.52 17.52 17.52 17.52 17.52
g3 0.89 0.89 0.89 0.89 0.89 0.89 0.89 0.89
Component 9 10 11 12 13 14 15 16 17
all amounts in wt % Invention Invention Invention Invention Invention
Invention Invention Comp. Comp.
a2 73.3 73.21 73.34 73.44 73.21 73.21 73.21 62.58 73.3
a9 4.92
B8 1.49
B9 1.9
B10 1.25
B11 1.67
B12 1.9
B13 1.9
B14 1.9
B15 6.53
B16 1.94
c1 0.2 0.73 0.72
f3 6.8 6.8 6.8 6.8 6.8 6.8 6.8 6.82 6.15
f7 17.52 17.2 17.52 17.2 17.2 17.2 17.2 17.54 17
g3 0.89 0.89 0.89 0.89 0.89 0.89 0.89 0.88 0.89
Component 18 19 20 21 22 23 24 25
all amount in wt % Comp. acc. to inv. Comp. acc. to inv. Comp. acc. to
inv. Comp. acc. to inv.
a1 22 21.9
a2 42.2 42.2
a3 59.89 59.89
a4 95 95
a5 95 95
a9 4.44 4.44 4.44 4.44
B3 1.5 1 0.32
B5 0.28
b1 0.75 0.5 0.16 0.16
c1 0.75 0.4 0.4 0.24 0.4 0.28
f1 17.1 17.1
f2 8.84 8.84 15.8 15.8
f4 2.95 2.95 3 3
f7 9.4 9.4
g1 14.9 14.9
g2 0.8 0.8
g3 0.32 0.32 0.4 0.4 0 0 0 0
Component 26 27 28 29 30 31
a2 95.6
a3 62.4
a6 95 95
a7 95 95
a8 3.82 1.04
a9 4.54 4.54 4.84 4.72
B5 0.28 0.28 0.28
b1 0.16 0.16 0.16
c1 0.4 0.28 0.3 0.18
g3 0.02 0 0 0 0 0
Component 32 33 34 35 36
all amount in wt % Comp. Comp. acc. to inv. Comp. acc. to inv.
a2 48.61 48.76 48.47
a3 74.19 75.11
a8 1.04 0.94 1.03
B5 0.51
B16 0.59
b1 0.3 0.9
b3 0.25 0.25
b4 0.057 0.057
c1 0.4 0.2 0.18 0.73
d1 31.84 31.75 31.75
d2 0.561 0.5525 0.765
f5 14.95 14.91 14.95
f6 8.77 8.75
f7 13.21 13.14
g3 0.299 0.2975 0.347 0.89 0.89
g4 2 2 2
1st 2nd Housing
Carbon black/ housing housing single- Co-
demoulding Test Through- half co- half co- shaft Nozzle kneader
agent master- arrange- Formula- Carbon black put Speed Power SME kneader
kneader extruder head shaft
batch no. ment tion metering site kg/h min-1 kW kWh/kg ° C.
° C. ° C. ° C. ° C.
B1 1 50% b1 Feed hopper 1 9 190 3.4 0.378 30 30 40 95 30
B2 2 50% b1 Feed hopper 1 12 190 3.3 0.275 90 60 35 130 35
B3 3 50% b1 Feed hopper 1: 32% 20 250 3.8 0.190 60 35 75 110 35
50% c1 Feed hopper 7: 18%
B4 3 50% b2 Feed hopper 1: 20% 12 250 2.3 0.192 60 35 75 110 35
50% c1 Feed hopper 7: 30%
demoulding Test Through- Spec. Heating temperatures of the housing
agent master- arrange- Formula- Carbon black put Speed power 9 10 11
batch no. ment tion metering site kg/h min-1 kWh/kg ° C.
B8 4 50% b1 Feed hopper 8: 25% 25 200 0.084 30 60 65
50% c1 Housing part 15: 25%
B9 4 40% b1 Feed hopper 8: 10% 25 300 0.0096 30 60 65
60% c1 Housing part 15: 30%
B10 4 60% b1 Feed hopper 8: 15% 25 200 0.248 30 60 65
40% c1 Housing part 15: 45%
B11 4 45% b1 Feed hopper 8: 10% 25 300 0.037 30 60 65
55% c1 Housing part 15: 35%
B12 4 40% b1 Feed hopper 8: 20% 25 200 0.032 30 60 65
60% c3 Housing part 15: 20%
B13 4 40% b1 Feed hopper 8: 20% 25 200 0.073 30 60 65
60% c2 Housing part 15: 20%
B14 4 40% b1 Feed hopper 8: 20% 25 200 0.073 30 60 65
60% c4 Housing part 15: 20%
Heating temperatures of the housing parts:
Carbon black/ Nozzle
demoulding (not
agent master- 12 13 14 15 16 17 18 19 shown)
batch no. ° C. ° C. ° C. ° C. ° C.
° C. ° C. °C. ° C.
B8 65 65 65 70 50 50 50 35 110
B9 65 65 65 70 50 50 50 35 110
B10 65 65 65 70 50 50 50 35 130
B11 65 65 65 70 50 50 50 35 110
B12 65 65 65 70 50 50 50 35 110
B13 65 65 65 70 50 50 50 35 130
B14 65 65 65 70 50 50 50 35 115
Surface defects Notched impact Notched impact
Test Through- per cm2 strength strength
Formula- arrange- put Speed SME Mean of 3 at 23° C. at 0°
Example tion ment kg/h 1/min kWh/kg sheets kJ/m2 kJ/m2
1 Comparison 1 7 103 400 0.129 199 46.9 13.75
2 Invention 4 7 97 400 0.137 19 50.94 15.09
3 Comparison 18 7 92 400 0.145 53
4 Invention 19 7 92 400 0.145 24
5 Comparison 20 8 99 600 0.145 17 12.77
6 Invention 21 8 98 600 0.147 11 13.06
7 Comparison 22 7 62 350 0.188 12
8 Invention 23 7 64 350 0.182 9
9 Comparison 24 7 62 350 0.188 5
10 Invention 25 7 62 350 0.188 4
11 Comparison 28 7 52 350 0.224 257
12 Invention 29 7 52 350 0.224 34
13 Comparison 30 7 58 350 0.201 60
14 Invention 31 7 57 350 0.204 31
15 Comparison 35 9 20 400 0.247
16 Invention 36 9 20 400 0.24
17 Comparison 17 7 73 400 0.131 34
18 Comparison 16 7 73 400 0.131 63
19 Invention 4 7 75 400 0.133 18
20 Comparison 32 10 3100 187 0.131 2191
21 Comparison 33 10 3091 175 0.124 1122
22 Invention 34 10 3092 188 0.131 446
23 Comparison 26 11 2975 493 0.141 247
24 Invention 27 11 3003 485 0.132 11
25 Invention 10 7 95 400 0.14 6
26 Invention 12 7 95 400 0.14 6
27 Invention 9 7 90 400 0.148 10
28 Invention 6 7 95 400 0.14 5
29 Invention 11 7 95 400 0.14 5
30 Invention 8 7 90 400 0.148 21
31 Invention 7 7 90 400 0.148 11
32 Invention 13 7 90 400 0.148 7
33 Invention 14 7 95 400 0.14 48
34 Invention 15 7 95 400 0.14 6
35 Invention 5 7 97 400 0.137 23 56.2 19.22
36 Invention 3 7 97 400 0.137 19 48.3 16.16
37 Invention 2 7 97 400 0.137 17 52.73 15.93
Patent applications by Hans-Jüergen Thiem, Dormagen DE
Patent applications in class Oxygen atom other than as part of a carboxylic acid group, e.g., glycolic ester, etc. Patent applications in all subclasses Oxygen atom other than as part of a carboxylic acid group, e.g., glycolic ester, etc. User Contributions:
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