U.S. patent application number 16/303229 was filed with the patent office on 2019-07-04 for copolycarbonate lenses, methods of manufacture, and applications thereof.
This patent application is currently assigned to SABIC GLOBAL TECHNOLOGIES B.V.. The applicant listed for this patent is SABIC GLOBAL TECHNOLOGIES B.V.. Invention is credited to ROLAND SEBASTIAN ASSINK, JOHANNES DE BROUWER, TAMARA MARIJKE EGGENHUISEN, NATHALIE GONZALEZ VIDAL, FABRIZIO MICCICHE, KAZUHIKO MITSUI, SHAHRAM SHAFAEI, ROBERT DIRK VAN DE GRAMPEL, MARK ADRIANUS JOHANNES VAN DER MEE, HENDRIKUS PETRUS CORNELIS VAN HEERBEEK.
Application Number | 20190203043 16/303229 |
Document ID | / |
Family ID | 59325577 |
Filed Date | 2019-07-04 |
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United States Patent
Application |
20190203043 |
Kind Code |
A1 |
VAN DER MEE; MARK ADRIANUS JOHANNES
; et al. |
July 4, 2019 |
COPOLYCARBONATE LENSES, METHODS OF MANUFACTURE, AND APPLICATIONS
THEREOF
Abstract
A copolycarbonate lens formed from a polycarbonate composition
comprising: a copolycarbonate comprising bisphenol A carbonate
units and of phthalimide carbonate and optionally, a bisphenol A
homopolycarbonate; wherein the second carbonate units are present
in an amount of 18 to 35 mol % based on the sum of the moles of the
copolycarbonate and the bisphenol A homopolycarbonate, the
copolycarbonate comprises less than 2 ppm by weight of each of an
ion of lithium, sodium, potassium, calcium, magnesium, ammonium,
chlorine, bromine, fluorine, nitrite, nitrate, phosphite,
phosphate, sulfate, formate, acetate, citrate, oxalate,
trimethylammonium, and triethylammonium, as measured by ion
chromatography, and the polycarbonate composition has a bisphenol A
purity of at least 99.7% as determined by high performance liquid
chromatography. The polycarbonate composition has: a Vicat B120 of
155.degree. C. or higher; and an increase in yellowness index of
less than 10 during 1000 hours of heat aging at 155.degree. C.
Inventors: |
VAN DER MEE; MARK ADRIANUS
JOHANNES; (BREDA, NL) ; GONZALEZ VIDAL; NATHALIE;
(BERGEN OP ZOOM, NL) ; MICCICHE; FABRIZIO; (BREDA,
NL) ; ASSINK; ROLAND SEBASTIAN; (MIDDELBURG, NL)
; MITSUI; KAZUHIKO; (MOKA, JP) ; DE BROUWER;
JOHANNES; (OISTERWIJK, NL) ; SHAFAEI; SHAHRAM;
(BERGEN OP ZOOM, NL) ; VAN HEERBEEK; HENDRIKUS PETRUS
CORNELIS; (BERGEN OP ZOOM, NL) ; EGGENHUISEN; TAMARA
MARIJKE; (BREDA, NL) ; VAN DE GRAMPEL; ROBERT
DIRK; (THOLEN, NL) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC GLOBAL TECHNOLOGIES B.V. |
Bergen Op Zoom |
|
NL |
|
|
Assignee: |
SABIC GLOBAL TECHNOLOGIES
B.V.
Bergen Op Zoom
NL
|
Family ID: |
59325577 |
Appl. No.: |
16/303229 |
Filed: |
May 27, 2017 |
PCT Filed: |
May 27, 2017 |
PCT NO: |
PCT/IB2017/053140 |
371 Date: |
November 20, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62342422 |
May 27, 2016 |
|
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|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08J 2469/00 20130101;
C08J 2369/00 20130101; C08L 69/00 20130101; C08L 2205/025 20130101;
C08L 2201/10 20130101; C08G 64/12 20130101; C08J 7/04 20130101;
C08L 2201/08 20130101; C08L 2205/02 20130101; G02B 1/04 20130101;
C08L 2205/03 20130101; G02B 1/041 20130101; C08L 69/00 20130101;
G02B 1/04 20130101; C08G 64/06 20130101 |
International
Class: |
C08L 69/00 20060101
C08L069/00; C08G 64/12 20060101 C08G064/12; C08J 7/04 20060101
C08J007/04; G02B 1/04 20060101 G02B001/04 |
Claims
1. A copolycarbonate lens formed from a polycarbonate composition
comprising: a copolycarbonate comprising bisphenol A carbonate
units and of second carbonate units of the formula ##STR00017##
wherein R.sup.a and R.sup.b are each independently a C.sub.1-12
alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, each R.sup.3 is independently a C.sub.1-6 alkyl, R.sup.4 is
hydrogen, C.sub.2-6 alkyl or phenyl optionally substituted with 1
to 5 C.sub.1-6 alkyl groups, p, q, and j are each independently 0
to 4; and optionally, a bisphenol A homopolycarbonate; wherein the
second carbonate units are present in an amount of 10 to 49 mol %
based on the sum of the moles of the copolycarbonate and the
bisphenol A homopolycarbonate, the copolycarbonate comprises less
than 2 ppm by weight of each of an ion of lithium, sodium,
potassium, calcium, magnesium, ammonium, chlorine, bromine,
fluorine, nitrite, nitrate, phosphite, phosphate, sulfate, formate,
acetate, citrate, oxalate, trimethylammonium, and triethylammonium,
as measured by ion chromatography, and the polycarbonate
composition has a bisphenol A purity of at least 99.6% as
determined by high performance liquid chromatography; and wherein
the polycarbonate composition has: a Vicat B120 of 155.degree. C.
or higher, preferably 165.degree. C. or higher, as measured
according to ISO 306; and an increase in yellowness index of less
than 10 during 1000 hours of heat aging at 155.degree. C., as
measured by ASTM D1925 on a 1 mm thick molded plaque.
2. A copolycarbonate lens formed from a polycarbonate composition
comprising: a copolycarbonate comprising bisphenol A carbonate
units and of second carbonate units of the formula ##STR00018##
wherein R.sup.a and R.sup.b are each independently a C.sub.1-12
alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, each R.sup.3 is independently a C.sub.1-6 alkyl, R.sup.4 is
hydrogen, C.sub.2-6 alkyl or phenyl optionally substituted with 1
to 5 C.sub.1-6 alkyl groups, p, q, and j are each independently 0
to 4; and wherein the second carbonate units are present in an
amount of 10 to 49 mol % based on the sum of the moles of the
copolycarbonate and the bisphenol A homopolycarbonate, the
copolycarbonate comprises less than 2 ppm by weight of each of an
ion of lithium, sodium, potassium, calcium, magnesium, ammonium,
chlorine, bromine, fluorine, nitrite, nitrate, phosphite,
phosphate, sulfate, formate, acetate, citrate, oxalate,
trimethylammonium, and triethylammonium, as measured by ion
chromatography, and the polycarbonate composition has a bisphenol A
purity of at least 99.6% as determined by high performance liquid
chromatography; and wherein the polycarbonate composition has: a
Vicat B 120 of 155.degree. C. or higher as measured according to
ISO 306; and a yellowness index which is at least 20% lower
compared to the same composition having a Bisphenol A purity below
99.6%, as measured by ASTM D1925 on a 2.5 mm thick molded plaque
with a melt temperature of 355.degree. C. and a residence time of
10 min.
3. The copolycarbonate lens of claim 1, wherein the lens is a flat
or planar lens, a curved lens, a cylindrical lens, a toric or
sphero-cylindrical lens, a fresnel lens, a convex lens, a biconvex
lens, a concave lens, a biconcave lens, a convex-concave lens, a
plano-convex lens, a plano-concave lens, a lenticular lens, a
gradient index lens, an axicon lens, a conical lens, an astigmatic
lens, an aspheric lens, a corrective lens, a diverging lens, a
converging lens, a compound lens, a photographic lens, a doublet
lens, a triplet lens, an achromatic lens, or a multi-array
lens.
4. The copolycarbonate lens of claim 1, further comprising a
macrotexture, a microtexture, a nanotexture, or a combination
thereof on a surface of the lens.
5. (canceled)
6. The copolycarbonate lens of claim 1, further comprising an
indicia or a coating disposed on at least a portion of one or both
surface of the polycarbonate lens.
7. The copolycarbonate lens of claim 6, wherein the coating is a
hard coat, a UV protective coat, an anti-refractive coat, an
anti-reflective coat, a scratch resistant coat, a hydrophobic coat,
a hydrophilic coat, or a combination comprising at least one of the
foregoing, or wherein at least a portion of a surface of the
polycarbonate lens is metallized.
8. The copolycarbonate lens of claim 1, wherein the copolycarbonate
lens is a camera lens, a sensor lens, an illumination lens, a
safety glass lens, an ophthalmic corrective lens, or an imaging
lens.
9. The copolycarbonate lens of claim 8, wherein the camera lens is
a mobile phone camera lens, a table camera lens, a security camera
lens, a mobile phone camera lens, a tablet camera lens, a laptop
camera lens, a security camera lens, a camera sensor lens, or a
vehicle camera lens, the sensor lens can be a motion detector lens,
a proximity sensor lens, a gesture control lens, an infrared sensor
lens, or a camera sensor lens, the illumination lens is an indoor
lighting lens, an outdoor lighting lens, vehicle headlamp lens, a
vehicle foglight lens, a vehicle rearlight lens, a vehicle running
light lens, a vehicle foglight lens, a vehicle interior lens, an a
light emitting diode lens, or an organic light emitting diode lens,
the safety glass lens is a glasses lens, a goggles lens, a visor,
or a helmet lens, the ophthalmic corrective lens is a monocle lens,
a corrective glasses lens, or a contact lens, or the imaging lens
is a scanner lens, a projector lens, a magnifying glass lens, a
microscope lens, a telescope lens, a security lens, or a reading
glasses lens.
10. The copolycarbonate lens of claims 1 to 9, wherein the second
carbonate repeating units in the copolycarbonate are of the formula
##STR00019## wherein R.sup.5 is hydrogen, phenyl or methyl.
11. The copolycarbonate lens of claim 1, wherein the
copolycarbonate comprises from 60 to 85 mol % of the bisphenol A
carbonate units and 15 to 40 mol % of the second carbonate units,
each based on the total number of carbonate units in the
copolycarbonate.
12. The copolycarbonate lens of claim 1, wherein the
copolycarbonate further comprises at least 5 mol % of third
carbonate units different from the bisphenol A carbonate units and
the second carbonate unit, based on the total number of carbonate
units in the copolycarbonate, the third carbonate units comprising
carbonate units of the formula: ##STR00020## or a combination
thereof, wherein R.sup.c and R.sup.d are each independently a
C.sub.1-12 alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or
C.sub.1-12 alkoxy, each R.sup.6 is independently C.sub.1-3 alkyl or
phenyl, X.sup.a is a C.sub.6-12 polycyclic aryl, C.sub.3-18 mono-
or polycycloalkylene, C.sub.3-18 mono- or polycycloalkylidene,
-(Q.sup.1).sub.x-G-(Q.sup.2).sub.y- group wherein Q.sup.1 and
Q.sup.2 are each independently a C.sub.1-3 alkylene, G is a
C.sub.3-10 cycloalkylene, x is 0 or 1, and y is 1, or
--C(P.sup.1)(P.sup.2)-- wherein P.sup.1 is C.sub.1-12 alkyl and
P.sup.2 is C.sub.6-12 aryl, and m and n are each independently 0 to
4, or a combination thereof.
13. (canceled)
14. The copolycarbonate lens of claim 1, wherein the
copolycarbonate has a hydroxyl end group content of less than 200
ppm and the bisphenol A homopolycarbonate has a hydroxyl end group
content of less than 150 ppm and a sulfur content of less than 2
ppm as measured by a Total Sulfur Analysis based on combustion and
coulometric detection.
15. (canceled)
16. (canceled)
17. The copolycarbonate lens of claim 1, wherein the optional
bisphenol A homopolycarbonate has a sulfur content of less than 2
ppm, or the copolycarbonate, the optional bisphenol A
homopolycarbonate, or both are derived from a bisphenol A having a
sulfur content of less than 2 ppm, each as measured by a Total
Sulfur Analysis based on combustion and coulometric detection, or
the the optional bisphenol A homopolycarbonate.
18. The copolycarbonate lens of claim 1, wherein the polycarbonate
composition further comprises 2 to 25 ppm of an acid stabilizer,
the acid stabilizer comprising a Bronsted acid, a Lewis acid, an
acid or an ester thereof containing a sulfur atom, or a combination
comprising at least one of the foregoing.
19. The copolycarbonate lens of claim 18, wherein the acid
stabilizer comprises phosphoric acid; phosphorus acid;
hypophosphorous acid; pyrophosphoric acid; polyphosphoric acid; an
organo sulfonic stabilizer of the formula ##STR00021## wherein each
R.sup.7 is independently a C.sub.1-30 alkyl, C.sub.6-30 aryl,
C.sub.7-30 alkylarylene, C.sub.7-30 arylalkylene, or a polymer unit
derived from a C.sub.2-32 ethylenically unsaturated aromatic
sulfonic acid or its ester, and R.sup.8 is hydrogen; or R.sup.8 is
C.sub.1-30 alkyl; or R.sup.8 is a group of the formula
--S(.dbd.O).sub.2--R.sup.7; or a combination comprising at least
one of the foregoing.
20. The copolycarbonate lens of claim 1, wherein the
copolycarbonate is present in an amount of 90 to 99.8 wt % based on
the total weight of the polycarbonate composition.
21. The copolycarbonate lens of claim 1, wherein the
copolycarbonate is present in an amount of 45 to 75 wt % and the
bisphenol A homopolycarbonate is present in an amount of 25 to 55
wt %, each based on the total weight of the polycarbonate
composition.
22. The copolycarbonate lens of claim 1, wherein the polycarbonate
composition comprising, based on the total weight of the
polycarbonate composition: 60 to 70 wt % of a copolycarbonate
comprising bisphenol A carbonate units and second carbonate units
of the formula ##STR00022## wherein R.sup.5 is hydrogen, phenyl or
methyl, preferably phenyl; 25 to 40 wt % of a bisphenol A
homopolycarbonate; and optionally 6 to 12 ppm of butyl tosylate;
wherein the second carbonate units are present in an amount of 18
to 35 mol % based on the sum of the moles of the copolycarbonate
and the bisphenol A homopolycarbonate, the copolycarbonate
comprises less than 2 ppm by weight of each of an ion of lithium,
sodium, potassium, calcium, magnesium, ammonium, chlorine, bromine,
fluorine, nitrite, nitrate, phosphite, phosphate, sulfate, formate,
acetate, citrate, oxalate, trimethylammonium, and triethylammonium,
as measured by ion chromatography, and the polycarbonate
composition has a bisphenol A purity of at least 99.7% as
determined by high performance liquid chromatography; and wherein
the polycarbonate composition has: an increase in yellowness index
of less than 10 during 1000 hours of heat aging at 155.degree. C.,
as measured by ASTM D1925 on a 2.5 mm thick molded plaque.
23. The copolycarbonate lens of claim 1, wherein the polycarbonate
composition comprises, based on the total weight of the
polycarbonate composition: 96 to 99.9 wt % of a copolycarbonate
comprising bisphenol A carbonate units and second carbonate units
of the formula ##STR00023## wherein R.sup.5 is hydrogen, phenyl or
methyl, preferably phenyl; and optionally 6 to 12 ppm of butyl
tosylate; wherein the second carbonate units are present in an
amount of 18 to 35 mol % based on the sum of the moles of the
copolycarbonate and the bisphenol A homopolycarbonate, the
copolycarbonate comprises less than 2 ppm by weight of each of an
ion of lithium, sodium, potassium, calcium, magnesium, ammonium,
chlorine, bromine, fluorine, nitrite, nitrate, phosphite,
phosphate, sulfate, formate, acetate, citrate, oxalate,
trimethylammonium, and triethylammonium, as measured by ion
chromatography, and the polycarbonate composition has a bisphenol A
purity of at least 99.7% as determined by high performance liquid
chromatography; and wherein the polycarbonate composition has: a
Vicat B120 of 180.degree. C. or higher as measured according to ISO
306; and an increase in yellowness index of less than 10 during
1000 hours of heat aging at 155.degree. C., as measured by ASTM
D1925 on a 2.5 mm thick molded plaque.
24. (canceled)
25. (canceled)
26. A device comprising the copolycarbonate lens of claim 1,
wherein the device is a camera, an electronic device, a vehicle, a
flashlight, a business machine, a lighting device, an imaging
device, a protective article, a vision corrective article, or a
toy.
Description
BACKGROUND
[0001] This disclosure generally relates to polycarbonate lenses,
and more particularly, to copolycarbonate lenses, methods of
manufacture, and uses thereof.
[0002] Polycarbonates are useful in the manufacture of articles and
components for a wide range of applications, from automotive parts
to electronic appliances. Because of their beneficial properties
such as transparency and impact resistance, polycarbonates have
been used in applications such as camera lenses, eyeglass and
safety glass lenses, illumination lenses such as light fixtures,
flashlight and lantern lenses, and motor vehicle headlight lenses
and covers. Since many of the lenses are used in high-temperature
environment or have to be processed under abusive conditions, it is
desirable for the lenses materials to have the ability to withstand
elevated temperatures without deformation or discoloration, and/or
ability to maintain good optical properties even when processed
under abusive conditions.
[0003] Some known "high heat" copolycarbonates can have high glass
transition temperatures of 150.degree. C. or higher. But such
polycarbonates are typically more yellow after processing and have
lower transmission values. There accordingly remains a need for
polycarbonate lenses having improved balance of high heat
performance and optical properties.
SUMMARY
[0004] In an embodiment, a copolycarbonate lens formed from a
polycarbonate composition comprises: a copolycarbonate comprising
bisphenol A carbonate units and of second carbonate units of the
formula
##STR00001##
wherein R.sup.a and R.sup.b are each independently a C.sub.1-12
alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, each R.sup.3 is independently a C.sub.1-6 alkyl, R.sup.4 is
hydrogen, C.sub.2-6 alkyl or phenyl optionally substituted with 1
to 5 C.sub.1-6 alkyl groups, p, q, and j are each independently 0
to 4; and optionally, a bisphenol A homopolycarbonate; wherein the
second carbonate units are present in an amount of 10 to 49 mol %,
preferably 13 to 40 mol % or 35 to 49 mol %, more preferably 18 to
35 mol % based on the sum of the moles of the copolycarbonate and
the bisphenol A homopolycarbonate, the copolycarbonate comprises
less than 2 ppm by weight of each of an ion of lithium, sodium,
potassium, calcium, magnesium, ammonium, chlorine, bromine,
fluorine, nitrite, nitrate, phosphite, phosphate, sulfate, formate,
acetate, citrate, oxalate, trimethylammonium, and triethylammonium,
as measured by ion chromatography, and the polycarbonate
composition has a bisphenol A purity of at least 99.6%, or at least
99.7% as determined by high performance liquid chromatography; and
wherein the polycarbonate composition has: a Vicat B 120 of
155.degree. C. or higher, preferably 165.degree. C. or higher, more
preferably 180.degree. C. or higher as measured according to ISO
306; and an increase in yellowness index of less than 10, or of
less than 7 during 1000 hours of heat aging at 155.degree. C., as
measured by ASTM D1925 on a 1 mm thick molded plaque.
[0005] In another embodiment, a copolycarbonate lens formed from a
polycarbonate composition comprises a copolycarbonate comprising
bisphenol A carbonate units and of second carbonate units of the
formula
##STR00002##
wherein R.sup.a and R.sup.b are each independently a C.sub.1-12
alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, each R.sup.3 is independently a C.sub.1-6 alkyl, R.sup.4 is
hydrogen, C.sub.2-6 alkyl or phenyl optionally substituted with 1
to 5 C.sub.1-6 alkyl groups, p, q, and j are each independently 0
to 4; and wherein the second carbonate units are present in an
amount of 10 to 49 mol %, preferably 13 to 40 mol % or 35 to 49 mol
%, more preferably 18 to 35 mol % based on the sum of the moles of
the copolycarbonate and the bisphenol A homopolycarbonate, the
copolycarbonate comprises less than 2 ppm by weight of each of an
ion of lithium, sodium, potassium, calcium, magnesium, ammonium,
chlorine, bromine, fluorine, nitrite, nitrate, phosphite,
phosphate, sulfate, formate, acetate, citrate, oxalate,
trimethylammonium, and triethylammonium, as measured by ion
chromatography, and the polycarbonate composition has a bisphenol A
purity of at least 99.6%, or at least 99.7% as determined by high
performance liquid chromatography; and wherein the polycarbonate
composition has: a Vicat B 120 of 155.degree. C. or higher,
preferably 165.degree. C. or higher, more preferably 180.degree. C.
or higher as measured according to ISO 306; and a yellowness index
which is at least 20% or at least 30% lower compared to the same
composition having a Bisphenol A purity below 99.6% or below 99.5%,
as measured by ASTM D1925 on a 2.5 mm thick molded plaque with a
melt temperature of 355.degree. C. and a residence time of 10
min.
[0006] The lens can be a molded lens, a thermoformed lens, an
extruded lens, a cast lens, or a layer of a multi-layer lens.
[0007] In still another embodiment, a method of manufacture of a
lens comprises injection molding, injection-compression molding,
heat-cool molding, extrusion, rotational molding, blow molding, or
thermoforming the above-described polycarbonate composition into
the lens.
[0008] A device comprising the lens can be a camera, an electronic
device, a vehicle, a flashlight, a business machine, a lighting
device, an imaging device, a protective article, a vision
corrective device, or a toy.
[0009] The above described and other features are exemplified by
the following detailed description, examples, and claims.
DETAILED DESCRIPTION
[0010] Surprisingly, it has now been found that a copolycarbonate
lens having desirable high heat performance and enhanced optical
properties can be formed from a polycarbonate composition
comprising phthalimidine copolycarbonates such as
N-phenylphenolphthaleinylbisphenol, 2,2-bis(4-hydro)-bisphenol A
copolycarbonate ("PPPBP-BPA") and optionally a bisphenol A
homopolymer, when one or both of the phthalimidine copolycarbonate
and the bisphenol A homopolycarbonate are derived from a high
purity bisphenol A. In particular, the polycarbonate composition
can not only have good initial color and transmission after molding
under standard conditions but also lower color change after heat
aging at elevated temperatures. Further, the polycarbonate
composition can have improved color after molding at aggressive
conditions.
[0011] As used herein, phthalimidine copolycarbonates in the
polycarbonate compositions from which the lenses are formed are
high heat copolycarbonates having a glass transition temperature of
155.degree. C. or higher, and comprising bisphenol A carbonate
units and second carbonate units of formula (1)
##STR00003##
wherein R.sup.a and R.sup.b are each independently a C.sub.1-12
alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, preferably a C.sub.1-3 alkyl, each R.sup.3 is independently
a C.sub.1-6 alkyl, R.sup.4 is hydrogen, C.sub.1-6 or C.sub.2-6
alkyl or phenyl optionally substituted with 1 to 5 C.sub.1-6 alkyl
groups, and p and q are each independently 0 to 4, preferably 0 to
1. For example, the second carbonate units can be of formula
(1a)
##STR00004##
wherein R.sup.5 is hydrogen, phenyl optionally substituted with up
to five C.sub.1-6 alkyl groups, or C.sub.1-4 alkyl, such as methyl
or C.sub.2-4 alkyl. In an embodiment, R.sup.5 is hydrogen or
phenyl, preferably phenyl. Carbonate units (1a) wherein R.sup.5 is
phenyl can be derived from 2-phenyl-3,3'-bis(4-hydroxy
phenyl)phthalimidine (also known as
3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one or N-phenyl
phenolphthalein or "PPPBP").
##STR00005##
[0012] The optical properties of the polycarbonate composition can
be further improved when the bisphenol A carbonate units in the
high heat copolycarbonates, in the bisphenol A homopolymer or both,
are derived from a bisphenol A monomer having a purity of greater
than 99.70% as determined by high performance liquid chromatography
(HPLC).
[0013] The copolycarbonate comprises from 50 to 90 mole percent
(mol %) of the bisphenol A carbonate units and 10 to 50 mol % of
the second carbonate units, preferably the copolycarbonate
comprises from 60 to 85 mol % of the bisphenol A carbonate units
and 15 to 40 mol % of the second carbonate units, and in an
embodiment the copolycarbonate comprises from 50 to 70 mol % of the
bisphenol A carbonate units and 30 to 50 mol % of the second
carbonate units, each based on the total number of carbonate units
in the copolycarbonate.
[0014] In some embodiments, the high heat copolycarbonates further
include at least 5 mol % of third carbonate units different from
bisphenol A carbonate units and second carbonate units based on the
sum of the moles of the bisphenol A carbonate units, second
carbonate units, and third carbonate units. The third carbonate
units can have the formula
##STR00006##
wherein R.sup.c and R.sup.d are each independently a C.sub.1-12
alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, each R.sup.6 is independently C.sub.1-3 alkyl or phenyl,
preferably methyl, X.sup.a is a C.sub.6-12 polycyclic aryl,
C.sub.3-18 mono- or polycycloalkylene, C.sub.3-18 mono- or
polycycloalkylidene, -(Q.sup.1).sub.x-G-(Q.sup.2).sub.y- group
wherein Q.sup.1 and Q.sup.2 are each independently a C.sub.1-3
alkylene, G is a C.sub.3-10 cycloalkylene, x is 0 or 1, and y is 1,
or --C(P.sup.1)(P.sup.2)-- wherein P.sup.1 is C.sub.1-12 alkyl and
P.sup.2 is C.sub.6-12 aryl; and m and n are each independently 0 to
4.
[0015] Exemplary third carbonate units include the following
##STR00007## ##STR00008##
or a combination thereof, wherein R.sup.c and R.sup.d are the same
as defined herein for formulas (3) to (7), each R.sup.1 is
independently hydrogen or C.sub.1-4 alkyl, each R.sup.2 is
independently C.sub.1-4 alkyl, and g is 0 to 10. Preferably, each
R.sup.1 is independently hydrogen or methyl, each R.sup.2 is
independently methyl or hydrogen, g is 0 to 2, and m and n are 0.
In a specific embodiment the third carbonate units are
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane carbonate
units, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, or a
combination thereof. Preferably, the third carbonate units are
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (BPA TMC)
carbonate units.
[0016] When the third carbonate units are present, the
copolycarbonates can comprise 15 to 70 mol % of the bisphenol A
carbonate units, 5 to 50 mol % of the second carbonate units, and 5
to 50 mol % of the third carbonate units, each based on the sum of
moles of the bisphenol A carbonate units, second carbonate units,
and third carbonate units. Preferably, the copolycarbonates
comprise 30 to 60 mol % of the bisphenol A carbonate units, 5 to 35
mol % of the second carbonate units, 5 to 35 mol % of the third
carbonate units, each based on the sum of the moles of the
bisphenol A carbonate units, second carbonate units, and third
carbonate units.
[0017] In an embodiment, the copolycarbonates are highly random
copolymers, which have less than 15 mol % or less than 10 mol % of
the second carbonate units directly coupled to another second
carbonate unit based on the total number of carbonate units in the
copolycarbonates. The molar percent can be determined by nuclear
magnetic resonance spectroscopy (NMR). Without wishing to be bound
by theory, it is believed that by keeping the randomness of the
high heat polymer, the properties of the high heat polymer remains
consistent from batch to batch.
[0018] To further enhance the optical properties of the
thermoplastic compositions, the high heat copolycarbonates are
essentially free of certain metal ions, anions, and preferably, low
molecular weight molecules (those having a molecular weight of less
than 150 Dalton) arising from manufacture of the copolymers. In an
embodiment, the copolycarbonates comprise less than 2 ppm of each
of triethyl amine, calcium ions, magnesium ions, potassium ions,
iron ions, and chloride ions. In another embodiment, the high heat
copolycarbonates comprise less than 2 ppm of each chloride, sodium,
calcium, iron, nickel, copper, and zinc ions as residual
impurities.
[0019] In another embodiment, which is preferred, the
copolycarbonates have a low residual impurity content, in
particular less than 2 ppm by weight of each of lithium, sodium,
potassium, calcium, magnesium, ammonium, chloride, bromide,
fluoride, nitrite, nitrate, phosphite, phosphate, sulfate, acetate,
citrate, oxalate, trimethylammonium, and triethylammonium. It is to
be understood that the foregoing residual impurities can exist in
the thermoplastic compositions in un-ionized form (for example as
triethylamine or formic acid), but are determined based on their
ionized form.
[0020] The residual impurity content can be determined by methods
known in the art, for example those described in 2016/0237210 and
U.S. Pat. No. 9,287,471 via ion chromatography. For example,
determination can be accomplished via ion exchange, of a sample
obtained by dissolving 2.4 gram of copolycarbonate in 20 mL of
dichloromethane and extracting with 10 mL of distilled, deionized
water for 1 hour. The water layer is analyzed by ion chromatography
with respect to the desired anions, cations, and amines, in
particular fluoride, acetate, formate, chloride, nitrite, bromide,
nitrate, phosphite, sulphate, oxalate, phosphate, citrate, lithium,
sodium, potassium, ammonium, magnesium, calcium, and diethylamine,
and triethylamine. In another embodiment of quantitative analysis
of ions, the sample can be submerged in de-ionized water kept at
55.degree. C. for 24 hours, the anions released into the water then
analyzed via ion chromatography, e.g., with a Dionex DX500 Ion
Chromatograph. Alternatively, quantitative analysis of metals and
other compounds can be carried out by conventional inductively
coupled plasma emission spectroscopy (ICP) methods to determine the
presence of each constituent to the parts per billion (ppb)
level.
[0021] The high heat copolycarbonates have a weight average
molecular weight of 10,000 to 50,000 Daltons, preferably 16,000 to
30,000 Daltons, as measured by gel permeation chromatography (GPC),
using a crosslinked styrene-divinylbenzene column and calibrated to
bisphenol A homopolycarbonate references. GPC samples are prepared
at a concentration of 1 mg per ml, and are eluted at a flow rate of
1.5 ml per minute.
[0022] The high heat copolycarbonates have a high glass transition
temperature (Tg). The Tg of the high heat copolycarbonates is 155
to 280.degree. C., more preferably 165 to 260.degree. C., even more
preferably 185 to 230.degree. C., determined by differential
scanning calorimetry (DSC) as per ASTM D3418 with a 20.degree.
C./min heating rate.
[0023] The high heat copolycarbonates can have high heat
resistance. The heat deflection temperature (HDT) of the high heat
copolycarbonates is 145 to 270.degree. C., more preferably 155 to
260.degree. C., even more preferably 175 to 220.degree. C.,
measured flat on a 80.times.10.times.4 mm bar with a 64 mm span at
0.45 MPa according to ISO 75/Bf.
[0024] The high heat copolycarbonates can have high Vicat softening
temperature. In an embodiment, the high heat copolycarbonates have
a Vicat B 120 of 150 to 275.degree. C., preferably 160 to
255.degree. C., even more preferably 180 to 225.degree. C.,
measured according to ISO 306.
[0025] The high heat copolycarbonates can be present in an amount
of 10 to 99 weight percent (wt %), 90 to 99.8 wt %, 20 to 80 wt %,
45 to 75 wt %, or 50 to 70 wt % based on the total weight of the
polycarbonate compositions. Preferably the second carbonate units
of the high heat copolycarbonates are present in the composition in
an amount of 10 to 49 mol %, preferably 13 to 40 mol % or 35 to 49
mol %, more preferably 18 to 35 mol % of second carbonate units
based on sum of the moles of the copolycarbonate and the bisphenol
A homopolycarbonate.
[0026] The high heat copolycarbonates can be produced using a BPA
monomer having both a high level of organic purity (e.g., measured
by HPLC of greater than or equal to 99.7 wt %) and a sulfur level
of less than or equal to 2 parts per million (ppm) as measured by a
commercially available Total Sulfur Analysis based on combustion
and coulometric detection. The organic purity can be defined as 100
wt % minus the sum of known and unknown impurities detected using
ultraviolet (UV) (see HPLC method in Nowakowska et al., Polish J.
Appl. Chem., XI(3), 247-254 (1996)). In addition, an end-capping
agent is present during manufacture of the high heat
copolycarbonate such that high heat copolycarbonate comprises a
free hydroxyl level of less than or equal to 200 ppm, more
preferably less than or equal to 150 ppm.
[0027] Optionally, the thermoplastic compositions include a
bisphenol A homopolycarbonate. The bisphenol A homopolymer
carbonate can be derived from a bisphenol A monomer having a purity
less than 99.7% determined by HPLC. Alternatively, the bisphenol A
homopolycarbonate can be derived from a high purity bisphenol A
monomer having a purity equal to or greater than 99.7% determined
by HPLC.
[0028] It has been found by the inventors hereof that the optical
properties of the thermoplastic composition can be further improved
using bisphenol A homopolycarbonates having specific additional
properties. In an embodiment, the bisphenol A homopolycarbonate is
manufactured via an interfacial process using a BPA monomer having
both a high level of organic purity (e.g., measured by HPLC of
greater than or equal to 99.7 wt %) and a sulfur level of less than
or equal to 2 parts per million (ppm) as measured by a commercially
available Total Sulfur Analysis based on combustion and coulometric
detection. The organic purity can be defined as 100 wt % minus the
sum of known and unknown impurities detected using ultraviolet (UV)
(see HPLC method in Nowakowska et al., Polish J. Appl. Chem.,
XI(3), 247-254 (1996)). In addition, an end-capping agent is
present during manufacture of the bisphenol A homopolycarbonate
such that bisphenol A homopolycarbonate comprises a free hydroxyl
level less than or equal to 150 ppm. The bisphenol A
homopolycarbonate derived from high purity BPA can also have a
sulfur level of less than or equal to 2 parts per million (ppm) as
measured by a commercially available Total Sulfur Analysis based on
combustion and coulometric detection. Bisphenol A
homopolycarbonates of high purity, suitable for use in the present
compositions, can also be manufactured via the melt process.
[0029] These bisphenol A homopolycarbonates are characterized by
specific properties. In particular, the preferred bisphenol A
homopolycarbonates have a low yellowness index and are heat stable.
For example, a molded sample comprising the bisphenol A
homopolycarbonate has a yellowness index (YI) of 2.5 or less, 2.0
or less, 1.5 or less, 1.2 or less, or 1.1 or less as measured by
ASTM D1925 on a plaque with 2.5 mm thickness. The bisphenol A
homopolycarbonates can further be characterized by a molded sample
thereof with a thickness of 2.5 mm having an increase in YI
(.DELTA.YI) of less than 12, less than 12, or less than 10 after
5,000 hours of heat aging at 130.degree. C. as measured by ASTM
D1925. Alternatively, or in addition, the bisphenol A
homopolycarbonates can have an increase in YI (.DELTA.YI) of less
than 3, less than 2.5, or less than 2 after 2,000 hours of heat
aging at 130.degree. C.
[0030] The preferred bisphenol A homopolycarbonates are also
transparent in the absence of any light diffusers or other fillers.
For example, a molded article of the bisphenol A homopolycarbonate
has transmission level greater than or equal to 90.0% at 2.5
millimeter (mm) thickness as measured by ASTM D1003-00, Procedure
A, measured, e.g., using a HAZE-GUARD DUAL from BYK-Gardner, using
and integrating sphere (0.degree./diffuse geometry), wherein the
spectral sensitivity conforms to the International Commission on
Illumination (CIE) standard spectral value under standard lamp
D65.
[0031] Alternatively, the bisphenol A homopolycarbonate can be
derived from a bisphenol A monomer having a purity less than 99.70%
determined by HPLC, provided that when the bisphenol A
homopolycarbonate is derived from a bisphenol A monomer having a
purity of less than 99.70%, the high heat copolycarbonate is
derived from a high purity BPA so that the BPA purity of the
polycarbonate composition is at least 99.6% or at least 99.7% as
determined by HPLC.
[0032] As used herein, the bisphenol A purity of the polycarbonate
composition refers to the overall purity of the bisphenol A monomer
used to prepare the high heat copolycarbonate and the bisphenol A
homopolymer, if present. The bisphenol A purity of a polycarbonate
composition can be determined by a mild depolymerization followed
by a HPLC analysis. For example, about 200 milligrams (mg) of the
polycarbonate composition is dissolved in 5 ml of tetrahydrofuran
(THF) and 2 ml of a 10% solution of potassium hydroxide diluted in
methanol. The depolymerization of copolycarbonate is carried out
with the use of these solvents. The solution is shaken for 2 hours.
Then, 2 milliliters (ml) of acetic acid are added to protonate the
BPA carbonate salts and decrease the pH. The solution is shaken
again for half an hour for homogenization and dissolution of all
precipitates. The sample is analyzed by HPLC. The wt % of BPA
impurities in the polycarbonate composition can be calculated
by:
wt % of impurities in BPA = wt % of impurities * 254 228 . (
equation 1 ) ##EQU00001##
[0033] In equation 1, wt % of impurities refers to the impurities
percent measured by HPLC after depolymerization. Because the BPA
molar mass is different from the carbonated BPA, the wt % of
impurities is multiplied by 254 grams per mole (g/mol, or Da) and
divide by 228 g/mol. 254 g/mol corresponds to the BPA carbonate
molar mass and the BPA molar mass is equal to 228 g/mol. The purity
of BPA can be determined by subtracting the wt % of calculated BPA
impurities from 100.
[0034] In an embodiment, the bisphenol A polycarbonate homopolymer
is a linear bisphenol A polycarbonate homopolymer having a weight
average molecular weight of 10,000 to 100,000 Daltons, specifically
15,000 to 50,000 Daltons, more specifically 17,000 to 35,000
Daltons, as measured by gel permeation chromatography (GPC), using
a crosslinked styrene-divinylbenzene column and calibrated to
bisphenol A homopolycarbonate references. GPC samples are prepared
at a concentration of 1 mg per ml, and are eluted at a flow rate of
1.5 ml per minute.
[0035] More than one bisphenol A polycarbonate homopolymer can be
present. For example, the polycarbonate compositions can comprise a
first bisphenol A polycarbonate homopolymer having a weight average
molecular weight of 20,000 Daltons to 25,000 Daltons and a second
bisphenol A polycarbonate homopolymer having a weight average
molecular weight of 28,000 to 32,000 Daltons, or a second bisphenol
A polycarbonate homopolymer having a weight average molecular
weight of 16,000 Daltons to 20,000 Daltons, each measured by GPC
using bisphenol A homopolycarbonate standards. The weight ratio of
the first bisphenol A polycarbonate homopolymer relative to the
second bisphenol A polycarbonate homopolymer is 10:1 to 1:10,
specifically 5:1 to 1:5, more specifically 3:1 to 1:3 or 2:1 to
1:2.
[0036] The polycarbonate homopolymer can be present in an amount of
10 to 90 wt %, preferably 10 to 80 wt %, 10 to 60 wt %, 15 to 50 wt
%, or 25 to 55 wt %, or 30 to 50 wt %, each based on the total
weight of the polycarbonate composition.
[0037] In some embodiments, it can be advantageous to use
copolycarbonates and bisphenol A homopolycarbonates with very low
residual contents of volatile impurities. For example, the polymer
components can have a content of chlorobenzene and other aromatic
chlorine compounds of less than 10 ppm, preferably less than 5 ppm
and more preferably less than 2 ppm, dichloromethane of less than 1
ppm, preferably less than 0.5 ppm, monohydric phenols such as
phenol, tert-butylphenol and cumylphenol of less than 15 ppm,
preferably less than 5 ppm and more preferably less than 2 ppm, and
alkanes of less than 10 ppm, preferably less than 5 ppm. In other
embodiments, the polymers can preferably have residual contents of:
carbon tetrachloride of less than 0.01 ppm, diaryl carbonates, in
particular diphenyl carbonate and di-tert-butyl phenolcarbonate, of
less than 5 ppm, preferably less than 2 ppm, bisphenol A and other
bisphenols of less than 5 ppm, preferably less than 2 ppm and more
preferably less than 0.5 ppm, sodium and other alkali metals and
alkaline earth metals of less than 0.05 ppm, cresols of less than 1
ppm, preferably less than 0.2 ppm, phenolic OH groups of less than
300 ppm, preferably less than 200 ppm, more preferably less than
100 ppm, alkaline earth metals of less than 0.1 ppm, more
preferably less than 0.05 ppm, pyridine of less than 1 ppm,
preferably less than 0.1 ppm, nonhalogenated aromatic compounds
such as xylene and toluene of less than 10 ppm, preferably less
than 5 ppm. Methods for obtaining and measuring these amount is
described, for example, in US2012/0157653.
[0038] The polycarbonates can be manufactured by processes such as
interfacial polymerization and melt polymerization, which are
known, and are described, for example, in WO 2013/175448 A1 and WO
2014/072923 A1. An end-capping agent (also referred to as a chain
stopper agent or chain terminating agent) can be included during
polymerization to provide end groups, for example monocyclic
phenols such as phenol, p-cyanophenol, and C.sub.1-C.sub.22
alkyl-substituted phenols such as p-cumyl-phenol, resorcinol
monobenzoate, and p- and tertiary-butyl phenol, monoethers of
diphenols, such as p-methoxyphenol, monoesters of diphenols such as
resorcinol monobenzoate, functionalized chlorides of aliphatic
monocarboxylic acids such as acryloyl chloride and methacryoyl
chloride, and mono-chloroformates such as phenyl chloroformate,
alkyl-substituted phenyl chloroformates, p-cumyl phenyl
chloroformate, and toluene chloroformate. Combinations of different
end groups can be used. Branched polycarbonate blocks can be
prepared by adding a branching agent during polymerization, for
example trimellitic acid, trimellitic anhydride, trimellitic
trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol,
tris-phenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene),
tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha,
alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride,
trimesic acid, and benzophenone tetracarboxylic acid. The branching
agents can be added at a level of 0.05 to 2.0 wt %. Combinations
comprising linear polycarbonates and branched polycarbonates can be
used.
[0039] It has been found that including an acid stabilizer in the
polycarbonate compositions can further improve the color stability
of the compositions after the compositions are molded under
aggressive conditions and/or after the compositions are aged at an
elevated temperature for a prolonged period of time.
[0040] Any Arrhenius acid (i.e., protic acid) can be used so long
as the type and amount selected is such that molding properties are
improved, and color and polycarbonate degradation are minimized.
Any acid with a pKa of less than or equal to about 5 (measured in
water) can be used. Use of a stronger acid, i.e., an acid having a
pKa (measured in water) of less or equal to about 2, specifically
about 2 to about -1, over a weaker acid, i.e., having a pKa
(measured in water) of greater than about 2, specifically greater
than about 2 to about 4.5, has a stronger effect on both molding
and heat aging. Lower amounts of the stronger acid can therefore be
used relative to the weaker acid, for the same color stabilization
effect. In one embodiment, a stronger acid having a pKa of less
than 2 is used; in other embodiments, a weaker acid having a pKa of
greater than 2 is used. In some embodiments, an acid having a pKa
of less than 4.5 is used. Exemplary acid stabilizers include
Bronsted acid, a Lewis acid, an ester of an acid or an ester
thereof containing a sulfur atom, or a combination thereof.
[0041] Acid stabilizers can include, in an embodiment, phosphoric
acid; phosphorus acid; hypophosphorous acid; pyrophosphoric acid;
polyphosphoric acid; an organo sulfonic stabilizer; sulfurous
acids; ammonium salts of sulfuric acids, halogenated carboxylic
acids such as, for example, trifluoroacetic acid, trichloroacetic
acid, and the like. In an exemplary embodiment, a useful weaker
acid is phosphoric acid or phosphorous acid, and a useful stronger
acid is p-toluenesulfonic acid.
[0042] The organosulfonic stabilizer can be an aryl or aliphatic
sulfonic acid, including a polymer thereof, an aryl or an aliphatic
sulfonic acid anhydride, or an aryl or aliphatic ester of an aryl
or aliphatic sulfonic acid, or a polymer thereof. In particular,
the organosulfonic stabilizer is a C.sub.1-30 alkyl sulfonic acid,
a C.sub.6-30 aryl sulfonic acid, a C.sub.7-30 alkylarylene sulfonic
acid, a C.sub.7-30 arylalkylene sulfonic acid, or an aromatic
sulfonic acid polymer; an anhydride of a C.sub.1-30 alkyl sulfonic
acid, a C.sub.6-30 aryl sulfonic acid, a C.sub.7-30 alkylarylene
sulfonic acid, or a C.sub.7-30 arylalkylene sulfonic acid; or a
C.sub.6-30 aryl ester of a C.sub.1-30 alkyl sulfonic acid, a
C.sub.6-30 aryl sulfonic acid, a C.sub.7-30 alkylarylene sulfonic
acid, a C.sub.7-30 arylalkylene sulfonic acid, or an aromatic
sulfonic acid polymer; or a C.sub.1-30 aliphatic ester of a
C.sub.1-30 alkyl sulfonic acid, a C.sub.6-30 aryl sulfonic acid, a
C.sub.7-30 alkylarylene sulfonic acid, a C.sub.7-30 arylalkylene
sulfonic acid, or an aromatic sulfonic acid polymer. A combination
of one or more of the foregoing can be used.
[0043] In preferred embodiments, the organosulfonic stabilizers are
represented by formula (8)
##STR00009##
[0044] In formula (8), R.sup.7 is each independently a C.sub.1-30
alkyl, C.sub.6-30 aryl, C.sub.7-30 alkylarylene, C.sub.7-30
arylalkylene, or a polymer unit derived from a C.sub.2-32
ethylenically unsaturated aromatic sulfonic acid or its
corresponding C.sub.1-32 alkyl ester. The C.sub.2-32 ethylenically
unsaturated aromatic sulfonic acid can be of the formula
##STR00010##
[0045] wherein R.sup.9 is hydrogen or methyl, and R.sup.8 is as
defined in formula (8). Preferably the ethylenically unsaturated
group and the sulfonic acid or ester group are located para on the
phenyl ring.
[0046] Further in formula (8), R.sup.8 is hydrogen; or R.sup.8 is
C.sub.1-30 alkyl; or R.sup.8 is a group of the formula
--S(.dbd.O).sub.2--R.sup.7. When R.sup.8 is a group of the formula
--S(.dbd.O).sub.2--R.sup.7, each R.sup.7 in the compound of formula
(8) can be the same or different, but preferably each R.sup.7 is
the same.
[0047] In an embodiment in formula (8), R.sup.7 is a C.sub.6-12
aryl, C.sub.7-24 alkylarylene, or a polymer unit derived from a
C.sub.2-14 ethylenically unsaturated aromatic sulfonic acid or its
ester; and R.sup.8 is hydrogen, C.sub.1-24 alkyl, or a group of the
formula --S(.dbd.O).sub.2--R.sup.7 wherein R.sup.7 is a C.sub.6-12
aryl or C.sub.7-24 alkylarylene.
[0048] In a preferred embodiment, R.sup.7 is a C.sub.7-10
alkylarylene or a polymer unit derived from a C.sub.2-14
ethylenically unsaturated aromatic sulfonic acid, and R.sup.8 is a
hydrogen, C.sub.1-25 alkyl, or a group of the formula
--S(.dbd.O).sub.2--R.sup.7 wherein R.sup.7 is a C.sub.7-10
alkylarylene. In a specific embodiment, R.sup.7 is a C.sub.7-10
alkylarylene and R.sup.8 is a hydrogen or C.sub.1-6 alkyl. In still
another embodiment, R.sup.7 is a C.sub.7-10 alkylarylene and
R.sup.8 is a hydrogen or C.sub.12-25 alkyl, or R.sup.8 is a
C.sub.14-20 alkyl.
[0049] In specific embodiment, R.sup.7 is a polymer unit derived
from a C.sub.2-14 ethylenically unsaturated aromatic sulfonic acid,
preferably p-styrene sulfonic acid or para-methyl styrene sulfonic
acid, such that in formula (8) R.sup.8 is hydrogen.
[0050] In an embodiment, the organosulfonic stabilizer is a
C.sub.1-10 alkyl ester of a C.sub.7-12 alkylarylene sulfonic acid,
preferably of p-toluene sulfonic acid. More preferably the
stabilizer is a C.sub.1-6 alkyl ester of p-toluene sulfonic acid,
and even more preferably is butyl tosylate.
[0051] In another embodiment, the organosulfonic stabilizer is an
anhydride of a C.sub.7-12 alkylarylene sulfonic acid, preferably
para-toluene sulfonic anhydride.
[0052] In still another embodiment, R.sup.7 is a C.sub.11-24
alkylarylene sulfonic acid, and R.sup.8 is hydrogen. Alternatively,
R.sup.7 is a C.sub.16-22 alkylarylene sulfonic acid, and R.sup.8 is
hydrogen.
[0053] The acid stabilizer can be used in an amount of 2 ppm to 25
ppm, preferably 4 ppm to 15 ppm or 6 ppm to 12 ppm, or 1 ppm to 40
ppm, 4 ppm to 20 ppm or 6 ppm to 10 ppm by weight based on the
total weight of the polycarbonate composition.
[0054] The polycarbonate composition can also contain an epoxy
additive. Epoxy compounds useful as additives include epoxy
modified acrylic oligomers or polymers (such as a
styrene-acrylate-epoxy polymer, prepared from for example a
combination of: a substituted or unsubstituted styrene such as
styrene or 4-methylstyrene; an acrylate or methacrylate ester of a
C.sub.1-22 alkyl alcohol such as methyl acrylate, methyl
methacrylate, ethyl acrylate, butyl acrylate, or the like; and an
epoxy-functionalized acrylate such as glycidyl acrylate, glycidyl
methacrylate, 2-(3,4-epoxycyclohexyl)ethyl acrylate,
2-(3,4-epoxycyclohexyl)ethyl methacrylate, or the like), or an
epoxy carboxylate oligomer based on cycloaliphatic epoxides (such
as, for example,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, or the
like). Specific commercially available exemplary epoxy
functionalized stabilizers include Cycloaliphatic Epoxide Resin
ERL-4221 supplied by Union Carbide Corporation (a subsidiary of Dow
Chemical), Danbury, Conn.; and epoxy modified acrylates such as
JONCRYL ADR-4300 and JONCRYL ADR-4368, available from BASF. Epoxy
additives are typically used in amounts of up to 1 wt %,
specifically 0.001 to 1 wt %, more specifically 0.001 to 0.5 wt %,
based on the total weight of the polycarbonate composition. In an
embodiment, the epoxy additive can be included in an amount of
0.001 to 0.3 wt %, specifically 0.01 to 0.3 wt %, and more
specifically 0.1 to 0.3 wt %, based on the total weight of the
polycarbonate composition. Use of greater amounts of epoxy compound
may cause more splay, i.e., mold lines which fan outward from the
point of injection into the mold, and observable to the unaided eye
in molded articles comprising the polycarbonate composition.
[0055] The polycarbonate compositions can include various additives
ordinarily incorporated into polymer compositions of this type,
with the proviso that the additive(s) are selected so as to not
significantly adversely affect the desired properties of the
polycarbonate composition, in particular melt flow, thermal,
transparency, and surface properties. Such additives can be mixed
at a suitable time during the mixing of the components for forming
the composition. Additives include fillers, reinforcing agents,
antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV)
light stabilizers, plasticizers, lubricants, mold release agents,
antistatic agents, colorants such as titanium dioxide, carbon
black, and organic dyes, surface effect additives, radiation
stabilizers, flame retardants, anti-drip agents, and impact
modifiers. In an embodiment, the polycarbonate composition further
comprises a processing aid, a heat stabilizer, an ultraviolet light
absorber, a colorant, a flame retardant, an impact modifier, or a
combination thereof. A combination of additives can be used, for
example a combination of a heat stabilizer, mold release agent, and
ultraviolet light stabilizer. In general, the additives are used in
the amounts generally known to be effective. For example, the total
amount of the additives (other than any impact modifier, filler, or
reinforcing agents) can be 0 to 5 wt % or 0.01 to 5 wt %, based on
the total weight of the polycarbonate composition.
[0056] Antioxidant additives include organophosphites such as
tris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl
pentaerythritol diphosphite; alkylated monophenols or polyphenols;
alkylated reaction products of polyphenols with dienes, such as
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]
methane; butylated reaction products of para-cresol or
dicyclopentadiene; alkylated hydroquinones; hydroxylated
thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds;
esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid
with monohydric or polyhydric alcohols; esters of
beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with
monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl
compounds such as distearylthiopropionate, dilaurylthiopropionate,
ditridecylthiodipropionate,
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;
amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid,
or combinations comprising at least one of the foregoing
antioxidants. Antioxidants are used in amounts of 0.01 to 0.1 parts
by weight, based on 100 parts by weight of the total composition,
excluding any filler.
[0057] Heat stabilizer additives include organophosphites such as
triphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite,
tris-(mixed mono- and di-nonylphenyl)phosphite; phosphonates such
as dimethylbenzene phosphonate, phosphates such as trimethyl
phosphate, or combinations comprising at least one of the foregoing
heat stabilizers. Heat stabilizers are used in amounts of 0.01 to
0.1 parts by weight, based on 100 parts by weight of the total
composition, excluding any filler.
[0058] Light stabilizers, including ultraviolet light (UV)
absorbers, can also be used. Light stabilizers include
benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole
and 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole,
2-hydroxy-4-n-octoxy benzophenone, or combinations comprising at
least one of the foregoing light stabilizers. UV absorbing
additives include hydroxybenzophenones; hydroxybenzotriazoles;
hydroxybenzotriazines; cyanoacrylates; oxanilides; benzoxazinones;
2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol
(CYASORB* 5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB* 531);
2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol
(CYASORB* 1164); 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)
(CYASORB* UV-3638);
1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenyl-
acryloyl)oxy]methyl]propane (UVINUL* 3030); 2,2'-(1,4-phenylene)
bis(4H-3,1-benzoxazin-4-one);
1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenyl-
acryloyl)oxy]methyl]propane; phenol,
2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)-(TINUVIN*
234); BCAP bismalonate from Clariant; nano-size inorganic materials
such as titanium oxide, cerium oxide, and zinc oxide, all with
particle size less than or equal to 100 nanometers, or combinations
comprising at least one of the foregoing UV absorbers. Light
stabilizers are used in amounts of 0.01 to 5 parts by weight, based
on 100 parts by weight of the polycarbonate composition, excluding
any filler.
[0059] Flame retardants can also be used. Flame retardants include
flame retardant salts such as alkali metal salts of perfluorinated
C.sub.1-16 alkyl sulfonates such as potassium perfluorobutane
sulfonate (Rimar salt), potassium perfluoroctane sulfonate,
tetraethylammonium perfluorohexane sulfonate, potassium
diphenylsulfone sulfonate (KSS), and the like, sodium benzene
sulfonate, sodium toluene sulfonate (NATS) and the like; and salts
formed by reacting for example an alkali metal or alkaline earth
metal (for example lithium, sodium, potassium, magnesium, calcium
and barium salts) and an inorganic acid complex salt, for example,
an oxo-anion, such as alkali metal and alkaline-earth metal salts
of carbonic acid, such as Na.sub.2CO.sub.3, K.sub.2CO.sub.3,
MgCO.sub.3, CaCO.sub.3, and BaCO.sub.3 or fluoro-anion complex such
as Li.sub.3AlF.sub.6, BaSiF.sub.6, KBF.sub.4, K.sub.3AlF.sub.6,
KAlF.sub.4, K.sub.2SiF.sub.6, and/or Na.sub.3AlF.sub.6 or the like.
Rimar salt and KSS and NATS, alone or in combination with other
flame retardants, are particularly useful in the compositions
disclosed herein. Flame retardant salts are typically used in
amounts of 0.01 to 1.0 parts by weight, based on 100 parts by
weight of the polycarbonate composition.
[0060] Organophosphorus flame retardants can be used.
Organophosphorus compounds include aromatic organophosphorus
compounds having at least one organic aromatic group and at least
one phosphorus-containing group, as well as organic compounds
having at least one phosphorus-nitrogen bond.
[0061] In the aromatic organophosphorus compounds that have at
least one organic aromatic group, the aromatic group can be a
substituted or unsubstituted C.sub.3-30 group containing one or
more of a monocyclic or polycyclic aromatic moiety (which can
optionally contain with up to three heteroatoms (N, O, P, S, or
Si)) and optionally further containing one or more nonaromatic
moieties, for example alkyl, alkenyl, alkynyl, or cycloalkyl. The
aromatic moiety of the aromatic group can be directly bonded to the
phosphorus-containing group, or bonded via another moiety, for
example an alkylene group. The aromatic moiety of the aromatic
group can be directly bonded to the phosphorus-containing group, or
bonded via another moiety, for example an alkylene group. In an
embodiment the aromatic group is the same as an aromatic group of
the polycarbonate backbone, such as a bisphenol group (e.g.,
bisphenol A), a monoarylene group (e.g., a 1,3-phenylene or a
1,4-phenylene), or a combination thereof.
[0062] The phosphorus-containing group can be a phosphate
(P(.dbd.O)(OR).sub.3), phosphite (P(OR).sub.3), phosphonate
(RP(.dbd.O)(OR).sub.2), phosphinate (R.sub.2P(.dbd.O)(OR)),
phosphine oxide (R.sub.3P(.dbd.O)), or phosphine (R.sub.3P),
wherein each R in the foregoing phosphorus-containing groups can be
the same or different, provided that at least one R is an aromatic
group. A combination of different phosphorus-containing groups can
be used. The aromatic group can be directly or indirectly bonded to
the phosphorus, or to an oxygen of the phosphorus-containing group
(i.e., an ester).
[0063] In an embodiment the aromatic organophosphorus compound is a
monomeric phosphate. Representative monomeric aromatic phosphates
are of the formula (GO).sub.3P.dbd.O, wherein each G is
independently an alkyl, cycloalkyl, aryl, alkylarylene, or
arylalkylene group having up to 30 carbon atoms, provided that at
least one G is an aromatic group. Two of the G groups can be joined
together to provide a cyclic group. In some embodiments G
corresponds to a monomer used to form the polycarbonate, e.g.,
resorcinol. Exemplary phosphates include phenyl bis(dodecyl)
phosphate, phenyl bis(neopentyl) phosphate, phenyl
bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate,
2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl
phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate,
tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl
phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl
bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl
phosphate, and the like. A specific aromatic phosphate is one in
which each G is aromatic, for example, triphenyl phosphate,
tricresyl phosphate, isopropylated triphenyl phosphate, and the
like.
[0064] Di- or polyfunctional aromatic phosphorus-containing
compounds are also useful, for example, compounds of the formulas
below
##STR00011##
[0065] wherein each G.sup.1 is independently a C.sub.1-30
hydrocarbyl; each G.sup.2 is independently a C.sub.1-30 hydrocarbyl
or hydrocarbyloxy; each X is independently a bromine or chlorine; m
is 0 to 4, and n is 1 to 30. Di- or polyfunctional aromatic
phosphorus-containing compounds of this type include resorcinol
tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of
hydroquinone and the bis(diphenyl) phosphate of bisphenol A,
respectively, their oligomeric and polymeric counterparts, and the
like.
[0066] Specific aromatic organophosphorus compounds have two or
more phosphorus-containing groups, and are inclusive of acid esters
of the formula (9)
##STR00012##
[0067] wherein R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are each
independently C.sub.1-8 alkyl, C.sub.5-6 cycloalkyl, C.sub.6-20
aryl, or C.sub.7-12 arylalkylene, each optionally substituted by
C.sub.1-12 alkyl, specifically by C.sub.1-4 alkyl and X is a mono-
or poly-nuclear aromatic C.sub.6-30 moiety or a linear or branched
C.sub.2-30 aliphatic radical, which can be OH-substituted and can
contain up to 8 ether bonds, provided that at least one of
R.sup.16, R.sup.17, R.sup.18, R.sup.19, and X is an aromatic group.
In some embodiments R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are
each independently C.sub.1-4 alkyl, naphthyl,
phenyl(C.sub.1-4)alkylene, or aryl groups optionally substituted by
C.sub.1-4 alkyl. Specific aryl moieties are cresyl, phenyl,
xylenyl, propylphenyl, or butylphenyl. In some embodiments X in
formula (9) is a mono- or poly-nuclear aromatic C.sub.6-30 moiety
derived from a diphenol. Further in formula (9), n is each
independently 0 or 1; in some embodiments n is equal to 1. Also in
formula (9), q is from 0.5 to 30, from 0.8 to 15, from 1 to 5, or
from 1 to 2. Specifically, X can be represented by the following
divalent groups (9), or a combination comprising one or more of
these divalent groups.
##STR00013##
[0068] In these embodiments, each of R.sup.16, R.sup.17, R.sup.18,
and R.sup.19 can be aromatic, i.e., phenyl, n is 1, and p is 1-5,
specifically 1-2. In some embodiments at least one of R.sup.16,
R.sup.17, R.sup.18, R.sup.19, and X corresponds to a monomer used
to form the polycarbonate, e.g., bisphenol A or resorcinol. In
another embodiment, X is derived especially from resorcinol,
hydroquinone, bisphenol A, or diphenylphenol, and R.sup.16,
R.sup.17, R.sup.18, R.sup.19, is aromatic, specifically phenyl. A
specific aromatic organophosphorus compound of this type is
resorcinol bis(diphenyl phosphate), also known as RDP. Another
specific class of aromatic organophosphorus compounds having two or
more phosphorus-containing groups are compounds of formula (10)
##STR00014##
[0069] wherein R.sup.16, R.sup.17, R.sup.18, R.sup.19, n, and q are
as defined for formula (9) and wherein Z is C.sub.1-7 alkylidene,
C.sub.1-7 alkylene, C.sub.5-12 cycloalkylidene, --O--, --S--,
--SO.sub.2--, or --CO--, specifically isopropylidene. A specific
aromatic organophosphorus compound of this type is bisphenol A
bis(diphenyl phosphate), also known as BPADP, wherein R.sup.16,
R.sup.17, R.sup.18, and R.sup.19 are each phenyl, each n is 1, and
q is from 1 to 5, from 1 to 2, or 1.
[0070] Organophosphorus compounds containing at least one
phosphorus-nitrogen bond includes phosphazenes, phosphorus ester
amides, phosphoric acid amides, phosphonic acid amides, phosphinic
acid amides, and tris(aziridinyl) phosphine oxide. Phosphazenes
(11) and cyclic phosphazenes (12)
##STR00015##
[0071] in particular can used, wherein w1 is 3 to 10,000 and w2 is
3 to 25, specifically 3 to 7, and each R.sup.w is independently a
C.sub.1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or
polyoxyalkylene group. In the foregoing groups at least one
hydrogen atom of these groups can be substituted with a group
having an N, S, O, or F atom, or an amino group. For example, each
R.sup.w can be a substituted or unsubstituted phenoxy, an amino, or
a polyoxyalkylene group. Any given R.sup.w can further be a
crosslink to another phosphazene group. Exemplary crosslinks
include bisphenol groups, for example bisphenol A groups. Examples
include phenoxy cyclotriphosphazene, octaphenoxy
cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the
like. A combination of different phosphazenes can be used. A number
of phosphazenes and their synthesis are described in H. R. Allcook,
"Phosphorus-Nitrogen Compounds" Academic Press (1972), and J. E.
Mark et al., "Inorganic Polymers" Prentice-Hall International, Inc.
(1992).
[0072] Depending on the particular organophosphorus compound used,
the polycarbonate compositions can comprise 0.5 to 15 wt % or 3.5
to 12 wt % of the organophosphorus flame retardant, each based on
the total weight of the composition. Specifically, the
organophosphorus compounds can be bisphenol A bis(diphenyl
phosphate), triphenyl phosphate, resorcinol bis(diphenyl
phosphate), tricresyl phosphate, or a combination thereof.
[0073] The polycarbonate compositions can further comprise a cyclic
siloxane and/or a linear siloxane to impart fire/flame-retardant
properties. The cyclic siloxane can include those with the general
formula below
##STR00016##
wherein R is each independently C.sub.1-36 alkyl, fluorinated or
perfluorinated C.sub.1-36 alkyl, C.sub.1-36 alkoxy, C.sub.6-14
aryl, aryloxy of 6 to 14 carbon atoms, arylalkoxy of 7 to 36 carbon
atoms, or C.sub.1-36 alkyl-substituted aryl of 6 to 14 carbon
atoms. In an embodiment, at least one R may be a phenyl. Examples
of cyclic siloxanes include, but not limited to, a cyclic phenyl
containing siloxane, octaphenylcyclotetrasiloxane,
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
trimethyltriphenylcyclotrisiloxane, and
tetramethyltetraphenylcyclotetrasiloxane.
Octaphenylcyclotetrasiloxane is specifically mentioned.
[0074] Linear siloxanes can also be used. The linear siloxanes can
be a linear phenyl containing siloxane such as a
poly(phenylmethylsiloxane). In an embodiment, the polycarbonate
compositions contain 0.01% to 1% of a cyclic siloxane, a linear
siloxane, or a combination thereof.
[0075] The polycarbonate compositions can be manufactured by
various methods known in the art. For example, powdered
polycarbonate, and other optional components are first blended,
optionally with any fillers, in a high speed mixer or by hand
mixing. The blend is then fed into the throat of a twin-screw
extruder via a hopper. Alternatively, at least one of the
components can be incorporated into the composition by feeding it
directly into the extruder at the throat and/or downstream through
a sidestuffer, or by being compounded into a masterbatch with a
desired polymer and fed into the extruder. The extruder is
generally operated at a temperature higher than that necessary to
cause the composition to flow. The extrudate can be immediately
quenched in a water bath and pelletized. The pellets so prepared
can be one-fourth inch long or less as desired. Such pellets can be
used for subsequent molding, shaping, or forming.
[0076] The polycarbonate compositions can have a glass transition
temperature of 155.degree. C. or higher, preferably 155.degree. C.
to 280.degree. C., more preferably 165.degree. C. to 260.degree.
C., and even more preferably 185.degree. C. to 230.degree. C.,
determined by differential scanning calorimetry (DSC) as per ASTM
D3418 with a 20.degree. C./min heating rate.
[0077] The polycarbonate compositions can have high heat
resistance. The heat deflection temperature (HDT) of the
polycarbonate compositions is 150.degree. C. or higher, preferably
150 to 270.degree. C., more preferably 155 to 260.degree. C., even
more preferably 175 to 220.degree. C., measured flat on a
80.times.10.times.4 mm bar with a 64 mm span at 0.45 MPa according
to ISO 75/Bf.
[0078] The polycarbonate compositions can have high Vicat softening
temperature. In an embodiment, the polycarbonate compositions have
a Vicat B 120 of a Vicat B 120 of 155.degree. C. or higher,
preferably 165.degree. C. or higher, more preferably 180.degree. C.
or higher as measured according to ISO 306.
[0079] The polycarbonate compositions can have excellent
transparency. In an embodiment, the polycarbonate compositions have
a haze less of less than 1.5, more preferably less than 1.0, more
preferably less than 0.5%, and a transmission greater than 86%,
more preferably greater than 88%, more preferably greater than 89%,
even more preferably greater than 90%, each measured according to
ASTM D1003-00 using the color space CIE1931 (Illuminant C and a
2.degree. observer) with a 1.0 mm thickness. The polycarbonate
compositions can have a haze of less than 1.5, or less than 1.0 and
a total transmission greater than 84% or greater than 86%, each
measured according to ASTM D1003-00 using the color space CIE1931
(Illuminant C and a 2.degree. observer) on a molded plaque with a
3.0 mm thickness. The polycarbonate compositions are molded under
standard molding conditions in range of 300 to 350.degree. C.
depending on the glass transition temperature of the composition.
For example, the polycarbonate compositions are molded at a
temperature of 100.degree. C. to 175.degree. C. above the glass
transition temperature of the polycarbonate composition for a
residence time of 2 to 20 minutes.
[0080] The polycarbonate compositions can have excellent
transparency in the infrared wavelength range. In an embodiment,
the polycarbonate compositions have a transmission at wavelength of
940 nm of greater than 88%, or greater than 89% or greater than 90%
measured with Perkin Elmer 950 spectrometer equipped with 15 cm
integrated sphere on a molded plaque with a thickness of 1 mm; and
a refractive index of greater than 1.59 or greater than 1.60 at
587.6 nm or a refractive index of greater than 1.57 or greater than
1.58 at 940 nm measured according to IS 489 on a molded plaque with
a thickness of 1 mm. The compositions can have a transmission at
wavelength of 840 nm of greater than 88.0%, preferably greater than
89.0%, more preferably greater than 90.0%, as measured with Perkin
Elmer 950 spectrometer equipped with 15 cm integrated sphere on 1
mm. The compositions have a transmission at wavelength of 550 nm of
greater than 85%, or greater than 87% or greater than 88% measured
with Perkin Elmer 950 spectrometer equipped with 15 cm integrated
sphere on a molded plaque with a thickness of 1 mm; and the
compositions can have a transmission at wavelength of 400 nm of
greater than 75%, or greater than 80% or greater than 85% measured
with Perkin Elmer 950 spectrometer equipped with 15 cm integrated
sphere on a molded plaque with a thickness of 1 mm. In still
another embodiment, the compositions have a transmission at
wavelength of 1310 nm of greater than 87%, preferably greater than
88.0%, more preferably greater than 89.0%, as measured with Perkin
Elmer 950 spectrometer equipped with 15 cm integrated sphere on 1
mm.
[0081] The polycarbonate compositions have an Abbe number of less
than 32 or less than 30 measured according to ISO 489 on a molded
plaque with a thickness of 1 mm.
[0082] The polycarbonate compositions have a melt volume flow rate
(MVR) greater than 10 cc/min or greater than 12 cc/min or greater
than 15 cc/min, measured at 330.degree. C./2.16 Kg at 360 second
dwell according to ISO 1133.
[0083] The polycarbonate compositions have an Izod notched impact
energy of at least 6 kJ/m.sup.2, or of at least 8 kJ/m.sup.2, as
measured at 23.degree. C. according to ISO 180/1A using a
multipurpose test specimen in accordance with ISO 3167 TYPE A. The
polycarbonate compositions can have an Izod notched impact energy
of at least 70 J/m, or of at least 88 J/m, as measured at
23.degree. C. according to ASTM D256.
[0084] The polycarbonate compositions have excellent color
stability during exposure for prolonged time at elevated
temperatures in the absence of moisture, referred to further as
heat ageing. The polycarbonate compositions can have an increase in
yellowness index of less than 5, less than 4, more preferably less
than 3, during 1500 hours of heat aging at 140.degree. C., as
measured by ASTM D1925 on a 1.0 mm thick molded plaque. The
polycarbonate compositions have an increase in yellowness index of
less than 15, equal to or less than 10, or equal to or less than 7
during 1000 hours of heat aging at 155.degree. C., as measured by
ASTM D1925 on a 1 mm thick molded plaque. In an embodiment, the
polycarbonate compositions can have an increase in yellowness index
of less than 10, more preferably less than 8, more preferably less
than 6, during 1500 hours of heat aging at 155.degree. C., as
measured by ASTM D1925 on a 1.0 mm thick molded plaque. The
polycarbonate compositions can have an increase in yellowness index
of less than 20, more preferably less than 10, more preferably less
than 5, during 1000 hours of heat aging at 160.degree. C., as
measured by ASTM D1925 on a 2.5 mm thick molded plaque. In still
another embodiment, the polycarbonate compositions can have an
increase in yellowness index of less than 20, more preferably less
than 10, more preferably less than 5, during 500 hours of heat
aging at 170.degree. C., as measured by ASTM D1925 on a 2.5 mm
thick molded plaque.
[0085] The polycarbonate compositions have excellent color
stability during exposure for prolonged time at elevated
temperatures in the presence of moisture, referred to further as
hydro ageing. In an embodiment, the polycarbonate compositions have
an increase in yellowness index of less than 5, more preferably
less than 3, more preferably less than 1, after 1000 hours of hydro
ageing at 80.degree. C. and 85% relative humidity, as measured by
ASTM D1925 on a 2.5 mm thick molded plaque. In another embodiment,
the polycarbonate compositions have an increase in yellowness index
of less than 0.5, or of less than 0.3 after 100 hours of hydro
ageing at 121.degree. C. in an autoclave, as measured by ASTM D1925
on a 2.5 mm thick molded plaque.
[0086] The polycarbonate compositions have excellent color
stability during exposure for prolonged time to autoclave
conditions or multiple cycle of autoclave sterilization. In an
embodiment, the polycarbonate compositions have an increase in
yellowness index of less than 2, more preferably less than 1, after
100 hours of autoclaving at 121.degree. C., as measured by ASTM
D1925 on a 2.5 mm thick molded plaque. In another embodiment, the
polycarbonate compositions have an increase in yellowness index of
less than 5, more preferably less than 3, more preferably less than
1, after 100 hours of autoclaving at 134.degree. C., as measured by
ASTM D1925 on a 2.5 mm thick molded plaque. In an embodiment, the
polycarbonate compositions have an increase in yellowness index of
less than 10, more preferably less than 5, more preferably less
than 3, after 100 hours of autoclaving at 143.degree. C., as
measured by ASTM D1925 on a 2.5 mm thick molded plaque.
[0087] The polycarbonate compositions can have excellent color
after molding under demanding conditions. In an embodiment, the
polycarbonate compositions have a yellowness index of less than 20,
more preferably less than 10, more preferably less than 5, more
preferably less than 3, as measured by ASTM D1925 on a 2.5 mm
plaque. For example, the polycarbonate compositions are molded at a
temperature of 100 to 175.degree. C. above the glass transition
temperature of the polycarbonate composition for a residence time
of 2 to 20 minutes. Typical conditions would be molding at melt
temperatures of 350.degree. C. or higher and residence times of 3
min or longer.
[0088] In an embodiment, the polycarbonate composition has a
yellowness index which is at least 20% or at least 30% lower
compared to the same composition having a Bisphenol A purity below
99.6% or below 99.5%, as measured by ASTM D1925 on a 2.5 mm thick
molded plaque with a melt temperature of 355.degree. C. and a
residence time of 10 min. In another embodiment, the polycarbonate
compositions have a yellowness index of less than 10 measured
according to ASTM D1925 on a plaque of 2.5 mm thickness molded at a
temperature of 355.degree. C. for a residence time of 10
minutes.
[0089] The polycarbonate compositions can have a change in
yellowness index of less than 100%, more preferably less than 50%,
more preferably less than 30%, following molding under aggressive
conditions as compared to a reference article of an identical
composition molded under standard process conditions, when tested
at thickness of 2.5 mm determined according to ASTM D1925. As used
herein, aggressive molding conditions include a molding temperature
of equal to or greater than 330.degree. C., and standard molding
conditions include a molding temperature of less than 330.degree.
C.
[0090] The polycarbonate compositions can have a yellowness index
(YI) determined according to ASTM D1925 at least 30% lower, more
preferably at least 50% lower, more preferably at least 75% lower,
as compared to a reference sample of an otherwise identical
composition
[0091] A molded part of the composition with a thickness of 2.5 mm
has a yellowness index (YI) determined according to ASTM D1925 at
least 30% lower, more preferably at least 50% lower, more
preferably at least 75% lower, as compared to the same composition
having a Bisphenol A purity below 99.6% or below 99.5%, following
molding at a temperature of equal to or greater than 330.degree. C.
for a residence time of 10 minutes.
[0092] The polycarbonate compositions can have good flame retardant
properties. Flammability tests are performed following the
procedure of Underwriter's Laboratory Bulletin 94 entitled "Tests
for Flammability of Plastic Materials for Parts in Devices and
Appliances" (ISBN 0-7629-0082-2), Fifth Edition, Dated Oct. 29,
1996, incorporating revisions through and including Dec. 12, 2003.
Several ratings can be applied based on the rate of burning, time
to extinguish, ability to resist dripping, and whether or not drips
are burning. According to this procedure, materials can be
classified as HB, V0, UL94 V1, V2, VA and/or VB. In an embodiment,
the polycarbonate compositions have a UL94-V0 rating at a thickness
of 2.5 mm or higher; or a UL94-V2 rating at a thickness of 0.8 mm
to 1.5 mm.
[0093] The polycarbonate compositions can be provided as pellets,
and are useful to form lenses by a variety of methods. All known
methods can be used. Exemplary methods include via multi-cavity
tools; molding such as injection molding, gas assist injection
molding, vacuum molding, extrusion, compression molding,
calendaring, rotary molding, heat/cool molding, blow molding,
overmolding, transfer molding, cavity molding, thermoforming, or
casting.
[0094] Advantageously, the lenses have no significant part
distortion or discoloration when the lenses are subjected to a
secondary operation such as over-molding, lead-free soldering, low
temperature soldering, or coating with high temperature curing, or
a combination thereof. High temperature cure of a coating can be,
for example, 100.degree. C. or higher, for example 100 to
250.degree. C. In some embodiments, "no significant part
distortion" includes a volume distortion of less than 10 volume
percent (vol %), or less than 5 vol %, or less than 1 vol %.
Significant discoloration can be detected by the unaided eye at a
distance of 18 inches. The polycarbonate compositions, which has
good flow (MVR) for excellent mold filling properties while
maintaining desirable mechanical properties can, in the manufacture
of lenses, provide a high degree of reproducibility for successive
lenses molded from the polycarbonate composition.
[0095] The lenses can be defined by several dimensional features
such as thickness, effective lens area, diameter of an effective
lens area, and an overall diameter. Lens thickness, as defined
herein, is measured at the center of the lens (i.e., along the z
axis, orthogonal to the diameter of the lens which is measured in
the x-y plane of the lens). Since lenses have curvature, the
thickness of the lens may vary along the contour of the surface.
Also, depending upon the type of the lens (convex, concave, etc.)
the variation of the thickness can differ widely. In an embodiment,
the lens has a thickness of a thickness of 0.1 mm to 50 cm, or 0.1
mm to 10 cm, 0.1 mm to 1 cm, or 0.1 mm to 0.5 cm, or 0.1 mm to 50
mm, measured at the thickest part of the lens. In a specific
embodiment, the lens has a thickness of 0.25 to 2.5 mm, or 0.5 to
2.4 mm, or 0.8 to 2.3 mm, measured at the center of the lens.
[0096] The size of the lens is characterized by the term "effective
lens area", which is defined as the area of the lens where the
curvature is positive, and hence light which is refracted through
this area is usable in actual imaging. "Curvature" as defined
herein, is the reciprocal of the optical radius of the lens (as
defined by the light path). For example a flat surface has infinite
radius and therefore zero curvature. For those lenses that include
a flat portion around the periphery of the lens, which is used for
mounting the lens into the optical assembly, this flat portion is
not considered part of the effective lens area. A typical lens has
at least two surfaces, a first and a second surface. On the first
(incident) surface, light enters the lens and exits through the
second (refractive) surface. One or both of these surfaces may have
a curvature. The effective lens area as defined above may be the
same for the first and second surfaces, or may be different for the
first and second surfaces. Where different, the larger value of the
effective surface area for the first and second surfaces is
considered to be the effective lens area for the overall lens. The
lens can have an effective lens area of 0.2 mm.sup.2 to 10 m.sup.2,
or 0.2 mm.sup.2 to 1 m.sup.2, or 0.2 mm.sup.2 to 10 cm.sup.2, or
0.2 mm.sup.2 to 5 mm.sup.2, or 0.2 mm.sup.2 to 100 mm.sup.2
[0097] Effective lens area diameter as defined herein describes the
diameter measured at the outermost periphery of the effective
(optically useable) area of the lens; whereas overall diameter of
the lens is the diameter which includes the non-optically relevant
flat portion. The lenses disclosed herein can have a diameter of an
effective lens area of 0.1 mm to 500 cm, or 0.25 mm to 50 cm, or
0.5 mm to 1 cm, or 0.5 mm to 10 mm; or an overall diameter of 0.1
mm to 2 m, or 0.25 mm to 100 cm, or 0.5 mm to 2 cm, or 0.5 mm to 20
mm.
[0098] The lens can have an overall diameter of 0.1 mm to 500 cm,
or 0.25 mm to 100 cm, or 0.5 mm to 2 cm, or 0.5 mm to 20 mm.
[0099] The lenses can have surface textures such as a macrotexture,
a microtexture, a nanotexture, or a combination thereof on a
surface of the lenses. Textures can be imparted to the lenses using
methods known in the art including but not limited to calendaring
or embossing techniques. In an embodiment, the lenses can pass
through a gap between a pair of rolls with at least one roll having
an embossed pattern thereon, to transfer the embossed pattern to a
surface of the lenses. Textures can be applied to control gloss or
reflection.
[0100] The shape of the lenses is not particularly limited. The
lenses can also have different types. For example, the lenses can
be a flat or planar lens, a curved lens, a cylindrical lens, a
toric or sphero-cylindrical lens, a fresnel lens, a convex lens, a
biconvex lens, a concave lens, a biconcave lens, a convex-concave
lens, a plano-convex lens, a plano-concave lens, a lenticular lens,
a gradient index lens, an axicon lens, a conical lens, an
astigmatic lens, an aspheric lens, a corrective lens, a diverging
lens, a converging lens, a compound lens, a photographic lens, a
doublet lens, a triplet lens, an achromatic lens, or a multi-array
lens.
[0101] The lenses can further comprise an indicia or a coating
disposed on at least a portion of one or both sides of the
copolycarbonate lens to impart additional properties such as
scratch resistance, ultra violet light resistance, aesthetic
appeal, hydrophilicity, hydrophobicity, and the like. In an
embodiment, the coating is a hard coat, a UV protective coat, an
anti-refractive coat, an anti-reflective coat, a scratch resistant
coat, a hydrophobic coat, a hydrophilic coat, or a combination
comprising at least one of the foregoing.
[0102] Coatings can be applied through standard application
techniques such as overmolding, rolling, spraying, dipping,
brushing, flow coating, wiping, knife coating, notch coating,
reverse roll coating, gravure coating, soaking, bar coating, flood
coating, spin coating or combinations comprising at least one of
the foregoing application techniques.
[0103] The coating can be in any suitable form including a
continuous or discontinuous layer (e.g., in a pattern, dots,
stripes and swirls) and can be the result of multiple layers
disposed on top of one another.
[0104] The coating can be applied at any thickness as long as the
coating does not substantially change the appearance and optical
characteristics of the lenses. In an embodiment, the coating has a
thickness of from 1 micron to 100 microns, from 1 micron to 10
microns, from 2 microns to 5 microns, 20 Angstroms to 1 micron, or
even from 40 nanometers to 100 nanometers.
[0105] Depending on the applications, at least a portion of a
surface of the lens is metallized in some embodiments. A metal
layer can be disposed onto the surface of the lenses with the aid
of electrocoating deposition, physical vapor deposition, or
chemical vapor deposition or a suitable combination of these
methods. Sputtering processes can also be used. The metal layer
resulting from the metallizing process (e.g., by vapor deposition)
can be 0.001 to 50 micrometers (.mu.m) thick. Chrome, nickel,
aluminum, and the like can be listed as examples of vaporizing
metals. Aluminum vapor deposition is used in one embodiment as
metal vapor deposition. The surface of the molded substrate can be
treated with plasma, cleaned, or degreased before vapor deposition
in order to increase adhesion.
[0106] The lenses can have low birefringence, which means that the
lenses can have low light distortion and a better quality
image.
[0107] Exemplary lenses include a camera lens, a sensor lens, an
illumination lens, a safety glass lens, an ophthalmic corrective
lens, or an imaging lens.
[0108] The foregoing types of lenses can be used in a wide variety
of applications. For example, the camera lens can be a mobile phone
camera lens, a table camera lens, a security camera lens, a mobile
phone camera lens, a tablet camera lens, a laptop camera lens, a
security camera lens, a camera sensor lens, or a vehicle camera
lens (e.g., an automotive camera lens).
[0109] The sensor lens can be a motion detector lens, a proximity
sensor lens, a gesture control lens, an infrared sensor lens, or a
camera sensor lens.
[0110] The illumination lens can be an indoor lighting lens, an
outdoor lighting lens, vehicle headlamp lens, a vehicle foglight
lens, a vehicle rearlight lens, a vehicle running light lens, a
vehicle foglight lens, a vehicle interior lens, an a light emitting
diode (LED) lens, or an organic light emitting diode (OLED)
lens.
[0111] The safety glass lens is a glasses lens, a goggles lens, a
visor, a helmet lens, or other protective gear.
[0112] The ophthalmic corrective lens can be incorporated into
monocles, corrective glasses (including bifocals, trifocals,
progressive lens, and the like), contact lenses, and the like.
[0113] The imaging lens can be a scanner lens, a projector lens, a
magnifying glass lens, a microscope lens, a telescope lens, a
security lens, reading glasses lens, and the like.
[0114] Accordingly, the lenses can be incorporated into a wide
variety of devices, including a camera (including reflex cameras),
an electronic device (such as mobile phones, tablets, laptop
computers, and desk computers), a vehicle (which as used herein
refers to any transportation devices, for example bicycles,
scooters, motorcycles, automobiles, buses, trains, boats, ships,
and aircraft) a flashlight, a business machine (such as a copier or
a scanner), a lighting device (including indoor lighting such as
table lamps and ceiling lights, outdoor lighting such as
floodlights and streetlights, vehicle headlights, rearlights, side
lights, running lights, foglights, and interior lights), an imaging
device (such as a microscope, a telescope, a projector, a security
lens (e.g. in a door), or reading glasses), a safety article (such
as goggles, glasses, and headgear such as helmets), a vision
corrective article (glasses or contact lens), or a toy.
[0115] The polycarbonate compositions are further illustrated by
the following non-limiting examples.
EXAMPLES
[0116] The materials used in the Examples are described in Table
1.
TABLE-US-00001 TABLE 1 Component Chemical Description Source CPC-1
PPP-BP (N-phenylphenolphthaleinylbisphenol, 2,2-bis(4-hydro) -
bisphenol A SABIC copolycarbonate, 33 mol % PPP-BP, Mw = 21-25 kDa
as determined by GPC using bisphenol A polycarbonate standards,
para-cumylphenol (PCP) end-capped, with BPA carbonate units derived
from BPA having 99.4-99.5% purity CPC-2 PPP-BP
(N-phenylphenolphthaleinylbisphenol, 2,2-bis(4-hydro) - Bisphenol A
SABIC polycarbonate copolymer, 33 mol % PPP-BP, Mw = 22-23 kDa as
determined by GPC using BPA polycarbonate standards,
para-cumylphenol (PCP) end-capped, with BPA carbonate units derived
from BPA having 99.7% purity PC-1A Linear Bisphenol A
polycarbonate, produced via interfacial polymerization from BPA
SABIC having a purity of 99.4-99.5% wt % determined by HPLC, Mw =
30-31 kDa as determined by GPC using BPA polycarbonate standards,
phenol end-capped PC-1B Linear Bisphenol A polycarbonate, produced
via interfacial polymerization from BPA SABIC having a purity of
99.7 wt % determined by HPLC, Mw = 30-31 kDa as determined by GPC
using BPA polycarbonate standards, phenol end-capped PC-2A Linear
Bisphenol A polycarbonate, produced via interfacial polymerization
from BPA SABIC having a purity of 99.4-99.5% wt % determined by
HPLC, Mw = 22-23 kDa as determined by GPC using BPA polycarbonate
standards, PCP end-capped PC-2B Linear Bisphenol A polycarbonate,
produced via interfacial polymerization from BPA SABIC having a
purity of 99.7 wt % determined by HPLC, Mw = 22-23 kDa as
determined by GPC using BPA polycarbonate standards, PCP end-capped
PC3 Linear Bisphenol A polycarbonate, produced via interfacial
polymerization from BPA SABIC having a purity of 99.4-99.5 wt %
determined by HPLC, Mw = 18-19 kDa as determined by GPC using BPA
polycarbonate standards, PCP end-capped. Tosylate Premix of 0.06 wt
% of butyl tosylate in PC-2A SABIC Premix-1 Tosylate Premix of 0.3
wt % of butyl tosylate in PC-2A SABIC Premix-2 AO-1
Tris(2,4-di-t-butylphenyl)phosphite (IRGAFOS 168) Ciba AO-2
Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate IRGANOX
1076 BASF PETS Palmitic/stearic acid (50/50) ester of
dipenta/pentaerythritol (Loxiol EP8578) Cognis Oleochemicals
H.sub.3PO.sub.3 Premix of 0.6262 wt % of a 45 wt % of phosphorous
acid aqueous solution in PC-1 Aldrich Premix UVA 234
2-[2-hydroxy-3,5-di-(1,1-dimethylbenzyl)]-2H-benzotriazol BASF
Blending, Extrusion, and Molding Conditions
[0117] The compositions were made as follows. All solid were dry
blended off-line as concentrates using one of the primary polymer
powders as a carrier and starve-fed via gravimetric feeder(s) into
the feed throat of the extruder. The remaining polymer(s) were
starve-fed via gravimetric feeder(s) into the feed throat of the
extruder as well. The liquid additives, if any, were fed before the
vacuum using a liquid injection system. It will be recognized by
one skilled in the art that the method is not limited to these
processing steps or processing equipment.
[0118] Extrusion of all materials was performed on a 25 mm
Werner-Pfleiderer ZAK twin-screw extruder (L/D ratio of 33/1) with
a vacuum port located near the die face. The extruder has 9 zones,
which were set at temperatures of 40.degree. C. (feed zone),
200.degree. C. (zone 1), 250.degree. C. (zone 2), 270.degree. C.
(zone 3) and 290-330.degree. C. (zone 4 to 8). Screw speed was 300
rpm and throughput was between 10 and 25 kg/hr. It will be
recognized by one skilled in the art that the method is not limited
to these temperatures or processing equipment.
[0119] The compositions were molded after drying at 100-110.degree.
C. for 6 hours on a 45-ton Engel molding machine with 22 mm screw
or 75-ton Engel molding machine with 30 mm screw operating at a
temperature 310 to 360.degree. C. with a mold temperature of 80 to
150.degree. C. It will be recognized by one skilled in the art that
the method is not limited to these temperatures or processing
equipment.
Testing Methods
[0120] Yellowness Index (YI) was calculated from the transmission
spectrum from a MacBeth ColorEye7000A according to ASTM D1925, at
1.0 mm or 2.5 mm thickness as specified in the examples.
[0121] Tensile stress and tensile modulus were measured in
accordance with ISO 527 with speed of 50 mm/min.
[0122] Flexural stress and flexural modulus were measured in
accordance with ISO 178.
[0123] ASTM Izod notched impact energy was as measured at
23.degree. C. according to ASTM D256 using a 80 mm.times.10
mm.times.4 mm specimen.
[0124] ISO notched Izod impact was measured at 23.degree. C.
according to ISO 180/1A using a multipurpose test specimen in
accordance with ISO 3167 TYPE.
[0125] A Vicat B 120 softening temperature was measured according
to ISO 306.
[0126] Heat deflection temperature (HDT) was measured flat on a 80
mm.times.10 mm.times.4 mm bar with a 64 mm span at 0.45 MPa
according to ISO 75/Bf.
[0127] Melt volume flow rate (MVR) was measured at 330.degree.
C./2.16 Kg at 300 second dwell according to ISO 1133.
[0128] Transmission at 400 nm, 550 nm, 940 nm, or 1310 nm was
measured with Perkin Elmer 950 spectrometer equipped with 15 cm
integrated sphere on a molded plaque with a thickness of 1 mm, 2
mm, or 3 mm.
[0129] Haze was measured according to ASTM D1003-00 on a molded
plaque with thickness between 1 and 3 mm.
[0130] Refractive index was measured according to ISO 489 on a
molded plaque with a thickness of 1 mm.
[0131] Abbe number was measured according to ISO 489 on a molded
plaque with a thickness of 1 mm.
[0132] Flammability tests were performed following the procedure of
Underwriter's Laboratory Bulletin 94 entitled "Tests for
Flammability of Plastic Materials for Parts in Devices and
Appliances" (ISBN 0-7629-0082-2), Fifth Edition, Dated Oct. 29,
1996, incorporating revisions through and including Dec. 12, 2003.
Several ratings can be applied based on the rate of burning, time
to extinguish, ability to resist dripping, and whether or not drips
are burning. According to this procedure, materials can be
classified as HB, UL94 V0, V1, V2, VA, and/or VB.
BPA Purity Determination
[0133] The BPA purity was determined on the compositions and/or on
the polycarbonate or copolycarbonate.
[0134] About 200 milligrams (mg) of the sample was weighed. It was
dissolved in 5 ml of tetrahydrofuran (THF) and 2 ml of a 10%
solution of potassium hydroxide diluted in methanol. The
depolymerization of polycarbonate was carried out with the use of
these solvents.
[0135] The solution was shaken for 2 hours. Then, 2 milliliters
(ml) of acetic acid was added to protonate the BPA carbonate salts
and decrease the pH. The solution was shaken again for half an hour
for homogenization and dissolution of all precipitates.
[0136] The device used for the HPLC analysis was an Agilent 1100
system. The software used was Agilent ChemStation. The analysis was
carried out on a C18 column. A gradient of polar solvents was used.
It was a mixture of water and methanol. THF was used at the end of
the analysis to clean the column.
[0137] The impurities concentration in the depolymerized
composition is determined by HPLC. Then, the BPA purity can be
deduced via the equation:
wt % of BPA purity=100%-wt % of impurities in depolymerized
composition*254/228.
Examples 1 and Comparative Example 2
[0138] Example 1 and comparative example 2 demonstrate the effect
of using bisphenol A homopolycarbonate made from a high purity BPA
on color stability when blended with PPPBP-BPA copolycarbonate and
molded under aggressive molding conditions. Formulations and
results are shown in Table 2.
TABLE-US-00002 TABLE 2 Component Unit Ex 1 CEx 2 CPC-1 Wt % 63.70
63.70 PC-1B Wt % 11.30 PC-1A Wt % 11.30 PC-2B Wt % 23.95 PC-2A Wt %
23.95 PETS Wt % 0.30 0.30 AO-1 Wt % 0.08 0.08 AO-2 Wt % 0.04 0.04
UVA 234 Wt % 0.30 0.30 Tosylate premix Wt % 0.33 0.33 Total Wt %
100 100 Tosylate ppm 4 4 BPA purity % 99.5 99.4 Property YI after
molding at 310.degree. C./5 min 2.79 2.97 YI after molding at
335.degree. C./10 min 3.72 4.04 YI after molding at 355.degree.
C./5 min 3.45 4.06 YI after molding at 355.degree. C./10 min 4.21
6.87 YI after molding at 355.degree. C./15 min 5.03 10.26
[0139] The data in Table 2 indicates that the use of bisphenol A
homopolycarbonate derived from a high purity BPA (Ex1) provides
improved color stability as compared to a composition containing a
bisphenol A homopolycarbonate derived from a lower purity BPA
(CEx2) when samples are molded at a standard temperature
(310.degree. C.) as well as at aggressive temperatures (335.degree.
C. and 355.degree. C.). The difference is more pronounced at high
temperatures, where the color improvement is almost 50%
(355.degree. C./15) and 39% at 355/10 min
Examples 3-10
[0140] Examples 3-10 demonstrate that effect of using PPPBP-BPA
copolycarbonate derived from a high purity BPA on color stability
under various molding conditions. Formulations and results are
shown in Table 3.
TABLE-US-00003 TABLE 3 Component (wt %) Ex3 CEx4 Ex5 CEx6 Ex7 CEx8
Ex9 CEx10 CPC-1 99.59 98.58 98.25 99.47 CPC-2 99.59 98.58 98.25
99.47 PETS 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 AO-1 0.08 0.08 0.08 0.08
0.08 0.08 0.08 0.08 AO-2 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04
H.sub.3PO.sub.3 premix 0.11 0.11 Tosylate premix-1 1.00 1.00 1.33
1.33 Tosylate premix-2 Total 100 100 100 100 100 100 100 100
Tosylate content (ppm) 0 0 6 6 8 8 0 0 H.sub.3PO.sub.3 content
(ppm) 0 0 0 0 0 0 3 3 BPA purity 99.7 99.4 99.7 99.4 99.7 99.4 99.7
99.4 YI after molding* at 330.degree. C./5 min 2.9 3.72 2.9 2.84
2.8 2.82 3.4 3.55 at 355.degree. C./10 min 24.9 35.59 7.6 15.71 6.5
9.25 21.1 26.74 YI improvement vs CEx at -30 -52 -30 -21
355.degree. C./10 min
[0141] The results in Table 3 indicate that the use of a PPPBP-BPA
copolycarbonate based on a high purity BPA improves color under all
molding conditions, compared to the same composition based on less
pure BPA (Ex 3 versus CEx4, Ex5 versus CEx6, and so on). The use of
an acid stabilizer (butyl tosylate or H.sub.3PO.sub.3) can further
improve the color stability of the composition (for example, Ex5
versus Ex3).
Comparative Example 11 and Example 12
[0142] Comparative example 11 and Example 12 demonstrate the effect
of using BPA homopolycarbonate derived from high purity BPA on
color stability after heat aging. Formulations and results are
shown in Table 5.
TABLE-US-00004 TABLE 5 Component Unit Cex 11 Cex 12 CPC-1 Wt. %
63.7 63.7 PC-1A Wt. % 18.1 PC-2A Wt. % 17.8 PC-1B Wt. % 18.1 PC-2B
Wt. % 17.8 AO-1 Wt. % 0.08 0.08 PETS Wt. % 0.3 0.3 AO-2 Wt. % 0.04
0.04 Total Wt. % 100.00 100.00 BPA purity % 99.5 99.6 Property Heat
aging at 140.degree. C.; .DELTA.YI t = 0* 0 0 Heat aging at
140.degree. C.; .DELTA.YI t = 2658 hrs 11.5 8.3 Heat aging at
140.degree. C.; .DELTA.YI t = 5182 hrs 30.3 22.8 *Thickness of 2.5
mm
[0143] The results in Table 5 indicate that color shifting after
heat aging is significantly improved when using bisphenol A
homopolycarbonate derived from a high purity BPA. Comparing Ex 12
with CEx 11, delta YI is decreased from 11.5 to 8.3 after 2658
hours of aging at 140.degree. C. and the delta YI is decreased from
30.3 to 22.8 after 5000 hours of aging at 140.degree. C.
Examples 13-26
[0144] Examples 13-26 demonstrate the effect of using a blend of
BPA homopolycarbonate and PPPBP-BPA copolycarbonate, both derived
from a high purity, on color stability after heat aging.
Formulations and results are shown in Table 6.
[0145] The data indicates that blends containing bisphenol A
homopolycarbonate and PPPBP-BPA copolycarbonate have excellent
color stability after heat aging when both the bisphenol A
homopolycarbonate and PPPBP-BPA copolycarbonate are derived from a
high purity BPA. The use of a small amount of an acid stabilizer
(butyl tosylate or H.sub.3PO.sub.3 or a combination thereof) can
further improve the color stability of the blends after standard or
abusive molding.
Examples 27-30
[0146] Examples 27-30 compare the heat aging performance of
compositions containing a standard or high purity PPPBP-BPA
copolycarbonate and a standard or high purity bisphenol A
homopolycarbonate, and an ultraviolet light stabilizer, with or
without the presence of an acid stabilizer. Formulations and
results are shown in Table 7.
[0147] The data indicates that blends containing high purity
bisphenol A homopolycarbonate and high purity PPPBP-BPA
copolycarbonate (99.7% purity for total composition) have better
color stability after heat aging as compared to blends containing
standard purity bisphenol A homopolycarbonate and standard purity
PPPBP-BAP copolycarbonate (99.4% purity for total composition).
TABLE-US-00005 TABLE 6 Component (wt %) Ex 13 Ex 14 Ex 15 Ex 16 Ex
17 Ex 18 Ex 19 Ex 20 Ex 21 Ex 22 Ex 23 Ex 24 Ex 25 Ex 26 CPC-2 63.7
63.7 63.7 63.7 63.7 63.7 63.7 63.7 63.7 63.7 63.7 63.7 63.7 63.7
PC-1B 35.58 35.48 35.38 35.42 35.37 35.47 PC-2B 35.58 35.58 35.42
35.37 PC3 35.58 35.48 35.42 35.37 PETS 0.3 0.3 0.3 0.3 0.3 0.3 0.3
0.3 0.3 0.3 0.3 0.3 0.3 0.3 AO-1 0.08 0.08 0.08 0.08 0.08 0.08 0.08
0.08 0.08 0.08 0.08 0.08 0.08 0.08 AO-2 0.04 0.04 0.04 0.04 0.04
0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 UVA 234 0.3 0.3 0.3
0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 H.sub.3PO.sub.3 premix
0.055 0.11 0.055 0.11 0.11 0.055 0.11 Tosylate 0.10 0.10 0.10 0.10
0.20 0.10 0.10 0.10 0.10 0.10 premix-2 Total 100 100 100 100 100
100 100 100 100 100 100 100 100 100 Property YI after molding* at
310.degree. C./ 2.1 1.7 1.8 1.7 2.3 1.8 1.8 1.7 1.8 1.8 2.2 1.8 1.8
1.7 5 min at 330.degree. C./ 3.7 2.0 2.0 2.0 4.7 2.1 1.9 2.0 1.9
2.3 3.8 2.0 1.9 1.9 10 min YI after heat aging* 140.degree. C./0 h
2.1 1.7 1.8 1.7 2.3 1.8 1.8 1.7 1.8 1.8 2.2 1.8 1.8 1.7 140.degree.
C./200 h 2.4 2.1 2.2 2.2 2.4 2.1 2.2 2.2 2.2 2.1 2.1 2.2 2.2 2.2
140.degree. C./550 h 2.9 2.4 2.6 2.6 2.6 2.5 2.6 2.6 2.6 2.5 2.3
2.5 2.7 2.7 140.degree. C./1000 h 3.9 3.0 3.2 3.4 3.0 3.1 3.2 3.2
3.2 3.0 2.7 3.1 3.4 3.4 140.degree. C./1500 h 5.3 3.8 4.1 4.4 3.5
3.9 4.1 4.0 4.0 3.8 3.2 3.9 4.2 4.2 Delta YI after heat ageing at
140.degree. C. compared to 0 hrs 140.degree. C./200 h 0.3 0.4 0.4
0.5 0.1 0.3 0.4 0.5 0.4 0.3 -0.1 0.4 0.4 0.5 140.degree. C./550 h
0.8 0.7 0.8 0.9 0.3 0.7 0.8 0.9 0.8 0.7 0.1 0.7 0.9 1 140.degree.
C./1000 h 1.8 1.3 1.4 1.7 0.7 1.3 1.4 1.5 1.4 1.2 0.5 1.3 1.6 1.7
140.degree. C./1500 h 3.2 2.1 2.3 2.7 1.2 2.1 2.3 2.3 2.2 2 1 2.1
2.4 2.5 155.degree. C./0 h 2.1 1.7 1.8 1.7 2.3 1.8 1.8 1.7 1.8 1.8
2.2 1.8 1.8 1.7 155.degree. C./150 h 2.7 2.2 2.4 2.4 2.4 2.3 2.3
2.3 2.4 2.3 2.3 2.4 2.4 2.3 155.degree. C./300 h 3.6 2.8 2.9 3.1
2.7 3.0 3.0 3.0 3.1 2.9 2.7 3.1 3.1 3.0 155.degree. C./550 h 5.5
3.8 4.0 4.4 3.4 4.1 4.3 4.2 4.4 4.1 3.4 4.3 4.4 4.3 155.degree.
C./1000 h 10.3 6.0 6.4 7.7 5.3 6.7 7.1 7.0 7.4 6.9 5.4 7.1 7.7 7.6
155.degree. C./1500 h 16.6 9.3 10.1 12.5 8.6 10.4 11.3 11.3 12.0
11.2 9.1 11.4 13.0 13.0 Delta YI after heat ageing at 155.degree.
C. compared to 0 hrs 155.degree. C./150 h 0.6 0.5 0.6 0.7 0.1 0.5
0.5 0.6 0.6 0.5 0.1 0.6 0.6 0.6 155.degree. C./300 h 1.5 1.1 1.1
1.4 0.4 1.2 1.2 1.3 1.3 1.1 0.5 1.3 1.3 1.3 155.degree. C./550 h
3.4 2.1 2.2 2.7 1.1 2.3 2.5 2.5 2.6 2.3 1.2 2.5 2.6 2.6 155.degree.
C./1000 h 8.2 4.3 4.6 6 3 4.9 5.3 5.3 5.6 5.1 3.2 5.3 5.9 5.9
155.degree. C./1500 h 14.5 7.6 8.3 10.8 6.3 8.6 9.5 9.6 10.2 9.4
6.9 9.6 11.2 11.3 *All the samples tested have a thickness of 1
mm
TABLE-US-00006 TABLE 7 Component (wt %) CEx 27 Ex 28 CEx 29 Ex 30
CPC-1 63.7 63.7 CPC-2 63.7 63.7 PC-1A 24.6 23.0 PC-1B 24.6 23.0
PC-2A 11.3 11.3 PC-2B 11.3 11.3 PETS 0.3 0.3 0.3 0.3 AO-1 0.08 0.08
0.08 0.08 AO-2 0.04 0.04 0.04 0.04 UVA 234 0.3 0.3 0.3 0.3 Tosylate
premix-1 0 0 1.33 1.33 Total 100 100 100 100 Tosylate content (ppm)
0 0 8 8 BPA Purity 99.4 99.7 99.4 99.7 Property YI after heat
aging* 140.degree. C./0 h 3.1 3.3 3.0 3.2 140.degree. C./500 h 4.2
3.9 5.0 4.8 140.degree. C./3000 h 12.0 8.2 19.1 14.5 140.degree.
C./4000 h 13.3 8.9 21.3 16.1 Delta YI after heat ageing at
140.degree. C. compared to 0 hrs 140.degree. C./500 h 1.1 0.6 2 1.6
140.degree. C./3000 h 8.9 4.9 16.1 11.3 140.degree. C./4000 h 10.2
5.6 18.3 12.9 155.degree. C./0 h 3.1 3.3 3.0 3.1 155.degree. C./100
h 3.7 3.4 4.0 4.1 155.degree. C./250 h 4.7 4.0 5.8 5.4 155.degree.
C./500 h 7.3 5.1 10.1 8.2 155.degree. C./750 h 10.2 6.4 15.1 11.0
155.degree. C./1500 h 22.6 12.4 35.0 25.3 155.degree. C./2000 h
30.7 17.6 46.6 35.4 Delta YI after heat ageing at 155.degree. C.
compared to 0 hrs 155.degree. C./100 h 0.6 0.1 1 1 155.degree.
C./250 h 1.6 0.7 2.8 2.3 155.degree. C./500 h 4.2 1.8 7.1 5.1
155.degree. C./750 h 7.1 3.1 12.1 7.9 155.degree. C./1500 h 19.5
9.1 32 22.2 155.degree. C./2000 h 27.6 14.3 43.6 32.3 *All the
samples tested have a thickness of 2.5 mm.
TABLE-US-00007 TABLE 8 Component (wt %) Ex 31 Ex 32 Ex 33 Ex 34 Ex
35 Ex 36 Ex 37 Ex 38 Ex 39 Ex 40 CEx 41 CEx 42 CPC-2 99.28 99.21
99.18 99.16 99.15 99.09 99.08 99.01 99.22 99.17 PETS 0.3 0.3 0.3
0.3 0.3 0.3 0.3 0.3 0.3 0.3 AO-1 0.08 0.08 0.08 0.08 0.08 0.08 0.08
0.08 0.08 0.08 AO-2 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03
0.03 UVA 234 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
H.sub.3PO.sub.3 premix 0.028 0.055 0.055 0.055 0.11 Tosylate
premix-2 0.668 0.067 0.067 0.134 0.134 0.200 0.267 Total 100 100
100 100 100 100 100 100 100 100 Property YI after molding* at
330.degree. C./5 min 4.89 2.79 2.42 2.38 2.54 2.17 2.36 2.34 2.83
2.55 0.75 8.69 at 355.degree. C./10 min 14.80 10.67 11.83 7.84 7.11
5.35 5.78 7.10 12.44 10.92 0.83 at 365.degree. C./5 min 0.87 7.11
at 375.degree. C./5 min 1.12 YI after heat aging* 140.degree. C./0
h 4.20 2.79 2.42 2.38 2.54 2.17 2.36 2.34 2.83 2.55 0.70 10.20
140.degree. C./200 h 4.24 3.10 2.82 2.85 3.09 2.72 2.85 3.03 3.25
2.92 140.degree. C./250 h 1.60 14.33 140.degree. C./550 h 4.54 3.39
3.17 3.26 3.53 3.21 3.32 3.58 3.55 3.25 2.44 17.45 140.degree.
C./1000 h 4.99 3.89 3.72 3.93 4.25 4.02 4.13 4.39 4.09 3.80 4.54
24.11 140.degree. C./1500 h 5.71 4.63 4.50 4.85 5.26 5.10 5.19 5.50
4.88 4.62 Delta YI after heat ageing at 140.0 compared to 0 hrs
140.degree. C./200 h 0.04 0.31 0.4 0.47 0.55 0.55 0.49 0.69 0.42
0.37 140.degree. C./250 h 0.9 4.13 140.degree. C./550 h 0.34 0.6
0.75 0.88 0.99 1.04 0.96 1.24 0.72 0.7 1.74 7.25 140.degree.
C./1000 h 0.79 1.1 1.3 1.55 1.71 1.85 1.77 2.05 1.26 1.25 3.84
13.91 140.degree. C./1500 h 1.51 1.84 2.08 2.47 2.72 2.93 2.83 3.16
2.05 2.07 155.degree. C./0 h 4.19 2.79 2.42 2.38 2.54 2.17 2.36
2.34 2.83 2.55 0.70 10.20 155.degree. C./100 h 1.85 16.14
155.degree. C./150 h 4.68 3.21 2.89 2.98 3.31 2.97 3.19 3.16 3.49
3.11 155.degree. C./250 h 3.29 21.71 155.degree. C./300 h 5.04 3.57
3.30 3.54 3.90 3.61 3.74 3.86 3.88 3.59 155.degree. C./500 h 6.02
30.09 155.degree. C./550 h 5.81 4.30 4.03 4.42 4.86 4.70 4.82 5.04
4.65 4.40 155.degree. C./1000 h 7.75 6.09 5.89 6.49 7.10 7.02 7.12
7.64 6.65 6.45 14.31 44.84 155.degree. C./1500 h 10.76 8.93 8.87
9.60 10.22 10.38 10.39 11.32 9.64 9.60 155.degree. C./2000 h 35.11
66.55 Delta YI after heat ageing at 155.degree. C. compared to 0
hrs 155.degree. C./100 h 1.15 5.94 155.degree. C./150 h 0.49 0.42
0.47 0.6 0.77 0.8 0.83 0.82 0.66 0.56 155.degree. C./250 h 2.59
11.51 155.degree. C./300 h 0.85 0.78 0.88 1.16 1.36 1.44 1.38 1.52
1.05 1.04 155.degree. C./500 h 5.32 19.89 155.degree. C./550 h 1.62
1.51 1.61 2.04 2.32 2.53 2.46 2.7 1.82 1.85 155.degree. C./1000 h
3.56 3.3 3.47 4.11 4.56 4.85 4.76 5.3 3.82 3.9 13.61 34.64
155.degree. C./1500 h 6.57 6.14 6.45 7.22 7.68 8.21 8.03 8.98 6.81
7.05 155.degree. C./2000 h 34.41 56.35 *All the samples tested have
a thickness of 1 mm.
Examples 31-42
[0148] Examples 31-42 illustrate the heat aging performance of
compositions containing a PPPBP-BPA copolycarbonate derived from a
high purity BPA with or without the presence of an acid stabilizer.
Formulations and results are shown in Table 8. CEx 41 is commercial
product APEC 2097, and CEx 42 is a known formulation U-100.
[0149] The data indicates that high purity PPPBP-BPA
copolycarbonate has better color stability after heat aging as
compared to other known high heat compositions. The presence of a
small amount of an acid stabilizer (butyl tosylate,
H.sub.3PO.sub.3, or a combination thereof) can further improve the
heat aging performance of high purity PPPBP-BPA
copolycarbonate.
Examples 43-47
[0150] Examples 43-47 compare the heat aging performance of
compositions containing a high purity PPPBP-BPA copolycarbonate or
a standard purity PPPBP-BPA copolycarbonate with or without the
presence of an acid stabilizer. Formulations and results are in
Table 9.
TABLE-US-00008 TABLE 9 Component (wt %) CEx 43 Ex 44 CEx 45 Ex 46
CEx 47 CPC-2 98.5801 99.47 CPC-1 98.5801 99.47 99.58 PETS 0.3 0.3
0.3 0.3 0.3 AO-1 0.08 0.08 0.08 0.08 0.08 AO-2 0.04 0.04 0.04 0.04
0.04 H.sub.3PO.sub.3 premix 0.11 0.11 Tosylate premix-1 0.9999
0.9999 Total 100 100 100 100 100 Property YI after heat aging*
155.degree. C./0 h 2.8 2.9 3.5 3.4 3.7 155.degree. C./250 h 5.6 5.1
6.5 4.6 6.1 155.degree. C./500 h 8.2 7.1 19.6 5.8 8.7 155.degree.
C./1000 h 14.2 11.4 21.1 8.5 15.3 Delta YI after heat ageing at
155.degree. C. compared to 0 hrs 155.degree. C./250 h 2.8 2.2 3 1.2
2.4 155.degree. C./500 h 5.4 4.2 16.1 2.4 5 155.degree. C./1000 h
11.4 8.5 17.6 5.1 11.6 *The samples tested had a thickness of 2.5
mm and were molded at 330.degree. C. at residence time of five
minutes.
[0151] The data indicates that high purity PPPBP-BPA
copolycarbonate has better color stability after heat aging as
compared to standard purity PPPBP-BPA copolycarbonate. The data
also shows that the presence of an acid stabilizer (butyl tosylate
or H.sub.3PO.sub.3) does not improve the heat aging performance of
standard purity PPPBP-BPA copolycarbonate.
Examples 48-53
[0152] Examples 48-53 illustrates various properties of
compositions containing high purity PPPBP-BPA, butyl tosylate, and
optionally a high purity BPA homopolycarbonate. Formulations and
results are shown in Table 10. About 0.0002 wt % of a dye package
was also present.
TABLE-US-00009 TABLE 10 Component Unit Ex 48 Ex 49 Ex 50 Ex 51 Ex
52 Ex 53 CPC-2 wt % 63.7 63.7 63.7 99.31 99.01 98.83 PC-1A wt %
28.68 28.38 23.9 0 0 0 PC-2A wt % 7 7 11.3 0 0 0 Tosylate premix-2
wt % 0.2 0.2 0.2 0.27 0.27 0.27 AO-1 wt % 0.08 0.08 0.08 0.08 0.08
0.08 AO-2 wt % 0.04 0.04 0.04 0.04 0.04 0.04 PETS wt % 0.3 0.3 0.3
0.3 0.3 0.3 UVA234 wt % 0 0.3 0.3 0 0.3 0.3 Rimar salt wt % 0 0
0.08 0 0 0.08 Octaphenylcyclotetrasiloxane wt % 0 0 0.1 0 0 0.1
Tensile Modulus, 1 mn/min MPa 2488 2511 2522 2550 2589 2571 Tensile
Stress, yield, 50 mm/mm MPa 76 77 77 82 83 82 Tensile Stress,
break, 50 mm/mm MPa 64 69 67 65 65 65 Tensile Strain, yield, 50
mm/mm % 6.4 6.9 6.9 7.3 7.3 7.2 Tensile Strain, break, 50 mm/mm %
60 84 78 40 30 27 Flexural Modulus, 2 mm/mm MPa 2524 2518 2526 2547
2634 2574 Flexural Stress, yield, 2 mm/mm MPa 116 117 114 123 125
124 Izod Impact, notched, +23.degree. C. J/m 89 83 80 74 72 76 Izod
Impact, notched, -30.degree. C. J/m NA 79 78 73 68 74 Izod Impact,
notched* +23.degree. C. kJ/m.sup.2 8 8 8 8 7 7 Izod Impact,
notched* -30.degree. C. kJ/m.sup.2 NA 6 7 6 6 7 Vicat Softening
Temp, B/120 .degree. C. 173.1 171.7 171.6 192.9 191.0 189.7 HDT
.degree. C. 164.7 165.5 165.4 186.0 185.0 184.4 MVR at 330.degree.
C./2.16 kg, 300s cm.sup.3/10 min 29.51 30.77 33.27 14.1 15.0 16.7
Transmission at 400 nm, 1 mm % 86.5 85.5 71.4 82.9 Transmission at
400 nm, 2 mm % 84.8 82.4 58.7 78.2 Transmission at 400 nm, 3 mm %
82.8 79.6 48.5 73.6 Transmission at 550 nm, 1 mm % 88.1 88.1 87.2
87.8 Transmission at 550 nm, 2 mm % 86.8 86.7 85.2 86.5
Transmission at 550 nm, 3 mm % 85.5 85.3 83.1 85.0 Transmission at
940 nm, 1 mm % 90.3 90.1 90.1 90.0 Transmission at 940 nm, 2 mm %
90.2 90.0 89.9 89.9 Transmission at 940 nm, 3 mm % 89.9 89.8 89.8
89.6 Transmission at 1310 nm, 1 mm % 90.0 89.8 89.8 89.8
Transmission at 1310 nm, 2 mm % 89.3 89.2 89.1 89.1 Transmission at
1310 nm, 3 mm % 88.6 88.5 88.5 88.4 Total transmission, 1 mm % 89.5
89.0 90.0 89.5 88.7 89.3 Total transmission, 2 mm % 88.4 88.7 88.9
88.1 86.6 88.0 Total transmission, 3 mm % 87.1 7.4 87.8 86.8 84.7
86.7 Haze, 1 mm % 0.4 0.3 0.3 0.4 0.4 0.3 Haze, 2 mm % 0.7 0.3 0.3
0.6 0.6 0.4 Haze, 3 mm % 0.9 0.4 0.4 0.8 0.8 0.5 Refractive index
at 587.6 nm -- 1.602 1.602 NA 1.609 1.609 NA Refractive index at
940 nm -- 1.583 1.583 NA 1.589 1.589 NA Refractive index at 1310 nm
-- 1.577 1.577 NA 1.583 1.583 NA Abbe number -- 30 30 NA 29 29 NA
UL94 rating at 2.5 mm -- NA NA V0 NA NA V0 UL94 rating at 2.0 mm --
NA NA V2 NA NA V2 UL94 rating at 1.5 mm -- NA NA V2 NA NA V2 UL94
rating at 0.8 mm -- NA NA V2 NA NA V2
[0153] Set forth below are various embodiments of the
disclosure.
Embodiment 1
[0154] A copolycarbonate lens formed from a polycarbonate
composition comprising: a copolycarbonate comprising bisphenol A
carbonate units and of second carbonate units of the formula (1)
wherein R.sup.a and R.sup.b are each independently a C.sub.1-12
alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, each R.sup.3 is independently a C.sub.1-6 alkyl, R.sup.4 is
hydrogen, C.sub.2-6 alkyl or phenyl optionally substituted with 1
to 5 C.sub.1-6 alkyl groups, p, q, and j are each independently 0
to 4; and optionally, a bisphenol A homopolycarbonate; wherein the
second carbonate units are present in an amount of 10 to 49 mol %,
preferably 13 to 40 mol % or 35 to 49 mol %, more preferably 18 to
35 mol % based on the sum of the moles of the copolycarbonate and
the bisphenol A homopolycarbonate, the copolycarbonate comprises
less than 2 ppm by weight of each of an ion of lithium, sodium,
potassium, calcium, magnesium, ammonium, chlorine, bromine,
fluorine, nitrite, nitrate, phosphite, phosphate, sulfate, formate,
acetate, citrate, oxalate, trimethylammonium, and triethylammonium,
as measured by ion chromatography, and the polycarbonate
composition has a bisphenol A purity of at least 99.6%, or at least
99.7% as determined by high performance liquid chromatography; and
wherein the polycarbonate composition has: a Vicat B 120 of
155.degree. C. or higher, preferably 165.degree. C. or higher, more
preferably 180.degree. C. or higher as measured according to ISO
306; and an increase in yellowness index of less than 10, or of
less than 7 during 1000 hours of heat aging at 155.degree. C., as
measured by ASTM D1925 on a 1 mm thick molded plaque.
Embodiment 2
[0155] A copolycarbonate lens formed from a polycarbonate
composition comprising: a copolycarbonate comprising bisphenol A
carbonate units and of second carbonate units of the formula (1)
wherein R.sup.a and R.sup.b are each independently a C.sub.1-12
alkyl, C.sub.1-12 alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12
alkoxy, each R.sup.3 is independently a C.sub.1-6 alkyl, R.sup.4 is
hydrogen, C.sub.2-6 alkyl or phenyl optionally substituted with 1
to 5 C.sub.1-6 alkyl groups, p, q, and j are each independently 0
to 4; and wherein the second carbonate units are present in an
amount of 10 to 49 mol %, preferably 13 to 40 mol % or 35 to 49 mol
%, more preferably 18 to 35 mol % based on the sum of the moles of
the copolycarbonate and the bisphenol A homopolycarbonate, the
copolycarbonate comprises less than 2 ppm by weight of each of an
ion of lithium, sodium, potassium, calcium, magnesium, ammonium,
chlorine, bromine, fluorine, nitrite, nitrate, phosphite,
phosphate, sulfate, formate, acetate, citrate, oxalate,
trimethylammonium, and triethylammonium, as measured by ion
chromatography, and the polycarbonate composition has a bisphenol A
purity of at least 99.6%, or at least 99.7% as determined by high
performance liquid chromatography; and wherein the polycarbonate
composition has: a Vicat B 120 of 155.degree. C. or higher,
preferably 165.degree. C. or higher, more preferably 180.degree. C.
or higher as measured according to ISO 306; and a yellowness index
which is at least 20% or at least 30% lower compared to the same
composition having a Bisphenol A purity below 99.6% or below 99.5%,
as measured by ASTM D1925 on a 2.5 mm thick molded plaque with a
melt temperature of 355.degree. C. and a residence time of 10
min.
Embodiment 3
[0156] The copolycarbonate lens of Embodiment 1 or Embodiment 2,
wherein the lens is a flat or planar lens, a curved lens, a
cylindrical lens, a toric or sphero-cylindrical lens, a fresnel
lens, a convex lens, a biconvex lens, a concave lens, a biconcave
lens, a convex-concave lens, a plano-convex lens, a plano-concave
lens, a lenticular lens, a gradient index lens, an axicon lens, a
conical lens, an astigmatic lens, an aspheric lens, a corrective
lens, a diverging lens, a converging lens, a compound lens, a
photographic lens, a doublet lens, a triplet lens, an achromatic
lens, or a multi-array lens.
Embodiment 4
[0157] The copolycarbonate lens of any one or more of Embodiments 1
to 3, further comprising a macrotexture, a microtexture, a
nanotexture, or a combination thereof on a surface of the lens.
Embodiment 5
[0158] The copolycarbonate lens of any one or more of Embodiments 1
to 4, wherein the lens has one or more of: a thickness of 0.1 mm to
50 cm, or 0.1 mm to 10 cm, 0.1 mm to 1 cm, or 0.1 mm to 0.5 cm, or
0.1 mm to 50 mm measured at the thickest part of the lens,
preferably a thickness of 0.25 to 2.5 mm, or 0.5 to 2.4 mm, or 0.8
to 2.3 mm, measured at the center of the lens; an effective lens
area of 0.2 mm.sup.2 to 10 m.sup.2, or 0.2 mm.sup.2 to 1 m.sup.2,
or 0.2 mm.sup.2 to 10 cm.sup.2, or 0.2 mm.sup.2 to 5 mm.sup.2, or
0.2 mm.sup.2 to 100 mm.sup.2; a diameter of an effective lens area
of 0.1 mm to 500 cm, or 0.25 mm to 50 cm, or 0.5 mm to 1 cm, or 0.5
mm to 10 mm; or an overall diameter of 0.1 mm to 500 cm, or 0.25 mm
to 100 cm, or 0.5 mm to 2 cm, or 0.5 mm to 20 mm.
Embodiment 6
[0159] The copolycarbonate lens of any one or more of Embodiments 1
to 5, further comprising an indicia or a coating disposed on at
least a portion of one or both surface of the polycarbonate
lens.
Embodiment 7
[0160] The copolycarbonate lens of Embodiment 6, wherein the
coating is a hard coat, a UV protective coat, an anti-refractive
coat, an anti-reflective coat, a scratch resistant coat, a
hydrophobic coat, a hydrophilic coat, or a combination comprising
at least one of the foregoing, or wherein at least a portion of a
surface of the polycarbonate lens is metallized.
Embodiment 8
[0161] The copolycarbonate lens of any Embodiments 1 to 7, wherein
the copolycarbonate lens wherein the copolycarbonate lens is a
camera lens, a sensor lens, an illumination lens, a safety glass
lens, an ophthalmic corrective lens, or an imaging lens.
Embodiment 9
[0162] The copolycarbonate lens of Embodiment 8, wherein the camera
lens is a mobile phone camera lens, a table camera lens, a security
camera lens, a mobile phone camera lens, a tablet camera lens, a
laptop camera lens, a security camera lens, a camera sensor lens,
or a vehicle camera lens, the sensor lens can be a motion detector
lens, a proximity sensor lens, a gesture control lens, an infrared
sensor lens, or a camera sensor lens, the illumination lens is an
indoor lighting lens, an outdoor lighting lens, vehicle headlamp
lens, a vehicle foglight lens, a vehicle rearlight lens, a vehicle
running light lens, a vehicle foglight lens, a vehicle interior
lens, an a light emitting diode lens, or an organic light emitting
diode lens, the safety glass lens is a glasses lens, a goggles
lens, a visor, or a helmet lens, the ophthalmic corrective lens is
a monocle lens, a corrective glasses lens, or a contact lens, or
the imaging lens is a scanner lens, a projector lens, a magnifying
glass lens, a microscope lens, a telescope lens, a security lens,
or a reading glasses lens.
Embodiment 10
[0163] The copolycarbonate lens of any one or more of Embodiments 1
to 9, wherein the second carbonate repeating units in the
copolycarbonate are of the formula (1a) wherein R.sup.5 is
hydrogen, phenyl or methyl, preferably phenyl.
Embodiment 11
[0164] The copolycarbonate lens of any one or more of Embodiments 1
to 10, wherein the copolycarbonate comprises from 60 to 85 mol % of
the bisphenol A carbonate units and 15 to 40 mol % of the second
carbonate units, each based on the total number of carbonate units
in the copolycarbonate.
Embodiment 12
[0165] The copolycarbonate lens of any one or more of Embodiments 1
to 11, wherein the copolycarbonate further comprises at least 5 mol
% of third carbonate units different from the bisphenol A carbonate
units and the second carbonate unit, based on the total number of
carbonate units in the copolycarbonate, the third carbonate units
comprising carbonate units of the formulas (3)-(7): wherein R.sup.c
and R.sup.d are each independently a C.sub.1-12 alkyl, C.sub.1-12
alkenyl, C.sub.3-8 cycloalkyl, or C.sub.1-12 alkoxy, each R.sup.6
is independently C.sub.1-3 alkyl or phenyl, X.sup.a is a C.sub.6-12
polycyclic aryl, C.sub.3-18 mono- or polycycloalkylene, C.sub.3-18
mono- or polycycloalkylidene, -(Q.sup.1).sub.x-G-(Q.sup.2).sub.y-
group wherein Q.sup.1 and Q.sup.2 are each independently a
C.sub.1-3 alkylene, G is a C.sub.3-10 cycloalkylene, x is 0 or 1,
and y is 1, or --C(P)(P.sup.2)-- wherein P.sup.1 is C.sub.1-12
alkyl and P.sup.2 is C.sub.6-12 aryl, and m and n are each
independently 0 to 4, or a combination thereof.
Embodiment 13
[0166] The copolycarbonate lens of Embodiment 5 wherein the
copolycarbonate comprises from 15 to 70 mole percent of the
bisphenol A carbonate units, 5 to 50 mole percent of the second
carbonate units, and 5 to 50 mole percent of the third carbonate
units, each based on the total number of carbonate units in the
copolycarbonate.
Embodiment 14
[0167] The copolycarbonate lens of any one or more of Embodiments 1
to 14, wherein the copolycarbonate has a hydroxyl end group content
of less than 200 ppm and the bisphenol A homopolycarbonate has a
hydroxyl end group content of less than 150 ppm and a sulfur
content of less than 2 ppm as measured by a Total Sulfur Analysis
based on combustion and coulometric detection.
Embodiment 15
[0168] The copolycarbonate lens of any one or more of Embodiments 1
to 14, wherein the polycarbonate composition comprises less than 2
ppm by weight of each of an ion of lithium, sodium, potassium,
calcium, magnesium, ammonium, chlorine, bromine, fluorine, nitrite,
nitrate, phosphite, phosphate, sulfate, formate, acetate, citrate,
oxalate, trimethylammonium, and triethylammonium, as measured by
ion chromatography.
Embodiment 16
[0169] The copolycarbonate lens of Embodiments 1 to 15, wherein the
copolycarbonate has a hydroxyl end group content of less than 200
ppm and the optional bisphenol A homopolycarbonate has a hydroxyl
end group content of less than 150 ppm.
Embodiment 17
[0170] The copolycarbonate lens of any one or more of Embodiments 1
to 16, wherein the optional bisphenol A homopolycarbonate has a
sulfur content of less than 2 ppm, or the copolycarbonate, the
optional bisphenol A homopolycarbonate, or both are derived from a
bisphenol A having a sulfur content of less than 2 ppm, each as
measured by a Total Sulfur Analysis based on combustion and
coulometric detection, or the the optional bisphenol A
homopolycarbonate.
Embodiment 18
[0171] The copolycarbonate lens of any one or more of Embodiments 1
to 17, wherein the polycarbonate composition further comprises 2 to
25 ppm, preferably 4 to 15 ppm, more preferably 6 to 12 ppm of an
acid stabilizer, the acid stabilizer comprising a Bronsted acid, a
Lewis acid, an acid or an ester thereof containing a sulfur atom,
or a combination comprising at least one of the foregoing.
Embodiment 19
[0172] The copolycarbonate lens of Embodiment 18, wherein the acid
stabilizer comprises phosphoric acid; phosphorus acid;
hypophosphorous acid; pyrophosphoric acid; polyphosphoric acid; an
organo sulfonic stabilizer of the formula (8) wherein each R.sup.7
is independently a C.sub.1-30 alkyl, C.sub.6-30 aryl, C.sub.7-30
alkylarylene, C.sub.7-30 arylalkylene, or a polymer unit derived
from a C.sub.2-32 ethylenically unsaturated aromatic sulfonic acid
or its ester, and R.sup.8 is hydrogen; or R.sup.8 is C.sub.1-30
alkyl; or R.sup.8 is a group of the formula
--S(.dbd.O).sub.2--R.sup.7; or a combination comprising at least
one of the foregoing, preferably wherein the acid stabilizer
comprises phosphoric acid, phosphorus acid, butyl tosylate,
p-toluene sulfonic acid, or a combination thereof.
Embodiment 20
[0173] The copolycarbonate lens of any one or more of Embodiments 1
to 19, wherein the copolycarbonate is present in an amount of 90 to
99.8 wt % or 95 to 99.8 wt % based on the total weight of the
polycarbonate composition.
Embodiment 21
[0174] The copolycarbonate lens of any one or more of Embodiments 1
to 20, wherein the copolycarbonate is present in an amount of 45 to
75 wt %, preferably 50 to 70 wt % and the bisphenol A
homopolycarbonate is present in an amount of 25 to 55 wt %,
preferably 30 to 50 wt %, each based on the total weight of the
polycarbonate composition.
Embodiment 22
[0175] The copolycarbonate lens of any one or more of Embodiments 1
to 20, wherein the polycarbonate composition comprising, based on
the total weight of the polycarbonate composition: 60 to 70 wt % of
a copolycarbonate comprising bisphenol A carbonate units and second
carbonate units of the formula (1a) wherein R.sup.5 is hydrogen,
phenyl or methyl, preferably phenyl; 25 to 40 wt % of a bisphenol A
homopolycarbonate; and optionally 6 to 12 ppm of butyl tosylate;
wherein the second carbonate units are present in an amount of 18
to 35 mol % based on the sum of the moles of the copolycarbonate
and the bisphenol A homopolycarbonate, the copolycarbonate
comprises less than 2 ppm by weight of each of an ion of lithium,
sodium, potassium, calcium, magnesium, ammonium, chlorine, bromine,
fluorine, nitrite, nitrate, phosphite, phosphate, sulfate, formate,
acetate, citrate, oxalate, trimethylammonium, and triethylammonium,
as measured by ion chromatography, and the polycarbonate
composition has a bisphenol A purity of at least 99.7% as
determined by high performance liquid chromatography; and wherein
the polycarbonate composition has: an increase in yellowness index
of less than 10 during 1000 hours of heat aging at 155.degree. C.,
as measured by ASTM D1925 on a 2.5 mm thick molded plaque.
Embodiment 23
[0176] The copolycarbonate lens of any one or more of Embodiments 1
to 20, wherein the polycarbonate composition comprises, based on
the total weight of the polycarbonate composition: 96 to 99.9 wt %
of a copolycarbonate comprising bisphenol A carbonate units and
second carbonate units of the formula (1a) wherein R.sup.5 is
hydrogen, phenyl or methyl, preferably phenyl; and optionally 6 to
12 ppm of butyl tosylate; wherein the second carbonate units are
present in an amount of 18 to 35 mol % based on the sum of the
moles of the copolycarbonate and the bisphenol A homopolycarbonate,
the copolycarbonate comprises less than 2 ppm by weight of each of
an ion of lithium, sodium, potassium, calcium, magnesium, ammonium,
chlorine, bromine, fluorine, nitrite, nitrate, phosphite,
phosphate, sulfate, formate, acetate, citrate, oxalate,
trimethylammonium, and triethylammonium, as measured by ion
chromatography, and the polycarbonate composition has a bisphenol A
purity of at least 99.7% as determined by high performance liquid
chromatography; and wherein the polycarbonate composition has: a
Vicat B 120 of 180.degree. C. or higher as measured according to
ISO 306; and an increase in yellowness index of less than 10 during
1000 hours of heat aging at 155.degree. C., as measured by ASTM
D1925 on a 2.5 mm thick molded plaque.
Embodiment 24
[0177] The copolycarbonate lens of any one or more of Embodiments 1
to 23, wherein the polycarbonate composition has one or more of the
following properties: a yellowness index of less than 10 measured
according to ASTM D1925 on a plaque of 2.5 mm thickness molded at a
temperature of 355.degree. C. for a residence time of 10 minutes; a
heat deflection temperature of greater than 150.degree. C. measured
flat on a 80.times.10.times.4 mm bar with a 64 mm span at 0.45 MPa
according to ISO 75/Bf; a haze of less than 1.5, or less than 1.0
and a total transmission greater than 86% or greater than 88%, each
measured according to ASTM D1003-00 using the color space CIE1931
(Illuminant C and a 20 observer) on a molded plaque with a 1.0 mm
thickness; a haze of less than 1.5, or less than 1.0 and a total
transmission greater than 84% or greater than 86%, each measured
according to ASTM D1003-00 using the color space CIE1931
(Illuminant C and a 2.degree. observer) on a molded plaque with a
3.0 mm thickness; a transmission at wavelength of 400 nm of greater
than 75%, or greater than 80% or greater than 85% measured with
Perkin Elmer 950 spectrometer equipped with 15 cm integrated sphere
on a molded plaque with a thickness of 1 mm; a transmission at
wavelength of 550 nm of greater than 85%, or greater than 87% or
greater than 88% measured with Perkin Elmer 950 spectrometer
equipped with 15 cm integrated sphere on a molded plaque with a
thickness of 1 mm; a transmission at wavelength of 940 nm of
greater than 88%, or greater than 89% or greater than 90% measured
with Perkin Elmer 950 spectrometer equipped with 15 cm integrated
sphere on a molded plaque with a thickness of 1 mM; a refractive
index of greater than 1.59 or greater than 1.60 at 587.6 nm or a
refractive index of greater than 1.57 or greater than 1.58 at 940
nm measured according to ISO 489 on a molded plaque with a
thickness of 1 mm; an Abbe number of less than 32 or less than 30
measured according to ISO 489 on a molded plaque with a thickness
of 1 mm; a melt volume flow rate greater than 10 cc/min, measured
at 330.degree. C./2.16 Kg at 360 second dwell according to ISO
1133; an Izod notched impact energy of at least 6 kJ/m.sup.2, or of
at least 8 kJ/m.sup.2, as measured at 23.degree. C. according to
ISO 180/1A using a multipurpose test specimen in accordance with
ISO 3167 TYPE A; an Izod notched impact energy of at least 70 J/m,
or of at least 88 J/m, as measured at 23.degree. C. according to
ASTM D256; an increase in yellowness index of less than 10 during
5000 hours of heat aging at 130.degree. C., as measured by ASTM
D1925 on a 2.5 mm thick molded plaque; an increase in yellowness
index of less than 6, or of less than 5 during 1500 hours of heat
aging at 140.degree. C., as measured by ASTM D1925 on a 1.0 mm
thick molded plaque; an increase in yellowness index of less than
0.5, or of less than 0.3 after 100 hours of hydro ageing at
121.degree. C. in an autoclave, as measured by ASTM D1925 on a 2.5
mm thick molded plaque; a UL94-V0 rating at a thickness of 2.5 mm
or higher; or a UL94-V2 rating at a thickness of 0.8 mm to 1.5
mm.
Embodiment 25
[0178] A method of forming the copolycarbonate lens of any
Embodiments 1 to 24, comprising molding, thermoforming, extruding,
calendaring, or casting the polycarbonate composition to form the
lens.
Embodiment 26
[0179] A device comprising the copolycarbonate lens of any one or
more of Embodiments 1 to 24, wherein the device is a camera, an
electronic device, a vehicle, a flashlight, a business machine, a
lighting device, an imaging device, a protective article, a vision
corrective article, or a toy.
[0180] The singular forms "a," "an," and "the" include plural
referents unless the context clearly dictates otherwise. "Or" means
"and/or." The endpoints of all ranges directed to the same
component or property are inclusive and independently combinable.
Unless defined otherwise, technical and scientific terms used
herein have the same meaning as is commonly understood by one of
skill in the art to which this invention belongs. As used herein, a
"combination" is inclusive of blends, mixtures, alloys, reaction
products, and the like. A "combination thereof" includes any
combination comprising at least one of the listed components or
properties optionally together with a like component or property
not listed.
[0181] Compounds are described using standard nomenclature. For
example, any position not substituted by any indicated group is
understood to have its valency filled by a bond as indicated, or a
hydrogen atom. A dash ("-") that is not between two letters or
symbols is used to indicate a point of attachment for a
substituent. For example, --CHO is attached through carbon of the
carbonyl group.
[0182] As used herein, the term "hydrocarbyl" and "hydrocarbon"
refers broadly to a substituent comprising carbon and hydrogen,
optionally with 1 to 3 heteroatoms, for example, oxygen, nitrogen,
halogen, silicon, sulfur, or a combination thereof; "alkyl" refers
to a straight or branched chain, saturated monovalent hydrocarbon
group; "alkylene" refers to a straight or branched chain,
saturated, divalent hydrocarbon group; "alkylidene" refers to a
straight or branched chain, saturated divalent hydrocarbon group,
with both valences on a single common carbon atom; "alkenyl" refers
to a straight or branched chain monovalent hydrocarbon group having
at least two carbons joined by a carbon-carbon double bond;
"cycloalkyl" refers to a non-aromatic monovalent monocyclic or
multicyclic hydrocarbon group having at least three carbon atoms;
"aryl" refers to an aromatic monovalent group containing only
carbon in the aromatic ring or rings; "arylene" refers to an
aromatic divalent group containing only carbon in the aromatic ring
or rings; "alkylarylene" refers to an aryl group that has been
substituted with an alkyl group as defined above, with
4-methylphenyl being an exemplary alkylarylene group;
"arylalkylene" refers to an alkyl group that has been substituted
with an aryl group as defined above, with benzyl being an exemplary
arylalkylene group.
[0183] Unless otherwise indicated, each of the foregoing groups can
be unsubstituted or substituted, provided that the substitution
does not significantly adversely affect synthesis, stability, or
use of the compound. The term "substituted" as used herein means
that at least one hydrogen on the designated atom or group is
replaced with another group, provided that the designated atom's
normal valence is not exceeded. When the substituent is oxo (i.e.,
.dbd.O), then two hydrogens on the atom are replaced. Combinations
of substituents and/or variables are permissible provided that the
substitutions do not significantly adversely affect synthesis or
use of the compound. Groups that can be present on a substituted
position include (--NO.sub.2), cyano (--CN), halogen, thiocyano
(--SCN), C.sub.2-6 alkanoyl (e.g., acyl (H.sub.3CC(.dbd.O)--);
carboxamido; C.sub.1-6 or C.sub.1-3 alkyl, cycloalkyl, alkenyl, and
alkynyl; C.sub.1-6 or C.sub.1-3 alkoxy; C.sub.6-10 aryloxy such as
phenoxy; C.sub.1-6 alkylthio; C.sub.1-6 or C.sub.1-3 alkylsulfinyl;
C.sub.1-6 or C.sub.1-3 alkylsulfonyl; C.sub.6-12 aryl having at
least one aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the
like, each ring either substituted or unsubstituted aromatic);
C.sub.7-19 arylalkylene having 1 to 3 separate or fused rings and
from 6 to 18 ring carbon atoms; or arylalkoxy having 1 1 to 3
separate or fused rings and from 6 to 18 ring carbon atoms. The
stated number of carbon atoms includes any substituents.
[0184] All references cited herein are incorporated by reference in
their entirety. While typical embodiments have been set forth for
the purpose of illustration, the foregoing descriptions should not
be deemed to be a limitation on the scope herein. Accordingly,
various modifications, adaptations, and alternatives can occur to
one skilled in the art without departing from the spirit and scope
herein.
* * * * *