U.S. patent application number 16/003706 was filed with the patent office on 2018-10-11 for fluidity modifier for thermoplastic resin and thermoplastic resin composition containing same.
This patent application is currently assigned to Mitsubishi Chemical Corporation. The applicant listed for this patent is Mitsubishi Chemical Corporation. Invention is credited to Toshiki MONDEN.
Application Number | 20180291146 16/003706 |
Document ID | / |
Family ID | 59014201 |
Filed Date | 2018-10-11 |
United States Patent
Application |
20180291146 |
Kind Code |
A1 |
MONDEN; Toshiki |
October 11, 2018 |
FLUIDITY MODIFIER FOR THERMOPLASTIC RESIN AND THERMOPLASTIC RESIN
COMPOSITION CONTAINING SAME
Abstract
An object of the present invention is to provide a fluidity
modifier whose inclusion in a transparent amorphous thermoplastic
resin represented by a polycarbonate resin enables improvement of
the fluidity without deteriorating the original favorable physical
properties of the thermoplastic resin, and a thermoplastic resin
composition containing it. This object is achieved by a fluidity
modifier for thermoplastic resin, which fluidity modifier includes
an aromatic polycarbonate copolymer containing a carbonate
structural unit (A) represented by Formula (1) and a carbonate
structural unit (B) represented by Formula (2), wherein the ratio
of the carbonate structural unit (A) to a total of 100 mol % of the
carbonate structural unit (A) and the carbonate structural unit (B)
is more than 10 mol % and not more than 36.5 mol %.
Inventors: |
MONDEN; Toshiki;
(Chiyoda-ku, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mitsubishi Chemical Corporation |
Chiyoda-ku |
|
JP |
|
|
Assignee: |
Mitsubishi Chemical
Corporation
Chiyoda-ku
JP
|
Family ID: |
59014201 |
Appl. No.: |
16/003706 |
Filed: |
June 8, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2016/086771 |
Dec 9, 2016 |
|
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|
16003706 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 5/524 20130101;
C08G 64/04 20130101; C08L 2201/10 20130101; B29K 2069/00 20130101;
C08L 2205/025 20130101; C08G 64/06 20130101; C08J 2369/00 20130101;
B29K 2105/0005 20130101; C08K 5/005 20130101; C08J 5/00 20130101;
C08J 2469/00 20130101; B29C 45/0001 20130101; C08G 65/34 20130101;
C08L 69/00 20130101 |
International
Class: |
C08G 64/06 20060101
C08G064/06; C08L 69/00 20060101 C08L069/00; C08J 5/00 20060101
C08J005/00; B29C 45/00 20060101 B29C045/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 11, 2015 |
JP |
2015-242170 |
Dec 18, 2015 |
JP |
2015-247592 |
Dec 21, 2015 |
JP |
2015-248695 |
Claims
1. A fluidity modifier for thermoplastic resin, said fluidity
modifier comprising an aromatic polycarbonate copolymer containing:
a carbonate structural unit (A) represented by the following
Formula (1): ##STR00014## (wherein in Formula (1), R.sup.1
represents C.sub.8-C.sub.24 alkyl or alkenyl; R.sup.2 and R.sup.3
each independently represent a C.sub.1-C.sub.15 monovalent
hydrocarbon group; and a and b each independently represent an
integer of 0 to 4); and a carbonate structural unit (B) represented
by the following Formula (2): ##STR00015## wherein the ratio of the
carbonate structural unit (A) to a total of 100 mol % of the
carbonate structural unit (A) and the carbonate structural unit (B)
is more than 10 mol % and not more than 36.5 mol %.
2. The fluidity modifier for thermoplastic resin according to claim
1, wherein said carbonate structural unit (A) is represented by the
following Formula (3) or (4): ##STR00016##
3. The fluidity modifier for thermoplastic resin according to claim
1, wherein the flow value (Q value) as measured using a Koka flow
tester according to Appendix C of JIS (1999) K7210 at 240.degree.
C. at 160 kgf is not less than (unit: 10.sup.-2 cm.sup.3/sec.).
4. A thermoplastic resin composition comprising 2 to 100 parts by
mass of the fluidity modifier for thermoplastic resin recited in
claim 1 and 100 parts by mass of a thermoplastic resin.
5. The thermoplastic resin composition according to claim 4,
further comprising at least one selected from the group consisting
of heat stabilizers, antioxidants, ultraviolet absorbers,
brightness improvers, dyes, pigments, and mold release agents.
6. The thermoplastic resin composition according to claim 4,
wherein said thermoplastic resin is a polycarbonate resin.
7. The thermoplastic resin composition according to claim 4,
wherein said thermoplastic resin is a polycarbonate resin, and the
ratio of said carbonate structural unit (A) to total carbonate
structural units in said thermoplastic resin composition is 1 to 20
mol %.
8. The thermoplastic resin composition according to claim 4,
wherein the flow value (Q value) as measured using a Koka flow
tester according to Appendix C of JIS (1999) K7210 at 240.degree.
C. at 160 kgf is not less than 6 (unit: 10.sup.-2
cm.sup.3/sec.).
9. The thermoplastic resin composition according to claim 4, having
a glass transition temperature (Tg) of 90 to 145.degree. C.
10. A method for producing a thermoplastic resin molded article,
said method comprising a step of obtaining a molded article by
injection molding of the thermoplastic resin composition recited in
claim 4.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a continuation of International Application No.
PCT/JP2016/086771, filed on Dec. 9, 2016, and designated the U.S.,
and claims priority from Japanese Patent Application No.
2015-242170 which was filed on Dec. 11, 2015, Japanese Patent
Application No. 2015-247592 which was filed on Dec. 18, 2015, and
Japanese Patent Application No. 2015-248695 which was filed on Dec.
21, 2015, the entire contents of which are incorporated herein by
reference.
TECHNICAL FIELD
[0002] The present invention relates to a fluidity modifier for
thermoplastic resin, and a thermoplastic resin composition
containing it. More specifically, the present invention relates to
a novel fluidity modifier whose inclusion in a thermoplastic resin
represented by an engineering plastic enables improvement of
moldability without deteriorating physical properties such as
mechanical properties, thermal properties, and optical properties,
and a novel thermoplastic resin composition containing it.
BACKGROUND ART
[0003] Since thermoplastic resins can be easily processed by
melt-molding, they are used in various industrial fields. In
particular, engineering plastics and super-engineering plastics,
because of their well-balanced heat resistance and strength, are
widely used as automobile materials, electric and electronic device
materials, housing and building materials, and materials for
producing components in other industrial fields.
[0004] In general, a thermoplastic resin is melted by heat, and
subjected to a molding process such as injection molding or
extrusion molding to obtain a molded article. It is known that, in
this process, while processing at a high processing temperature
needs to be avoided for causing of decomposition and coloring of
the thermoplastic resin, an excessively low processing temperature
causes a remarkable decrease in the melt viscosity, leading to a
partially or totally unmelted state in some cases, which makes the
processing impossible. That is, each thermoplastic resin material
has its own appropriate processing temperature. Thus, even in a
thermoplastic resin having excellent properties, there are
limitations in the thickness, size, and shape of the obtained
molded article depending on the melt viscosity at the appropriate
processing temperature of the resin.
[0005] The simplest method for increasing the moldability of a
thermoplastic resin is to decrease the molecular weight of the
thermoplastic resin to thereby decrease the melt viscosity.
However, in general, since a thermoplastic resin is a polymer
material, its physical properties including thermal properties and
mechanical properties are strongly correlated with the molecular
weight, and a decrease in the molecular weight results in
deterioration of the above-described excellent physical properties
of the thermoplastic resin. Therefore, a method for increasing the
fluidity to improve the moldability without remarkably
deteriorating the excellent physical properties of thermoplastic
resins has been strongly demanded.
[0006] For example, polycarbonate resins are known to be
engineering plastics having excellent heat resistance, impact
resistance, transparency, electrical properties, and fire
retardancy, and used in a wide range of fields as described above.
However, since they have low fluidity upon melting and show poor
moldability, various methods for improvement of the fluidity have
been conventionally studied. Examples of the methods conventionally
proposed for the improvement of the fluidity of polycarbonate
resins include methods in which a polycarbonate resin is alloyed
with a styrene-based resin such as polystyrene or an
acrylonitrile-butadiene-styrene resin (ABS resin) (see, for
example, Patent Documents 1 and 2), methods in which a
polycarbonate resin is alloyed with a polyester resin (see, for
example, Patent Documents 3 and 4), methods in which a
polycarbonate resin is alloyed with an acrylic resin (see, for
example, Patent Document 5), and methods in which a polycarbonate
resin is alloyed with a particular phenolic resin (see, for
example, Patent Document 6).
[0007] However, the above methods have drawbacks in, for example,
that the transparency, one of the excellent properties of the
polycarbonate resins, is lost, that detachment occurs in the molded
article during injection molding, and that the heat resistance,
impact resistance, and fire retardancy remarkably decrease.
PRIOR ART DOCUMENTS
Patent Documents
[0008] Patent Document 1: JP 43-6295 B
[0009] Patent Document 2: JP 38-15225 B
[0010] Patent Document 3: JP 2009-1619 A
[0011] Patent Document 4: JP 1-96245 A
[0012] Patent Document 5: JP 5269585 B
[0013] Patent Document 6: JP 2007-31682 A
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0014] Although a number of methods have been proposed for
improvement of the fluidity of thermoplastic resins, those methods
failed to achieve a satisfactory balance between the fluidity and
the physical properties of the thermoplastic resins such as thermal
properties and mechanical properties.
[0015] In particular, regarding optical materials such as
polycarbonate resins for light guide plates and the like, materials
having both high fluidity (for example, with a flow value (Q value)
of not less than 6 (unit: 10.sup.2 cm/sec.) as measured using a
Koka flow tester according to Appendix C of JIS (1999) K7210 at
240.degree. C. at 160 kgf) and high mechanical strength while
maintaining high transparency have recently been demanded. However,
no technique or fluidity modifier that provides such a
polycarbonate resin having an excellent balance among the
transparency, mechanical properties, and fluidity has been
discovered.
[0016] In view of the problems described above, an object of the
present invention is to provide a fluidity modifier whose inclusion
in an existing thermoplastic resin, especially a transparent
amorphous resin such as a polycarbonate resin, enables improvement
of the fluidity without deteriorating the original favorable
physical properties of the thermoplastic resin, a thermoplastic
resin composition containing it, and a method for producing a
molded article by injection molding of the composition.
Means for Solving the Problems
[0017] As a result of intensive study, the present inventors
discovered that an aromatic polycarbonate copolymer containing
particular amounts of structural units derived from two particular
kinds of aromatic dihydroxy compounds is effective as a fluidity
modifier for thermoplastic resin, and that a thermoplastic resin
composition containing a thermoplastic resin and the fluidity
modifier has an excellent balance between the mechanical strength
and the fluidity, and also has high transparency in cases where the
composition is a polycarbonate resin composition, thereby
completing the present invention.
[0018] That is, the present invention is constituted by the
following [1] to [10].
[1] A fluidity modifier for thermoplastic resin, the fluidity
modifier comprising an aromatic polycarbonate copolymer
containing:
[0019] a carbonate structural unit (A) represented by the following
Formula (1):
##STR00001##
(wherein in Formula (1), R.sup.1 represents C.sub.8-C.sub.24 alkyl
group or alkenyl group; R.sup.2 and R.sup.3 each independently
represent a C.sub.1-C.sub.15 monovalent hydrocarbon group; and a
and b each independently represent an integer of 0 to 4); and
[0020] a carbonate structural unit (B) represented by the following
Formula (2):
##STR00002##
wherein the ratio of the carbonate structural unit (A) to a total
of 100 mol % of the carbonate structural unit (A) and the carbonate
structural unit (B) is more than 10 mol % and not more than 36.5
mol %. [2] The fluidity modifier for thermoplastic resin according
to [1], wherein the carbonate structural unit (A) is represented by
the following Formula (3) or (4):
##STR00003##
[3] The fluidity modifier according to [1] or [2], wherein the flow
value (Q value) as measured using a Koka flow tester according to
Appendix C of JIS (1999) K7210 at 240.degree. C. at 160 kgf is not
less than 30 (unit: 10.sup.-2 cm/sec.). [4] A thermoplastic resin
composition comprising 100 parts by mass of a thermoplastic resin
and 2 to 100 parts by mass of the fluidity modifier for
thermoplastic resin recited in any one of [1] to [3]. [5] The
thermoplastic resin composition according to [4], further
comprising at least one selected from the group consisting of heat
stabilizers, antioxidants, ultraviolet absorbers, brightness
improvers, dyes, pigments, and mold release agents. [6] The
thermoplastic resin composition according to [4] or [5], wherein
the thermoplastic resin is a polycarbonate resin. [7] The
thermoplastic resin composition according to [4] or [5], wherein
the thermoplastic resin is a polycarbonate resin, and the ratio of
the carbonate structural unit (A) to the total carbonate structural
units in the thermoplastic resin composition is 1 to 20 mol %. [8]
The thermoplastic resin composition according to any one of [4] to
[7], wherein the flow value (Q value) as measured using a Koka flow
tester according to Appendix C of JIS (1999) K7210 at 240.degree.
C. at 160 kgf is not less than (unit: 10.sup.-2 cm.sup.3/sec.). [9]
The thermoplastic resin composition according to any one of [4] to
[8], having a glass transition temperature (Tg) of 90 to
145.degree. C. [10] A method for producing a thermoplastic resin
molded article, the method comprising a step of obtaining a molded
article by injection molding of the thermoplastic resin composition
recited in any one of [4] to [9].
Effect of the Invention
[0021] By inclusion of the fluidity modifier for thermoplastic
resin of the present invention in a thermoplastic resin,
moldability of the resin can be increased without deteriorating
physical properties of the thermoplastic resin such as the
mechanical strength and thermal properties. Thus, according to the
thermoplastic resin composition containing the fluidity modifier
for thermoplastic resin of the present invention, a thermoplastic
resin composition having an excellent balance among thin
moldability, strength, and thermal properties can be provided, and
therefore industrial applicability of the composition is very high.
In particular, by inclusion of the fluidity modifier in a
polycarbonate resin, a polycarbonate resin composition having
excellent thin moldability, transparency, hue, impact strength, and
bending strength can be provided, and the composition can be
suitably used for optical members for electric and electronic
devices, large-sized automobile window members, and the like.
MODE FOR CARRYING OUT THE INVENTION
[0022] The present invention is described below in more detail by
way of embodiments, examples, and the like. However, the present
invention should not be interpreted as being limited to the
embodiments, examples, and the like described below.
[0023] Unless otherwise specified, the term "to" in the present
description is used such that the values described before and after
it are included as the lower limit and the upper limit,
respectively. Unless otherwise specified, the term "part" means
part by mass, which is expressed on a mass basis.
Aromatic Polycarbonate Copolymer
[0024] The fluidity modifier for thermoplastic resin of the present
invention includes an aromatic polycarbonate copolymer containing a
carbonate structural unit (A) represented by the following Formula
(1) and a carbonate structural unit (B) represented by the
following Formula (2), wherein the ratio of the carbonate
structural unit (A) to a total of 100 mol % of the carbonate
structural unit (A) and the carbonate structural unit (B) is more
than 10 mol % and not more than 36.5 mol %.
##STR00004##
[0025] In Formula (1), R.sup.1 represents C.sub.8-C.sub.24 alkyl or
alkenyl; R.sup.2 and R.sup.3 each independently represent a
C.sub.1-C.sub.15 monovalent hydrocarbon group; and a and b each
independently represent an integer of 0 to 4.
[0026] By inclusion, in a thermoplastic resin, of such a fluidity
modifier for thermoplastic resin containing an aromatic
polycarbonate copolymer including a carbonate structural unit (A)
and a carbonate structural unit (B) at particular ratios, the
thermoplastic resin can be provided with a remarkably favorable
balance between the fluidity and strengths such as the impact
strength, bending strength, and cyclic fatigue strength. In
particular, by inclusion of the fluidity modifier in a
polycarbonate resin, high transparency, hue, and brightness can
also be given to the resin.
[0027] In the aromatic polycarbonate copolymer contained in the
fluidity modifier for thermoplastic resin of the present invention,
the above-described carbonate structural unit (A) has R.sup.1,
which is an aliphatic hydrocarbon chain substituent such as an
alkyl group or an alkenyl group having a carbon number of not less
than 8. By the inclusion of the carbonate structural unit (A)
having such an aliphatic hydrocarbon chain, when the fluidity
modifier is included in a thermoplastic resin to prepare a
thermoplastic resin composition, entangling of polymer chains of
the thermoplastic resin during melting can be moderately inhibited
by the aliphatic hydrocarbon chain contained in the carbonate
structure (A) in the aromatic polycarbonate copolymer to reduce
friction between the polymer chains, so that high fluidity can be
achieved. As a result, the thermoplastic resin composition of the
present invention can have high fluidity.
[0028] The carbon number of the alkyl group or alkenyl group of
R.sup.1 in the carbonate structural unit (A) is more preferably not
less than 9, still more preferably not less than 10, especially
preferably not less than 11.
[0029] On the other hand, the carbon number of the alkyl group or
alkenyl group of R.sup.1 in the carbonate structural unit (A) is
not more than 24. In cases where the long-chain aliphatic chain is
too long, heat resistance and mechanical properties are remarkably
low, and compatibility with the thermoplastic resin is low, so that
mechanical properties and transparency may be deteriorated, which
is not preferred. From such a point of view, the carbon number of
the R.sup.1 is more preferably not more than 22, still more
preferably not more than 18, especially preferably not more than
16.
[0030] Examples of the C.sub.8-C.sub.24 alkyl group include linear
or branched alkyl groups, and alkyl groups partially having a
cyclic structure. In particular, for effective enhancement of the
fluidity of the aromatic polycarbonate resin of the present
invention, the C.sub.8-C.sub.24 alkyl group is preferably a linear
or branched alkyl group.
[0031] Specific examples of the linear alkyl groups include
n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,
n-nonadecyl, n-icosyl, n-icosyl, n-henicosyl, n-docosyl,
n-tricosyl, and n-tetracosyl. n-Nonyl, n-decyl, n-undecyl,
n-dodecyl, n-hexadecyl, and n-octadecyl are preferred. n-Nonyl,
n-decyl, n-undecyl, and n-dodecyl are more preferred. n-Dodecyl is
especially preferred. By the presence of such an alkyl group,
fluidity and mechanical strength of the thermoplastic resin
composition of the present invention can be more effectively
increased.
[0032] Specific examples of the branched alkyl groups include
methylheptyl, methyloctyl, methylnonyl, methyldecyl, methylundecyl,
methyldodecyl, methyltridecyl, methyltetradecyl, methylpentadecyl,
methylhexadecyl, methylheptadecyl, methyloctadecyl,
methylnonadecyl, methylicosyl, methylicosyl, methylhenicosyl,
methyldocosyl, methyltricosyl,
[0033] dimethylheptyl, dimethyloctyl, dimethylnonyl, dimethyldecyl,
dimethylundecyl, dimethyldodecyl, dimethyltridecyl,
dimethyltetradecyl, dimethylpentadecyl, dimethylhexadecyl,
dimethylheptadecyl, dimethyloctadecyl, dimethylnonadecyl,
dimethylicosyl, dimethylicosyl, dimethylhenicosyl,
dimethyldocosyl,
[0034] trimethylheptyl, trimethyloctyl, trimethylnonyl,
trimethyldecyl, trimethylundecyl, trimethyldodecyl,
trimethyltridecyl, trimethyltetradecyl, trimethylpentadecyl,
trimethylhexadecyl, trimethylheptadecyl, trimethyloctadecyl,
trimethylnonadecyl, trimethylicosyl, trimethylicosyl,
trimethylhenicosyl,
[0035] ethylhexyl, ethylheptyl, ethyloctyl, ethylnonyl, ethyldecyl,
ethylundecyl, ethyldodecyl, ethyltridecyl, ethyltetradecyl,
ethylpentadecyl, ethylhexadecyl, ethylheptadecyl, ethyloctadecyl,
ethylnonadecyl, ethylicosyl, ethylicosyl, ethylhenicosyl,
ethyldocosyl,
[0036] propylhexyl, propylheptyl, propyloctyl, propylnonyl,
propyldecyl, propylundecyl, propyldodecyl, propyltridecyl,
propyltetradecyl, propylpentadecyl, propylhexadecyl,
propylheptadecyl, propyloctadecyl, propylnonadecyl, propylicosyl,
propylicosyl, propylhenicosyl,
[0037] butylhexyl, butylheptyl, butyloctyl, butylnonyl, butyldecyl,
butylundecyl, butyldodecyl, butyltridecyl, butyltetradecyl,
butylpentadecyl, butylhexadecyl, butyiheptadecyl, butyloctadecyl,
butylnonadecyl, butylicosyl, and butylicosyl. In the above examples
of branched alkyl groups, the position(s) of branching is/are
arbitrary.
[0038] The alkenyl group is not limited as long as it has a
structure wherein one or more carbon-carbon double bonds are
included in the structure of a linear alkyl group or branched alkyl
group described above. Specific examples of the alkenyl group
include octenyl, nonenyl, decenyl, undecenyl, dodecenyl,
tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl,
octadecenyl, nonadecenyl, icosenyl, henicosenyl, docosenyl,
tricosenyl, tetracosenyl, and 4,8,12-trimethyltridecyl.
[0039] In the carbonate structural unit (A) described above, the
carbon atom to which the substituent of R.sup.1 is bound has a
hydrogen atom bound thereto. In cases where R.sup.1 has a
substituent such as an alkyl group instead of the hydrogen atom,
the fluidity-modifying effect and the mechanical strength-improving
effect described above cannot be obtained, and heat resistance may
be extremely deteriorated.
[0040] R.sup.2 and R.sup.3 in the carbonate structural unit (A)
represent C.sub.1-C.sub.15 monovalent hydrocarbon groups. By having
the C.sub.1-C.sub.15 monovalent hydrocarbon groups, the
thermoplastic resin composition of the present invention can have
increased fluidity, strength, hardness, chemical resistance, and
the like. Examples of the C.sub.1-C.sub.15 monovalent hydrocarbon
groups include C.sub.1-C.sub.15 alkyl groups and C.sub.2-C.sub.15
alkenyl groups. These may be linear, branched, or cyclic. Examples
of such monovalent hydrocarbon groups include methyl, ethyl,
propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,
n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,
phenyl, and tolyl. Among these, methyl is preferred. Further, a and
b in the carbonate structural unit (A) each independently represent
an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1,
still more preferably 0.
[0041] Specific examples of the carbonate structural unit (A)
include the structural units represented by the following Formulae
(3), (4), (7), (9), and (11) to (16). Among these, the structural
units of Formulae (3), (4), (7), (9), and (11) to (14) are more
preferred; the structural units of Formulae (3), (4), (9), and (11)
are still more preferred; the structural units of Formulae (3) and
(4) are especially preferred; and the structural unit of Formula
(4) is most preferred.
##STR00005## ##STR00006##
[0042] Specific examples of the carbonate structural unit (A)
included in the aromatic polycarbonate copolymer contained in the
fluidity modifier for thermoplastic resin of the present invention
include the structural units represented by the following Formulae
(17) to (19). Among these, the structural unit represented by
Formula (17) is more preferred since it tends to increase the
thermal stability. However, the isomeric structures of Formulae
(18) and (19) may also be included at arbitrary ratios.
##STR00007##
[0043] From such a point of view, more preferred specific examples
of the carbonate structure (A) include the structural units
represented by the following Formulae (20) to (29). Among these,
the structural units of Formulae (20) to (27) are more preferred;
the structural units of Formulae (21) to (24) are still more
preferred; the structural units of Formulae (21) and (23) are
especially preferred; and the structural unit of Formula (23) is
most preferred.
##STR00008##
[0044] The carbonate structural unit (B) included in the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention is preferably the
bisphenol A-derived structural unit represented by the following
Formula (2). However, the isomeric structural unit represented by
Formula (31) may also be included at an arbitrary ratio. By the
inclusion of such a carbonate structural unit (B), when a
thermoplastic resin is blended with the aromatic polycarbonate
copolymer contained in the fluidity modifier for thermoplastic
resin of the present invention, compatibility and dispersibility
can be increased, and favorable mechanical properties can be
obtained.
##STR00009##
[0045] As long as the effect of the present invention is not
inhibited, the aromatic polycarbonate copolymer contained in the
fluidity modifier for thermoplastic resin of the present invention
may be either a copolymer composed only of the carbonate structural
unit (A) and the carbonate structural unit (B) described above, or
a copolymer containing one or more kinds of carbonate structural
units each derived from another dihydroxy compound different from
the carbonate structural unit (A) and the carbonate structural unit
(B). In terms of the form of the copolymer, various forms of
copolymers including random copolymers and block copolymers may be
selected.
[0046] In the aromatic polycarbonate copolymer contained in the
fluidity modifier for thermoplastic resin of the present invention,
the ratio of the carbonate structural unit (A) to the total
carbonate structural units in the aromatic polycarbonate copolymer
is more than 10 mol % and not more than 36.5 mol %. As described
above, the carbonate structural unit (A) acts as a unit that
moderately inhibits tangling of polymer chains to reduce friction
between the polymer chains, thereby giving a fluidity-imparting
effect. The carbonate structural unit (B) acts as a unit that gives
compatibility and heat resistance to the thermoplastic resin, and
also acts to increase the thermal stability of the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention. Thus, the ratio
between the carbonate structural unit (A) and the carbonate
structural unit (B) is important for efficiently giving the
fluidity-improving effect upon inclusion of the aromatic
polycarbonate copolymer of the present invention in the
thermoplastic resin, and for increasing dispersibility of the
aromatic polycarbonate copolymer in the thermoplastic resin so as
to suppress deterioration of physical properties such as mechanical
properties, thermal properties, and transparency as much as
possible. In cases where the ratio of the carbonate structural unit
(A) is not more than the lower limit of the above-described range,
when the copolymer is included in the thermoplastic resin, the
fluidity-modifying effect may be insufficient, and, compared to
thermoplastic resins having the same viscosity, the impact strength
may be low, which is not preferred. On the other hand, in cases
where the ratio is not less than the upper limit of the
above-described range, when the copolymer is included in the
thermoplastic resin, the mechanical strength may be low, and the
thermal properties and the transparency may be remarkably low,
which is not preferred.
[0047] The ratio of the carbonate structural unit (A) to the total
carbonate structural units in the aromatic polycarbonate copolymer
is defined as follows: 100.times.(the number of moles of the
monomers constituting the carbonate structural unit (A)/the total
number of moles of bisphenol constituting the total carbonate
structural units).
[0048] From such a point of view, the ratio of the carbonate
structural unit (A) is preferably not less than 12 mol %, more
preferably not less than 14 mol %, still more preferably not less
than 16 mol %, especially preferably not less than 18 mol %, most
preferably not less than 22 mol %. Further, the ratio is preferably
not more than 36.0 mol %, more preferably not more than 35.0 mol %,
still more preferably not more than 34.5 mol %, especially
preferably not more than 34.0 mol %, most preferably not more than
33.0 mol %.
[0049] In cases where the aromatic polycarbonate copolymer contains
a carbonate structural unit derived from another dihydroxy
compound, the content of this carbonate structural unit in the
copolymer is not limited as long as the effect of the fluidity
modifier of the present invention is not inhibited. For example,
the ratio of the carbonate structural unit derived from another
dihydroxy compound to the total carbonate structural units is
usually 0 to 70 mol %, preferably 0 to 50 mol %, more preferably 0
to 40 mol %, still more preferably 0 to 30 mol %, especially
preferably 0 to 20 mol %, most preferably 0 to 10 mol %.
Flow Value (Q Value) of Aromatic Polycarbonate Copolymer
[0050] The melt viscosity of the aromatic polycarbonate copolymer
contained in the fluidity modifier for thermoplastic resin of the
present invention is not limited, and may be appropriately selected
depending on the viscosity of the thermoplastic resin in which the
fluidity modifier is to be included and the desired viscosity of
the thermoplastic resin composition. Usually, the melt viscosity is
not less than 1 (unit: 10.sup.-2 cm.sup.3/sec.) in terms of the
flow value (Q value) measured using a Koka flow tester according to
Appendix C of JIS (1999) K7210 at 240.degree. C. at 160
kgf/cm.sup.2. The Q value is an index of the melt viscosity. A
higher Q value indicates a lower viscosity and a better fluidity.
The Q value may be not less than 6, or may be not less than 20. It
is preferably not less than 30, more preferably not less than 40.
On the other hand, the upper limit of the Q value of the aromatic
polycarbonate copolymer of the present invention is not limited as
long as the excellent physical properties of the thermoplastic
resin composition of the present invention are not deteriorated.
The Q value is usually not more than 150, preferably not more than
120, more preferably not more than 100, still more preferably not
more than 80, especially preferably not more than 60.
[0051] The Q value of the aromatic polycarbonate copolymer
contained in the fluidity modifier for thermoplastic resin of the
present invention is influenced by physical properties such as the
types and the ratios of the carbonate structural unit (A) and the
carbonate structural unit (B) described above and the molecular
weight of the aromatic polycarbonate copolymer. Those skilled in
the art can easily obtain an arbitrary Q value by controlling these
physical properties.
Glass Transition Temperature (Tg) of Aromatic
Polycarbonate Copolymer
[0052] The glass transition temperature (Tg) of the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention is not limited, and
may be appropriately selected and used. The glass transition
temperature is usually 25.degree. C. to 135.degree. C. In cases
where the glass transition temperature (Tg) is less than the lower
limit, the fluidity modifier for thermoplastic resin of the present
invention may be in a liquid state, and bleed-out may occur when it
is included in a thermoplastic resin, which is not preferred. On
the other hand, in cases where the glass transition temperature
(Tg) exceeds the upper limit, the fluidity-modifying effect of the
fluidity modifier for thermoplastic resin of the present invention
is low, so that the processing temperature of the thermoplastic
resin composition tends to be high, which is not preferred. The
glass transition temperature (Tg) of the aromatic polycarbonate
copolymer contained in the fluidity modifier for thermoplastic
resin of the present invention is preferably not less than
30.degree. C., more preferably not less than 35.degree. C., still
more preferably not less than 40.degree. C., especially preferably
not less than 50.degree. C. On the other hand, the glass transition
temperature is preferably not more than 130.degree. C., more
preferably not more than 120.degree. C., still more preferably not
more than 110.degree. C., especially preferably not more than
100.degree. C.
[0053] The glass transition temperature (Tg) of the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention means the extrapolated
glass transition temperature determined as follows. Using a
differential scanning calorimeter (DSC 6220, manufactured by SII),
about 10 mg of an aromatic polycarbonate copolymer sample is heated
at a heating rate of 20.degree. C./min. while measuring the amount
of heat. According to JIS-K7121, a straight line is drawn by
extending the base line in the low-temperature side toward the
high-temperature side, and a tangent line is drawn at the point
where the slope of the curve becomes maximum in the portion showing
the stepwise change due to glass transition. The temperature at the
intersection of these lines corresponds to the extrapolated glass
transition temperature.
[0054] The glass transition temperature (Tg) of the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention is also influenced by
physical properties such as the types and the ratios of the
carbonate structural unit (A) and the carbonate structural unit (B)
described above and the molecular weight of the aromatic
polycarbonate copolymer. Those skilled in the art can easily obtain
an aromatic polycarbonate copolymer having an arbitrary glass
transition temperature by controlling these physical
properties.
Molecular Weight of Aromatic Polycarbonate Copolymer
[0055] The molecular weight of the aromatic polycarbonate copolymer
contained in the fluidity modifier for thermoplastic resin of the
present invention is not limited, and usually 5000 to 50,000 in
terms of the viscosity average molecular weight (Mv) as calculated
from the solution viscosity. In cases where the viscosity average
molecular weight is less than the lower limit, the mechanical
properties of the thermoplastic resin composition of the present
invention are likely to be poor, and the aromatic polycarbonate
copolymer tends to cause bleeding. In cases where the viscosity
average molecular weight exceeds the upper limit, the fluidity
tends to be insufficient, which is not preferred. From such a point
of view, the viscosity average molecular weight (Mv) of the
aromatic polycarbonate copolymer in the present invention is
preferably not less than 9000, more preferably not less than
10,000, still more preferably not less than 11,000, and preferably
not more than 30,000, more preferably not more than 25,000, still
more preferably not more than 20,000, especially preferably not
more than 18,000.
[0056] When the viscosity average molecular weight of the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin is controlled to within the range described
above, two or more kinds of aromatic polycarbonate copolymers
having different viscosity average molecular weights may be mixed
and used. In such a case, the viscosity average molecular weight
(Mv) of the aromatic polycarbonate copolymer of the present
invention may be controlled by mixing an aromatic polycarbonate
copolymer having a viscosity average molecular weight outside the
above-described preferred range.
[0057] The viscosity average molecular weight (Mv) of the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention of the present
invention means a value calculated by determining the intrinsic
viscosity (limiting viscosity) [.eta.] (unit, dL/g) at a
temperature of 20.degree. C. using an Ubbelohde viscometer with
methylene chloride as a solvent, and applying the determined value
to the Schnell's viscosity equation, that is,
.eta.=1.23.times.10.sup.-4 Mv.sup.0.83. The intrinsic viscosity
(limiting viscosity) [.eta.] is a value calculated by measuring the
specific viscosity [.eta.sp] at each solution concentration [C]
(g/dL) and applying the measured value to the following
equation.
.eta. = lim c .fwdarw. 0 .eta. sp / c ##EQU00001##
Amount of Terminal Hydroxyl Groups in Aromatic Polycarbonate
Copolymer
[0058] The amount of terminal hydroxyl groups in the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention is not limited, and
usually 10 to 2000 ppm. The amount of terminal hydroxyl groups is
preferably not less than 20 ppm, more preferably not less than 50
ppm, still more preferably not less than 100 ppm. On the other
hand, the amount of terminal hydroxyl groups is preferably not more
than 1500 ppm, more preferably not more than 1000 ppm, still more
preferably not more than 700 ppm. In cases where the amount of
terminal hydroxyl groups is not less than the lower limit of this
range, the hue and the productivity of the fluidity modifier for
thermoplastic resin of the present invention can be improved, and
moreover, the hue of the thermoplastic resin composition containing
the fluidity modifier for thermoplastic resin of the present
invention can be improved. In cases where the amount of terminal
hydroxyl groups is not more than the upper limit, the thermal
stabilities and the moist heat stabilities of the fluidity modifier
for thermoplastic resin and the thermoplastic resin composition of
the present invention can be further improved.
[0059] The amount of terminal hydroxyl groups in the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention can be adjusted to
within the range described above by an arbitrary known method. For
example, in cases where the aromatic polycarbonate copolymer is
produced by polycondensation by transesterification reaction, the
amount of terminal hydroxyl groups can be adjusted to within the
above-described range by adjusting the mixing ratio between the
carbonate ester and the dihydroxy compounds, the degree of pressure
reduction during the transesterification reaction, and/or the
like.
[0060] Examples of more positive control methods include a method
in which a terminating agent is separately mixed during the
reaction of the aromatic polycarbonate copolymer. Examples of the
terminating agent in this process include monohydric phenols,
monovalent carboxylic acids, and diester carbonates. A single type
of terminating agent may be used, or two or more types of
terminating agents may be used in an arbitrary combination at
arbitrary ratios.
[0061] In cases where the aromatic polycarbonate copolymer
contained in the fluidity modifier for thermoplastic resin of the
present invention is produced by interfacial polymerization, the
amount of terminal hydroxyl groups can be arbitrarily adjusted by
adjusting the amount of a molecular weight modifier (terminating
agent) included.
[0062] The terminal hydroxyl group concentration is represented by
the mass, expressed in ppm units, of the terminal hydroxyl groups
with respect to the mass of the aromatic polycarbonate copolymer.
For its measurement, colorimetry by the titanium
tetrachloride/acetic acid method (the method described in Macromol.
Chem. 88 215 (1965)) is used. In an aromatic polycarbonate
copolymer composed of a plurality of dihydroxy compounds, the
corresponding dihydroxy compounds are mixed depending on the
copolymerization ratio, and samples with at least three levels of
concentrations are provided. A calibration curve is then drawn with
the data obtained at the three or more points, and the amount of
terminal hydroxyl groups in the aromatic polycarbonate copolymer is
measured thereafter. The detection wavelength is 546 nm.
Method for Producing Aromatic Polycarbonate Copolymer
[0063] The aromatic polycarbonate copolymer contained in the
fluidity modifier for thermoplastic resin of the present invention
is obtained by polycondensation of dihydroxy compounds including an
aromatic dihydroxy compound necessary for forming the carbonate
structural unit (A), an aromatic dihydroxy compound necessary for
forming the carbonate structural unit (B), and another dihydroxy
compound optionally selected; with a carbonate-forming
compound.
[0064] Examples of the aromatic dihydroxy compound necessary for
forming the carbonate structural unit (A) include the aromatic
dihydroxy compounds represented by the following Formula (32).
##STR00010##
[0065] Specific examples of the aromatic dihydroxy compound
necessary for forming the carbonate structural unit (A) include the
aromatic dihydroxy compounds represented by the following Formulae
(33) to (35). Among these, the aromatic dihydroxy compounds
represented by Formula (33) are more preferred since they tend to
increase the thermal stability. However, the aromatic dihydroxy
compounds of Formulae (34) and (35) may also included at arbitrary
ratios.
##STR00011##
[0066] In Formulae (32) to (35), the definitions and preferred
examples of R.sup.1, R.sup.2, R.sup.3, a, and b are the same as
those described for Formula (1) of the carbonate structural unit
(A).
[0067] From such a point of view, more preferred specific examples
of the aromatic dihydroxy compound necessary for forming the
carbonate structural unit (A) include the following:
[0068] 1,1-bis(4-hydroxyphenyl)nonane,
1,1-bis(2-hydroxyphenyl)nonane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)nonane,
1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(2-hydroxyphenyl)decane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)decane,
1,1-bis(4-hydroxyphenyl)undecane, 1,1-bis(2-hydroxyphenyl)undecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)undecane,
1,1-bis(4-hydroxyphenyl)dodecane, 1,1-bis(2-hydroxyphenyl)dodecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)dodecane,
1,1-bis(4-hydroxyphenyl)tridecane,
1,1-bis(2-hydroxyphenyl)tridecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)tridecane,
1,1-bis(4-hydroxyphenyl)tetradecane,
1,1-bis(2-hydroxyphenyl)tetradecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)tetradecane,
1,1-bis(4-hydroxyphenyl)pentadecane,
1,1-bis(2-hydroxyphenyl)pentadecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)pentadecane,
1,1-bis(4-hydroxyphenyl)hexadecane,
1,1-bis(2-hydroxyphenyl)hexadecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)hexadecane,
1,1-bis(4-hydroxyphenyl)heptadecane,
1,1-bis(2-hydroxyphenyl)heptadecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)heptadecane,
1,1-bis(4-hydroxyphenyl)octadecane,
1,1-bis(2-hydroxyphenyl)octadecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)octadecane,
1,1-bis(4-hydroxyphenyl)nonadecane,
1,1-bis(2-hydroxyphenyl)nonadecane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)nonadecane,
1,1-bis(4-hydroxyphenyl)icosane, 1,1-bis(2-hydroxyphenyl)icosane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)icosane,
1,1-bis(4-hydroxyphenyl)henicosane,
1,1-bis(2-hydroxyphenyl)henicosane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)henicosane,
1,1-bis(4-hydroxyphenyl)docosane, 1,1-bis(2-hydroxyphenyl)docosane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)docosane,
1,1-bis(4-hydroxyphenyl)tricosane,
1,1-bis(2-hydroxyphenyl)tricosane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)tricosane,
1,1-bis(4-hydroxyphenyl)tetracosane,
1,1-bis(2-hydroxyphenyl)tetracosane,
1-(2-hydroxyphenyl)-1-(4-hydroxyphenyl)tetracosane,
1,1-bis(3-methyl-4-hydroxyphenyl)nonane,
1,1-bis(2-hydroxy-3-methylphenyl)nonane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)nonane,
1,1-bis(3-methyl-4-hydroxyphenyl)decane,
1,1-bis(2-hydroxy-3-methylphenyl)decane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)decane,
1,1-bis(3-methyl-4-hydroxyphenyl)undecane,
1,1-bis(2-hydroxy-3-methylphenyl)undecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)undecane,
1,1-bis(3-methyl-4-hydroxyphenyl)dodecane,
1,1-bis(2-hydroxy-3-methylphenyl)dodecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)dodecane,
1,1-bis(3-methyl-4-hydroxyphenyl)tridecane,
1,1-bis(2-hydroxy-3-methylphenyl)tridecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)tridecane,
1,1-bis(3-methyl-4-hydroxyphenyl)tetradecane,
1,1-bis(2-hydroxy-3-methylphenyl)tetradecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)tetradecane,
1,1-bis(3-methyl-4-hydroxyphenyl)pentadecane,
1,1-bis(2-hydroxy-3-methylphenyl)pentadecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)pentadecane,
1,1-bis(3-methyl-4-hydroxyphenyl)hexadecane,
1,1-bis(2-hydroxy-3-methylphenyl)hexadecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)hexadecane,
1,1-bis(3-methyl-4-hydroxyphenyl)heptadecane,
1,1-bis(2-hydroxy-3-methylphenyl)heptadecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)heptadecane,
1,1-bis(3-methyl-4-hydroxyphenyl)octadecane,
1,1-bis(2-hydroxy-3-methylphenyl)octadecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)octadecane,
1,1-bis(3-methyl-4-hydroxyphenyl)nonadecane,
[0069] 1,1-bis(2-hydroxy-3-methylphenyl)nonadecane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)nonadecane,
1,1-bis(3-methyl-4-hydroxyphenyl)icosane,
1,1-bis(2-hydroxy-3-methylphenyl)icosane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)icosane,
1,1-bis(3-methyl-4-hydroxyphenyl)henicosane,
1,1-bis(2-hydroxy-3-methylphenyl)henicosane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)henicosane,
1,1-bis(3-methyl-4-hydroxyphenyl)docosane,
1,1-bis(2-hydroxy-3-methylphenyl)docosane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)docosane,
1,1-bis(3-methyl-4-hydroxyphenyl)tricosane,
1,1-bis(2-hydroxy-3-methylphenyl)tricosane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)tricosane,
1,1-bis(3-methyl-4-hydroxyphenyl)tetracosane,
1,1-bis(2-hydroxy-3-methylphenyl)tetracosane,
1-(2-hydroxy-3-methyl-phenyl)-1-(3-methyl-4-hydroxyphenyl)tetracosane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)octane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)nonane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)decane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)undecane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)dodecane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)tridecane,
1,1-bis(3,5-dimethyl-4-hydroxyphenyl)tetradecane,
1,1-bis(3-ethyl-4-hydroxyphenyl)nonane,
1,1-bis(3-ethyl-4-hydroxyphenyl)decane,
1,1-bis(3-ethyl-4-hydroxyphenyl)undecane,
1,1-bis(3-ethyl-4-hydroxyphenyl)dodecane,
1,1-bis(3-propyl-4-hydroxyphenyl)nonane,
1,1-bis(3-propyl-4-hydroxyphenyl)decane,
1,1-bis(3-propyl-4-hydroxyphenyl)undecane,
1,1-bis(3-propyl-4-hydroxyphenyl)dodecane,
1,1-bis(3-butyl-4-hydroxyphenyl)nonane,
1,1-bis(3-butyl-4-hydroxyphenyl)decane,
1,1-bis(3-butyl-4-hydroxyphenyl)undecane,
1,1-bis(3-butyl-4-hydroxyphenyl)dodecane,
1,1-bis(3-nonyl-4-hydroxyphenyl)nonane,
1,1-bis(3-nonyl-4-hydroxyphenyl)decane,
1,1-bis(3-nonyl-4-hydroxyphenyl)undecane, and
1,1-bis(3-nonyl-4-hydroxyphenyl)dodecane.
[0070] Among these, from the viewpoint of the thermal stability,
hue, and impact strength, the aromatic dihydroxy compound necessary
for forming the carbonate structural unit (A) of the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention is more preferably
1,1-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane,
1,1-bis(4-hydroxyphenyl)undecane, 1,1-bis(4-hydroxyphenyl)dodecane,
1,1-bis(4-hydroxyphenyl)tridecane,
1,1-bis(4-hydroxyphenyl)tetradecane,
1,1-bis(4-hydroxyphenyl)pentadecane,
1,1-bis(4-hydroxyphenyl)hexadecane,
1,1-bis(4-hydroxyphenyl)heptadecane,
1,1-bis(4-hydroxyphenyl)octadecane, or
1,1-bis(4-hydroxyphenyl)nonadecane, still more preferably
1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)undecane,
1,1-bis(4-hydroxyphenyl)dodecane, or
1,1-bis(4-hydroxyphenyl)tridecane, most preferably
1,1-bis(4-hydroxyphenyl)dodecane.
[0071] Specific examples of the aromatic dihydroxy compound
necessary for forming the carbonate structural unit (B) include
2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(2-hydroxyphenyl)propane,
and 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane. Among these,
from the viewpoint of the thermal stability, hue, and impact
strength, 2,2-bis(4-hydroxyphenyl)propane (the so-called bisphenol
A) is more preferred.
[0072] The other dihydroxy compound, which is different from the
aromatic dihydroxy compound necessary for forming the carbonate
structural unit (A) and the aromatic dihydroxy compound necessary
for forming the carbonate structural unit (B), is not limited, and
may be either an aromatic dihydroxy compound having an aromatic
ring in the molecular skeleton, or an aliphatic dihydroxy compound
having no aromatic ring. Further, the other dihydroxy compound may
be a dihydroxy compound in which a hetero atom(s) such as N
(nitrogen), S (sulfur), P (phosphorus), and/or Si (silicon), and/or
a hetero-bond(s), is/are introduced for giving various
properties.
[0073] From the viewpoint of the heat resistance, thermal
stability, and strength, the other dihydroxy compound preferably
used is an aromatic dihydroxy compound. Specific examples of such
an aromatic dihydroxy compound include the following:
[0074] dihydroxybenzenes such as 1,2-dihydroxybenzene,
1,3-dihydroxybenzene (that is, resorcinol), and
1,4-dihydroxybenzene; dihydroxybiphenyls such as
2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and
4,4'-dihydroxybiphenyl; dihydroxynaphthalenes such as
2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene,
1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene,
1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,
1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;
dihydroxydiaryl ethers such as 2,2'-dihydroxydiphenyl ether,
3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether,
4,4'-dihydroxy-3,3'-dimethyldiphenyl ether,
1,4-bis(3-hydroxyphenoxy)benzene, and
1,3-bis(4-hydroxyphenoxy)benzene; bis(hydroxyaryl)alkanes such as
1,1-bis(4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,2-bis(3-methoxy-4-hydroxyphenyl)propane,
2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane,
1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,
2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,
2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane,
.alpha.,.alpha.'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene,
1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene,
4,4-dihydroxydiphenylmethane,
bis(4-hydroxyphenyl)cyclohexylmethane,
bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)
(4-propenylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane,
bis(4-hydroxyphenyl)naphthylmethane,
1,1-bis(4-hydroxyphenyl)ethane,
1,1-bis(4-hydroxyphenyl)-1-phenylethane,
1,1-bis(4-hydroxyphenyl)-1-naphthylethane,
1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane,
2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane,
2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)hexane,
4,4-bis(4-hydroxyphenyl)heptane, and
2,2-bis(4-hydroxyphenyl)nonane; bis(hydroxyaryl)cycloalkanes such
as 1,1-bis(4-hydroxyphenyl)cyclopentane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane,
1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane,
1,1-bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane,
1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, and
1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane; cardo
structure-containing bisphenols such as
9,9-bis(4-hydroxyphenyl)fluorene and
9,9-bis(4-hydroxy-3-methylphenyl)fluorene; dihydroxydiaryl sulfides
such as 4,4'-dihydroxydiphenyl sulfide and
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl
sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; and dihydroxydiaryl
sulfones such as 4,4'-dihydroxydiphenyl sulfone and
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.
[0075] A single type of aromatic dihydroxy compound may be used, or
two or more types of aromatic dihydroxy compounds may be used in an
arbitrary combination at arbitrary ratios.
[0076] As the other dihydroxy compound described above, the
following aliphatic dihydroxy compounds may also be used depending
on the purpose. Specific examples of such aliphatic dihydroxy
compounds include the following:
[0077] alkanediols such as ethane-1,2-diol, propane-1,2-diol,
propane-1,3-diol, 2,2-dimethylpropane-1,3-diol,
2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol,
pentane-1,5-diol, hexane-1,6-diol, and decane-1,10-diol;
cycloalkanediols such as cyclopentane-1,2-diol,
cyclohexane-1,2-diol, cyclohexane-1,4-diol,
1,4-cyclohexanedimethanol, 4-(2-hydroxyethyl)cyclohexanol, and
2,2,4,4-tetramethyl-cyclobutane-1,3-diol; glycols such as ethylene
glycol, 2,2'-oxydiethanol (that is, diethylene glycol), triethylene
glycol, propylene glycol, and spiroglycol; aralkyldiols such as
1,2-benzenedimethanol, 1,3-benzenedimethanol,
1,4-benzenedimethanol, 1,4-benzenediethanol,
1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene,
2,3-bis(hydroxymethyl)naphthalene,
1,6-bis(hydroxyethoxy)naphthalene, 4,4'-biphenyldimethanol,
4,4'-biphenyldiethanol, 1,4-bis(2-hydroxyethoxy)biphenyl, bisphenol
A bis(2-hydroxyethyl)ether, and bisphenol S bis
(2-hydroxyethyl)ether; cyclic ethers such as 1,2-epoxyethane (that
is, ethylene oxide), 1,2-epoxypropane (that is, propylene oxide),
1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane,
1-methyl-1,2-epoxycyclohexane, 2,3-epoxynorbornane, and
1,3-epoxypropane; and oxygen-containing heterocyclic dihydroxy
compounds such as isosorbide, isomannide, and isoidide.
[0078] A single type of aliphatic dihydroxy compound may be used,
or two or more types of aliphatic dihydroxy compounds may be used
in an arbitrary combination at arbitrary ratios. Examples of the
carbonate-forming compound include carbonyl halides and carbonate
esters. A single type of carbonate-forming compound may be used, or
two or more types of carbonate-forming compounds may be used in an
arbitrary combination at arbitrary ratios.
[0079] Specific examples of the carbonyl halides include phosgene;
haloformates such as bischloroformate bodies of dihydroxy
compounds, and monochloroformate bodies of dihydroxy compounds.
[0080] Specific examples of the carbonate esters include the
compounds represented by the following Formula (36), for example,
aryl carbonates; dialkyl carbonates; biscarbonate bodies of
dihydroxy compounds; monocarbonate bodies of dihydroxy compounds;
and carbonate bodies of dihydroxy compounds such as cyclic
carbonates.
##STR00012##
[0081] In Formula (36), R.sup.4 and R.sup.5 each independently
represent C.sub.1-C.sub.30 alkyl, aryl, or arylalkyl group.
Hereinafter, when R.sup.4 and R.sup.5 are alky and/or arylalkyl,
the carbonate ester may be referred to as dialkyl carbonate, and
when R.sup.4 and R.sup.5 are aryl, the carbonate ester may be
referred to as diaryl carbonate. In particular, from the viewpoint
of reactivity with the dihydroxy compounds, both R.sup.4 and
R.sup.5 are preferably aryl. The carbonate ester is more preferably
a diaryl carbonate represented by the following Formula (37).
##STR00013##
[0082] In Formula (37), R.sup.6 and R.sup.7 each independently
represent a halogen atom, nitro, cyano, C.sub.1-C.sub.20 alkyl,
C.sub.1-C.sub.20 alkoxycarbonyl, C.sub.4-C.sub.20 cycloalkyl, or
C.sub.6-C.sub.20 aryl, and p and q each independently represent an
integer of 0 to 5.
[0083] Specific examples of such a carbonate ester include dialkyl
carbonates such as dimethyl carbonate, diethyl carbonate, and
di-t-butyl carbonate; and (substituted) diaryl carbonates such as
diphenyl carbonate (which may be hereinafter referred to as "DPC"),
bis(4-methylphenyl)carbonate, bis(4-chlorophenyl)carbonate,
bis(4-fluorophenyl)carbonate, bis(2-chlorophenyl)carbonate,
bis(2,4-difluorophenyl)carbonate, bis(4-nitrophenyl)carbonate,
bis(2-nitrophenyl)carbonate, bis(methylsalicylphenyl)carbonate, and
ditolyl carbonate. Among these, diphenyl carbonate is preferred.
These carbonate esters may be used individually, or two or more of
these may be used as a mixture.
[0084] Preferably not more than 50 mol %, more preferably not more
than 30 mol % of the carbonate ester may be substituted with a
dicarboxylic acid(s) and/or dicarboxylic acid ester(s).
Representative examples of the dicarboxylic acid(s) and/or
dicarboxylic acid ester(s) include terephthalic acid, isophthalic
acid, diphenyl terephthalate, and diphenyl isophthalate. In cases
of substitution with such a dicarboxylic acid(s) and/or
dicarboxylic acid ester(s), a polyester carbonate is obtained.
[0085] The aromatic polycarbonate copolymer contained in the
fluidity modifier for thermoplastic resin of the present invention
can be produced by a conventionally known polymerization method,
and the polymerization method is not limited. Examples of the
polymerization method include interfacial polymerization, melt
transesterification, pyridine method, ring-opening polymerization
of cyclic carbonate compounds, and solid-phase transesterification
of prepolymers. Methods especially preferred among these are
concretely described below.
Interfacial Polymerization
[0086] First, a case where the aromatic polycarbonate copolymer
contained in the fluidity modifier for thermoplastic resin of the
present invention is produced by interfacial polymerization is
described. In the interfacial polymerization, the pH is usually
maintained at not less than 9 in the presence of an organic solvent
inert to the reaction, and an aqueous alkali solution. After
reacting the material dihydroxy compounds with the
carbonate-forming compound (preferably phosgene), interfacial
polymerization is carried out in the presence of a polymerization
catalyst to obtain an aromatic polycarbonate copolymer. If
necessary, in the reaction system, a molecular weight modifier
(terminating agent) may be allowed to be present, and, for
prevention of oxidation of the dihydroxy compounds, an antioxidant
may be allowed to present.
[0087] The material dihydroxy compounds and the carbonate-forming
compound are as described above. Among carbonate-forming compounds,
phosgene is preferably used. In cases where phosgene is used, the
method is specifically called the phosgene method.
[0088] Examples of the organic solvent inert to the reaction
include, but are not limited to, chlorinated hydrocarbons such as
dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene,
and dichlorobenzene; and aromatic hydrocarbons such as benzene,
toluene, and xylene. A single type of organic solvent may be used,
or two or more types of organic solvents may be used in an
arbitrary combination at arbitrary ratios.
[0089] Examples of the alkali compound contained in the aqueous
alkali solution include, but are not limited to, alkali metal
compounds such as sodium hydroxide, potassium hydroxide, lithium
hydroxide, and sodium hydrogen carbonate; and alkaline earth metal
compounds. Sodium hydroxide and potassium hydroxide are especially
preferred. A single type of alkali compound may be used, or two or
more types of alkali compounds may be used in an arbitrary
combination at arbitrary ratios.
[0090] The concentration of the alkali compound in the aqueous
alkali solution is not limited. The alkali compound is usually used
in an amount of 5 to 10% by mass for the purpose of controlling the
pH of the aqueous alkali solution to 10 to 12 for the reaction. In
cases where phosgene is blown, for controlling the pH of the
aqueous phase to 10 to 12, preferably 10 to 11, the molar ratio
between the material dihydroxy compounds and the alkali compound is
preferably adjusted to usually 1:1.9 or more, especially 1:2.0 or
more, and usually 1:3.2 or less, especially 1:2.5 or less.
[0091] Examples of the polymerization catalyst include, but are not
limited to, aliphatic tertiary amines such as trimethylamine,
triethylamine, tributylamine, tripropylamine, and trihexylamine;
alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and
N,N'-diethylcyclohexylamine; aromatic tertiary amines such as
N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium
salts such as trimethylbenzylammonium chloride, tetramethylammonium
chloride, and triethylbenzylammonium chloride; pyridine; guanine;
and salts of guanidine. A single type of polymerization catalyst
may be used, or two or more types of polymerization catalysts may
be used in an arbitrary combination at arbitrary ratios.
[0092] Examples of the molecular weight modifier include, but are
not limited to, aromatic phenols having a monohydric phenolic
hydroxyl group; aliphatic alcohols such as methanol and butanol;
mercaptan; and phthalic imide. Aromatic phenols are especially
preferred. Specific examples of such aromatic phenols include
phenol, o-n-butylphenol, m-n-butylphenol, p-n-butylphenol,
o-isobutylphenol, m-isobutylphenol, p-isobutylphenol,
o-t-butylphenol, m-t-butylphenol, p-t-butylphenol,
o-n-pentylphenol, m-n-pentylphenol, p-n-pentylphenol,
o-n-hexylphenol, m-n-hexylphenol, p-n-hexylphenol, p-t-octylphenol,
o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol,
o-phenylphenol, m-phenylphenol, p-phenylphenol, o-n-nonylphenol,
m-nonylphenol, p-n-nonylphenol, o-cumylphenol, m-cumylphenol,
p-cumylphenol, o-naphthylphenol, m-naphthylphenol, and
p-naphthylphenol; 2,5-di-t-butylphenol; 2,4-di-t-butylphenol;
3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol;
p-cresol, bromophenol, tribromophenol, and monoalkylphenols having
a linear or branched alkyl group having an average carbon number of
12 to 35 at the ortho position, meta position, or para position;
9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene;
9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene;
and 4-(1-adamantyl)phenol. Among these, p-t-butyl phenol,
p-phenylphenol, and p-cumylphenol are preferably used. A single
type of molecular weight modifier may be used, or two or more types
of molecular weight modifiers may be used in an arbitrary
combination at arbitrary ratios.
[0093] The amount of the molecular weight modifier used is not
limited. For example, the amount is usually not less than 0.5 mole,
preferably not less than 1 mole, and usually not more than 50
moles, preferably not more than 30 moles, with respect to 100 moles
of the material dihydroxy compounds. In cases where the amount of
the molecular weight modifier used is within this range, thermal
stability and hydrolysis resistance of the aromatic polycarbonate
copolymer can be increased.
[0094] In the reaction, a reaction substrate(s) (reaction
material(s)), reaction medium/media (organic solvent(s)),
catalyst(s), additive(s), and/or the like may be mixed in an
arbitrary order as long as a desired aromatic polycarbonate
copolymer can be obtained. An appropriate order may be arbitrarily
set. For example, in cases where phosgene is used as the
carbonate-forming compound, a molecular weight modifier may be
mixed at an arbitrary timing between the reaction of the material
dihydroxy compounds with phosgene (phosgenation) and the beginning
of the polymerization reaction.
[0095] The reaction temperature is not limited, and usually 0 to
40.degree. C. The reaction time is not limited, and usually several
minutes (for example, 10 minutes) to several hours (for example, 6
hours).
Melt Transesterification
[0096] Next, a case where the aromatic polycarbonate copolymer
contained in the fluidity modifier for thermoplastic resin of the
present invention is produced by melt transesterification is
described. In the melt transesterification, transesterification
reaction between, for example, a carbonate ester and the material
dihydroxy compounds is performed.
[0097] The material dihydroxy compounds and the carbonate ester are
as described above.
[0098] The ratio between the material dihydroxy compounds and the
carbonate ester (including the substituted dicarboxylic acid or
dicarboxylic acid ester; the same applies hereinafter) is arbitrary
as long as a desired aromatic polycarbonate copolymer can be
obtained. In the polymerization with the dihydroxy compounds, the
carbonate ester is preferably used in an excess amount to the
material dihydroxy compounds. That is, the amount of the carbonate
ester is preferably 1.01 to 1.30 times the amount (molar ratio),
more preferably 1.02 to 1.20 times the amount (molar ratio) of the
dihydroxy compounds. In cases where the molar ratio is too low, the
amount of terminal OH groups in the resulting aromatic
polycarbonate copolymer is large, and the thermal stability of the
resin tends to be poor. In cases where the molar ratio is too high,
the reaction rate in the transesterification is low, so that
production of an aromatic polycarbonate copolymer having a desired
molecular weight may be difficult, or a large amount of the
carbonate ester remains in the resin, resulting in generation of
odor during molding or after production of a molded article in some
cases.
[0099] Usually, in cases where the aromatic polycarbonate copolymer
is produced by melt transesterification, a transesterification
catalyst is used. The transesterification catalyst is not limited,
and a conventionally known transesterification catalyst may be
used. For example, an alkali metal compound(s) and/or an alkaline
earth metal compound(s) is/are preferably used. In addition, a
basic compound(s) such as a basic boron compound(s), basic
phosphorus compound(s), basic ammonium compound(s), and/or amine
compound(s) may be supplementarily used in combination. A single
type of transesterification catalyst may be used, or two or more
types of transesterification catalysts may be used in an arbitrary
combination at arbitrary ratios.
[0100] In the melt transesterification, the reaction temperature is
not limited, and usually 100 to 320.degree. C. The pressure during
the reaction is also not limited. The reaction is usually carried
out under a reduced pressure of not more than 2 mmHg. More
specifically, the operation may be carried out by allowing melt
polycondensation reaction to proceed under the above conditions
while removing by-products.
[0101] In terms of the reaction mode, the reaction may be carried
out by either a batch method or a continuous method. In cases where
the reaction is carried out by a batch method, a reaction
substrate(s), reaction medium/media, catalyst(s), additive(s),
and/or the like may be mixed in an arbitrary order as long as a
desired aromatic polycarbonate copolymer can be obtained. An
appropriate order may be arbitrarily set. In particular, taking
into account the stability and the like of the aromatic
polycarbonate copolymer, the melt polycondensation reaction is
preferably carried out by a continuous method.
[0102] In the melt transesterification, a catalyst deactivator may
be used, if necessary. As the catalyst deactivator, a compound that
neutralizes the transesterification catalyst may be arbitrarily
used. Examples of the catalyst deactivator include
sulfur-containing acidic compounds and derivatives thereof, and
phosphorus-containing compounds and derivatives thereof. A single
type of catalyst deactivator may be used, or two or more types of
catalyst deactivators may be used in an arbitrary combination at
arbitrary ratios.
[0103] The amount of the catalyst deactivator used is not limited,
and usually not less than 0.5 equivalent, preferably not less than
1 equivalent, and usually not more than 20 equivalents, preferably
not more than 10 equivalents, with respect to the alkali metal or
alkaline earth metal contained in the transesterification catalyst.
Further, the amount of the catalyst deactivator is usually not less
than 1 ppm, and usually not more than 100 ppm, preferably not more
than 50 ppm, with respect to the aromatic polycarbonate
copolymer.
Thermoplastic Resin Composition
[0104] The thermoplastic resin composition of the present invention
comprises 100 parts by mass of a thermoplastic resin and 2 to 100
parts by mass of the fluidity modifier for thermoplastic resin
described above. By inclusion of the fluidity modifier for
thermoplastic resin of the present invention in the thermoplastic
resin within the above-described range, fluidity and moldability of
the thermoplastic resin can be increased without significantly
deteriorating physical properties such as mechanical properties,
thermal properties, and optical properties of the resin. In cases
where the content of the fluidity modifier for thermoplastic resin
of the present invention with respect to the thermoplastic resin is
less than the lower limit of this range, the thermoplastic resin
composition of the present invention has insufficient fluidity,
while in cases where the content exceeds the upper limit of this
range, the thermoplastic resin composition of the present invention
may have low heat resistance and low mechanical strength, which is
not preferred. From such a point of view, the content of the
fluidity modifier for thermoplastic resin described above in the
thermoplastic resin composition of the present invention is
preferably not less than 5 parts by mass, more preferably not less
than 7 parts by mass, still more preferably not less than 10 parts
by mass, especially preferably not less than 12 parts by mass, with
respect to 100 parts by mass of the thermoplastic resin. Further,
the content is preferably not more than 90 parts by mass, more
preferably not more than 80 parts by mass, still more preferably
not more than 70 parts by mass, especially preferably not more than
60 parts by mass. The optimum amount of the fluidity modifier for
thermoplastic resin to be included may be appropriately selected
and determined in consideration of the type and the content of the
carbonate structural unit (A) in the fluidity modifier for
thermoplastic resin to be applied, and the type of the
thermoplastic resin, as well as the balance between the physical
properties and the fluidity required for the thermoplastic resin
composition of the present invention.
[0105] In cases where the thermoplastic resin composition is a
polycarbonate resin composition composed of the later-described
polycarbonate resin and the fluidity modifier for thermoplastic
resin of the present invention, the ratio of the carbonate
structural unit (A) to the total carbonate structural units in the
thermoplastic resin composition (the total of the carbonate
structural units in the polycarbonate resin and the carbonate
structural units in the aromatic polycarbonate copolymer contained
in the fluidity modifier for thermoplastic resin of the present
invention) is preferably 1 to 20 mol %. Within such a range, a
thermoplastic resin composition having not only excellent fluidity
and mechanical strength, but also excellent heat resistance, can be
obtained.
Flow Value (Q Value) of Thermoplastic Resin Composition
[0106] The melt viscosity of the thermoplastic resin composition of
the present invention is not limited as long as the effect of the
present invention is not deteriorated. The melt viscosity, in terms
of the flow value (Q value) as measured using a Koka flow tester
according to Appendix C of JIS (1999) K7210 at 240.degree. C. at
160 kgf/cm.sup.2, is usually not less than 1 (unit: 10.sup.-2
cm/sec.), preferably not less than 2, more preferably not less than
6, still more preferably not less than 10, especially preferably
not less than 20. On the other hand, the upper limit of the Q value
is not limited as long as the excellent physical properties of the
thermoplastic resin composition of the present invention are not
deteriorated. The Q value is usually not more than 100, preferably
not more than 90, more preferably not more than 80, still more
preferably not more than 70, especially preferably not more than
60.
Glass Transition Temperature (Tg) of Thermoplastic Resin
Composition
[0107] The heat resistance of the thermoplastic resin composition
of the present invention is not limited, and may be appropriately
selected depending on the properties of the thermoplastic resin. In
cases of an amorphous resin such as a polycarbonate resin, the
glass transition temperature (Tg) is preferably from 90.degree. C.
to 145.degree. C. Since a thermoplastic resin having a glass
transition temperature (Tg) within this range has an excellent
balance between heat resistance and fluidity (moldability), it can
be suitably used for automobile and electric/electronic device
members, and optical members such as lenses and light guide plates.
From such a point of view, the glass transition temperature (Tg) of
the thermoplastic resin composition of the present invention is
preferably not less than 95.degree. C., more preferably not less
than 100.degree. C., still more preferably not less than
105.degree. C., especially preferably not less than 110.degree. C.
On the other hand, the glass transition temperature is preferably
not more than 142.degree. C., more preferably not more than
140.degree. C., still more preferably not more than 138.degree. C.,
especially preferably not more than 135.degree. C.
[0108] The measurement method and the definition for the glass
transition temperature (Tg) of the thermoplastic resin composition
of the present invention are the same as those for the glass
transition temperature (Tg) of the aromatic polycarbonate copolymer
described above.
Thermoplastic Resin
[0109] The thermoplastic resin used for the thermoplastic resin
composition of the present invention is not limited, and examples
of the thermoplastic resin include polycarbonate resins such as
aromatic polycarbonate and aliphatic polycarbonate; polyester
carbonate resins such as fatty acid-aromatic polycarbonate
copolymers and polyarylate resins; polyarylether resins such as
polyphenylene ether resins; polyphenylene sulfide resins; acrylic
resins such as polymethyl methacrylate and phenyl
methacrylate-methyl methacrylate copolymers; polyester resins such
as polyethylene terephthalate resins, polytrimethylene
terephthalate, polybutylene terephthalate resins, polycaprolactone
resins, and liquid crystal polyester resins; styrene resins such as
polystyrene resins, maleic anhydride-modified polystyrene resins,
high-impact polystyrene resins (HIPS), acrylonitrile-styrene
copolymers (AS resins), methyl methacrylate-styrene copolymers (MS
resins), butadiene rubber-acrylonitrile-styrene copolymers (ABS
resins), acrylonitrile-styrene-acrylic rubber copolymers (ASA
resins), and acrylonitrile-ethylene/propylene rubber-styrene
copolymers (AES resins); polyolefin resins such as polyethylene
resins, polypropylene resins, cyclic cycloolefin (COP) resins, and
cyclic cycloolefin copolymer resins (COC); polyamide resins;
polyimide resins; polyetherimide resins; polyurethane resins;
polysulfone resins; polyketone resins; and polyoxyalkylene resins
such as polyoxymethylene resins. The thermoplastic resin in the
present invention also includes, of course, thermoplastic resin
alloys containing a combination of two or more of the thermoplastic
resins described above. Examples of such alloys include
polycarbonate resin/acrylic resin alloys, polycarbonate
resin/polyester resin alloys, polycarbonate resin/styrene resin
alloys, polycarbonate resin/polyolefin resin alloys, polycarbonate
resin/polyphenylene sulfide resin alloys, polyphenylene ether
resin/styrene resin alloys (modified polyphenylene ether), and
polyphenylene ether resin/polyamide resin alloys.
[0110] In particular, the thermoplastic resin used for the
thermoplastic resin composition of the present invention is
preferably a polycarbonate resin, polyester carbonate resin, or an
alloy of a polycarbonate resin and another thermoplastic resin,
from the viewpoint of compatibility with the fluidity modifier of
the present invention. A polycarbonate resin is more preferred.
[0111] The polycarbonate resin as the thermoplastic resin described
above is not limited, and examples of the polycarbonate resin
include polycarbonate resins obtained by polycondensation of
[0112] a dihydroxy compound exemplified as the aromatic dihydroxy
compound necessary for forming the carbonate structural unit (B) in
the aromatic polycarbonate copolymer contained in the fluidity
modifier for thermoplastic resin of the present invention;
[0113] a dihydroxy compound exemplified as the other dihydroxy
compound different from the aromatic dihydroxy compound necessary
for forming the carbonate structural unit (A) and the aromatic
dihydroxy compound necessary for forming the carbonate structural
unit (B); and
[0114] a carbonate-forming compound.
[0115] Examples of the method for producing the polycarbonate resin
as the thermoplastic resin described above also include the same
method as the above-described method for producing the aromatic
polycarbonate copolymer contained in the fluidity modifier for
thermoplastic resin of the present invention.
[0116] The molecular weight of the polycarbonate resin as the
thermoplastic resin described above is not limited, and usually
5000 to 100,000, preferably 9000 to 50,000, more preferably 10,000
to 30,000, still more preferably 11,000 to 28,000, in terms of the
viscosity average molecular weight (Mv) calculated from the
solution viscosity.
[0117] When the molecular weight, in terms of the viscosity average
molecular weight, of the polycarbonate resin as the thermoplastic
resin described above is controlled to within the range described
above, two or more kinds of polycarbonate resins having different
viscosity average molecular weights may be mixed. In such a case,
the viscosity average molecular weight (Mv) of the polycarbonate
resin of the present invention may be controlled by mixing a
polycarbonate resin having a viscosity average molecular weight
outside the above-described preferred range.
[0118] The measurement method and the definition for the molecular
weight, in terms of the viscosity average molecular weight (Mv), of
the polycarbonate resin as the thermoplastic resin described above
are the same as those for the viscosity average molecular weight
(Mv) of the aromatic polycarbonate copolymer described above.
[0119] The thermoplastic resin composition of the present invention
may contain another component (resin additive) in addition to the
components described above as long as the effect of the present
invention and the desired physical properties are not remarkably
inhibited. Examples of the resin additive include heat stabilizers,
antioxidants, ultraviolet absorbers, brightness improvers, dyes,
pigments, mold release agents, flame retardants, reinforcing
materials, antistatic agents, anti-clouding agents, lubricants,
anti-blocking agents, dispersants, and antimicrobial agents. For
use as a common injection molding material, the thermoplastic resin
composition preferably further contains at least one selected from
the group consisting of heat stabilizers, antioxidants, ultraviolet
absorbers, brightness improvers, dyes, pigments, and mold release
agents.
[0120] A single type of resin additive may be included, or two or
more types of resin additives may be included in an arbitrary
combination at arbitrary ratios.
Heat Stabilizer
[0121] The heat stabilizer used in the thermoplastic resin
composition of the present invention is not limited as long as it
is a known heat stabilizer that has conventionally been added to
thermoplastic resins, and examples of the heat stabilizer include
phosphorus-based heat stabilizers and sulfur-based heat
stabilizers. In particular, phosphorus-based stabilizers are
preferred since they tend to allow production of a thermoplastic
resin of the present invention having a better initial hue and a
better residence heat stability.
[0122] Specific examples of the phosphorus-based heat stabilizers
include oxoacids of phosphorus such as phosphoric acid, phosphoric
acid, phosphorous acid, phosphinic acid, and polyphosphoric acid;
metal salts of acid pyrophosphoric acid such as sodium acid
pyrophosphate, potassium acid pyrophosphate, and calcium acid
pyrophosphate; phosphoric acid salts of Group 1 or Group 2B metals
such as potassium phosphate, sodium phosphate, cesium phosphate,
and zinc phosphate; organic phosphate compounds; organic phosphite
compounds; and organic phosphonite compounds. From the viewpoint of
thermal stability and moist heat stability, organic phosphite
compounds and organic phosphonite are especially preferred, and
organic phosphite compounds are most preferred.
[0123] Examples of the organic phosphite compounds include
triphenylphosphite, tris(4-methylphenyl)phosphite,
tris(4-t-butylphenyl)phosphite, tris(monononylphenyl)phosphite,
tris(2-methyl-4-ethylphenyl)phosphite,
tris(2-methyl-4-t-butylphenyl)phosphite,
tris(2,4-di-t-butylphenyl)phosphite,
tris(2,6-di-t-butylphenyl)phosphite,
tris(2,4-di-t-butyl-5-methylphenyl)phosphite,
tris(mono,dinonylphenyl)phosphite,
bis(monononylphenyl)pentaerythritol-di-phosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite,
bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite,
bis(2,4,6-tri-t-butylphenyl)pentaerythritol-di-phosphite,
bis(2,4-di-t-butyl-5-methylphenyl)pentaerythritol-di-phosphite,
(2,6-di-t-butyl-4methylphenyl)pentaerythritoldiphosphite,
2,2-methylenebis(4,6-dimethylphenyl)octylphosphite,
2,2-methylenebis(4-t-butyl-6-methylphenyl)octylphosphite,
2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite,
2,2-methylenebis(4,6-dimethylphenyl)hexylphosphite,
2,2-methylenebis(4,6-di-t-butylphenyl)hexylphosphite, and
2,2-methylenebis(4,6-di-t-butylphenyl)stearyl phosphite. Examples
of the organic phosphonite compounds include
tetrakis(2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite and
tetrakis(2,4-di-t-butyl-5-methylphenyl) 4,4'-biphenylene
diphosphonite.
[0124] Specific examples of such organic phosphite compounds
include "Adekastab 1178", "Adekastab (registered trademark) 2112",
"Adekastab PEP-8", "Adekastab PEP-36", and "Adekastab HP-10",
manufactured by ADEKA Corporation; "JP-351", "JP-360", and
"JP-3CP", manufactured by Johoku Chemical Co., Ltd.; and "Irgafos
(registered trademark) 168", manufactured by BASF. Examples of the
organic phosphonite compounds include "Irgafos P-EPQ", manufactured
by BASF.
[0125] A single type of phosphorus-based stabilizer may be
included, or two or more types of phosphorus-based stabilizers may
be included in an arbitrary combination at arbitrary ratios.
[0126] The content of the phosphorus-based stabilizer is not
limited, and usually not less than 0.001 part by mass, preferably
not less than 0.01 part by mass, more preferably not less than 0.03
part by mass, and usually not more than 1 part by mass, preferably
not more than 0.7 part by mass, more preferably not more than 0.5
part by mass, with respect to a total of 100 parts by mass of the
thermoplastic resin and the fluidity modifier for thermoplastic
resin. In cases where the content of the phosphorus-based
stabilizer is less than the lower limit of this range, the thermal
stability effect may be insufficient, while in cases where the
content of the phosphorus-based stabilizer exceeds the upper limit
of this range, the moist heat stability may be low, and generation
of gas tends to occur during injection molding.
Antioxidant
[0127] The thermoplastic resin composition of the present invention
also preferably contains an antioxidant. The antioxidant used in
the thermoplastic resin composition of the present invention is not
limited as long as it is a known antioxidant that has
conventionally been added to thermoplastic resins, and examples of
the antioxidant include hindered phenol antioxidants. Specific
examples of the hindered phenol antioxidants include
pentaerythritol
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
thiodiethylene
bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)-
, 2,4-dimethyl-6-(1-methylpentadecyl)phenol,
diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate,
3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p--
cresol, 4,6-bis(octylthiomethyl)-o-cresol,
ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]-
, hexamethylene
bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,-
5H)-trione,
2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol,
and
2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphe-
nyl acrylate.
[0128] Among these, pentaerythritol
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are
preferred. Specific examples of such phenolic antioxidants include
"Irganox 1010" and "Irganox 1076", manufactured by Ciba Specialty
Chemicals; and "Adekastab AO-50" and "Adekastab AO-60",
manufactured by ADEKA Corporation.
[0129] A single type of antioxidant may be included, or two or more
types of antioxidants may be included in an arbitrary combination
at arbitrary ratios.
[0130] The content of the antioxidant is not limited, and usually
not less than 0.001 part by mass, preferably not less than 0.01
part by mass, more preferably not less than 0.1 part by mass, and
usually not more than 1 part by mass, preferably not more than 0.5
part by mass, with respect to a total of 100 parts by mass of the
thermoplastic resin and the fluidity modifier for thermoplastic
resin. In cases where the content of the antioxidant is less than
the lower limit of this range, its effect as an antioxidant may be
insufficient, while in cases where the content of the phenolic
stabilizer exceeds the upper limit of this range, generation of gas
may tend to occur during injection molding.
Ultraviolet Absorber
[0131] Examples of the ultraviolet absorbers include inorganic
ultraviolet absorbers such as cerium oxide and zinc oxide; and
organic ultraviolet absorbers such as benzotriazole compounds,
benzophenone compounds, salicylate compounds, cyanoacrylate
compounds, triazine compounds, oxanilide compounds, malonate
compounds, and hindered amine compounds. Among these, organic
ultraviolet absorbers are preferred. Benzotriazole compounds are
more preferred. By selection of an organic ultraviolet absorber,
the thermoplastic resin composition of the present invention can
have favorable transparency and mechanical properties.
[0132] Specific examples of the benzotriazole compounds include
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-[2'-hydroxy-3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl]-benzotriaz-
ole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole,
2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole),
2-(2'-hydroxy-3',5'-di-tert-amyl)-benzotriazole,
2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, and
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)ph-
enol]. Among these, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole
and
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)ph-
enol are preferred. 2-(2'-Hydroxy-5'-tert-octylphenyl)benzotriazole
is especially preferred.
[0133] Examples of commercially available products of such
benzotriazole compounds include "Seesorb 701", "Seesorb 705",
"Seesorb 703", "Seesorb 702", "Seesorb 704", and "Seesorb 709",
manufactured by Shipro Kasei Kaisha, Ltd.; "Biosorb 520", "Biosorb
582", "Biosorb 580", and "Biosorb 583", manufactured by Kyodo
Chemical Co., Ltd.; "Kemisorb 71" and "Kemisorb 72", manufactured
by Chemipro Kasei Kaisha, Ltd.; "Cyasorb UV5411", manufactured by
Cytec Industries Inc.; "LA-32", "LA-38", "LA-36", "LA-34", and
"LA-31", manufactured by ADEKA Corporation; and "Tinuvin P",
"Tinuvin 234", "Tinuvin 326", "Tinuvin 327", and "Tinuvin 328",
manufactured by Ciba Specialty Chemicals.
[0134] Specific examples of the benzophenone compounds include
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid,
2-hydroxy-4-n-octoxybenzophenone,
2-hydroxy-n-dodecyloxybenzophenone,
bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane,
2,2'-dihydroxy-4-methoxybenzophenone, and
2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
[0135] Examples of commercially available products of such
benzophenone compounds include "Seesorb 100", "Seesorb 101",
"Seesorb 101S", "Seesorb 102", and "Seesorb 103", manufactured by
Shipro Kasei Kaisha, Ltd.; "Biosorb 100", "Biosorb 110", and
"Biosorb 130", manufactured by Kyodo Chemical Co., Ltd.; "Kemisorb
10", "Kemisorb 11", "Kemisorb 11S", "Kemisorb 12", "Kemisorb 13",
and "Kemisorb 111", manufactured by Chemipro Kasei Kaisha, Ltd.;
"Uvinul 400", manufactured by BASF; "Uvinul M-40", manufactured by
BASF; "Uvinul MS-40", manufactured by BASF; "Cyasorb UV9", "Cyasorb
UV284", "Cyasorb UV531", and "Cyasorb UV24", manufactured by Cytec
Industries Inc.; and "Adekastab 1413" and "Adekastab LA-51",
manufactured by ADEKA Corporation.
[0136] Specific examples of the salicylate compounds include phenyl
salicylate and 4-tert-butylphenyl salicylate. Examples of
commercially available products of such salicylate compounds
include "Seesorb 201" and "Seesorb 202", manufactured by Shipro
Kasei Kaisha, Ltd.; and "Kemisorb 21" and "Kemisorb 22",
manufactured by Chemipro Kasei Kaisha, Ltd.
[0137] Specific examples of the cyanoacrylate compounds include
ethyl-2-cyano-3,3-diphenylacrylate and
2-ethylhexyl-2-cyano-3,3-diphenylacrylate. Examples of commercially
available products of such cyanoacrylate compounds include "Seesorb
501", manufactured by Shipro Kasei Kaisha, Ltd.; "Biosorb 910",
manufactured by Kyodo Chemical Co., Ltd.; "Uvisolator 300",
manufactured by Daiichi Kasei Co., Ltd.; and "Uvinul N-35" and
"Uvinul N-539", manufactured by BASF.
[0138] Examples of the triazine compounds include compounds having
a 1,3,5-triazine skeleton. Specific examples of such triazine
compounds include "LA-46", manufactured by ADEKA Corporation; and
"Tinuvin 1577ED", "Tinuvin 400", "Tinuvin 405", "Tinuvin 460",
"Tinuvin 477-DW", and "Tinuvin 479", manufactured by Ciba Specialty
Chemicals.
[0139] Specific examples of the oxanilide compounds include
2-ethoxy-2'-ethyloxalinic acid bisanilide. Examples of commercially
available products of such oxanilide compounds include "Sanduvor
VSU", manufactured by Clariant.
[0140] As the malonate compounds, 2-(alkylidene) malonates are
preferred. 2-(1-Arylalkylidene) malonates are more preferred.
Examples of commercially available products of such malonate
compounds include "PR-25", manufactured by Clariant Japan K.K.; and
"B-CAP", manufactured by Ciba Specialty Chemicals.
[0141] The content of the ultraviolet absorber is usually not less
than 0.01 part by mass, preferably not less than 0.1 part by mass,
and usually not more than 3 parts by mass, preferably not more than
1 part by mass, with respect to a total of 100 parts by mass of the
thermoplastic resin and the fluidity modifier for thermoplastic
resin. In cases where the content of the ultraviolet absorber is
less than the lower limit of this range, the
weatherability-improving effect may be insufficient, while in cases
where the content of the ultraviolet absorber exceeds the upper
limit of this range, mold deposits and the like may be produced to
cause mold contamination. A single type of ultraviolet absorber may
be included, or two or more types of ultraviolet absorbers may be
included in an arbitrary combination at arbitrary ratios.
Brightness Improver
[0142] The thermoplastic resin composition of the present invention
also preferably contains a brightness improver. The brightness
improver used in the thermoplastic resin composition of the present
invention is not limited as long as it is a known brightness
improver that has conventionally been added to thermoplastic
resins, especially polycarbonate resins, and preferred examples of
the brightness improver include polyalkylene glycol and fatty acid
esters thereof, alicyclic epoxy compounds, low molecular weight
acrylic resins, and low molecular weight styrene-based resins.
[0143] Examples of the polyalkylene glycol include homopolymers and
copolymers of alkylene glycols, and derivatives thereof. Specific
examples of the polyalkylene glycol include C.sub.2-C.sub.6
polyalkylene glycols such as polyethylene glycol, polypropylene
glycol, and polytetramethylene glycol; random or block copolymers
of polyoxyethylene-polyoxypropylene; and copolymers such as
glyceryl ethers of polyoxyethylene-polyoxypropylene, and monobutyl
ethers of polyoxyethylene-polyoxypropylene.
[0144] Among these, polymers containing an oxyethylene unit, for
example, polyethylene glycol, polypropylene glycol,
polyoxyethylene-polyoxypropylene copolymers, and derivatives
thereof are preferred.
[0145] The number average molecular weight of the polyalkylene
glycol is usually 500 to 500,000, preferably 1000 to 100,000, more
preferably 1000 to 50,000.
[0146] As the fatty acid ester of the polyalkylene glycol fatty
acid ester, either a linear or branched fatty acid ester may be
used. The fatty acid constituting the fatty acid ester may be
either a saturated fatty acid or an unsaturated fatty acid. Fatty
acid esters in which a part of the hydrogen atoms are substituted
with a substituent(s) such as hydroxyl may also be used.
[0147] Examples of the fatty acid constituting the fatty acid ester
include monovalent or divalent fatty acids having a carbon number
of not less than 10, for example, monovalent saturated fatty acids
such as capric acid, lauric acid, tridecylic acid, myristic acid,
pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid,
nonadecanoic acid, arachic acid, behenic acid, lignoceric acid,
cerotic acid, heptacosanoic acid, montanic acid, melissic acid, and
lacceric acid; monovalent unsaturated fatty acids having a carbon
number of not less than 10 such as unsaturated fatty acids
including oleic acid, elaidic acid, linoleic acid, linolenic acid,
arachidonic acid, cetoleic acid, and erucic acid; and divalent
fatty acids having a carbon number of not less than 10 such as
sebacic acid, undecanedioic acid, dodecanedioic acid,
tetradecanedioic acid, thapsic acid and decenedioic acid,
undecenedioic acid, and dodecenedioic acid. These fatty acids may
be used individually, or as a combination of two or more thereof.
Examples of the fatty acid also include fatty acids having one or
more hydroxyl groups in the molecule.
[0148] Preferred specific examples of the polyalkylene glycol fatty
acid ester include polyethylene glycol monopalmitate, polyethylene
glycol dipalmitate, polyethylene glycol monostearate, polyethylene
glycol distearate, polyethylene glycol
(monopalmitate-monostearate), polypropylene glycol monopalmitate,
polypropylene glycol dipalmitate, polypropylene glycol
monostearate, polypropylene glycol distearate, and polypropylene
glycol (monopalmitate-monostearate).
[0149] The content of the brightness improver is not limited, and
preferably 0.01 to 1 part by mass with respect to a total of 100
parts by mass of the thermoplastic resin and the fluidity modifier
for thermoplastic resin of the present invention. The content is
more preferably not less than 0.02 part by mass, still more
preferably not less than 0.03 part by mass, and especially not more
than 0.9 part by mass, more preferably not more than 0.8 part by
mass, still more preferably not more than 0.7 part by mass,
especially not more than 0.6 part by mass. In cases where the
content of the brightness improver is less than the lower limit of
this range, improvement of the hue and suppression of yellowing may
be insufficient, while in cases where the content of the brightness
improver exceeds the upper limit of this range, the color tone may
be poor, and the light transmittance may be low.
Dye/Pigment
[0150] Examples of the dyes and pigments include inorganic
pigments, organic pigments, and organic dyes. Among these, organic
pigments and organic dyes are preferred for maintenance of high
transparency of transparent resins such as polycarbonate
resins.
[0151] Examples of the inorganic pigments include carbon black;
sulfide-based pigments such as cadmium red and cadmium yellow;
silicate-based pigments such as ultramarine blue; oxide-based
pigments such as titanium oxide, zinc white, red iron oxide,
chromium oxide, iron black, titan yellow, zinc-iron-based brown,
titanium-cobalt-based green, cobalt green, cobalt blue,
copper-chromium-based black, and copper-iron-based black; chromic
acid-based pigments such as chrome yellow and molybdate orange; and
ferrocyanide-based pigments such as Prussian blue.
[0152] Examples of the organic pigments and the organic dyes
include phthalocyanine-based dyes and pigments such as copper
phthalocyanine blue and copper phthalocyanine green; azo-based dyes
and pigments such as nickel azo yellow; condensed polycyclic dyes
and pigments such as thioindigo-based, perinone-based,
perylene-based, quinacridone-based, dioxazine-based,
isoindolinone-based, and quinophthalone-based dyes and pigments;
and anthraquinone-based, heterocycle-based, and methyl-based dyes
and pigments.
[0153] Among these, from the viewpoint of thermal stability,
titanium oxide; carbon black; cyanine-based, quinoline-based,
anthraquinone-based, and phthalocyanine-based compounds; and the
like are preferred.
[0154] A single type of dye/pigment may be included, or two or more
types of dye(s)/pigment(s) may be included in an arbitrary
combination at arbitrary ratios. For the purposes of ease of
handling during the extrusion, and improvement of dispersibility in
the resin composition, the dye/pigment may be prepared as a
masterbatch with a thermoplastic resin such as a polystyrene-based
resin, polycarbonate-based resin, or acrylic-based resin.
[0155] The content of the dye/pigment in the thermoplastic resin
composition of the present invention is usually not more than 5
parts by mass, preferably not more than 3 parts by mass, more
preferably not more than 2 parts by mass, with respect to a total
of 100 parts by mass of the thermoplastic resin and the fluidity
modifier for thermoplastic resin. In cases where the content of the
dye/pigment is too large, the impact resistance may be
insufficient.
Mold Release Agent
[0156] The thermoplastic resin composition of the present invention
also preferably contains a mold release agent. The mold release
agent used in the thermoplastic resin composition of the present
invention is not limited as long as it is a known mold release
agent that has conventionally been added to thermoplastic resins,
and examples of the mold release agent include aliphatic carboxylic
acids; esters of an aliphatic carboxylic acid and an alcohol;
aliphatic hydrocarbon compounds having a number average molecular
weight of 200 to 15,000; and polysiloxane-based silicone oils.
[0157] Examples of the aliphatic carboxylic acids include saturated
or unsaturated, aliphatic monovalent, divalent, or trivalent
carboxylic acids. The aliphatic carboxylic acids include alicyclic
carboxylic acids. Among these aliphatic carboxylic acids,
C.sub.6-C.sub.36 monovalent or divalent carboxylic acids are
preferred. C.sub.6-C.sub.36 aliphatic saturated monovalent
carboxylic acids are more preferred. Specific examples of such
aliphatic carboxylic acids include palmitic acid, stearic acid,
caproic acid, capric acid, lauric acid, arachic acid, behenic acid,
lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic
acid, montanic acid, adipic acid, and azelaic acid.
[0158] Examples of the aliphatic carboxylic acid in the esters of
an aliphatic carboxylic acid and an alcohol include the same
aliphatic carboxylic acids as described above. On the other hand,
examples of the alcohol include saturated or unsaturated,
monohydric or polyhydric alcohols. Each of these alcohols may have
a substituent such as a fluorine atom or an aryl group. Among
these, monohydric or polyhydric, saturated alcohols having a carbon
number of not more than 30 are preferred. Aliphatic saturated
monohydric alcohols and aliphatic saturated polyhydric alcohols
having a carbon number of not more than 30 are more preferred. The
term "aliphatic" herein is used as a term also including alicyclic
compounds.
[0159] Specific examples of such alcohols include octanol, decanol,
dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol,
diethylene glycol, glycerin, pentaerythritol,
2,2-dihydroxyperfluoropropanol, neopentylene glycol,
ditrimethylolpropane, and dipentaerythritol.
[0160] Each of the above esters may contain an aliphatic carboxylic
acid and/or alcohol as an impurity/impurities. Each of the above
esters may be either a pure substance or a mixture of a plurality
of compounds. Each of the aliphatic carboxylic acid and the alcohol
bound to each other to constitute one ester may be of a single
type, or two or more types thereof may be used in an arbitrary
combination at arbitrary ratios.
[0161] Specific examples of the ester of the aliphatic carboxylic
acid and the alcohol include bees waxes (mixtures containing
myricyl palmitate as a major component), stearyl stearate, behenyl
behenate, stearyl behenate, glycerin monopalmitate, glycerin
monostearate, glycerin distearate, glycerin tristearate,
pentaerythritol monopalmitate, pentaerythritol monostearate,
pentaerythritol distearate, pentaerythritol tristearate, and
pentaerythritol tetrastearate.
[0162] Examples of the aliphatic hydrocarbons having a number
average molecular weight of 200 to 15,000 include liquid paraffins,
paraffin waxes, microwaxes, polyethylene waxes, Fischer-Tropsch
waxes, and .alpha.-olefin oligomers having a carbon number of 3 to
12. The aliphatic hydrocarbons also include alicyclic hydrocarbons.
Each of these hydrocarbons may be partially oxidized.
[0163] Among these, paraffin waxes, polyethylene waxes, and
partially oxidized polyethylene waxes are preferred. Paraffin waxes
and polyethylene waxes are more preferred.
[0164] The number average molecular weight of the aliphatic
hydrocarbon is preferably not more than 5000.
[0165] The aliphatic hydrocarbon may be a single substance, or may
be a mixture of various constituents having different molecular
weights as long as the major component is contained within the
above-described range.
[0166] Examples of the polysiloxane-based silicone oils include
dimethyl silicone oils, methylphenyl silicone oils, diphenyl
silicone oils, and fluorinated alkyl silicone oils.
[0167] A single type of mold release agent described above may be
included, or two or more types of the mold release agents may be
included in an arbitrary combination at arbitrary ratios.
[0168] The content of the mold release agent is not limited, and
usually not less than 0.001 part by mass, preferably not less than
0.01 part by mass, and usually not more than 2 parts by mass,
preferably not more than 1 part by mass, with respect to a total of
100 parts by mass of the thermoplastic resin and the fluidity
modifier for thermoplastic resin. In cases where the content of the
mold release agent is less than the lower limit of this range, the
mold-releasing effect may be insufficient, while in cases where the
content of the mold release agent exceeds the upper limit of this
range, a decrease in the hydrolysis resistance, mold contamination
during injection molding, and the like may occur.
Method for Producing Thermoplastic Resin Composition
[0169] The method for producing the thermoplastic resin composition
of the present invention is not limited, and known methods for
production of thermoplastic resin compositions may be widely
employed.
[0170] Specific examples of the method include methods in which the
thermoplastic resin, the fluidity modifier for thermoplastic resin
of the present invention, and another/other component(s) blended as
required are preliminarily mixed using a mixer such as a tumbler or
Henschel mixer, and then the resulting mixture is melt-kneaded in a
mixer such as a Banbury mixer, roll, Brabender, single-screw
kneading extruder, twin-screw kneading extruder, kneader, or the
like.
[0171] The thermoplastic resin composition of the present invention
may also be produced by, for example, a method in which the
components are not mixed, or only a part of the components are
mixed, before the components are fed to an extruder using a feeder
to perform melt kneading.
[0172] During the production of the thermoplastic resin of the
present invention, an additive(s) may be directly added to the
molten resin after the polymerization, and the resulting mixture
may be kneaded. In cases where an additive(s) is/are added in this
manner, a method in which the molten resin is directly introduced
into an extruder after the polymerization, and then the additive(s)
is/are added thereto, followed by performing melt kneading and
pelletization is preferred.
[0173] The thermoplastic resin composition of the present invention
may also be produced by, for example, a method in which a part of
the components are preliminarily mixed and fed into an extruder,
and melt kneading is performed to obtain a resin composition as a
masterbatch, followed by mixing the masterbatch with the other
component(s) and performing melt kneading of the resulting
mixture.
[0174] In cases where a hardly dispersible component is to be
mixed, the hardly dispersible component may be preliminarily
dissolved or dispersed in a solvent such as water or an organic
solvent, and kneading may be performed with the resulting solution
or dispersion to increase the dispersibility.
Method for Producing Thermoplastic Resin Molded Article
[0175] The method for producing a thermoplastic resin molded
article of the present invention is a method for obtaining a
thermoplastic resin molded article by injection molding of the
thermoplastic resin composition of the present invention.
[0176] The shape, pattern, color, size, and the like of the
thermoplastic resin molded article of the present invention are not
limited, and may be appropriately selected depending of the
intended use of the molded article. Examples of the thermoplastic
resin molded article include those having various shapes such as
board-like shapes, plate-like shapes, rod-like shapes, sheet-like
shapes, film-like shapes, cylindrical shapes, ring-like shapes,
circular shapes, elliptical shapes, polygonal shapes, irregular
shapes, hollow shapes, frame-like shapes, box-like shapes, and
panel-like shapes, as well as special shapes. Further, for example,
the thermoplastic resin molded article may have an irregular
surface, or may have a three-dimensional shape with a
three-dimensional curved surface.
[0177] The method of the injection molding is not limited, and an
arbitrary molding method commonly employed for thermoplastic resins
may be employed. Examples of the method include ultra-high-speed
injection molding; injection compression molding; two-color
molding; hollow molding such as gas assist molding; molding methods
using an insulated mold; molding methods using a rapid heating
mold; foam molding (including supercritical fluid); insert molding;
and IMC (in-mold coating) molding. A molding method using a hot
runner method may also be used.
[0178] Examples of the molded article include electric and
electronic devices, office automation devices, information terminal
devices, mechanical components, household electrical appliances,
car parts, building components, containers, leisure
goods/miscellaneous goods, and components of illuminating devices
and the like. Among these, the production method can be especially
suitably used for transparent optical members of electric and
electronic devices, office automation devices, information terminal
devices, household electrical appliances, illuminating devices, and
the like.
EXAMPLES
[0179] The present invention is described below more concretely by
way of Examples. However, the present invention is not limited to
the following Examples, and may be carried out with an arbitrary
modification without departing from the spirit of the present
invention. Each value in the production conditions and the
evaluation results in the following Examples has a meaning as a
preferred upper limit or lower limit value in an embodiment of the
present invention, and a preferred range may be defined by
combination of an upper limit or lower limit value described above
and a value in the following Examples, or by combination of values
in the Examples. Unless otherwise specified, the term "part" in the
following description means "part by mass", which is expressed on a
mass basis.
Synthesis Example 1
Synthesis of 1,1-Bis(4-hydroxyphenyl)decane (BP-C10)
[0180] A synthesis example of 1,1-bis(4-hydroxyphenyl)decane, which
is listed in the later-mentioned Table-1, is described below.
[0181] Phenol (100 parts by weight) was melted by warming at
40.degree. C., and concentrated hydrochloric acid (1.33 parts by
weight) was added thereto. To the resulting mixture, a mixture of
decanal (33.1 parts by weight) and toluene (21.2 parts by weight)
was added dropwise for four hours. Thereafter, the mixture was aged
at 40.degree. C. for 1 hour, and the reaction was stopped with an
aqueous sodium hydrogen carbonate solution. After evaporating
phenol from the reaction mixture under reduced pressure, extraction
was performed with toluene, and the mixture was washed with water
three times. After removing the solvent by distillation,
crystallization from toluene and heptane was performed to obtain
23.3 parts by weight of the compound of interest as a white powder.
The purity was 99.4%, and the melting point was 93.degree. C.
Synthesis Example 2
Synthesis of 1,1-Bis(4-hydroxyphenyl)dodecane (BP-C12)
[0182] A synthesis example of 1,1-bis(4-hydroxyphenyl)dodecane,
which is listed in the later-mentioned Table-1, is described
below.
[0183] The same synthesis as in Synthesis Example 1 was carried out
except that dodecanal (39.0 parts by weight) was used instead of
decanal. As a result, 27.8 parts by weight of the compound of
interest was obtained as a white powder. The purity was 99.0%, and
the melting point was 86.degree. C.
[0184] The compounds of interest in Synthesis Examples 1 and 2 were
analyzed under the following analysis conditions.
[Purity]
[0185] In 1 part by mass of acetonitrile, 0.01 part by mass of a
sample was dissolved. The obtained solution was analyzed using an
HPLC analyzer (LC-2010, manufactured by Shimadzu Corporation). The
conditions were as follows.
[0186] Column: Inertsil ODS3V (manufactured by GL Sciences
Inc.)
[0187] Eluting solvent: acetonitrile/0.1% by mass ammonium acetate
solution
[0188] Detector: UV (254 nm)
[0189] The purity was determined from the area % at 254 nm.
[Melting Point]
[0190] An SMP3 melting point apparatus manufactured by Stuart
Scientific was used. The temperature was increased at 2.degree.
C./min., and the temperature at the time point when the solid was
totally melted was regarded as the melting point.
[0191] Table-1 shows the names (abbreviations) of the dihydroxy
compounds used as materials of the aromatic polycarbonate resins,
and the carbonate-forming compound, used in the following Examples
and Comparative Examples.
TABLE-US-00001 TABLE 1 Abbreviation BPA
2,2-Bis(4-hydroxyphenyl)propane manufactured by Mitsubishi Chemical
Corporation DPC Carbonate-forming compound Diphenyl carbonate,
manufactured by Mitsubishi Chemical Corporation BP-C10
1,1-Bis(4-hydroxyphenyl)decane BP-C12
1,1-Bis(4-hydroxyphenyl)dodecane BP-C8
1,1-Bis(4-hydroxyphenyl)-2-ethylhexane manufactured by Tokyo
Chemical Industry Co., Ltd.
Production Example 1 of Aromatic Polycarbonate Copolymer
[0192] The material dihydroxy compounds and the carbonate-forming
compound described in Table-1 were fed to a glass reactor having a
capacity of 150 mL equipped with a reactor heater and a reactor
pressure regulator, at the material feed ratios described in
Table-2, such that the total amount of dihydroxy compounds was 117
g. Further, as a catalyst, 2 wt % aqueous cesium carbonate solution
was added thereto such that cesium carbonate was contained at 1
.mu.mol per 1 mol of the total dihydroxy compounds, to prepare a
material mixture.
[0193] Subsequently, an operation of reducing the pressure in the
glass reactor to about 100 Pa (0.75 Torr) and then restoring the
pressure with nitrogen to atmospheric pressure was repeated three
times, thereby replacing the inside of the reactor with nitrogen.
Thereafter, the external temperature of the reactor was adjusted to
220.degree. C. to allow a slow increase in the internal temperature
of the reactor, thereby dissolving the mixture.
[0194] Subsequently, a stirrer was rotated at 100 rpm. Thereafter,
the pressure in the reactor, in terms of the absolute pressure, was
reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) for 40
minutes, during which phenol produced as a by-product of
oligomerization reaction of the dihydroxy compounds and DPC in the
reactor was removed by distillation.
[0195] Subsequently, while the pressure in the reactor was kept at
13.3 kPa, and while phenol was further removed by distillation,
transesterification reaction was carried out for 80 minutes.
Thereafter, the external temperature of the reactor was increased
to 250.degree. C., and the internal pressure, in terms of the
absolute pressure, of the reactor was reduced from 13.3 kPa (100
Torr) to 399 Pa (3 Torr) for 40 minutes while removing distilled
phenol to the outside of the system. Thereafter, the external
temperature of the reactor was increased to 260.degree. C., and the
absolute pressure in the reactor was reduced to 30 Pa (about 0.2
Torr). The rotation speed of the stirrer was reduced to 30 rpm.
Polycondensation reaction was thus allowed to proceed. When the
stirring power of the stirrer in the reactor reached a
predetermined value, the polycondensation reaction was stopped.
After restoring the absolute pressure in the rector with nitrogen
to 101.3 kPa, the polycarbonate resin copolymer was extracted from
the reactor. This operation was repeated a plurality of times, and
the whole amount of the polycarbonate resin copolymer obtained was
combined. The copolymer was then remelted at 250.degree. C. under
nitrogen atmosphere, and butyl paratoluenesulfonate was mixed
therewith at 5 ppm. After melt-kneading the resulting mixture, the
polycarbonate resin copolymer was extracted again.
Production Example 2 of Aromatic Polycarbonate Copolymer
[0196] The material dihydroxy compounds and the carbonate-forming
compound described in Table-1 were weighed at the material feed
ratios described in Table-2 such that the total amount of the
dihydroxy compounds was 6700 g. Further, as a catalyst, 2 wt %
aqueous cesium carbonate solution was added thereto such that
cesium carbonate was contained at 0.5 .mu.mol per 1 mol of the
total dihydroxy compounds, to prepare a material mixture. The
mixture was fed to a first reactor having a capacity of 200 L
equipped with a stirrer, heating medium jacket, vacuum pump, and
reflux condenser.
[0197] Subsequently, an operation of reducing the pressure in the
first reactor to 1.33 kPa (10 Torr) and then restoring the pressure
with nitrogen to atmospheric pressure was repeated five times,
thereby replacing the inside of the first reactor with nitrogen.
Thereafter, a heating medium at a temperature of 230.degree. C. was
passed through the heating medium jacket to allow a slow increase
in the internal temperature of the first reactor, thereby
dissolving the mixture. Thereafter, the stirrer was rotated at 300
rpm, and the temperature in the heating medium jacket was
controlled to keep the internal temperature of the first reactor at
220.degree. C. Thereafter, the pressure in the first reactor, in
terms of the absolute pressure, was reduced from 101.3 kPa (760
Torr) to 13.3 kPa (100 Torr) for 40 minutes, during which phenol
produced as a by-product of oligomerization reaction of the
dihydroxy compounds and DPC in the first reactor was removed by
distillation.
[0198] Subsequently, while the pressure in the first reactor was
kept at 13.3 kPa, and while phenol was further removed by
distillation, transesterification reaction was carried out for 80
minutes. The absolute pressure in the system was restored with
nitrogen to 101.3 kPa, and then increased to 0.2 MPa in terms of
the gauge pressure. The oligomer in the first reactor was
transferred under the pressure to a second reactor through a
transfer pipe preliminarily heated to not less than 200.degree. C.
The capacity of the second reactor was 200 L, and the reactor was
equipped with a stirrer, heating medium jacket, vacuum pump, and
reflux condenser. Its internal pressure had been adjusted to
atmospheric pressure, and its internal temperature had been
adjusted to 240.degree. C.
[0199] The oligomer transferred under the pressure into the second
reactor was stirred at 38 rpm, and the internal temperature was
increased by the heating medium jacket. The absolute pressure in
the second reactor was reduced from 101.3 kPa to 13.3 kPa for 40
minutes. Thereafter, the temperature was kept increased, and the
internal pressure, in terms of the absolute pressure, was reduced
from 13.3 kPa to 399 Pa (3 Torr) for 40 minutes while removing
distilled phenol to the outside of the system. The temperature was
further kept increased, and when the absolute pressure in the
second reactor reached 70 Pa (about 0.5 Torr), the pressure of 70
Pa was maintained to perform polycondensation reaction. The final
internal temperature of the second reactor was 255.degree. C. When
the stirring power of the stirrer in the second reactor reached a
predetermined value, the polycondensation reaction was stopped.
After restoring the pressure in the rector with nitrogen, pressure
was applied to allow extraction of the resulting product from the
bottom of the tank. By cooling the product in a water-cooling tank,
an aromatic polycarbonate copolymer was obtained. Thereafter, butyl
paratoluenesulfonate was mixed at 5 ppm with the obtained aromatic
polycarbonate copolymer, and the resulting mixture was melt-kneaded
in a 30-mm diameter twin-screw extruder at 240.degree. C. to form a
strand-shaped product, followed by cutting the product with a
pelletizer to obtain a pellet-shaped aromatic polycarbonate
copolymer.
Evaluation of Aromatic Polycarbonate Copolymers
[Viscosity Average Molecular Weight]
[0200] As described above, the viscosity average molecular weight
of each aromatic polycarbonate copolymer was calculated by
determining the intrinsic viscosity (limiting viscosity) [.eta.]
(unit, dL/g) of a solution in methylene chloride at 20.degree. C.
using an Ubbelohde viscometer (manufactured by Moritomo Rika
Kogyo), and applying the resulting value to the Schnell's viscosity
equation, that is, .eta.=1.23.times.10.sup.-4 Mv.sup.0.83. Table-2
shows each of the values obtained.
[Glass Transition Temperature (Tg)]
[0201] As described above, the glass transition temperature (Tg) of
each aromatic polycarbonate copolymer was determined using a
differential scanning calorimeter (DSC 6220, manufactured by SII)
according to JIS-K7121. Table-2 shows each of the values
obtained.
[Amount of Terminal Hydroxyl Groups]
[0202] As described above, the amount of terminal hydroxyl groups
in each aromatic polycarbonate copolymer was determined by
colorimetry by the titanium tetrachloride/acetic acid method.
Table-2 shows each of the values obtained.
[Flow Value (Q Value)]
[0203] As described above, the flow value (Q value) of each
aromatic polycarbonate copolymer was measured using a CFT-500A type
flow tester manufactured by Shimadzu Corporation and an orifice of
1-mm diameter.times.10 mm according to Appendix C of JIS (1999)
K7210 at 240.degree. C. at 160 kgf/cm.sup.2 with a preheating time
of 7 minutes. Table-2 shows each of the values obtained.
TABLE-US-00002 TABLE 2 Example 1 Example 2 Example 3 Example 4
Example 5 Example 6 Abbreviation FI-1 FI-2 FI-3 FI-7 FI-8 FI-9
Production method Production Production Production Production
Production Production Unit Example 1 Example 2 Example 2 Example 2
Example 2 Example 2 Composition BPA mol % 70 80 70 88 85 67 ratios
of BP-C10 30 dihydroxy BP-C12 20 30 12 15 33 compound BP-C8
structural units in aromatic polycarbonate copolymers Material feed
BPA Parts by 62.0 72.0 60.0 82.5 78.5 56.7 ratios of BP-C10 mass
38.0 dihydroxy BP-C12 28.0 40.0 17.5 21.5 43.3 compounds and BP-C8
carbonate- DPC 88.1 90.4 86.1 92.8 91.4 83.3 forming compound
Viscosity average 15300 14500 15500 12500 12900 15000 molecular
weight Intrinsic viscosity dL/g 0.366 0.350 0.372 0.309 0.317 0.360
Tg .degree. C. 97 83 109 104 77 Amount of terminal ppm 1900 530 750
1020 920 840 hydroxyl groups Q value 10.sup.-2 cm.sup.3/sec 48 35
48 51 52 61 Comparative Comparative Comparative Comparative Example
7 Example 1 Example 2 Example 3 Example 4 Abbreviation FI-10 FI-4
FI-5 FI-6 FI-11 Production method Production Production Production
Production Production Unit Example 2 Example 2 Example 2 Example 1
Example 2 Composition BPA mol % 54 90 60.83 70 62 ratios of BP-C10
dihydroxy BP-C12 36 10 39.17 38 compound BP-C8 30 structural units
in aromatic polycarbonate copolymers Material feed BPA Parts by
53.4 85.3 50.0 64.1 51.2 ratios of BP-C10 mass dihydroxy BP-C12
46.6 14.7 50.0 48.8 compounds and BP-C8 91.1 carbonate- DPC 82.2
95.6 82.8 91.1 81.4 forming compound Viscosity average 15600 13600
15400 11700 14800 molecular weight Intrinsic viscosity dL/g 0.372
0.532 0.368 0.293 0.356 Tg .degree. C. 75 119 66 71 Amount of
terminal ppm 900 570 360 2700 780 hydroxyl groups Q value 10.sup.-2
cm.sup.3/sec 60 30 62 31 72
Polycarbonate Resin (PC1)
[0204] A production example of the polycarbonate resin (PC1) listed
in Table-3 is described below.
[0205] A material mixture was prepared by mixing 6700 g of BPA,
listed in Table-1, as the material dihydroxy compound, and 6727 g
of DPC, listed in Table-1, as the carbonate-forming compound, with
2 wt % aqueous solution of cesium carbonate as the catalyst, such
that cesium carbonate was contained at 0.5 .mu.mol per 1 mol of the
total dihydroxy compounds. The mixture was fed to a first reactor
having a capacity of 200 L equipped with a stirrer, heating medium
jacket, vacuum pump, and reflux condenser. Subsequently, an
operation of reducing the pressure in the first reactor to 1.33 kPa
(10 Torr) and then restoring the pressure with nitrogen to
atmospheric pressure was repeated five times, thereby replacing the
inside of the first reactor with nitrogen. Thereafter, a heating
medium at a temperature of 230.degree. C. was passed through the
heating medium jacket to allow a slow increase in the internal
temperature of the first reactor, thereby dissolving the mixture.
Thereafter, the stirrer was rotated at 300 rpm, and the temperature
in the heating medium jacket was controlled to keep the internal
temperature of the first reactor at 220.degree. C. Thereafter, the
pressure in the first reactor, in terms of the absolute pressure,
was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) for 40
minutes, during which phenol produced as a by-product of
oligomerization reaction of the dihydroxy compound and DPC in the
first reactor was removed by distillation.
[0206] Subsequently, while the pressure in the first reactor was
kept at 13.3 kPa, and while phenol was further removed by
distillation, transesterification reaction was carried out for 80
minutes. The absolute pressure in the system was restored with
nitrogen to 101.3 kPa, and then increased to 0.2 MPa in terms of
the gauge pressure. The oligomer in the first reactor was
transferred under the pressure to a second reactor through a
transfer pipe preliminarily heated to not less than 200.degree. C.
The capacity of the second reactor was 200 L, and the reactor was
equipped with a stirrer, heating medium jacket, vacuum pump, and
reflux condenser. Its internal pressure had been adjusted to
atmospheric pressure, and its internal temperature had been
adjusted to 240.degree. C.
[0207] The oligomer transferred under the pressure into the second
reactor was stirred at 38 rpm, and the internal temperature was
increased by the heating medium jacket. The absolute pressure in
the second reactor was reduced from 101.3 kPa to 13.3 kPa for 40
minutes. Thereafter, the temperature was kept increased, and the
internal pressure, in terms of the absolute pressure, was reduced
from 13.3 kPa to 399 Pa (3 Torr) for 40 minutes while removing
distilled phenol to the outside of the system. The temperature was
further kept increased, and when the absolute pressure in the
second reactor reached 70 Pa (about 0.5 Torr), the pressure of 70
Pa was maintained to perform polycondensation reaction. The final
internal temperature of the second reactor was 255.degree. C. When
the stirring power of the stirrer in the second reactor reached a
predetermined value, the polycondensation reaction was stopped.
After restoring the pressure in the rector with nitrogen, pressure
was applied to allow extraction of the resulting product from the
bottom of the tank. By cooling the product in a water-cooling tank,
an aromatic polycarbonate copolymer was obtained. Thereafter, butyl
paratoluenesulfonate was mixed at 5 ppm with the obtained aromatic
polycarbonate copolymer, and the resulting mixture was melt-kneaded
in a 30-mm diameter twin-screw extruder at 240.degree. C. to form a
strand-shaped product, followed by cutting the product with a
pelletizer to obtain a pellet-shaped polycarbonate resin. The
viscosity average molecular weight (Mv) was 13,000; the amount of
terminal hydroxyl groups was 720 ppm; and the Q value was 16.
Polycarbonate Resin (PC2)
[0208] A production example of the polycarbonate resin (PC2) listed
in Table-3 is described below.
[0209] The resin was produced in the same manner as in the
Production Example for the polycarbonate resin (PC1) except that
6759 g of DPC, listed in Table-1, was used as the carbonate-forming
compound, and that the predetermined stirring power of the stirrer
of the second reactor was reduced. The viscosity average molecular
weight (Mv) was 11,400; the amount of terminal hydroxyl groups was
660 ppm; and the Q value was 39.
Production of Thermoplastic Resin Compositions
[0210] The aromatic polycarbonate copolymers listed in Table-2
(FI-1 to FI-11) and the aromatic polycarbonate resins described
above (PC1 and PC2) were mixed together at the ratios (parts by
mass) described in the following Table-3, and, as an additive, 0.03
part by mass of a heat stabilizer
3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosph-
aspiro[5.5]undecane, that is, Adekastab (registered trademark)
PEP-36 (abbreviated as PEP36), manufactured by ADEKA Corporation,
was added to a total of 100 parts by mass of the aromatic
polycarbonate copolymers and the aromatic polycarbonate resins,
followed by mixing each resulting mixture. Thereafter, the mixture
was fed to TEX30HSS, manufactured by Japan Steel Works, Ltd., which
has one vent, and kneaded at a screw speed of 150 rpm, discharge
rate of 15 kg/h, and barrel temperature of 240.degree. C. The
molten resin, extruded in a strand shape, was rapidly cooled in a
water tank, and then pelletized using a pelletizer to obtain
pellets of an aromatic polycarbonate resin composition.
Evaluation of Aromatic Polycarbonate Resin Compositions
[Q Value]
[0211] The evaluation method for the Q values in Table-3 is the
same as that for the aromatic polycarbonate copolymers described
above. Table-3 shows the values obtained.
[Evaluation of Impact Resistance]
[0212] The pellets of the aromatic polycarbonate resin composition
obtained by the production method described above were dried at
100.degree. C. for 5 to 7 hours using a hot-air drier, and then
subjected to injection molding using a J75EII type injection
molding machine manufactured by Japan Steel Works Ltd., at a
cylinder temperature of 240.degree. C. and a mold temperature of
70.degree. C. with a molding cycle of 40 seconds to mold an Izod
impact test piece having a thickness of 3.2 mm according to
ASTM-D256. Subsequently, using a notching tool manufactured by Toyo
Seiki Seisaku-sho, Ltd., a 0.25 R V-notch was formed by cutting,
and an Izod impact test according to the above ASTM-D256 was
carried out to determine the Izod impact strength (unit: J/m).
Table-3 shows the values obtained.
[Evaluation of Bending Resistance]
[0213] By the same method as described above, a molded article
having a length of 125 mm, width of 12.5 mm, and thickness of 3 mm
was molded. Using the obtained molded article as a test piece, and
using an RTM-100 type universal tester manufactured by Orientec
Co., Ltd., a bending stress was applied in the direction of the
thickness of 3 mm described above by a pressure wedge to give a
displacement of up to 10 mm under the following conditions:
distance between supporting points, 64 mm; test speed, 2 mm/sec.
This test was carried out three times, and the mean value of the
displacements in cases of breakage was determined as the bending
breaking displacement (unit: mm), and the mean value of the bending
strengths at breakage was determined as the bending breaking
strength (unit: MPa). A larger bending displacement is preferred
since it means that breakage is less likely to occur even with a
larger displacement. A higher bending strength is preferred since
it means a higher material strength. Table-3 shows the values
obtained.
[Evaluation of Transparency]
[0214] Under the same conditions as those for the Izod impact test
piece described above, a flat-plate-shaped test piece having a
length of 60 mm, a width of 60 mm, and a thickness of 3 mm was
molded. Using the obtained flat-plate-shaped test piece, evaluation
of the haze (unit: %) was carried out according to the JIS K
7136:2000 standard. The haze is an index of transparency. A lower
haze means higher transparency, which is preferred. Table-3 shows
the values obtained.
[Evaluation 1 of Compatibility]
[0215] Each aromatic polycarbonate copolymer listed in Table-2 and
the aromatic polycarbonate resin (PC1) described above were fed to
a glass reactor having a capacity of 150 mL at the material feed
ratios described in Table-4, such that the total amount of the
aromatic polycarbonate copolymer and the aromatic polycarbonate
resin was 100 g. An operation of reducing the pressure in the glass
reactor and then restoring the pressure with nitrogen to
atmospheric pressure was repeated three times, thereby replacing
the inside of the reactor with nitrogen. Thereafter, the external
temperature of the reactor was adjusted to 255.degree. C. to allow
a slow increase in the internal temperature of the reactor, thereby
dissolving the mixture. Thereafter, the stirrer was rotated at 10
rpm, and melt mixing was performed for 30 minutes. The pressure in
the glass container was reduced to 60 Torr to allow evaporation,
and then the pressure was restored again with nitrogen. The
polycarbonate resin composition was collected from the glass
container. In cases where both the polycarbonate resin composition
in the glass container after the melt mixing and the polycarbonate
resin composition obtained after cooling are transparent, the
aromatic polycarbonate copolymer is considered to have high
compatibility with the thermoplastic resin. This is preferred since
a thermoplastic resin composition having high mechanical strength
and transparency can be obtained. On the other hand, in cases where
these are cloudy (opaque), the aromatic polycarbonate copolymer has
low compatibility with the thermoplastic resin, which is not
preferred since the mechanical properties and the transparency may
be low. In cases where both the polycarbonate resin composition in
the glass container after the melt mixing and the polycarbonate
resin composition obtained could be judged to be transparent as
described above, the compatibility was represented as
".smallcircle.", while in cases where they were judged to be cloudy
(opaque), the compatibility was represented as ".times." in
Table-4.
Evaluation 2 of Compatibility
[0216] For detailed evaluation of the relationship between the
ratio of the carbonate structural unit (A) in the aromatic
polycarbonate copolymer of the present invention and the
compatibility with the thermoplastic resin, the aromatic
polycarbonate copolymers listed in Table-2 and the aromatic
polycarbonate resin (PC1) described above were mixed together as
pellets at the material feed ratios described in Table-4. Each
resulting mixture was fed to TEX30HSS, manufactured by Japan Steel
Works, Ltd., which has one vent, and kneaded at a screw speed of
300 rpm, discharge rate of 15 kg/h, and barrel temperature of
240.degree. C. The molten resin, extruded in a strand shape, was
rapidly cooled in a water tank, and then pelletized using a
pelletizer to obtain pellets of an aromatic polycarbonate resin
composition. In this process, the polycarbonate resin composition
extruded in a strand shape was visually observed. In cases where
the composition could be judged to be transparent, the
compatibility was represented as ".smallcircle.", while in cases
where it was judged to be cloudy (opaque), the compatibility was
represented as ".times." in Table-4. The obtained pellets were
further evaluated for the haze (unit: %) by the same method as in
the evaluation of transparency described above. In Table-4, the
values of the haze are shown in parentheses. A smaller haze value
indicates better transparency and better compatibility, which is
preferred.
TABLE-US-00003 TABLE 3 Example 8 Example 9 Example 10 Example 11
Example 12 Example 13 Example 14 Resin PC1 Parts by 55 42 48 49 50
51 54 composition PC2 mass 3 32 42 37 33 25 12 FI-1 42 FI-2 26 FI-3
10 14 17 24 34 FI-4 FI-6 FI-7 FI-8 FI-10 Ratio of carbonate mol %
9.2 5.2 2.6 3.7 4.5 6.4 9.2 structural unit (A) to polycarbonate
resin total carbonate structural units in thermoplastic resin
composition Tg .degree. C. 121 126 129 128 127 124 120 Q value
10.sup.-2 cm.sup.3/sec 28 28 28 28 29 29 28 Izod impact test J/m 26
17 27 31 43 46 48 Bending breaking mm 4.4 5.6 4.7 4.6 3.9 5.0 4.8
displacement Bending breaking MPa 39 48 42 40 34 44 42 strength
Haze % 0.7 0.7 0.6 0.6 0.7 0.6 0.7 Comparative Comparative
Comparative Example 15 Example 16 Example 17 Example 5 Example 6
Example 7 Resin PC1 Parts by 60 56 55 46 41 37 composition PC2 mass
15 30 54 42 29 FI-1 FI-2 FI-3 FI-4 17 FI-6 34 FI-7 40 FI-8 29 FI-10
15 Ratio of carbonate mol % 4.6 4.5 4.3 0.0 1.6 4.7 structural unit
(A) to polycarbonate resin total carbonate structural units in
thermoplastic resin composition Tg .degree. C. 126 127 126 133 131
132 Q value 10.sup.-2 cm.sup.3/sec 28 29 28 27 27 27 Izod impact
test J/m 30 38 38 11 13 13 Bending breaking mm 4.4 4.6 -- 3.4 3.9
3.3 displacement Bending breaking MPa 38 41 -- 32 35 31 strength
Haze % 0.7 0.8 0.9 0.7 0.6 0.7
[0217] It can be seen that the polycarbonate resin compositions
containing fluidity modifiers for thermoplastic resin of the
present invention (Examples 8 to 17) have better impact strength
and bending strength compared to the polycarbonate resin
composition containing no fluidity modifier for thermoplastic resin
of the present invention (Comparative Example 5) when the fluidity
of the final composition is at the equivalent level. It can also be
seen that Comparative Example 6 and Comparative Example 7, which
use fluidity modifiers composed of aromatic polycarbonate
copolymers outside the range defined in the present invention, have
insufficient impact strength compared to Examples 12 and 14,
respectively, which contain the same parts by mass of aromatic
polycarbonate copolymers. Thus, it is clear that the inclusion of a
particular carbonate structure (A) at a particular ratio in the
fluidity modifiers for thermoplastic resin of the present invention
is important.
TABLE-US-00004 TABLE 4 Comparative Comparative Example 18 Example
19 Example 20 Example 21 Example 22 Example 23 Example 8 Example 9
Resin PC1 Parts by 60.0 51.0 63.0 50.0 74.5 74.5 74.5 75.5
composition FI-1 mass 40.0 FI-2 49.0 FI-3 37.0 FI-5 25.5 FI-7 50.0
FI-9 25.5 FI-10 25.5 FI-11 24.5 Ratio of carbonate 10.2 10.0 10.1
6.3 8.0 8.0 6.5 8.0 structural unit (A) to polycarbonate resin
total carbonate structural units in thermoplastic resin composition
Evaluation of .smallcircle. .smallcircle. .smallcircle.
.smallcircle. x x compatibility 1 Evaluation of .smallcircle. (0.6)
.smallcircle. (0.6) .smallcircle. (0.9) x (3.6) compatibility 2
[0218] As is evident from Table-4, while the fluidity modifiers for
thermoplastic resin of the present invention have very high
compatibilities with the polycarbonate resin (Examples 18 to 23),
the aromatic polycarbonate copolymers in Comparative Examples 8 and
9, which use fluidity modifiers composed of aromatic polycarbonate
copolymers outside the range defined in the present invention, have
only insufficient compatibilities with the polycarbonate resin, and
fail to achieve the transparency. Thus, it is again clear that the
inclusion of a particular carbonate structure (A) at a particular
ratio in the fluidity modifiers of the present invention is
important. It was shown, in the Examples, that thermoplastic resins
having better mechanical properties can be obtained even when the
melt viscosity is adjusted to an equivalent level. On the other
hand, thermoplastic resin compositions having better fluidity can
be obtained even when equivalent levels of mechanical properties
are obtained.
Polycarbonate Resin (PC3)
[0219] A production example of the polycarbonate resin (PC3) listed
in Table-5 is described below.
[0220] The resin was produced in the same manner as in the
Production Example for the polycarbonate resin (PC1) except that
2,2-bis(4-hydroxy-3-methylphenyl)propane (manufactured by Honshu
Chemical Industry Co., Ltd.) (which may be hereinafter simply
referred to as BPC) was used as the material dihydroxy compound,
that the amount of DPC, listed in Table-1, was 5879 g, that the
amount of cesium carbonate was 1.5 .mu.mol per 1 mol of the total
hydroxy compounds, and that the target value of the stirring power
of the stirrer of the second reactor was separately set. The
viscosity average molecular weight (Mv) was 14,800; the amount of
terminal hydroxyl groups was 480 ppm; and the Q value was 24.
Polycarbonate Resin (PC4)
[0221] The resin was produced in the same manner as in the
Production Example for the polycarbonate resin (PC3) except that
the target value of the stirring power of the stirrer of the second
reactor was separately set. The viscosity average molecular weight
(Mv) was 15,400; the amount of terminal hydroxyl groups was 320
ppm; and the Q value was 16.
Polycarbonate Resin (PC5)
[0222] A production example of the polycarbonate resin (PC5) listed
in Table-5 is described below.
[0223] The resin was produced in the same manner as in the
Production Example for the polycarbonate resin (PC1) except that
3455 g of BPA, and 1,1-bis(4-hydroxyphenyl)ethane (manufactured by
Honshu Chemical Industry Co., Ltd.) (which may be hereinafter
simply referred to as BPE) were used as material dihydroxy
compounds, and that the target value of the stirring power of the
stirrer of the second reactor was separately set. The viscosity
average molecular weight (Mv) was 13,900; the amount of terminal
hydroxyl groups was 790 ppm; and the Q value was 21.
Polycarbonate Resin (PC6)
[0224] The resin was produced in the same manner as in the
Production Example for the polycarbonate resin (PC3) except that
the target value of the stirring power of the stirrer of the second
reactor was separately set. The viscosity average molecular weight
(Mv) was 15,100; the amount of terminal hydroxyl groups was 590
ppm; and the Q value was 15.
[0225] The polycarbonate resins (PC3) to (PC-6) described above and
an aromatic polycarbonate copolymer listed in Table-2 were mixed
together at the ratios (parts by mass) described in the following
Table-5. Each resulting mixture was fed to TEX30HSS, manufactured
by Japan Steel Works, Ltd., which has one vent, and kneaded at a
screw speed of 150 rpm, discharge rate of 15 kg/h, and barrel
temperature of 240.degree. C. The molten resin, extruded in a
strand shape, was rapidly cooled in a water tank, and then
pelletized using a pelletizer to obtain pellets of the aromatic
polycarbonate resin composition. The composition was subjected to
the same kinds of evaluation as those in Table-3. The results are
shown in Table-5.
TABLE-US-00005 TABLE 5 Comparative Comparative Example 24 Example
10 Example 25 Example 11 Resin PC3 Parts by 100 composition PC4
mass 78 PC5 100 PC6 78 FI-9 22 22 Ratio of carbonate mol % 0.0 8.7
0.0 6.2 structural unit (A) to polycarbonate resin total carbonate
structural units in thermoplastic resin composition Q value
10.sup.-2 cm.sup.3/sec 26 26 22 23 Izod impact test J/m 12 23 7 17
Haze % 0.7 0.8 0.6 0.7
[0226] From the results in Table-5, it is clear that the aromatic
polycarbonate copolymer of the present invention acts as a fluidity
modifier for thermoplastic resin that improves the balance between
the fluidity and mechanical properties in a variety of
thermoplastic resins.
[0227] A fluidity modifier for thermoplastic resin is required to
improve the fluidity without deteriorating the mechanical strength,
in other words, to improve the strength when the fluidity is
equivalent. When an attempt is made to increase the fluidity,
aromatic polycarbonate resins show remarkable decreases in the
strength compared to other thermoplastic resins. However, according
to the Examples, aromatic polycarbonate resin compositions having
excellent balances between the fluidity and mechanical properties
can be provided when the fluidity modifier for thermoplastic resin
of the present invention containing an aromatic polycarbonate
copolymer is included in aromatic polycarbonate resins. Thus, it
can be seen that the fluidity modifier is very useful for
thermoplastic resins.
[0228] Among thermoplastic resins, transparent resins, especially
aromatic polycarbonate resins, are required to have high
transparency even after inclusion of a fluidity modifier therein
for improvement of the fluidity. Therefore, the fluidity modifier
is required to achieve not only the balance between the fluidity
and the mechanical strength, but also high compatibility with
thermoplastic resins. It is thought that compatibility between a
thermoplastic resin and a fluidity modifier is influenced mainly by
the polarity, bulkiness, and the like of each molecular structure.
However, in the Examples, it was shown that similar favorable
compatibilities can be obtained for resins that are different in
these characteristics.
[0229] Thus, a thermoplastic resin composition having an excellent
balance between the fluidity and mechanical properties can be
provided by inclusion, in a thermoplastic resin, of the fluidity
modifier for thermoplastic resin of the present invention
containing an aromatic polycarbonate copolymer. It can therefore be
seen that the fluidity modifier is very useful for thermoplastic
resins.
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