Note: Descriptions are shown in the official language in which they were submitted.
I
LASER-TRANSPARENT POLYESTERS
The invention relates to the use of thermoplastic molding compositions
comprising, as
essential components,
A) from 29 to 99.95% by weight of a polyester,
B) from 0.05 to 2.0% by weight of Na2CO3, K2CO3, NaHCO3, KHCO3, or a
mixture of
these, based on 100% by weight of A) and B), and also
C) from 0 to 70% by weight of further additives, where the total of the %
by weight values
for A) to C) is 100%,
for producing laser-transparent moldings of any type.
The invention further relates to the use of the laser-transparent moldings for
producing
moldings by means of laser transmission welding processes. The invention
further relates to
a process for producing welded moldings comprising using laser transmission
welding to
bond laser-transparent moldings according to the invention or according to the
use of the
invention, to laser-absorbent moldings. The invention also relates to the use
of the laser-
transparent moldings of the invention in various application sectors.
Components B) of this type are by way of example described in EP-A 214581 and
DE-A
2014770 as nucleating agents for compounded PET materials. The optical
properties of the
compounded materials were not investigated.
There are various processes (Kunststoffe 87, (1997), 11, 1632 ¨ 1640) for
welding plastics
moldings. In the case of the widely used processes of heated-tool welding and
vibration
welding (e.g. of motor-vehicle inlet manifolds), precondition for a stable
weld is adequate
softening of the adherends in the contact zone prior to the actual step that
produces the join.
Laser transmission welding is a method providing an alternative to vibration
welding and
heated-tool welding, and has seen a constant increase in its use in recent
times, in particular
with use of diode lasers.
The technical literature describes the fundamental principles of laser
transmission welding
(Kunststoffe 87, (1997) 3, 348 ¨ 350; Kunststoffe 88, (1998), 2, 210 ¨ 212;
Kunststoffe 87(1997)
11, 1632 ¨ 1640; Plastverarbeiter 50 (1999) 4, 18 ¨ 19; Plastverarbeiter 46
(1995) 9, 42 - 46).
Precondition for the use for laser transmission welding is that the radiation
emitted from
the laser first passes through a molding which has adequate transparency for
laser light
of the wavelength used, and which in this patent application is hereinafter
termed
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laser-transparent molding, and is then absorbed, in a thin layer, by a second
molding
which is in contact with the laser-transparent molding and which hereinafter
is termed
laser-absorbent molding. Within the thin layer that absorbs the laser light,
the energy of
the laser is converted into heat, which leads to melting within the contact
zone and
finally to bonding of the laser-transparent and of the laser-absorbent molding
via a
weld.
Laser transmission welding usually uses lasers in the wavelength range from
600 to
1200 nm. In the wavelength range of the lasers used for thermoplastics
welding, it is
usual to use Nd:YAG laser (1064 nm) or high-power diode lasers (from 800 to
1000 nm). When the terms laser-transparent and laser-absorbent are used
hereinafter,
they always refer to the abovementioned wavelength range.
A requirement for the laser-transparent molding, in contrast to the laser-
absorbent
molding, is high laser transparency in the preferred wavelength range, so that
the laser
beam can penetrate as far as the weld area, with the necessary energy. By way
of
example, transmittance for IR laser light is measured by using a
spectrophotometer
and an integrating photometer sphere. This measurement system also detects the
diffuse fraction of the transmitted radiation. The measurement is carried out
not merely
at one wavelength but within a spectral range which comprises all of the laser
wavelengths currently used for the welding procedure.
Users presently have access to a number of laser-welding-process variants
based on
the transmission principle. By way of example, contour welding is a sequential
welding
process in which either the laser beam is conducted along a freely
programmable weld
contour or the component is moved relatively to the immovable laser. In the
simultaneous welding process, the linear radiation emitted from individual
high-power
diodes is arranged along the contour of the weld. The melting and welding of
the entire
contour therefore takes place simultaneously. The quasi-simultaneous welding
process
is a combination of contour welding and simultaneous welding. Galvanometric
mirrors
(scanners) are used to conduct the laser beam at very high velocity at 10 m/s
or more
along the contour of the weld. The high traverse rate provides progressive
heating and
melting of the region of the joint. In comparison with the simultaneous
welding process,
there is high flexibility for alterations in the contour of the weld. Mask
welding is a
process in which a linear laser beam is moved transversely across the
adherends. A
mask is used for controlled screening of the radiation, and this impacts the
area to be
joined only where welding is intended. The process can produce very precisely
positioned welds. These processes are known to the person skilled in the art
and are
described by way of example in "Handbuch Kunststoff-Verbindungstechnik"
[Handbook
of plastics bonding technology] (G. W. Ehrenstein, Hanser, ISBN 3-446-22668-0)
and/or DVS-Richtlinie 2243 "Laserstrahlschweiflen thermoplastischer
Kunststoffe"
[German Welding Society Guideline 2243 "Laser welding of thermoplastics"].
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Irrespective of the process variant used, the laser welding process is highly
dependent
on the properties of the materials of the two adherends. The degree of laser
transparency (LT) of the transparent component has a direct effect on the
speed of the
process, through the amount of energy that can be introduced per unit of time.
The
inherent microstructure, mostly in the form of spherulites, of semicrystalline
thermoplastics generally gives them relatively low laser transparency. These
spherulites scatter the incident laser light to a greater extent than the
internal structure
of a purely amorphous thermoplastic: back-scattering leads to reduced total
amount of
transmitted energy, and diffuse (lateral) scattering often leads to broadening
of the
laser beam and therefore to impaired weld precision. These phenomena are
particularly evident in polybutylene terephthalate (PBT), which in comparison
with other
thermoplastics that crystallize well, such as PA, exhibits particularly low
laser
transparency and a high level of beam expansion. PBT therefore continues to be
comparatively little used as material for laser-welded components, although
other
aspects of its property profile (e.g. good dimensional stability and low water
absorption)
make it very attractive for applications of this type. Although
semicrystalline
morphology is generally unhelpful for high laser transparency, it provides
advantages in
terms of other properties. By way of example, semicrystalline materials
continue to
have mechanical strength above the glass transition point and generally have
better
chemicals resistance than amorphous materials. Materials that crystallize
rapidly also
provide processing advantages, in particular quick demoldability and therefore
short
cycle times. It is therefore desirable to combine semicrystallinity with rapid
crystallization and high laser transparency.
There are various known approaches to laser-transparency improvement in
polyesters,
in particular PBT. In principle, these can be divided into blends/mixtures and
refractive-
index matching.
The approach using blends/mixtures is based on "dilution" of the low-laser-
transparency PBT by using a high-laser-transparency partner in the
blend/mixture. "
Examples of this are found in the following specifications: JP2004/315805A1
(PBT +
PC/PET/SA + filler + elastomer), DE-A1-10330722 (generalized blend of a
semicrystalline thermoplastic with an amorphous thermoplastic in order to
increase LT;
spec. PBT + PET/PC + glass fiber), JP2008/106217A (PBT + copolymer with
1,4-cyclohexanedimethanol; LT of 16% increased to 28%). A disadvantage here is
that
the resultant polymer blends inevitably have properties markedly different
from those of
products based predominantly on PBT as matrix.
The refractive-index matching approach is based on the different refractive
indices of
amorphous and crystalline PBT, and also of the fillers. By way of example,
comonomers have been used here: JP2008/163167 (copolymer of PBT and siloxane),
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JP2007/186584 (PBT + bisphenol A diglycidyl ether) and JP2005/133087 (PBT + PC
+
elastomer + high-refractive-index silicone oil) may be mentioned as examples.
Although this leads to an increase in laser transparency, this is achieved
with loss of
mechanical properties. The refractive-index difference between filler and
matrix can
also be reduced, see JP2009/019134 (epoxy resin coated onto glass fibers in
order to
provide matching at the optical interface between fiber and matrix), or
JP2007/169358
(PBT with high-refractive-index glass fiber). Starting materials of this type
are, however,
disadvantageous because of their high costs and/or the additional stages that
they
require within the production process.
The effects achieved in relation to laser-transparency increase are also
overall
relatively minor and therefore not entirely satisfactory.
The object of the present invention was therefore to improve the laser
transparency of
polyesters. The molding compositions defined in the introduction were
accordingly
found. The dependent claims give preferred embodiments.
The molding compositions of the invention comprise, as component A), from 29
to
99.85% by weight, preferably from 99.5 to 99.8% by weight, and in particular
from 99.6
to 99.7% by weight, of at least one thermoplastic polymer, based on components
A)
and B).
At least one of the polyesters in component A) is a semicrystalline polyester.
Preference is given to components A) which comprise at least 50% by weight of
semicrystalline polyesters. Said proportion is particularly preferably 70% by
weight
(based in each case on 100% by weight of A)).
Based on 100% of the molding compositions made of A) to C) (i.e. inclusive of
C)),
these comprise
from 30 to 100% by weight of A) + B), preferably from 50 to 100% by weight,
and
from 0 to 70% by weight of C), preferably from 0 to 50% by weight.
An essential constituent of the above relative magnitudes is that the
proportion of
component B) is always based on the polyester, since said relationship is
intended to
lie within the limits mentioned. The additives C) can have an effect on laser
transparency. This effect in essence depends on the scattering and absorption
properties of the additives. The optical properties of the compounded material
are in
essence a summation of the optical properties of the matrix of the invention
(components A+B) and those of the additives (components C).
The polyesters A) used generally comprise those based on aromatic dicarboxylic
acids
and on an aliphatic or aromatic dihydroxy compound.
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A first group of preferred polyesters is that of polyalkylene terephthalates
having in
particular from 2 to 10 carbon atoms in the alcohol moiety.
5 Polyalkylene terephthalates of this type are known per se and are
described in the
literature. Their main chain comprises an aromatic ring which derives from the
aromatic
dicarboxylic acid. There may also be substitution in the aromatic ring, e.g.
by halogen,
such as chlorine or bromine, or by C1-C4-alkyl, such as methyl, ethyl, iso- or
n-propyl,
or n-, iso- or tert-butyl groups.
These polyalkylene terephthalates may be produced by reacting aromatic
dicarboxylic
acids, or their esters or other ester-forming derivatives, with aliphatic
dihydroxy
compounds in a manner known per se.
Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid,
terephthalic acid
and isophthalic acid or mixtures of these. Up to 30 mol /0, preferably not
more than
10 mol%, of the aromatic dicarboxylic acids may be replaced by aliphatic or
cycloaliphatic dicarboxylic acids, such as adipic acid, azelaic acid, sebacic
acid,
dodecanedioic acids and cyclohexanedicarboxylic acids.
Preferred aliphatic dihydroxy compounds are diols having from 2 to 6 carbon
atoms, in
particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol,
1,4-
hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl
glycol, and
mixtures of these.
Particularly preferred polyesters (A) are polyalkylene terephthalates derived
from
alkanediols having from 2 to 6 carbon atoms. Among these, particular
preference is
given to polyethylene terephthalate, polypropylene terephthalate and
polybutylene
terephthalate, and mixtures of these. Preference is also given to PET and/or
PBT
which comprise, as other monomer units, up to 1% by weight, preferably up to
0.75%
by weight, of 1,6-hexanediol and/or 2-methyl-1,5-pentanediol.
The intrinsic viscosity of the polyesters (A) is generally in the range from
50 to 220,
preferably from 80 to 160 (measured in 0.5% strength by weight solution in a
phenol/o-dichlorobenzene mixture in a ratio by weight of 1:1) at 25 C to ISO
1628.
Particular preference is given to polyesters whose carboxy end group content
is from 0
to 100 meq/kg of polyester, preferably from 10 to 50 meq/kg of polyester and
in
particular from 15 to 40 meq/kg of polyester. Polyesters of this type may be
produced,
for example, by the process of DE-A 44 01 055. The carboxy end group content
is
usually determined by titration methods (e.g. potentiometry).
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Particularly preferred molding compositions comprise, as component A), a
mixture of
polyesters, at least one being PBT. An example of the proportion of the
polyethylene
terephthalate in the mixture is preferably up to 50% by weight, in particular
from 10 to
35% by weight, based on 100% by weight of A).
It is also advantageous to use PET recyclates (also termed scrap PET)
optionally in a
mixture with polyalkylene terephthalates, such as PBT.
Recyclates are generally:
1) those known as post-industrial recyclates: these are production wastes
during
polycondensation or during processing, e.g. sprues from injection molding,
start-
up material from injection molding or extrusion, or edge trims from extruded
sheets or films.
2) post-consumer recyclates: these are plastics items which are collected
and
treated after utilization by the end consumer. Blow-molded PET bottles for
mineral water, soft drinks and juices are easily the predominant items in
terms of
quantity.
Both types of recyclate may be used either as regrind or in the form of
pellets. In the
latter case, the crude recycled materials are isolated and purified and then
melted and
pelletized using an extruder. This usually facilitates handling and free-
flowing
properties, and metering for further steps in processing.
The recycled materials used may either be pelletized or in the form of
regrind. The
edge length should not be more than 10 mm and should preferably be less than 8
mm.
Because polyesters undergo hydrolytic cleavage during processing (due to
traces of
moisture) it is advisable to predry the recycled material. Residual moisture
content after
drying is preferably <0.2%, in particular <0.05%.
Another class to be mentioned is that of fully aromatic polyesters deriving
from
aromatic dicarboxylic acids and aromatic dihydroxy compounds.
Suitable aromatic dicarboxylic acids are the compounds previously described
for the
polyalkylene terephthalates. The mixtures preferably used are made from 5 to
100 mol% of isophthalic acid and from 0 to 95 mol% of terephthalic acid, in
particular
from about 50 to about 80% of terephthalic acid and from 20 to about 50% of
isophthalic acid.
The aromatic dihydroxy compounds preferably have the general formula
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HO * Z 1100 OH
in which Z is an alkylene or cycloalkylene group having up to 8 carbon atoms,
an
arylene group having up to 12 carbon atoms, a carbonyl group, a sulfonyl
group, an
oxygen atom or sulfur atom, or a chemical bond, and in which m has the value
from 0
to 2. The phenylene groups in the compounds may also have substitution by C1-
C6-
alkyl groups or alkoxy groups, and fluorine, chlorine, or bromine.
Examples of parent compounds for these compounds are
dihydroxybiphenyl,
di(hydroxyphenyl)alkane,
di(hydroxyphenyl)cycloalkane,
di(hydroxyphenyl) sulfide,
di(hydroxyphenyl) ether,
di(hydroxyphenyl) ketone,
di(hydroxyphenyl) sulfoxide,
axi-di(hydroxyphenyl)dialkylbenzene,
di(hydroxyphenyl) sulfone, di(hydroxybenzoyl)benzene,
resorcinol, and hydroquinone, and also the ring-alkylated and ring-halogenated
derivatives of these.
Among these, preference is given to
4,4'-dihydroxybiphenyl,
2,4-di(4'-hydroxyphenyI)-2-methylbutane,
a,a'-di(4-hydroxypheny1)-p-diisopropylbenzene,
2,2-di(3'-methyl-4'-hydroxyphenyl)propane, and
2,2-di(3'-chloro-4'-hydroxyphenyl)propane,
and in particular to
2,2-di(4'-hydroxyphenyl)propane,
2,2-di(3',5-dichlorodihydroxyphenyl)propane,
1,1-di(4'-hydroxyphenyl)cyclohexane,
3,4'-dihydroxybenzophenone,
4,4'-dihydroxydiphenyl sulfone and
2,2-di(3',5'-dimethy1-4'-hydroxyphenyl)propane
or a mixture of these.
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It is, of course, also possible to use mixtures of polyalkylene terephthalates
and fully
aromatic polyesters. These generally comprise from 20 to 98% by weight of the
polyalkylene terephthalate and from 2 to 80% by weight of the fully aromatic
polyester.
It is, of course, also possible to use polyester block copolymers, such as
copolyetheresters. Products of this type are known per se and are described in
the
literature, e.g. in US-A 3 651 014. Corresponding products are also available
commercially, e.g. Hytrel (DuPont).
In the invention, the term polyester includes halogen-free polycarbonates.
Examples of
suitable halogen-free polycarbonates are those based on biphenols of the
general
formula
HO OH
= Q
in which Q is a single bond, a C-1-C8-alkylene group, a C2-C3-alkylidene
group, a C3-C6-
cycloalkylidene group, a C6-C12-arylene group, or else -0-, -S- or -SO2-, and
m is a
whole number from 0 to 2.
The phenylene radicals of the biphenols may also have substituents, such as C1-
C6-
alkyl or Ci-C6-alkoxy.
Examples of preferred biphenols of this formula are hydroquinone, resorcinol,
4,4'-
dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyI)-2-
methylbutane and 1,1-bis(4-hydroxyphenyl)cyclohexane. Particular preference is
given
to 2,2-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)cyclohexane,
and
also to 1,1-bis(4-hydroxyphenyI)-3,3,5-trimethylcyclohexane.
Either homopolycarbonates or copolycarbonates are suitable as component A, and
preference is given to the copolycarbonates of bisphenol A, as well as to
bisphenol A
homopolymer.
Suitable polycarbonates may be branched in a known manner, specifically and
preferably by incorporating from 0.05 to 2.0 mol%, based on the total of the
biphenols
used, of at least trifunctional compounds, for example those having three or
more
phenolic OH groups.
Polycarbonates which have proven particularly suitable have relative
viscosities n f
-,rel O.
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from 1.10 to 1.50, in particular from 1.2510 1.40. This corresponds to an
average molar
mass M (weight average) of from 10 000 to 200 000 g/mol, preferably from 20
000 to
80 000 g/mol.
The biphenols of the general formula are known per se or can be produced by
known
processes.
The polycarbonates may, for example, be produced by reacting the biphenols
with
phosgene in the interfacial process, or with phosgene in the homogeneous-phase
process (known as the pyridine process), and in each case the desired
molecular
weight is achieved in a known manner by using an appropriate amount of known
chain
terminators. (In relation to polydiorganosiloxane-containing polycarbonates
see, for
example, DE-A 33 34 782.)
Examples of suitable chain terminators are phenol, p-tert-butylphenol, or else
long-
chain alkylphenols, such as 4-(1,3-tetramethylbutyl)phenol, as in DE-A 28 42
005, or
monoalkylphenols, or dialkylphenols with a total of from 8 to 20 carbon atoms
in the
alkyl substituents, as in DE-A 35 06 472, such as p-nonylphenol, 3,5-di-tert-
butylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol
and 4-
(3,5-dimethylheptyl)phenol.
For the purposes of the present invention, halogen-free polycarbonates are
polycarbonates made from halogen-free biphenols, from halogen-free chain
terminators and optionally from halogen-free branching agents, where the
content of
subordinate amounts at the ppm level of hydrolyzable chlorine, resulting, for
example,
from the production of the polycarbonates with phosgene in the interfacial
process, is
not regarded as meriting the term halogen-containing for the purposes of the
invention.
Polycarbonates of this type with contents of hydrolyzable chlorine at the ppm
level are
halogen-free polycarbonates for the purposes of the present invention.
Other suitable components A) which may be mentioned are amorphous polyester
carbonates, where phosgene has been replaced, during the preparation, by
aromatic
dicarboxylic acid units, such as isophthalic acid and/or terephthalic acid
units. For
further details reference may be made at this point to EP-A 711 810.
Other suitable copolycarbonates with cycloalkyl radicals as monomer units have
been
described in EP-A 365 916.
It is also possible to replace bisphenol A with bisphenol TMC. Polycarbonates
of this
type are commercially available from Bayer with the trademark APEC Hr.
The molding compositions of the invention comprise, as component B), from 0.05
to
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2.0% by weight, preferably from 0.1 to 0.8% by weight, and in particular from
0.25 to
0.5% by weight, based on 100% by weight of A) + B), of Na2CO3, NaHCO3, KHCO3,
K2003, or a mixture of these.
5 The carboxy end groups of the polyesters A) generally react with the salt
compounds B), whereupon the metal cation is transferred from the carbonate to
the
end group. The nucleating action of component B) is detectable even at
extremely low
concentrations. Surprisingly, laser transparency falls with very low
concentrations of
component B), and a rise in laser transparency is not achieved until higher
10 concentrations are reached.
NaHCO3 is a white, odor-free powder which is obtainable via saturation of soda
solution with CO2 in the Solvay process
NaCl + NH3+ H20 + CO2 NaHCO3 + NH4CI
or via introduction of CO2 into sodium hydroxide solution.
Sodium carbonate Na2CO3 (also termed soda) is obtainable commercially in the
form of
anhydrous soda or else with 10, 7, or 1 molecules of water of crystallization.
It is produced either by the Leblanc process (from NaCI + H2SO4) or by the
Solvay
process (calcination of NaHCO3), and it also occurs naturally in the form of
natural
soda.
K2003 (potash) is a white powder and is generally produced via the magnesia
process.
KHCO3 is generally produced via introduction of CO2 into K2CO3 solutions, and
is
obtainable commercially in the form of white crystalline powder.
The aspect ratio (ratio of the longest to shortest dimension of nonspherical
particles) of
particularly preferred components B), preferably Na2003, is from 1 to 6,
preferably from
1 to 2.9, and in particular from 1 to 2. This parameter is generally measured
visually
from optical micrographs.
The particle size distribution is usually determined by means of laser
scattering to
DIN 13320-1 (Mastersizer 2100 equipment from Malvern).
The d50 value for the particle size of particularly preferred components B,
preferably
Na2CO3, is <500 preferably from 20 to 200 pi, very particularly from
40 to 150 In
(d50 means that 50% by volume of the particles have a diameter smaller than
the stated
value; the definition is analogous for dlo and dm values.)
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The dio value is preferably s 250 11111, in particular from 10 to 100 En, and
very
particularly from 20 to 80 [in).
The cis value is preferably s 1000 run, in particular from 50 to 300 um and
very
particularly from 100 to 250 m.
The molding compositions of the invention can comprise, as component C), from
0 to
70% by weight, in particular up to 50% by weight, of further additives and
processing
aids where these differ from B) and/or A), based on 100% by weight of A), B),
and C).
Examples of conventional additives C) are amounts of up to 40% by weight,
preferably
up to 15% by weight, of elastomeric polymers (often also termed impact
modifiers,
elastomers, or rubbers).
These very generally involve copolymers, which are preferably composed of at
least
two of the following monomers: ethylene, propylene, butadiene, isobutene,
isoprene,
chloroprene, vinyl acetate, styrene, acrylonitrile, and acrylates and,
respectively,
methacrylates having from 1 to 18 carbon atoms in the alcohol component.
Polymers of this type are described, for example, in Houben-Weyl, Methoden der
organischen Chemie, Vol. 14/1 (Georg Thieme Verlag, Stuttgart, Germany, 1961),
pages 392-406, and in the monograph by C.B. Bucknall, "Toughened Plastics"
(Applied
Science Publishers, London, 1977).
Some preferred types of such elastomers are described below.
Preferred types of such elastomers are those known as ethylene-propylene (EPM)
and
ethylene-propylene-diene (EPDM) rubbers.
EPM rubbers generally have practically no residual double bonds, whereas EPDM
rubbers may have from 1 to 20 double bonds per 100 carbon atoms.
Examples which may be mentioned of diene monomers for EPDM rubbers are
conjugated dienes, such as isoprene and butadiene, non-conjugated dienes
having
from 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-
hexadiene,
2,5-dimethy1-1,5-hexadiene and 1,4-octadiene, cyclic dienes, such as
cyclopentadiene,
cyclohexadienes, cyclooctadienes and dicyclopentadiene, and also
alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-
norbornene,
2-methallyI-5-norbornene and 2-isopropeny1-5-norbornene, and tricyclodienes,
such as
3-methyltricyclo[5.2.1.021-3,8-decadiene, or a mixture of these. Preference is
given to
1,5-hexadiene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content
of
the EPDM rubbers is preferably from 0.5 to 50% by weight, in particular from 1
to 8%
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= PF 70591
12
by weight, based on the total weight of the rubber.
EPM and EPDM rubbers may preferably also have been grafted with reactive
carboxylic acids or with derivatives of these. Examples of these are acrylic
acid,
methacrylic acid and derivatives thereof, e.g. glycidyl (meth)acrylate, and
also maleic
anhydride.
Copolymers of ethylene with acrylic acid and/or methacrylic acid and/or with
the esters
of these acids are another group of preferred rubbers. The rubbers may also
comprise
dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of
these acids,
e.g. esters and anhydrides, and/or monomers comprising epoxy groups. These
monomers comprising dicarboxylic acid derivatives or comprising epoxy groups
are
preferably incorporated into the rubber by adding to the monomer mixture
monomers
comprising dicarboxylic acid groups and/or epoxy groups and having the general
formula I, II, Ill or IV
R1C(COOR2)=C(COOR3)R4 (I)
RI\ /R4
C ______________________________ C
1 (II)
coo¨Co
s=-.
/0\
CHR7=-CH¨ (CH2)m ¨ 0¨ (CHR6)g ¨CH¨ CHR5 (III)
CH2=---- CR9¨ COO ¨ ( ____________ CH2)p¨CH¨CHR8 (IV)
\ /
0
where R1 to R9 are hydrogen or alkyl groups having from 1 to 6 carbon atoms,
and m is
a whole number from 0 to 20, g is a whole number from 0 to 10 and p is a whole
number from 0 to 5.
R1 to R9 are preferably hydrogen, where m is 0 or 1 and g is 1. The
corresponding
compounds are maleic acid, fumaric acid, maleic anhydride, ally! glycidyl
ether and
vinyl glycidyl ether.
Preferred compounds of the formulae I, II and IV are maleic acid, maleic
anhydride and
(meth)acrylates comprising epoxy groups, such as glycidyl acrylate and
glycidyl
methacrylate, and the esters with tertiary alcohols, such as tert-butyl
acrylate. Although
the latter have no free carboxy groups, their behavior approximates to that of
the free
CA 02798879 2012-11-07
=
PF 70591
13
acids and they are therefore termed monomers with latent carboxy groups.
The copolymers are advantageously composed of from 50 to 98% by weight of
ethylene, from 0.1 to 20% by weight of monomers comprising epoxy groups and/or
methacrylic acid and/or monomers comprising anhydride groups, the remaining
amount
being (meth)acrylates.
Particular preference is given to copolymers composed of
from 50 to 98% by weight, in particular from 55 to 95% by weight, of ethylene,
from 0.1 to 40% by weight, in particular from 0.3 to 20% by weight, of
glycidyl acrylate
and/or glycidyl methacrylate, (meth)acrylic acid and/or maleic anhydride, and
from 1 to 45% by weight, in particular from 10 to 40% by weight, of n-butyl
acrylate
and/or 2-ethylhexyl acrylate.
Other preferred (meth)acrylates are the methyl, ethyl, propyl, isobutyl and
tert-butyl
esters.
Besides these, comononners which may also be used are vinyl esters and vinyl
ethers.
The ethylene copolymers described above may be produced by processes known per
se, preferably by random copolymerization at high pressure and elevated
temperature.
Appropriate processes are well known.
Other preferred elastomers are emulsion polymers whose production is
described, for
example, by Blackley in the monograph "Emulsion polymerization". The
emulsifiers and
catalysts which can be used are known per se.
In principle it is possible to use homogeneously structured elastomers or
those with a
shell structure. The shell-type structure is determined by the sequence of
addition of
the individual monomers. The morphology of the polymers is also affected by
this
sequence of addition.
Monomers which may be mentioned here, merely as examples, for the production
of
the rubber fraction of the elastomers are acrylates, such as n-butyl acrylate
and 2-
ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene, and
also
mixtures of these. These monomers may be copolymerized with other monomers,
such
as styrene, acrylonitrile, vinyl ethers and with other acrylates or
methacrylates, such as
methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate.
= CA 02798879 2012-11-07
PF 70591
14
The soft or rubber phase (with a glass transition temperature of below 0 C) of
the
elastomers may be the core, the outer envelope or an intermediate shell (in
the case of
elastomers whose structure has more than two shells). Elastomers having more
than
one shell may also have more than one shell made from a rubber phase.
If one or more hard components (with glass transition temperatures above 20 C)
are
involved, besides the rubber phase, in the structure of the elastomer, these
are
generally produced by polymerizing, as principal monomers, styrene,
acrylonitrile,
methacrylonitrile, a-methylstyrene, p-methylstyrene, or acrylates or
methacrylates,
such as methyl acrylate, ethyl acrylate or methyl methacrylate. Besides these,
it is also
possible to use relatively small proportions of other comonomers here.
It has proven advantageous in some cases to use emulsion polymers which have
reactive groups at their surfaces. Examples of groups of this type are epoxy,
carboxy,
latent carboxy, amino and amide groups, and also functional groups which may
be
introduced by concomitant use of monomers of the general formula
R10
R11
CH2----1--C¨ X¨ N¨C---R12
0
where the definitions of the substituents can be as follows:
R11) hydrogen or a Ci-C4-alkyl group,
R11 hydrogen or a Cl-C8-alkyl group or an aryl group, in particular phenyl,
R12 hydrogen, a C1-C10-alkyl group, a Ce-C12-aryl group, or -0R13
R13 a Cl-C8-alkyl group or a C6-C12-aryl group, optionally with
substitution by 0- or N-
containing groups,
X a chemical bond or a Ci-Clo-alkylene group, or a C6-C12-arylene
group, or
0
______________________________________ C ¨Y
Y 0-Z or NH-Z, and
CA 02798879 2012-11-07
PF 70591
Z a C1-C10-alkylene group or a C6-C12-arylene group.
The graft monomers described in EP-A 208 187 are also suitable for introducing
5 reactive groups at the surface.
Other examples which may be mentioned are acrylamide, methacrylamide and
substituted acrylates or methacrylates, such as (N-tert-butylamino)ethyl
methacrylate,
(N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)methyl acrylate and
10 (N,N-diethylamino)ethyl acrylate.
The particles of the rubber phase may also have been crosslinked. Examples of
crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and
dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A
50 265,
It is also possible to use the monomers known as graft-linking monomers, i.e.
monomers having two or more polymerizable double bonds which react at
different
rates during the polymerization. Preference is given to the use of compounds
of this
type in which at least one reactive group polymerizes at about the same rate
as the
other monomers, while the other reactive group (or reactive groups), for
example,
polymerize(s) significantly more slowly. The different polymerization rates
give rise to a
certain proportion of unsaturated double bonds in the rubber. If another phase
is then
grafted onto a rubber of this type, at least some of the double bonds present
in the
rubber react with the graft monomers to form chemical bonds, i.e. the phase
grafted on
has at least some degree of chemical bonding to the graft base.
Examples of graft-linking monomers of this type are monomers comprising allyl
groups,
in particular allyl esters of ethylenically unsaturated carboxylic acids, for
example allyl
acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl
itaconate, and
the corresponding monoallyl compounds of these dicarboxylic acids. Besides
these
there is a wide variety of other suitable graft-linking monomers. For further
details
reference may be made here, for example, to US-A 4 148 846.
The proportion of these crosslinking monomers in the impact-modifying polymer
is
generally up to 5% by weight, preferably not more than 3% by weight, based on
the
impact-modifying polymer.
Some preferred emulsion polymers are listed below. Mention may first be made
here of
graft polymers with a core and with at least one outer shell, and having the
following
structure:
Type Monomers for the core Monomers for the envelope
CA 02798879 2012-11-07
PF 70591
16
1,3-butadiene, isoprene, n-butyl styrene, acrylonitrile, methyl
acrylate, ethylhexyl acrylate, or a methacrylate
mixture of these
II as I, but with concomitant use of as I
crosslinking agents
Ill as I or II n-butyl acrylate, ethyl acrylate,
methyl acrylate, 1,3-butadiene,
isoprene, ethylhexyl acrylate
IV as I or II as I or III, but with concomitant use
of monomers having reactive
groups, as described herein
V styrene, acrylonitrile, methyl first envelope made of monomers
methacrylate, or a mixture of these as described under I and II for the
core, second envelope as
described under I or IV for the
envelope
These graft polymers, in particular ABS polymers and/or ASA polymers, are
preferably
used in amounts of up to 40% by weight for impact-modification of PBT,
optionally in a
mixture with up to 40% by weight of polyethylene terephthalate. Appropriate
blend
products are obtainable with trademark UltradurOS (previously UltrablendOS)
from
BASF AG.
Instead of graft polymers whose structure has more than one shell, it is also
possible to
use homogeneous, i.e. single-shell, elastomers made from 1,3-butadiene,
isoprene and
n-butyl acrylate or from copolymers of these. These products, too, may be
produced by
concomitant use of crosslinking monomers or of monomers having reactive
groups.
Examples of preferred emulsion polymers are n-butyl acrylate-(meth)acrylic
acid
copolymers, n-butyl acrylate-glycidyl acrylate or n-butyl acrylate-glycidyl
methacrylate
copolymers, graft polymers with an inner core made from n-butyl acrylate or
based on
butadiene and with an outer envelope made from the abovementioned copolymers,
and copolymers of ethylene with comonomers which supply reactive groups.
The elastomers described can also be produced by other conventional processes,
e.g.
via suspension polymerization.
Preference is likewise given to silicone rubbers, as described in DE-A 37 25
576,
EP-A 235 690, DE-A 38 00 603 and EP-A 319 290.
It is also possible, of course, to use a mixture of the types of rubber listed
above.
CA 02798879 2012-11-07
PF 70591
17
Fibrous or particulate fillers C) that may be mentioned are glass fibers,
glass beads,
amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium
carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, and feldspar.
The
amounts used of fibrous fillers C) are up to 60% by weight, in particular up
to 35% by
weight, and the amounts used of particulate fillers are up to 30% by weight,
in
particular up to 10% by weight.
Preferred fibrous fillers that may be mentioned are aramid fibers and
potassium titanate
fibers, and particular preference is given here to glass fibers in the form of
E glass.
These can be used in the form of rovings or of chopped glass in the forms
commercially obtainable.
The amounts used of fillers that have high laser absorbency, for example
carbon fibers,
carbon black, graphite, graphene, or carbon nanotubes, are preferably below 1%
by
weight, particularly preferably below 0.05% by weight.
The fibrous fillers can have been surface-pretreated with a silane compound in
order to
improve compatibility with the thermoplastic.
Suitable silane compounds are those of the general formula
(X--(CH2)n)k¨Si--(0¨CmHan-,1)4-k
where the definitions of the substituents are as follows:
X NH2-, CH2-CH-, HO-,
0
n is an integer from 2 to 10, preferably from 3 to 4
m is an integer from 1 to 5, preferably from 1 to 2
k is an integer from 1 to 3, preferably 1.
Preferred silane compounds are aminopropyltrimethoxysilane,
aminobutyltrimethoxy-
silane, aminopropyltriethoxysilane, aminobutyltriethoxysilane, and also the
corresponding silanes which comprise a glycidyl group as substituent X.
The amounts generally used for surface coating of the silane compounds are
from 0.05
to 5% by weight, preferably from 0.1 to 1.5% by weight, and in particular 0.2
to 0.5% by
weight (based on C).
Acicular mineral fillers are also suitable.
CA 02798879 2012-11-07
=
PF 70591
18
For the purposes of the invention, acicular mineral fillers are a mineral
filler with
pronounced acicular character. An example that may be mentioned is acicular
wollastonite. The L/D (length to diameter) ratio of the mineral is preferably
from 8:1 to
35:1, with preference from 8:1 to 11:1. The mineral filler can, optionally
have been
pretreated with the abovementioned silane compounds; however, the pretreatment
is
not essential.
The thermoplastic molding compositions of the invention can comprise, as
component C), conventional processing aids, such as stabilizers, oxidation
retarders,
agents to counteract decomposition by heat and decomposition by ultraviolet
light,
lubricants and mold-release agents, colorants, such as dyes and pigments,
plasticizers,
etc.
Examples of oxidation retarders and heat stabilizers are sterically hindered
phenols
and/or phosphites, hydroquinones, aromatic secondary amines, such as
diphenylamines, and various substituted representatives of these groups, and
mixtures
of these, at concentrations of up to 1% by weight, based on the weight of the
thermoplastic molding compositions.
UV stabilizers that may be mentioned, generally used in amounts of up to 2% by
weight, based on the molding composition, are various substituted resorcinols,
salicylates, benzotriazoles, and benzophenones.
Colorants that can be added comprise inorganic and organic pigments, and also
dyes,
such as nigrosin, and anthraquinones. Particularly suitable colorants are
mentioned by
way of example in EP 1722984 B1, EP 1353986 B1, or DE 10054859 Al.
Preference is further given to esters or amides of saturated or unsaturated
aliphatic
carboxylic acids having from 10 to 40, preferably from 16 to 22, carbon atoms
with
saturated aliphatic alcohols or amines which comprise from 2 to 40, preferably
from 2
to 6, carbon atoms.
The carboxylic acids can be monobasic or dibasic. Examples that may be
mentioned
are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic
acid,
behenic acid, and with particular preference stearic acid, and capric acid,
and also
montanic acid (a mixture of fatty acids having from 30 to 40 carbon atoms).
The aliphatic alcohols can be mono- to tetrahydric. Examples of alcohols are n-
butanol,
n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl
glycol, and
pentaerythritol, preference being given here to glycerol and pentaerythritol.
The aliphatic amines can be mono- to trifunctional. Examples of these are
= CA 02798879 2012-11-07
PF 70591
19
stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and
di(6-aminohexyl)amine, particular preference being given here to
ethylenediamine and
hexamethylenediamine. Preferred esters or amides are correspondingly glycerol
distearate, glycerol tristearate, ethylenediamine distearate, glycerol
monopalmitate,
glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.
It is also possible to use a mixture of various esters or amides, or esters
combined with
amides, in any desired mixing ratio.
The amounts usually used of further lubricants and mold-release agents are
usually up
to 1% by weight. It is preferable to use long-chain fatty acids (e.g. stearic
acid or
behenic acid), salts of these (e.g. Ca stearate or Zn stearate), or montan
waxes
(mixtures made of straight-chain, saturated carboxylic acids having chain
lengths of
from 28 to 32 carbon atoms), or else Ca montanate or Na montanate, or else low-
molecular-weight polyethylene waxes or low-molecular-weight polypropylene
waxes.
Examples that may be mentioned of plasticizers are dioctyl phthalate, dibenzyl
phthalate, butyl benzyl phthalate, hydrocarbon oils, and N-(n-
butyl)benzenesulfon-
amide.
The molding compositions of the invention can also comprise from 0 to 2% by
weight of
fluorine-containing ethylene polymers. These are polymers of ethylene having
fluorine
content of from 55 to 76% by weight, preferably from 70 to 76% by weight.
Examples here are polytetrafluoroethylene (PTFE), tetrafluoroethylene-
hexafluoropropylene copolymers, or tetrafluoroethylene copolymers having
relatively
small proportions (generally up to 50% by weight) of copolymerizable
ethylenically
unsaturated monomers. These are described by way of example by Schildknecht in
"Vinyl and Related Polymers", Wiley-Verlag, 1952, pages 484 to 494, and by
Wall in
"Fluorpolymers" (Wiley Interscience, 1972).
These fluorine-containing ethylene polymers have homogeneous distribution in
the
molding compositions and preferably have a (number-average) d50 particle size
in the
range from 0.05 to 10 pm, in particular from 0.1 to 5 pm. These small particle
sizes can
be particularly preferably achieved via use of aqueous dispersions of fluorine-
containing ethylene polymers and incorporation of these into a polyester melt.
The thermoplastic molding compositions of the invention can be produced by
processes known per se, by mixing the starting components in conventional
mixing
apparatuses, such as screw extruders, Brabender mixers, or Banbury mixers, and
then
extruding the same. The extrudate can be cooled and comminuted. It is also
possible
to premix individual components (e.g. applying component B) to the pellets,
for
. CA 02798879 2012-11-07
PF 70591
example in a drum), then adding the remaining starting materials individually
and/or
after they have been likewise mixed. The mixing temperatures are generally
from 230
to 290 C. Component B) can also preferably be added to the extruder inlet by
the hot-
feed or direct method.
5
In another preferred method of operation, components B) and also optionally C)
can be
mixed with a polyester prepolymer, and compounded and pelletized. The
resultant
pellets are then solid-phase condensed under inert gas continuously or
batchwise at a
temperature below the melting point of component A) until the desired
viscosity has
10 been reached.
The molding compositions that can be used in the invention are suitable for
producing
laser-transparent moldings. The laser transparency of these is preferably at
least 33%,
in particular at least 40% (at 1064 nm, measured on moldings of thickness 2 mm
by the
15 test method described in the examples).
The invention uses these laser-transparent moldings to produce moldings by
means of
laser transmission welding processes.
20 The laser-absorbent molding used can generally comprise moldings
made of any laser-
absorbent materials. By way of example, these can be composite materials,
thermosets, or preferably moldings made of specific thermoplastic molding
compositions. Suitable thermoplastic molding compositions are molding
compositions
which have adequate laser absorption in the wavelength range used. By way of
example, suitable thermoplastic molding compositions can preferably be
thermoplastics
which are laser-absorbent by virtue of addition of inorganic pigments, such as
carbon
black, and/or by virtue of addition of organic pigments or of other additives.
Examples
of preferred suitable organic pigments for achieving laser absorption are IR-
absorbent
organic compounds, for example those described in DE 199 16 104 Al.
The invention further provides moldings and/or molding combinations to which
moldings of the invention have been bonded by the laser transmission welding
process.
Moldings of the invention have excellent suitability for durable and stable
attachment to
laser-absorbent moldings by the laser transmission welding process. They are
therefore particularly suitable for materials for covers, housings, add-on
components,
and sensors, for example for applications in the electronics,
telecommunications,
information-technology, computer, household, sports, medical, motor-vehicle,
or
entertainment sector.
Examples
CA 02798879 2012-11-07
PF 70591
21
Component Ni:
Polybutylene terephthalate with intrinsic viscosity 130 nril/g and having a
carboxy end
group content of 34 meq/kg (Ultradur0 B 4500 from BASF SE) (IV measured in
0.5%
strength by weight solution of phenol/o-dichlorobenzene, 1:1 mixture at 25 C).
Component A/2:
Polyethylene terephthalate with intrinsic viscosity 105 ml/g and having a
carboxy end
group content of 35 meq/kg (IV measured in 0.5% strength by weight solution of
phenol/o-dichlorobenzene, 1:1 mixture at 25 C).
Component N3 comp:
Nylon-6,6 with intrinsic viscosity 150 measured in 5 g/I sulfuric acid (96%
strength).
(Ultramid0 A27 from BASF SE).
Component B/1
Sodium carbonate (Na2CO3)
Component B/2
Potassium carbonate (K2CO3)
Component B/3 comp (for comparison)
Calcium carbonate (CaCO3)
Component B/4 comp (for comparison)
Lithium carbonate (Li2CO3)
Component B/5 comp (for comparison)
Magnesium carbonate (MgCO3)
Component B/6 comp (for comparison)
Zinc carbonate (ZnCO3)
CA 02798879 2012-11-07
=
PF 70591
22
Component B/7 comp (for comparison)
Cesium carbonate (Cs2CO3)
Component B/8
Sodium hydrogencarbonate (NaHCO3)
Component B/9
Potassium hydrogencarbonate (KHCO3)
Component C
Glass fibers 0 : 10 um
The molding compositions were produced in a ZSK25 at from 250 to 260 C with
flat
temperature profile and pelletization.
Laser transparency measurement
Laser transmittance was determined at wavelength 1064 nm by means of
thermoelectric power measurement. The measurement geometry was set up as
follows: a beam divider (SQ2 non-polarizing beam divider from Laseroptik GmbH)
was
used to divide a reference beam of power 1 watt at an angle of 90 from a
laser beam
(diode-pumped Nd-YAG laser with wavelength 1064 nm, FOBA DP50) with total
power
of 2 watts. The reference beam impacted the reference sensor. That portion of
the
original beam that passed through the beam divider provides the measurement
beam
likewise with power of 1 watt. This beam was focused to a focal diameter of
0.18 pm
via a mode diaphragm (5.0) behind the beam divider. The laser transparency
(LT)
measurement sensor was positioned 80 mm below the focus. The test sheet was
positioned 2 mm above the LT measurement sensor. Injection-molded test sheets
are
used, with dimensions 60*60*2 mm3 and with edge gating. The measurement was
made in the middle of the sheet (point of intersection of the two diagonals).
The
injection-molding parameters were set to the following values:
Melt temp. Mold temp. Injection rate Hold
pressure
[ C] [ C] [cm3/s] [bar]
Unreinforced 260 60 48 600
materials
Reinforced 260 80 48 600
materials
CA 02798879 2012-11-07
PF 70591
=
23
The total measurement time was 30 s, and the result of the measurement is
determined within the final 5s. The signals from the reference sensor and
measurement sensor were recorded simultaneously. The measurement process
begins
with insertion of the specimen.
Transmittance, and therefore laser transparency, was obtained from the
following
formula:
LT = (Signal(measurement sensor) / Signal(reference sensor)) x 100%.
This measurement method excluded variations in the laser system and subjective
read-
out errors.
The average LT value for a sheet was calculated from at least five
measurements. For
each material, the average value was calculated on 10 sheets. The average
values
from the measurements on the individual sheets were used to calculate the
average
value, and also the standard deviation, for the material.
Transmittance spectra (Ulbricht measurement)
Transmission spectra were measured using Ulbricht sphere measurement geometry
in
the wavelength range from 300 to 2500 nm. Ulbricht spheres are hollow spheres,
the
inner surfaces of which provide high and unoriented (diffuse) reflection over
a broad
spectral range. When radiation impacts the inner surface of the sphere it
undergoes
multiple reflection until it has completely uniform distribution within the
sphere. This
integration of the radiation averages all of the effects due to angle of
incidence,
shadowing, modes, polarization, and other properties. As a function of the
configuration
of the Ulbricht sphere, the detector attached within the sphere records only
diffuse
transmittance, or the sum of directed and diffuse transmittance (= total
transmittance).
A Varian Cary 5000 spectrometer with attached DRA 2500 Ulbricht system was
used in
transmission mode (specimen between radiation source and Ulbricht sphere). To
measure total transmittance, a white reflector (Labsphere SpectraIon Standard)
was
used to close the reflection port opposite to the specimen. To measure diffuse
transmittance, a black light trap (DRA 2500 standard light trap) was used to
close the
reflection port. Transmittance was stated in relation to the intensity of
incident radiation.
Oriented transmittance was calculated as the difference between total
transmittance
and diffuse transmittance. Oriented transmittance is stated in relation to
total
transmittance:
(total transmittance - diffuse transmittance) x 100%
Oriented transmittance =
total transmittance
= CA 02798879 2012-11-07
PF 70591
24
Table 1
LT @
Component Amount of B/1 1064nnn
[% by wt.] [%T]
Reference,
100% of N1 - 30
B/1 0.01 28
B/1 0.1 41
B/1 0.2 57
B/1 0.3 62
B/1 0.4 64
B/1 0.5 64
B/1 0.75 62
B/1 1 60
B/1 1.5 58
B/1 2 56
Table 2
Mechanical properties of selected unreinforced formulations:
100% by wt. of A/1 99.5% of A/1 +
Reference 0.5% of B/1
Modulus of elasticity [MPa] 2511 2783
Tensile strength [MPa] 56.4 61.1 _
Tensile strain at break [%] 170 18.8
Impact resistance without notch [kJ/m2] no fracture 103
Tensile test to ISO 527. Impact resistance test to ISO 179.
CA 02798879 2012-11-07
PF 70591
Table 3a
LT @
Component Amount of B 1064nm
['A by wt.]
Reference,
100% of Ni 30
B/1 0.5 65
B/2 0.65 44
B/3 comp 0.47 29.4
B/4 comp 0.35 24.7
B/5 comp 0.4 32
B/6 comp 0.59 27.5
B/7 comp 1.54 20.3
B/8 0.5 62
8/9 0.47 33.1
5 Table 3b
LT @
Component Amount of B 1064nm
[% by wt.] [%-r]
Reference,
100% of A/2 40
B/1 0.4 55
Table 3c
LT @
Component Amount of B 1064nm
[io by wt.] [%T]
Reference,
100% of
A/3 comp 60
B/1 0.4 60
.. CA 02798879 2012-11-07
PF 70591
26
Table 4
Ulbricht transmittance measurements on selected formulations:
Wavelength
range Total transmittance
Oriented transmittance fraction
[nm] [%] FA]
Reference 99.5% of Ni Reference 99.5% of All
0.5% by wt. of B/1 0.5%
by wt. of B/1
400 - 600 10 - 20 5-32 0 ¨ 2 0 - 2
600 ¨ 800 20 ¨ 27 32 ¨ 48 0 ¨ 2 1-18
800 ¨ 1000 27 ¨ 30 48 ¨ 60 0 ¨ 2 18 - 45
1000 ¨ 1100 30 ¨ 32 60 ¨ 65 0 ¨ 2 45 - 52
1100 ¨ 1200 abs abs 0 ¨ 2 52 - 60
1200 ¨ 1600 18 ¨ 33 63 ¨ 77 0 ¨ 2 60 - 70
1600 ¨ 1630 20 ¨ 30 70 ¨ 75 0 ¨ 5 69 - 71
1630 ¨ 1800 abs abs 0 ¨ 5 70 - 73
1800 ¨ 2100 7-14 56 ¨ 64 0 ¨ 2 73 - 76
2100 - 2200 abs abs 0 ¨ 5 75 - 77
abs: absorption-dependent transparency change (band)
Table 5
Concentration series, reinforced (reference: 70% by weight of Ni + 30% by
weight of C)
CA 02798879 2012-11-07
PF 70591
27
LT @
Component Amount of B 1064nm
[(70 by wt.] [%T]
Reference 27
B/1 0.01 21
Bi1 0.1 30
0.2 56
B/1 0.3 59
B/1 0.4 59
B/1 0.5 58
B/1 0.75 , 56
1311 1 55
B/1 1.5 52
B/1 2 50
B/1 3 46
B/1 5 41
Table 6
Mechanical properties of selected reinforced formulations:
Reference + 0.5% of B/1
Modulus of elasticity [MPa] 9564 10041
Tensile strength [MPa] 136 142
Tensile strain at break [%] 3.4 3.2
Impact resistance with
notch [kJ/m2] 9.8 6.7
Reference: 70% by weight of All + 30% by weight of C
Table 7:
Different particle sizes of component B
Na2CO3 B/1 B/2 B/3
dio [Rm] 40 190 510
c150 [11ffi] 100 410 980
d90 [11111] 210 850 1500
Aspect ratio 1-2 1-2.9 3-6
CA 02798879 2012-11-07
PF 70591
28
Table 8
Ex.1 Ex.2 _Ex.3 Comp.1 Ex.4 Ex.5 Ex.6 Comp.2
Component
A (% by wt.] 99.5 99.5 99.5 100 69.65 69.65
69.65 69.65
B1 [ /0 by wt.] 0.5 0.35
B2 [% by wt.] 0.5 0.35
B3 [% by wt.] 0.5 0.35
C (glass fiber) (% by wt.] 30 30 30 30
Modulus of elasticity [MPa] 2839 2822 2801 2511 10158
10059 9891 9564
Tensile strength [MPa] 61 60 58 56 142 141 139 136
Tensile strain at break [ /.] 17 14 7 18 3.2 3.1 2.9
3.4
Impact resistance [kJ/m21 25 22 20 no 63 62 60 74
fracture
. -
Laser transparency 67 65 64 30 62 59 58 27
1064nm [%T, 2mm] _
I
