Title of Invention

SEMIAROMATIC POLYAMIDE MOLDING COMPOSITIONS

Abstract A polyamide molding composition with the following constitution is described: (A) from 30 to 100% by weight of at least one 10T/6T copolyamide, where this is composed of (A1) from 40 to 95 mol% of 10T units, formed from the monomers 1,10-decanediamine and terephthalic acid (A2) from 5 to 60 mol% of 6T units, formed from the monomers 1,6-hexanediamine and terephthalic acid (B) from 0 to 70% by weight of reinforcing materials and/or fillers (C) from 0 to 50% by weight of additives and/or further polymers where the entirety of components A to C is 100%, with the proviso that in component (A) up to 30 mol%, based on the entirety of the dicarboxylic acids, of the terephthalic acid can have been replaced by other aromatic, aliphatic, or cycloaliphatic dicarboxylic acids, and with the proviso that in component (A) up to 30 mol% of 1,10-decanediamine and respectively 1,6-hexanediamine, based on the entirety of the diamines, can have been replaced by other diamines, and with the proviso that not more than 30 mol% in component (A), based on the entirety of the monomers, can have been formed via lactams or amino acids. Uses of this polyamide molding composition are moreover described, as also are processes for the preparation of these polyamide molding compositions.
Full Text

DESCRIPTION
TECHNICAL FIELD
The present invention relates to polyamide molding
compositions based on a terephthalic acid copolyamide and to
processes for their preparation, and to uses thereof.
PRIOR ART
Known standard polyamides, such as PA6 and PA66, are easy to
process, and have high melting points and high heat deflection
temperatures, particularly when they have glass-fiber
reinforcement or comprise mineral fillers. However, they
typically have high water absorptions up to 10% on storage in
water. For many applications with stringent requirements for
dimensional stability, including under wet or moist
conditions, these aliphatic polyamides cannot be used. Water
absorption alters not only dimensions but also mechanical
properties. Water absorption reduces stiffness values and
strength values to a fraction of their previous levels. In
other words, problems arise when the standard polyamides are
used in applications with mechanical load in contact with
water or ambient moisture.
Long-chain aliphatic polyamides composed of aminoundecanoic
acid (PA11) or laurolactam (PA12), or composed of
dodecanediamine and dodecanedioic acid (PA1212) have low water
absorption but have undesirably low melting points below
200°C. PAll, PA12, and PA1212 have low modulus and strength,
even when dry. They are unsuitable for technical applications
at relatively high temperatures.


Semiaromatic polyamides of PA6T/6I type, as described
in US 4,607,073 have reduced water absorption when
compared with PA6 and PA66, and mechanical properties
are substantially retained after water absorption.
However, water absorption is still too high for
precision parts (swelling), melting points are likewise
too high, and the use of isophthalic acid markedly
lowers crystallinity and crystallization rate, and
there are problems with processability.
On the other hand, PA10T, as likewise disclosed in
US 4,607,073, has markedly reduced water absorption,
and mechanical properties do not change on storage in
water. The material is highly crystalline, and
crystallizes very rapidly, a result being freezing
within the nozzle during injection molding. Glass-
fiber-reinforced PA10T has very irregular surfaces.
Semiaromatic polyamides of PA6T/NDT/INDT type, as
described in US 4,617,342, or of PA6T/6I/66 type as
described in USRE34447E, or of PA6T/6/66 type as in
EP 0 299 444, or of PA6T/MPMDT type as in EP 0 522 027
and EP 0 561 886 have reduced water absorption when
comparison is made with PA6 and PA66, and mechanical
properties are retained after water absorption.
However, here again water absorption is still too high
for precision parts (swelling). According to
US 5,098,940, the polyphthalamides of the US RE34447E
mentioned and of the likewise abovementioned
US 4,617,342 also have long cycle times in injection
molding and require high mold temperatures which cannot
be achieved using water-heated molds.
The specification EP 0 659 799, EP 0 976 774,
EP 1 186 634, and EP 1 375 578 describe semiaromatic
polyamides composed of from 60 to 100 mol% of
terephthalic acid and from 60 to 100 mol% of a diamine
component composed of 1,9-nonanediamine and 2-methyl-


1,8-octanediamine. These products feature good
processability, excellent crystallinity, good heat
deflection temperature, low water absorption, good
chemicals resistance, and dimensional stability, and
toughness. However, 2-methyl-1,8-octanediamine is
currently not listed in the regulations either for
existing substances or for new substances, and is
therefore not approved in Europe. This inhibits rapid
product introduction in the European market.
The documents EP 1 710 482, EP 1 741 549, and
EP 1 741 553 claim multilayer pipes and multilayer
hoses for the transport of chemicals and/or gases at
high temperatures and multilayer structures with a
semiaromatic polyamide composed of from 60 to 100 mol%
of an aliphatic diamine having from 9 to 13 carbon
atoms and from 50 to 100 mol% of terephthalic acid
and/or naphthalenedicarboxylic acid. The examples use
PA9T, PA9N, PA12T, and PA12N, in each case with
100 mol% of aliphatic diamine having from 9 to 12
carbon atoms. The description points out that other
diamines, e.g. hexamethylenediamine, can be used within
a range in which the excellent properties of the
multilayer tubes, multilayer pipes, or multilayer
structures are not impaired, and in an amount which is
preferably 10 mol% or less.
EP 0 368 281 involves blends of ethylene-glycidyl
methacrylate copolymer optionally with polyarylate and
with a polyamide, prepared from an aliphatic or
alicyclic diamine and from an aromatic dicarboxylic
acid. Terephthalic acid is particularly emphasized as
aromatic dicarboxylic acid. In relation to the
aliphatic, linear or branched diamine having from 4 to
25 carbon atoms, said document mentions an enormous
variety of possibilities. In the context of the
enormous variety of possibilities mentioned, there is
no express indication that the individual members of


said list can also be used in the form of a mixture. If
the specific examples in said document are examined, it
is found that they disclose exclusively systems based
on 1,6-hexanediamine, terephthalic acid, and
isophthalic acid, or adipic acid (PA6T/6I and PA6T/66).
EP 0 697 429 very generally describes copolyamides
based on aliphatic diamines having from 4 to 14 carbon
atoms and terephthalic acid, having a particular
distribution of the segments. Said document gives a
wide variety of possibilities with regard to the
selection of the diamine. Preferred diamines are 1,6-
hexanediamine, 2-methyl-1,5-pentanediamine (MPMD), and
1,12-dodecanediamine. Preferred polyamides are PA6T/6I,
PA6T/66, PA6T/6, PA6T/66/6I, PA6T/66/6, PA12T/66,
PA12T/126, PA12T/6I, PA12T/12I, and PA12T/6. When the
specific examples are examined, they reveal only
systems with 1,6-hexanediamine, terephthalic acid,
adipic acid and caprolactam.
US 3,839,296 involves very generally systems of xT
structure, where an enormous list is given for the
diamine x. In the specific examples the only compound
cited is always x = 1,12-dodecanediamine.
The abstract of JP 2002293926 involves providing a
copolyamide in which the diamine (component a)
comprises 1,10-diaminodecane and in which, on the other
hand, the diacid always comprises terephthalic acid
and, if appropriate, comprises further systems, an
example being a further aromatic diacid differing from
terephthalic acid, or C4-20 diacids. A large list of
possible diamines is moreover cited as replacement for
1,10-decanediamine, but no specific indication is given
of use of a combination (mixture) . The specific
examples always use only 1,10-decanediamine. There is a
single example (comparative example 3) that uses
another diamine, replacing 1,10-decanediamine


completely by 1,6-hexanediamine in combination with
terephthalic acid and adipic acid.
BRIEF DESCRIPTION OF THE INVENTION
The invention is therefore based inter alia on the
object of providing a polyamide molding composition
improved over the prior art not only with respect to
mechanical properties, including under wet or moist
conditions, but also with respect to processing
possibilities. A further intention was to provide
moldings based on this molding composition, and
processes for the preparation of this molding
composition.
Accordingly, a polyamide molding composition with the
following constitution is presently and specifically
proposed:
(A) from 30 to 100% by weight of at least one
10T/6T copolyamide, where this is composed of
(A1) from 40 to 95 mol% of 10T units, formed
from the monomers 1,10-decanediamine and
terephthalic acid
(A2) from 5 to 60 mol% of 6T units, formed
from the monomers 1,6-hexanediamine and
terephthalic acid
(B) from 0 to 70% by weight of reinforcing
materials and/or fillers
(C) from 0 to 50% by weight of additives and/or
further polymers
where the entirety of components A to C is 100%.
Up to 30% of the monomers within component (A) can be
replaced here, and this means that the above applies
firstly with the proviso that in component (A) ,
independently of one another, in (Al) and/or (A2) up to
30 mol%, based on the entirety of the dicarboxylic


acids, of the terephthalic acid can have been replaced
by other aromatic, aliphatic, or cycloaliphatic
dicarboxylic acids having from 6 to 36 carbon atoms.
Secondly, furthermore, the above applies with the
proviso that in component (A) , independently of one
another, in (A1) and/or (A2) up to 30 mol% of 1,10-
decanediamine and respectively 1,6-hexanediamine, based
on the entirety of the diamines, can have been replaced
by other diamines having from 4 to 36 carbon atoms.
Finally, the above moreover applies with the proviso
that not more than 30 mol% in component (A) , based on
the entirety of the monomers, can have been formed via
lactams or amino acids.
However, it is preferable that this replacement of the
monomers within component (A) in accordance with the
above provisos amounts to less than 20%, and preferably
less than 10%, and it is particularly preferable to use
no such replacement at all. A further proviso that
applies overall is therefore that the concentration of
the entirety of the monomers which replace terephthalic
acid, 1,6-hexanediamine, and 1,10-decanediamine (i.e.
the total proportion of other aromatic, aliphatic, or
cycloaliphatic dicarboxylic acids having from 6 to 36
carbon atoms, and of other diamines having from 4 to 36
carbon atoms, and of lactams or aminoacids) does not
exceed 30 mol%, preferably 20 mol%, in particular
10 mol%, based on the entirety of the monomers used in
component A.
It has specifically and unexpectedly been found that
precisely the abovementioned ratios of the individual
components in the copolyamide lead to particular
properties. For example, it has been found that below a
concentration of 40 mol% of 10T the melting points of
the 10T/6T copolyamides rise rapidly, thus preventing


satisfactory processing of said compositions. The
proposed constitution leads to excellent mechanical
properties even under wet or moist conditions, and
unexpectedly high heat deflection temperatures are
achieved, particularly when reinforcing fibers are also
used.
The prior art does not particularly recommend the
specific combination of 1,10-decanediamine and 1,6-
hexanediamine, and there is certainly no indication in
the prior art of the specific molar ratios which can
provide the favorable properties presently found. Still
less is known from the prior art about the low water
absorption of a PA10T/6T combination, and nor is it
known from the prior art that this PA10T/6T combination
together with reinforcing fibers has high heat
deflection temperatures above 260°C.
The present invention accordingly provides a polyamide
molding composition with the following properties:
- high heat deflection temperature (melting
point above 270°C or HDT A greater than 260°C
for a PA reinforced with 50% of glass fibers)
- good processability (melting point below 320°
C; crystallization behavior)
- low water absorption ( water at 95°C)
- unaltered mechanical properties after water
absorption (e.g. wet tensile modulus of
elasticity > 100% of dry tensile modulus of
elasticity, wet yield strength or wet
breaking strength > 85% of dry yield strength
or dry breaking strength)
- good surface quality of glass-fiber-
reinforced products
high dimensional stability.


A first preferred embodiment is therefore one wherein
the melting point and respectively the temperature of
deflection to ISO-R 75, method A (DIN 53 461) of
component (A) and/or of the entire polyamide molding
composition is above 260°C or above 270°C, preferably
in the range from 270 to 320°C, particularly preferably
in the range from 270 to 310°C.
The ratios are moreover preferably adjusted in such a
way that the water sbsorption of component (A) and/or
of the entire polyamide molding composition is less
than 5% by weight, preferably less than 4% by weight
and in particular less than 3.5% by weight, e.g. after
240 h in water at 95°C.
It has moreover been found to be advantageous that the
ratio of wet:dry tensile moduli of elasticity is
greater than or equal to 0.95, preferably greater than
or equal to 1.00, with particular preference greater
than or equal to 1.05. It is likewise advantageous that
the ratio of wet:dry maximum tensile strengths is
greater than or equal to 0.85, preferably greater than
0.90, with particular preference greater than or equal
to 0.95. The maximum tensile strength corresponds to
the maximum strength in the tensile strain graph
determined to ISO 527.
For adequately high molecular weight and high relative
viscosity, together with good flowability and high MVR
(melt volume flow rate), it has proven advantageous
that the monomers used are adequately pure. In
particular in the case of the diamine, it is
advantageous to establish high purity, and it is
therefore preferable that the melting point of the
1,10-decanediamine used is above 63°C and/or that its
total diamine content is above 99%, and/or that its
aminonitrile content is below 0.5 percent, and/or that


its APHA (American Public Health Association color
index) color is below 10 units.
As in particular can be discerned from the graphs given
below, it has proven advantageous with regard to ideal
adjustment of melting point and respectively with
regard to water absorption that, within components (A),
the (A1) fractions make up from 40 to 90 mol% and that
the (A2) fractions make up from 10 to 60 mol%.
Particular preference is given here to the following
ratio: (A1) from 40 to 80 mol% and (A2) from 20 to
60 mol%, a particular ratio being the following: (Al)
from 40 to 75 mol% and (A2) from 25 to 60 mol%.
As explained above, it is preferable that the 10T/6T
copolyamide of component (A) is based in essence
exclusively, preferably completely exclusively, on
terephthalic acid as dicarboxylic acid, and/or that the
10T/6T copolyamide of component (A) is based in essence
exclusively, preferably completely exclusively, on
1,10-decanediamine for (Al) and 1,6-hexanediamine for
(A2) as diamine, and/or that component (A) is composed
in essence exclusively, preferably completely
exclusively, of the constituents (Al) and (A2).
According to another preferred embodiment, component
(B) involves at least to some extent glass fibers
and/or carbon fibers. Component (C) normally and
generally involves additives and/or further polymers,
for example selected from the following group: impact
modifiers, adhesion promoters, crystallization
accelerators or crystallization retarders, flow aids,
lubricants, mold-release agents, plasticizers,
stabilizers, processing aids, flame-retardant
additions, pigments, dyes and markers, antistatic
agents, nanoparticles in lamellar form, conductivity
additives, such as carbon black, graphite powder, or
carbon nanofibrils, residues from polymerization


processes, e.g. catalysts, salts and their derivatives,
and regulators, such as monoacids or monoamines.
In another embodiment, the inventive molding
composition also comprises moreover from 8 to 25% by
weight, preferably from 10 to 22% by weight, and in
particular from 10 to 18% by weight, of a flame
retardant (as one constituent of component (C) or
forming said component (C) in its entirety) . The flame
retardant is preferably halogen-free.
The flame retardant in component (C) or forming
component (C) in its entirety preferably encompasses
here from 60 to 100% by weight, with preference from 70
to 98% by weight, particularly from 80 to 96% by
weight, of a phosphinic salt and/or diphosphinic salt
(component (C1) ) and from 0 to 4 0% by weight,
preferably from 2 to 30% by weight, in particular from
4 to 20% by weight, of a nitrogen-containing synergist
and/or of a nitrogen- and phosphorus-containing flame
retardant (component (C2)).
Component (C2) preferably involves melamine or
condensates of melamine, e.g. melem, melam, or melon,
or reaction products of melamine with polyphosphoric
acid, or involves reaction products of condensates of
melamine with polyphosphoric acid, or involves a
mixture thereof.
Melamine polyphosphate is particularly preferred as
component (C2) . These flame retardants are known from
the prior art. Reference is made in this connection to
DE 103 46 3261, and the disclosure of said
specification is expressly incorporated herein in this
regard.
A phosphinic salt of the general formula (I) and/or
formula (II) and/or their polymers is preferred as

component (C1)

in which
R1 and R2 are identical or different and are preferably
C1-C8-alkyl, linear or branched, and/or aryl;
R3 is C1-C10-alkylene, linear or branched, or
C6-C10-arylene or -alkylarylene, or
arylalkylene;
M is a metal ion from the 2nd or 3rd main or
transition group of the Periodic Table of the
Elements; and
m is 2 or 3;
n is 1 or 3;
x is 1 or 2.
The metal ion M used preferably comprises Al, Ca, and
Zn.
In combination with the flame-retardant components (C1)
and (C2), it is also possible, if appropriate, to add
from 0.5 to 5% by weight, based on the entirety of (C1)
and (C2), of oxygen-, nitrogen-, or sulfur-containing
metal compounds, as stabilizers (component (C3)).
Metals preferred here are aluminum, calcium, magnesium,
and zinc. Suitable compounds are those selected from
the group of the oxides, hydroxides, carbonates,
silicates, borates, phosphates, and stannates, and
combinations and mixtures of said compounds, e.g. oxide


hydroxides or oxide hydroxide carbonates. Examples are
magnesium oxide, calcium oxide, aluminum oxide, zinc
oxide, magnesium hydroxide, aluminum hydroxide,
boehmite, dihydrotalcite, hydrocalumite, calcium
hydroxide, tin oxide hydrate, zinc hydroxide, zinc
borate, zinc sulfide, zinc phosphate, calcium
carbonate, calcium phosphate, magnesium carbonate,
basic zinc silicate, zinc stannate, calcium stearate,
zinc stearate, magnesium stearate, potassium palmitate,
magnesium behenate.
Another factor that should therefore be emphasized for
the inventive polyamide molding compositions and
respectively for the moldings produced therefrom is
that excellent flame retardancy is achieved in
combination with the exceptional properties described
above. The UL classification of the molding
composition, for a test specimen of thickness 0.8 mm,
is V-0 (UL 94, test to standards from Underwriters
Laboratories (U.L.), cf. www.ulstandards.com).
The invention further provides a short-fiber-reinforced
pelletized material, a long-fiber-reinforced elongate
pelletized material, or a semifinished product, or a
molding, composed of a polyamide molding composition as
described above, further details of which are also
described at a later stage below, particularly
preferably for use in a moist and/or wet environment.
The present invention also provides a process for the
preparation of a polyamide molding composition as
described above and further details of which are also
described at a later stage below, where said process
preferably comprises adding, to the monomer mixtures,
during the preparation of component (A) , at least one
polycondensation catalyst, preferably in a proportion
of from 0.005 to 1.5% by weight, where this can by way
of example involve phosphorus compounds, such as


phosphoric acid, phosphorous acid, hypophosphorous
acid, phenylphosphonic acid, phenylphosphinic acid,
and/or salts thereof with cations of valency from 1 to
3, e.g. Na, K, Mg, Ga, Zn, or Al, and/or their esters,
such as triphenyl phosphate, triphenyl phosphite, or
tris(nonylphenyl) phosphite, or a mixture thereof.
With regard to the dicarboxylic acids which, if
appropriate, replace the terephthalic acid, the
following applies: the inventive semiaromatic PA10T/6T
copolyamides (A) contain this, as dicarboxylic acid, in
a molar ratio which is in particular from 40 to 95/from
5 to 60, the material being in essence terephthalic
acid. Some of the terephthalic acid can have been
replaced by a subordinate amount, preferably not more
than 30 mol% (based on the entire amount of the
dicarboxylic acids) of other aromatic, aliphatic, or
cycloaliphatic dicarboxylic acids having from 6 to 36
carbon atoms. Among the suitable aromatic dicarboxylic
acids are naphthalenedicarboxylic acid (NDA) and
isophthalic acid (IPS). Suitable aliphatic dicarboxylic
acids are adipic acid, suberic acid, azelaic acid,
sebacic acid, undecanedioic acid, dodecanedioic acid,
brassylic acid, tetradecanedioic acid, pentadecanedioic
acid, hexadecanedioic acid, octadecanedioic acid, and
dimer acid. Suitable cycloaliphatic dicarboxylic acids
are cis- and/or trans-cyclohexane-1,4-dicarboxylic acid
and/or cis- and/or trans-cyclohexane-1,3-dicarboxylic
acid (CHDA).
With regard to the diamines which, if appropriate,
replace 1,6-hexanediamine and respectively 1,10-
decanediamine, the following applies: the inventive,
semiaromatic PA10T/6T copolyamides (A) contain in
essence a mixture composed of 1,6-hexanediamine and
1,10-decanediamine in a molar ratio of from 5/95 to
60/40. It is also possible that a subordinate amount,
which is preferably not more than 30 mol% (based on the


entire amount of the diamines) of the diamines has been
replaced by other diamines having from 4 to 36 carbon
atoms. Examples of linear or branched, aliphatic
diamines are 1,4-butanediamine, 1,5-pentanediamine, 2-
methyl-1,5-pentanediamine (MPMD), 1,8-octanediamine
(OMDA), 1,9-nonanediamine (NMDA), 2-methyl-1,8-octane-
diamine (MODA), 2,2,4-trimethylhexamethylenediamine
(TMHMD), 2,4,4-trimethylhexamethylenediamine (TMHMD),
5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 2-
butyl-2-ethyl-1, 5-pentanediamine, 1,12-dodecanediamine,
1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-
hexadecanediamine, and 1,18-octadecanediamine. Examples
of cycloaliphatic diamines that can be used are cyclo-
hexanediamine, 1,3-bis(aminomethyl)cyclohexane (BAC),
isophoronediamine, norbornanedimethylamine,
4,4' -diaminodicyclohexylmethane (PACM), 2,2-
(4,4'-diaminodicyclohexyl)propane (PACP), and
3,3' -dimethyl-4,4' -diaminodicyclohexylmethane (MACM).
m-Xylylenediamine (MXDA) may be mentioned as
araliphaticdiamine.
With respect to the lactams and amino acids which can
also be present, if appropriate, in component (A) , the
following applies: the inventive, semiaromatic PA10T/6T
copolyamides (A) can contain not only 1,6-
hexanediamine, 1,10-decanediamine, and terephthalic
acid (taking into account the at least optional partial
replacements discussed above for these constituents)
but also a subordinate amount, which is preferably not
more tham 30 mol% (based on the entire amount of the
monomers) of lactams or amino acids. Examples of
suitable compounds are caprolactam (CL) , α,ω-
aminocaproic acid, α,ω-aminononanoic acid, α,ω-
aminoundecanoic acid (AUA) , laurolactam (LL) , and ω-
aminododecanoic acid (ADA).
For higher glass transition temperatures, preference is
given to additions of NDA, IPS, CHDA, MPMD, MODA,


TMHMD, BAC, PACM, and MACM. NDA, BAC, and PACM are
particularly preferred.
For lower glass transition temperatures, preference is
given to additions of long-chain monomers, such as
dodecanedioic acid, brassylic acid, tetradecanedioic
acid, pentadecanedioic acid, hexadecanedioic acid,
octadecanedioic acid, dimer acid, 1,12-dodecanediamine,
1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-
hexadecanediamine, and 1,18-octadecanediamine.
Dodecanedioic acid and 1,12-dodecanediamine are
particularly preferred.
For adequately high molecular weight and high relative
viscosity, together with good flowability and high MVR,
the monomers used should preferably have adequate
purity. In particular in the case of 1,10-
decanediamine, it is advantageous that melting point is
above 63°C, total diamine content is above 99%,
aminonitrile content is below 0.5%, and APHA color is
below 10 units.
Polycondensation catalysts that can be added to the
monomer mixtures are from 0.005 to 1.5% by weight of
phosphorus compounds, such as phosphoric acid
phosphorous acid, hypophosphorous acid,
phenylphosphonic acid, phenylphosphinic acid, and/or
salts thereof with cations of valency from 1 to 3, e.g.
Na, K, Mg, Ga, Zn, or Al, and/or their esters, such as
triphenyl phosphate, triphenyl phosphite, or tris
(nonylphenyl) phosphite. Preference is given to
hypophosphorous acid and sodium hydrogen hypophosphite
monohydrate in an amount of from 100 to 500 ppm of
phosphorus, based on the semiaromatic PA10T/6T
copolyamide (A).
Because diamine compounds are more volatile than
dicarboxylic acids, diamine loss occurs during the


preparation process. Diamine is lost during evaporation
of the water, during discharge of the precondensate,
and during the post-condensation in the melt or in the
solid phase. To compensate the diamine loss, therefore,
it is preferable that a diamine excess of from 1 to 8%
by weight, based on the entirety of the diamines, is
added to the monomer mixture. The diamine excess is
also used to regulate the molecular weight and the
distribution of the end groups. In the process used
according to the examples, a diamine excess of smaller
than 3% gives a carboxy end group excess of from 10 to
150 mmol/kg. A diamine excess of more than 3% produces
an amino end group excess of from 10 to 150 mmol/kg.
Regulators in the form of monocarboxylic acids or of
monoamines can be added to the mixture and/or to the
precondensate (prior to post-condensation) in order to
regulate the molar mass, the relative viscosity or
respectively the flowability or the MVR. Aliphatic,
cycloaliphatic, or aromatic monocarboxylic acids or
monoamines suitable as regulators are acetic acid,
propionic acid, butyric acid, valeric acid, caproic
acid, lauric acid, stearic acid, 2-ethylhexanoic acid,
cyclohexanoic acid, benzoic acid, butylamine,
pentylamine, hexylamine, 2-ethylhexylamine, n-
octylamine, n-dodecylamine, n-tetradecylamine, n-
hexadecylamine, stearylamine, cyclohexylamine, 3-
(cyclohexylamino)propylamine, methylcyclohexylamine,
dimethylcyclohexylamine, benzylamine, 2-
phenylethylamine, etc. The regulators can be used
individually or in combination. It is also possible to
use, as regulators, other monofunctional compounds
which can react with an amino or acid group, e.g.
anhydrides, isocyanates, acyl halides or esters. The
usual amount used of the regulators is from 10 to
200 mmol per kg of polymer.
In order to obtain a mixture which is homogeneous and


can be stirred even at an early stage, it is
advantageous to admix water with the monomer mixture.
The amount of water can be from 5 to 50% by weight,
based on the entire mixture. The water can be added
together with the diamines in the form of aqueous
solutions of the diamines, or together with the
dicarboxylic acid in the form of an aqueous slurry, or
separately. The molecular weight and the bulk density
of the precondensate can be controlled via the amount
of water and the pressure set (at which the water is
evaporated), and the residence time.
The molding compositions can moreover be modified using
up to 70% by weight of fillers and reinforcing
materials (glass fibers and/or carbon fibers (including
graphite fibers)). Short fibers (e.g. chopped glass
whose length is from 2 to 50 mm) or continuous-filament
fibers (rovings) can be used for reinforcement.
The glass fibers preferably used here have non-circular
cross section and have a main cross-sectional axis:
secondary cross-sectional axis dimensional ratio of
more than 2, preferably from 2 to 8, in particular from
2 to 5. These glass fibers are known as flat glass
fibers and have an oval or elliptical cross section, or
elliptical cross section with narrowed portion(s)
(these being known as cocoon fibers), or have a
polygonal, rectangular, or almost rectangular cross
section. The glass fibers themselves here can have been
selected from the group of E glass fibers, A glass
fibers, C glass fibers, D glass fibers, M glass fibers,
S glass fibers, and/or R glass fibers, preference being
given here to E glass fibers. The glass fibers per se
can also have been provided with an aminosilane coating
or an epoxysilane coating, and this therefore applies
to flat and also to round or angular fibers whose main
cross-sectional axis: secondary cross-sectional axis
dimensional ratio is less than 2.


The inventive flat glass fibers with non-circular cross
section are preferably used in the form of short glass
fibers (chopped glass whose length is from 0.2 to
20 mm, preferably from 2 to 12 mm) .
A further characterizing feature of the flat glass
fibers used is that the length of the main cross-
sectional axis is preferably in the range from 6 to
40 µm, in particular in the range from 15 to 30 µm, and
the length of the secondary cross-sectional axis is in
the range from 3 to 20 µm, in particular in the range
from 4 to 10 µm.
Mixtures of glass fibers with circular and non-circular
cross section can also be used for reinforcement of the
inventive molding compositions, and the proportion of
flat glass fibers as defined above here is preferably
predominant, i.e. amounts to more than 50% by weight of
the total weight of the fibers. Combinations of the
glass fibers (glass fibers whose cross section is
circular and/or non-circular) with carbon fibers and/or
with synthetic fibers, e.g. aramid fibers, and/or
basalt fibers, can also be used as reinforcement.
If reinforced molding compositions with good
flowability and good surface quality are desired, in
particular in combination with flame retardants, the
reinforcing fibers are then preferably mainly (i.e. by
way of example to an extent of more than 80% by weight
or indeed more than 90% by weight) composed of flat
glass fibers or indeed exclusively composed of flat
glass fibers.
The diameter of the glass fibers used according to the
invention as rovings (filler component B) is from 10 to
20 µm, preferably from 12 to 18 µm, where the cross
section of the glass fibers can be round, oval,


elliptical, elliptical with narrowed portion (s),
polygonal, rectangular, or almost rectangular.
Particular preference is given to fibers known as flat
glass fibers whose ratio of cross-sectional axes is
from 2 to 5. E glass fibers are particularly used
according to the invention. However, it is also
possible to use any of the other types of glass fiber,
e.g. A, C, D, M, S, or R glass fibers, or any desired
mixture thereof, or a mixture with E glass fibers.
In the case of long-fiber-reinforced molding
compositions, higher toughness values, and properties
even more similar to those of metals, are obtained if,
instead of the usual continuous-filament glass fibers
whose diameter is from 15 to 19 µm, these fibers are
used with diameter of from 10 to 14 µm, in particular
with diameter of from 10 to 12 µm.
The inventive polyamide molding compositions can be
prepared via the known processes for the production of
long-fiber-reinforced elongate pelletized material, in
particular via pultrusion processes, in which the
continuous-filament fiber strand (roving) is completely
saturated with the polymer melt and then cooled and
chopped.
The long-fiber-reinforced elongate pelletized material
thus obtained, the pellet length of which is preferably
from 3 to 25 mm, in particular from 4 to 12 mm, can be
further processed using the usual processing methods
(e.g. injection molding, compression molding) to give
moldings, and particularly good properties of the
molding are achieved here, using non-aggressive
processing methods. Non-aggressive in this context
means especially substantial avoidance of excessive
fiber breakage and of the attendant marked reduction of
fiber length. In the case of injection molding, this
means that it is preferable to use screws with large


diameter and low compression ratio, in particular
smaller than 2, and generously dimensioned nozzle
channels and feed channels. A complementary factor to
which attention should be paid is that high cylinder
temperatures rapidly melt the elongate pelletized
material (contact heating) and that the fibers are not
excessively comminuted through excessive exposure to
shear. According to the invention when these measures
are taken into account, moldings are obtained whose
average fiber length is higher than that of comparable
moldings produced from short-fiber-reinforced molding
compositions. The result of this is an additional
improvement in properties, in particular in the case of
tensile modulus of elasticity, ultimate tensile
strength, and notched impact resistance.
The diameter of the continuous-filament carbon fibers
used during the pultrusion process is from 5 to 10 (am,
preferably from 6 to 8 µm. The continuous-filament
carbon fibers can be used alone or in combination with
continuous-filament glass fibers (circular and/or non-
circular cross section).
To accelerate fiber impregnation, the fibers can be
pre-heated to temperatures up to 400°C with the aid of
a suitable IR, contact, radiative, or hot-gas pre-
heating system. Apparatuses using spreader surfaces
within the impregnation chamber provide complete
impregnation of the fibers with the polymer melt.
Strands emerging from the impregnation unit can be
molded via controlled roll systems, thus giving
pelletized material with circular, elliptical, or
rectangular cross section.
To improve binding to the matrix and to improve fiber
handling, the fibers may have been coated with sizes of
different chemical nature, these being known in the
prior art for glass fibers and for carbon fibers.


The thermoplastic molding compositions can preferably
comprise, as further component, a particulate filler,
or a mixture composed of two or more different fillers,
also in combination with reinforcing materials. By way
of example, it is possible to use mineral particulate
fillers based on talc, on mica, on silicate, on quartz,
on titanium dioxide, on wollastonite, on kaolin, on
amorphous silicas, on magnesium carbonate, on magnesium
hydroxide, on chalk, on lime, on feldspar, on barium
sulfate, on solid glass beads, on hollow glass beads,
or on ground glass, or to use permanently magnetic or
respectively magnetizable metal compounds, and/or
alloys. The fillers can also have been surface-treated.
The molding compositions can comprise stabilizers,
processing aids, and impact modifiers, and further
additives.
In another embodiment, the inventive molding
composition comprises up to 45% by weight of one or
more impact modifiers (IM) . An IM concentration in the
range from 5 to 30% by weight is preferred.
The impact modifier, which can be used as a constituent
of component C, can be a natural rubber, polybutadiene,
polyisoprene, polyisobutylene, a copolymer of butadiene
and/or isoprene with styrene or with styrene
derivatives and with other comonomers, a hydrogenated
copolymer, and/or a copolymer produced via grafting or
copolymerization with anhydrides, (meth)acrylic acid,
or an ester thereof. The impact modifier (C) can also
be a graft rubber with a crosslinked elastomeric core
which is composed of butadiene, of isoprene, or of
alkyl acrylates, and which has a graft shell composed
of polystyrene, or can be a non-polar or polar olefin
homo- or copolymer, such as ethylene-propylene rubber,
ethylene-propylene-diene rubber, or ethylene-octene


rubber, or ethylene-vinyl acetate rubber, or a non-
polar or polar olefin homo- or copolymer produced via
grafting or copolymerization with anhydrides, (meth)
acrylic acid, or an ester thereof. The impact modifier
(C) can also be a carboxylic-acid-functionalized
copolymer, such as poly(ethene-co-(meth)acrylic acid)
or poly(ethene-co-1-olefin-co-(meth)acrylic acid),
where the 1-olefin is an alkene or an unsaturated
(meth)acrylic ester having more than 4 atoms, inclusive
of those copolymers in which the acid groups have been
neutralized to some extent with metal ions.
Preferred IMs based on styrene monomers (styrene and
styrene derivatives) and on other vinylaromatic
monomers are block copolymers composed of
alkenylaromatic compounds and of a conjugated diene,
and hydrogenated block copolymers composed of an
alkenylaromatic compound and of conjugated dienes, and
combinations of these types of IM. The block copolymer
contains at least one block derived from an
alkenylaromatic compound (A) and at least one block
derived from a conjugated diene (B). In the case of the
hydrogenated block copolymers, the proportion of
aliphatically unsaturated carbon-carbon double bonds
has been reduced via hydrogenation. Suitable block
copolymers are two-, three-, four-, and polyblock
copolymers with linear structure. However, branched and
star-shaped structures can likewise be used according
to the invention. Branched block copolymers are
obtained in a known manner, e.g. via graft reactions of
polymeric "side branches" onto a main polymer chain.
Other alkenylaromatic monomers that can be used
alongside styrene or in a mixture with styrene are
vinylaromatic monomers having substitution on the
aromatic ring and/or on the C=C double bond by C1-20-
hydrocarbon radicals or by halogen atoms.


Examples of alkenylaromatic monomers are styrene, p-
methylstyrene, a-methylstyrene, ethylstyrene, tert-
butylstyrene, vinyltoluene, 1,2-diphenylethylene, 1,1-
diphenylethylene, vinylxylenes, vinyltoluenes,
vinylnaphthalenes, divinylbenzenes, bromostyrenes, and
chlorostyrenes, and combinations thereof. Preference is
given to styrene, p-methylstyrene, alpha-methylstyrene,
and vinylnaphthalene.
It is preferable to use styrene, a-methylstyrene, p-
methylstyrene, ethylstyrene, tert-butylstyrene,
vinyltoluene, 1,2-diphenylethylene, 1,1-
diphenylethylene, or a mixture of these. It is
particularly preferable to use styrene. However, it is
also possible to use alkenylnaphthalenes.
Examples of diene monomers that can be used are 1,3-
butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-
butadiene, 1,3-pentadiene, 1,3-hexadiene, isoprene,
chloroprene, and piperylene. Preference is given to
1,3-butadiene and isoprene, particularly 1,3-butadiene
(hereinafter referred to by the abbreviated term
butadiene).
The alkenylaromatic monomer used preferably comprises
styrene,. and the diene monomer used preferably
comprises butadiene, and this means that preference is
given to styrene-butadiene block copolymer. The block
copolymers are generally prepared via anionic
polymerization in a manner known per se.
Other further comonomers can also be used
concomitantly, in addition to the styrene monomers and
diene monomers. The proportion of the comonomers is
preferably from 0 to 50% by weight, particularly
preferably from 0 to 30% by weight, and in particular
from 0 to 15% by weight, based on the total amount of
the monomers used. Examples of suitable comonomers are


acrylates, in particular C1-12-alkyl acrylates, such as
n-butyl acrylate or 2-ethylhexyl acrylate, and the
corresponding methacrylates, in particular Cl-12-alkyl
methacrylates, such as methyl methacrylate (MMA). Other
possible comonomers are (meth)acrylonitrile, glycidyl
(meth)acrylate, vinyl methyl ether, diallyl and divinyl
ethers of dihydric alcohols, divinylbenzene, and vinyl
acetate.
In addition to the conjugated diene, the hydrogenated
block copolymers also contain, if appropriate,
fractions of lower hydrocarbons, e.g. ethylene,
propylene, 1-butene, dicyclopentadiene, or non-
conjugated dienes. The proportion of the non-reduced
aliphatic unsaturated bonds which result from the block
B is smaller than 50% in the hydrogenated block
copolymers, preferably smaller than 25%, in particular
smaller than 10%. The aromatic fractions derived from
block A are reduced to an extent of at most 25%. The
hydrogenated block copolymers, styrene-(ethylene-
butylene) two-block and styrene-(ethylene-butylene)-
styrene three-block copolymers are obtained via
hydrogenation of styrene-butadiene copolymers and of
styrene-butadiene-styrene copolymers.
The block copolymers are preferably composed of from 20
to 90% by weight of block A, in particular from 50 to
85% by weight of block A. The diene can be incorporated
in 1,2-orientation or in 1,4-orientation into the block
B.
The molar mass of the block copolymers is from 5000 to
500 000 g/mol, preferably from 20 000 to 300 000 g/mol,
in particular from 40 000 to 200 000 g/mol.
Suitable hydrogenated block copolymers are the
commercially available products, such as KRATON®
(Kraton Polymers) G1650, G1651 and G1652, and TUFTEC®


(Asahi Chemicals) H1041, H1043, H1052, H1062, H1141,
and H1272.
Examples of non-hydrogenated block copolymers are
polystyrene-polybutadiene, polystyrene-poly(ethylene-
propylene) , polystyrene-polyisoprene, poly(a-
methylstyrene)-polybutadiene, polystyrene-
polybutadiene-polystyrene (SBS), polystyrene-poly
(ethylene-propylene)-polystyrene, polystyrene-
polyisoprene-polystyrene, and poly(α-methylstyrene)-
polybutadiene-poly(α-methylstyrene), and combinations
thereof.
Suitable non-hydrogenated block copolymers which are
commercially available are various products with the
trademarks SOLPRENE® (Phillips), KRATON® (Shell),
VECTOR® (Dexco), and SEPTON® (Kuraray).
According to another preferred embodiment, the
inventive molding compositions are those wherein
component C comprises a polyolefin homopolymer or an
ethylene-a-olefin copolymer, particularly preferably an
EP elastomer and/or EPDM elastomer (ethylene-propylene
rubber and respectively ethylene-propylene-diene
rubber). By way of example, an elastomer can be
involved which is based on an ethylene-C3-12-a-olefin
copolymer with from 20 to 96% by weight, preferably
from 25 to 85% by weight, of ethylene, where it is
particularly preferable here that the C3-12-α-olefin
involves an olefin selected from the group of propene,
1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,
and/or 1-dodecene, and it is particularly preferable
that component C involves ethylene-propylene rubber
and/or LLDPE, and/or VLDPE.
Alternatively or additionally (by way of example in a
mixture), C can comprise a terpolymer based on
ethylene-C3-12-α-olefin with an unconjugated diene, and


it is preferable here that this contains from 25 to 85%
by weight of ethylene and up to at most amounts in the
region of 10% by weight of an unconjugated diene, and
it is particularly preferable here that the C3-12-CC-
olefin involves an olefin selected from the group of
propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-
decene, and/or 1-dodecene, and/or where the
unconjugated diene has preferably been selected from
the group of bicyclo[ 2 . 2 .1] heptadiene, 1,4-hexadiene,
dicyclopentadiene, and/or in particular 5-
ethylidenenorbornene.
Ethylene-acrylate copolymers can also be used as
constituent for component C.
Other possible forms of constituents for component C
are the ethylene-butylene copolymers and respectively
mixtures (blends) which comprise these systems.
It is preferable that component C comprises
constituents having anhydride groups, these being
introduced via thermal or free-radical reaction of the
main-chain polymer with an unsaturated dicarboxylic
anhydride, with an unsaturated dicarboxylic acid, or
with a monoalkyl ester of an unsaturated dicarboxylic
acid, at a concentration sufficient for good binding to
the polyamide, and it is preferable here to use
reagents selected from the following group:
maleic acid, maleic anhydride, monobutyl maleate,
fumaric acid, aconitic acid, and/or itaconic anhydride.
It is preferable that from 0.1 to 4.0% by weight of an
unsaturated anhydride are grafted onto the impact-
resistant component as a constituent of C, or that the
unsaturated dicarboxylic anhydride or its precursor is
applied by grafting together with another unsaturated
monomer. It is generally preferable that the degree of
grafting is in the range from 0.1 to 1.0%, particularly


preferably in the range from 0.3 to 0.7%. Another
possible constituent of component C is a mixture
composed of an ethylene-propylene copolymer and of an
ethylene-butylene copolymer, the degree of maleic
anhydride grafting (degree of MA grafting) here being
in the range from 0.3 to 0.7%.
The possible systems cited above for this component can
also be used in mixtures.
Component C can moreover comprise components which have
functional groups, e.g. carboxylic acid groups, ester
groups, epoxy groups, oxazoline groups, carbodiimide
groups, isocyanate groups, silanol groups, and
carboxylate groups, or can comprise a combination of
two or more of the functional groups mentioned.
Monomers which bear said functional groups can be
bonded via copolymerization or grafting to the
elastomeric polyolefin.
The IMs based on the olefin polymers can moreover also
have been modified via grafting with an unsaturated
silane compound, e.g. vinyltrimethoxysilane,
vinyltriethoxysilane, vinyltriacetosilane, meth-
acryloxypropyltrimethoxysilane, or propenyltrimethoxy-
silane.
The elastomeric polyolefins are random, alternating, or
segmented copolymers having linear, branched, or core-
shell structure, and contain functional groups which
can react with the end groups of the polyamides, thus
giving adequate compatibility between polyamide and IM.
The inventive IMs therefore include homopolymers or
copolymers of olefins, e.g. ethylene, propylene, 1-
butene, or copolymers of olefins and of copolymerizable
monomers, such as vinyl acetate, (meth)acrylic ester,
and methylhexadiene.


Examples of crystalline olefin polymers are low-,
medium-, and high-density polyethylenes, polypropylene,
polybutadiene, poly-4-methylpentene, ethylene-propylene
block copolymers or ethylene-propylene random
copolymers, ethylene-methylhexadiene copolymers,
propylene-methylhexadiene copolymers, ethylene-
propylene-butene copolymers, ethylene-propylene-hexene
copolymers, ethylene-propylene-methylhexadiene
copolymers, poly(ethylene-vinyl acetate) (EVA), poly
(ethylene-ethyl acrylate) (EEA), ethylene-octene
copolymer, ethylene-butene copolymer, ethylene-hexene
copolymer, ethylene-propylene-diene terpolymers, and
combinations of the polymers mentioned.
Examples of commercially available impact modifiers
which can be used for the purposes of the constituents
of component C are:
TAFMER MC201: g-MA (-0.6%) blend from 67% EP copolymer
(20 mol% propylene) + 33% EB copolymer (15 mol% 1-
butene)): Mitsui Chemicals, Japan.
TAFMER MH5010: g-MA (-0.6%) ethylene-butylene
copolymer; Mitsui.
TAFMER MH7010: g-MA (-0.7%) ethylene-butylene
copolymer; Mitsui.
TAFMER MH7020: g-MA (-0.7%) EP copolymer; Mitsui.
EXXELOR VA1801: g-MA (-0.7%) EP copolymer; Exxon Mobile
Chemicals, US.
EXXELOR VA18 03: g-MA (0.5-0.9%) EP copolymer,
amorphous, Exxon.
EXXELOR VA1810: g-MA (-0.5%) EP copolymer, Exxon.
EXXELOR MDEX 94-1 1: g-MA (0.7%) EPDM, Exxon.
FUSABOND MN493D: g-MA (-0.5%) ethylene-octene
copolymer, DuPont, US.
FUSABOND A EB560D: (g-MA) ethylene-n-butyl acrylate
copolymer, DuPont.
ELVALOY, DuPont.


Preference is also given to an ionomer in which the
polymer-bonded carboxy groups have been bonded to one
another entirely or to some extent via metal ions.
Particular preference is given to maleic-anhydride-
grafting-functionalized copolymers of butadiene with
styrene, to non-polar or polar olefin homo- and
copolymers produced via grafting with maleic anhydride,
and to carboxylic-acid-functionalized copolymers, such
as poly(ethene-co-(meth)acrylic acid) or poly(ethene-
co-1-olefin-co-(meth)acrylic acid), in which the acid
groups have to some extent been neutralized with metal
ions.
The inventive PA10T/6T polyamides can be mixed with
polyphenylene ethers (PPE). The polyphenylene ethers
are known per se. They are prepared (cf. US patents
3661848, 3378505, 3306874, 3306875 and 3639656) by
conventional processes via oxidative coupling, from
phenols disubstituted by alkyl groups in the ortho
position. The preparation process usually uses catalyst
based on heavy metals, such as copper, manganese, or
cobalt, in combination with other substances, such as
secondary amines, tertiary amines, halogens, or a
combination thereof. Mixtures of polyamides with
polyphenylene ethers are also known per se, but not
with the copolyamide component proposed. By way of
example WO-A-2005/0170039, WO-A-2005/0170040,
WO-A-2005/0170041, and WO-A-2005/0170042 disclose
mixtures composed of polyamide and PPE.
Suitable polyphenylene ethers are poly(2,6-diethyl-1,4-
phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene)
ether, poly (2-methyl-6-propyl-1,4-phenylene) ether,
poly(2,6-dipropyl-1,4-phenylene) ether, poly(2-ethyl-6-
propyl-1,4-phenylene) ether, or copolymers such as
those which contain 2,3,6-trimethylphenol, and also


polymer mixtures. Preference is given to poly(2,6-
dimethyl-1,4-phenylene) ether optionally in combination
with 2,3,6-trimethylphenol units. The polyphenylene
ethers can be used in the form of homopolymers,
copolymer, graft copolymers, block copolymer, or
ionomers.
The intrinsic viscosity of suitable polyphenylene
ethers is generally in the range from 0.1 to 0.6 dl/g,
measured in CHCl3 at 25°C. This corresponds to a
molecular weight Mn (number average) of from 3000 to
40 000 and to a weight-average molecular weight value
Mw of from 5000 to 80 000. It is possible to use a
combination of a high-viscosity polyphenylene ether and
a low-viscosity polyphenylene ether. The ratio of the
two polyphenylene ethers of different viscosity depends
on the viscosities and on the physical properties
desired.
The blends of the inventive PA10T/6T can comprise from
10 to 45% by weight of polyphenylene ether and
optionally up to 30% by weight, preferably up to 15% by
weight, of impact modifier. For better compatibility,
compatibilizers are used in the form of polyfunctional
compounds which interact with the polyphenylene ether,
the polyamide, or both. The interaction can be chemical
(e.g. via grafting) and/or physical (e.g. via influence
on the surface properties of the disperse phase).
The compatibilizers can be polyfunctional compounds
which contain at least one carboxylic acid group,
carboxylic anhydride group, ester group, amide group,
or imide group. Mention may be made by way of example
of maleic acid, maleic anhydride, fumaric acid, acrylic
acid, methacrylic acid, methylmaleic acid, methylmaleic
anhydride, itaconic acid, itaconic anhydride,
butenylsuccinic acid, butenylsuccinic anhydride,
tetrahydrophthalic acid, tetrahydrophthalic anhydride,


N-phenylmaleimide, citric acid, malic acid, and 2-
hydroxynonadecane-1,2,3-tricarboxylic acid, the mono-
or diesters of the acids mentioned with C1-C12
alcohols, such as methanol or ethanol, the mono- or
diamides of the acids mentioned which, if appropriate,
can have substitution on the nitrogen by alkyl or aryl
radicals having up to 12 carbon atoms, and the salts
with alkali metals or with alkaline earth metals, e.g.
calcium and potassium. Particularly advantageous
compounds are maleic acid, fumaric acid, maleic
anhydride, and citric acid. An amount of from 0.05 to
2% by weight of the compatibilizers can be added
directly during blend preparation, or the polyphenylene
ether and/or the polyamide is functionalized in a
separate step via the compatibilizers.
The invention further provides for the use of the
inventive molding compositions for the production of
thermoplastically processable molded items, and also
the molded items obtainable from the inventive
compositions.
Examples of these molded items include: casings and
functional parts for pumps, gearboxes, valves and water
meters, throttle valves, cylinders, pistons, headlamp
casings, reflectors, bend-adaptive lighting,
gearwheels, engine mountings and gearbox mountings,
connectors, including plug connectors, profiles, foils,
or layers of multilayer foils; they also include
fibers, electronic components, casings for electronic
components, tools, composite materials, fluid-
conducting lines and containers, in particular in the
automobile sector, smooth and corrugated mono- or
multilayer tubes, tube sections, spigots, fittings for
the connection of hoses, of corrugated tubes, and of
lines conducting fluids, a constituent of multilayer
lines (inner, outer, or intermediate layer), individual
layers in multilayer containers, hydraulic lines, brake


lines, clutch lines, coolant lines, brake-fluid
containers, etc.
The molded items can be produced by the processes of
injection molding, extrusion, or blow molding.
The present invention further provides a powder based
on the PA10T/6T copolyamides, a layer-by-layer process
in which regions of the respective pulverulent layer
are melted selectively, and are hardened after cooling,
and also moldings produced from said powder.
It is preferable here to use powders whose average
grain size is from 30 to 200 µm, in particular from 50
to 150 µm, an example being those obtained via grinding
processes and precipitation processes. Preferred
processes here are particularly those which lead to
particles whose shape is as close as possible to
spherical, since these exhibit advantages during
application of powder in layers in the selective laser
sintering process (SLS process).
It is preferable to use unregulated or regulated
copolyamide powders whose solution viscosity (0.5% by
weight in m-cresol at 20°C) is in the range from 1.3 to
2.0, in particular in the range from 1.35 to 1.85.
Mono- and/or dicarboxylic acids, or mono- and/or
diamines, are used for regulation. The ratio of carboxy
to amino end groups in the regulated copolyamide
powders is preferably greater than or equal to 1:2 and,
respectively, 2:1, in particular greater than or equal
to 1:3 and, respectively, 3:1, where the concentration
of the predominant carboxy or amino end groups is at
least 50 mmol/kg, in particular at least 100 mmol/kg.
One preferred embodiment of the sintering powder is a
mixture of oppositely difunctionally regulated
PA10T/6T. This means that the powders are composed of a


combination of separately amine-regulated and carboxy-
regulated powder particles. This mixed copolyamide
powder retains its solution viscosity at an almost
constant level on exposure to thermal stress below the
melting point, for example the stress occurring during
the SLS process for the non-sintered powder, and said
mixed powder can therefore be used repeatedly in the
rapid prototyping/rapid manufacturing process with only
small amounts of virgin powder or indeed without
addition of virgin powder. Disposal of powder residue
often becomes unnecessary by virtue of these excellent
recycling qualities.
One process which has particularly good suitability for
the purposes of rapid prototyping or rapid
manufacturing is laser sintering. In this process,
plastics powders are selectively and briefly irradiated
with a laser beam in a chamber, thus melting the powder
particles impacted by the laser beam. The molten
particles coalesce and, after cooling, solidify again
to give a solid mass. This process can produce complex
three-dimensional bodies simply and rapidly, via
repeated irradiation of a succession of newly applied
layers. However, there are a number of other suitable
processes, as well as laser sintering. The selectivity
of the layer-by-layer processes here can be achieved by
way of application of susceptors, absorber, inhibitors,
or masks, or by way of focused introduction of energy,
for example via a laser beam or via a glass fiber
cable.
Polyamide-12 powder has proven particularly successful
in industry for laser sintering for the production of
components. Although the parts manufactured from PA12
powder are often adequate for mechanical stresses and
their properties are therefore close to those of the
subsequent mass-produced injection-molded or extruded
parts, PA12 has a low melting point of 178 °C and low


stiffness of about 1300 MPa, which is inadequate for
many applications. These disadvantages can be overcome
via the inventive copolyamide powders based on PA10T/6T
whose melting point is in the range from 270 to 320°C
and whose tensile modulus of elasticity is above
2500 MPa.
The sintering powder can comprise at least one further
filler, as well as the 10T/6T copolyamide particles.
These fillers can by way of example be glass particles
or metal particles, or ceramic particles, or else the
abovementioned particulate fillers. In particular, the
sintering powder can comprise solid or hollow glass
beads, steel shot, or granular metal as fillers. Glass
beads whose average diameter is from 20 to 80 µm are
typically used. In one preferred embodiment, these
fillers have been coated with a thin layer of the
inventive copolyamide, the layer thickness here
preferably being from 2 to 30 µm, in particular from 5
to 20 µm. The average particle size of the filler
particles here is preferably smaller than or
approximately equal to that of the particles of the
polyamides. The amount by which the average particle
size of the fillers exceeds the average particle size
of the polyamides should preferably be not more than
30%, preferably not more than 20%, and very
particularly preferably not more than 10%. There is a
particular limitation on particle size via the
permissible layer thickness in the respective laser
sintering apparatus.
The inventive copolyamide molding compositions can also
be spun to give fibers which are resistant to
temperature change and which have high strength and low
water absorption. Together with other polymers, it is
possible to produce the fibers known as bicomponent
fibers, of side-by-side type and of core-shell type.

BRIEF EXPLANATION OF THE ACCOMPANYING FIGURES
The invention will be explained in more detail below using
inventive examples in conjunction with the figures.
Fig. 1 shows the melting points of PA 10T/6T; and
Fig. 2 shows the water absorption of PA 10T/6T.
METHODS OF WORKING THE INVENTION
Production of the products/preparation processes:
The semiaromatic PA 10T/6T copolyamides (A) can be prepared by
processes known per se. Suitable processes have been described
in various publications, and some of the possible processes
discussed in the patent literature will be cited below, and
the disclosure of the documents discussed hereinafter is
expressly incorporated by way of reference into the disclosure
of this document with regard to the process for the
preparation of the copolyamide of component (A) of the present
invention:
DE 195 13 940 describes a process which encompasses the
following stages, and this process can be used for the
preparation of component (A):
a) a salt-formation stage for the formation of salts
composed of diamine(s) and dicarboxylic acid(s) in an
aqueous solution of strength from 5 to 50% by weight
comprising the components, and, if appropriate, partial
prereaction to give low-molecular-weight oligoamides at
temperatures of from 120°C to 220°C and under pressures
of up to 23 bar,
b) if appropriate, transfer of the solution from stage a)
into a second reaction vessel or into a stirred
autoclave, under the conditions prevailing at the end of
its preparation process,

c) conduct of the reaction phase during which the
reaction takes place to give the precondensates,
with heating of the reactor contents to a
prescribed temperature and controlled adjustment
of the partial water vapor pressure to the
prescribed value, which is maintained via
controlled discharge of water vapor or, if
appropriate, controlled infeed of water vapor from
a steam generator associated with the autoclave,
d) a stationary-state phase to be maintained for at
least 10 minutes, in which the temperature of the
reactor contents and the partial water vapor
pressure are respectively adjusted in a controlled
manner - using the measures listed under c) in the
case of the partial water vapor pressure - to the
values intended for the transfer of the
precondensates to the following stage of the
process,
the above with the proviso that in the case of
precondensates of semicrystalline polyamides or
copolyamides whose melting point is more than 28 0°
C (melting point maximum measured by means of
differential scanning calorimetry) the temperature
of the reactor contents during this phase d) and
phase c) is not permitted to exceed 265°C, and
that, for said semicrystalline polyamides or
copolyamides, during phases d) and c) , the
boundary conditions described are to be maintained
with respect to the dependency of the minimum
partial water vapor pressure to be used on the
temperature of the reactor contents and on the
amide group concentration of the polymer,
e) a discharge phase, during which the precondensates
can be introduced into a final reaction apparatus,

while the temperature prevailing at the end of
phase d) is kept constant, and the partial water
vapor pressure prevailing at said juncture is at
least maintained, via infeed of water vapor from
said steam generator into the autoclave, and all
discharge lines/assemblies associated therewith,
either in the molten state by way of a buffer
device directly or by way of a separator apparatus
and passage through the solid state, with
subsequent optional drying and/or comminution and,
if appropriate, further stages of the process.
EP 0 976 774 describes a process for the preparation of
polyamides which encompasses the following steps in the
stated sequence and which likewise can be used for the
preparation of the copolyamide of component (A), if the
corresponding constituents are replaced according to
the invention:
(i) a step in which a dicarboxylic acid component
with terephthalic acid content and a diamine
component are polycondensed in the presence of
from 15 to 35% by weight of water at a reaction
temperature of from 250°C to 280°C and at a
reaction pressure (P) which complies with the
following formula P0 ≥ P ≥ 0.7 P0, where P0 is
the saturated vapor pressure of water at the
reaction temperature, in order to form a
primary polycondensate;
(ii) a step in which the resultant polycondensate
formed as in the preceding step (i) is taken
from the reactor into an atmospheric
environment while its temperature is in the
range from 250°C to 280°C and its water content
is in the range from 15 to 35% by weight;
(iii) a step in which the primary polycondensate thus


taken from the preceding step (ii) is subjected
to solid-phase polymerization or polymerization
in the melt, in order to give a polyamide with
an increased molecular weight.
EP 0 129 195, EP 0 129 196, and EP 0 299 444 describe
processes for the continuous preparation of polyamides
which are also suitable in appropriately modified form
for the production of component (A) , by first heating
aqueous solutions of strength from 30 to 70% of salts
composed of dicarboxylic acids and of diamines under
elevated pressure of from 1 to 10 bar, with
simultaneous evaporation of water, within a residence
time of less than 60 seconds, to a temperature of from
250 to 300°C, and then continuously separating
prepolymers and vapors, rectifying the vapors, and
returning the entrained diamines. Finally, the
prepolymer is passed to a polycondensation zone and
polycondensed at a gage pressure of from 1 to 10 bar
and at a temperature of from 250 to 300°C. On exit from
the evaporator zone, the degree of conversion is
advantageously at least 93% and the water content of
the prepolymer is at most 7% by weight. Formation of
diamines is substantially avoided by these short
residence times.
US 4,831,108 describes a polycondensation process for
the preparation of polyamides, polyamideimides,
polyesters, and polyarylates, which likewise can be
used in appropriately modified form for the preparation
of component (A) , and which is characterized in that a
heated solution of a salt or of a prepolymer, or of a
mixture composed of a salt and of a prepolymer, is
first formed, and practically is homogeneous, and forms
a single phase, and is stable at the selected
polycondensation temperature, and readily atomizes, and
then this solution is fed, with formation of an
aerosol, into a vaporization reactor, which is operated


at a pressure of from about 0 to 2.76 MPa (from 0 to
400 psig), for purposes of condensation and
polymerization, where said vaporization reactor has
been designed for high heat flux with wall temperatures
of from about 204 to 538°C (from 400 to 1000°F) and
melting points of from about 177 to 399°C (from 350 to
750°F), and where the resultant polymer is kept in the
reactor for from about 0.1 to about 20 seconds.
US 4,607,073 reveals that semiaromatic polyamides can
also be prepared from terephthaloyl chloride or
dimethyl terephthalate with the corresponding diamines.
Polyamide is prepared via precondensation of the dry
salt at 310°C under nitrogen and at atmospheric
pressure and then 12 hours of solid-phase
postcondensation at 295°C. This type of process can
also be used for preparation of component (A) after
appropriate modification.
According to DE 14 95 393 and US 3,454,536, it is
preferable, when preparing the polyamides from the
dicarboxylic esters, to begin by heating the starting
components in the presence of water to from 90 °C to
100°C, and to remove the resultant methanol practically
completely by distillation, and then to polycondense
the distillation residue either at superatmospheric
pressure with subsequent depressurization or at
atmospheric pressure throughout, at temperatures of
from 250 to 290°C. This type of process can also be
used for the preparation of component (A).
The most familiar process for the preparation of
polyamides with high melting points, and a suitable
process for the preparation of component (A) , is the
two-stage preparation first of a low-viscosity, low-
molecular-weight precondensate, with subsequent post-
condensation in the solid phase or in the melt (e.g. in
an extruder). A three-stage process is also possible,


composed of 1. precondensation, 2. solid-phase
polymerization, and 3. polymerization in the melt, as
cited in DE 696 30 260.
For products with melting points below 300°C, another
suitable process is the single-stage batch process
described by way of example in US 3,843,611 and
US 3,839,296, in which the mixture of the monomers or
their salts is heated for from 1 to 16 hours to
temperatures of from 250 to 320°C, and the pressure is
reduced from a maximum to the lowest pressure of up to
1 mmHg, with evaporation of gaseous material, if
appropriate with the aid of an inert gas.
Specific examples will be given below, and compared
with comparative examples (C) and discussed. Storage in
water for determination of the appropriate parameters
here took place at 95°C for a time of 240 hours.
The measurements were conducted to the following
standards and on the following test specimens.
Tensile modulus of elasticity:
ISO 527 using a tensile test velocity of 50 mm/min
(unreinforced variants) or a tensile test velocity
of 5 mm/min (reinforced variants)
ISO tensile specimen, standard: ISO/CD 3167, Al
type, 170 x 20/10 x 4 mm, temperature 23°C
Transverse stiffness was determined on a BIAX test
specimen (BIAX, published in Noss' Ovra Staff
Magazine, December 2006, No. 12, volume 29, EMS-
CHEMIE AG) , which permits direction-dependent
measurement of stiffness and strength.

Maximum tensile strength, ultimate tensile strength,
and transverse strength:
ISO 527 using a tensile test velocity of 50 mm/min
(unreinforced variants) or a tensile test velocity
of 5 mm/min (reinforced variants)
ISO tensile specimen, standard: ISO/CD 3167, Al
type, 170 x 20/10 x 4 mm, temperature 23°C
Transverse strength (transverse ultimate tensile
strength) was determined on a BIAX test specimen
(BIAX, published in Noss'Ovra Staff Magazine,
December 2006, No. 12, volume 29, EMS-CHEMIE AG),
which permits direction-dependent measurement of
stiffness and strength.
Thermal behavior:
Melting point, enthalpy of fusion, and glass
transition temperature (Tg):
ISO standard 11357-11-2
Granulated material
Differential scanning calorimetry (DSC) was
carried out using a heating rate of 20°C/min. The
onset temperature is stated for the glass
transition temperature (Tg).
Relative viscosity:
DIN EN ISO 307, in 0.5% strength by weight
m-cresol solution, 20°C, granulated material
HPT A (1.8 MPa), HPT B (0.45 MPa), and HDT C (8 MPa):
ISO 75
ISO impact specimen, 80 x 10 x 4


Tube tests:
Low-temperature impact, breaking stress,
elongation at break:
VW TL 52435
The low-temperature impact test was carried out at
-40°C using 500 g, and the longitudinal tensile
test was carried out at 23°C and 50% humidity,
using 100 mm/min, on 8 x 1 mm tubes.
Bursting pressure
DIN 73378
8x1 mm tube
Inventive examples 1-7 (IE 1-IE 7) and comparative
examples 1, 2, 7, and 8 (CE1, CE2, CE7, and CE8), PreC
Diamine(s), terephthalic acid, catalyst, regulator, and
water are placed in a 20 1 autoclave and are heated to
the product temperature within the heating time, kept
at the prescribed pressure for the pressure phase time,
and then discharged by way of a nozzle. The
precondensate is dried for 24 hours at 120°C under a
vacuum of 30 mbar.
Inventive examples 1-7 (IE 1-IE 7) and comparative
examples 1-4, 7, and 8 (CE1-CE4, CE7, and CE8), PostC
The precondensate from example PreC is postcondensed in
a twin-screw extruder from Werner and Pfleiderer using
a screw diameter of 25 mm with prescribed process
parameters (barrel temperature, screw rotation rate,
throughput) . The melt is devolatilized in zone 10 by a
stream of nitrogen.
The product is drawn off in the form of a strand from a

die with diameter 3 mm and pelletized. The pellets are
dried for 24 hours at 120°C in a vacuum of 30 mbar.
Inventive examples 1-15 (IE 1-IE 15) and comparative
examples 1-12 (CE1-CE12), IMTS
The postcondensate from inventive example PostC and
from the comparative example PostC, or, respectively,
the compounded material (IE 11-IE 15, and CE 9-CE 12)
is injection-molded in an Arburg Allrounder 320-210-750
injection-molding machine, to give ISO tensile
specimens, at defined cylinder temperatures for zones 1
to 4 and at a defined mold temperature.









As can be seen from the graph in Fig. 1 of the results
cited above, ideal melting points are obtained for the
inventively claimed ratios of 1,10-decanediamine and

1,6-hexanediamine, a minimum being observed in the
range from 60 to 70 mol% of 10T.
As can be seen from the further graph provided in
Fig. 2 of the results cited above, water absorption is
always substantially greater for the systems in the
comparative examples than for the polyamide molding
compositions proposed in the invention. It can moreover
be seen that a fall in water absorption can be observed
for increasing 10T proportions. Both melting point and
water absorption are parameters that have to be taken
into account, and the result is therefore the
inventively claimed ideal ranges.



Comparative examples CE7 and CE8 show that although a
combination of terephthalic acid with long-chain
dicarboxylic acids can reduce water absorption, the
modulus ratios and strength ratios are below those of
the PA10T/6T copolyamides.
Inventive examples 8-10 (IE8-IE10), PreC
Diamine(s), terephthalic acid, catalyst, regulator, and
water are placed in a dissolver and heated to 180°C,
and, after homogenization of the monomer mixture,
discharged into a feed vessel. The salt solution is

continuously heated to 258°C in two heat exchangers and
kept at a pressure of 34 bar in a tubular reactor and
then discharged by way of a nozzle. The precondensate
is dried for 24 hours at 120°C under a vacuum of
30 mbar.

Inventive examples 11-15 (IE11-IE15) and comparative
examples 10 and 11 (CE10 and CE11)
The postcondensate from inventive examples IE8-IE10,
PostC is compounded in a twin-screw extruder from
Werner and Pfleiderer using a screw diameter of 25 mm

with prescribed process parameters (barrel temperature,
screw rotation rate, and throughput). The product is
drawn off in the form of a strand from a die of 3 mm
diameter, and pelletized. The pellets are dried for 24
hours at 120°C.

Grivory HTV-5H1 is a 50%-glassfiber-reinforced PA6T/6I,



compounded materials, processing by injection molding
is very difficult, because material freezes in the
injection-molding nozzle, because of the high
crystallization rate. The surface quality of 10 x 10 cm
plaques is poor because of the high crystallinity,
whereas that of the PA10T/6T copolyamides is
substantially better.



Grilamid XE 3835 is an impact-modified PA12 from EMS-
CHEMIE AG, Switzerland.
Tubes of dimensions 8x1 mm were produced under the
stated conditions from the products listed in table 8,
using a BMA 60-24D Nokia Maillefer pipe extruder.
Examples using flat glass fibers, inventive examples
IE16-IE18




Flat glass fibers: NITTOBO CSG3PA-820, 3 mm long, 28 µm
wide, 7 µm thick,
aspect ratio of cross-sectional
axes = 4,
aminosilane size, NITTO BOSEKI,
Japan (flat glass fibers for the
purposes of the description above)
Inventive examples IE16 to IE18 are based on a
postcondensate of the copolyamide PA10T/6T with a molar
ratio of 85:15, which was prepared by analogy with the
preceding inventive examples from the corresponding
precondensate.
The compounded materials reinforced with flat glass
fibers in particular have relatively high transverse
stiffness and transverse strength, and also a
relatively high HDT C value, in comparison with the
conventionally reinforced compounded materials, i.e.
those reinforced with glass fibers whose cross section
is circular.
Examples of flame-retardant molding compositions,
inventive examples IE19-IE21 and comparative examples
CE13 and CE14:



The examples IE19 to IE21 are based on a postcondensate
of the copolyamide PA10T/6T with a molar ratio of
85:15, prepared by analogy with the preceding inventive
examples from the corresponding precondensate.
The halogen-free flame-retardant molding compositions
of inventive examples 19 to 21 are reliably V-0, with
and without glassfiber reinforcement, whereas the
molding compositions of CE13 and CE14 achieve merely
the UL classification V-2, despite identical flame-
retardant modification.

Therefore, the "polyamide molding composition" according to
the present invention is not a mere admixture resulting only
in the aggregation of the properties of the components
thereof or a process for producing such "composition"

WE CLAIM :
1. A polyamide molding composition with the following
constitution:
(A) from 30 to 100% by weight of at least one
copolyamide 10T/6T, wherein this is composed of
(A1) from 40 to 95 mol% of 10T units, formed from
the monomers 1,10-decanediamine and
terephthalic acid
(A2) from 5 to 60 mol% of 6T units, formed from the
monomers 1,6-hexanediamine and terephthalic
acid
(B) from 0 to 70% by weight of reinforcing materials
and/or fillers
(C) from 0 to 50% by weight of additives and/or further
polymers
where the entirety of components A to C is 100%,
with the proviso that in component (A) , independently of
one another, in (Al) and/or (A2) up to 30 mol%, based on
the entirety of the dicarboxylic acids, of the
terephthalic acid can have been replaced by other
aromatic, aliphatic, or cycloaliphatic dicarboxylic acids
having from 6 to 36 carbon atoms,
and with the proviso that in component (A), independently
of one another, in (A1) and/or (A2) up to 30 mol% of
1,10-decanediamine and respectively 1,6-hexanediamine,
based on the entirety of the diamines, can have been
replaced by other diamines having from 4 to 36 carbon
atoms,
and with the proviso that not more than 30 mol% in
component (A), based on the entirety of the monomers, can
have been formed via lactams or amino acids,

and with the proviso that the concentration of the
entirety of the monomers which replace the terephthalic
acid, 1,6-hexanediamine, and 1,10-decanediamine does not
exceed 30 mol%, based on the entirety of the monomers
used in component A.
2. The polyamide molding composition as claimed in claim 1,
wherein the melting point and respectively the
temperature of deflection to ISO-R 75, method A
(DIN 53 461) of component (A) and/or of the entire
polyamide molding composition is above 2 60°C or above
270°C, preferably in the range from 270 to 320°C,
particularly preferably in the range from 270 to 310°C.
3. The polyamide molding composition as claimed in any of
the preceding claims, wherein the water absorption of
component (A) and/or of the entire polyamide molding
composition is less than 5% by weight, in particular less
than 4% by weight, after 240 h in water at 95°C.
4. The polyamide molding composition as claimed in any of
the preceding claims, wherein the ratio of wet:dry
tensile moduli of elasticity is greater than or equal to
0.95, preferably greater than or equal to 1.00.
5. The polyamide molding composition according to any of the
preceding claims, wherein the ratio of wet:dry maximum
tensile strengths is greater than or equal to 0.85,
preferably greater than or equal to 0.90.
6. The polyamide molding composition as claimed in any of
the preceding claims, wherein, within component (A) , the
(A1) fractions make up from 40 to 90 mol% and the (A2)
fractions make up from 10 to 60 mol%, and with preference
the (A1) fractions make up from 40 to 80 mol% and the
(A2) fractions make up from 20 to 60 mol%, and with

particular preference the (A1) fractions make up from 40
to 75 mol% and the (A2) fractions make up from 25 to
60 mol%.
7. The polyamide molding composition according to any of the
preceding claims, wherein the 10T/6T copolyamide of
component (A) is based in essence exclusively, preferably
completely exclusively, on terephthalic acid as
dicarboxylic acid.
8. The polyamide molding composition as claimed in any of
the preceding claims 1 to 6, wherein the other aromatic,
aliphatic, or cycloaliphatic dicarboxylic acids having
from 6 to 36 carbon atoms, which to some extent replace
the terephthalic acid, have been selected from the
following group: naphthalenedicarboxylic acid (NDA),
isophthalic acid (IPS), adipic acid, suberic acid,
azaleic acid, sebacic acid, undecanedioic acid,
dodecanedioic acid, brassylic acid, tetradecanedioic
acid, pentadecanedioic acid, hexadecanedioic acid,
octadecanedioic acid, dimer acid, cis- and/or trans-
cyclohexane-1,4-dicarboxylic acid, cis- and/or trans-
cyclohexane-1,3-dicarboxylic acid (CHDA), and
combinations thereof.
9. The polyamide molding composition as claimed in claim 8,
wherein, for a higher glass transition temperature, the
other aromatic, aliphatic, or cycloaliphatic dicarboxylic
acids having from 6 to 36 carbon atoms, which to some
extent replace the terephthalic acid, have been selected
from the following group: naphthalenedicarboxylic acid
(NDA), isophthalic acid (IPS), trans-cyclohexane-1,3-
dicarboxylic acid (CHDA) or combinations thereof,
preference being given to naphthalenedicarboxylic acid
(NDA), and for a lower glass transition temperature they
have been selected from the following group:
dodecanedioic acid, brassylic acid, tetradecanedioic

acid, pentadecanedioic acid, hexadecanedioic acid,
octadecanedioic acid, dimer acid, or combinations
thereof, preference being given to dodecanedioic acid.
10. The polyamide molding composition as claimed in any of
the preceding claims, wherein the 10T/6T copolyamide of
component (A) is based in essence exclusively, preferably
completely exclusively, on 1,10-decanediamine for (A1)
and 1,6-hexanediamine for (A2), as diamine.
11. The polyamide molding composition as claimed in any of
the preceding claims 1 to 9, wherein the other diamines
having from 4 to 36 carbon atoms which in component (A) ,
independently of one another, in (A1) and/or (A2) replace
up to 30 mol% of 1,10-decanediamine and respectively 1,6-
hexanediamine, based on the entirety of the diamines,
have been selected from the following group: linear or
branched, aliphatic diamines, such as 1,4-butanediamine,
1,5-pentanediamine, 2-methyl-1,5-pentanediamine (MPMD),
1,8-octanediamine (OMDA), 1,9-nonanediamine (NMDA), 2-
methyl-1,8-octanediamine (MODA), 2,2,4-trimethyl-
hexamethylenediamine (TMHMD), 2,4,4-trimethylhexa-
methylenediamine (TMHMD), 5-methyl-1,9-nonanediamine,
1,11-tridecanediamine, 2-butyl-2-ethyl-1,5-
pentanediamine, 1,12-dodecanediamine, 1,13-
tridecanediamine, 1,14-tetradecanediamine, 1,16-
hexadecanediamine, 1,18-octadecanediamine,
cycloaliphaticdiamines such as cyclohexanediamine, 1,3-
bis(aminomethyl)cyclohexane (BAC), isophoronediamine,
norbornanedimethylamine, 4,4' -diaminodicyclohexylmethane
(PACM), 2,2-(4,4'-diaminodicyclohexyl)propane (PACP), and
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM),
araliphatic diamines, such as m-xylylenediamine (MXDA),
and combinations thereof.
12. The polyamide molding composition as claimed in claim 11,
wherein, for a higher glass transition temperature, the

other diamines having from 4 to 36 carbon atoms which in
component (A), independently of one another, in (A1) and/
or (A2) replace up to 30 mol% of 1,10-decanediamine and
respectively 1,6-hexanediamine, based on the entirety of
the diamines, have been selected from the following
group: 2-methyl-1,5-pentanediamine (MPMD), 2-methyl-1,8-
octanediamine (MODA), 2,2,4-trimethylhexamethylenediamine
(TMHMD), 1,3-bis(aminomethyl)cyclohexane (BAC), 4,4'-
diaminodicyclohexylmethane (PACM), 3,3'-dimethyl-4,4'-
diaminodicyclohexylmethane (MACM), and combinations
thereof, preference being given here to 1,3-
bis(aminomethyl)cyclohexane (BAC) and/or 4,4'-
diaminodicyclohexylmethane (PACM), and, for a lower glass
transition temperature they have been selected from the
following group: 1,12-dodecanediamine, 1,13-
tridecanediamine, 1,14-tetradecanediamine, 1,16-
hexadecanediamine, 1,18-octadecanediamine, and
combinations thereof, preference being given here to
1,12-dodecanediamine.
13. The polyamide molding composition as claimed in any of
the preceding claims, wherein component (A) is in essence
exclusively, preferably completely exclusively, composed
of the constituents (A1) and (A2).
14. The polyamide molding composition as claimed in any of
the preceding claims 1 to 12, wherein the lactams or
amino acids have been selected from the following group:
caprolactam (CL) , α,ω-aminocaproic acid, α,ω-
aminononanoic acid, α,ω-aminoundecanoic acid (AUA),
laurolactam (LL), ω-aminododecanoic acid (ADA), and
combinations of these.
15. The polyamide molding composition as claimed in any of
the preceding claims, wherein component (B) is at least
to some extent glass fibers and/or carbon fibers, where
these can preferably involve short fibers, such as

chopped glass whose length is from 2 to 50 mm, or
continuous-filament fibers, and where further preference
is given to fibers which have non-circular cross section
and which have a main cross-sectional axis: secondary
cross-sectional axis dimensional ratio of more than 2,
preferably in the range from 2 to 8, in particular from 2
to 5.
16. The polyamide molding composition as claimed in claim 15,
wherein component (B) involves short fibers and/or
continuous-filament fibers in the form of glass fibers,
where these preferably have a diameter of from 10 to
20 µm, particularly preferably from 12 to 18 µm, and
where the cross section of the glass fibers can be round,
oval, or angular.
17. The polyamide molding composition as claimed in claim 16,
which involves short fibers and/or continuous-filament
glass fibers whose diameter is from 10 to 14 µm, in
particular those whose diameter is from 10 to 12 µm.
18. The polyamide molding composition as claimed in any of
the preceding claims, wherein component (C) involves
additives and/or further polymers selected from the
following group: impact modifiers, adhesion promoters or
compatibilizers, crystallization accelerators or
crystallization retarders, flow aids, lubricants, mold-
release agents, pigments, dyes and markers, plasticizers,
stabilizers, processing aids, flame-retardant additions,
preferably halogen-free flame-retardant additions,
antistatic agents, nanoparticles in lamellar form,
conductivity additives, such as carbon black, graphite
powder, or carbon nanofibrils, residues from
polymerization processes, e.g. catalysts, salts and their
derivatives, and regulators, such as monoacids,
monoamines.

19. The polyamide molding composition as claimed in any of
the preceding claims, wherein the concentration of the
entirety of the monomers which replace terephthalic acid,
1,6-hexanediamine, and 1,10-decanediamine does not exceed
20 mol%, preferably 10 mol%, based on the entirety of the
monomers used in component A.
20. A polyamide mixture comprising a polyamide molding
composition as claimed in any of the preceding claims.
21. A polyamide mixture comprising a polyamide molding
composition as claimed in any of the preceding claims and
polyphenylene ether, in particular in the form of
homopolymers, of copolymer, of graft copolymers, of block
copolymer, or of ionomers, particularly preferably
poly(2,6-diethyl-1,4-phenylene) ether, poly(2-methyl-6-
ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-
phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether,
poly(2-ethyl-6-propyl-1,4-phenylene) ether, or copolymers
such as those which contain 2,3,6-trimethylphenol, or a
mixture thereof, particular preference being given here
to the presence of from 10 to 45% by weight of
polyphenylene ether and, if appropriate up to 30% by
weight, preferably up to 15% by weight, of impact
modifier in the mixture.
22. A pelletized material, in particular a long-fiber-
reinforced elongate pelletized material, or a
semifinished product, or a molding, composed of a
polyamide molding composition as claimed in any of the
preceding claims 1 to 19, or composed of a polyamide
mixture as claimed in either of claims 21 and 20,
particularly preferably for use in a moist and/or wet
environment.
23. A powder composed of a polyamide molding composition as
claimed in any of the preceding claims 1 to 19, or

composed of a polyamide mixture as claimed in either of
claims 21 and 20, particularly preferably with an average
grain size of from 30 to 200 µm.
24. The powder as claimed in claim 23, whose solution
viscosity at 0.5% by weight in m-cresol at 20°C is in the
range from 1.3 to 2.0, where the polyamide molding
composition has preferably been regulated, particularly
preferably using a carboxy end group: amino end group
ratio greater than or equal to 1:2 and respectively 2:1,
preferably greater than or equal to 1:3 and respectively
3:1.
25. The powder as claimed in either of claims 23 and 24,
which involves a mixture of oppositely difunctionally
regulated PA10T/6T composed of separately amine-regulated
and carboxy-regulated powder particles.
26. The powder as claimed in any of claims 23 to 25, which
comprises, alongside 10T/6T copolyamide particles, a
further filler, particularly preferably in the form of
solid or hollow glass beads, preferably with an average
diameter of from 20 to 80 µm.
27. The use of a powder as claimed in any of claims 23 to 26
in a selective laser-sintering process.
28. A molding produced using a polyamide molding composition
as claimed in any of claims 1 to 19, using a polyamide
mixture as claimed in either of claims 20 to 21, using a
pelletized material as claimed in claim 22, or using a
powder as claimed in any of claims 23 to 26, in the
latter case preferably produced in a selective laser-
sintering process.
29. A process for the preparation of a polyamide molding
composition as claimed in any of the preceding claims 1

to 19, which comprises adding, to the mononomer mixtures,
during the preparation of component (A), a proportion of
from 0.005 to 1.5% by weight of at least one
polycondensation catalyst, where this preferably involves
phosphorus compounds, such as phosphoric acid,
phosphorous acid, hypophosphorous acid, phenylphosphonic
acid, phenylphosphinic acid, and/or salts thereof with
cations of valency from 1 to 3, e.g. Na, K, Mg, Ga, Zn,
or Al, and/or their esters, such as triphenyl phosphate,
triphenyl phosphite, or tris(nonylphenyl) phosphite, or a
mixture thereof.
30. The process as claimed in claim 29, wherein the
polycondensation catalyst involves hypophosphorous acid
and sodium hydrogen hypophosphite monohydrate in an
amount of from 100 to 500 ppm of phosphorus, based on the
semiaromatic 10T/6T copolyamide (A).
31. The process as claimed in either of claims 29 and 30,
wherein, to compensate diamine loss, a diamine excess of
from 1 to 8% by weight, based on the entirety of the
diamines, is added to the monomer mixture.
32. The process as claimed in any of claims 29 to 31,
wherein, for regulation of the molar mass, of the
relative viscosity and respectively of the flowability or
the MVR, regulators are added to the mixture and/or to
the precondensate and these can involve monoacids or
monoamines, preferably selected from the following group:
aliphatic, cycloaliphatic or aromatic monocarboxylic
acids, or monoamines, e.g. acetic acid, propionic acid,
butyric acid, valeric acid, caproic acid, lauric acid,
stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid,
benzoic acid, butylamine, pentylamine, hexylamine, 2-
ethylhexylamine, n-octylamine, n-dodecylamine, n-
tetradecylamine, n-hexadecylamine, stearylamine,
cyclohexylamine, 3-(cyclohexylamino)propylamine,

methylcyclohexylamine, dimethylcyclohexylamine,
benzylamine, 2-phenylethylamine, and respectively
combinations thereof, or monofunctional compounds which
can react with an amino group or acid group, e.g.
anhydrides, isocyanates, acyl halides, or esters, and
respectively combinations of these, where the amount used
of the regulators is preferably from 10 to 200 mmol/kg -
regulator/polymer.


ABSTRACT
A polyamide molding composition with the following
constitution is described:
(A) from 30 to 100% by weight of at least one
10T/6T copolyamide, where this is composed of
(Al) from 40 to 95 mol% of 10T units, formed
from the monomers 1,10-decanediamine and
terephthalic acid
(A2) from 5 to 60 mol% of 6T units, formed
from the monomers 1,6-hexanediamine and
terephthalic acid
(B) from 0 to 70% by weight of reinforcing
materials and/or fillers
(C) from 0 to 50% by weight of additives and/or
further polymers
where the entirety of components A to C is 100%, with
the proviso that in component (A) up to 30 mol%, based
on the entirety of the dicarboxylic acids, of the
terephthalic acid can have been replaced by other
aromatic, aliphatic, or cycloaliphatic dicarboxylic
acids, and with the proviso that in component (A) up to
30 mol% of 1,10-decanediamine and respectively 1,6-
hexanediamine, based on the entirety of the diamines,
can have been replaced by other diamines, and with the
proviso that not more than 30 mol% in component (A) ,
based on the entirety of the monomers, can have been
formed via lactams or amino acids. Uses of this
polyamide molding composition are moreover described,
as also are processes for the preparation of these
polyamide molding compositions.

Documents:

00802-kol-2008-abstract.pdf

00802-kol-2008-claims.pdf

00802-kol-2008-correspondence others.pdf

00802-kol-2008-description complete.pdf

00802-kol-2008-drawings.pdf

00802-kol-2008-form 1.pdf

00802-kol-2008-form 2.pdf

00802-kol-2008-form 3.pdf

00802-kol-2008-form 5.pdf

802-KOL-2008-(02-01-2012)-EXAMINATION REPORT REPLY RECIEVED.pdf

802-KOL-2008-(02-01-2012)-OTHERS.pdf

802-KOL-2008-(02-01-2012)-PA-CERTIFIED COPIES.pdf

802-KOL-2008-(09-07-2012)-ABSTRACT.pdf

802-KOL-2008-(09-07-2012)-AMANDED CLAIMS.pdf

802-KOL-2008-(09-07-2012)-AMANDED PAGES OF SPECIFICATION.pdf

802-KOL-2008-(09-07-2012)-CORRESPONDENCE.pdf

802-KOL-2008-(09-07-2012)-DESCRIPTION (COMPLETE).pdf

802-KOL-2008-(09-07-2012)-DRAWINGS.pdf

802-KOL-2008-(09-07-2012)-FORM-1.pdf

802-KOL-2008-(09-07-2012)-FORM-2.pdf

802-KOL-2008-(09-07-2012)-FORM-3.pdf

802-KOL-2008-(09-07-2012)-OTHERS.pdf

802-KOL-2008-(09-07-2012)-PA.pdf

802-KOL-2008-(09-07-2012)-PETITION UNDER RULE 137.pdf

802-KOL-2008-ASSIGNMENT.pdf

802-KOL-2008-CORRESPONDENCE 1.1.pdf

802-KOL-2008-CORRESPONDENCE 1.2.pdf

802-KOL-2008-EXAMINATION REPORT.pdf

802-KOL-2008-FORM 1.pdf

802-kol-2008-form 18.pdf

802-KOL-2008-FORM 3 1.2.pdf

802-KOL-2008-FORM 3.1.pdf

802-KOL-2008-FORM 5.pdf

802-KOL-2008-GRANTED-ABSTRACT.pdf

802-KOL-2008-GRANTED-CLAIMS.pdf

802-KOL-2008-GRANTED-DESCRIPTION (COMPLETE).pdf

802-KOL-2008-GRANTED-DRAWINGS.pdf

802-KOL-2008-GRANTED-FORM 1.pdf

802-KOL-2008-GRANTED-FORM 2.pdf

802-KOL-2008-GRANTED-SPECIFICATION.pdf

802-KOL-2008-OTHERS.pdf

802-KOL-2008-PA.pdf

802-KOL-2008-PRIORITY DOCUMENT.pdf

802-KOL-2008-REPLY TO EXAMINATION REPORT.pdf

802-KOL-2008-TRANSLATED COPY OF PRIORITY DOCUMENT 1.1.pdf

802-KOL-2008-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf

abstract-00802-kol-2008.jpg


Patent Number 254299
Indian Patent Application Number 802/KOL/2008
PG Journal Number 42/2012
Publication Date 19-Oct-2012
Grant Date 17-Oct-2012
Date of Filing 01-May-2008
Name of Patentee EMS-PATENT AG
Applicant Address REICHENAUERSTRASSE 7013 DOMAT/EMS
Inventors:
# Inventor's Name Inventor's Address
1 HEWEL, MANFRED DR. VIA TUARGA 6, 7013 DOMAT/EMS
PCT International Classification Number C08K 3/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 07 107 474.4 2007-05-03 EUROPEAN UNION