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Patent 2384432 Summary

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(12) Patent Application: (11) CA 2384432
(54) English Title: POLYCARBONATE SLABS
(54) French Title: PLAQUES EN POLYCARBONATE
Status: Deemed Abandoned and Beyond the Period of Reinstatement - Pending Response to Notice of Disregarded Communication
Bibliographic Data
(51) International Patent Classification (IPC):
  • C8G 64/24 (2006.01)
  • B32B 27/00 (2006.01)
  • B60J 1/00 (2006.01)
  • C8J 5/18 (2006.01)
  • C8L 69/00 (2006.01)
  • E4D 3/06 (2006.01)
  • E6B 3/00 (2006.01)
(72) Inventors :
  • GORNY, RUDIGER (Germany)
  • ANDERS, SIEGFRIED (Germany)
  • NISING, WOLFGANG (Germany)
  • ROHNER, JURGEN (Germany)
  • KUHLING, STEFFEN (Germany)
  • LANZE, ROLF (Germany)
  • PREIN, MICHAEL (Belgium)
  • NEUMANN, RAINER (Germany)
  • KAUTH, HERMANN (Germany)
  • HEYDENREICH, FRIEDER (Germany)
  • VAN OSSELAER, TONY (Germany)
(73) Owners :
  • BAYER AKTIENGESELLSCHAFT
(71) Applicants :
  • BAYER AKTIENGESELLSCHAFT (Germany)
(74) Agent: SMART & BIGGAR LP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2000-09-04
(87) Open to Public Inspection: 2001-03-22
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/EP2000/008605
(87) International Publication Number: EP2000008605
(85) National Entry: 2002-03-08

(30) Application Priority Data:
Application No. Country/Territory Date
199 43 640.1 (Germany) 1999-09-13

Abstracts

English Abstract


The invention relates to slabs consisting of polycarbonate. Said polycarbonate
is produced according to the interface method and the aqueous solution of an
alkaline salt of a bisphenol that is used, contains less than 150 ppb
dissolved oxygen.


French Abstract

L'invention concerne des plaques en polycarbonate. Ce polycarbonate est produit selon le procédé d'interphase et la solution aqueuse utilisée, solution aqueuse d'un sel alcalin d'un bisphénol, présente une teneur en oxygène dissous inférieure à 150 ppb.

Claims

Note: Claims are shown in the official language in which they were submitted.


-17-
Claims
1. Polycarbonate sheets, wherein the polycarbonate is produced by the
interfacial polycondensation process and the aqueous solution of an alkali
salt
of a bisphenol used therefore has a dissolved oxygen content of less than 150
ppb.
2. Use of the sheets according to claim 1 to produce glazing.
3. Glazing comprising sheets according to claim 1.
4. Glazing for automobiles or for buildings or for greenhouses or for winter-
gardens or for bus shelters or for advertising panels or signboards or
protective screens or for windows or roofing comprising sheets according to
claim 1.
5. Multi-layered sheet, wherein at least one layer contains the polycarbonate
according to claim 1.
6. Proces for the production of the sheets according to claim 1 by extrusion.
7. Process for the production of the multi-layered sheets according to claim 5
by
co-extrusion.
8. Multi-layered sheets according to claim 5, wherein at least one layer
contains
UV-Absorber, the concentration of the UV-Absorber in the layer being
preferably 0.01 to 20 % by weight.

Description

Note: Descriptions are shown in the official language in which they were submitted.


. ~ " ~ Le A 33 570-Foreign Countries Gi/ngb/NT
-1-
Polycarbonate sheets
The present invention relates to polycarbonate sheets, the use thereof to
produce
glazing and said glazing. ,.
Polycarbonate sheets are used to produce glazing, for example. In this case,
it is
desirable to use sheets with as high as possible light transmissions and as
lo~.v as
possible yellowness indexes. Although it is possible to reduce the yellowness
index
by adding of blue pigments, this is achieved at the expense of light
transmission and
greying of the sheets. During weathering of the sheets, it is important that
the
mechanical properties of the sheets are kept at the highest possible level.
Even after
weathering, the sheets must retain a high resistance to mechanical influences
e.g.
hail.
Polycarbonates may be produced by the so-called interfacial polycondensation
process. In said process, dihydroxydiarylalkanes (also known as bisphenols)
are
reacted in the form of their alkali salts in aqueous solution with phosgene in
the
heterogeneous phase in the presence of inorganic bases such as sodium
hydroxide
solution and an organic solvent, in which the product polycarbonate is readily
soluble.
More details relating to the interfacial polycondensation process for
producing poly-
carbonates are disclosed in Schnell, "Chemistry and Physics of
Polycarbonates",
Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney
1964.
The polycarbonate sheets known from the prior art exhibit the disadvantage
that they
do not adequately meet the above-mentioned requirements of high light
transmission,
low yellowness index and good retention of mechanical properties on
weathering.
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The object of the present invention is therefore to produce polycarbonate
sheets
which do not exhibit the above-mentioned disadvantages of the prior art.
This object is achieved according to,the invention by polycarbonate sheets,
wherein
S the polycarbonate is produced by the interfacial polycondensation process
and the
aqueous solution of an alkali salt of a bisphenol used therein has a content
of
dissolved oxygen of less than 150 ppb.
The content of dissolved oxygen in the aqueous solution of the alkali salt of
bisphenol is <150 ppb, preferably <100 ppb, particularly preferably <50 ppb.
The invention thus provides polycarbonate sheets, wherein the polycarbonate is
produced by the interfacial polycondensation process and the aqueous solution
of an
alkali salt of a bisphenol used therein has a content of dissolved oxygen of
less than
150 ppb.
In addition, the present invention also provides glazing, for example for
automobiles
or buildings, in particular for greenhouses, winter gardens, bus shelters,
advertising
panels, signboards, protective screens, automotive glazing, windows or
roofing.
The polycarbonates are produced according to the invention in that the other
raw
materials apart from the aqueous solution of the alkali salt of bisphenol do
not
contain a noteworthy amount of oxygen. In addition, production is performed
with
the exclusion of oxygen, as described for example in DE-A 4 227 272.
For example, in a reaction vessel and tubular reactor configuration, the
forced
circulation loop and the tubular reactors are flooded and the reaction vessel
is
blanketed with nitrogen, to ensure the exclusion of oxygen.
The polycarbonate sheets according to the invention are, for example, solid
sheets,
hollow sheets (also known as mufti wall sheets e.g: twin wall sheets, triple
wall
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sheets...) or corrugated sheets, which are e.g. used as glazing materials. The
sheets
may be produced in a manner known in principle to the person skilled in the
art, for
example by extrusion or by injection moulding.
S Subsequent processing of the sheets, such as thermoforming or surface
modification,
such as application of scratch-proof lacquers, water-dispersing layers and the
like, is
also possible. The patent also relates to the moulded articles produced by
these
processes.
To produce the polycarbonate for the sheets according to the invention,
aqueous
solutions of an alkali salt of a bisphenol with a content of dissolved oxygen
<150 ppb, preferably <100 ppb, particularly preferably <50 ppb are used, which
may
preferably be obtained by reacting bisphenols with a dissolved oxygen content
<10 ppb with an aqueous alkali hydroxide solution with a dissolved oxygen
content
<100 ppb under oxygen exclusion.
Preferred alkali salts are the sodium salts of bisphenols.
Bisphenols which may be used according to the invention are those which may be
obtained by reacting ketones with aromatic hydroxy compounds which are not
substituted in the para position and do not contain any second order
substituents,
such as cyano, carboxy or nitro groups, for example phenol, o- and m-cresol,
2,6-
dimethylphenol, o-tert.-butylphenol, 2-methyl-6-tert.-butylphenol, o-
cyclohexyl-
phenol, o-phenylphenol, o-isopropylphenol, 2-methyl-6-cyclopentylphenol, o-
and
m-chlorophenol, 2,3,6-trimethylphenol, preferably phenol, o- and m-cresol, 2,6-
dimethylphenol, o-tert.-butylphenol and o-phenylphenol. Phenol is particularly
preferred. Ketones with at least one aliphatic group on the carbonyl function
are
preferred, for example acetone, methyl ethyl ketone, methyl propyl ketone,
methyl
isopropyl ketone, diethyl ketone, acetophenone, cyclohexanone, cyclopentanone,
methyl-, dimethyl- and trimethylcyclohexanones, which may also comprise
geminal
methyl groups, e.g. 3,3-dimethyl-5-methylcyclohexanone (hydroisophorone).
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Acetone, acetophenone, cyclohexanone and the homologues thereof bearing methyl
groups are very particularly preferred. Acetone is the most preferable. By
providing
an intensive inert nitrogen atmosphere throughout the production process, it
is
ensured that the residual content of dissolved oxygen in the bisphenols is
less than
10 ppb.
Bisphenols which may be used according to the invention are, additionally: 3-
(4-
hydroxyphenyl)-1,1,3-trimethylindan-5-ol; 1,3-di-(2-(4-hydroxyphenyl)-2-
propyl)-
benzene and 1,4-di-(2-(4-hydroxyphenyl)-2-propyl)benzene.
Bisphenols which are particularly preferred are 2,2-bis(4-
hydroxyphenyl)propane
(i.e. bisphenol A) and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
The bisphenols or the mixtures thereof are preferably reacted, with the
exclusion of
oxygen (e.g. by providing an inert nitrogen atmosphere), with aqueous alkali
hydroxide solution having a dissolved oxygen content <100 ppb, preferably <20
ppb.
The concentration of aqueous alkali hydroxide solution is preferably such that
the
concentration of the resultant aqueous solutions of an alkali salt of a
bisphenol is as
close as possible to the solubility limit, i.e. in the range of from 15 to 20
wt.%,
preferably 16.5 to 18.5 wt.%. The molar ratio of alkali hydroxide to bisphenol
is in
particular from 1.8:1 to 2.5:1, preferably 1.9:1 to 2.4:1, particularly
preferably 2.0:1
to 2.3:1. The bisphenol may be dissolved as a solid in aqueous alkali
hydroxide
solution. However, it is preferable for it to be added to the aqueous alkali
hydroxide
solution directly as a melt at temperatures of from 20°C to
90°C, preferably 30°C to
70°C, without its having to pass through the solid state.
The virtually oxygen-free aqueous alkali hydroxide solution used to produce
the
aqueous solutions of an alkali salt of a bisphenol may be produced by
electrolysis.
After production, the aqueous alkali hydroxide solution should be stored and
transported under inert gas. For use in the process according to the
invention, the
concentration of aqueous alkali hydroxide solution ~ obtained during
electrolysis is
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generally reduced by dilution with virtually oxygen-free, fully deionised
water.
Oxygen is removed from the fully deionised water in a manner known in
principle,
e.g. catalytically, by degassing or by inert gas stripping.
,.
The aqueous solutions thus obtained of an alkali salt of a bisphenol exhibit
particularly low colour indexes, which are naturally also dependent on the
colour
index of the bisphenol used. If a bisphenol is used which has a colour index
<10
Hazen (measured according to ASTM D 1686), colour indexes of <1.5 Hazen,
preferably <1.0 Hazen may be achieved.
The polycarbonates may be branched deliberately and in a controlled manner by
the
use of small amounts of branching agent. Examples of suitable branching agents
are:
phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-2-heptene; 4,6-
dimethyl-
2,4,6-tri-(4-hydroxyphenyl)heptane; 1,3,5-tri-(4-hydroxyphenyl)benzene; 1,1,1-
tri-
1 S (4-hydroxyphenyl)ethane; tri-(4-hydroxyphenyl)phenylmethane; 2,2-bis-[4,4-
bis(4-
hydroxyphenyl)cyclohexyl]propane; 2,4-bis(4-hydroxyphenylisopropyl)phenol; 2,6-
bis(2-hydroxy-5'-methylbenzyl)-4-methylphenol; 2-(4-hydroxyphenyl)-2-(2,4-dihy-
droxyphenyl)propane; hexa-(4-(4-
hydroxyphenylisopropyl)phenyl)orthoterephthalic
acid ester; tetra-(4-hydroxyphenyl)methane; tetra-(4-(4-
hydroxyphenylisopropyl)-
20- phenoxy)methane); a,a',a"-tris-(4-hydroxyphenyl)-1,3,5-
triisopropylbenzene; 2,4-
dihydroxybenzoic acid; trimesic acid; cyanuric chloride; 3,3-bis(3-methyl-4-
hydroxyphenyl)-2-oxo-2,3-dihydroindole; 1,4-bis(4',4"-
dihydroxytriphenyl)methyl)-
benzene. 1,1,1-tri-(4-hydroxyphenyl)ethane and bis-(3-methyl-4-hydroxyphenyl)-
2-
oxo-2,3-dihydroindole (= isatinbiscresol).
The branching agents or mixtures of branching agents which may optionally also
be
used, preferably in an amount of 0.05 to 2 mol-% relative to the bisphenols
used,
may be introduced together with the bisphenols or added at a later stage of
the
synthesis.
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Chain terminators may be used according to the invention. The chain
terminators
used according to the invention are preferably phenols such as phenol,
alkylphenols
such as cresol and 4-tert.-butylphenol, chlorophenol, bromophenol, cumylphenol
or
mixtures thereof. Phenol, 4-tert.-l~.utylphenol or cumylphenol are
particularly
preferred.
Chain terminators and branching agents may be added to the reaction mixture as
a
separate solution or together with the bisphenolate, wherein care must be
taken to
ensure that the solutions have the same low oxygen content according to the
invention as the aqueous solutions of an alkali salt of a bisphenol.
Other additives which may be used according to the invention and which may be
added to the polycarbonate from which the sheets according to the invention
are
produced, are mentioned in EP-A 0 500 496 and WO 96/15102. According to the
invention, mixtures of these additives may also be introduced into the
polycarbonate.
Additives which are particularly preferred are UV absorbers such as the
compounds
described in WO 99/05205 of formula (I)
~Rt~n
~ SRO"
~N H R3 Ra H
-N
N-N, ~ ~ ~ ~N
(I)
~R2~"' \(Ry)m
in which
R' and R2 are the same or different and mean H, halogen, C,-Clo alkyl, CS-Clo
cycloalkyl, CrC~3 aralkyl, C6-Ct4 aryl, -ORS or -(CO)-O-RS, with RS
being H or C1-C4 alkyl,
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_7_
R3 and Ra are also the same or different and mean H, C~-C4 alkyl, C6
cycloaikyl,
benzyl or C6-C~4 aryl,
m is l, 2 or 3 and ,.
n is 1, 2, 3 or 4,
and also those of formula (II)
(R~~n (Rt)n
I \N N/
N ~ _'-
N / Bridge \ N .
HO
OH (II)
(R2)n
(R2)n
in which the bridge means
O O
(CHR3)P C-O-(Y-O)q CI-(CHR4)p
RI, R2, m and n have the meaning stated in relation to formula (I),
in which, moreover, p is a whole number from 0 to 3,
q is a whole number from 1 to 10,
Y is -CH2-CHZ-, -(CHZ)s-, -(CH2~4-, -(CHZ)5-, -(CH2)s-, or CH(CH3)-CH2
and
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_g_
R3 and R4 have the meaning stated in relation to formula (I).
Other suitable UV absorbers are those comprising substituted triazines, such
as 2,4-
bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine
(CYASORB~ UV-
1164) or 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl)oxyphenol (Tinuvin~
1577).
The UV absorber which is particularly preferred is 2,2-methylene bis(4-
(1,1,3,3-
tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol), which is sold commercially
under the names Tinuvin~ 360 or Adeka Stab~ LA 31. The W absorber Uvinul
3030, made by BASF AG and obtained in accordance with Example 1 of WO
96/15102, is also suitable, as are the UV absorbers given in EP 0 500 496 A1.
Other suitable UV absorbers are 5'-methyl-, 3',S'-di-tert.-butyl-, 5'-tert.-
butyl-, 5'-
(1,1,3,3-tetramethylbutyl)-, (= Tinuvin 329), S-chloro-3',5'-di-tert.-butyl-,
S-chloro-
3'-tert.-butyl-5'-methyl-, 3'-sec.-butyl-5'-tert.-butyl, 4'-octoxy-, 3',5'-di-
tert.-amyl-,
3',5'-bis(a,a-dimethylbenzyl)-, mixture of 5-chloro-3'-tert.-butyl-5'-(2-
octyloxycarb-
onylethyl)- and 5-chloro-3'-tert.-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-
, 5-
chloro-3'-tert.-butyl-5'-(2-methoxycarbonylethyl)-, 3'-tert.-butyl-5'-(2-
methoxycarb-
onylethyl)-, 3'-tert.-butyl-S'-(2-octyloxycarbonylethyl)-, 3'-tert.-butyl-S'-
[2-(2-ethyl-
hexyloxy)-carbonylethyl]-, 3'-dodecyl-5'-methyl- and 3'-tert.-butyl-5'-(2-
isooctyl-
oxycarbonylethyl)-2'-hydroxyphenyl-2H-benzotriazole(2), 2,2'-methylenebis[4-
(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol] together with 3'-sec.-
butyl-5'-
(1,1,3,3-tetramethylbutyl-2'-hydroxyphenyl-2H-benzotriazole (= Tinuvin 350)
and 2-
[2'-hydroxy-3',5'-bis(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole (= Tinuvin
234)
and 2-hydroxybenzophenones, such as for example 4-hydroxy-, 4-methoxy-, 4-
octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4-trihydroxy-, 2'-
hydroxy-
4,4'-dimethoxy derivative, ethyl-2-cyano-3,3-diphenyl acrylate (= Uvinul 3035)
made by BASF AG, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (= Uvinul 3039)
made by BASF AG.
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Examples of suitable stabilisers, which may be used as additives according to
the
invention, are phosphines, phosphites or Si-containing stabilisers and other
compounds described in EP-A 0 500 496. Triphenyl phosphites, diphenylalkyl
phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, triphenyl
phosphine, tetrakis(2,4-di-tert.-butylphenyl)-4,4'-biphenylene diphosphonite
and tri-
arylphosphite may be cited by way of example. Triphenylphosphine and tris(2,4-
di-
tert.-butylphenyl)phosphite are particularly preferred.
The polycarbonates, from which the sheets according to the invention are
produced,
may additionally contain additives to improve the surface slip
characteristics, for
example esters of polyhydric alcohols with long-chain fatty acids, such as for
example pentaerythritol tetrastearate/-palmitate, glycerol monostearate/-
palmitate,
glycerol tristearate/-palmitate. Furthermore, the addition of flame
retardants,
pigments, colorants, finely divided minerals, optical brighteners and other
additives
is also possible.
All the feed materials and solvents used for synthesis may be contaminated
with
impurities from the production and storage thereof, wherein the aim is to work
with
starting materials which are as clean as possible.
Glazing according to the invention comprises, in particular, glazing for
automobiles
or buildings, for example glazing for greenhouses, winter. gardens, bus
shelters,
advertising panels, signboards, protective screens, automotive glazing,
windows or
roofing.
Subsequent processing of the sheets according to the invention, such as
thermoforming or surface modification, such as application of scratch-proof
lacquers,
water-dispersing layers and the like, is possible.
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Examples
In the following Examples, the colour indexes were determined according to
ASTM
D 1686 by measuring absorption up to 400 nm over an irradiation length of 50
cm.
Weathering of these sheets (according to ISO 4892-2A) was performed in a
Weatherometer made by Atlas, USA, using a 6.5 W xenon lamp and a cycle
involving 102 mins of exposure to light and 18 mins of spraying with deionised
water together with light exposure. The maximum black body temperature was
60°C
(~ 5°C). After 1000 hours, samples of the sheets were taken and
toughness was
tested under practical conditions using a modified falling dart test which was
developed for mufti-walled sheets on the basis of DIN 53 443. The fracture
energy
WS being measured using a 5 mm diameter puncture body intended to cause
biaxial
stress similar to that caused by a falling hailstone. At room temperature, a
falling
mass of 36 kg falling from a height of 0.2 m struck the samples, which lay
freely on a
supporting ring with an internal diameter of 20 mm.
Testing was performed with the weathered side of the sample in the compression
zone. The fracture appearance (BB) was characterised by numbers: 1 =
splintered, 2
= smooth crack, 3 = ductile/brittle, 4 = ductile.
The yellowness index determined according to ASTM E 313 was stated as
Yellowness Index YI.
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Example 1
To produce 1.022 t/h of a 15% aqueous NaBPA solution, 867.5 kg/h of a 6.5%
aqueous sodium hydroxide solution,. and 154.5 kg/h of bisphenol A melt were
S combined continuously. The entire process was performed under an inert
atmosphere
of nitrogen. The 6.5% aqueous sodium hydroxide solution comprised an oxygen
content of 10 ppb. The Hazen colour index of the resultant 15% aqueous sodium
bisphenolate solution amounted to 0.5 Hazen. This sodium bisphenolate solution
was
used to produce polycarbonate by the interfacial polycondensation process.
Comparative Example 2
To produce 1.022 t/h of a 15 % aqueous sodium bisphenolate solution, 867.5
kg/h of
a 6.5% aqueous sodium hydroxide solution and 154.5 kg/h of bisphenol A melt
were
combined continuously. The entire process was performed under an inert
atmosphere
of nitrogen. The 6.5% aqueous sodium hydroxide solution comprised an oxygen
content of 250 ppb. The Hazen colour index of the resultant 15% aqueous sodium
bisphenolate solution amounted to 2 Hazen. This sodium bisphenolate solution
was
used to produce polycarbonate by the interfacial polycondensation process.
Example 3
A polycarbonate with phenol end groups, a melt flow index (MFR) of 3 (measured
according to ISO 1133), a branching agent content of 0.3 mol% isatinbiscresol
and a
UV absorber content of 0.25% Tinuvin~ 350 (3'-sec.-butyl-5'-(1,1,3,3-
tetramethyl-
butyl-2'-hydroxyphenyl-2H-benzotriazole) was produced from the sodium bis-
phenolate solution obtained in Example 1. This polycarbonate was processed in
the
following plant to produce 10 mm coextruded twin-wall sheets:
- main extruder having a screw of length 33D and a diameter of 70 mm with
venting
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- coextruder for applying the outer layer having a screw of length 25D and a
diameter of 30 mm
- special sheet die with a width of 350 mm
- calibrator ,.
- roller conveyor
- take-off unit
- cutting device (saw)
- stacking table.
The polycarbonate obtained from Example 1 was fed introduced into the
coextruder.
Coextrusion as such is known in the art (see for example EP-A 110 221 and EP-A
110 238). In the present instance, the process was performed as follows:
Extruders for producing the core layer and the outer layers) were connected to
a
coextrusion adapter. The adapter was designed that the melt forming the outer
layer
was applied as a thin layer adhering to the core layer melt.
The mufti-layer melt strand thereby produced was then given the desired form
(twin-
walled sheet) in the die connected downstream. The melt was then cooled in a
known
way under controlled conditions by means of vacuum calibration and
subsequently
sawn into pieces 1 metre in length.
Comparative Examine 4
A polycarbonate with phenol end groups, a melt flow index (MFR) of 3 (measured
according to ISO 1133), a branching agent content of 0.3 mol% isatinbiscresol
and a
L1V absorber content of 0.25% Tinuvin~ 350 (3'-sec.-butyl-S'-(1,1,3,3-
tetramethyl-
butyl-2'-hydroxyphenyl-2H-benzotriazole) was produced from the sodium bis-
phenolate solution obtained in Example 2. This polycarbonate was processed in
the
same plant and under the same conditions as in Example 3 to produce 10 mm
coextruded twin-wall sheets.
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Example 5
A polycarbonate with phenol end groups and a melt flow index (MFR) of 3
(according to ISO 1133) was produced from the sodium bisphenolate solution
obtained in Example 1. This polycarbonate was processed in the same plant and
under the same conditions as in Example 3 to produce 10 mm coextruded twin-
wall
sheets.
A compound of the polycarbonate obtained from Example 1 and 5% of a benzo
triazole UV absorber (Tinuvin~ 360 = 2,2-methylenebis-(4-(1,1,3,3-tetramethyl
butyl)-6-(2H-benzotriazol-2-yl)phenol) was introduced into the coextruder.
This
compound was produced in the following manner: the IIV absorber was mixed into
the polycarbonate in a twin-screw extruder (ZSK 32, Werner & Pfleiderer) at
280°C
and 80 rev/min and the extrudate was then pelletised.
Comparative Example 6
A polycarbonate with phenol end groups and a melt flow index (MFR) of 3
(according to ISO 1133) was produced from the sodium bisphenolate solution
obtained in Example 2. This polycarbonate was processed in the same plant and
under the same conditions as in Example 3 to produce 10 mm coextruded double-
wall sheets.
A compound of the polycarbonate obtained from Example 1 and 5% of a benzo
triazole UV absorber (Tinuvin~ 360 = 2,2-methylenebis-(4-(1,1,3,3-tetramethyl
butyl)-6-(2H-benzotriazol-2-yl)phenol) was introduced into the coextruder.
This
compound was produced in the following manner: the UV absorber was mixed into
the polycarbonate in a double-shaft extruder (ZSK 32, Werner & Pfleiderer) at
280°C
and 80 rev/min and the extrudate was then pelletised.
CA 02384432 2002-03-08

Le A 33 570-Foreign Countries
-14-
Example 7
A polycarbonate with phenol end groups, a melt flow index (MFR) of 3 (measured
according to ISO 1133) and a W absorber content of 0.3% Tinuvin~ 350 (3'-sec.-
butyl-5'-(1,1,3,3-tetramethylbutyl-2'-hydroxyphenyl-2H-benzotriazole) was
produced
from the sodium bisphenolate solution obtained in Example 1. This
polycarbonate
was processed by injection moulding to produce colour chips 3 mm thick.
Comparative Example 8
A polycarbonate with phenol end groups, a melt flow index (MFR) of 3 (measured
according to ISO 1133) and a W absorber content of 0.3% Tinuvin~ 350 (3'-sec.-
butyi-5'-{1,1,3,3-tetramethylbutyl-2'-hydroxyphenyl-2H-benzotriazole) was
produced
from the sodium bisphenolate solution obtained in Example 2. This
polycarbonate
was processed by injection moulding to produce colour chips 3 mm thick.
The sheets obtained were then subjected to colorimetric assessment, using the
following measuring methods:
1. Transmission (on the basis of standard ASTM D 1003)
Apparatus: Pye-Unicam (measuring. geometry: 0°/diffuse, calculated
accord-
ing to illuminant C)
2. Yellowness index YI according to ASTM E 313
3. Weathering of these sheets was performed according to ISO 4892-2A in the
Weatherometer made by Atlas, USA using a 6.5 W xenon lamp and a cycle
involving 102 mins of exposure to light and 18 mins of spraying with
deionised water together with light exposure. The maximum black body
temperature was 60°C (t 5°C). After 1000 hours, samples of the
sheets were
taken and toughness was tested under practical conditions using a modified
CA 02384432 2002-03-08

Le A 33 570-Foreign Countries
-15-
falling dart test developed for mufti wall sheets on the basis of DIN 53 443,
the fracture energy WS being measured using a 5 mm diameter puncture body
intended to cause biaxial stress similar to that caused by a falling
hailstone.
At room temperature, a falling mass of 36 kg falling from a height of 0.2 m
struck the samples, which lay freely on a supporting ring with an internal
diameter of 20 mm.
Testing was performed with the weathered side of the sample in the
compression zone. The fracture appearance (BB) was characterised by
numbers: 1 = splintered, 2 = smooth crack, 3 = ductile/brittle, 4 = ductile.
The yellowness index determined according to ASTM E 313 was stated as
Yellowness Index YI.
Results:
Transmission (%) Yellowness Index
Example 3 79.5 1.2
Comparative Example77.4 2.7
4
Example 7 87.3 3.0
Comparative Example84.0 5.5
8
Appearance Appearance of fractureAppearance
of of
fracture (0 (4000 hours weatheringfracture (5000
hours as
weathering stated) hours weathering
as as
stated) stated
Example 4x4 4x4 4x4
3
Comparative
4x4 4x3 4x3
example
4
Example 4x4 4x4 4x4
5
Comparative
4x4 3x4, 1x3 3x4, 1x3
example
6
CA 02384432 2002-03-08

Le A 33 570-Foreign Countries
- 16-
The results show that sheets produced according to the invention have higher
transmission values together with lower Yellowness Index values and better
mechanical stability after weathering than the sheets according to comparative
tests.
CA 02384432 2002-03-08

Representative Drawing

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Administrative Status

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Event History

Description Date
Inactive: IPC expired 2019-01-01
Inactive: IPC from MCD 2006-03-12
Application Not Reinstated by Deadline 2005-09-06
Time Limit for Reversal Expired 2005-09-06
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2004-09-07
Letter Sent 2002-09-19
Inactive: Cover page published 2002-09-03
Inactive: First IPC assigned 2002-09-01
Inactive: Notice - National entry - No RFE 2002-08-30
Application Received - PCT 2002-06-12
Inactive: Single transfer 2002-04-17
National Entry Requirements Determined Compliant 2002-03-08
Application Published (Open to Public Inspection) 2001-03-22

Abandonment History

Abandonment Date Reason Reinstatement Date
2004-09-07

Maintenance Fee

The last payment was received on 2003-08-25

Note : If the full payment has not been received on or before the date indicated, a further fee may be required which may be one of the following

  • the reinstatement fee;
  • the late payment fee; or
  • additional fee to reverse deemed expiry.

Patent fees are adjusted on the 1st of January every year. The amounts above are the current amounts if received by December 31 of the current year.
Please refer to the CIPO Patent Fees web page to see all current fee amounts.

Fee History

Fee Type Anniversary Year Due Date Paid Date
Basic national fee - standard 2002-03-08
Registration of a document 2002-04-17
MF (application, 2nd anniv.) - standard 02 2002-09-04 2002-08-16
MF (application, 3rd anniv.) - standard 03 2003-09-04 2003-08-25
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
BAYER AKTIENGESELLSCHAFT
Past Owners on Record
FRIEDER HEYDENREICH
HERMANN KAUTH
JURGEN ROHNER
MICHAEL PREIN
RAINER NEUMANN
ROLF LANZE
RUDIGER GORNY
SIEGFRIED ANDERS
STEFFEN KUHLING
TONY VAN OSSELAER
WOLFGANG NISING
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
Documents

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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Cover Page 2002-09-02 2 32
Description 2002-03-07 16 647
Abstract 2002-03-07 1 11
Claims 2002-03-07 1 30
Notice of National Entry 2002-08-29 1 192
Courtesy - Certificate of registration (related document(s)) 2002-09-18 1 113
Courtesy - Abandonment Letter (Maintenance Fee) 2004-11-01 1 176
Reminder - Request for Examination 2005-05-04 1 116
PCT 2002-03-07 11 450
PCT 2002-03-08 6 231