U.S. patent application number 14/050901 was filed with the patent office on 2014-02-06 for polyamide blend film.
This patent application is currently assigned to EVONIK DEGUSSA GmbH. The applicant listed for this patent is Kirsten Alting, Franz-Erich Baumann, Michael Beyer, Sonja Bollmann, Harald Haeger, Martin Wielpuetz, Roland Wursche. Invention is credited to Kirsten Alting, Franz-Erich Baumann, Michael Beyer, Sonja Bollmann, Harald Haeger, Martin Wielpuetz, Roland Wursche.
Application Number | 20140037937 14/050901 |
Document ID | / |
Family ID | 36201384 |
Filed Date | 2014-02-06 |
United States Patent
Application |
20140037937 |
Kind Code |
A1 |
Wursche; Roland ; et
al. |
February 6, 2014 |
POLYAMIDE BLEND FILM
Abstract
A film whose outer layer is composed of a molding composition
which is in essence composed of the following components: a) from 3
to 50% by weight of a polyamide, selected from the group of PA11
and PA12, and b) from 50 to 97% by weight of a polyamide, selected
from the group of PA1012 and PA1212, where the percentages are
based on the entirety of components a) and b), is suitable for
decoration of moldings which retain their gloss during their
service time.
Inventors: |
Wursche; Roland; (Duelmen,
DE) ; Bollmann; Sonja; (Haltern am See, DE) ;
Haeger; Harald; (Luedinghausen, DE) ; Wielpuetz;
Martin; (Senden, DE) ; Alting; Kirsten;
(Muenster, DE) ; Beyer; Michael; (Raesfeld,
DE) ; Baumann; Franz-Erich; (Duelmen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Wursche; Roland
Bollmann; Sonja
Haeger; Harald
Wielpuetz; Martin
Alting; Kirsten
Beyer; Michael
Baumann; Franz-Erich |
Duelmen
Haltern am See
Luedinghausen
Senden
Muenster
Raesfeld
Duelmen |
|
DE
DE
DE
DE
DE
DE
DE |
|
|
Assignee: |
EVONIK DEGUSSA GmbH
Essen
DE
|
Family ID: |
36201384 |
Appl. No.: |
14/050901 |
Filed: |
October 10, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13332470 |
Dec 21, 2011 |
8614005 |
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14050901 |
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11816556 |
Jan 28, 2008 |
|
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PCT/EP06/50038 |
Jan 4, 2006 |
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13332470 |
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Current U.S.
Class: |
428/319.7 ;
428/339; 428/474.9; 428/475.5; 524/606 |
Current CPC
Class: |
Y10T 428/31732 20150401;
Y10T 428/269 20150115; C09D 177/00 20130101; C09D 177/06 20130101;
Y10T 428/12493 20150115; Y10T 428/26 20150115; C08L 77/02 20130101;
C08L 77/06 20130101; C08L 77/02 20130101; C08L 2205/02 20130101;
Y10T 428/31728 20150401; Y10T 428/249992 20150401; C09D 177/06
20130101; C09D 177/00 20130101; B32B 5/18 20130101; B32B 27/34
20130101; Y10T 428/31725 20150401; C08L 77/06 20130101; Y10T
428/31739 20150401; C08L 2666/20 20130101; C08L 2666/20 20130101;
C08L 2666/20 20130101; C08L 2666/20 20130101 |
Class at
Publication: |
428/319.7 ;
428/475.5; 428/474.9; 428/339; 524/606 |
International
Class: |
C08L 77/06 20060101
C08L077/06; B32B 5/18 20060101 B32B005/18; B32B 27/34 20060101
B32B027/34 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 19, 2005 |
DE |
10 2005 007 665.3 |
Claims
1. A composite part, comprising a substrate and a film capable of
accepting printing and/or coloring thereon whose outer layer is
transparent, and has initial gloss and retained gloss during use,
and comprises a molding composition comprising the following
components: a) from 3 to 50% by weight of polyamide PA12, and b)
from 50 to 97% by weight of a polyamide, selected from the group
consisting of PA1012 and PA1212, where the percentages are based on
the entirety of components a) and b), wherein the composite part is
a bodywork part of a motor vehicle, a constituent of the
motor-vehicle interior, a cladding, a decorative strip, a cover
strip, a panel, or a decorative element.
2. The composite part as claimed in claim 1, which is produced via
reverse coating by an injection-molding, foaming, or
compression-molding method.
3. The composite part as claimed in claim 1, wherein the film is
composed only of the outer layer.
4. The composite part as claimed in claim 1, wherein the film is
composed of two or more layers.
5. The composite part as claimed in claim 4, wherein the film
comprises a color layer, a carrier layer, and/or an
adhesion-promoter layer.
6. The composite part as claimed in claim 5, wherein the color
layer and/or the carrier layer is present and comprises a polyamide
elastomer or an impact-modifying rubber other than a polyamide
elastomer.
7. The composite part as claimed in claim 1, wherein the film has a
thickness of from 0.02 to 1.2 mm.
8. The composite part as claimed in claim 1, wherein the thickness
of the outer layer is from 0.01 to 0.5 mm.
9-11. (canceled)
12. The composite part as claimed in claim 1, wherein component b)
is PA1012.
13. The composite part as claimed in claim 1, wherein component a)
is present in an amount of 10 to 45% by weight and component b) is
in an amount of 55 to 90% by weight.
14-16. (canceled)
17. The composite part as claimed in claim 12, wherein component a)
is present in an amount of 10 to 45% by weight and component b) is
in an amount of 55 to 90% by weight.
18. The composite part as claimed in claim 1, wherein component a)
is present in an amount of 3 to 40% by weight and component b) is
in an amount of 60 to 97% by weight.
19. The composite part as claimed in claim 1, wherein component a)
is present in an amount of 3 to 20% by weight and component b) is
in an amount of 80 to 97% by weight.
20. A ski or snowboard topcoated with a film thereon capable of
printed and/or colored having an outer layer which is transparent,
and has initial gloss and retained gloss during use, and comprises:
a) from 3 to 50% by weight of polyamide PA12, and b) from 50 to 97%
by weight of a polyamide, selected from the group consisting of
PA1012 and PA1212, where the percentages are based on the entirety
of components a) and b).
Description
[0001] This is a divisional application of U.S. application Ser.
No. 11/816,556, filed Jan. 28, 2008, which is a 371 of
PCT/EP06/050038 filed on Jan. 4, 2006.
[0002] The present invention relates to a film which comprises a
layer composed of a polyamide blend, and is suitable for decoration
of moldings.
[0003] The current standard process for decoration of external
areas on automobiles is painting. However, this procedure firstly
generates high manufacturing costs, resulting from provision of
specific plant and the operating cost associated therewith for the
automobile producer, and secondly causes pollution of the
environment. Pollution of the environment derives by way of example
from solvent constituents released from the paints used, and also
from accumulation of paint residues, which have to follow correct
disposal routes.
[0004] Another factor is that painting has only limited suitability
for decorating the surfaces of plastics components, which in recent
years have become more popular in automobile construction, because
of the saving in weight and cost.
[0005] The process of painting plastics components which are
components of bodywork can, for example, be carried out on-line,
the plastics part being subjected to a paint treatment identical
with that for the metallic components. This leads to a uniform
color, but is attended by high temperatures resulting from the
cathodic electrodeposition method conventional here, and this makes
the selection of material more difficult. In addition, identical
adhesion of the paint formulation has to be ensured on very
different substrates. If the process of painting the plastics parts
is carried out in a separate step (known as off-line painting),
comprising process conditions more advantageous for plastics, the
problem of colormatching arises, meaning that the shade achieved on
the metal has to be matched precisely. However, the differences in
substrate and in the underlying paint formulation that can be used,
and process conditions, make this very difficult to achieve. If
there is a color difference prescribed via the design, a serious
disadvantage that remains is provision of a second set of painting
equipment for the plastics parts and the cost associated therewith,
and additional time required for manufacture of the automobile also
has to be considered. Direct use of the untreated, generally
injection-molded plastics parts is aesthetically disadvantageous,
because surface defects resulting from the process, such as weld
lines, air inclusions, and also necessary reinforcing fillers, such
as glass fibers, are clearly discernible here. This is intolerable
in visible regions. Consequently, improvement of surface quality
has to be undertaken, for example in the context of a painting
process, frequently requiring much work for pretreatment via
polishing and application of relatively thick layers of a
primer.
[0006] One proposed solution consists in the use of multilayered
plastics films, used to cover the components and then requiring no
painting. The bond between substrate and decorating film here can
be achieved via a number of manufacturing processes. By way of
example, the film can be laminated to the substrate, or it is
possible to select a process of reverse coating by an
injection-molding process, in which the film is placed in the
injection mold during component production. The concept of a film
as carrier of decoration is also in line with a trend toward
individualization of design elements on automobiles. Specifically,
this trend leads to a wider range of models in the manufacturing
process, but with a reduction in the number of respective
components manufactured per series. The use of films permits rapid,
problem-free design change, and can therefore meet this challenge.
An important factor here is that the film complies with the
standards demanded in the automobile industry with respect to
surface properties (class A surface), solvent resistance, and
appearance. These films likewise have good capability for use in
the design of interior surfaces in automobiles.
[0007] Decorative films of this type are in principle known. EP 0
949 120 A1 describes by way of example decorative films with a
transparent outer layer composed of polyurethane, polyacrylate,
fluoropolymer, or mixtures composed of fluoropolymer and
polyacrylate. WO 94/03337 and EP 0 285 071 A2 disclose similar
decorative films.
[0008] Another application sector for decorative films is as a
carrier of decoration, for example for topcoats of sports
equipment, e.g. skis or snowboards, or of household items.
Single-layer films whose topsides or undersides have been printed
are often used here. For example, the utility model DE 295 19 867
U1 describes a decorable film composed of a copolyamide which is
composed of the following monomer units: laurolactam, and also
caprolactam and/or hexamethylenediamine/dicarboxylic acid. The
article by M. Beyer and J. Lohmar, Kunststoffe 90 (2000) 1, pp.
98-101 gives examples of printable films composed of PA12 molding
compositions.
[0009] The property profile of polyamides, for example impact
resistance and chemical resistance, very generally gives them, and
in particular polyamides based on PA12 or PA11, good suitability
for production of these decorative films. Accordingly, the patent
literature has descriptions of decorative films or else protective
films which comprise an outer layer composed of a polyamide.
Examples which may be mentioned here are the specifications
JP60155239A, JP2003118055A, EP 1 302 309 A, EP 0 522 240 A, EP 0
694 377 A, EP 0 734 833 A, WO 9212008 A, and EP 0 568 988 A.
[0010] While high polarity of outer layers composed of polyamides
with a high density of carboxamide groups gives them inadequate
chemicals resistance and excessive water absorption, in practice it
is found that use of polyamides which have a low density of
carboxamide groups and which have been prepared from lactams or
from the corresponding aminocarboxylic acids (AB polyamides) leads
to formation of deposits on the surface of the films under ambient
conditions over the course of time, these deposits considerably
reducing gloss and being unacceptable for this application.
Improvement in transparency and in initial gloss would also be
desirable. If, in contrast, polyamides composed of diamine and
dicarboxylic acid (AABB polyamides) which have a low density of
carboxamide groups are used, no deposits are formed, but here again
an improvement in transparency and gloss would be advantageous.
[0011] It was therefore an object, for decorative purposes, to
provide a film which gives reduced deposit formation, and whose
outer layer is sufficiently transparent, and which has high initial
gloss.
[0012] This object is achieved via a film whose outer layer is
composed of a molding composition which is in essence composed of
the following components: [0013] a) from 3 to 50%, preferably from
4 to 49% by weight, particularly preferably from 5 to 47% by
weight, and with particular preference from 10 to 45% by weight, of
a polyamide, selected from the group of PA11 and PA12, and [0014]
b) from 50 to 97%, preferably from 51 to 96% by weight,
particularly preferably from 53 to 95% by weight, and with
particular preference from 55 to 90% by weight, of a polyamide,
selected from the group of PA1012 and PA1212, where the percentages
are based on the entirety of components a) and b).
[0015] The polyamides used and their preparation are known. They
are commercially available in a wide variety of marketed grades.
According to the invention, the respective homopolyamides are
mainly used, but it is also possible to use copolyamides based
thereon and incorporating at most 20 mol %, at most 15 mol %, at
most 10 mol %, or at most 5 mol %, of comonomers. Suitable
comonomers are lactams, the corresponding aminocarboxylic acids, or
the combination of diamine and dicarboxylic acid. Diamine and
dicarboxylic acid are respectively counted individually in the
calculation of the constitution.
[0016] Incorporation of comonomers leads to improved transparency
and to higher gloss, but there is some impairment of resistance to
chemicals and to environmental effects. The latter can be accepted
if use of the comonomers is successful in giving better
compatibility for example with respect to the following layer or
with respect to the substrate, by bringing the constitution
somewhat closer.
[0017] The molding composition is prepared from the individual
components according to the prior art via mixing in the melt. It
can also comprise the following other components: [0018] a)
nucleating agents, selected from nanoscale fillers and basic metal
salts, metal oxides, or metal hydroxides; the amount added of the
latter, in order to ensure the desired transparency, is at most
that which can be dissolved in the melt by reaction with the
carboxy end groups of the polyamides; [0019] b) conventional
auxiliaries and conventional additives, the amounts being those
conventional for polyamide molding compositions, examples being
stabilizers or lubricants, [0020] c) colorants which do not
significantly affect transparency, [0021] d) fillers whose
refractive index differs only to a very slight extent from that of
the matrix, or is precisely identical (isorefractive fillers), and
also [0022] e) other polymer components whose refractive index
differs only very slightly from that of the matrix or is precisely
identical.
[0023] The amount of these other components present in the molding
composition is preferably at most 30% by weight, at most 25% by
weight, at most 20% by weight, at most 15% by weight, at most 10%
by weight, or at most 5% by weight.
[0024] Surprisingly, if the molding composition comprises at most
50% by weight of the AB polyamide (PA11 or PA12), gloss is retained
as for the pure AABB polyamides during service life, although this
would not be expected in view of the mixing ratio of the
polyamides. Apparently, as long as at least 50% by weight of the
AABB polyamide is present, it inhibits diffusion of the substances
that form deposits and are present in the AB polyamide, possibly
cyclic oligomers. Another advantage here is that the mixture of the
semicrystalline polyamides give blends which are semicrystalline,
but sufficiently transparent. Transparency and initial gloss are
above the level of the pure components, while resistance to
chemicals and environmental effects is retained. Explicit mention
may be made here of the combinations PA11/PA1012, PA11/PA1212,
PA12/PA1012, and PA12/PA1212, but the AB component can moreover be,
independently of one another, a mixture of PA11 and PA12, and the
AABB component a mixture of PA1012 and PA1212.
[0025] The film is a single- or multilayer film. In the case of a
multilayer structure, the nature and number of the other layers
depend on the technical requirements of the application; the only
decisive factor is that the outer layer is composed of the
inventively used molding composition. By way of example, the
following embodiments are possible: [0026] 1. The film is a
single-layer film. In this case it is defined as composed only of
the outer layer; decorative effects can be applied either to the
topside or to the underside via printing, e.g. by means of thermal
sublimation printing. [0027] 2. The film comprises not only the
outer layer but also a lower color layer. The color layer can be a
paint layer; however, as in the prior art it is preferably composed
of a colored thermoplastics layer. The thermoplastic can by way of
example be a mixture identical with or similar to that of the outer
layer, one component thereof, or another polyamide, or another
polymer, which either adheres directly to the outer layer or has
been adhesive-bonded with the aid of a sufficiently transparent
adhesion promoter (for example a polyolefin functionalized by
carboxy or anhydride groups or by epoxy groups, a thermoplastic
polyurethane, or a blend composed of the constituents of the layers
to be bonded). Examples of colorants that may be used are organic
dyes, inorganic or organic pigments, or metal flakes. [0028] 3. The
film comprises not only an outer layer and, if appropriate, a color
layer, but also another layer which, as carrier layer, brings about
sufficient mechanical strength and, if appropriate, also brings
about coupling to the substrate. [0029] 4. The film comprises not
only the outer layer and, if appropriate, a color layer, but also a
lower adhesion-promoter layer for coupling to the substrate.
Examples of suitable adhesion promoters are a polyolefin
functionalized by carboxy or anhydride groups or by epoxy groups, a
thermoplastic polyurethane, a blend composed of the materials of
the layer to be bonded and of the substrate, or one of the adhesion
promoters disclosed in the German patent application No.
102004029217.5 of 16.06.2004. [0030] 5. The film comprises not only
the outer layer, and, if appropriate, a color layer and carrier
layer, but also a lower adhesion-promoter layer for coupling to the
substrate. The comments made under item 4 again apply to the
adhesion promoter. [0031] 6. The film, e.g. a film in one of items
1 to 5, also comprises, if necessary, for example in the case of
increased scratch-resistance requirements, a protective layer, such
as a polyurethane-based clear lacquer, on the outer layer. A
protective layer in the form of a lacquer can also have been
modified as in the prior art in order to increase scratch
resistance. Besides this, another possibility is to generate a
protective layer by way of vacuum deposition processes. The film
can, if appropriate, also comprise a peelable protective film
applied by lamination, which provides protection during transport
or installation, and which is peeled away after production of the
composite part.
[0032] In the case of embodiments 2 to 6, the transparent outer
layer may first, like a monofilm, be printed from one side or from
both sides and then be bonded in a second step to the other layers
to give the multilayer film. In multilayer films, the transparent
outer layer can be printed from above. The outer layer may also
have transparent or opaque coloring.
[0033] In one preferred embodiment, the color layer and/or the
carrier layer comprises a molding composition in particular of a
polyetheramide or of a polyetheresteramide, and preferably of a
polyetheramide or polyetheresteramide based on a linear aliphatic
diamine having from 6 to 18, preferably from 6 to 12, carbon atoms,
on a linear aliphatic, or an aromatic, dicarboxylic acid having
from 6 to 18, preferably from 6 to 12, carbon atoms, and on a
polyether having an average of more than 2.3 carbon atoms per
oxygen atom and having a number-average molecular weight of from
200 to 2000 for the polyether blocks. The molding composition of
this layer can comprise other blend components, e.g. polyacrylates
or polyglutarimides having carboxy or anhydride groups or epoxy
groups, a rubber containing functional groups, and/or a polyamide.
Molding compositions of this type are prior art; by way of example,
they are described in EP 1 329 481 A2 and DE-A 103 33 005,
expressly incorporated herein by way of reference. In order to
ensure good layer adhesion, it is advantageous here for the
polyamide content of the polyamide elastomer to be composed of
monomers which are identical with those used in one of the
components of the outer layer. As an alternative to the polyamide
elastomers, the color layer and/or the carrier layer can also
comprise a conventional impact-modifying rubber alongside a
polyamide. An advantage of these embodiments is that in many cases
there is no need for any thermoforming of the film as a separate
step prior to reverse coating by an injection-molding method,
because reverse coating by an injection-molding method also
simultaneously subjects the film to a forming process.
[0034] In one preferred embodiment, the thickness of the film or
multilayer film with the inventive outer layer is from 0.02 to 1.2
mm, particularly preferably from 0.05 to 1 mm, very particularly
preferably from 0.1 to 0.8 mm, and with particular preference from
0.2 to 0.6 mm. If the material is a multilayer film, the thickness
of the inventive outer layer in one preferred embodiment is from
0.01 to 0.5 mm, particularly preferably from 0.02 to 0.3 mm, very
particularly preferably from 0.04 to 0.2 mm, and with particular
preference from 0.05 to 0.15 mm. The film is produced by means of
known methods, for example via extrusion, or in the case of
multilayered systems via coextrusion or lamination. It can then, if
appropriate, be subjected to a forming process.
[0035] In one embodiment, the film is a decorative film. For the
purposes of the invention, decorative films are films which can be
printed and/or comprise a color layer, and moreover are intended
for bonding to a substrate in order to decorate its surface. The
decoration can also be brought about by using a lamination process
on visual surface defects, e.g. by hiding surface roughness
deriving from fillers or from reinforcing materials.
[0036] Examples of methods of coherent bonding of the film to the
substrate are adhesive bonding, pressing, lamination, or
coextrusion, or reverse coating by an injection-molding, foaming,
or compression-molding method. In order to achieve better adhesion,
the film can by way of example be previously flame-treated or
treated with a plasma. Prior to formation of the bond between film
and substrate, the film can also be subjected to mechanical
treatment or forming processes, e.g. via thermoforming or other
processes. The surface can be structured via embossing, for
example. The surface can also be pre-structured in the context of
film extrusion, for example using specifically designed rolls. The
resultant composite part can then also be subjected to a forming
process.
[0037] Examples of suitable substrates are molding compositions
based on polyolefins, on polyamides, on polyesters, on
polycarbonates, on ABS, on polystyrene, or on styrene
copolymers.
[0038] In one preferred embodiment, the inventive film is used as
outer layer of a film composite for the design or decoration of
surfaces on and in automobiles and utility vehicles, the film
having been adhesive-bonded to a plastics substrate. The
correspondingly designed component can be of sheet-like structure,
an example being a bodywork part, for example a roof module, wheel
surround, engine cover, or door. Other possible embodiments are
those in which the components produced are elongate, with or
without curvature, for example cladding, e.g. the cladding on what
are known as A columns of an automobile, or decorative and cover
strips of any type. Another example is provided by protective
cladding for door sills. Alongside applications in motor-vehicle
exteriors, constituents of the interior can also be advantageously
decorated via the inventive films, in particular decorative
elements such as strips and panels, because impact resistance and
resistance to chemicals, such as cleaners, is also required in the
interior.
[0039] In another preferred embodiment, the inventive film is used
as topcoat for snowboard-like equipment of any type, such as skis
or snowboards.
[0040] The film can moreover be used by way of example as a
protective film to counter soiling, UV radiation, effects of
weathering, chemicals, or abrasion, or as a barrier film on
vehicles, in the household, on floors, on tunnels, on tents, and on
buildings, or as a carrier of decorative effects, for example for
topcoats of sports equipment, of boats, of aircraft, in the
household, or on buildings.
[0041] The invention is illustrated below by way of example.
[0042] The PA12 used was a grade whose relative solution viscosity
.eta..sub.rel, determined to ISO 307, was 2.1 and whose crystallite
melting point T.sub.m, determined to ISO 11357, was 178.degree.
C.
[0043] The PA1012 used was a grade whose relative solution
viscosity .eta..sub.rel was 1.9 and whose crystallite melting point
T.sub.m was 191.degree. C.
[0044] The molding composition was prepared via mixing in the melt
in a Werner+Pfleiderer ZSK M9/2 twin-screw extruder. The barrel
temperature was 250.degree. C., the rotation rate was 250 rpm, and
the throughput was 10 kg/h. The melt was filtered at 25.mu..
[0045] Injection-molded plaques were produced on an Engel ES
600/150 injection molding machine The melt temperature was
250.degree. C., and the mold temperature was 80.degree. C.
Dimensions of the plaques produced were 130 mm.times.130 mm.times.1
mm.
[0046] Monofilms were produced by the calendering process on a
Collin 168/400 multilayer film calendar at a processing temperature
of 240.degree. C. The thickness was 400 .mu.m.
[0047] Monofilms were produced by the calendering process on a
Collin 168/400 multilayer film calendar at a processing temperature
of 240.degree. C. (outer layer) and 240-250.degree. C. (color
layer).
[0048] The thickness of the outer layer was 100 .mu.m, and the
thickness of the color layer was 400 .mu.m. The colorant layer used
comprised a blend composed of 28.0% by weight of PA12
(.eta..sub.rel=2.1), 68.5% by weight of a polyetheresteramide
having PA12 hard blocks (M.sub.n=7000) and having PTHF soft blocks
(M.sub.n=1000), and 2.0% by weight of a stabilizer masterbatch, and
also 1.5% by weight of color powder masterbatch, the color used
being E70237.
[0049] Accelerated weathering was carried out on monofilms, using
Q-UV/se accelerated-weathering equipment from Q-Panel with a cycle
(Step 1: 55.degree. C., exposure to light at 0.98 W/m.sup.2 at 340
nm, 4 h/Step 2: 45.degree. C., water condensation in dark
conditions, 4 h).
[0050] Injection-molded plaques were stored in a cabinet under
controlled temperature and humidity conditions at 85.degree. C. and
99% relative humidity.
[0051] Gloss measurements were carried out on plaques and films to
DIN 67 530.
[0052] Transmittance was measured on films of thickness 400 .mu.m
to ISO 13468-2.
INVENTIVE EXAMPLES 1-4 AND COMPARATIVE EXAMPLES A-E
[0053] Tables 1 to 5 give constitutions and results.
TABLE-US-00001 TABLE 1 Constitution of outer layer PA1012 (parts by
PA12 (parts by Stabilizers Example weight) weight) (parts by
weight) A 100 B 100 C 20 80 1 60 40 2 80 20 D 20 80 0.8 E 40 60 0.8
3 60 40 0.8 4 80 20 0.8
TABLE-US-00002 TABLE 2 Transparency of monofilms (400 .mu.m)
Example A B C 1 2 Transparency 88.2% 87.6% 89.4% 89.8% 89.1% (at
500 nm)
TABLE-US-00003 TABLE 3 Formation of deposit on accelerated
weathering (gloss measurement at 60.degree. on 400 .mu.m films;
data in gloss units) Time (h) A B 3 4 D E 0.sup.a) 126 97 131 129
116 115 24 124 78 127 131 107 80 168 120 84 126 130 100 98 336 118
60 121 131 78 92 504 120 58 120 132 82 91 672 125 69 119 133 81 94
840 120 132 83 87 1008 118 131 78 92 1176 120 132 75 89 1344 120
131 70 92 1512 120 132 67 95 1680 121 132 68 97 2016 117 134 75 88
2352 119 129 72 67 3192 116 126 .sup.a)Initial gloss
TABLE-US-00004 TABLE 4 Formation of deposit on storage in moist
conditions (gloss measurement at 85.degree. on plaques; data in
gloss units) Storage time in days A 3 4 D E 0 94.7 101.4 94.9 102.8
100.7 3 98 102.3 99.2 96.6 101.1 6 98.4 101.4 98.3 58.8 88.8 10
97.7 101.8 99.2 59.1 89.5 14 97.6 102.2 99.5 53.9 84.6 21 97.1
101.3 98.7 33.3 77.4 25 96.3 101.4 98.3 41.9 75.1 32 96.1 101.3
98.1 26.4 61 39 95.7 100.4 97.6 17 56.1 46 97.4 103.6 100.5 14.7
45.5 52 94.5 100.2 98.5 15 44.1
TABLE-US-00005 TABLE 5 Multilayer film, initial gloss at 20.degree.
(data in gloss units) Example D 3 4 Gloss 80 84 85
* * * * *