U.S. patent application number 15/513926 was filed with the patent office on 2017-10-19 for polycarbonate based resin composition and molded articles thereof.
This patent application is currently assigned to LG CHEM, LTD.. The applicant listed for this patent is LG CHEM, LTD.. Invention is credited to Moo Ho HONG, Ki Jae LEE, Jung Jun PARK, Young Wook SON.
Application Number | 20170298221 15/513926 |
Document ID | / |
Family ID | 56092030 |
Filed Date | 2017-10-19 |
United States Patent
Application |
20170298221 |
Kind Code |
A1 |
SON; Young Wook ; et
al. |
October 19, 2017 |
POLYCARBONATE BASED RESIN COMPOSITION AND MOLDED ARTICLES
THEREOF
Abstract
The present invention relates to a polycarbonate based resin
composition and molded articles thereof, and more particularly, to
a polycarbonate based resin composition of which impact strength,
flowability (fluidity), and the like, are improved, and molded
articles thereof.
Inventors: |
SON; Young Wook; (Daejeon,
KR) ; HONG; Moo Ho; (Daejeon, KR) ; LEE; Ki
Jae; (Daejeon, KR) ; PARK; Jung Jun; (Daejeon,
KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LG CHEM, LTD. |
Seoul |
|
KR |
|
|
Assignee: |
LG CHEM, LTD.
Seoul
KR
|
Family ID: |
56092030 |
Appl. No.: |
15/513926 |
Filed: |
December 4, 2015 |
PCT Filed: |
December 4, 2015 |
PCT NO: |
PCT/KR2015/013244 |
371 Date: |
March 23, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 2201/10 20130101;
C08G 64/1691 20130101; C08L 2205/025 20130101; C08J 5/08 20130101;
C08L 69/005 20130101; C08L 2201/08 20130101; C08G 64/24 20130101;
C08L 83/04 20130101; C09K 21/08 20130101; C08K 5/521 20130101; C08K
2201/003 20130101; C08G 64/085 20130101; C08J 5/00 20130101; C08G
64/186 20130101; C08K 5/005 20130101; C08L 2205/05 20130101; C08K
5/3475 20130101; C09K 21/14 20130101; C08G 77/448 20130101; C08K
5/42 20130101; C08L 2205/03 20130101; C08G 64/06 20130101; C08G
77/14 20130101; C08L 2207/53 20130101; C08G 64/307 20130101; C08L
2205/035 20130101; C08K 5/0066 20130101; C08L 83/10 20130101; C08G
64/22 20130101; C08K 7/14 20130101; C08K 2201/004 20130101; C08L
69/00 20130101; C08L 2205/06 20130101; C08K 3/40 20130101; C08L
83/06 20130101; C08L 2205/02 20130101; C08G 64/18 20130101; C08G
64/1666 20130101; C08G 77/20 20130101; C08K 2201/016 20130101; C08G
64/38 20130101; C08L 51/04 20130101; C08L 69/00 20130101; C08L
83/10 20130101; C08L 69/00 20130101; C08L 83/04 20130101; C08L
83/10 20130101; C08L 83/00 20130101; C08L 83/10 20130101; C08L
69/00 20130101; C08L 69/00 20130101; C08K 5/3475 20130101; C08L
83/04 20130101; C08L 83/10 20130101 |
International
Class: |
C08L 69/00 20060101
C08L069/00; C08G 64/06 20060101 C08G064/06; C08L 83/04 20060101
C08L083/04; C08G 64/08 20060101 C08G064/08; C08G 77/14 20060101
C08G077/14 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 4, 2014 |
KR |
10-2014-0173005 |
Claims
1. A polycarbonate based resin composition comprising: a
copolycarbonate resin including a repeating unit represented by the
following Chemical Formula 1, a repeating unit represented by the
following Chemical Formula 3, and a repeating unit represented by
the following Chemical Formula 4; and a first polycarbonate resin
including a repeating unit represented by the following Chemical
Formula 2: ##STR00020## in Chemical Formula 1, R.sub.1 to R.sub.4
are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10
alkoxy, or halogen, Z.sub.1 is C.sub.1-10 alkylene unsubstituted or
substituted with phenyl, C.sub.3-15 cycloalkylene unsubstituted or
substituted with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO,
##STR00021## in Chemical Formula 2, R.sub.5 to R.sub.12 are each
independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or
halogen, Z.sub.2 and Z.sub.3 are each independently C.sub.1-10
alkylene unsubstituted or substituted with phenyl, C.sub.3-15
cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl,
O, S, SO, SO.sub.2, or CO, and A is C.sub.1-15 alkylene,
##STR00022## in Chemical Formula 3, each of X.sub.1 is
independently C.sub.1-10 alkylene, each of R.sub.13 is
independently hydrogen; C.sub.1-15 alkyl unsubstituted or
substituted with oxiranyl, oxiranyl-substituted C.sub.1-10 alkoxy,
or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy; allyl; C.sub.1-10
haloalkyl; or C.sub.6-20 aryl, and n is an integer of 10 to 200,
##STR00023## in Chemical Formula 4, each of X.sub.2 is
independently C.sub.1-10 alkylene, each of Y.sub.1 is independently
hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy, or
C.sub.6-20 aryl, each of R.sub.14 is independently hydrogen;
C.sub.1-15 alkyl unsubstituted or substituted with oxiranyl,
oxiranyl-substituted C.sub.1-10 alkoxy, or C.sub.6-20 aryl;
halogen; C.sub.1-10 alkoxy; allyl; C.sub.1-10 haloalkyl; or
C.sub.6-20 aryl, and m is an integer of 10 to 200.
2. The polycarbonate based resin composition of claim 1, wherein:
the first polycarbonate resin further includes a repeating unit
represented by Chemical Formula 1.
3. The polycarbonate based resin composition of claim 1, further
comprising a second polycarbonate resin including only a repeating
unit represented by Chemical Formula 1.
4. (canceled)
5. The polycarbonate based resin composition of claim 1, wherein:
the repeating unit represented by Chemical Formula 1 is derived
from one or more aromatic diol compounds selected from the group
consisting of bis(4-hydroxyphenyl)methane,
bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone,
bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane,
bisphenol A, 2,2-bis(4-hydroxyphenyl)butane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane,
2,2-bis(4-hydroxy-3-bromophenyl)propane,
2,2-bis(4-hydroxy-3-chlorophenyl)propane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
bis(4-hydroxyphenyl)diphenylmethane, and
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.
6. The polycarbonate based resin composition of claim 1, wherein:
the repeating unit represented by Chemical Formula 1 is represented
by the following Chemical Formula 1-1: ##STR00024##
7. The polycarbonate based resin composition of claim 1, wherein:
R.sub.5 to R.sub.12 are each independently hydrogen, methyl,
chloro, or bromo.
8. The polycarbonate based resin composition of claim 1, wherein:
Z.sub.1 and Z.sub.2 are each independently a linear or branched
C.sub.1-10 alkylene unsubstituted or substituted with phenyl,
cyclohexane-1,1-diyl, O, S, SO, SO.sub.2, or CO.
9. The polycarbonate based resin composition of claim 1, wherein: A
is a linear C.sub.1-10 alkylene.
10. The polycarbonate based resin composition of claim 1, wherein:
the repeating unit represented by Chemical Formula 2 is represented
by Chemical Formula 2-1: ##STR00025##
11. The polycarbonate based resin composition of claim 2, wherein:
the first polycarbonate resin includes the repeating unit
represented by Chemical Formula 1 and the repeating unit
represented by Chemical Formula 2 at a weight ratio of 1:0.001 to
1:0.3.
12. The polycarbonate based resin composition of claim 1, wherein:
the copolycarbonate resin includes the respective repeating units
so that a weight ratio of the repeating unit represented by
Chemical Formula 1 and a sum of weights of the repeating units
represented by Chemical Formulae 3 and 4 is 1:0.001 to 1:0.5.
13. The polycarbonate based resin composition of claim 1, wherein:
the repeating unit represented by Chemical Formula 3 is represented
by Chemical Formula 3-2: ##STR00026##
14. The polycarbonate based resin composition of claim 12, wherein:
R.sub.13 is methyl.
15. The polycarbonate based resin composition of claim 1, wherein:
the repeating unit represented by Chemical Formula 4 is represented
by Chemical Formula 4-2: ##STR00027##
16. The polycarbonate based resin composition of claim 14, wherein:
R.sub.14 is methyl.
17.-18. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to and the benefit of
Korean Patent Application No. 10-2014-0173005 filed in the Korean
Intellectual Property Office on Dec. 4, 2014, the entire contents
of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a polycarbonate based resin
composition and molded articles thereof, and more particularly, to
a polycarbonate based resin composition of which impact strength,
flowability (fluidity), and the like, are improved, and molded
articles thereof.
BACKGROUND ART
[0003] Polycarbonate resins are prepared by
condensation-polymerization of an aromatic diol such as bisphenol A
with a carbonate precursor such as a phosgene and have excellent
impact strength, dimensional stability, heat resistance,
transparency, and the like. Thus, the polycarbonate resins have
application in a wide range of uses, such as exterior materials of
electrical and electronic products, automobile parts, building
materials, optical components, and the like.
[0004] Recently, in order to apply these polycarbonate resins to
more various fields, many studies have been made to obtain desired
physical properties by copolymerizing two or more aromatic diol
compounds having different structures from each other and
introducing units having different structures in a main chain of
the polycarbonate. In addition, studies for introducing a
polysiloxane structure in a main chain of the polycarbonate have
been undergone, but most of these technologies have disadvantages
in that when a specific physical property is improved, but other
physical properties are deteriorated.
[0005] Meanwhile, recently, as a necessity for forming a thin film
using the polycarbonate resin has increased, a demand for a
polycarbonate based resin having high flowability (fluidity) during
a melting process and thus having excellent melt-processability, or
a composition thereof has increased. In addition, recently,
requirements for various physical properties such as chemical
resistance, impact strength, or the like, required in the
polycarbonate resin have further increased.
[0006] However, generally, in the case of further improving
chemical resistance, impact strength, or the like, of the
polycarbonate based resin or the composition thereof, flowability
may be deteriorated, such that it is difficult to sufficiently
achieve thin-film moldability and melt-processability. Therefore,
it was difficult to satisfy high flowability and melt-fluidity to
exhibit excellent thin-film moldability, or the like, while having
excellent chemical resistance, impact strength, and the like,
required in the polycarbonate based resin.
[0007] Therefore, a polycarbonate based resin of which impact
strength such as low-temperature impact strength, or the like,
flowability (fluidity), melt-processability, and the like, are
simultaneously improved, or a composition thereof has been
continuously required.
DISCLOSURE
Technical Problem
[0008] The present invention has been made in an effort to provide
a polycarbonate based resin composition having advantages of
improved impact strength, flowability (fluidity), processability,
and the like.
[0009] The present invention has been made in an effort to provide
molded articles containing the polycarbonate based resin
composition.
[0010] An exemplary embodiment of the present invention provides a
polycarbonate based resin composition comprising: a copolycarbonate
resin including a repeating unit represented by the following
Chemical Formula 1, a repeating unit represented by the following
Chemical Formula 3, and a repeating unit represented by the
following Chemical Formula 4; and a first polycarbonate resin
including a repeating unit represented by the following Chemical
Formula 2:
##STR00001##
[0011] in Chemical Formula 1,
[0012] R.sub.1 to R.sub.4 are each independently hydrogen,
C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and,
[0013] Z.sub.1 is C.sub.1-10 alkylene unsubstituted or substituted
with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted
with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO,
##STR00002##
[0014] in Chemical Formula 2,
[0015] R.sub.5 to R.sub.12 are each independently hydrogen,
C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen,
[0016] Z.sub.2 and Z.sub.3 are each independently C.sub.1-10
alkylene unsubstituted or substituted with phenyl, C.sub.3-15
cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl,
O, S, SO, SO.sub.2, or CO, and
[0017] A is C.sub.1-15 alkylene,
##STR00003##
[0018] in Chemical Formula 3,
[0019] each of X.sub.1 is independently C.sub.1-10 alkylene,
[0020] each of R.sub.13 is independently hydrogen; C.sub.1-15 alkyl
unsubstituted or substituted with oxiranyl, oxiranyl-substituted
C.sub.1-10 alkoxy, or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy;
allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and
[0021] n is an integer of 10 to 200,
##STR00004##
[0022] in Chemical Formula 4,
[0023] each of X.sub.2 is independently C.sub.1-10 alkylene,
[0024] each of Y.sub.1 is independently hydrogen, C.sub.1-6 alkyl,
halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl,
[0025] each of R.sub.14 is independently hydrogen; C.sub.1-15 alkyl
unsubstituted or substituted with oxiranyl, oxiranyl-substituted
C.sub.1-10 alkoxy, or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy;
allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and
[0026] m is an integer of 10 to 200.
[0027] Another exemplary embodiment of the present invention
provides molded articles containing the polycarbonate based resin
composition.
[0028] Hereinafter, polycarbonate based resin compositions
according to exemplary embodiments of the present invention and
molded articles thereof will be described in more detail.
[0029] Technical terms used herein are only to describe a specific
embodiment, and do not limit the present invention. In addition,
singular forms used in the present specification include plural
forms as long as they do not have clearly different meanings.
[0030] Further, the term `include` or `contain` used in the present
specification is to specify a specific property, region, integer,
step, operation, factor, and/or component, but dose not exclude
presence or addition of another specific property, region, integer,
step, operation, factor, component, and/or group.
[0031] According to the exemplary embodiment of the present
invention, there is provided a polycarbonate based resin
composition comprising a copolycarbonate resin including a
repeating unit represented by the following Chemical Formula 1, a
repeating unit represented by the following Chemical Formula 3, and
a repeating unit represented by the following Chemical Formula 4;
and
[0032] a first polycarbonate resin including a repeating unit
represented by the following Chemical Formula 2:
##STR00005##
[0033] in Chemical Formula 1,
[0034] R.sub.1 to R.sub.4 are each independently hydrogen,
C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and
[0035] Z.sub.1 is C.sub.1-10 alkylene unsubstituted or substituted
with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted
with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO,
##STR00006##
[0036] in Chemical Formula 2,
[0037] R.sub.5 to R.sub.12 are each independently hydrogen,
C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen,
[0038] Z.sub.2 and Z.sub.3 are each independently C.sub.1-10
alkylene unsubstituted or substituted with phenyl, C.sub.3-15
cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl,
O, S, SO, SO.sub.2, or CO, and
[0039] A is C.sub.1-15 alkylene,
##STR00007##
[0040] in Chemical Formula 3,
[0041] each of X.sub.1 is independently C.sub.1-10 alkylene,
[0042] each of R.sub.13 is independently hydrogen; C.sub.1-15 alkyl
unsubstituted or substituted with oxiranyl, oxiranyl-substituted
C.sub.1-10 alkoxy, or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy;
allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and
[0043] n is an integer of 10 to 200,
##STR00008##
[0044] in Chemical Formula 4,
[0045] each of X.sub.2 is independently C.sub.1-10 alkylene,
[0046] each of Y.sub.1 is independently hydrogen, C.sub.1-6 alkyl,
halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl,
[0047] each of R.sub.14 is independently hydrogen; C.sub.1-15 alkyl
unsubstituted or substituted with oxiranyl, oxiranyl-substituted
C.sub.1-10 alkoxy, or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy;
allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and
[0048] m is an integer of 10 to 200.
[0049] The first polycarbonate resin may selectively further
include a repeating unit repeating unit represented by Chemical
Formula 1 in addition to the repeating unit represented by Chemical
Formula 2. The repeating unit represented by Chemical Formula 1 may
have a structure equal to or different from that of the repeating
unit represented by Chemical Formula 1, included in the
copolycarbonate resin.
[0050] As described above, the resin composition according to the
exemplary embodiment may include both of the first polycarbonate
resin having the repeating unit represented by Chemical Formula 2,
including an aliphatic alkylene A group and the copolycarbonate
resin including specific polysiloxane group-containing repeating
units represented by Chemical Formulae 3 and 4, together with the
repeating unit represented by Chemical Formula 1, which is a
repeating unit of a general aromatic polycarbonate. The first
polycarbonate resin and a second polycarbonate resin to be
described below may be distinguished from the copolycarbonate resin
in that a polysiloxane structure is not introduced in a main chain
in the first and second polycarbonate resins, but is introduced in
a main chain in the copolycarbonate resin as in Chemical Formulae 3
and 4. Hereinafter, unless particularly described, the first and
second polycarbonate resins and the copolycarbonate resin may be
distinguished and defined as described above.
[0051] The first polycarbonate resin having the repeating unit
represented by Chemical Formula 2 may allow the resin composition
according to the exemplary embodiment to have higher flowability
(fluidity) by containing the repeating unit having the aliphatic
group A. Further, as a result of continuous experiments by the
present inventors, it was confirmed that the copolycarbonate resin
having the repeating units represented by Chemical Formulae 3 and 4
may allow the resin composition according to the exemplary
embodiment to have improved impact strength (particularly,
low-temperature impact strength) and chemical resistance and a low
yellow index (YI) value by containing a specific polysiloxane
group.
[0052] Therefore, it was confirmed that as the resin composition
according to the exemplary embodiment simultaneously include the
first polycarbonate resin and the copolycarbonate resin, which have
these specific repeating unit structures, the resin composition may
have excellent flowability and melt-fluidity to thereby have
excellent thin-film moldability, and the molded articles thereof
may have excellent chemical resistance, excellent impact strength
such as low-temperature impact strength, or the like, and a low YI
value. Therefore, the resin composition according to the exemplary
embodiment may solve problems of polycarbonate based resins known
in the art, or the like, and be suitably applied to various fields
and uses in which excellent physical properties, and thin-film
molding are required.
[0053] Hereinafter, each of the components capable of being
included in the polycarbonate based resin composition according to
the exemplary embodiment of the present invention will be described
in detail.
(1) Copolycarbonate Resin
[0054] The copolycarbonate resin, which is a component capable of
improving physical properties of an existing aromatic polycarbonate
resin, particularly, impact strength, chemical resistance, a YI
value, and the like, may be included in the resin composition
according to the exemplary embodiment. The copolycarbonate resin
may include the repeating unit represented by Chemical Formula 1,
which is a basic repeating unit of an aromatic polycarbonate based
resin, and the repeating units represented by Chemical Formulae 3
and 4, having a specific polysiloxane unit.
[0055] First, the repeating unit represented by Chemical Formula 1,
which form a basic backbone of the copolycarbonate resin, may be
formed by a reaction of an aromatic diol compound and a carbonate
precursor. The repeating unit represented by Chemical Formula 1 as
described above may also be included to first and second
polycarbonate resins to be described below, and the repeating unit
represented by Chemical Formula 1, included in the copolycarbonate
resin may have a structure equal to or different from that of the
repeating unit represented by Chemical Formula 1, included in the
first and second polycarbonate resins.
[0056] In Chemical Formula 1, R.sub.1 to R.sub.4 may be each
independently, hydrogen, methyl, chloro, or bromo.
[0057] Further, Z.sub.1 may be preferably a linear or branched
C.sub.1-10 alkylene unsubstituted or substituted with phenyl, and
more preferably, methylene, ethane-1,1-diyl, propane-2,2-diyl,
butane-2,2-diyl, 1-phenylethane-1,1-diyl or diphenylmethylene. In
addition, Z.sub.1 may be preferably cyclohexane-1,1-diyl, O, S, SO,
SO.sub.2, or CO.
[0058] Preferably, the repeating unit represented by Chemical
Formula 1 may be derived from one or more aromatic diol compounds
selected from the group consisting of bis(4-hydroxyphenyl)methane,
bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone,
bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide,
bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane,
bisphenol A, 2,2-bis(4-hydroxyphenyl)butane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(4-hydroxy-3,5-dibromophenyl)propane,
2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane,
2,2-bis(4-hydroxy-3-bromophenyl)propane,
2,2-bis(4-hydroxy-3-chlorophenyl)propane,
2,2-bis(4-hydroxy-3-methylphenyl)propane,
2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
bis(4-hydroxyphenyl)diphenylmethane, and
.alpha.,.omega.-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.
[0059] As used herein, `derived from aromatic diol compounds` means
that a hydroxy group of the aromatic diol compound and a carbonate
precursor are reacted to form the repeating unit represented by
Chemical Formula 1.
[0060] For example, when bisphenol A, i.e., an aromatic diol
compound, and triphosgene, i.e., a carbonate precursor, are
polymerized, the repeating unit represented by Chemical Formula 1
is represented by the following Chemical Formula 1-1:
##STR00009##
[0061] As the carbonate precursor, one or more selected from the
group consisting of dimethyl carbonate, diethyl carbonate, dibutyl
carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl
carbonate, bis(chlorophenyl)carbonate, di-m-cresyl carbonate,
dinaphthyl carbonate, bis(diphenyl) carbonate, phosgene,
triphosgene, diphosgene, bromo phosgene, and bishaloformate may be
used. Preferably, triphosgene or phosgene may be used.
[0062] Meanwhile, the copolycarbonate resin may further include the
repeating units represented by Chemical Formulae 3 and 4, wherein
the repeating units represented by Chemical Formulae 3 and 4, which
have a specific polyorganosiloxane structure, may be introduced in
the copolycarbonate resin to improve various physical properties
such as chemical resistance, low-temperature impact strength, the
YI value, and the like.
[0063] In Chemical Formula 3, each of X.sub.1 may be independently
preferably C.sub.2-10 alkylene, more preferably C.sub.2-4 alkylene,
and most preferably propane-1,3-diyl.
[0064] Further, preferably, each of R.sub.13 may be independently
hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl,
3-(oxiranylmethoxy)propyl, fluoro, chloro, bromo, iodo, methoxy,
ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl,
3,3,3-trifluoropropyl, phenyl, or naphthyl. In addition, each of
R.sub.13 may be independently preferably C.sub.1-10 alkyl, more
preferably C.sub.1-6 alkyl, still more preferably C.sub.1-3 alkyl,
and most preferably methyl.
[0065] Further, preferably, n may be an integer of 10 or more, 15
or more, 20 or more, 25 or more, 30 or more, 31 or more, or 32 or
more; and not more than 50, not more than 45, not more than 40, not
more than 39, not more than 38, or not more than 37.
[0066] In Chemical Formula 4, each of X.sub.2 may be independently
preferably C.sub.2-10 alkylene, more preferably C.sub.2-6 alkylene,
and most preferably isobutylene.
[0067] In addition, preferably, Y.sub.1 may be hydrogen.
[0068] Further, preferably, each of R.sub.14 may be independently
hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl,
3-(oxiranylmethoxy)propyl, fluoro, chloro, bromo, iodo, methoxy,
ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl,
3,3,3-trifluoropropyl, phenyl, or naphthyl. In addition, each of
R.sub.14 may be independently preferably C.sub.1-10 alkyl, more
preferably C.sub.1-6 alkyl, still more preferably C.sub.1-3 alkyl,
and most preferably methyl.
[0069] Further, preferably, m may be an integer of 40 or more, 45
or more, 50 or more, 55 or more, 56 or more, 57 or more, or 58 or
more; and not more than 80, not more than 75, not more than 70, not
more than 65, not more than 64, not more than 63, or not more than
62.
[0070] The repeating unit represented by Chemical Formula 3 and the
repeating unit represented by Chemical Formula 4 may be derived
from a siloxane compound represented by Chemical Formula 3-1 and a
siloxane compound represented by Chemical Formula 4-1,
respectively.
##STR00010##
[0071] in Chemical Formula 3-1,
[0072] X.sub.1, R.sub.13, and n are as previously defined.
##STR00011##
[0073] in Chemical Formula 4-1,
[0074] X.sub.2, Y.sub.1, R.sub.14, and m are as previously
defined.
[0075] As used herein, `derived from a siloxane compound` means
that a hydroxy group of each of the siloxane compounds and a
carbonate precursor are reacted to form the repeating unit
represented by Chemical Formula 3 and the repeating unit
represented by the Chemical Formula 4. Further, descriptions of the
carbonate precursors that may be used for the formation of the
repeating units represented by Chemical Formulae 3 and 4 are the
same as those described for the carbonate precursor that can be
used for the formation of the repeating unit represented by
Chemical Formula 1 described above.
[0076] The methods for preparing the siloxane compound represented
by Chemical Formula 3-1 and the siloxane compound represented by
Chemical Formula 4-1 are represented by the following Reaction
Schemes 1 and 2, respectively:
##STR00012##
[0077] in Reaction Scheme 1,
[0078] X.sub.1' is C.sub.2-10 alkenyl, and
[0079] X.sub.1, R.sub.13, and n are as previously defined,
##STR00013##
[0080] in Reaction Scheme 2,
[0081] X.sub.2' is C.sub.2-10 alkenyl, and
[0082] X.sub.2, Y.sub.1, R.sub.14, and m are as previously
defined.
[0083] In Reaction Scheme 1 and Reaction Scheme 2, the reaction may
be preferably conducted in the presence of a metal catalyst. As the
metal catalyst, a Pt catalyst may be preferably used. The Pt
catalyst used herein may include one or more selected from the
group consisting of Ashby catalyst, Karstedt catalyst, Lamoreaux
catalyst, Speier catalyst, PtCl.sub.2 (COD),
PtCl.sub.2(benzonitrile).sub.2, and H.sub.2PtBr.sub.6. The metal
catalyst may be used in an amount of 0.001 parts by weight or more,
0.005 parts by weight or more, or 0.01 parts by weight or more; and
not more than 1 part by weight, not more than 0.1 part by weight,
or not more than 0.05 part by weight, based on 100 parts by weight
of compounds represented by the Chemical Formula 7 or 9.
[0084] Further, a reaction temperature is preferably 80 to
100.degree. C. Further, a reaction time is preferably 1 to 5
hours.
[0085] In addition, the compound represented by Chemical Formula 7
or 9 may be prepared by reacting an organodisiloxane and an
organocyclosiloxane in the presence of an acid catalyst, and n and
m may be adjusted by adjusting amounts of the reactants. A reaction
temperature is preferably 50 to 70.degree. C. Further, a reaction
time is preferably 1 to 6 hours.
[0086] As the organodisiloxane, one or more selected from the group
consisting of tetramethyldisiloxane, tetraphenyldisiloxane,
hexamethyldisiloxane, and hexaphenyldisiloxane may be used. In
addition, as the organocyclosiloxane, for example,
organocyclotetrasiloxane may be used. Examples of the
organocyclotetrasiloxane may include octamethylcyclotetrasiloxane,
octaphenylcyclotetrasiloxane, and the like.
[0087] The organodisiloxane may be used in an amount of 0.1 parts
by weight or more, or 2 parts by weight or more; and not more than
10 parts by weight or not more than 8 parts by weight, based on 100
parts by weight of the organocyclosiloxane.
[0088] As the acid catalyst, one or more selected from the group
consisting of H.sub.2SO.sub.4, HClO.sub.4, AlCl.sub.3, SbCl.sub.5,
SnCl.sub.4 and acid clay (fuller's earth) may be used. Further, the
acid catalyst may be used in an amount of 0.1 parts by weight or
more, 0.5 parts by weight or more, or 1 part by weight or more; and
not more than 10 parts by weight, not more than 5 parts by weight,
or not more than 3 parts by weight, based on 100 parts by weight of
the organocyclosiloxane.
[0089] Physical properties such as chemical resistance, impact
resistance, the YI value, and the like, may be simultaneously and
suitably improved by adjusting the amounts of the repeating units
represented by Chemical Formulae 3 and 4, simultaneously included
in the copolycarbonate resin. To this end, a weight ratio between
the repeating units represented by Chemical Formulae 3 and 4 may be
from 1:99 to 99:1. Preferably, the weight ratio is from 3:97 to
97:3, from 5:95 to 95:5, from 10:90 to 90:10, or from 15:85 to
85:15, and more preferably from 20:80 to 80:20. The weight ratio of
the repeating units may correspond to a weight ratio of siloxane
compounds, for example, the siloxane compound represented by
Chemical Formula 3-1 and the siloxane compound represented by
Chemical Formula 4-1.
[0090] Preferably, the repeating unit represented by Chemical
Formula 3 may be represented by the following Chemical Formula
3-2:
##STR00014##
[0091] In Chemical Formula 3-2, R.sub.13 and n are as previously
defined. Preferably, R.sub.13 may be methyl.
[0092] In addition, preferably, the repeating unit represented by
Chemical Formula 4 may be represented by the following Chemical
Formula 4-2:
##STR00015##
[0093] In Chemical Formula 4-2, R.sub.14 and m are as previously
defined. Preferably, R.sub.14 may be methyl.
[0094] In addition, the above-mentioned copolycarbonate resin may
include each of the repeating units represented by Chemical
Formulae 1, 3, and 4 so that a weight ratio of the repeating unit
represented by Chemical Formula 1 and a sum of weights of the
repeating unit represented by Chemical Formula 3 and the repeating
unit represented by Chemical Formula 4 is from 1:0.001 to 1:0.5,
preferably, from 1:0.005 to 1:0.3, and more preferably, from 1:0.01
to 1:0.2. The weight ratio of the repeating units may correspond to
a weight ratio of the aromatic diol compound used to form the
repeating unit represented by Chemical Formula 1 and the siloxane
compounds used to form the repeating unit represented by Chemical
Formula 3 and the repeating unit represented by Chemical Formula
4.
[0095] As the copolycarbonate resin includes each of the repeating
units at the above-mentioned weight ratio, the copolycarbonate
resin and the resin composition according to the exemplary
embodiment may have excellent low-temperature impact strength,
chemical resistance and low YI values, and a synergic effect with a
first polycarbonate resin to be described below may also be
optimized, such that the resin composition according to the
exemplary embodiment may have more excellent flowability and
thin-film moldability.
[0096] Preferably, the copolycarbonate resin including the
repeating units represented by Chemical Formulae 1, 3, and 4 may be
a random copolymer. In addition, the copolycarbonate resin as
described above may be prepared by a preparation method including
the step of polymerizing two or more aromatic diol compounds
corresponding to the respective repeating units, a carbonate
precursor, and two or more siloxane compounds. The aromatic diol
compounds, the carbonate precursor, and the siloxane compounds are
the same as previously described.
[0097] At the time of the polymerization, the siloxane compounds
may be used in an amount of 0.1 wt % or more, 0.5 wt % or more, 1
wt % or more, or 1.5 wt % or more; and not more than 20 wt %, not
more than 10 wt %, not more than 7 wt %, not more than 5 wt %, not
more than 4 wt %, not more than 3 wt %, or not more than 2 wt %,
based on 100 wt % in total of the aromatic diol compounds, the
carbonate precursor, and the siloxane compounds.
[0098] Further, the aromatic diol compounds may be used in an
amount of 40 wt % or more, 50 wt % or more, or 55 wt % or more; and
not more than 80 wt %, not more than 70 wt %, or not more than 65
wt %, based on 100 wt % in total of the aromatic diol compounds,
the carbonate precursor, and the siloxane compounds.
[0099] The carbonate precursor may be used in an amount of 10 wt %
or more, 20 wt % or more, or 30 wt % or more; and not more than 60
wt %, not more than 50 wt %, or not more than 40 wt %, based on 100
wt % in total of two aromatic diol compounds, the carbonate
precursor, and the siloxane compounds.
[0100] Further, as a polymerization method, an interfacial
polymerization method may be used as one example. In this case, the
polymerization reaction may be carried out at a low temperature
under an atmospheric pressure, and it may be easy to control a
molecular weight. The interfacial polymerization may be preferably
conducted in the presence of an acid binder and an organic solvent.
Furthermore, the interfacial polymerization may include, for
example, the steps of conducting pre-polymerization, then adding a
coupling agent and conducting polymerization again. In this case, a
copolycarbonate having a high molecular weight may be obtained.
[0101] The materials used in the interfacial polymerization are not
particularly limited as long as they may be used in polymerization
of polycarbonates. The used amount thereof maybe controlled as
required.
[0102] The acid binder may include, for example, alkali metal
hydroxides such as sodium hydroxide, potassium hydroxide, or the
like, or amine compounds such as pyridine, or the like.
[0103] The organic solvent is not particularly limited as long as
it is a solvent that can be usually used in the polymerization of
polycarbonates. As one example, halogenated hydrocarbon such as
methylene chloride or chlorobenzene, or the like, may be used.
[0104] Further, during the interfacial polymerization, a reaction
accelerator, for example, a tertiary amine compound such as
triethylamine, tetra-n-butylammonium bromide,
tetra-n-butylphosphonium bromide, or the like, a quaternary
ammonium compound, a quaternary phosphonium compound, or the like,
may be further used for accelerating the reaction.
[0105] In the interfacial polymerization, a reaction temperature
may be preferably from 0 to 40.degree. C. and a reaction time may
be preferably from 10 minutes to 5 hours. Further, during the
interfacial polymerization reaction, pH may be preferably
maintained at 9 or more, or 11 or more.
[0106] In addition, during the interfacial polymerization reaction,
a molecular weight modifier may be additionally used. The molecular
weight modifier may be added before the initiation of
polymerization, during the initiation of polymerization, or after
the initiation of polymerization.
[0107] As the molecular weight modifier, mono-alkyl phenol may be
used. As one example, the mono-alkyl phenol may be one or more
selected from the group consisting of p-tert-butyl phenol, p-cumyl
phenol, decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl
phenol, octadecyl phenol, eicosyl phenol, docosyl phenol and
triacontyl phenol. Preferably, the mono-alkyl phenol may be
p-tert-butyl phenol. In this case, the effect of adjusting the
molecular weight control may be great.
[0108] The molecular weight modifier may be included, for example,
in an amount of 0.01 parts by weight or more, 0.1 parts by weight
or more, or 1 part by weight; and not more than 10 parts by weight,
not more than 6 parts by weight, or not more than 5 parts by
weight, based on 100 parts by weight of the aromatic diol compound.
The required molecular weight may be obtained within the range as
described above.
[0109] Meanwhile, the above-mentioned copolycarbonate resin may
have a weight average molecular weight (g/mol) of 1,000 to 100,000.
More preferably, the weight average molecular weight may be 15,000
or more, 16,000 or more, 17,000 or more, 18,000 or more, 19,000 or
more, 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or
more, 24,000 or more, or 25,000 or more; and not more than 40,000,
not more than 39,000, not more than 38,000, not more than 37,000,
not more than 36,000, not more than 35,000, or not more than
34,000.
(2) First Polycarbonate Resin
[0110] The resin composition according to the exemplary embodiment
may include the first polycarbonate resin including the repeating
unit represented by Chemical Formula 2, having aliphatic alkylene A
and further including the repeating unit represented by Chemical
Formula 1, as needed, together with the above-mentioned
copolycarbonate resin. As the first polycarbonate resin as
described above includes the repeating unit represented by Chemical
Formula 2, having the aliphatic group, this resin and the resin
composition according the exemplary embodiment comprising the same
may have high flowability, processability, thin-film moldability,
and the like.
[0111] Since a description of the repeating unit represented by
Chemical Formula 1, selectively included in this first
polycarbonate resin is provided above in the description of the
copolycarbonate resin, a detailed description thereof will be
omitted.
[0112] Meanwhile, the first polycarbonate resin may essentially
include the repeating unit represented by Chemical Formula 2, which
may distinguish the first polycarbonate resin from a second
polycarbonate resin to be described below, that is, a general
aromatic polycarbonate resin. In Chemical Formula 2, preferably,
R.sub.5 to R.sub.12 may be each independently hydrogen, methyl,
chloro, or bromo. In addition, preferably, R.sub.5 to R.sub.12 may
be the same as each other.
[0113] Further, preferably, Z.sub.1 and Z.sub.2 may be each
independently a linear or branched C.sub.1-10 alkylene
unsubstituted or substituted with phenyl. More preferably, Z.sub.1
and Z.sub.2 may be each independently methylene, ethane-1,1-diyl,
propane-2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl or
diphenylmethylene. In addition, preferably, Z.sub.1 and Z.sub.2 may
be each independently cyclohexane-1,1-diyl, O, S, SO, SO.sub.2, or
CO. Further, preferably, Z.sub.1 and Z.sub.2 may be the same as
each other.
[0114] Furthermore, preferably, A may be a linear or branched
C.sub.1-10 alkylene. In addition, A may be preferably a linear
C.sub.1-10 alkylene, more preferably, a linear C.sub.3-9 alkylene,
and most preferably, octylene.
[0115] More specifically, the repeating unit represented by
Chemical Formula 2 may be represented by Chemical Formula 2-1:
##STR00016##
[0116] The repeating unit represented by Chemical Formula 2 may be
formed by a reaction of an aromatic diol compound represented by
the following Chemical Formula 2-2 and a carbonate precursor.
##STR00017##
[0117] In Chemical Formula 2-2, R.sub.5 to R.sub.12, Z.sub.2,
Z.sub.3, and A are as previously defined.
[0118] A description of the carbonate precursor that may be used
for the formation of the repeating unit represented by Chemical
Formula 2 is the same as that described for the carbonate precursor
that can be used for the formation of the repeating unit
represented by Chemical Formula 1 described above.
[0119] The first polycarbonate resin may include the repeating unit
represented by Chemical Formula 1 and the repeating unit
represented by Chemical Formula 2 so as to have a weight ratio of
preferably from 1:0.001 to 1:0.3, more preferably from 1:0.004 to
1:0.15, and most preferably from 1:0.01 to 1:0.1. The first
polycarbonate resin may have suitable mechanical properties and
high flowability within the above-mentioned range. The weight ratio
may correspond to a weight ratio of the aromatic diol compounds
used to form the repeating units represented by Chemical Formulae 1
and 2.
[0120] Meanwhile, the above-mentioned first polycarbonate resin may
have a weight average molecular weight (g/mol) of 1,000 to 100,000.
More preferably, the weight average molecular weight may be 15,000
or more, 16,000 or more, 17,000 or more, 18,000 or more, 19,000 or
more, 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or
more, 24,000 or more, or 25,000 or more; and not more than 40,000,
not more than 39,000, not more than 38,000, not more than 37,000,
not more than 36,000, not more than 35,000, or not more than
34,000.
[0121] In the polycarbonate based resin composition according to
the exemplary embodiment, contents of the copolycarbonate resin and
the first polycarbonate resin may be changed depending on physical
properties of a composition to be adjusted. For example, the
content of the copolycarbonate resin included in the resin
composition according to the exemplary embodiment may be from 1 to
99 wt %, from 10 to 90 wt %, from 30 to 70 wt %, or from 40 to 60
wt %, based on 100 wt % of the entire resin composition according
to the exemplary embodiment, and the content of the first
polycarbonate resin may be the rest except for the content of the
copolycarbonate resin, for example, from 1 to 99 wt %, from 10 to
90 wt %, from 30 to 70 wt %, or from 40 to 60 wt %, based on 100 wt
% of the resin composition according to the exemplary
embodiment.
[0122] Therefore, flowability and processability (thin-film
moldability), impact strength such as low-temperature impact
strength, or the like, chemical resistance, the YI value, and the
like, of the resin composition according to the exemplary
embodiment may be optimized. However, in the case in which an
excessive content of the copolycarbonate resin is added,
transparency of the resin composition may be deteriorated, or
flowability may not be sufficient, and an effect of improving heat
resistance and impact strength may reach a critical value or be
rather deteriorated. Further, in the case in which an excessive
content of the first polycarbonate resin is added, impact strength,
chemical resistance, and the like, of the resin composition may not
be sufficient.
[0123] Meanwhile, the resin composition according to the exemplary
embodiment may further include a second polycarbonate resin
corresponding to a general aromatic polycarbonate resin which does
not include the repeating units represented by Chemical Formulae 2
to 4 but includes only the repeating unit represented by Chemical
Formula 1. The second polycarbonate resin as described above may be
distinguished from the copolycarbonate resin and the first
polycarbonate resin by the fact that the second polycarbonate resin
does not include the repeating units represented by Chemical
Formulae 2 to 4.
[0124] The repeating unit represented by Chemical Formula 1,
included in the second polycarbonate resin may have a structure
equal to or different from the repeating unit represented by
Chemical Formula 1 within the same category, included in the
copolycarbonate resin and the first polycarbonate resin described
above.
[0125] Since a description of the repeating unit represented by
Chemical Formula 1 is provided above in the description of the
copolycarbonate resin, the second polycarbonate resin corresponding
to the general aromatic polycarbonate resin including the repeating
unit represented by Chemical Formula 1 may be prepared and provided
by a method well-known to those skilled in the art, an additional
description thereof will be omitted.
[0126] A suitable content of the second polycarbonate resin as
described above may be added to the resin composition according to
the exemplary embodiment by those skilled in the art depending on
the desired physical properties or purposes. However, the second
polycarbonate resin may be included in a content range of 5 to 100
parts by weight based on 100 parts by weight of a sum of the
copolycarbonate resin and the first polycarbonate resin described
above, so as not to inhibit excellent physical properties and
effects of the resin composition according to the exemplary
embodiment obtained by including the copolycarbonate resin and the
first polycarbonate resin.
[0127] Room-temperature impact strength of the above-mentioned
resin composition according to the exemplary embodiment measured in
accordance with ASTM D256 (1/8 inch, Notched Izod) at 23.degree. C.
may be from 500 to 1100 J/m. More preferably, the room-temperature
impact strength (J/m) may be 650 or more, 700 or more, or 750 or
more. In addition, the higher the room-temperature impact strength
(J/m), the more excellent, such that there is no upper limit in the
room-temperature impact strength (J/m), but the room-temperature
impact strength (J/m) may be, for example, not more than 1050, or
not more than 1000.
[0128] In addition low-temperature impact strength of the resin
composition according to the exemplary embodiment measured in
accordance with ASTM D256 (1/8 inch, Notched Izod) at -30.degree.
C. may be from 350 to 1,000 J/m. More preferably, the
low-temperature impact strength (J/m) may be 450 or more, 550 or
more, 650 or more, or 680 or more. In addition, the higher the
low-temperature impact strength (J/m), the more excellent, such
that there is no upper limit in the low-temperature impact strength
(J/m), but the low-temperature impact strength (J/m) may be, for
example, not more than 990, or not more than 980.
[0129] A YI value of the resin composition according to the
exemplary embodiment measured in accordance with ASTM D1925 may be
not more than 3. More preferably, the YI value may be not more than
2.5, not more than 2, not more than 1.99, or not more than 1.98. In
addition, since the lower the YI value, the more excellent, there
is no lower limit in the YI value, but for example, the YI value
may be 0.5 or more, 1 or more or 1.5 or more.
[0130] In addition, flowability of the resin composition according
to the exemplary embodiment measured in accordance with ASTM D 1238
(300.degree. C., 1.2 kg condition) may be from 5 to 20 g/10 min.
More preferably, the flowability (g/10 min) may be 5.5 or more, 6
or more, or 6.5 or more; and not more than 19, not more than 18,
not more than 17, not more than 16, not more than 15, or not more
than 14.
[0131] Meanwhile, another exemplary embodiment of the present
invention provides molded articles containing the polycarbonate
based resin composition according to the exemplary embodiment
described above.
[0132] Preferably, the molded articles may be injection-molded
articles. In addition, the molded articles may further include, for
example, one or more additives selected from the group consisting
of antioxidants, heat stabilizers, light stabilizers, plasticizers,
antistatic agents, nucleating agents, flame retardants, lubricants,
impact reinforcing agents, fluorescent brightening agents,
ultraviolet absorbers, pigments, and dyes.
[0133] A method for preparing the molded article may include the
steps of mixing the resin composition according to the exemplary
embodiment and additives such as antioxidants, or the like, using a
mixer, extrusion-molding the mixture with an extruder to produce a
pellet, drying the pellet and then injecting the dried pellet with
an injection molding machine.
Advantageous Effects
[0134] As set forth above, according to an embodiment of the
present invention, the polycarbonate based resin composition of
which flowability (fluidity), processability, thin-film moldability
and the like, in addition to impact strength, chemical resistance,
and the YI value are improved, and molded articles thereof may be
provided.
MODE FOR INVENTION
[0135] Hereinafter, preferable Examples of the present invention
will be provided for better understanding of the present invention.
However, the following Examples are provided only for illustration
of the present invention, and should not be construed as limiting
the present invention by the examples.
Preparation Example 1: Preparation of Polyorganosiloxane AP-30
##STR00018##
[0137] After 42.5 g (142.8 mmol) of octamethylcyclotetrasiloxane
and 2.26 g (16.8 mmol) of tetramethyldisiloxane were mixed with
each other, the mixture was placed in a 3 L flask with 1 part by
weight of acid clay (DC-A3) based on 100 parts by weight of
octamethylcyclotetrasiloxane, and reacted at 60.degree. C. for 4
hours. After the reaction was terminated, the reaction product was
diluted with ethylacetate and quickly filtered using a celite. A
repeating unit (n) of the unmodified polyorganosiloxane obtained as
described above was 30 when confirmed through .sup.1H NMR.
[0138] 9.57 g (71.3 mmol) of 2-allylphenol and 0.01 g (50 ppm) of
Karstedt's platinum catalyst were added to the obtained
terminal-unmodified polyorganosiloxane and reacted at 90.degree. C.
for 3 hours. After the reaction was terminated, the unreacted
polyorganosiloxane was removed by evaporation at 120.degree. C. and
1 torr. The terminal-modified polyorganosiloxane obtained as
described above was designated as AP-30. AP-30 was pale yellow oil,
the repeating unit(n) was 30 when confirmed through .sup.1HNMR
using Varian 500 MHz, and further purification was not
required.
Preparation Example 2: Preparation of Polyorganosiloxane MB-60
##STR00019##
[0140] After 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and
1.5 g (11 mmol) of tetramethyldisiloxane were mixed with each
other, the mixture was placed in a 3 L flask together with 1 part
by weight of acid clay (DC-A3) based on 100 parts by weight of
octamethylcyclotetrasiloxane, and reacted at 60.degree. C. for 4
hours. After the reaction was terminated, the reaction product was
diluted with ethylacetate and quickly filtered using a celite. A
repeating unit (n) of the terminal-unmodified polyorganosiloxane
obtained as described above was 60 when confirmed through .sup.1H
NMR.
[0141] 6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate
and 0.01 g (50 ppm) of Karstedt's platinum catalyst were added to
the obtained terminal-unmodified polyorganosiloxane and reacted at
90.degree. C. for 3 hours. After the reaction was terminated, the
unreacted polyorganosiloxane was removed by evaporation at
120.degree. C. and 1 torr. The terminal-modified polyorganosiloxane
obtained as described above was designated as MB-60. MB-60 was pale
yellow oil, the repeating unit (m) was 60 when confirmed through
.sup.1HNMR using Varian 500 MHz, and further purification was not
required.
Preparation Example 3: Preparation 1 of Copolycarbonate Resin
[0142] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32%
aqueous NaOH solution, and 7,500 g of distilled water in a 20 L
glass reactor and confirming that BPA was completely dissolved
under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of
p-tert-butylphenol (PTBP), 79.3179 g of previously prepared
polyorganosiloxane (AP-30), and 8.8191 g of polyorganosiloxane
(MB-60) of Preparation Example 2 were added thereto and mixed
therewith (9 wt % of polyorganosiloxanes (AP-30+MB-60) were used
based on BPA; repeating units represented by Chemical Formulae 1,
3, and 4 were formed so as to have contents corresponding thereto).
3,850 g of methylene chloride in which 542.5 g of triphosgene was
dissolved was added thereto dropwise for 1 hour. In this case, a PH
of the aqueous NaOH solution was maintained at 12. After the
dropwise addition was completed, the mixture was aged for 15
minutes, and 195.7 g of triethylamine was dissolved in methylene
chloride and added thereto. After 10 minutes, a pH was adjusted to
3 with 1N aqueous hydrochloric acid solution, and then the
resultant was washed with distilled water three times. Thereafter,
a methylene chloride phase was separated, and precipitated in
methanol, thereby obtaining a copolycarbonate resin (Mw: 34000) as
powder.
Preparation Example 4: Preparation 2 of Copolycarbonate Resin
[0143] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32%
aqueous NaOH solution, and 7,500 g of distilled water in a 20 L
glass reactor and confirming that BPA was completely dissolved
under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of
p-tert-butylphenol (PTBP), 83.7814 g of previously prepared
polyorganosiloxane (AP-30), and 4.4096 g of polyorganosiloxane
(MB-60) of Preparation Example 2 were added thereto and mixed
therewith (9 wt % of polyorganosiloxanes (AP-30+MB-60) were used
based on BPA; repeating units represented by Chemical Formulae 1,
3, and 4 were formed so as to have contents corresponding thereto).
3,850 g of methylene chloride in which 542.5 g of triphosgene was
dissolved was added thereto dropwise for 1 hour. In this case, a PH
of the aqueous NaOH solution was maintained at 12. After the
dropwise addition was completed, the mixture was aged for 15
minutes, and 195.7 g of triethylamine was dissolved in methylene
chloride and added thereto. After 10 minutes, a pH was adjusted to
3 with 1N aqueous hydrochloric acid solution, and then the
resultant was washed with distilled water three times. Thereafter,
a methylene chloride phase was separated, and precipitated in
methanol, thereby obtaining a copolycarbonate resin (Mw: 34000) as
powder.
Preparation Example 5: Preparation 3 of Copolycarbonate Resin
[0144] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32%
aqueous NaOH solution, and 7,500 g of distilled water in a 20 L
glass reactor and confirming that BPA was completely dissolved
under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of
p-tert-butylphenol (PTBP), 52.914 g of previously prepared
polyorganosiloxane (AP-30), and 5.88 g of polyorganosiloxane
(MB-60) of Preparation Example 2 were added thereto and mixed
therewith (6 wt % of polyorganosiloxanes (AP-30+MB-60) were used
based on BPA; repeating units represented by Chemical Formulae 1,
3, and 4 were formed so as to have contents corresponding thereto).
3,850 g of methylene chloride in which 542.5 g of triphosgene was
dissolved was added thereto dropwise for 1 hour. In this case, a PH
of the aqueous NaOH solution was maintained at 12. After the
dropwise addition was completed, the mixture was aged for 15
minutes, and 195.7 g of triethylamine was dissolved in methylene
chloride and added thereto. After 10 minutes, a pH was adjusted to
3 with 1N aqueous hydrochloric acid solution, and then the
resultant was washed with distilled water three times. Thereafter,
a methylene chloride phase was separated, and precipitated in
methanol, thereby obtaining a copolycarbonate resin (Mw: 34000) as
powder.
Preparation Example 6: Preparation 4 of Copolycarbonate Resin
[0145] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32%
aqueous NaOH solution, and 7,500 g of distilled water in a 20 L
glass reactor and confirming that BPA was completely dissolved
under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of
p-tert-butylphenol (PTBP), and 88.191 g of previously prepared
polyorganosiloxane (AP-30) were added thereto and mixed therewith
(9 wt % of polyorganosiloxane (AP-30) was used based on BPA;
repeating units represented by Chemical Formulae 1 and 3 were
formed so as to have contents corresponding thereto). 3,850 g of
methylene chloride in which 542.5 g of triphosgene was dissolved
was added thereto dropwise for 1 hour. In this case, a PH of the
aqueous NaOH solution was maintained at 12. After the dropwise
addition was completed, the mixture was aged for 15 minutes, and
195.7 g of triethylamine was dissolved in methylene chloride and
added thereto. After 10 minutes, a pH was adjusted to 3 with 1N
aqueous hydrochloric acid solution, and then the resultant was
washed with distilled water three times. Thereafter, a methylene
chloride phase was separated, and precipitated in methanol, thereby
obtaining a copolycarbonate resin (Mw: 34000) as powder.
Preparation Example 7: Preparation 1 of First Polycarbonate
Resin
[0146] After placing 976.9 g of bisphenol A (BPA), 1,620 g of 32%
aqueous NaOH solution, and 7,500 g of distilled water in a 20 L
glass reactor and confirming that BPA was completely dissolved
under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of
p-tert-butylphenol (PTBP), and 7.81 g of previously prepared
bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate (BPDA)
were added thereto and mixed therewith (0.8 wt % of BPDA was used
based on BPA; repeating units represented by Chemical Formulae 1
and 2 were formed so as to have contents corresponding thereto).
3,850 g of methylene chloride in which 542.5 g of triphosgene was
dissolved was added thereto dropwise for 1 hour. In this case, a PH
of the aqueous NaOH solution was maintained at 12. After the
dropwise addition was completed, the mixture was aged for 15
minutes, and 195.7 g of triethylamine was dissolved in methylene
chloride and added thereto. After 10 minutes, a pH was adjusted to
3 with 1N aqueous hydrochloric acid solution, and then the
resultant was washed with distilled water three times. Thereafter,
a methylene chloride phase was separated, and precipitated in
methanol, thereby obtaining a polycarbonate resin (Mw: 34000) as
powder.
Preparation Example 8: Preparation 2 of First Polycarbonate
Resin
[0147] After placing 968.9 g of bisphenol A (BPA), 1,620 g of 32%
aqueous NaOH solution, and 7,500 g of distilled water in a 20 L
glass reactor and confirming that BPA was completely dissolved
under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of
p-tert-butylphenol (PTBP), and 29.32 g of previously prepared
bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate (BPDA)
were added thereto and mixed therewith (3.0 wt % of BPDA was used
based on BPA; repeating units represented by Chemical Formulae 1
and 2 were formed so as to have contents corresponding thereto).
3,850 g of methylene chloride in which 542.5 g of triphosgene was
dissolved was added thereto dropwise for 1 hour. In this case, a PH
of the aqueous NaOH solution was maintained at 12. After the
dropwise addition was completed, the mixture was aged for 15
minutes, and 195.7 g of triethylamine was dissolved in methylene
chloride and added thereto. After 10 minutes, a pH was adjusted to
3 with 1N aqueous hydrochloric acid solution, and then the
resultant was washed with distilled water three times. Thereafter,
a methylene chloride phase was separated, and precipitated in
methanol, thereby obtaining a polycarbonate resin (Mw: 34000) as
powder.
Preparation Example 9: Preparation 3 of First Polycarbonate
Resin
[0148] After placing 943.7 g of bisphenol A (BPA), 1,620 g of 32%
aqueous NaOH solution, and 7,500 g of distilled water in a 20 L
glass reactor and confirming that BPA was completely dissolved
under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of
p-tert-butylphenol (PTBP), and 96.34 g of previously prepared
bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate (BPDA)
were added thereto and mixed therewith (10.0 wt % of BPDA was used
based on BPA; repeating units represented by Chemical Formulae 1
and 2 were formed so as to have contents corresponding thereto).
3,850 g of methylene chloride in which 542.5 g of triphosgene was
dissolved was added thereto dropwise for 1 hour. In this case, a PH
of the aqueous NaOH solution was maintained at 12. After the
dropwise addition was completed, the mixture was aged for 15
minutes, and 195.7 g of triethylamine was dissolved in methylene
chloride and added thereto. After 10 minutes, a pH was adjusted to
3 with 1N aqueous hydrochloric acid solution, and then the
resultant was washed with distilled water three times. Thereafter,
a methylene chloride phase was separated, and precipitated in
methanol, thereby obtaining a polycarbonate resin (Mw: 34000) as
powder.
Preparation Example 10: Preparation 4 of Polycarbonate Resin
[0149] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32%
aqueous NaOH solution, and 7,500 g of distilled water in a 20 L
glass reactor and confirming that BPA was completely dissolved
under nitrogen atmosphere, 3,670 g of methylene chloride and 17.9 g
of p-tert-butylphenol (PTBP) were added thereto and mixed
therewith. 3,850 g of methylene chloride in which 542.5 g of
triphosgene was dissolved was added thereto dropwise for 1 hour. In
this case, a PH of the aqueous NaOH solution was maintained at 12.
After the dropwise addition was completed, the mixture was aged for
15 minutes, and 195.7 g of triethylamine was dissolved in methylene
chloride and added thereto. After 10 minutes, a pH was adjusted to
3 with 1N aqueous hydrochloric acid solution, and then the
resultant was washed with distilled water three times. Thereafter,
a methylene chloride phase was separated, and precipitated in
methanol, thereby obtaining a polycarbonate resin (Mw: 34000) as
powder.
Examples 1 to 5 and Comparative Examples 1 to 5: Preparation of
Polycarbonate Based Resin Composition and Molded Articles
Thereof
[0150] The copolycarbonate resin and the polycarbonate resin were
mixed according to the composition illustrated in the following
Table 1. Additionally, based on 1 part by weight of the resin
mixture, 0.050 parts by weight of
tris(2,4-di-tert-butylphenyl)phosphite, 0.010 parts by weight of
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and
0.030 parts by weight of pentaerythritoltetrastearate were added
thereto, and the resulting mixture was pelletized using a .phi.30
mm twin-screw extruder provided with a vent, and was
injection-molded at a cylinder temperature of 300.degree. C. and a
mold temperature of 80.degree. C. using a N-20C injection-molding
machine (JSW Co.), thereby preparing a desired specimen.
TABLE-US-00001 TABLE 1 Comparative Comparative Comparative
Comparative Comparative Example 1 Example 2 Example 3 Example 4
Example 5 Example 1 Example 2 Example 3 Example 4 Example 5 Co-PC
Prepara- Preparation Preparation Preparation Preparation X
Preparation X Preparation Preparation Resin* tion Example 3 Example
3 Example 4 Example 5 (0) Example 3 (0) Example 6 Example 6 (wt %)
Example 3 (50) (50) (50) (50) (100) (100) (50) (50) First PC
Prepara- Preparation Preparation Preparation Preparation
Preparation X Preparation X Preparation resin* tion Example 8
Example 9 Example 8 Example 8 Example (0) Example 9 (0) Example 9
(wt %) Example 7 (50) (50) (50) (50) 10* (100) (50) (50) (100)
*Co-PC Resin: Copolycarbonate resin *First PC resin: first
polycarbonate resin *Preparation Example 10: Since the specimen was
prepared without using BPDA, the specimen did not correspond to the
first polycarbonate resin, but corresponded to a general
polycarbonate resin (corresponding to the second polycarbonate
resin).
Experimental Example: Confirm of Characteristics of Polycarbonate
Based Resin Composition and Injected Specimen
[0151] Weight average molecular weights of the copolycarbonate
resins and the polycarbonate resins prepared in Examples and
Comparative Examples were measured by GPC using PC standard and
Agilent 1200 series.
[0152] In addition, physical properties of the compositions and
injection specimens obtained in Examples and Comparative Examples
were measured by the following methods, and the results were
illustrated in the following Table 2.
[0153] 1) Room-Temperature Impact Strength: measured at 23.degree.
C. in accordance with ASTM D256 (1/8 inch, Notched Izod).
[0154] 2) Low-Temperature Impact Strength: measured at -30.degree.
C. in accordance with ASTM D256 (1/8 inch, Notched Izod).
[0155] 3) YI (Yellow Index): Specimen (width/length/thickness=60
mm/40 mm/3 mm) was injection-molded at 300.degree. C., and then YI
(Yellow Index) was measured under the following conditions by using
Color-Eye 7000A (X-rite Inc.) in accordance with ASTM D1925. [0156]
Measurement temperature: room temperature (23.degree. C.) [0157]
Aperture size: Large area of view
[0158] Measurement method: transmittance was measured in a spectral
range (360 nm to 750 nm) [0159] 4) Flowability (MI): measured in
accordance with ASTM D1238 (300.degree. C., 1.2 kg condition).
TABLE-US-00002 [0159] TABLE 2 Room-Temperature Low-temperature
Impact Strength Impact Strength MI (J/m) (J/m) YI (g/10 min)
Example 1 980 900 1.98 6.8 Example 2 900 830 1.98 7.1 Example 3 830
810 1.95 12.2 Example 4 845 780 1.96 6.8 Example 5 800 680 1.94 8.1
Comparative 950 190 1.75 5.7 Example 1 Comparative 1090 980 6.8 3.1
Example 2 Comparative 820 230 0.93 15.9 Example 3 Comparative 800
520 6.3 4.3 Example 4 Comparative 720 460 1.98 10.9 Example 5
[0160] Referring to Table 2, it was confirmed that in Examples 1 to
5, high room-temperature impact strength and low-temperature impact
strength, a low YI value, and relatively high flowability (MI) were
simultaneously exhibited. On the contrary, it was confirmed that in
Comparative Examples 1, 3, and 5, low-temperature impact strength
was low. Particularly, as illustrated in Comparative Example 5, it
was confirmed that in a case in which a structure of the
copolycarbonate resin was different from that in Examples,
low-temperature impact strength was deteriorated.
[0161] Further, it was confirmed that in Comparative Examples 2 and
4, flowability was poor, a YI value was high as compared to
Examples, and in Comparative Example 4, low-temperature impact
strength was also not sufficient.
* * * * *