U.S. patent application number 15/027019 was filed with the patent office on 2016-09-01 for polycarbonate compositions having improved adhesion to polyurethane layers.
The applicant listed for this patent is COVESTRO DEUTSCHLAND AG. Invention is credited to Thomas ECKEL, Sven HOBEIKA, Ralf HUFEN, Timo KUHLMANN, Johannes SCHERER.
Application Number | 20160251513 15/027019 |
Document ID | / |
Family ID | 49382342 |
Filed Date | 2016-09-01 |
United States Patent
Application |
20160251513 |
Kind Code |
A1 |
HUFEN; Ralf ; et
al. |
September 1, 2016 |
Polycarbonate compositions having improved adhesion to polyurethane
layers
Abstract
The present invention relates to compositions and composite
components formed from these compositions and a polyurethane layer,
which are notable for improved adhesion between the two layers, and
a process for producing the composite components.
Inventors: |
HUFEN; Ralf; (Duisburg,
DE) ; ECKEL; Thomas; (Dormagen, DE) ; HOBEIKA;
Sven; (Solingen, DE) ; KUHLMANN; Timo;
(Leichlingen, DE) ; SCHERER; Johannes;
(Leverkusen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
COVESTRO DEUTSCHLAND AG |
Leverkusen |
|
DE |
|
|
Family ID: |
49382342 |
Appl. No.: |
15/027019 |
Filed: |
October 13, 2014 |
PCT Filed: |
October 13, 2014 |
PCT NO: |
PCT/EP2014/071880 |
371 Date: |
April 4, 2016 |
Current U.S.
Class: |
428/304.4 |
Current CPC
Class: |
C08L 69/00 20130101;
C08J 2475/00 20130101; B32B 2605/18 20130101; B29C 67/246 20130101;
B32B 3/28 20130101; B32B 2307/308 20130101; B32B 27/08 20130101;
B32B 2307/306 20130101; B32B 27/36 20130101; B32B 2605/10 20130101;
B32B 5/18 20130101; B32B 27/302 20130101; B32B 27/18 20130101; B32B
2307/54 20130101; B29C 45/0003 20130101; C08J 7/0427 20200101; B29C
45/1676 20130101; B32B 27/30 20130101; B32B 2250/02 20130101; C08L
69/00 20130101; C08L 69/005 20130101; B32B 2250/24 20130101; B32B
2605/003 20130101; C08J 2475/04 20130101; B29K 2069/00 20130101;
B32B 27/20 20130101; C08L 69/005 20130101; B32B 2307/50 20130101;
B32B 27/365 20130101; C08J 2369/00 20130101; B32B 5/20 20130101;
B32B 27/065 20130101; B32B 27/40 20130101; B29L 2009/00 20130101;
B32B 2266/0278 20130101; B32B 2307/558 20130101; B32B 27/32
20130101; B32B 2605/08 20130101; B29K 2075/00 20130101; B32B
2605/00 20130101; C08L 55/02 20130101; C08L 55/02 20130101 |
International
Class: |
C08L 69/00 20060101
C08L069/00; B29C 45/00 20060101 B29C045/00; B32B 27/06 20060101
B32B027/06; B32B 27/36 20060101 B32B027/36; C08J 7/04 20060101
C08J007/04; B32B 5/20 20060101 B32B005/20 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 18, 2013 |
EP |
13189298.6 |
Claims
1. A composition omprising A) 55 to 75 parts by weight of at least
one polymer selected from the group consisting of aromatic
polycarbonate and aromatic polyester carbonate, B) 25 to 45 parts
by weight of at least one mixture comprising at least one
polybutadiene-based graft polymer prepared by emulsion, suspension
or solution polymerization and at least one polybutadiene-free
vinyl (co)polymer, C) 0.1 to 20.0 parts by weight (based in each
case on the sum total of components A and B) of at least one
polymer additive, where the polybutadiene content based on the sum
total of the parts by weight of components A and B is 10% to 20% by
weight, and where the total content of butadiene-free vinyl
(co)polymer from component B based on the sum total of the parts by
weight of components A and B is 12% to 23% by weight, and where the
sum total of the parts by weight of components A and B in the
polycarbonate composition is normalized to 100.
2. A composition according to claim 1, wherein the butadiene-based
graft polymer of Component B is prepared by emulsion
polymerization.
3. A composition according to claim 1, wherein the
polybutadiene-based graft polymer comprises B.1 5% to 95% by
weight, based on the graft polymer, of at least one vinyl monomer
on B.2 95% to 5% by weight, based on the graft polymer, of one or
more polybutadiene graft bases.
4. A composition according to claim 3, wherein component B.1
comprises mixtures of B.1.1 50% to 99% by weight, based on B.1, of
vinylaromatics and/or ring-substituted vinylaromatics (optionally
styrene, .alpha.-methylstyrene, p-methylstyrene, p-chlorostyrene)
and B.1.2 1% to 50% by weight, based on B.1, of vinyl cyanides
(unsaturated nitriles optionally acrylonitrile and
methacrylonitrile) and/or derivatives (optionally anhydrides and
imides) of unsaturated carboxylic acids, optionally maleic
anhydride and N-phenylmaleimide.
5. A composition according to claim 1 wherein, 57 to 74 parts by
weight of component A); 26 to 43 parts by weight of component B);
0.2 to 15.0 parts by weight of component C); where the
polybutadiene content based on the sum total of the parts by weight
of components A and B is 11% to 18% by weight and where the total
content of butadiene-free vinyl (co)polymer from component B, based
on the sum total of the parts by weight of components A and B, is
12% to 20% by weight, and where the sum total of the parts by
weight of components A and B in the polycarbonate composition has
been normalized to 100.
6. A composition according to claim 1, wherein 64 to 73 parts by
weight of component A); 27 to 36 parts by weight of component B);
0.3 to 10.0 parts by weight of component C); where the
polybutadiene content based on the sum total of the parts by weight
of components A and B is 12% to 17% by weight and where the total
content of butadiene-free vinyl (co)polymer from component B, based
on the sum total of the parts by weight of components A and B, is
13% to 19% by weight, and where the sum total of the parts by
weight of components A and B in the polycarbonate composition has
been normalized to 100.
7. A composition according to claim 1 wherein component C comprises
at least one polymer additive selected from the group consisting of
thermal stabilizers, demoulding agents, colourants and UV
absorbers.
8. A composite component comprising a) a carrier composed of a
thermoplastic composition according to claim 1 b) at least one
polyurethane layer selected from the group consisting of coating
materials, foams and compact skins, comprising at least one
polyisocyanate component, least one polyfunctional H-active
compound, and optionally at least one polyurethane additive and/or
processing aid, and having a molar ratio of NCO- to H-active groups
of 1:1 to 1.1:1.
9. A composite component according to claim 8, wherein the
polyurethane layer is a coating material having a layer thickness
of 50-300 .mu.m.
10. A composite component according to claim 8, wherein the
polyurethane layer is a foam having a layer thickness of 1 mm to 1
cm.
11. A composite component according to claim 8, wherein the
polyurethane layer is a compact skin having a layer thickness of 1
mm to 4 mm.
12. A process for producing a composite component according to
claim 8, wherein the polyurethane layer has been produced by full
polymerization of a reactive polyurethane raw material mixture
comprising at least one polyisocyanate component, at least one
polyfunctional H-active compound, and optionally at least one
polyurethane additive and/or processing aid, in direct contact with
the carrier which has been shaped beforehand from the thermoplastic
composition and solidified.
13. A process for producing a composite component according to
claim 8, wherein (i) the melt of the thermoplastic composition is
injected into a first mould cavity and then cooled, (ii) the cooled
thermoplastic component is transferred into a larger cavity and a
defined gap is produced thereby, (iii) the gap which thus results
between the thermoplastic component and the mould surface of the
enlarged cavity is injected with a reactive polyurethane raw
material mixture comprising at least one polyisocyanate component,
at least one polyfunctional H-active compound, and optionally at
least one polyurethane additive and/or processing aid, the
polyurethane raw material mixture polymerizing fully in direct
contact with the surface of the thermoplastic carrier to give a
compact polyurethane layer or to give a polyurethane foam layer,
(iv) the composite component is demoulded from the mould cavity,
and wherein (i) to (iv) following one another in immediate
succession.
14. A process according to claim 13, wherein in (iii) the surface
of the injection mould in contact with the thermoplastic
composition is heated to a temperature in the range of 60 to
90.degree. C. and the surface of the injection mould in contact
with the reactive polyurethane mixture to a temperature in the
range of 60 to 90.degree. C.
15. A composite component according to claim 8 capable of being
used as an interior or exterior component of a rail vehicle,
aircraft or motor vehicle and for electrical/electronic components
and IT components.
Description
[0001] The present invention provides polycarbonate compositions
having improved adhesion to polyurethane systems, composite systems
comprising these polycarbonate compositions and polyurethane
systems, and also shaped bodies formed from these composite systems
and processes for producing the composite systems. The
polycarbonate compositions are notable not only for improved
adhesion to the polyurethane system but also for constantly high
toughness, high heat distortion resistance, good melt stability and
high elongation at break.
[0002] WO 2006/072366 A1 describes a process for forming and
coating a substrate in a mould having at least two cavities. The
process comprises the steps of:
[0003] a) forming a substrate in a first cavity of the mould,
[0004] b) introducing the substrate produced in the previous step
into a second cavity of the mould and
[0005] c) coating the substrate in the second cavity with a coating
material, the coating being effected under elevated pressure.
[0006] By way of example and with preference, polyurethane coating
materials and PC+ABS substrates
(polycarbonate+acrylonitrile-butadiene-styrene substrates) are
mentioned. No pointers are given in this application as to the
influence of the carrier material composition on the adhesive
properties of the material composite.
[0007] EP 2089207 A1 discloses a process for producing a composite
component, especially comprising an injection moulding and a
polyurethane element, comprising the steps of
[0008] a) producing a carrier component,
[0009] b) moving or transferring the carrier component to an opened
cavity of a mould,
[0010] c) closing the mould to a predetermined position, creating
an enlarged cavity having a first size,
[0011] d) generating a reduced pressure in the enlarged cavity of
the first size,
[0012] e) introducing a flooding material into the enlarged cavity
and
[0013] f) conducting an embossing step simultaneously with the
introduction and/or after the introduction of the flooding
material, while at least slightly reducing the size of the
cavity.
[0014] For improvement of the composite adhesion, activation of the
surface of the thermoplastic by flaming, plasma treatment or gas is
described here. No pointers are given in this publication as to the
influence of the carrier material composition on the adhesion
properties of the material composite.
[0015] DE 10 2006 033 059 A1 discloses a process for producing
plastic interior components. In this process, in a first step, the
carrier is formed in a first mould, then the first mould is at
least partly replaced by a second mould and then the top layer is
formed on the carrier in a second step. The carrier material used
is a hard component, e.g. PA+ABS blends
(polyamide+acrylonitrile-butadiene-styrene) or PC+ABS blends
(polycarbonate+acrylonitrile-butadiene-styrene), and the top layer
used is a soft component, preferably polyurethane foam. No pointers
are given in the application as to the influence of the composition
of the carrier materials on the composite properties of the
components thus produced. Instead, DE 10 206 033 059 A1 likewise
proposes improving the adhesion by preparing the surface by primers
or by laser, corona or plasma treatment.
[0016] WO 99/20464 A1 discloses composites of at least two
different polymer materials bonded directly to one another: a) a
thermoplastic polymer or a thermoplastic mixture of polymers which
contain at least one polar compound of at least one of the metals
of main groups 1 to 5 or of transition groups 1 to 8 of the
Periodic Table as ultrafinely distributed inorganic powder and b)
polyurethane present in the form of a foam, coating material or
compact material. No adhesion promoter layer is required for the
composite. No pointers are given in this publication with regard to
the influence of the carrier material composition in terms of ABS
content and rubber content on the adhesion properties of the
material composite.
[0017] DE 101 09 226 A1 discloses a polycarbonate composition
comprising a) aromatic polycarbonate and/or polyester carbonate, b)
graft polymer and c) copolymer of styrene and a monomer containing
carboxyl groups, where said copolymer has a mean molecular weight
Mw of >=10 500 g/mol, and where said copolymer may contain one
or more vinyl monomers. Component C is preferably a copolymer of
styrene and maleic anhydride. DE 101 09 226 A1 further discloses
composite components comprising at least one first layer (1) and a
second layer (2), in which layer (1) includes at least one
polycarbonate composition (as specified in a, b and c) and layer
(2) contains at least one polyurethane It is a feature of the
composite that the decrease in foam adhesion between layer (1) and
layer (2) is at most 35% after a double alternating climate test.
No pointers are given in this publication as to the influence of
the carrier material composition in terms of ABS content and rubber
content on the adhesion properties of the material composite.
[0018] US 2008/0194756 A1 discloses thermoplastic compositions
comprising polycarbonate, an impact modifier comprising ABS, a
further impact modifier other than ABS, an aromatic vinyl copolymer
and an additive in gel form. The compositions are notable for good
mechanical, thermal and rheological properties, and low surface
gloss. However, composite systems having polyurethane coatings and
improved adhesion properties are not disclosed.
[0019] It was an object of the present invention to provide
improved polycarbonate compositions having improved adhesion to
polyurethane systems, composite systems comprising these
polycarbonate compositions and polyurethane layers, and shaped
bodies formed from these composite systems. Polycarbonate
compositions should be notable for improved adhesion to the
polyurethane system, and for a constantly high toughness, high heat
distortion resistance, good melt stability and high elongation at
break.
[0020] In addition, a process for producing these composite
components is to be provided.
[0021] The polyurethane layer may serve, for example, to improve
the surface properties, for example scratch resistance,
self-healing, weathering stability, tactile properties, optical
properties, sound insulation and thermal insulation, of the
composite components.
[0022] The object of the present invention is achieved by
polycarbonate compositions comprising
[0023] A) 55 to 75 parts by weight, preferably 57 to 74 parts by
weight, more preferably 64 to 73 parts, by weight of at least one
polymer selected from the group consisting of aromatic
polycarbonate and aromatic polyester carbonate,
[0024] B) 25 to 45 parts by weight, preferably 26 to 43 parts by
weight, more preferably 27 to 36 parts by weight, of at least one
mixture comprising at least one polybutadiene-based graft polymer
prepared by emulsion, suspension or solution polymerization and at
least one butadiene-free vinyl (co)polymer,
[0025] C) 0.1 to 20.0 parts by weight, preferably 0.2 to 15.0 parts
by weight, more preferably 0.3 to 10.0 parts by weight (based in
each case on the sum total of components A and B), of at least one
polymer additive,
[0026] where the polybutadiene content based on the sum total of
the parts by weight of components A and B is 10% to 20% by weight,
preferably 11% to 18% by weight, more preferably 12% to 17% by
weight,
[0027] and where the total content of butadiene-free vinyl
(co)polymer from component B based on the sum total of the parts by
weight of components A and B is 12% to 23% by weight, preferably
12% to 20% by weight, more preferably 13% to 19% by weight,
[0028] and where the sum total of the parts by weight of components
A and B in the polycarbonate composition is normalized to 100.
[0029] While the ranges of preference mentioned can be combined
freely with one another, preference is given to combining the
respective first, middle and last ranges with one another.
[0030] The present invention also provides compositions
comprising
[0031] A) 55 to 75 parts by weight of at least one polymer selected
from the group consisting of aromatic polycarbonate and aromatic
polyester carbonate,
[0032] B) 25 to 45 parts by weight of at least one mixture
comprising at least one polybutadiene-based graft polymer and at
least one polybutadiene-free vinyl (co)polymer,
[0033] C) 0.1 to 20.0 parts by weight (based in each case on the
sum total of components A and B), of at least one polymer
additive,
[0034] where the polybutadiene content based on the sum total of
the parts by weight of components A and B is 10% to 20% by
weight,
[0035] and where the total content of butadiene-free vinyl
(co)polymer from component B based on the sum total of the parts by
weight of components A and B is 12% to 23% by weight,
[0036] and where the sum total of the parts by weight of components
A and B in the polycarbonate composition is normalized to 100,
[0037] and [0038] i) the graft polymer is prepared by emulsion,
suspension or solution polymerization or [0039] ii) the composition
is free of graft polymers having a graft shell of methyl
methacrylate or [0040] iii) the graft polymer has been prepared by
emulsion, suspension or solution polymerization and the composition
is free of graft polymers having a graft shell of methyl
methacrylate.
[0041] In a further preferred embodiment, the compositions
comprise
[0042] A) 55 to 75 parts by weight of at least one polymer selected
from the group consisting of aromatic polycarbonate and aromatic
polyester carbonate,
[0043] B) 25 to 45 parts by weight of at least one mixture
comprising at least one polybutadiene-based graft polymer prepared
by emulsion polymerization and at least one butadiene-free vinyl
(co)polymer,
[0044] C) 0.1 to 20.0 parts by weight (based in each case on the
sum total of components A and B) of at least one polymer
additive,
[0045] where the polybutadiene content based on the sum total of
the parts by weight of components A and B is 10% to 20% by
weight,
[0046] and where the total content of butadiene-free vinyl
(co)polymer from component B based on the sum total of the parts by
weight of components A and B is 12% to 23% by weight,
[0047] and where the graft base of the polybutadiene-based graft
polymer has a median particle size (d.sub.50) of 0.2 to 1.0 .mu.m,
measured by ultracentrifuge methodology,
[0048] and where the graft polymer of component B, based on the
graft polymer, comprises 25% to 60% by weight of at least one vinyl
monomer and 75% to 40% by weight of one or more polybutadiene-based
graft bases,
[0049] and where the sum total of the parts by weight of components
A and B in the polycarbonate composition is normalized to 100.
[0050] In a further preferred embodiment, the compositions
comprise
[0051] A) 64 to 73 parts by weight of at least one polymer selected
from the group consisting of aromatic polycarbonate and aromatic
polyester carbonate,
[0052] B) 27 to 36 parts by weight of at least one mixture
comprising at least one polybutadiene-based graft polymer prepared
by emulsion polymerization and at least one butadiene-free
copolymer of styrene and acrylonitrile,
[0053] C) 0.3 to 10.0 parts by weight (based in each case on the
sum total of components A and B) of at least one polymer
additive,
[0054] where the polybutadiene content based on the sum total of
the parts by weight of components A and B is 12% to 17% by
weight,
[0055] and where the total content of butadiene-free vinyl
(co)polymer from component B based on the sum total of the parts by
weight of components A and B is 13% to 19% by weight,
[0056] and where the graft base of the polybutadiene-based graft
polymer has a median particle size (d.sub.50) of 0.2 to 0.5 .mu.m,
measured by ultracentrifuge methodology,
[0057] and where the graft polymer of component B, based on the
graft polymer, comprises 25% to 60% by weight of at least one vinyl
monomer and 75% to 40% by weight of one or more polybutadiene-based
graft bases,
[0058] and where the graft polymer of component B contains no
methyl methacrylate,
[0059] and where the sum total of the parts by weight of components
A and B in the polycarbonate composition is normalized to 100.
[0060] In a further preferred embodiment, the polycarbonate
compositions consist only of components A, B and C.
[0061] In a further preferred embodiment, the polycarbonate
compositions are free of fillers and reinforcers, for example talc,
glass fibres or carbon fibres (optionally including ground fibres),
(hollow) glass or ceramic beads, mica, kaolin, CaCO.sub.3 and glass
flakes.
[0062] In a further preferred embodiment, the polycarbonate
compositions are free of flame retardants and from flame retardant
synergists such as anti-dripping agents.
[0063] In addition and with preference, the object of the present
invention is achieved by composite components comprising [0064] a)
a carrier composed of a polycarbonate composition as specified
above [0065] b) at least one polyurethane layer.
[0066] Said polyurethane layer may, for example, be a PU coating
material, a PU foam or else a compact PU skin having polyurethane
layer thicknesses of, for example, 1 .mu.m up to 20 cm.
[0067] In a preferred embodiment, the polyurethane layer is a
coating material having a layer thickness of 1-1000 .mu.m, further
preferably 10-500 .mu.m and more preferably 50-300 .mu.m.
[0068] In a further preferred embodiment, the polyurethane layer is
a foam having a layer thickness of 1 mm-20 cm, further preferably 1
mm-10 cm and more preferably 1 mm-1 cm.
[0069] In a further preferred embodiment, the polyurethane layer is
a compact skin having a layer thickness of 0.5 mm-10.0 mm,
preferably 0.5 mm-5.0 mm and more preferably 1.0 mm-4.0 mm
[0070] The composite components can in principle be produced in any
known manner
[0071] Preferably, the polyurethane layer is produced by full
polymerization of a reactive polyurethane raw material mixture
comprising
[0072] at least one polyisocyanate component,
[0073] at least one polyfunctional H-active compound, and
[0074] optionally at least one polyurethane additive and/or
processing aid,
[0075] in direct contact with the carrier which has been shaped
beforehand from the thermoplastic composition and solidified.
[0076] The carrier component may be prefabricated, for example,
from the thermoplastic PC+ABS composition and the reactive
polyurethane raw material mixture may be applied thereto and
reacted fully. According to the reactivity of the polyurethane
reaction components, they may already have been premixed or may be
mixed in a known manner during the application. The application can
be effected by methods including spraying, knife-coating or
calendering.
[0077] If foamed composites are to be produced, it is possible in a
manner known per se to introduce the reaction mixture into a mould
containing the previously formed and solidified support component.
Optionally, the mould may also contain a further decorative layer
(often called "skin") composed of, for example, polyvinyl chloride
(PVC), thermoplastic polyolefins (TPO), thermoplastic polyurethane
(TPU) or sprayable polyurethane skin. In the mould, the foamable
reaction mixture foams in contact with the carrier component and
any decorative layer, and forms the composite component. The
in-mould foaming can be performed in such a way that the composite
component has a cell structure at its surface. Alternatively, it
can be conducted in such a way that the composite component has a
compact skin and a cellular core (integral foams). The polyurethane
components can be introduced into the mould with high-pressure or
low-pressure machines. Polyurethane foams can also be produced as
slabstock foam.
[0078] Polyurethane composites can also be produced in sandwich
mode. The method may be configured either as a depot method or a
shell-building method. Both the depot method and the shell-building
method are known per se. In the depot method (filling mode), two
half-shells (for example outer layers made from polymers) are
prefabricated and inserted into a mould, and the cavity between the
shells is filled by foaming with the PUR foam. In shell-building
mode, a core of PUR foam is placed in a mould and then encased with
a suitable shell material, for example with one of the
thermoplastics mentioned. In the production of sandwich composites,
preference is given to shell-building mode.
[0079] In a preferred embodiment of the invention, the composite
components are produced by a process in which [0080] (i) in a first
process step the melt of the thermoplastic composition is injected
into a first mould cavity and then cooled, [0081] (ii) in a second
process step the thermoplastic component is transferred into a
larger cavity and a defined gap is produced thereby, [0082] (iii)
in the third process step the gap which thus results between the
thermoplastic component and the mould surface of the enlarged
cavity is injected with a reactive polyurethane raw material
mixture comprising
[0083] at least one polyisocyanate component,
[0084] at least one polyfunctional H-active compound, and
[0085] optionally at least one polyurethane additive and/or
processing aid,
[0086] the polyurethane raw material mixture polymerizing fully in
direct contact with the surface of the thermoplastic carrier to
give a compact polyurethane layer or to give a polyurethane foam
layer, and [0087] (iv) in the fourth process step the composite
component is demoulded from the mould cavity.
[0088] In a further preferred embodiment of the invention, process
steps (i) to (iv) follow one another in immediate succession in the
composite component production.
[0089] If required, the larger cavity is treated with a separating
agent prior to process step (iii).
[0090] The immediate succession of the process steps prevents the
workpiece from cooling down to room temperature during the process.
This achieves a reduction in the production times and a higher
energy efficiency of the overall process.
[0091] Process steps (ii) and (iii) can be repeated at least once
with variation of the polyurethane system, in which case one or
more polyurethane layers are applied to one or both sides of the
carrier, so as to result in a composite component composed of
thermoplastic carrier and at least two identical or different PU
components which may optionally also have a more than two-layer
structure.
[0092] Before the demoulding of the workpiece in steps (ii) and
(iv), the workpiece is cooled down until it is dimensionally
stable.
[0093] To produce the gap in process step (ii), it is possible to
open the injection mould and subsequently to exchange half of the
injection mould cavity for a new half with greater cavity
dimensions, or to move the component from the first mould cavity to
a second cavity which is larger in terms of its cavity dimensions
or to a second mould, or to open up the first cavity to create a
gap.
[0094] The movement of the substrate in process step (ii) can be
effected by known processes, as employed, for example, in
multicolour injection moulding. Typical methods are firstly
movement with a turntable, a turning plate, a sliding cavity or an
index plate, or comparable methods in which the substrate remains
on a core. If the substrate for movement remains on the core, this
has the advantage that the position is defined accurately even
after the movement. Secondly, the prior art discloses methods for
moving a substrate in which the substrate is removed from a cavity,
for example with the aid of a handling system, and placed into
another cavity. Movement with removal of the substrate offers
greater freedom of configuration in the coating operation, for
example in the generation of an edge fold or masked regions.
[0095] In a preferred embodiment, in the first process step, a
thermoplastic polymer composition which at room temperature and
more preferably also at -20.degree. C. has high toughness in the
notched impact test to ISO 180-1A, characterized by a notched
impact resistance value of greater than 30 kJ/m.sup.2, is used.
[0096] The reactive polyurethane raw material mixtures used in the
production of the inventive composite components preferably have an
index of >80 to <125, further preferably >90 to <120,
and more preferably von 100 to 110.
[0097] The index is defined as the percentage ratio of the amount
of isocyanate actually used to the calculated stoichiometric amount
in the case of complete reaction with the H-active polyfunctional
component, i.e. index=(amount of isocyanate used/calculated
stoichiometric amount of isocyanate)*100.
[0098] In an alternative embodiment, rather than the reactive
polyurethane raw material mixture, it is also possible to use a
thermoplastic polyurethane
[0099] In a further preferred embodiment, the surface of the
injection mould in contact with the thermoplastic polymer
composition is heated in process step (iii) to a temperature in the
range of 50 to 100.degree. C., preferably 55 to 95.degree. C., and
more preferably 60 to 90.degree. C.
[0100] In a further preferred embodiment, the surface of the
injection mould in contact with the reactive polyurethane mixture
is heated in process step (iii) to a temperature in the range of 50
to 160.degree. C., preferably 50 to 120.degree. C., further
preferably 60 to 110.degree. C., and more preferably 60 to
90.degree. C.
[0101] In a further preferred embodiment, the surface of the
injection mould in contact with the thermoplastic polymer
composition is heated in process step (iii) to a temperature in the
range of 50 to 100.degree. C., preferably 55 to 95.degree. C., and
more preferably 60 to 90.degree. C., and the surface of the
injection mould in contact with the reactive polyurethane mixture
to a temperature in the range of 50 to 160.degree. C., preferably
50 to 120.degree. C., further preferably 60 to 110.degree. C., and
more preferably 60 to 90.degree. C.
[0102] If a foamed polyurethane system with a decorative layer is
involved, in an alternative embodiment, the surface of the foaming
mould in contact with the thermoplastic polymer composition or with
the decorative skin can be heated to a temperature in the range of
20 to 80.degree. C., preferably 30 to 60.degree. C.
[0103] The inventive composite components are particularly suitable
as an interior or exterior component of a rail vehicle, aircraft or
motor vehicle, and for electrical/electronic components and IT
components.
[0104] The composite adhesion between the carrier composed of
polycarbonate composition and the polyurethane coating in the
inventive composite components, in a preferred embodiment, is at
least 1 N/mm, measured on strip samples taken from the component
having a width of 20 mm in a floating roller test to DIN EN 1464
with a traversing speed of 100 mm/min.
[0105] The polymer compositions used in the process according to
the invention comprise:
[0106] Component A
[0107] Aromatic polycarbonates and/or aromatic polyester carbonates
of component A which are suitable in accordance with the invention
are known from the literature or preparable by processes known from
the literature (for preparation of aromatic polycarbonates see, for
example, Schnell, "Chemistry and Physics of Polycarbonates",
Interscience Publishers, 1964, and also DE-B 1 495 626, DE-A 2 232
877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832
396; for preparation of aromatic polyester carbonates, for example
DE-A 3 077 934).
[0108] Aromatic polycarbonates and polyester carbonates are
prepared, for example, by reacting diphenols with carbonic halides,
preferably phosgene, and/or with aromatic dicarbonyl dihalides,
preferably benzenedicarbonyl dihalides, by the interfacial process,
optionally using chain terminators, for example monophenols, and
optionally using trifunctional or more than trifunctional branching
agents, for example triphenols or tetraphenols. Preparation is
likewise possible via a melt polymerization process through
reaction of diphenols with, for example, diphenyl carbonate.
[0109] Diphenols for preparation of the aromatic polycarbonates
and/or aromatic polyester carbonates are preferably those of the
formula (I)
##STR00001##
[0110] where
[0111] A is a single bond, C.sub.1 to C.sub.5-alkylene, C.sub.2 to
C.sub.5-alkylidene, C.sub.5 to C.sub.6-cycloalkylidene, --O--,
--SO--, --CO--, --S--, --SO.sub.2--, C.sub.6 to C.sub.12-arylene,
onto which may be fused further aromatic rings optionally
containing heteroatoms, or a radical of the formula (II) or
(III)
##STR00002##
[0112] B in each case is C.sub.1 to C.sub.12-alkyl, preferably
methyl, halogen, preferably chlorine and/or bromine,
[0113] x in each case is independently 0, 1 or 2,
[0114] p is 1 or 0, and
[0115] R.sup.5 and R.sup.6 can be chosen individually for each
X.sup.1 and are each independently hydrogen or C.sub.1 to
C.sub.6-alkyl, preferably hydrogen, methyl or ethyl,
[0116] X.sup.1 is carbon and
[0117] m is an integer from 4 to 7, preferably 4 or 5, with the
proviso that R.sup.5 and R.sup.6 on at least one X.sup.1 atom are
simultaneously alkyl.
[0118] Preferred diphenols are hydroquinone, resorcinol,
dihydroxydiphenols, bis(hydroxyphenyl)-C.sub.1-C.sub.5-alkanes,
bis(hydroxyphenyl)-C.sub.5-C.sub.6-cycloalkanes,
bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)sulphoxides,
bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulphones and
.alpha.,.alpha.-bis(hydroxyphenyl)diisopropylbenzenes, and the
ring-brominated and/or ring-chlorinated derivatives thereof.
[0119] Particularly preferred diphenols are 4,4'-dihydroxydiphenyl,
bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
4,4'-dihydroxydiphenyl sulphide, 4,4'-dihydroxydiphenyl sulphone
and the di- and tetrabrominated or -chlorinated derivatives
thereof, for example 2,2-bis(3-chloro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane or
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
2,2-Bis(4-hydroxyphenyl)propane (bisphenol A) is especially
preferred.
[0120] It is possible to use the diphenols individually or in the
form of any desired mixtures. The diphenols are known from the
literature or obtainable by processes known from the
literature.
[0121] Examples of chain terminators suitable for the preparation
of the thermoplastic aromatic polycarbonates include phenol,
p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but
also long-chain alkylphenols such as
4-[2-(2,4,4-trimethylpentyl)]phenol, 4-(1,3-tetramethylbutyl)phenol
according to DE-A 2 842 005 or monoalkylphenols or dialkylphenols
having a total of 8 to 20 carbon atoms in the alkyl substituents,
such as 3,5-di-tert-butylphenol, p-isooctylphenol,
p-tert-octylphenol, p-dodecylphenol and
2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The
amount of chain terminators to be used is generally between 0.5 mol
% and 10 mol %, based on the molar sum of the diphenols used in
each case.
[0122] The thermoplastic aromatic polycarbonates may be branched in
a known manner, preferably through the incorporation of 0.05 to 2.0
mol %, based on the sum total of the diphenols used, of
trifunctional or more than trifunctional compounds, for example
those having three or more phenolic groups.
[0123] Both homopolycarbonates and copolycarbonates are suitable.
For preparation of inventive copolycarbonates of component A, it is
also possible to use 1% to 25% by weight, preferably 2.5% to 25% by
weight, based on the total amount of diphenols to be used, of
polydiorganosiloxanes having hydroxyaryloxy end groups. These are
known (U.S. Pat. No. 3,419,634) and are preparable by processes
known from the literature. The preparation of
polydiorganosiloxane-containing copolycarbonates is described in
DE-A 3 334 782.
[0124] Preferred polycarbonates are, as well as the bisphenol A
homopolycarbonates, the copolycarbonates of bisphenol A with up to
15 mol %, based on the molar sums of diphenols, of other diphenols
specified as preferred or particularly preferred, especially
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.
[0125] Aromatic dicarbonyl dihalides for preparation of aromatic
polyester carbonates are preferably the diacid dichlorides of
isophthalic acid, terephthalic acid, diphenyl ether
4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
[0126] Particular preference is given to mixtures of the diacid
dichlorides of isophthalic acid and terephthalic acid in a ratio
between 1:20 and 20:1.
[0127] In the preparation of polyester carbonates, a carbonic
halide, preferably phosgene, is also used as a bifunctional acid
derivative.
[0128] Useful chain terminators for the preparation of the aromatic
polyester carbonates include, apart from the monophenols already
mentioned, the chlorocarbonic esters thereof and the acid chlorides
of aromatic monocarboxylic acids, which may optionally be
substituted by C.sub.1 to C.sub.22-alkyl groups or by halogen
atoms, and aliphatic C.sub.2 to C.sub.22-monocarbonyl
chlorides.
[0129] The amount of chain terminators in each case is 0.1 to 10
mol %, based on moles of diphenol in the case of the phenolic chain
terminators and on moles of dicarbonyl dichloride in the case of
monocarbonyl chloride chain terminators.
[0130] The aromatic polyester carbonates may also contain
incorporated aromatic hydroxycarboxylic acids.
[0131] The aromatic polyester carbonates may be either linear or
branched in a known manner (see DE-A 2 940 024 and DE-A 3 007
934).
[0132] Branching agents used may, for example, be tri- or
multifunctional carbonyl chlorides, such as trimesyl trichloride,
cyanuric trichloride, 3,3',4,4'-benzophenonetetracarbonyl
tetrachloride, 1,4,5,8-naphthalenetetracarbonyl tetrachloride or
pyromellitic tetrachloride, in amounts of 0.01 to 1.0 mol % (based
on dicarbonyl dichlorides used), or tri- or multifunctional
phenols, such as phloroglucinol,
4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)hept-2-ene,
4,6-dimethyl-2,4-6-tri(4-hydroxyphenyl)heptane,
1,3,5-tri(4-hydroxyphenyl)benzene,
1,1,1-tri(4-hydroxyphenyl)ethane,
tri(4-hydroxyphenyl)phenylmethane,
2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane,
2,4-bis(4-hydroxyphenylisopropyl)phenol,
tetra(4-hydroxyphenyl)methane,
2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol,
2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane,
tetra(4-[4-hydroxyphenylisopropyl]phenoxy)methane,
1,4-bis[4,4'-dihydroxytriphenyl)methyl]benzene, in amounts of 0.01
to 1.0 mol %, based on diphenols used. Phenolic branching agents
may be initially charged together with the diphenols; acid chloride
branching agents may be introduced together with the acid
dichlorides.
[0133] The proportion of carbonate structural units in the
thermoplastic aromatic polyester carbonates may vary as desired.
Preferably, the proportion of carbonate groups is up to 100 mol %,
especially up to 80 mol %, more preferably up to 50 mol %, based on
the sum total of ester groups and carbonate groups. Both the ester
fraction and the carbonate fraction of the aromatic polyester
carbonates may be present in the form of blocks or in random
distribution in the polycondensate.
[0134] The relative solution viscosity (.eta..sub.rel) of aromatic
polycarbonates and polyester carbonates is preferably in the range
of 1.18 to 1.4, more preferably in the range of 1.20 to 1.32
(measured in solutions of 0.5 g of polycarbonate or polyester
carbonate in 100 ml of methylene chloride at 25.degree. C.). The
weight-average molecular weight Mw of aromatic polycarbonates and
polyester carbonates is preferably in the range from 15 000 to 35
000, further preferably in the range from 20 000 to 33 000, more
preferably 23 000 to 30 000, determined by GPC (gel permeation
chromatography in methylene chloride with polycarbonate as
standard).
[0135] Component B
[0136] Component B comprises polybutadiene-based graft polymers or
mixtures of polybutadiene-based graft polymers with butadiene-free
vinyl (co)polymers, the polybutadiene content of component B being
at least 25.0% by weight.
[0137] Polybutadiene-based graft polymers used in component B
comprise [0138] B.1 5% to 95%, preferably 15% to 92% and especially
25% to 60% by weight, based on the graft polymer, of at least one
vinyl monomer on [0139] B.2 95% to 5%, preferably 85% to 8% and
especially 75% to 40% by weight, based on the graft polymer, of one
or more polybutadiene-based graft bases.
[0140] The graft base B.2 generally has a median particle size
(d.sub.50) of 0.05 to 10.00 .mu.m, preferably 0.1 to 5.0 .mu.m,
more preferably 0.2 to 1.0 .mu.m, and most preferably 0.2 to 0.5
.mu.m.
[0141] The mean particle size d.sub.50 is the diameter above which
and below which 50% by weight of the particles lie. It can be
determined by means of ultracentrifuge measurement (W. Scholtan, H.
Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
[0142] Monomers B.1 are preferably mixtures of [0143] B.1.1 50% to
99%, preferably 65% to 85% and especially 75% to 80% by weight,
based on B.1, of vinylaromatics and/or ring-substituted
vinylaromatics (such as styrene, .alpha.-methylstyrene,
p-methylstyrene, p-chlorostyrene) and/or (C.sub.1-C.sub.8)-alkyl
methacrylates such as methyl methacrylate, ethyl methacrylate), and
[0144] B.1.2 1% to 50%, preferably 15% to 35% and especially 20% to
25% by weight, based on B.1, of vinyl cyanides (unsaturated
nitriles such as acrylonitrile and methacrylonitrile) and/or
(C.sub.1-C.sub.8)-alkyl(meth)acrylates such as methyl methacrylate,
n-butyl acrylate, t-butyl acrylate, and/or derivatives (such as
anhydrides and imides) of unsaturated carboxylic acids, for example
maleic anhydride and N-phenylmaleimide.
[0145] Monomers B.1 are further preferably mixtures of [0146] B.1.1
50% to 99%, preferably 65% to 85% and especially 75% to 80% by
weight, based on B.1, of vinylaromatics and/or ring-substituted
vinylaromatics (such as styrene, .alpha.-methylstyrene,
p-methylstyrene, p-chlorostyrene), and [0147] B.1.2 1% to 50%,
preferably 15% to 35% and especially 20% to 25% by weight, based on
B.1, of vinyl cyanides (unsaturated nitriles such as acrylonitrile
and methacrylonitrile) and/or derivatives (such as anhydrides and
imides) of unsaturated carboxylic acids, for example maleic
anhydride and N-phenylmaleimide.
[0148] Particularly preferred monomers B.1.1 are selected from at
least one of the monomers styrene, .alpha.-methylstyrene and methyl
methacrylate; preferred monomers B.1.2 are selected from at least
one of the monomers acrylonitrile and maleic anhydride. The most
preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile.
[0149] Graft bases B.2 suitable for the graft polymers in component
B are pure polybutadiene rubbers or mixtures of polybutadiene
rubbers or copolymers of polybutadiene rubbers or mixtures thereof
with further copolymerizable monomers (for example according to
B.1.1 and B.1.2), with the proviso that the glass transition
temperature of component B.2 is below <10.degree. C., preferably
<0.degree. C., more preferably <-20.degree. C.
[0150] The glass transition temperature was determined by means of
differential thermoanalysis (DSC) according to the standard DIN EN
61006 at a heating rate 10 K/min with T.sub.g defined as the
midpoint temperature (tangent method).
[0151] A particularly preferred graft base B.2 is pure
polybutadiene rubber.
[0152] Particularly preferred graft polymers in component B are,
for example, ABS polymers as described, for example, in DE-A 2 035
390 (=U.S. Pat. No. 3,644,574) or in DE-A 2 248 242 (=GB-A 1 409
275) or in Ullmanns, Enzyklopadie der Technischen Chemie
[Encyclopaedia of Industrial Chemistry], vol. 19 (1980), p. 280
ff.
[0153] The graft polymers in component B are prepared by
free-radical polymerization, for example by emulsion, suspension or
solution polymerization, especially by emulsion polymerization.
[0154] In a particularly preferred embodiment, no graft polymers
which have been prepared by bulk polymerization are present.
[0155] In the case of graft polymers in component B which have been
prepared in an emulsion polymerization process, the content of
graft base B.2 is preferably 20% to 95% by weight, more preferably
40% to 85% by weight, especially 50% to 75% by weight, based in
each case on the graft polymer.
[0156] The gel content of the graft base B.2 is at least 30% by
weight, preferably at least 40% by weight, especially at least 60%
by weight, based in each case on B.2 and measured as the insoluble
component in toluene.
[0157] Since the grafting reaction, as is well known, does not
necessarily graft the graft monomers completely onto the graft
base, according to the invention, graft polymers in component B are
also understood to mean those products which are obtained by
(co)polymerization of the graft monomers B.1 in the presence of the
graft base B.2 and are also obtained in the workup. These products
may accordingly also contain free (co)polymer of the graft monomers
B.1 not chemically bonded to the polybutadiene.
[0158] The gel content of the graft base B.2 or of the graft
polymers in component B is determined at 25.degree. C. in a
suitable solvent as the component insoluble in these solvents (M.
Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II [Polymer
Analysis I and II], Georg Thieme-Verlag, Stuttgart 1977).
[0159] The butadiene-free vinyl (co)polymers in component B are
preferably butadiene-free homo- and/or copolymers B.1 of at least
one monomer from the group of the vinylaromatics, vinyl cyanides
(unsaturated nitriles), (C.sub.1 to C.sub.8)-alkyl(meth)acrylates,
unsaturated carboxylic acids and derivatives (such as anhydrides
and imides) of unsaturated carboxylic acids.
[0160] These (co)polymers B.1 are resinous, thermoplastic and
butadiene-free. More preferably, the copolymer is formed from B.1.1
styrene and B.1.2 acrylonitrile.
[0161] (Co)polymers B.1 of this kind are known and can be prepared
by free-radical polymerization, especially by emulsion, suspension,
solution or bulk polymerization. The (co)polymers preferably have
average molecular weights M.sub.w (weight-average, determined by
GPC) between 15 000 g/mol and 250 000 g/mol, preferably in the
range of 80 000 to 150 000 g/mol.
[0162] Component C
[0163] The composition may comprise conventional polymer additives
as component C. Possible conventional polymer additives for
component C include additives such as for example internal and
external lubricants and demoulding agents (for example
pentaerythrityl tetrastearate, stearyl stearate, montan wax or
polyethylene wax), flowability aids, antistats (for example block
copolymers of ethylene oxide and propylene oxide, other polyethers
or polyhydroxy ethers, polyether amides, polyester amides or
sulphonic salts), conductivity additives (for example conductive
black or carbon nanotubes), stabilizers (for example UV/light
stabilizers, thermal stabilizers, antioxidants, hydrolysis
stabilizers), antibacterial additives (for example silver or silver
salts), scratch resistance-improving additives (for example
silicone oils or hard fillers such as (hollow) ceramic beads), IR
absorbents, optical brighteners, fluorescent additives, and also
dyes and pigments (for example carbon black, titanium dioxide or
iron oxide), impact modifiers not covered by the definition of B,
and Bronsted-acidic compounds as base scavengers, or else mixtures
of a plurality of the additives mentioned.
[0164] More preferably, the inventive compositions comprise at
least one demoulding agent, preferably 0.1 to 1.0 part by weight of
pentaerythrityl tetrastearate based on the sum total of components
A and B, and at least one stabilizer, preferably a phenolic
antioxidant, more preferably 0.01 to 1.0 part by weight of
2,6-di-tert-butyl-4-(octadecanoxycarbonylethyl)phenol or based on
the sum total of components A and B.
[0165] Further preference is given to a stabilizer combination of
at least two stabilizers, the second stabilizer comprising 0.01 to
1.0 part by weight of a Bronsted-acidic compound based on the sum
total of components A and B. Preferably, the second stabilizer is
phosphoric acid, aqueous phosphoric acid solution or a free-flowing
blend of phosphoric acid or an aqueous phosphoric acid solution
with a finely divided hydrophilic silica gel in a concentration of
0.01 to 1.0 part by weight, based on the sum total of components A
and B.
[0166] Another further preferred additive is citric acid in a
concentration of 0.05 to 1.0 part by weight, based on the sum total
of components A and B.
[0167] In a preferred embodiment, the compositions do not comprise,
as component C, any fillers and reinforcers, for example talc,
glass fibres or carbon fibres (optionally including ground fibres),
(hollow) glass or ceramic beads, mica, kaolin, CaCO.sub.3 and glass
flakes.
[0168] In a further preferred embodiment, the compositions do not
comprise any flame retardants or any flame retardant synergists
such as anti-dripping agents as component C.
[0169] Polyurethane Layer
[0170] The polyurethane layer used is preferably a polyurethane
foam or a compact polyurethane layer.
[0171] The polyurethanes used in accordance with the invention are
obtained by reacting polyisocyanates with H-active polyfunctional
compounds, preferably polyols.
[0172] In the context of this invention, the term "polyurethane" is
also understood to mean polyurethaneureas in which the H-active
polyfunctional compounds used are those compounds having N--H
functionality, optionally in a blend with polyols.
[0173] Suitable polyisocyanates are the aromatic, araliphatic,
aliphatic or cycloaliphatic polyisocyanates which are known per se
to those skilled in the art and have NCO functionality of
preferably .gtoreq.2, which may also have iminooxadiazinedione,
isocyanurate, uretdione, urethane, allophanate, biuret, urea,
oxadiazinetrione, oxazolidinone, acylurea and/or carbodiimide
structures. These can be used individually or in any desired
mixtures with one another.
[0174] The aforementioned polyisocyanates are based on di- or
triisocyanates which are known per se to those skilled in the art
and have aliphatically, cycloaliphatically, araliphatically and/or
aromatically bonded isocyanate groups, it being unimportant whether
these have been prepared using phosgene or by phosgene-free
methods. Examples of such di- or triisocyanates are
1,4-diisocyanatobutane, 1,5-diisocyanatopentane,
1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane,
1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or
2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane,
1,3- and 1,4-diisocyanatocyclohexane, 1,3- and
1,4-bis(isocyanatomethyl)-cyclohexane,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
(isophorone diisocyanate, IPDI),
4,4'-diisocyanatodicyclohexylmethane (Desmodur.RTM. W, Bayer AG,
Leverkusen, DE), 4-isocyanatomethyl-1,8-octane
diisocyanate(triisocyanatononane, TIN),
.omega.,.omega.'-diisocyanato-1,3-dimethylcyclohexane (H.sub.6XDI),
1-isocyanato-1-methyl-3-isocyanatomethyl-cyclohexane,
1-isocyanato-1-methyl-4-isocyanatomethylcyclohexane,
bis(isocyanatomethyl)-norbornane, naphthalene 1,5-diisocyanate,
1,3- and 1,4-bis(2-isocyanatoprop-2-yl)benzene (TMXDI), 2,4- and
2,6-diisocyanatotoluene (TDI), especially the 2,4 and the 2,6
isomer, and technical mixtures of the two isomers, 2,4'- and
4,4'-diisocyanatodiphenylmethane (MDI), polymeric MDI (pMDI),
1,5-diisocyanatonaphthalene, 1,3-bis(isocyanatomethyl)benzene (XDI)
and any desired mixtures of the compounds mentioned.
[0175] The polyisocyanates preferably have an average NCO
functionality of 2.0 to 5.0, preferably of 2.2 to 4.5, more
preferably of 2.2 to 2.7, and a content of isocyanate groups of
5.0% to 37.0% by weight, preferably of 14.0% to 34.0% by
weight.
[0176] In a preferred embodiment, polyisocyanates or polyisocyanate
mixtures of the above-specified type having exclusively
aliphatically and/or cycloaliphatically bonded isocyanate groups
are used.
[0177] Most preferably, the polyisocyanates of the above-specified
type are based on hexamethylene diisocyanate, isophorone
diisocyanate, the isomeric bis(4,4'-isocyanatocyclohexyl)methanes
and mixtures thereof.
[0178] Among the modified polyisocyanates of relatively high
molecular weight, the prepolymers known from polyurethane chemistry
which have terminal isocyanate groups and are of the molecular
weight range of 400 to 15 000, preferably 600 to 12 000, are of
particular interest. These compounds are prepared in a manner known
per se by reaction of excess amounts of simple polyisocyanates of
the type specified by way of example with organic compounds having
at least two groups reactive toward isocyanate groups, especially
organic polyhydroxyl compounds. Suitable polyhydroxyl compounds of
this kind are simple polyhydric alcohols of the molecular weight
range of 62 to 599, preferably 62 to 200, for example ethylene
glycol, trimethylolpropane, propane-1,2-diol or butane-1,4-diol or
butane-2,3-diol, but especially high molecular weight polyether
polyols and/or polyester polyols of the kind known per se from
polyurethane chemistry, having molecular weights of 600 to 12 000,
preferably 800 to 4000, and having at least two, generally 2 to 8,
but preferably 2 to 6, primary and/or secondary hydroxyl groups. It
is of course also possible to use those NCO prepolymers which, for
example, have been obtained from lower molecular weight
polyisocyanates of the type specified by way of example and less
preferred compounds having groups reactive toward isocyanate
groups, for example polythioether polyols, polyacetals having
hydroxyl groups, polyhydroxypolycarbonates, polyester amides having
hydroxyl groups or hydroxyl-containing copolymers of olefinically
unsaturated compounds.
[0179] Compounds which have groups reactive toward isocyanate
groups, especially hydroxyl groups, and are suitable for
preparation of the NCO prepolymers are, for example, the compounds
disclosed in U.S. Pat. No. 4,218,543. In the preparation of the NCO
prepolymers, these compounds having groups reactive toward
isocyanate groups are reacted with simple polyisocyanates of the
type specified above by way of example while maintaining an NCO
excess. The NCO prepolymers generally have an NCO content of 10% to
26% and preferably 15% to 26% by weight. It is already clear from
this that, in the context of the present invention, "NCO
prepolymers" and "prepolymers having terminal isocyanate groups"
are understood to mean both the reaction products and the mixtures
with excess amounts of unconverted starting polyisocyanates, which
are often also referred to as "semiprepolymers".
[0180] Useful aliphatic diols having an OH number of >500 mg
KOH/g includes the chain extenders customarily used in polyurethane
chemistry, such as ethylene glycol, diethylene glycol, propylene
glycol, dipropylene glycol, butane-1,4-diol, propane-1,3-diol.
Preference is given to diols such as 2-butane-1,4-diol,
butane-1,3-diol, butane-2,3-diol and/or 2-methylpropane-1,3-diol.
It will be appreciated that it is also possible to use the
aliphatic diols in a mixture with one another.
[0181] Suitable H-active components are polyols having an average
OH number of 5 to 600 mg KOH/g and an average functionality of 2 to
6. Polyols suitable in accordance with the invention are, for
example, polyhydroxy polyethers obtainable by alkoxylation of
suitable starter molecules such as ethylene glycol, diethylene
glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane,
dimethylolpropane, glycerol, pentaerythritol, sorbitol or sucrose.
Starters used may likewise be ammonia or amines such as
ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline
or amino alcohols or phenols such as bisphenol A. The alkoxylation
is effected using propylene oxide and/or ethylene oxide in any
desired sequence or as a mixture.
[0182] As well as polyols, it is additionally possible for at least
one crosslinker and/or chain extender to be present, selected from
the group comprising the amines and amino alcohols, for example
ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine,
triethanolamine, isophoronediamine,
N,N'-dimethyl(diethyl)ethylenediamine, 2-amino-2-methyl(or
ethyl)-1-propanol, 2-amino-1-butanol, 3-amino-1,2-propanediol,
2-amino-2-methyl(ethyl)-1,3-propanediol, and alcohols, for example
ethylene glycol, diethylene glycol, 1,4-dihydroxybutane,
1,6-dihydroxyhexane, dimethylolpropane, glycerol and
pentaerythritol, and also sorbitol and sucrose, or mixtures of
these compounds.
[0183] Also suitable are polyester polyols as obtainable in a
manner known per se by reaction of low molecular weight alcohols
with polybasic carboxylic acids such as adipic acid, phthalic acid,
hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides
of these acids, provided that the viscosity of the H-active
component does not become too great. A preferred polyol having
ester groups is castor oil. Also additionally suitable are
formulations comprising castor oil, as obtainable by dissolution of
resins, for example of aldehyde-ketone resins, and modifications of
castor oil and polyols based on other natural oils.
[0184] Likewise suitable are those polyhydroxy polyethers of
relatively high molecular weight in which high molecular weight
polyadducts or polycondensates or polymers are present in finely
dispersed, dissolved or grafted form. Modified polyhydroxyl
compounds of this kind are obtainable in a manner known per se, for
example, when polyaddition reactions (e.g. reactions between
polyisocyanates and amino-functional compounds) or polycondensation
reactions (for example between formaldehyde and phenols and/or
amines) are allowed to proceed in situ in the compounds having
hydroxyl groups. Alternatively, it is also possible to mix a
finished aqueous polymer dispersion with a polyhydroxyl compound
and then to remove the water from the mixture.
[0185] Polyhydroxyl compounds modified by vinyl polymers, as
obtained, for example, by polymerization of styrene and
acrylonitrile in the presence of polyethers or polycarbonate
polyols, are also suitable for the preparation of polyurethanes
When polyether polyols which have been modified according to DE-A 2
442 101, DE-A 2 844 922 and DE-A 2 646 141 by graft polymerization
with vinyl phosphonates and optionally (meth)acrylonitrile,
(meth)acrylamide or OH-functional (meth)acrylic esters are used,
polymers of exceptional flame retardancy are obtained.
[0186] Representatives of the compounds to be used as H-active
compounds mentioned are described, for example, in High Polymers,
Vol. XVI, "Polyurethanes Chemistry and Technology", Saunders-Frisch
(ed.) Interscience Publishers, New York, London, vol. 1, p. 32-42,
44, 54 and vol. II, 1984, p. 5-6 and p. 198-199.
[0187] It is also possible to use mixtures of the compounds
enumerated.
[0188] The limitation of the average OH number and the average
functionality of the H-active component arises particularly from
the increasing embrittlement of the resulting polyurethane In
principle, however, the person skilled in the art is aware of the
ways of influencing the physical polymer properties of the
polyurethane, such that NCO component, aliphatic diol and polyol
can be matched to one another in a favourable manner
[0189] The polyurethane layer (b) may be in foamed or solid form,
for example as a lacquer or coating.
[0190] It can be produced using any of the assistants and additives
known per se, for example separating agents, blowing agents,
fillers, catalysts and flame retardants.
[0191] Assistants and additives for optional use are:
[0192] a) Water and/or volatile inorganic or organic substances as
blowing agents
[0193] Useful organic blowing agents include, for example, acetone,
ethyl acetate, halogen-substituted alkanes such as methylene
chloride, chloroform, ethylidene chloride, vinylidene chloride,
monofluorotrichloromethane, chlorodifluoromethane,
dichlorodifluoromethane, and also butane, hexane, heptane or
diethyl ether, and useful inorganic blowing agents include air,
CO.sub.2 or N.sub.2O. A blowing effect can also be achieved through
addition of compounds that decompose at temperatures exceeding room
temperature with elimination of gases, for example of nitrogen,
examples being azo compounds such as azodicarbonamide and
azoisobutyronitrile.
[0194] b) Catalysts
[0195] The catalysts are, for example, tertiary amines (such as
triethylamine, tributylamine, N-methylmorpholine,
N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine,
pentamethyldiethylenetriamine and higher homologues,
1,4-diazabicyclo[2.2.2]octane,
N-methyl-N'-dimethylaminoethylpiperazine,
bis(dimethylaminoalkyl)piperazines, N,N-dimethylbenzylamine,
N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine,
bis(N,N-diethylaminoethyl)adipate,
N,N,N',N'-tetramethyl-1,3-butanediamine,
N,N-dimethyl-.beta.-phenylethylamine, 1,2-dimethyl-imidazole,
2-methylimidazole), monocyclic and bicyclic amides,
bis(dialkylamino)alkyl ethers, tertiary amines having amide groups
(preferably formamide groups), Mannich bases formed from secondary
amines (such as dimethylamine) and aldehydes (preferably
formaldehyde or ketones such as acetone, methyl ethyl ketone or
cyclohexanone) and phenols (such as phenol, nonylphenol or
bisphenol), tertiary amines having hydrogen atoms active toward
isocyanate groups (e.g. triethanolamine, triisopropanolamine,
N-methyldiethanolamine, N-ethyldiethanolamine,
N,N-dimethylethanolamine), and the reaction products thereof with
alkylene oxides such as propylene oxide and/or ethylene oxide,
secondary/tertiary amines, silaamines having carbon-silicon bonds
(2,2,4-trimethyl-2-silamorpholine and
1,3-diethylaminomethyltetramethyldisiloxane), nitrogen-containing
bases (such as tetraalkylammonium hydroxides), alkali metal
hydroxides (such as sodium hydroxide, alkali metal phenoxides such
as sodium phenoxide), alkali metal alkoxides (such as sodium
methoxide), and/or hexahydrotriazines.
[0196] The reaction between NCO groups and Zerewitinoff-active
hydrogen atoms, in a manner known per se, is greatly accelerated by
lactams and azalactams as well, with initial formation of an
associate between the lactam and the compound having acidic
hydrogen.
[0197] It is also possible to use organic metal compounds,
especially organic tin and/or bismuth compounds, as catalysts.
Useful organic tin compounds include, as well as sulphur compounds
such as di-n-octyltin mercaptide, preferably tin(II) salts of
carboxylic acids such as tin(II) acetate, tin(II) octoate, tin (II)
ethylhexoateand tin(II) laurate, and the tin(IV) compounds, for
example dibutyltin oxide, dibutyltin dichloride, dibutyltin
diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin
diacetate. Organic bismuth catalysts are described, for example, in
patent application WO 2004/000905.
[0198] It is of course possible to use any of the catalysts
mentioned above as mixtures. Of particular interest in this context
are combinations of organic metal compounds and amidines,
aminopyridines or hydrazinopyridines.
[0199] The catalysts are generally used in an amount of about
0.001% to 10% by weight, based on the total amount of compounds
having at least two hydrogen atoms reactive toward isocyanates.
[0200] c) Surface-active additives such as emulsifiers and foam
stabilizers
[0201] Useful emulsifiers include, for example, the sodium salts of
castor oil sulphonates or salts of fatty acids with amines, such as
diethylammonium oleate or diethanolammonium stearate. It is also
possible to use alkali metal or ammonium salts of sulphonic acids
as surface-active additives as well, for instance of
dodecylbenzenesulphonic acid or dinaphthylmethanedisulphonic acid
or of fatty acids such as ricinoleic acid or of polymeric fatty
acids.
[0202] Useful foam stabilizers include particularly polyether
siloxanes, especially water-soluble representatives. The structure
of these compounds is generally such that a copolymer of ethylene
oxide and propylene oxide is bonded to a polydimethylsiloxane
radical. Of particular interest are polysiloxane-polyoxyalkylene
copolymers with multiple branching via allophanate groups.
[0203] d) Reaction retardants
[0204] Useful reaction retardants include, for example, acidic
substances (such as hydrochloric acid or organic acid halides).
[0205] e) Additives
[0206] Useful PU additives include, for example, cell regulators of
the type known per se (such as paraffins or fatty alcohols) or
dimethylpolysiloxanes, and also pigments or dyes and flame
retardants of the type known per se (for example tris(chloroethyl)
phosphate, tricresyl phosphate or ammonium phosphate and
polyphosphate), and also stabilizers against aging and weathering
influences, plasticizers and fungistatic and bacteriostatic
substances, and also fillers (such as barium sulphate, kieselguhr,
carbon black or precipitated chalk)
[0207] Further examples of surface-active additives and foam
stabilizers, and also cell regulators, reaction retardants,
stabilizers, flame-retardant substances, plasticizers, dyes and
fillers, and also fungistatic and bacteriostatic substances, for
optional additional use in accordance with the invention are known
to those skilled in the art and are described in the
literature.
EXAMPLES
[0208] Component A
[0209] Linear polycarbonate based on bisphenol A having a
weight-average molecular weight M.sub.w of 26 000 g/mol.
[0210] Component B-1
[0211] ABS emulsion polymer having an
acrylonitrile:butadiene:styrene ratio of 20:26:54 parts by weight
and a median particle size d.sub.50 of the graft base of 230 nm,
determined by ultracentrifuge measurement.
[0212] Component B-2
[0213] ABS emulsion polymer having an
acrylonitrile:butadiene:styrene weight ratio of 12:57:31 parts by
weight and a median particle size d.sub.50 of the graft base of 340
nm, determined by ultracentrifuge measurement.
[0214] Component B-3
[0215] ABS bulk polymer having a acrylonitrile:butadiene:styrene
ratio of 24:10:66 parts by weight and a median particle size
d.sub.50 of the graft base of 700 nm, determined by ultracentrifuge
measurement.
[0216] Component B-4
[0217] Rubber-free copolymer, prepared in a bulk polymerization
process, from 76 parts by weight of styrene and 24 parts by weight
of acrylonitrile, having a weight-average molecular weight M.sub.w
of 130 000 g/mol (determined by GPC with polystyrene as
standard).
[0218] Component C-1
[0219] Pentaerythrityl tetrastearate is commercially available as
Loxiol VPG 861 from Emery Oleochemicals.
[0220] Component C-2
[0221] Irganox.RTM. B900
[0222] Mixture of 80 parts by weight of Irgafos.RTM. 168
(tris(2,4-di-tert-butyl)phenyl phosphite) and 20 parts by weight of
Irganox.RTM. 1076 (octadecyl
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (BASF,
Germany)
[0223] Component C-3
[0224] Irganox.RTM. 1076
(octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate) (BASF,
Germany).
[0225] Component C-4
[0226] Citric acid is commercially available from Hamann and
Reimer.
[0227] Component C-5
[0228] The black pigment Black Pearls 800 (carbon black) is
commercially available from Cabot Corporation.
[0229] Component C-6
[0230] Phosphorous ester of
bis(2-hydroxy-3-cyclohexyl-5-methylphenyl)methane, commercially
available as Addovate ThermoStab from Rhein Chemie Rheinau
GmbH.
##STR00003##
[0231] Reactive Polyurethane Coating System
[0232] The polyurethane coating system used was a mixture of
Desmophen.RTM. XP 2488 (polyol component) and Desmodur.RTM. N3600
(polyisocyanate component), both from Bayer MaterialScience AG,
Leverkusen, Germany, in a mixing ratio of 1:1.7 parts by
weight.
[0233] Desmophen.RTM. XP 2488 is a branched polyester polyol having
a viscosity to DIN 53019 of 13 250 mPas at 20.degree. C., a density
to DIN 51757 of 1.12 g/cm.sup.3 at 20.degree. C. and an OH content
of 16.0%.
[0234] Desmodur N3600 is an aliphatic isocyanate based on
hexamethylene diisocyanate having an NCO content to DIN EN ISO
11909 of 23.5% by weight, a viscosity at 23.degree. C. to DIN EN
ISO 3219/A.3 of 1200 mPas and a density at 20.degree. C. to DIN EN
ISO 2811 of 1.16 g/cm.sup.3.
[0235] The crosslinking of the polyurethane coating system was
catalysed with a dibutyltin dilaurate (DBTL) commercially available
from OMG Borchers GmbH, Langenfeld. The amount added was 0.5 part
by weight based on the sum total of polyol component and
polyisocyanate component.
[0236] Production and Characterization of the Polycarbonate
Moulding Compositions
[0237] In a twin-screw extruder (ZSK-25) (from Werner and
Pfleiderer), the feedstocks listed in Table 1 are compounded at a
speed of 220 rpm and with a throughput of 20 kg/h at a melt
temperature in the range from 260 to 280.degree. C. and pelletized
after cooling and solidification of the melt of the compound.
[0238] The pellets resulting from the particular compounding
operation are processed in an injection-moulding machine (from
Arburg) at a melt temperature of 260.degree. C. and a mould
temperature of 80.degree. C. to give test specimens of dimensions
80 mm.times.10 mm.times.4 mm
[0239] Unless stated otherwise, the parameters specified in the
present application are determined by the following methods:
[0240] The ductility of the moulding compositions is assessed using
the notched impact resistance value a.sub.k measured on these test
specimens to ISO 180-1A at 23.degree. C. and -20.degree. C.
[0241] The ductility of the moulding compositions is assessed using
the impact resistance value a.sub.n measured on these test
specimens to ISO 180-1U at -30.degree. C.
[0242] Heat distortion resistance is assessed using the Vicat B120
value measured on these test specimens to ISO 306.
[0243] Melt stability is assessed using the melt viscosity measured
at 260.degree. C. and a shear rate of 1000 s.sup.-1 to ISO
11443.
[0244] Elongation at break is measured in a tensile test to ISO
527-1,-2 with an extension rate of 50 mm/min
[0245] The composite adhesion between the substrate composed of
polycarbonate composition and the polyurethane skin is determined
on strip samples having a width of 20 mm which were sawn out of the
partially PU-coated 2-component composite sheets thus produced, by
a floating roller test to DIN EN 1464 with a testing speed of 100
mm/min.
[0246] Production of the Composite Components
[0247] Partially surface-coated mouldings having a projected area
of 412 cm.sup.2 were produced in an injection-moulding machine in
an injection mould having two cavities (a substrate-side cavity and
a polyurethane-side coating cavity which was connected to an RIM
system). The composite component was a sheetlike component composed
of thermoplastic polymer (carrier), the surface of which had been
partly coated with a polyurethane layer. The wall thickness of the
carrier moulding was about 4 mm The polyurethane layer thickness
was 200 gm.
[0248] The process according to the invention for producing the
inventive composite components described in the examples is shown
in FIG. 1 for better illustration.
[0249] In the first process step, the carrier moulding was
produced. For this purpose, thermoplastic polymer pellets of the
compositions as described in Table 1 were melted in an
injection-moulding barrel and injected at a temperature of
270.degree. C. into the first mould cavity of the closed mould
(steps 1 and 2 in FIG. 1). This mould cavity was heated to a
temperature of 80.degree. C. After the hold-pressure time and
cooling time, which led to the solidification of the carrier, had
elapsed, the mould was opened in the second process step (step 3 in
FIG. 1). This was done by holding the carrier component produced on
the ejector side of the injection mould and moving it from the
carrier position (step 3 in FIG. 1) together with the mould core
into the coating position using a slider (step 4 in FIG. 1).
Thereafter, the injection mould was closed again (step 5 in FIG.
1), a clamping force for a maximum pressure of 200 bar was applied
and, in the third process step, the solvent-free reactive
polyurethane system (see above) was injected into the coating
cavity under a pressure of about 30 bar (step 6 in FIG. 1). This
was done by conveying the two reactive components of the
polyurethane coating system from the RIM system into a
high-pressure countercurrent mixing head and mixing them therein
prior to injection. The PU-side cavity was heated to a temperature
of 80.degree. C. After the end of the injection, the injection
nozzle of the polyurethane mixing head was sealed by means of a
hydraulic cylinder under a pressure of 50 bar at first, in order to
prevent backflow of the coating material. After the reaction and
cooling time had elapsed, in the fourth process step, the mould was
opened once more (step 7 in FIG. 1) and the coated moulding was
demoulded (step 8 in FIG. 1).
[0250] Table 1 shows the influence of the carrier material
compositions on the adhesion between the layers of the composite
component.
[0251] The proportions of the components are reported in parts by
weight.
TABLE-US-00001 TABLE 1 Compo- Compar- Compar- Compar- Exam- Exam-
Exam- Exam- Exam- Exam- Exam- nent Unit ison 1 ison 2 ison 3 ple 1
ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 A 72.00 43.09 58.00 65.08 58.00
65.08 69.11 68.62 72.14 71.94 B-1 12.00 30.00 16.85 12.00 9.97 6.94
10.77 4.94 10.00 B-2 3.00 25.43 12.00 18.07 30.00 24.95 23.96 20.61
22.91 18.05 B-3 13.00 B-4 31.48 C-1 0.75 0.75 0.75 0.75 0.75 0.75
0.75 0.75 0.75 0.75 C-2 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 C-3
0.20 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 C-4 0.10 0.10 0.10
0.10 0.10 0.10 0.10 0.10 0.10 C-5 0.51 0.50 0.51 0.51 0.51 0.51
0.51 0.51 0.51 0.51 C-6 0.15 Polybutadiene content % 6.0 14.2 14.4
14.4 19.9 16.5 15.2 14.3 14.1 12.7 based on A + B Butadiene-free
vinyl % 22.0 42.7 27.6 20.5 22.1 18.4 15.7 17.1 13.8 15.4
(co)polymer content based on A + B Adhesion N/mm 0.34 0.17 0.66
1.66 2.11 2.33 2.93 2.37 3.9 2.54 Melt viscosity 260.degree. C. Pas
254 178 285 375 450 486 503 460 531 483 Izod notched 23.degree. C.
kJ/m.sup.2 49.9 36.2 45.8 43.2 41.1 44.4 44.6 46.1 45 48.2 impact
resistance Izod notched -20.degree. C. kJ/m.sup.2 36.1 25.7 37.6
33.9 35.1 37.1 37.5 38.8 38.5 39.5 impact resistance Izod impact
-30.degree. C. kJ/m.sup.2 7 .times. n.f./ 2 .times. n.f./ 8 .times.
n.f./ n.f n.f n.f n.f n.f n.f n.f resistance 3 .times. 240 8
.times. 168 2 .times. 207 Elongation at break 23.degree. C. % 110
34.9 117.8 104.3 117.7 111.2 109 103.7 104.5 105.5 Vicat .degree.
C. 130 110 118 128 120 127 130 130 132 132 n.f.: No fracture
[0252] As apparent from Table 1, Inventive Examples 1-7 exhibit not
only a distinct improvement in adhesion to the polyurethane system
but also constantly high or improved toughness and constantly high
heat distortion resistance in combination with good melt stability
and high elongation at break. The optimal combination of properties
is achieved only when the polybutadiene content based on components
A+B is within the inventive range and, at the same time, the
content of butadiene-free vinyl (co)polymer is likewise within the
inventive range. If, as in Comparative Example 1, the polybutadiene
content is too low and a polybutadiene-based graft polymer which
was not prepared by emulsion, suspension or solution polymerization
is used, the adhesion does not reach the level required in
industry. Furthermore, the required impact resistance and the
required melt stability are not achieved. If, as in Comparative
Examples 2 and 3, the butadiene-free vinyl (co)polymer content is
too high, the adhesion likewise does not reach the level required
in industry. Moreover, the required, heat distortion resistance and
the required melt stability are not achieved.
* * * * *