U.S. patent application number 13/930007 was filed with the patent office on 2013-10-31 for polycarbonate resin composition having excellent chemical resistance.
The applicant listed for this patent is Cheil Industries Inc.. Invention is credited to Gi Ho Ahn, Jung Ki Kim, Tae Uk Kim.
Application Number | 20130289194 13/930007 |
Document ID | / |
Family ID | 46383606 |
Filed Date | 2013-10-31 |
United States Patent
Application |
20130289194 |
Kind Code |
A1 |
Ahn; Gi Ho ; et al. |
October 31, 2013 |
Polycarbonate Resin Composition Having Excellent Chemical
Resistance
Abstract
A polycarbonate resin composition includes: (A) an aromatic
polycarbonate in an amount of about 5 to about 95% by weight, (B) a
siloxane-based polycarbonate in an amount of about 5 to about 90%
by weight, and (C) a syndiotactic polystyrene in an amount of 0 to
about 5% by weight. The polycarbonate resin composition can have
excellent flowability, injection moldability, impact strength,
chemical resistance, and transparency.
Inventors: |
Ahn; Gi Ho; (Uiwang-si,
KR) ; Kim; Tae Uk; (Uiwang-si, KR) ; Kim; Jung
Ki; (Uiwang-si, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Cheil Industries Inc. |
Gumi-si |
|
KR |
|
|
Family ID: |
46383606 |
Appl. No.: |
13/930007 |
Filed: |
June 28, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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PCT/KR2011/008930 |
Nov 22, 2011 |
|
|
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13930007 |
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Current U.S.
Class: |
524/506 ;
525/101 |
Current CPC
Class: |
C08L 69/00 20130101;
C08G 64/186 20130101; C08L 83/10 20130101; C08L 25/06 20130101;
C08L 25/06 20130101; C08L 83/10 20130101; C08L 69/00 20130101 |
Class at
Publication: |
524/506 ;
525/101 |
International
Class: |
C08L 69/00 20060101
C08L069/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 30, 2010 |
KR |
10-2010-0138606 |
Claims
1. A polycarbonate resin composition comprising: (A) an aromatic
polycarbonate in an amount of about 5 to about 95% by weight, (B) a
siloxane-based polycarbonate in an amount of about 5 to about 90%
by weight, and (C) a syndiotactic polystyrene in an amount of 0 to
about 5% by weight.
2. The polycarbonate resin composition of claim 1, wherein the
aromatic polycarbonate is prepared by reacting (A-1) aromatic
dihydroxy compound with (A-2) carbonate precursor.
3. The polycarbonate resin composition of claim 2, wherein the
aromatic dihydroxy compound (A-2) is a compound represented by
following Chemical Formula 1 or a combination thereof: ##STR00018##
wherein in Chemical Formula 1, R.sub.1 and R.sub.2 are the same or
different and are each independently hydrogen, halogen, or C.sub.1
to C.sub.8 alkyl; a and b are the same or different and are each
independently an integer from 0 to 4; and Z is a single bond,
C.sub.1 to C.sub.8 alkylene, C.sub.2 to C.sub.8 alkylidene, C.sub.5
to C.sub.15 cycloalkylene, C.sub.5 to C.sub.15 cycloalkylidene,
--S--, --SO--, --SO.sub.2--, --O--, or --CO--.
4. The polycarbonate resin composition of claim 2, wherein the
carbonate precursor (A-2) comprises diaryl carbonate in an amount
of about 60 to about 95 mol % and a compound represented by the
following Chemical Formula 3 in an amount of about 5 to about 40
mol %. ##STR00019## wherein in Chemical Formula 3, R.sub.1 is
hydrogen, tertiary butyl, or p-cumyl, and R.sub.2 is tertiary butyl
or p-cumyl.
5. The polycarbonate resin composition of claim 1, wherein the
siloxane-based polycarbonate comprises a compound represented by
the following Chemical Formula 5 in the main chain of a
polycarbonate: ##STR00020## wherein in Chemical Formula 5, R.sub.1
to R.sub.8 are the same or different and are each independently
C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.18 aryl, halogen or
C.sub.1 to C.sub.10 alkoxy substituted C.sub.1 to C.sub.10 alkyl,
or halogen or C.sub.1 to C.sub.10 alkoxy substituted C.sub.6 to
C.sub.18 aryl; A and B are the same or different and are each
independently C.sub.2 to C.sub.12 alkylene, C.sub.8 to C.sub.20
arylene, C.sub.2 to C.sub.12 alkylene including --O-- or --S-- in
the chain thereof, or C.sub.8 to C.sub.20 arylene including --O--
or --S-- in the chain thereof; X and Y are the same or different
and are each independently hydrogen, halogen, C.sub.1 to C.sub.18
alkoxy, C.sub.1 to C.sub.10 alkyl, or C.sub.6 to C.sub.18 aryl; Z
is substituted or unsubstituted C.sub.1 to C.sub.18 alkylene,
substituted or unsubstituted C.sub.6 to C.sub.18 cycloalkylene, or
substituted or unsubstituted C.sub.6 to C.sub.18 arylene; and m and
n are the same or different and are each independently an integer
of 1 to 60, and m+n is a an integer of 8 to 100.
6. The polycarbonate resin composition of claim 5, wherein the
siloxane-based polycarbonate includes the compound represented by
Chemical Formula 5 in an amount of about 1 to about 20% by weight
based on 100% by weight of the siloxane-based polycarbonate.
7. The polycarbonate resin composition of claim 5, wherein the
siloxane-based polycarbonate includes Si in an amount of about 0.3
to about 10% by weight based on 100% by weight of the
siloxane-based polycarbonate.
8. The polycarbonate resin composition of claim 1, wherein the
siloxane-based polycarbonate is prepared by reacting (B-1) one or
more diphenyls and (B-2) bishydroxyarylsiloxane with (B-3) a
carbonate precursor.
9. The polycarbonate resin composition of claim 8, wherein the
diphenyls are compounds represented by the following Chemical
Formula 3 or a combination thereof. ##STR00021## wherein in
Chemical Formula 3, A is a single bond, substituted or
unsubstituted linear or branched C.sub.1 to C.sub.30 alkylene,
substituted or unsubstituted C.sub.2 to C.sub.5 alkenylene,
substituted or unsubstituted C.sub.2 to C.sub.5 alkylidene,
substituted or unsubstituted linear or branched C.sub.1 to C.sub.30
haloalkylene, substituted or unsubstituted C.sub.5 to C.sub.6
cycloalkylene, substituted or unsubstituted C.sub.5 to C.sub.10
cycloalkenylene, substituted or unsubstituted C.sub.5 to C.sub.10
cycloalkylidene, substituted or unsubstituted C.sub.6 to C.sub.30
arylene, substituted or unsubstituted linear or branched C.sub.1 to
C.sub.20 alkoxylene, halogen acid ester group, carbonic acid ester
group, CO, S, or SO.sub.2; R.sub.1 and R.sub.2 are the same or
different and are each independently substituted or unsubstituted
C.sub.1 to C.sub.30 alkyl or substituted or unsubstituted C.sub.6
to C.sub.30 aryl; and n1 and n2 are the same or different and are
each independently an integer from 0 to 4.
10. The polycarbonate resin composition of claim 8, wherein the
bishydroxyarylsiloxane is a compound represented by the following
Chemical Formula 4 or a combination thereof: ##STR00022## wherein
in Chemical Formula 4, R.sub.1 to R.sub.8 are the same or different
and are each independently C.sub.1 to C.sub.10 alkyl, C.sub.6 to
C.sub.18 aryl, halogen or C.sub.1 to C.sub.10 alkoxy substituted
C.sub.1 to C.sub.10 alkyl, or halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.6 to C.sub.18 aryl; A and B are the same or
different and are each independently C.sub.2 to C.sub.12 alkylene,
C.sub.8 to C.sub.20 arylene, C.sub.2 to C.sub.12 alkylene including
--O-- or --S in the chain thereof, or C.sub.8 to C.sub.20 arylene
including --O-- or --S in the chain thereof; X and Y are the same
or different and are each independently hydrogen, halogen, C.sub.1
to C.sub.18 alkoxy, C.sub.1 to C.sub.10 alkyl, or C.sub.6 to
C.sub.18 aryl; Z is substituted or unsubstituted C.sub.1 to
C.sub.18 alkylene, substituted or unsubstituted C.sub.6 to C.sub.18
cycloalkylene, or substituted or unsubstituted C.sub.6 to C.sub.18
arylene; and m and n are the same or different and are each
independently an integer from 1 to 60, and n+m is an integer from 8
to 100.
11. The polycarbonate resin composition of claim 10, wherein the
bishydroxyarylsiloxane is a compound of Chemical Formula 4-1,
Chemical Formula 4-2, Chemical Formula 4-3, Chemical Formula 4-4,
Chemical Formula 4-5, Chemical Formula 4-6, Chemical Formula 4-7,
Chemical Formula 4-8, or a combination thereof. ##STR00023##
##STR00024##
12. The polycarbonate resin composition of claim 10, wherein the
compound represented by Chemical Formula 4 is prepared by (1)
reacting a siloxane which is terminated with hydrogen represented
by the following Chemical Formula 4A and a phenol derivative
represented by the following Chemical Formula 4B to synthesize a
monohydroxysiloxane represented by the following Chemical Formula
4C; and (2) reacting the monohydroxysiloxane and a diene to
synthesize bishydroxyarylsiloxane: ##STR00025## wherein in Chemical
Formula 4A, R.sub.1 and R.sub.2 are the same or different and each
independently C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.18 aryl,
halogen or C.sub.1 to C.sub.10 alkoxy substituted C.sub.1 to
C.sub.10 alkyl, or halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.6 to C.sub.18 aryl; and n is an integer from 4 to
100; ##STR00026## wherein in Chemical Formula 4B, B is C.sub.2 to
C.sub.12 alkylene having a double bond at its terminal, C.sub.8 to
C.sub.20 arylene having a double bond at its terminal, C.sub.2 to
C.sub.12 alkylene having a double bond at its terminal and
including --O-- or --S-- in the chain thereof, or C.sub.8 to
C.sub.20 arylene having a double bond at its terminal and including
--O-- or --S-- in the chain thereof; and Y is hydrogen, halogen,
C.sub.1 to C.sub.18 alkoxy, C.sub.1 to C.sub.10 alkyl, or C.sub.6
to C.sub.18 aryl; ##STR00027## wherein in Chemical Formula 4C,
R.sub.1 and R.sub.2 are the same or different and are each
independently C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.18 aryl,
halogen or C.sub.1 to C.sub.10 alkoxy substituted C.sub.1 to
C.sub.10 alkyl, or halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.6 to C.sub.18 aryl; A is a single bond, C.sub.1
to C.sub.10 alkylene, C.sub.6 to C.sub.18 arylene, C.sub.1 to
C.sub.10 alkylene including --O-- or --S-- in the chain thereof,
C.sub.6 to C.sub.18 arylene including --O-- or --S-- in the chain
thereof; Y is hydrogen, halogen, C.sub.1 to C.sub.18 alkoxy,
C.sub.1 to C.sub.10 alkyl, or C.sub.6 to C.sub.18 aryl; and n is an
integer from 4 to 100.
13. The polycarbonate resin composition of claim 1, wherein the
siloxane-based polycarbonate has a weight average molecular weight
(Mw) of about 10,000 to about 200,000 g/mol.
14. The polycarbonate resin composition claim 1, wherein the
syndiotactic polystyrene has a syndiotactic degree of about 97 to
about 100%.
15. The polycarbonate resin composition of claims 1, wherein the
polycarbonate resin composition further comprises UV stabilizer,
fluorescent brightening agent, lubricant, releasing agent,
nucleating agent, antistatic agent, antioxidant, thermo-stabilizer,
reinforcing material, inorganic additive, pigment, dye, or a
combination thereof.
16. The polycarbonate resin composition of claim 1, having a notch
Izod impact strength of about 45 to 60 kgfcm/cm, wherein the notch
impact strength is measured for a specimen having a thickness of
6.35 mm in accordance with ASTM D256.
17. The polycarbonate resin composition of claim 1, having a
brittle fracture rate of about 0 to about 5%, wherein the brittle
fracture rate is measured by preparing specimens with a size of 5
cm.times.20 cm.times.2 mm by injection molding, immersing the
specimens into a thinner for two minutes, drying the specimens,
placing a metal tip at gate portions of twenty specimens and
dropping a 2 kg load from a height of 70 cm height to hit the gate
portions, and measuring the brittle fracture rate based on the
number of broken specimens.
18. The polycarbonate resin composition of claim 1, having a haze
of about 1.0 to about 2.5%, wherein the haze is measured for a
specimen having a thickness of 2 mm using a Haze meter YDP02-OD
manufactured by Nippon Denshoku.
19. The polycarbonate resin composition of claim 1, having a
transmittance of about 85 to about 90%, wherein the transmittance
is measured for a specimen having a thickness of 2 mm using a Haze
meter YDP02-OD manufactured by Nippon Denshoku.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of International
Application No. PCT/KR2011/008930, filed Nov. 22, 2011, pending,
which designates the U.S., published as WO2012/091293, and is
incorporated herein by reference in its entirety, and claims
priority therefrom under 35 USC Section 120. This application also
claims priority under 35 USC Section 119 to and the benefit of
Korean Patent Application No. 10-2010-0138606, filed Dec. 30, 2010,
the entire disclosure of which is incorporated herein by
reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a polycarbonate resin that
can have excellent chemical resistance.
BACKGROUND OF THE INVENTION
[0003] Polycarbonate resin is a polymeric material which is widely
used as an exterior material for portable electronic devices such
as mobile phones due to its excellent transparency and impact
strength.
[0004] However, if a polycarbonate resin is used as an exterior
material for portable electronic devices, typically a painting
process is required to express a variety of colors. The
polycarbonate resin can be exposed to the diluents solution of the
paint during the painting process. The diluents solution can
penetrate into the polycarbonate resin, which can reduce mechanical
properties and impact strength of the polycarbonate resin.
[0005] Methods used to address these problems include blending the
polycarbonate resin with ester-based polymers, blending the
polycarbonate resin with sulfone-based polymers, and adding a
rubber-based impact reinforcing agent to the polycarbonate resin.
However, the polycarbonate resin may still have insufficient
transparency and impact strength.
SUMMARY OF THE INVENTION
[0006] The present invention provides a polycarbonate resin
composition that can have excellent fluidity. The polycarbonate
resin composition can also have excellent injection moldability,
impact strength, chemical resistance, and/or transparency.
[0007] The polycarbonate resin composition comprises (A) aromatic
polycarbonate in an amount of about 5 to about 95% by weight, (B)
siloxane-based polycarbonate in an amount of about 5 to about 90%
by weight, and (C) syndiotactic polystyrene in an amount of 0 to
about 5% by weight.
[0008] In one embodiment of the present invention, the aromatic
polycarbonate can be prepared by reacting (A-1) aromatic dihydroxy
compound with (A-2) carbonate precursor.
[0009] In one embodiment of the present invention, the
siloxane-based polycarbonate includes a unit represented by the
following Chemical Formula 5 in the main chain of
polycarbonate.
##STR00001##
[0010] In Chemical Formula 5,
[0011] R.sub.1 to R.sub.8 are the same or different and are each
independently C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.18 aryl,
halogen or C.sub.1 to C.sub.10 alkoxy substituted C.sub.1 to
C.sub.10 alkyl, or halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.6 to C.sub.18 aryl;
[0012] A and B are the same or different and are each independently
C.sub.2 to C.sub.12 alkylene, C.sub.8 to C.sub.20 arylene, C.sub.2
to C.sub.12 alkylene including --O-- or --S-- in the chain thereof,
or C.sub.8 to C.sub.20 arylene including O-- or --S-- in the chain
thereof;
[0013] X and Y are the same or different and are each independently
hydrogen, halogen, C.sub.1 to C.sub.18 alkoxy, C.sub.1 to C.sub.10
alkyl, or C.sub.6 to C.sub.18 aryl;
[0014] Z is substituted or unsubstituted C.sub.1 to C.sub.18
alkylene, substituted or unsubstituted C.sub.6 to C.sub.18
cycloalkylene, or substituted or unsubstituted C.sub.6 to C.sub.18
arylene;
[0015] m and m are the same or different and are each independently
an integer of 1 to 60, wherein m+n is an integer of 8 to 100.
[0016] As used herein, unless otherwise defined, the term
"substituted" means that one or more hydrogen atoms of a
substituent is replaced with C.sub.1 to C.sub.6 alkyl, C.sub.6 to
C.sub.18 aryl, halogen or a combination thereof.
[0017] In one embodiment of the present invention, the unit
represented by Chemical Formula 5 can be included in an amount of
about 1 to about 20% by weight based on 100% by weight (the total
weight) of the siloxane-based polycarbonate.
[0018] In another embodiment of the present invention, the amount
of Si in the siloxane-based polycarbonate can be about 0.3 to about
10% by weight based on 100% by weight (the total weight) of the
siloxane-based polycarbonate.
[0019] In another embodiment of the present invention, the
siloxane-based polycarbonate can be prepared by reacting (B-1) one
or more diphenyls and (B-2) bishydroxyarylsiloxane with (B-3)
carbonate precursor.
[0020] In one embodiment of the present invention, the
bishydroxyarylsiloxane can be prepared by (1) reacting siloxane
which is terminated with hydrogen represented by the following
Chemical Formula 4A and a phenol derivative represented by the
following Chemical Formula 4B to synthesize a monohydroxysiloxane
represented by the following Chemical Formula 4C; and (2) reacting
the monohydroxysiloxane and a diene to synthesize
bishydroxyarylsiloxane.
##STR00002##
[0021] In Chemical Formula 4A, R.sub.1 and R.sub.2 are the same or
different and are each independently C.sub.1 to C.sub.10 alkyl,
C.sub.6 to C.sub.15 aryl, halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.1 to C.sub.10 alkyl, or halogen or C.sub.1 to
C.sub.10 alkoxy substituted C.sub.6 to C.sub.18 aryl; and n is an
integer from 4 to 100;
##STR00003##
[0022] In Chemical Formula 4B, B is C.sub.2 to C.sub.12 alkylene
having a double bond at a terminal end thereof, C.sub.8 to C.sub.20
arylene having a double bond at a terminal end thereof, C.sub.2 to
C.sub.12 alkylene group having a double bond at a terminal end
thereof and including --O-- or --S-- in the chain thereof, or
C.sub.8 to C.sub.20 arylene having a double bond at a terminal end
thereof and including --O-- or --S-- in the chain thereof; and Y is
hydrogen, halogen, C.sub.1 to C.sub.18 alkoxy, C.sub.1 to C.sub.10
alkyl, or C.sub.6 to C.sub.18 aryl;
##STR00004##
[0023] In Chemical Formula 4C, R.sub.1 and R.sub.2 are the same or
different and are each independently C.sub.1 to C.sub.10 alkyl,
C.sub.6 to C.sub.18 aryl, halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.1 to C.sub.10 alkyl, or halogen or C.sub.1 to
C.sub.10 alkoxy substituted C.sub.6 to C.sub.18 aryl; A is a single
bond, C.sub.1 to C.sub.10 alkylene, C.sub.6 to C.sub.18 arylene,
C.sub.1 to C.sub.10 alkylene including --O-- or --S-- in the chain
thereof, or C.sub.6 to C.sub.18 arylene including --O-- or --S-- in
the chain thereof; Y is hydrogen, halogen, C.sub.1 to C.sub.18
alkoxy, C.sub.1 to C.sub.10 alkyl, or C.sub.6 to C.sub.18 aryl; and
n is an integer from 4 to 100.
[0024] In one embodiment of the present invention, the
siloxane-based polycarbonate can have a weight average molecular
weight (Mw) from about 10,000 to about 200,000 g/mol.
[0025] In one embodiment of the present invention, the syndiotactic
polystyrene can have a degree of syndiotacticity from about 97 to
about 100%.
[0026] In yet another embodiment of the present invention, the
polycarbonate resin composition further can comprise one or more
additives selected from the group consisting of UV stabilizers,
fluorescent brightening agents, lubricants, releasing agents,
nucleating agents, antistatic agents, antioxidants,
thermo-stabilizers, reinforcing materials, inorganic additives,
pigments, dyes, and combinations thereof.
[0027] In one embodiment of the present invention, the
polycarbonate resin composition can have a melt flow index of about
19 to about 22 g/10 min, wherein the melt flow index is measured
for a 10 kg load at 250.degree. C. in accordance with ASTM
D1238
[0028] In another embodiment of the present invention, the
polycarbonate resin composition can have a flow field length of
about 115 to about 130 mm, wherein the flow field length is
measured for an injection molded spiral specimen having a thickness
of 1 mm prepared at an injection molding temperature of 300 to
320.degree. C. and a mold temperature of 50 to 90.degree. C. using
a 10 oz injection molding machine
[0029] In one embodiment of the present invention, the
polycarbonate resin composition can have a notch Izod impact
strength of about 45 to about 60 kgfcm/cm, wherein the notch Izod
impact strength is measured for a specimen having a thickness 6.35
mm in accordance with ASTM D256.
[0030] In yet another embodiment of the present invention, the
polycarbonate resin composition can have a brittle fracture rate of
about 0 to about 5%, wherein the brittle fracture rate is measured
by preparing specimens with a size of 5 cm.times.20 cm.times.2 mm
by injection molding, immersing these specimens into thinner for
two minutes, followed by drying. A metal tip is placed at the gate
portions of 20 specimens and a 2 kg of load is dropped from a
height of 70 cm to hit the gate portions. The brittle fracture rate
is measured for the broken number of the specimens as a result of
dropping.
[0031] In one embodiment of the present invention, the
polycarbonate resin composition can have a haze of about 1.0 to
about 2.5%, wherein the haze is measured for a specimen having a
thickness of 2 mm using a Haze meter YDP02-OD manufactured by
Nippon Denshoku.
[0032] In one embodiment of the present invention, the
polycarbonate resin composition can have a transmittance of about
85 to about 90%, wherein the transmittance is measured for a
specimen having a thickness of 2 mm using a Haze meter YDP02-OD
manufactured by Nippon Denshoku.
[0033] The polycarbonate resin composition according to the present
invention can have excellent fluidity, injection moldability,
impact strength, chemical resistance, and/or transparency.
DETAILED DESCRIPTION OF THE INVENTION
[0034] The present invention now will be described more fully
hereinafter in the following detailed description of the invention
in which some but not all embodiments of the invention are
described. Indeed, this invention may be embodied in many different
forms and should not be construed as limited to the embodiments set
forth herein; rather, these embodiments are provided so that this
disclosure will satisfy applicable legal requirements.
[0035] The polycarbonate resin composition according to the present
invention can comprise (A) aromatic polycarbonate in an amount of
about 5 to about 95% by weight, (B) siloxane-based polycarbonate in
an amount of about 5 to about 90% by weight, and (C) syndiotactic
polystyrene in an amount of 0 to about 5% by weight.
[0036] (A) Aromatic Polycarbonate
[0037] The aromatic polycarbonate can be prepared by reacting (A-1)
one or more aromatic dihydroxy compounds with (A-2) a carbonate
precursor.
[0038] (A-1) Aromatic Dihydroxy Compound
[0039] The aromatic dihydroxy compound can be a compound
represented by the follow Chemical Formula 1 or a combination
thereof.
##STR00005##
[0040] In Chemical Formula 1,
[0041] R.sub.1 and R.sub.2 are the same or different and are each
independently hydrogen, halogen, or C.sub.1 to C.sub.8 alkyl;
[0042] a and b are the same or different and are each independently
integers from 0 to 4; and
[0043] Z is a single bond, C.sub.1 to C.sub.8 alkylene, C.sub.2 to
C.sub.8 alkylidene, C.sub.5 to C.sub.15 cycloalkylene, C.sub.5 to
C.sub.15 cycloalkylidene, --S--, --SO--, SO.sub.2, --O--, or
--CO--.
[0044] Examples of aromatic dihydroxy compound can include without
limitation bis(hydroxyl aryl) alkanes, such as
bis(4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxy phenyl)methane,
bis(3-chloro-4-hydroxy phenyl)methane, bis(3,5-dibromo-4-hydroxy
phenyl)methane, 1,1-bis(4-hydroxy phenyl)ethane,
1,1-bis(2-tert-butyl-4-hydroxy-3-methyl phenyl)ethane,
2,2-bis(4-hydroxy phenyl)propane (bisphenol A),
2,2-bis(3-methyl-4-hydroxy phenyl)propane,
2,2-bis(2-methyl-4-hydroxy phenyl)propane,
2,2-bis(3,5-dimethyl-4-hydroxy phenyl)propane,
1,1-bis(2-tert-butyl-4-hydroxy-5-methyl phenyl)propane,
2,2-bis(3-chloro-4-hydroxy phenyl)propane,
2,2-bis(3-fluoro-4-hydroxy phenyl)propane,
2,2-bis(3-bromo-4-hydroxy phenyl)propane,
2,2-bis(3,5-difluoro-4-hydroxy phenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxy phenyl)propane,
2,2-bis(3,5-dibromo-4-hydroxy phenyl)propane, 2,2-bis(4-hydroxy
phenyl)butane, 2,2-bis(4-hydroxy phenyl)octane, 2,2-bis(4-hydroxy
phenyl)phenyl methane, 2,2-bis(4-hydroxy-1-methyl phenyl)propane,
1,1-bis(4-hydroxy-tert-butyl phenyl)propane,
2,2-bis(4-hydroxy-3-bromophenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethyl phenyl)propane,
2,2-bis(4-hydroxy-3-chlorophenyl)propane,
2,2-bis(4-hydroxy-3,5-dichloro phenyl)propane,
2,2-bis(4-hydroxy-3,5-dibromo phenyl)propane,
2,2-bis(3-bromo-4-hydroxy-5-chloro phenyl)propane,
2,2-bis(3-phenyl-4-hydroxy phenyl)propane, 2,2-bis(4-hydroxy
phenyl)butane, 2,2-bis(3-methyl-4-hydroxy phenyl)butane,
1,1-bis(2-butyl-4-hydroxy-5-methyl phenyl)butane,
1,1-bis(2-tert-butyl-4-hydroxy-5-methyl phenyl)butane,
1,1-bis(2-tert-butyl-4-hydroxy-5-methyl phenyl)isobutane,
1,1-bis(2-tert-amyl-4-hydroxy-5-methyl phenyl)butane,
2,2-bis(3,5-dichloro-4-hydroxy phenyl)butane,
2,2-bis(3,5-dibromo-4-hydro phenyl)butane, 4,4-bis(4-hydroxy
phenyl)heptane, 1,1-bis(2-tert-butyl-4-hydroxy-5-methyl
phenyl)heptane, 2,2-bis(4-hydroxy phenyl)octane, and 1,1-(4-hydroxy
phenyl)ethane; bis(hydroxyl aryl)cycloalkanes such as
1,1-bis(4-hydroxy phenyl)cyclopentane, 1,1-bis(4-hydroxy
phenyl)cyclohexane, 1,1-bis(3-methyl-4-hydroxy phenyl)cyclohexane,
1,1-bis(3-cyclohexyl-4-hydroxy phenyl)cyclohexane,
1,1-bis(3-phenyl-4-hydroxy phenyl)cyclohexane, and
1,1-bis(4-hydroxy phenyl)-3,5,5-trimethylcyclohexane; bis(hydroxyl
aryl)ethers such as bis(4-hydroxy phenyl)ether, and
bis(4-hydroxy-3-methyl phenyl)ether; bis(hydroxyl aryl)sulfides
such as bis(4-hydroxy phenyl)sulfide and bis(3-methyl-4-hydroxy
phenyl)sulfide; bis(hydroxyl aryl)sulfoxides such as bis(hydroxyl
phenyl)sulfoxide, bis(3-methyl-4-hydroxy phenyl)sulfoxide, and
bis(3-phenyl-4-hydroxy phenyl)sulfoxide; bis(hydroxyl aryl)sulfones
such as bis(4-hydroxy phenyl)sulfone, bis(3-methyl-4-hydroxy
phenyl)sulfone and bis(3-phenyl-4-hydroxy phenyl)sulfone; biphenyl
compounds such as 4,4'-dihydroxy biphenyl,
4,4'-dihydroxy-2,2'-dimethylbiphenyl,
4,4'-dihydroxy-3,3'-dimethylbiphenyl,
4,4'-dihydroxy-3,3'-dicyclobiphenyl, and
3,3'-difluoro-4,4'-dihydroxy biphenyl; and the like; and
combinations thereof.
[0045] Aromatic dihydroxy compounds which can be used other than or
in addition to the compounds represented by the Chemical Formula 1
can include without limitation dihydroxy benzene, halogen or
C.sub.1-C.sub.10 alkyl substituted dihydroxy benzene and the like,
and combinations thereof. Examples can include without limitation
resorcinol, 3-methylresorcinol, 3-ethylresorcinol,
3-propylresorcinol, 3-butylresorcinol, 3-tert-butylresorcinol,
3-phenyl resorcinol, 2,3,4,6-tetrafluororesorcinol,
2,3,4,6-tetrabromoresorcinol, catechol, hydroquinone,
3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone,
3-butylhydroquinone, 3-tert-butylhydroquinone,
3-phenylhydroquinone, 3-cumylhydroquinione,
2,5-dichlorohydroquinone, 2,3,5,6-tetramethylhydroquinone,
2,3,5,6-tetra-tert-butylhydroquinone,
2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromo hydroquinone
and the like, and combinations thereof.
[0046] In one embodiment of the present invention,
2,2-bis(4-hydroxy phenyl)propane (bisphenol A) can be used as the
aromatic dihydroxy compound.
[0047] (A-2) Carbonate Precursors
[0048] Examples of the carbonate precursor can include without
limitation dimethyl carbonate, diethyl carbonate, dibutyl
carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl
carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate,
dinaphthyl carbonate, bis(diphenyl) carbonate, carbonyl
chloride(phosgene), triphosgen, diphosgene, carbonyl bromide,
bishaloformate and the like. These compounds can be used singly or
as a mixture of two or more. In interfacial polymerization,
carbonyl chloride (phosgene) can be used as the carbonate
precursor
[0049] In one embodiment of the present invention, the carbonate
precursor can be used in molar ratio of about 0.9 to about 1.5
based on about 1 mol of the aromatic dihydroxy compound.
[0050] In another embodiment of the present invention, the
carbonate precursor can comprise diaryl carbonate and the compound
represented by the following Chemical Formula 2. In this case, the
thermal resistance and color stability of the polycarbonate resin
composition can be further improved.
##STR00006##
[0051] In Chemical Formula 2, R.sub.1 is hydrogen, tertiary butyl,
or p-cumyl, and R.sub.2 is tertiary butyl or p-cumyl.
[0052] In one embodiment of the present invention, the carbonate
precursor can comprise the diaryl carbonate in an amount of about
60 to 95 about mol % and the compound represented by Chemical
Formula 2 in an amount of about 5 to about 40 mol %.
[0053] The compound represented by Chemical Formula 2 can be input
before or during the ester exchange reaction. These ester exchange
reaction can be executed in the same reaction system.
[0054] In one embodiment of the present invention, the aromatic
dihydroxy compound can be used in a molar ratio of about 0.7 to
about 1.5, for example about 0.8 to about 1.2, based on about 1 mol
of the diaryl carbonate. In this case, the mechanical strength of
the polycarbonate resin composition can be further improved.
[0055] In the present invention, the polycarbonate resin
composition can include the aromatic polycarbonate in an amount of
about 5 to about 95% by weight, for example, about 40 to about 90%
by weight, based on 100% by weight (the total weight) of the
polycarbonate resin composition. In some embodiments, the
polycarbonate resin composition can include the aromatic
polycarbonate in an amount of about 5, 6, 7, 8, 9, 10, 11, 12, 13,
14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30,
31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,
48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64,
65, 66, 67, 68, 69, 70 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81,
82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, or 95% by
weight. Further, according to some embodiments of the present
invention, the aromatic polycarbonate may be present in an amount
of from about any of the foregoing amounts to about any other of
the foregoing amounts.
[0056] When the polycarbonate resin composition includes the
aromatic polycarbonate in an amount within the above range,
fluidity, impact strength, chemical resistance, and/or transparency
can be excellent.
[0057] In exemplary embodiments of the present invention, the
polycarbonate resin composition can include the aromatic
polycarbonate in an amount of about 45% by weight, about 60% by
weight, about 75% by weight, or about 87% by weight based on 100%
by weight of the polycarbonate resin composition.
[0058] (B) Siloxane-Based Polycarbonate
[0059] The siloxane-based polycarbonate can comprise a compound
represented by the following Chemical Formula 5 in the main chain
of polycarbonate.
##STR00007##
[0060] In the above Chemical Formula 5,
[0061] R.sub.1 to R.sub.8 are the same or different and are each
independently C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.18 aryl,
halogen or C.sub.1 to C.sub.10 alkoxy substituted C.sub.1 to
C.sub.10 alkyl, or halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.6 to C.sub.18 aryl;
[0062] A and B are the same or different and are each independently
C.sub.2 to C.sub.12 alkylene, C.sub.8 to C.sub.20 arylene, C.sub.2
to C.sub.12 alkylene including --O-- or --S-- in the chain thereof,
or C.sub.8 to C.sub.20 arylene having --O-- or --S-- in the chain
thereof;
[0063] X and Y are the same or different and are each independently
hydrogen, halogen, C.sub.1 to C.sub.18 alkoxy, C.sub.1 to C.sub.10
alkyl, or C.sub.6 to C.sub.18 aryl;
[0064] Z is substituted or unsubstituted C.sub.1 to C.sub.18
alkylene, substituted or unsubstituted C.sub.6 to C.sub.18
cycloalkylene, or substituted or unsubstituted C.sub.6 to C.sub.18
arylene; and
[0065] m and m are the same or different and are each independently
an integer of 1 to 60, wherein m+n is an integer of 8 to 100.
[0066] As used here, unless otherwise defined, the term
"substituted" means that one or more hydrogen atoms of a
substituent is replaced with C.sub.1 to C.sub.6 alkyl, C.sub.6 to
C.sub.18 aryl, halogen or a combination thereof.
[0067] In the Chemical Formula 5, "alkyl" includes linear or
branched alkyl.
[0068] In the Si--Z--Si bond, Si can be directly bonded to Z or to
a substituent which is included in the Z group.
[0069] In one embodiment of the present invention, R.sub.1 to
R.sub.8 are each independently C.sub.1 to C.sub.6 alkyl, for
example methyl.
[0070] In one embodiment of the present invention, A and B are each
independently C.sub.2 to C.sub.6 alkylene, for example
propylene.
[0071] In yet another embodiment of the present invention, X and Y
are each independently hydrogen or C.sub.1 to C.sub.3 alkoxy, for
example hydrogen or methoxy.
[0072] In one embodiment of the present invention, one to four of
each of X and Y can be independently present on the benzene ring,
for example one to two of each of X and Y can be independently
present on the benzene ring.
[0073] In another embodiment of the present invention, Z is
substituted or unsubstituted C.sub.1 to C.sub.10 alkylene,
substituted or unsubstituted C.sub.6 to C.sub.10 cycloalkylene, or
substituted or unsubstituted C.sub.6 to C.sub.10 arylene. As used
herein with reference to Z, the term substituted can mean that one
or more hydrogen atoms of the substituent is replaced with C.sub.1
to C.sub.6 alkyl, for example C.sub.1 to C.sub.3 alkyl.
[0074] In one embodiment of the present invention, Z has the
following structure:
##STR00008##
[0075] In one embodiment of the present invention, m+n is an
integer from 20 to 50, for example 20 to 40.
[0076] In Chemical Formula 5, since Z is present, it is possible to
modify the interior structure of the siloxane-based polycarbonate
chain by controlling Z. This in turn can allow one to adjust the
physical properties of polycarbonate resin composition depending on
the end use of the same. For example, if Z is arylene, both
transparency and chemical resistance can be further improved as
compared to linear alkylene.
[0077] In another embodiment of the present invention, the
siloxane-based polycarbonate can include the compound represented
by the above Chemical Formula 5 in an amount of about 1 to about
20% by weight, for example about 1 to about 13% by weight, based on
100% by weight (the total weight) of the siloxane-based
polycarbonate. In some embodiments, the siloxane-based
polycarbonate can include the compound represented by the above
Chemical Formula 5 in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20% by weight. Further,
according to some embodiments of the present invention, the
polycarbonate may be present in an amount of from about any of the
foregoing amounts to about any other of the foregoing amounts.
[0078] When the siloxane-based polycarbonate includes the compound
represented by Chemical Formula 5 in an amount within the above
range, both impact strength and transparency of the polycarbonate
resin composition can be excellent.
[0079] In one embodiment of the present invention, the
siloxane-based polycarbonate can comprise Si in an amount of about
0.3 to about 10% by weight, for example about 0.3 to about 7% by
weight, based on 100% by weight (the total weight) of the
siloxane-based polycarbonate. In some embodiments, the
siloxane-based polycarbonate can include Si in an amount of about
0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or
10% by weight. Further, according to some embodiments of the
present invention, Si may be present in an amount of from about any
of the foregoing amounts to about any other of the foregoing
amounts.
[0080] When the siloxane-based polycarbonate includes Si in an
amount within the above range, the polycarbonate resin composition
can have excellent impact strength and transparency.
[0081] In another embodiment of the present invention, the
siloxane-based polycarbonate can be prepared by reacting (B-1) one
or more diphenyls and (B-2) bishydroxyarlysiloxane with (B-3)
carbonate precursor.
[0082] (B-1) Diphenyls
[0083] The diphenyls are compounds represented by the following
Chemical Formula 3 or a combination thereof.
##STR00009##
[0084] In Chemical Formula 3,
[0085] A is a single bond, substituted or unsubstituted linear or
branched C.sub.1 to C.sub.30 alkylene, substituted or unsubstituted
C.sub.2 to C.sub.5 alkenylene, substituted or unsubstituted C.sub.2
to C.sub.5 alkylidene, substituted or unsubstituted linear or
branched C.sub.1 to C.sub.30 haloalkylene, substituted or
unsubstituted C.sub.5 to C.sub.6 cycloalkyene, substituted or
unsubstituted C.sub.5 to C.sub.6 cycloalkenylene group, substituted
or unsubstituted C.sub.5 to C.sub.10 cycloalkylidene, substituted
or unsubstituted C.sub.6 to C.sub.30 arylene, substituted or
unsubstituted linear or branched C.sub.1 to C.sub.20 alkoxylene,
halogen acid ester group, carbonic ester, CO, S, or SO.sub.2;
[0086] R.sub.1 and R.sub.2 are the same or different and are each
independently substituted or unsubstituted C.sub.1 to C.sub.30
alkyl or substituted or unsubstituted C.sub.6 to C.sub.30 aryl;
and
[0087] n.sub.1 and n.sub.2 are the same or different and are each
independently an integer from 0 to 4.
[0088] In Chemical Formula 3, the term "substituted" means that one
or more hydrogen atoms is substituted with halogen, C.sub.1 to
C.sub.30 alkyl, C.sub.1 to C.sub.30 haloalkyl, C.sub.6 to C.sub.30
aryl, C.sub.1 to C.sub.20 alkoxy or a combination thereof.
[0089] Examples of compound represented by Chemical Formula 3 can
include without limitation hydroquinone, resorcinol,
4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (called as
`bisphenol-A`), 2,4-bis(4-hydroxyphenyl)-2-methylbutane,
bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(3-chloro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,
bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone,
bis(4-hydroxyphenyl)ether and the like, and combinations
thereof.
[0090] In one embodiment, the compound represented by Chemical
Formula 3 can include 2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,
1.1-bis(4-hydroxyphenyl)cyclohexane, or a combination thereof, for
example 2,2-bis(4-hydroxyphenyl)propane.
[0091] (B-2) Bishydroxyarylsiloxane
[0092] The bishydroxyarylsiloxane is a compound represented by the
following Chemical Formula 4 or a combination thereof.
##STR00010##
[0093] In Chemical Formula 4,
[0094] R.sub.1 to R.sub.8 are the same or different and are each
independently C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.18 aryl,
halogen or C.sub.1 to C.sub.10 alkoxy substituted C.sub.1 to
C.sub.10 alkyl, or halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.6 to C.sub.18 aryl;
[0095] A and B are the same or different and are each independently
C.sub.2 to C.sub.12 alkylene, C.sub.8 to C.sub.20 arylene, C.sub.2
to C.sub.12 alkylene including --O-- or --S-- in the chain thereof,
or C.sub.8 to C.sub.20 arylene including --O-- or --S-- in the
chain thereof;
[0096] X and Y are the same or different and are each independently
hydrogen, halogen, C.sub.1 to C.sub.18 alkoxy, C.sub.1 to C.sub.10
alkyl, or C.sub.6 to C.sub.18 aryl;
[0097] Z is substituted or unsubstituted C.sub.1 to C.sub.18
alkylene, substituted or unsubstituted C.sub.6 to C.sub.18
cycloalkylene, or substituted or unsubstituted C.sub.6 to C.sub.18
arylene, wherein in the definition of Z, the term "substituted"
means that one or more hydrogen atoms is replaced with C.sub.1 to
C.sub.6 alkyl, C.sub.6 to C.sub.18 aryl, halogen, or a combination
thereof; and
[0098] m and n each are the same or different and are each
independently an integer from 1 to 60, and m+n is an integer from 8
to 100.
[0099] In Chemical Formula 4, the term "alkyl" includes linear
and/or branched alkyl.
[0100] In the Si--Z--Si bond, Si can be bound directly to Z itself
or bound to a substituent included in Z.
[0101] In one embodiment of the present invention, R.sub.1 to
R.sub.8 each are independently C.sub.1 to C.sub.6 alkyl, for
example methyl.
[0102] In one embodiment of the present invention, A and B each are
independently C.sub.2 to C.sub.6 alkylene, for example
propylene.
[0103] In another embodiment of the present invention, X and Y each
are independently hydrogen or C.sub.1 to C.sub.3 alkoxy, for
example hydrogen or methoxy.
[0104] In one embodiment of the present invention, one to four, for
example one to two, of each of X and Y can be independently present
on the benzene ring.
[0105] In another example of the present invention, Z is
substituted or unsubstituted C.sub.1 to C.sub.10 alkylene,
substituted or unsubstituted C.sub.6 to C.sub.10 cycloalkylene, or
substituted or unsubstituted C.sub.6 to C.sub.10 arylene. As used
herein with respect to Z, the term "substituted" means that one or
more hydrogen atoms is replaced with C.sub.1 to C.sub.6 alkyl, for
example C.sub.1 to C.sub.3 alkyl.
[0106] In one embodiment of the present invention, m+n is an
integer from 20 to 50, for example an integer from 20 to 40.
[0107] In one embodiment of the present invention, the
bishydroxyarylsiloxane is a compound represented by one of the
following Chemical Formula 4-1, 4-2, 4-3, 4-4, 4-5, 4-6, 4-7, 4-8,
or a combination thereof.
##STR00011## ##STR00012##
[0108] In one embodiment of the present invention, the compound
represented by Chemical Formula 4 can be prepared by (1) reacting a
siloxane which is terminated with hydrogen represented by the
following Chemical Formula 4A and a phenol derivative represented
by the following Chemical Formula 4B to synthesize
monohydroxysiloxane represented by the following Chemical Formula
4C; and (2) reacting the monohydroxysiloxane and a diene to
synthesize a bishydroxyarylsiloxane.
##STR00013##
[0109] In Chemical Formula 4A, R.sub.1 and R.sub.2 are the same or
different and are each independently C.sub.1 to C.sub.10 alkyl,
C.sub.6 to C.sub.18 aryl, halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.1 to C.sub.10 alkyl, or halogen or C.sub.1 to
C.sub.10 alkoxy substituted C.sub.6 to C.sub.18 aryl; and n is an
integer from 4 to 100;
##STR00014##
[0110] In Chemical Formula 4B, B is C.sub.2 to C.sub.12 alkylene
having a double bond at its terminal, C.sub.8 to C.sub.20 arylene
having a double bond at its terminal, C.sub.2 to C.sub.12 alkylene
having a double bond at its terminal and including --O-- or --S--
in the chain thereof, or C.sub.8 to C.sub.20 arylene having a
double bond at its terminal and including --O-- or --S-- in the
chain thereof; and Y is hydrogen, halogen, C.sub.1 to C.sub.18
alkoxy, C.sub.1 to C.sub.10 alkyl, or C.sub.6 to C.sub.18 aryl;
##STR00015##
[0111] In Chemical Formula 4C, R.sub.1 and R.sub.2 are the same or
different and are each independently C.sub.1 to C.sub.10 alkyl,
C.sub.6 to C.sub.18 aryl, halogen or C.sub.1 to C.sub.10 alkoxy
substituted C.sub.1 to C.sub.10 alkyl, or halogen or C.sub.1 to
C.sub.10 alkoxy substituted C.sub.6 to C.sub.18 aryl; A is a single
bond, C.sub.1 to C.sub.10 alkylene, C.sub.6 to C.sub.18 arylene,
C.sub.1 to C.sub.10 alkylene including --O-- or --S-- in the chain
thereof, or C.sub.6 to C.sub.18 arylene having --O-- or --S-- in
the chain thereof; Y is hydrogen, halogen, C.sub.1 to C.sub.18
alkoxy, C.sub.1 to C.sub.10 alkyl, or C.sub.6 to C.sub.18 aryl; and
n is an integer from 4 to 100.
[0112] The First Stage
[0113] The first stage is a step which synthesizes the monohydroxy
siloxane represented by Chemical Formula 4C by reacting siloxane
which is terminated with hydrogen represented by Chemical Formula
4A and phenol derivative represented by Chemical Formula 4B.
[0114] A catalyst including platinum can be used. For example, the
catalyst can be a platinum atom itself or a compound including
platinum.
[0115] Examples of the catalyst can include without limitation
H.sub.2PtCl.sub.6, Pt.sub.2
{[(CH.sub.2.dbd.CH)Me.sub.2Si].sub.2O}.sub.3,
Rh[(cod).sub.2]BF.sub.4, Rh(PPh.sub.3).sub.4Cl, Pt/C and the like.
These can be used alone or in combination. In exemplary
embodiments, the catalyst can be a Pt/C catalyst, for example 10%
Pt/C catalyst.
[0116] The catalyst can be used in an amount of about 10 to about
500 ppm, for example about 50 to about 150 ppm.
[0117] The first stage reaction can be carried out in an organic
solvent. Examples of the organic solvent can include without
limitation 1,2-dichloroethane, toluene, xylene, dichlorobenzene and
the like. These can be used singly or in combination. In exemplary
embodiments, the solvent can include toluene.
[0118] In the first stage, the reaction temperature and time can be
adjusted according to the reactivity of siloxane which is
terminated with hydrogen represented by Chemical Formula 4A and
phenol derivative represented by Chemical Formula 4B. For example
the first stage can be conducted at a reaction temperature of about
60.degree. C. to about 140.degree. C., for example about
110.degree. C. to about 120.degree. C. and for about 2 to about 12
hours, for example about 3 to about 5 hours.
[0119] The monohydroxysiloxane prepared during the first stage and
represented by Chemical Formula 4C can be purified and then used in
the next stage after purification or can be used in situ during the
next stage without additional purification.
[0120] The Second Stage
[0121] In the second stage the bishydroxyarylsiloxane represented
by Chemical Formula 4 by is synthesized by reacting the
monohydroxysiloxane and diene.
[0122] The diene can be a diene including substituted or
unsubstituted C.sub.1 to C.sub.18 alkyl, substituted or
unsubstituted C.sub.6 to C.sub.18 cycloalkyl, or substituted or
unsubstituted C.sub.6 to C.sub.18 aryl. As used herein with
reference to the diene, the term "substituted" means that one or
hydrogen atoms is replaced with C.sub.1 to C.sub.6 alkyl, C.sub.6
to C.sub.18 aryl, halogen, or a combination thereof.
[0123] In one embodiment of the present invention, the diene can
include substituted or unsubstituted C.sub.1 to C.sub.10 alkyl,
substituted or unsubstituted C.sub.6 to C.sub.10 cycloalkyl, or
substituted or unsubstituted C.sub.6 to C.sub.10 aryl. As used
herein with reference to the diene, the term "substituted" means
that one or more hydrogen atoms is replaced with C.sub.1 to C.sub.6
alkyl, for example C.sub.1 to C.sub.3 alkyl.
[0124] After completing the first stage, the bishydroxyarylsiloxane
can be prepared by reacting monohydroxysiloxane represented by
Chemical Formula 4C with diene in situ without purification by
directly adding diene.
[0125] In the second stage, the reaction temperature and time can
be adjusted according to the reactivity of the monohydroxysiloxane
and diene. For example, the second stage can be conducted at a
temperature of about 60 to about 140.degree. C., for example about
110 to about 120.degree. C. and for about 2 to about 12 hours, for
example about 3 to about 5 hours.
[0126] The bishydroxyarylsiloxane prepared in the second stage can
be purified and recovered through general methods. For example, the
bishydroxyarylsiloxane represented by Chemical Formula 4 can be
obtained by removing the catalyst after filtering the product
prepared by the second stage, concentrating the filtrate from which
catalyst was removed to remove the organic solvent as well as a
by-product of low molecular weight. Also, depending on the purity
of the bishydroxyarylsiloxane, additional purification process can
be further performed.
[0127] For example, the bishydroxyarylsiloxane can be prepared by a
process as set forth in the following Reaction Equation 1.
##STR00016##
[0128] In the above Reaction Equation 1, R.sub.1, R.sub.2, A, B, Y,
Z, and n are the same as defined in Chemical Formula 4A, 4B, 4C,
and 4.
[0129] In Reaction Equation 1, in the presence of a catalyst (for
example Pt/C) and organic solvent (for example toluene), the phenol
derivative and siloxane terminated with hydrogen are reacted with
each other to synthesize monohydroxysiloxane. The diene can be
continuously added in an in situ process in the synthesis of the
bishydroxyarylsiloxane.
[0130] (B-3) Carbonate Precursors
[0131] A carbonate precursor used in the preparation of the
aromatic polycarbonate can be used as a carbonate precursor in the
preparation of the siloxane-based polycarbonate.
[0132] In one embodiment of the present invention, the carbonate
precursor can be used in a molar ratio of about 0.9 to about 1.5
based on about 1 mol of a mixture of the diphenyls and the
bishydroxyarylsiloxane.
[0133] In another embodiment of the present invention, the
weight-average molecular weight (Mw) of the siloxane-based
polycarbonate can be about 10,000 to about 200,000 g/mol, for
example about 20,000 to about 50,000 g/mol.
[0134] In the present invention, the polycarbonate resin
composition can include the siloxane-based polycarbonate in an
amount of about 5 to about 90% by weight, for example about 10 to
about 60% by weight, based on 100% by weight of the polycarbonate
resin composition. In some embodiments, the polycarbonate resin
composition can include the siloxane-based polycarbonate in an
amount of about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,
19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35,
36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52,
53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69,
70 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86,
87, 88, 89, or 90% by weight. Further, according to some
embodiments of the present invention, the siloxane-based
polycarbonate may be present in an amount of from about any of the
foregoing amounts to about any other of the foregoing amounts.
[0135] When the polycarbonate resin composition includes the
siloxane-based polycarbonate in an amount within the above range,
the polycarbonate resin composition can have excellent fluidity,
impact strength, chemical resistance, and transparency.
[0136] In one embodiment of the present invention, the
polycarbonate resin composition can include the siloxane-based
polycarbonate in an amount of about 10% by weight, about 25% by
weight, about 38% by weight, about 40% by weight, or about 55% by
weight based on 100% by weight of the polycarbonate resin
composition.
[0137] (C) Syndiotactic Polystyrene
[0138] In one embodiment of the present invention, the
polycarbonate resin composition can further include (C)
syndiotactic polystyrene.
[0139] Polystyrene is generally categorized as atactic, isotactic,
and syndiotactic, depending on the location of the side chain
benzene ring. Atactic polystyrene has a structure in which the
benzene rings are randomly distributed on both sides of the main
chain (hydrocarbon backbone) of the polymer and syndiotactic
polystyrene has a structure in which benzene rings are positioned
on alternating sides of the hydrocarbon backbone.
[0140] Syndiotactic polystyrene can be prepared using styrene
monomer and a catalyst system comprised of metallocene catalyst and
a cocatalyst. The metallocene catalyst has a structure in which one
or two cycloalkane dienyl group (cyclopentadienyl group, indenyl
group, fluorenyl group, and its derivatives) are bonded to a
transition metal of Group IV of the periodic table of the elements,
such as Ti, Zr, and Hf.
[0141] U.S. Pat. No. 6,010,974, the entire disclosure of which is
incorporated herein by reference, discloses a method of
polymerizing styrene monomer using a new alkyl-bridge dinuclei
metallocene catalyst, silyl-bridge dinuclei metallocene catalyst
and alkyl-silyl bridge dinuclei metallocene catalyst which can
provide polystyrene having high stereo-regularity, high melting
point, and excellent molecular weight distribution.
[0142] U.S. Pat. No. 6,284,700, the entire disclosure of which is
also incorporated herein by reference, discloses a new syndiotactic
polystyrene produced using a catalyst system comprising metallocene
catalyst and cocatalyst.
[0143] In the present invention, the syndiotactic polystyrene can
be about 97% to about 100% syndiotactic, which can provide
excellent chemical resistance.
[0144] In the present invention, the polycarbonate resin
composition can include the syndiotactic polystyrene in an amount
of 0 to about 5% by weight, for example about 1 to about 3% by
weight, based on 100% by weight of the polycarbonate resin
composition. In some embodiments, the polycarbonate resin
composition can include the syndiotactic polystyrene in an amount
of 0 (the syndiotactic polystyrene is not present), about 0 (the
syndiotactic polystyrene is present), 1, 2, 3, 4, or 5% by weight.
Further, according to some embodiments of the present invention,
the syndiotactic polystyrene may be present in an amount of from
about any of the foregoing amounts to about any other of the
foregoing amounts.
[0145] When the polycarbonate resin composition includes the
syndiotactic polystyrene in an amount greater than about 5% by
weight, transparency of polycarbonate resin can be
deteriorated.
[0146] In one embodiment of the present invention, the
polycarbonate resin composition can include the syndiotactic
polystyrene in an amount of 0% by weight, about 1% by weight, about
2% by weight, or about 3% by weight, based on 100% by weight of the
polycarbonate resin composition.
[0147] In another embodiment of this invention, the polycarbonate
resin composition can further contain one or more additives
according to its individual use.
[0148] Examples of the additives can include without limitation UV
stabilizers, fluorescent brightening agents, lubricants, releasing
agents, nucleating agents, anti-static agents, antioxidants,
thermo-stabilizers, reinforcing materials, inorganic additives,
pigments, dyes, and the like. The additives can be used singly or
in combination of two or more.
[0149] The additives can be included in an amount of about 1 to
about 20 parts by weight, for example about 1 to about 5 parts by
weight, based on about 100 parts by weight of a base resin
comprising (A)+(B)+(C) defined above.
[0150] In one embodiment of the present invention, the
polycarbonate resin composition can have a melt flow index of about
19 to about 22 g/10 min. The melt flow index is measured using a 10
kg load at 250.degree. C. in accordance with ASTM D1238.
[0151] In one embodiment of the present invention, the
polycarbonate resin composition can have a flow field length of
about 115 to about 130 mm, wherein the flow field length is
measured for an injection molded spiral specimen having a thickness
of 1 mm prepared at an injection molding temperature of 300 to
320.degree. C. and a mold temperature of 50 to 90.degree. C. with a
10 oz injection molding machine.
[0152] In one embodiment of the present invention, the
polycarbonate resin composition can have a notch Izod impact
strength of about 45 to about 60 kgfcm/cm, wherein the notch Izod
impact strength is measured in accordance with ASTM D256 using a
specimen having a thickness of 6.35 mm.
[0153] In another embodiment of the present invention, the
polycarbonate resin composition can have a brittle fracture rate of
about 0 to about 5%, wherein the brittle fracture rate is measured
by preparing specimens with a size of 5 cm.times.20 cm.times.2 mm
by injection molding, immersing these specimens into thinner for 2
minutes followed by drying, placing a metal tip at the gate
portions of 20 specimens and dropping a 2 kg load from a height of
70 cm to hit the gate portions. The brittle fracture rate is
measured for the broken number of the specimens.
[0154] In one embodiment of the present invention, the
polycarbonate resin composition can have a haze of about 1.0 to
about 2.5%, wherein the haze is measured for a specimen having a
thickness of 2 mm using a Haze meter YDP02-OD manufactured by
Nippon Denshoku.
[0155] In one embodiment of the present invention, the
polycarbonate resin composition can have a transmittance of about
85 to about 90%, wherein the transmittance is measured for a
specimen having a thickness of 2 mm using a Haze meter YDP02-OD
manufactured by Nippon Denshoku.
[0156] The polycarbonate resin composition according to the present
invention can be prepared using conventional techniques for making
a resin composition. For example, the polycarbonate resin
composition according to the present invention can be prepared in
the form of pellets after mixing the components and other optional
additives and then melting and extruding the mixture using an
extruder.
[0157] The polycarbonate resin composition according to the present
invention can be used to manufacture molded products which require
excellent impact strength, chemical resistance, and transparency at
the same time.
[0158] Also, the polycarbonate resin composition according to this
invention can have excellent chemical resistance, and therefore, it
can be used in the manufacture of molded products subject to a
coating/painting process after injection molding, such as portable
electronic devices like cellular phones, digital cameras, MP3
devices, PMPs and the like.
[0159] There is no particular limit in the methods of making the
molded products using the polycarbonate resin composition according
to the present invention. For example, the molded products can be
made using extrusion, injection molding, and casting methods known
in the art. The molded products can be readily made by the skilled
artisan without undue experimentation.
[0160] The present invention can be more easily understood with the
following examples. The following examples are provided to
exemplify the present invention and not intended to limit the scope
of protection which is sought by the scope of the attached
claims.
EXAMPLES OF THE PRESENT INVENTION
Examples
[0161] The composition components used in the examples and
comparative examples are as below.
[0162] (A) Aromatic Polycarbonate
[0163] The polycarbonate (product name: INFINO SC-1080) derived
from bisphenol-A from Cheil Industries is used.
[0164] (B) Siloxane-Based Polycarbonate
[0165] After mixing 130 ml of 9.1% NaOH aqueous solution,
2,2-bis(4-hydroxy phenyl)propane (BPA) (21.1 g, 92.4 mmol),
methyltributylammoniumchloride (1.3 g, 5.3 mmol), and 150 ml of
methylene chloride, these are strongly stirred, and then 50 ml of
methyl chloride solution which is dissolved in triphosgene (10.1 g,
101.7 mmol) is input into the reactor while maintaining the
temperature of the solution at 20.about.25.degree. C. at a pH of
6.about.7 for 10 min. After that, siloxane polymer A (14.3 g, 6.9
mmol) as set forth below in table 1 which is dissolved in 15 ml of
methyl chloride is added and then this solution is stirred for 10
min, while maintaining a pH of 10.about.12 with 50% NaOH solution.
After that, 2,2-bis(4-hydroxy phenyl)propane (BPA) (84.7 g, 371.0
mmol), 150 ml of water, and 150 ml of methylene chloride are input
before stirring the mixture for 1 hour. Here, triethylamine (1.0 g,
9.9 mmol), para-cumylphenyl (3.8 g, 17.9 mmol) are added and then
200 ml of methylene chloride solution which is dissolved in
triphosgene (40.7 g, 411.6 mmol) is slowly added into the reactor
for 1 hour while maintaining a pH of the solution of 10.about.12
with 50% NaOH solution. After completing the stirring, again
stirring is performed for 1 hour to separate the organic layer and
then 200 ml of 10% HCl solution is added to neutralize the
solution. The solution is washed for several times with water till
it reaches to a neutral pH. After removing some of solvent from
organic layer, polymer is precipitated using methanol. This
precipitate is filtered and dried to obtain the polymer in the form
of powder. DOSY analysis of polymer indicates that the silicone
polymer is bound inside the main chain of polycarbonate. .sup.1H
NMR analysis shows that the Si content is 2.5% by weight. The
weight average molecular weight (Mw) of the resin estimated by GPC
analysis is 21,248 g/mol.
TABLE-US-00001 TABLE 1 Substituent in Chemical Formula 5 Siloxane
polymer A A C.sub.3H.sub.6 B C.sub.3H.sub.6 Z ##STR00017##
R.sub.1~R.sub.8 CH.sub.3 X OCH.sub.3 Y OCH.sub.3 m + n 20
[0166] (C) Syndiotactic Polystyrene
[0167] The syndiotactic polystyrene (Product name: 130ZC) from
Idemitsu Kosan is used.
Examples 1-5 and Comparative Examples 1-4
[0168] The above composition components are mixed in the amounts
set forth below in Table 1, dried, and then this mixture is fed
into an extruder at a speed at 60 kg/hr. By using a twin screw
extruder with a screw rpm of 250, diameter of 45 mm, and L/D=36,
the extrusion is performed with a nozzle temperature of
250.about.260.degree. C. The extrusion product is made into pellet
form. Prepared pellets are dried for longer than 3 hours at
110.degree. C. and the injection molding is performed at
300.degree. C. to prepare specimens. The physical properties of the
prepared specimens are measured using the below methods and the
results are indicated in Table 1.
[0169] (1) Fluidity: The melt flow index (MI) is measured at
250.degree. C. and 10 kg load in accordance with ASTM D1238.
[0170] (2) Injection moldability: Flow field length of the specimen
is measured after injection molding a spiral specimen having a
thickness of 1 mm at an injection molding temperature of
300.about.320.degree. C. and a mold temperature of
50.about.90.degree. C. using a 10 oz injection molding machine.
[0171] (3) Impact strength: Izod notch impact strength is measured
for a specimen having a thickness of 1/4'' (6.35 mm) in accordance
with ASTM D256.
[0172] (4) Chemical resistance: After injection molding a specimen
sized 5 cm.times.20 cm.times.2 mm with a pinpoint mold, these
specimens are immersed into thinner from Aekyung Paint for 2 min
and then dried. For 20 numbers of specimens, a metal tip is placed
on the gate portion and a 2 kg of load is dropped from a height of
70 cm so that it hits the gate portion. The brittle fracture rate
is measured based on the number of specimens that are broken by
dropping.
The brittle fracture rate=number of broken specimen/total number of
specimen.times.100
[0173] (5) Transparency: Haze and transmission of a specimen having
a thickness of 2 mm is measured using a Haze meter (model:
YDP02-OD) from Nippon Denshoku.
TABLE-US-00002 TABLE 2 Examples Comparative examples 1 2 3 4 5 1 2
3 4 (A)Aromatic polycarbonate 87 75 60 60 45 100 97 93 90 (B)
Siloxane-based polycarbonate 10 25 40 38 55 0 0 0 0 (C)
Syndiotactic polystyrene 3 0 0 2 0 0 3 7 10 Melt flow index (g/10
min) 20.5 21.0 20.8 20.8 21.0 20.9 20.1 21.1 21.0 Spiral (mm) 120
117 117 127 118 111 117 120 120 Izod impact strength (kgf cm/cm) 55
48 49 57 50 22 31 27 25 Brittle fracture rate (%) 0 0 0 0 0 100 75
60 60 Haze (%) 2.3 1.2 1.5 1.9 2.4 1.2 2.0 7.3 12.4 Transmissivity
(%) 86 89 88 87 85 88 86 71 66 The unit of the amount of each
component is % by weight.
[0174] As shown in the above Table 2, examples 2, 3, and 5 which
include aromatic polycarbonate and siloxane-based polycarbonate
exhibit excellent fluidity, injection moldability, impact strength,
chemical resistance, and transparency. Also, examples 1 and 4
further include syndiotactic polystyrene, and exhibit improved
impact strength and injection moldability.
[0175] In contrast, comparative example 1, which includes only
aromatic polycarbonate, exhibits deteriorated injection
moldability, impact strength, and chemical resistance. Comparative
example 2, which include only aromatic polycarbonate and
syndiotactic polystyrene, exhibit significantly reduced impact
strength and chemical resistance. Comparative examples 2 to 4,
which include increasing amounts of syndiotactic polystyrene,
exhibit significantly decreased transparency.
[0176] Many modifications and other embodiments of the invention
will come to mind to one skilled in the art to which this invention
pertains having the benefit of the teachings presented in the
foregoing description. Therefore, it is to be understood that the
invention is not to be limited to the specific embodiments
disclosed and that modifications and other embodiments are intended
to be included within the scope of the appended claims. Although
specific terms are employed herein, they are used in a generic and
descriptive sense only and not for purposes of limitation, the
scope of the invention being defined in the claims.
* * * * *