U.S. patent application number 14/366365 was filed with the patent office on 2014-10-30 for thermoplastic resin composition and molding form for same.
This patent application is currently assigned to Chell Industries Inc.. The applicant listed for this patent is Sung Hee Ahn, Dong Kil Choi, Jae Won Lee, Dong Min Park. Invention is credited to Sung Hee Ahn, Dong Kil Choi, Jae Won Lee, Dong Min Park.
Application Number | 20140322487 14/366365 |
Document ID | / |
Family ID | 48668703 |
Filed Date | 2014-10-30 |
United States Patent
Application |
20140322487 |
Kind Code |
A1 |
Choi; Dong Kil ; et
al. |
October 30, 2014 |
Thermoplastic Resin Composition and Molding Form for Same
Abstract
The thermoplastic resin composition of the present invention
comprises: (A) a rubber-modified aromatic vinyl-based graft
copolymer resin; (B) a polyester resin; (C) a maleimide-based
polymer; (D) a copolymer resin of a modified aromatic vinyl
compound-cyanide vinyl compound comprising a functional group which
can react with a polyester; and (E) an aromatic vinyl-based resin
copolymerized with an alkyl(meth)acrylate, wherein the aromatic
vinyl-based resin copolymerized with the alkyl(meth)acrylate (E) is
included in the composition at approximately 6 to 12 percent by
weight.
Inventors: |
Choi; Dong Kil; (Uiwang-si,
KR) ; Park; Dong Min; (Uiwang-si, KR) ; Ahn;
Sung Hee; (Uiwang-si, KR) ; Lee; Jae Won;
(Uiwang-si, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Choi; Dong Kil
Park; Dong Min
Ahn; Sung Hee
Lee; Jae Won |
Uiwang-si
Uiwang-si
Uiwang-si
Uiwang-si |
|
KR
KR
KR
KR |
|
|
Assignee: |
Chell Industries Inc.
Gumi-si, Gyeongsangbuk-do
KR
|
Family ID: |
48668703 |
Appl. No.: |
14/366365 |
Filed: |
September 14, 2012 |
PCT Filed: |
September 14, 2012 |
PCT NO: |
PCT/KR2012/007379 |
371 Date: |
June 18, 2014 |
Current U.S.
Class: |
428/141 ;
525/64 |
Current CPC
Class: |
C08L 55/02 20130101;
Y10T 428/24355 20150115; C08L 51/04 20130101; B32B 15/08 20130101;
C08L 47/00 20130101; C08L 2205/035 20130101; C08L 25/12 20130101;
C08L 55/02 20130101; C08L 67/02 20130101; C08L 33/04 20130101; C08L
25/14 20130101; C08L 55/02 20130101 |
Class at
Publication: |
428/141 ;
525/64 |
International
Class: |
C08L 47/00 20060101
C08L047/00; B32B 15/08 20060101 B32B015/08 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 22, 2011 |
KR |
10-2011-0140658 |
Claims
1. A thermoplastic resin composition comprising: (A) a
rubber-modified aromatic vinyl graft copolymer resin; (B) a
polyester resin; (C) a maleimide-based polymer; (D) a modified
aromatic vinyl compound-vinyl cyanide compound copolymer resin
containing a functional group capable of reacting with polyester;
and (E) an aromatic vinyl resin copolymerized with an
alkyl(meth)acrylate, wherein the (E) aromatic vinyl resin
copolymerized with an alkyl(meth)acrylate is present in an amount
of about 6 wt % to about 12 wt % based on a total amount of the
thermoplastic resin composition.
2. The thermoplastic resin composition according to claim 1,
wherein the polyester resin (B) is a recycled polyester resin.
3. The thermoplastic resin composition according to claim 1,
wherein the maleimide-based polymer (C) has a weight average
molecular weight from about 80,000 g/mol to about 200,000
g/mol.
4. The thermoplastic resin composition according to claim 1,
wherein the maleimide-based polymer (C) comprises about 20 mol % to
about 55 mol % of repeat units derived from maleimide.
5. The thermoplastic resin composition according to claim 1,
wherein the maleimide-based polymer (C) is a copolymer of an
N-substituted maleimide, an unsaturated dicarboxylic acid
anhydride, and a vinyl monomer.
6. The thermoplastic resin composition according to claim 1,
wherein the modified aromatic vinyl compound-vinyl cyanide compound
copolymer resin (D) has a weight average molecular weight from
about 50,000 g/mol to about 200,000 g/mol.
7. The thermoplastic resin composition according to claim 1,
wherein the maleimide-based polymer (C) is present in an amount of
about 1 wt % to about 40 wt % based on the total amount of the
thermoplastic resin composition.
8. The thermoplastic resin composition according to claim 1,
wherein the modified aromatic vinyl compound-vinyl cyanide compound
copolymer resin (D) is a copolymer of about 0.01 mol % to about 5
mol % of (d1) an unsaturated compound represented by the following
Formula 1 and (d2) about 95 mol % to about 99.99 mol % of a
vinyl-based compound. ##STR00004## wherein in Formula 1, R.sub.3,
R.sub.4 and R.sub.5 are each independently hydrogen (H), a
C.sub.1.about.C.sub.12 alkyl group or unsaturated alkyl group, a
C.sub.6.about.C.sub.14 aryl group, or a C.sub.1.about.C.sub.12
alkyl-substituted aryl group or unsaturated alkyl-substituted aryl
group; Y is an ether group (--O--), a carboxyl group
(--O--[C.dbd.O]--, --[O.dbd.C]--O--), a C.sub.1.about.C.sub.12
alkylene group, a C.sub.6.about.C.sub.14 arylene group, or a
C.sub.1.about.C.sub.12 alkyl-substituted arylene group; when Y is
an ether group or a carboxyl group, each of R.sub.1 and R.sub.2 is
a C.sub.1.about.C.sub.12 alkylene group, a C.sub.6.about.C.sub.14
arylene group, or a C.sub.1.about.C.sub.12 alkyl-substituted
arylene group, and when Y is a C.sub.1.about.C.sub.12 alkylene
group or a C.sub.6.about.C.sub.14 arylene group or
alkyl-substituted arylene group, Y represents
(R.sub.1--Y--R.sub.2); x is 0 or 1; and Z is an epoxy group, a
carboxylic acid group, an isocyanate group, an oxadiazol group, an
amine group, or a hydroxyl group.
9. The thermoplastic resin composition according to claim 1,
wherein the (E) aromatic vinyl resin copolymerized with an
alkyl(meth)acrylate has a weight average molecular weight from
about 80,000 g/mol to about 200,000 g/mol.
10. A molded product prepared by molding the thermoplastic resin
composition according to claim 1, the molded product having an
average surface roughness (Ra) from about 10 nm to about 62 nm as
measured using an optical profiler (NT1100).
11. The molded product according to claim 10, wherein the molded
product has a metal layer formed on a surface thereof.
Description
TECHNICAL FIELD
[0001] The present invention relates to a thermoplastic resin
composition. More particularly, the present invention relates to a
thermoplastic resin composition having improved heat resistance and
surface roughness, and a molded product including the same.
BACKGROUND ART
[0002] Recently, with the introduction of regulations on TCO
Certified Edge and EPEATs (Electronic Product Environmental
Assessment Tools), demand for post-consumer materials (PCMs) is
increasing together with interest in the development of recycled
materials, such as PCM-ABS (acrylonitril-butadiene-styrene
copolymer), PCM-PS (polystyrene), PCM-PET (polyethylene
terephthalate), PCM-PC (polycarbonate), and the like. Particularly,
plastic extrusion/injection technologies employing PET bottle PCMs,
which contain small amounts of toxic substances to be broadly used
for beverage bottles in the art and are readily available, become
an important issue.
[0003] Although PET exhibits good properties in terms of weather
resistance, impact resistance, chemical resistance, high gloss, and
the like, PET has limitations in use for products requiring high
heat resistance, such as electric/electronic products,
interior/exterior materials of automobiles, and the like, due to
hydrolytic characteristics at high temperature and low glass
transition temperature thereof.
[0004] Korean Patent Publication No. 10-2008-0043143A and No.
10-2007-0066553A disclose a method for improving the degree of
crystallization of PET in order to overcome low heat deflection
temperature of PET. However, since this method requires a
complicated process and complicated equipment and causes
contraction and deformation of products, this method has
limitations in application to universal products, such as housing
materials for electric/electronic products, interior/exterior
materials of automobiles, and the like.
[0005] In addition, although a method of improving heat deflection
temperature using inorganic fillers is disclosed, use of the
inorganic fillers provides problems, such as increase in specific
gravity, deterioration in inherent elongation, impact resistance
and appearance of resins due to deterioration in compatibility with
different resins, and the like.
[0006] Therefore, there is a need for a technology for blending
with a resin having high heat deflection temperature to overcome
low heat deflection temperature of polyester resins, and for
development of products applicable to automobile components and
exterior materials for buildings by overcoming the problem of
uneven surface roughness due to low compatibility with other
materials.
DISCLOSURE
Technical Problem
[0007] It is an aspect of the present invention to provide a
thermoplastic resin composition which has good compatibility to
provide improved surface roughness and high heat deflection
temperature, and a molded product including the same.
[0008] It is another aspect of the present invention to provide a
thermoplastic resin composition which allows application of
recycled materials to achieve eco-friendliness, and a molded
product including the same.
[0009] It is a further aspect of the present invention to provide a
thermoplastic resin composition which has improved wettability
through improvement in uniform surface roughness and is applicable
to automobile components, electric/electronic products, interior
products, and the like.
Technical Solution
[0010] One aspect of the present invention relates to a
thermoplastic resin composition. The thermoplastic resin
composition includes: (A) a rubber-modified aromatic vinyl graft
copolymer resin; (B) a polyester resin; (C) a maleimide-based
polymer; (D) a modified aromatic vinyl compound-vinyl cyanide
compound copolymer resin containing a functional group capable of
reacting with polyester; and (E) an aromatic vinyl resin
copolymerized with an alkyl(meth)acrylate, wherein the (E) aromatic
vinyl resin copolymerized with an alkyl(meth)acrylate is present in
an amount of about 6 wt % to about 12 wt % based on a total amount
of the thermoplastic resin composition.
[0011] In one embodiment, the polyester resin (B) may be a recycled
polyester resin.
[0012] In one embodiment, the maleimide-based polymer (C) may have
a weight average molecular weight of about 80,000 g/mol to about
200,000 g/mol.
[0013] In one embodiment, the maleimide-based polymer (C) may
contain about 20 mol % to about 55 mol % of repeat units derived
from maleimide.
[0014] In one embodiment, the maleimide-based polymer (C) may be a
copolymer of an N-substituted maleimide, an unsaturated
dicarboxylic acid anhydride, and a vinyl monomer.
[0015] In one embodiment, the modified aromatic vinyl
compound-vinyl cyanide compound copolymer resin (D) may have a
weight average molecular weight of about 50,000 g/mol to about
200,000 g/mol.
[0016] In one embodiment, the thermoplastic resin composition may
include about 1 wt % to about 40 wt % of the maleimide-based
polymer (C) based on a total weight of the composition.
[0017] In one embodiment, the modified aromatic vinyl
compound-vinyl cyanide compound copolymer resin (D) may be a
copolymer of about 0.01 mol % to about 5 mol % of (d1) an
unsaturated compound represented by the following Formula 1 and
(d2) about 95 mol % to about 99.99 mol % of a vinyl-based
compound.
##STR00001##
[0018] In Formula 1, R.sub.3, R.sub.4 and R.sub.5 are each
independently hydrogen (H), a C.sub.1.about.C.sub.12 alkyl group or
unsaturated alkyl group, a C.sub.6.about.C.sub.14 aryl group, or a
C.sub.1.about.C.sub.12 alkyl-substituted aryl group or unsaturated
alkyl-substituted aryl group; Y is an ether group (--O--), a
carboxyl group (--O--[C.dbd.O]--, --[O.dbd.C]--O--), a
C.sub.1.about.C.sub.12 alkylene group, a C.sub.6.about.C.sub.14
arylene group, or a C.sub.1.about.C.sub.12 alkyl-substituted
arylene group; when Y is an ether group or a carboxyl group, each
of R.sub.1 and R.sub.2 is a C.sub.1.about.C.sub.12 alkylene group,
a C.sub.6.about.C.sub.14 arylene group, or a C.sub.1.about.C.sub.12
alkyl-substituted arylene group, and when Y is a
C.sub.1.about.C.sub.12 alkylene group or a C.sub.6.about.C.sub.14
arylene group or alkyl-substituted arylene group, Y represents
(R.sub.1--Y--R.sub.2); x is 0 or 1; and Z is an epoxy group, a
carboxylic acid group, an isocyanate group, an oxadiazol group, an
amine group, or a hydroxyl group.
[0019] In one embodiment, the (E) aromatic vinyl resin
copolymerized with an alkyl(meth)acrylate may have a weight average
molecular weight of about 80,000 g/mol to about 200,000 g/mol.
[0020] Another aspect of the present invention relates to a molded
product formed from the thermoplastic resin composition. The molded
product is obtained by molding the thermoplastic resin composition
and has an average surface roughness (Ra) of about 10 nm to about
62 nm as measured using an optical profiler (NT 1100).
[0021] In one embodiment, the molded product may have a metal layer
formed on a surface thereof.
Advantageous Effects
[0022] The present invention provides a thermoplastic resin
composition, which has good compatibility to provide excellent
surface roughness and high heat deflection temperature, allows
application of recycled materials to achieve eco-friendliness, and
has excellent wettability to be applicable to automobile
components, electric/electronic products, interior products, and
the like, and molded products thereof.
BEST MODE
[0023] According to the present invention, a thermoplastic resin
composition includes (A) a rubber-modified aromatic vinyl graft
copolymer resin, (B) a polyester resin, (C) a maleimide-based
polymer, (D) a modified aromatic vinyl compound-vinyl cyanide
compound copolymer resin including a functional group capable of
reacting with polyester, and (E) an aromatic vinyl resin
copolymerized with an alkyl(meth)acrylate.
[0024] In one embodiment, the thermoplastic resin composition
includes about 10 wt % to about 50 wt % of the (A) rubber-modified
aromatic vinyl graft copolymer resin; about 10 wt % to about 60 wt
% of the (B) polyester resin; about 1 wt % to about 40 wt % of the
(C) maleimide-based polymer; about 5 wt % to about 40 wt % of the
(D) modified aromatic vinyl compound-vinyl cyanide compound
copolymer resin including a functional group capable of reacting
with polyester; and about 6 wt % to about 12 wt % of the (E)
aromatic vinyl resin copolymerized with an alkyl(meth)acrylate.
[0025] Now, each component of the thermoplastic resin composition
according to the present invention will be described in detail.
[0026] (A) Rubber-Modified Aromatic Vinyl Graft Copolymer Resin
[0027] The rubber-modified aromatic vinyl graft copolymer resin (A)
according to the present invention is a polymer in which a rubber
phase polymer is dispersed in particle form in a matrix (continuous
phase) composed of an aromatic vinyl copolymer.
[0028] The rubber-modified aromatic vinyl graft copolymer resin (A)
may be prepared by any known polymerization method, such as
emulsion polymerization, suspension polymerization, bulk
polymerization, and the like. For example, the rubber-modified
aromatic vinyl graft copolymer resin may be prepared by mixing and
extruding an aromatic vinyl graft copolymer resin alone or in
combination with an aromatic vinyl copolymer resin. In bulk
polymerization, the rubber-modified aromatic vinyl graft copolymer
resin may be prepared by a single step reaction without separate
preparation of the aromatic vinyl graft copolymer resin and the
aromatic vinyl copolymer resin.
[0029] In the rubber-modified aromatic vinyl graft copolymer resin
(A), the rubber phase polymer may be present in an amount of about
5 wt % to about 30 wt %. Within this range, the thermoplastic resin
composition provides effective impact resistance without
deteriorating flowability of the resin.
[0030] To secure suitable properties in melt mixing of the
rubber-modified aromatic vinyl graft copolymer resin (A) and the
polyester resin (B), the rubber phase polymer may have a Z-average
particle size from about 0.1 .mu.m to about 1 .mu.m. Preferably,
the rubber phase polymer has a Z-average particle size from about
0.2 .mu.m to about 0.5 .mu.m.
[0031] Examples of the rubber-modified aromatic vinyl graft
copolymer resin (A) may include acrylonitrile-butadiene-styrene
(ABS), acrylonitrile-styrene-acrylic rubber (ASA),
acrylonitrile-ethylene propylene rubber-styrene (AES) copolymer
resins, and the like.
[0032] The rubber-modified aromatic vinyl graft copolymer resin (A)
may be prepared using (A1) an aromatic vinyl graft resin alone or
in combination with (A2) an aromatic vinyl copolymer resin. Each of
these resins may be formulated in consideration of compatibility
thereof.
[0033] In one embodiment, the rubber-modified aromatic vinyl graft
copolymer resin (A) may be prepared by mixing about 20 wt % to
about 100 wt % of the (A1) aromatic vinyl graft resin and,
optionally, about 80 wt % or less of the (A2) aromatic vinyl
copolymer resin, without being limited thereto.
[0034] In one embodiment, the rubber-modified aromatic vinyl graft
copolymer resin (A) may be present in an amount of about 10 wt % to
about 50 wt %, preferably about 20 wt % to about 40 wt %, based on
the total amount of the resin composition. Within this range, the
resin composition can exhibit excellent properties in terms of
impact resistance, chemical resistance, and hydrolysis
resistance.
[0035] (A1) Aromatic Vinyl Graft Copolymer Resin
[0036] The aromatic vinyl graft copolymer resin (A1) may be
prepared by adding an aromatic vinyl monomer capable of being
grafted to the rubber phase polymer and a monomer copolymerizable
with the aromatic vinyl monomer to the rubber phase polymer,
followed by polymerization.
[0037] Examples of the rubber phase polymer may include diene
rubbers such as polybutadiene, poly(styrene-butadiene), and
poly(acrylonitrile-butadiene) rubbers; acrylic rubbers, such as
saturated rubbers produced by adding hydrogen to the diene rubbers,
isoprene rubbers, chloroprene rubbers, and butyl acrylate rubbers;
and ethylene/propylene/diene monomer (EPDM) terpolymer, and the
like. Among these rubbers, polybutadiene rubber is preferred.
[0038] The rubber phase polymer may be present in an amount about 5
wt % to about 30 wt % in the aromatic vinyl graft copolymer resin
(A1). In addition, the rubber particles (the rubber phase polymer)
may have a Z-average particle size of about 0.1 .mu.m to about 1
.mu.m by taking into account impact resistance and appearance in
preparation of the graft copolymer.
[0039] Examples of the aromatic vinyl monomer capable of being
grafted to the rubber phase polymer may include styrene,
.alpha.-methyl styrene, .beta.-methyl styrene, p-methyl styrene,
p-t-butyl styrene, ethyl styrene, vinyl xylene, monochlorostyrene,
dichlorostyrene, dibromostyrene, vinyl naphthalene, and the like.
Styrene is preferably used. The aromatic vinyl monomer may be
present in an amount of about 30 wt % to about 94 wt % in the
aromatic vinyl graft copolymer resin (A1).
[0040] Examples of the monomer copolymerizable with the aromatic
vinyl monomer may include saturated nitriles such as acrylonitrile,
unsaturated nitriles such as methacrylonitrile, and mixtures
thereof. Acrylonitrile is preferably used. The copolymerizable
monomer may be present in an amount of about 1 wt % to about 40 wt
% in the aromatic vinyl graft copolymer resin (A1).
[0041] When preparing the aromatic vinyl graft copolymer, monomers
for imparting processability and heat resistance may be further
added. For example, monomers such as acrylic acid, methacrylic
acid, maleic anhydrides, N-substituted maleimides, and the like may
be further added. These monomers may be optionally added in an
amount of about 50 wt % or less in the aromatic vinyl graft
copolymer resin (A1).
[0042] (A2) Aromatic Vinyl Copolymer Resin
[0043] The aromatic vinyl copolymer resin (A2) may be prepared by
polymerizing the aromatic vinyl monomer and the monomer
copolymerizable with the aromatic vinyl monomer excluding the
rubber phase polymer among the components of the aromatic vinyl
graft copolymer resin (A1).
[0044] Examples of the aromatic vinyl monomer used in the aromatic
vinyl copolymer resin (A2) may include styrene, .alpha.-methyl
styrene, .beta.-methyl styrene, p-methyl styrene, p-t-butyl
styrene, ethyl styrene, vinyl xylene, monochlorostyrene,
dichlorostyrene, dibromostyrene, vinyl naphthalene, and the like.
The aromatic vinyl monomer may be present in an amount of about 60
wt % to about 90 wt % in the aromatic vinyl copolymer resin
(A2).
[0045] Examples of the monomer copolymerizable with the aromatic
vinyl monomer may include saturated nitriles such as acrylonitrile,
unsaturated nitriles such as methacrylonitrile, and mixtures
thereof. Acrylonitrile is preferably used. The copolymerizable
monomer may be present in an amount of about 10 wt % to about 40 wt
% in the aromatic vinyl copolymer resin (A2).
[0046] The aromatic vinyl copolymer resin (A2) may further include
monomers such as acrylic acid, methacrylic acid, maleic anhydrides,
N-substituted maleimides, and the like to improve processability
and heat resistance. These monomers may be optionally added in an
amount of about 80 wt % or less in the aromatic vinyl copolymer
resin (A2).
[0047] The aromatic vinyl copolymer resin (A2) may have a weight
average molecular weight of about 80,000 g/mol to about 200,000
g/mol. Within this range, the resin composition can secure
excellent mechanical properties.
[0048] (B) Polyester Resin
[0049] According to the present invention, the polyester resin (B)
may be polyester resins having an intrinsic viscosity from about
0.3 dL/g to about 1.5 dL/g or a copolymer thereof.
[0050] The polyester resin (B) is generally obtained by
polycondensation of, terephthalic acid (TPA), isophthalic acid
(IPA), 1,2-naphthalene dicarboxylic acid, 1,4-naphthalene
dicarboxylic acid, 1,5-naphthalene dicarboxylic acid,
1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic
acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene
dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and
2,7-naphthalene dicarboxylic acid, aromatic dicarboxylates whose
acids are substituted with methyl groups such as dimethyl
terephthalate (DMT), dimethyl isophthalate, alkyl ester of
naphthalene dicarboxylate, dimethyl-1,2-naphthalate,
dimethyl-1,5-naphthalate, dimethyl-1,7-naphthalate,
dimethyl-1,7-naphthalate, dimethyl-1,8-naphthalate,
dimethyl-2,3-naphthalate, dimethyl-2,6-naphthalate,
dimethyl-2,7-naphthalate, or mixtures thereof, with diols, such as
C.sub.2 to C.sub.12 ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 2,2-dimethyl-1,3-propanedoil,
2,2-dimethyl-1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-cyclohexane
dimethanol, 1,4-cyclohexane dimethanol, or mixtures thereof.
Preparation of the polyester resin can be easily carried out by
those skilled in the art.
[0051] In one embodiment, the polyester resin (B) may be a recycled
polyester resin. The recycled polyester resin may be obtained from
various products such as PET bottles, PBT, polyester fibers,
polyester films, and the like. Examples of usable recycled
polyester resins may include polyethylene terephthalate,
polybutylene terephthalate, polyethylene naphthalate, polybutylene
naphthalate, polypropylene terephthalate, polyethylene
terephthalate glycol, and the like, without being limited
thereto.
[0052] In one embodiment, the recycled polyester resin may have an
intrinsic viscosity from about 0.4 dL/g to about 1.5 dL/g. Within
this range, the polyester resin can secure impact resistance and
chemical resistance, and does not cause any process problems.
Preferably, the recycled polyester resin has an intrinsic viscosity
from about 0.5 dL/g to about 1.2 dL/g, more preferably from about
0.6 dL/g to about 1.0 dL/g.
[0053] Recycled polyester resin obtained from PET bottles or
polyester extrudates, injection molded articles and the like
typically has an intrinsic viscosity of about 0.4 dL/g or higher.
Recycled polyester resin having an intrinsic viscosity of about 0.4
dL/g to about 1.5 dL/g may be used without additional processing,
or may be used as a raw material after washing and pulverization.
Alternatively, such a recycled polyester resin may be used in
pellet form after extrusion, as needed.
[0054] Recycled polyester resin obtained from polyester fibers,
films and the like typically has an intrinsic viscosity of less
than about 0.4 dL/g. When such a recycled polyester resin having an
intrinsic viscosity of less than about 0.4 dL/g is used, it can be
difficult to achieve desired mechanical properties due to reduction
in molecular weight. Accordingly, when the recycled polyester resin
having an intrinsic viscosity of less than 0.4 dL/g is used as a
raw material, the recycled polyester resin is used after increasing
the intrinsic viscosity thereof to fall within the range of about
0.4 dL/g to about 1.5 dL/g. In some embodiments, the recycled
polyester resin having an intrinsic viscosity of about 0.4 dL/g to
about 1.5 dL/g is used by mixing a recycled polyester resin having
an intrinsic viscosity of less than about 0.4 dL/g with a
thickening agent and extruding the mixture to adjust the intrinsic
viscosity of the recycled polyester resin. Here, the thickening
agent may be a compound having at least two functional groups
capable of reacting with a hydroxyl group and a carboxyl group of
the polyester and capable of linking polyester polymer chains.
Although not particularly limited to certain functional groups, an
epoxy group, maleic anhydride, maleic acid, an amine group, and the
like may be used as the functional groups. In some embodiments,
triglycidyl isocyanurate may be used. The thickening agent may be
added in an amount of about 0.001 to about 5 parts by weight,
preferably about 0.005 to about 2.5 parts by weight, more
preferably about 0.01 to about 1 part by weight, based on 100 parts
by weight of the recycled polyester resin. In some embodiments,
after the recycled polyester resin is mixed with the thickening
agent, the mixture is subjected to extrusion molding using a
typical twin-screw extruder at about 160.degree. C. to about
280.degree. C. to prepare pellets.
[0055] According to the present invention, the polyester resin (B)
may be present in an amount of about 10 wt % to about 60 wt %,
preferably about 11 wt % to about 50 wt %, more preferably about 12
wt % to about 40 wt %, in the total weight of the thermoplastic
resin composition. Within this range, the thermoplastic resin
composition can exhibit good balance of impact resistance and
chemical resistance.
[0056] (C) Maleimide-Based Polymer
[0057] The maleimide-based polymer (C) may contain about 20 mol %
to about 55 mol %, preferably about 25 mol % to about 50 mol % of
repeat units derived from maleimide. Within this range, the
thermoplastic resin composition can exhibit good balance of impact
resistance and chemical resistance.
[0058] In one embodiment, the maleimide-based polymer (C) may be a
copolymer of an N-substituted maleimide and a vinyl monomer.
[0059] In exemplary embodiments, the maleimide-based polymer (C)
may be a copolymer of an N-substituted maleimide, an unsaturated
dicarboxylic acid anhydride, and a vinyl monomer. For example, the
maleimide-based polymer (C) may be a copolymer of about 20 wt % to
about 60 wt % of a first monomer comprising maleic anhydride and an
N-substituted maleimide; and about 40 wt % to about 80 wt % of a
second monomer selected from among an aromatic vinyl compound, a
mixture of the aromatic vinyl compound and a vinyl cyanide
compound, and combinations thereof. Within these ranges of the
first and second monomers, the thermoplastic resin composition can
exhibit good impact resistance and heat resistance.
[0060] In one embodiment, the maleimide-based polymer (C) may be
composed of about 44 wt % to about 50 wt % of styrene, about 45 wt
% to about 55 wt % of N-phenyl maleimide and about 1 wt % to about
5 wt % of maleic anhydride.
[0061] The first monomer may be composed of about 90 wt % to about
99 wt % of maleic anhydride and about 1 wt % to about 10 wt % of
the N-substituted maleimide.
[0062] The N-substituted maleimide constituting the first monomer
may include N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl
maleimide, N-phenyl maleimide, and the like. These may be used
alone or as mixtures thereof.
[0063] The aromatic vinyl compound constituting the second monomer
may include styrene, .alpha.-methyl styrene, p-t-butyl styrene,
2,4-dimethyl styrene, vinyl toluene, and the like. These may be
used alone or as mixtures thereof. In addition, the vinyl cyanide
compound may include acrylonitrile, methacrylonitrile,
ethacrylonitrile, and the like. These may be used alone or as
mixtures thereof.
[0064] The maleimide-based polymer (C) may have a weight average
molecular weight from about 80,000 g/mol to about 200,000 g/mol.
Within this weight average molecular weight range of the
maleimide-based polymer, the thermoplastic resin composition
exhibits excellent heat deflection temperature and impact
resistance.
[0065] The maleimide-based polymer (C) may have a glass transition
temperature of 190.degree. C. to 200.degree. C. and a fluidity of
2.0 g/10 min. to 5.0 g/10 min (at 260.degree. C./10 kg).
[0066] The thermoplastic resin composition may include 1 wt % to 40
wt % of the maleimide-based polymer (C) based on the total weight
of the composition. Within this range, the thermoplastic resin
composition has uniform surface roughness and excellent heat
resistance without deterioration in flowability. The
maleimide-based polymer (C) is preferably present in an amount of 5
wt % to 35 wt %, more preferably 10 wt % to 30 wt % in the
thermoplastic resin composition.
[0067] (D) Modified Aromatic Vinyl Compound-Vinyl Cyanide Compound
Copolymer Resin Containing Functional Group Capable of Reacting
with Polyester
[0068] According to the present invention, the modified aromatic
vinyl compound-vinyl cyanide compound copolymer resin (D) includes
a functional group capable of reacting with polyester. For example,
the modified aromatic vinyl compound-vinyl cyanide compound
copolymer resin (D) is a resin which is prepared by polymerization
such that the functional group capable of reacting with polyester
is present in a vinyl-based resin.
[0069] In one embodiment, the modified aromatic vinyl
compound-vinyl cyanide compound copolymer resin (D) is a copolymer
of (d1) an unsaturated compound including the functional group
capable of reacting with polyester and (d2) a vinyl-based compound.
For example, the modified aromatic vinyl compound-vinyl cyanide
compound copolymer resin (D) is a copolymer of about 0.01 mol % to
about 5 mol % of the (d1) unsaturated compound including the
functional group capable of reacting with polyester and about 95
mol % to about 99.99 mol % of (d2) the vinyl-based compound.
[0070] The modified aromatic vinyl compound-vinyl cyanide compound
copolymer resin (D) of the present invention may have a weight
average molecular weight from about 50,000 g/mol to about 200,000
g/mol. Within this range of the weight average molecular weight,
the copolymer resin can secure excellent reactivity and mechanical
properties.
[0071] In the present invention, the modified aromatic vinyl
compound-vinyl cyanide compound copolymer resin (D) may be present
in an amount of about 5 wt % to about 40 wt %, preferably about 10
wt % to about 35 wt %, in the composition. Within this content
range, the thermoplastic resin composition has good balance between
flowability, heat resistance and surface roughness.
[0072] (d1) Unsaturated Compound including a Functional Group
Capable of Reacting with Polyester
[0073] The unsaturated compound (d1) may be represented by Formula
1.
##STR00002##
[0074] In Formula 1, R.sub.3, R.sub.4 and R.sub.5 are each
independently hydrogen (H), a C.sub.1.about.C.sub.12 alkyl group or
unsaturated alkyl group, a C.sub.6.about.C.sub.14 aryl group, or a
C.sub.1.about.C.sub.12 alkyl-substituted aryl group or unsaturated
alkyl-substituted aryl group; Y is an ether group (--O--), a
carboxyl group (--O--[C.dbd.O]--, --[O.dbd.C]--O--), a
C.sub.1.about.C.sub.12 alkylene group, a C.sub.6.about.C.sub.14
arylene group, or a C.sub.1.about.C.sub.12 alkyl-substituted
arylene group; when Y is an ether group or a carboxyl group, each
of R.sub.1 and R.sub.2 is a C.sub.1.about.C.sub.12 alkylene group,
a C.sub.6.about.C.sub.14 arylene group, or a C.sub.1.about.C.sub.12
alkyl-substituted arylene group, and when Y is a
C.sub.1.about.C.sub.12 alkylene group or a C.sub.6.about.C.sub.14
arylene group or alkyl-substituted arylene group, Y represents
(R.sub.1--Y--R.sub.2); x is 0 or 1; and Z is an epoxy group, a
carboxylic acid group, an isocyanate group, an oxadiazol group, an
amine group, or a hydroxyl group.
[0075] Examples of the unsaturated compound (d1) may include epoxy
group-containing monomers such as epoxy alkyl acrylate, allyl
glycidyl ester, aryl glycidyl ester, glycidyl methacrylate,
glycidyl acrylate, butadiene monoxide, vinyl glycidyl ether, and
glycidyl itaconate; carboxylic acid group-containing monomers such
as acrylic acid, methacrylic acid, 2-butanoic acid,
2-methyl-2-butanoic acid, undecylenic acid, oleic acid, sorbic
acid, linoleic acid, crotonic acid, and itaconic acid; isocyanate
group-containing monomers such as vinyl isocyanate, acryl
isocyanate, and methacryl isocyanate; amine group-containing
monomers such as vinyl amine, acryl amine, and methacryl amine; and
hydroxy group-containing monomers such as hydroxy vinyl ether,
hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl
acrylate, hydroxy propyl methacrylate, 2-hydroxy acrylate, and
3-phenoxypropyl acrylate, without being limited thereto.
Thereamong, the epoxy group-containing monomers are preferable.
These unsaturated compounds may be used alone or in combination
thereof.
[0076] The unsaturated compound (d1) may be present in an amount of
about 0.01 mol % to about 5 mol %, preferably about 0.1 mol % to
about 4 mol %, in the form of a monomer for copolymerization.
Within this range, the thermoplastic resin composition can obtain
improvement of impact strength in an optimal range and can minimize
gelation upon extrusion.
[0077] (d2) Vinyl-Based Compound
[0078] The vinyl-based compound (d2) includes an aromatic vinyl
monomer and a monomer copolymerizable with the aromatic vinyl
monomer.
[0079] In one embodiment, the aromatic vinyl monomer may be
represented by Formula 2.
##STR00003##
[0080] In Formula 2, R.sub.9 is hydrogen or a methyl group;
R.sub.10 is a phenyl group, a halophenyl group, an alkylphenyl
group, an alkylhalophenyl group, a naphthalene group, or an
alkylnaphthalene group; and R.sub.11 is hydrogen, a methyl group,
and the like.
[0081] Wherein, the halophenyl group is a phenyl group substituted
with one to three halogen compounds, the alkylphenyl group is a
phenyl group substituted with one or two alkyl groups, the
alkylhalophenyl group is a phenyl group substituted with an alkyl
group containing a halogen compound or a phenyl group substituted
with halogen and an alkyl group, and the alkylnaphthalene group is
naphthalene substituted with one to four alkyl groups.
[0082] Examples of the aromatic vinyl monomer may include styrene,
.alpha.-methyl styrene, .beta.-methyl styrene, p-methyl styrene,
p-t-butyl styrene, ethyl styrene, vinyl xylene, monochlorostyrene,
dichlorostyrene, dibromostyrene, and vinyl naphthalene, without
being limited thereto. Styrene is most preferable. These aromatic
vinyl monomers may be used alone or as mixtures thereof.
[0083] The monomer copolymerizable with the aromatic vinyl monomer
is preferably a vinyl cyanide monomer, such as acrylonitrile,
methacrylonitrile, and ethacrylonitrile, without being limited
thereto. These may be used alone or as mixtures thereof.
Thereamong, acrylonitrile is preferred.
[0084] The amounts of the aromatic vinyl monomer and the monomer
copolymerizable with the aromatic vinyl monomer are determined
depending upon compatibility and the ratio of monomers excluding
rubbers among the components of the aromatic vinyl graft copolymer
resin (A). Preferably, the aromatic vinyl monomer is present in an
amount of about 50 wt % to about 99 wt % and the monomer
copolymerizable with the aromatic vinyl monomer is present in an
amount of about 1 wt % to about 50 wt %. More preferably, the
aromatic vinyl monomer is present in an amount of about 60 wt % to
about 90 wt % and the monomer copolymerizable with the aromatic
vinyl monomer is present in an amount of about 10 wt % to about 40
wt %. Within this range, the thermoplastic resin composition can
obtain desired effects in terms of processability and strength.
[0085] The vinyl-based compound (d2) according to the invention may
optionally further include an ethylenically unsaturated monomer to
improve the properties of a copolymer such as processability and
heat resistance. Examples of the ethylenically unsaturated monomer
may include aromatic esters of acrylic or methacrylic acid such as
methyl methacrylate, C.sub.1.about.C.sub.4 alkyl methacrylates,
phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl
methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate,
2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate;
N-substituted maleimides such as N-methylmaleimide,
N-phenylmaleimide and N-cyclohexylmaleimide; acrylic acid,
methacrylic acid and dicarboxylic acid such as maleic acid, fumaric
acid, itaconic acid and anhydrides thereof and nitrogen-functional
monomers such as dimethylaminoethyl acrylate, diethylaminoethyl
acrylate, vinylimidazole, vinylpyrrolidone, vinyl caprolactam,
vinylcarbazole, vinylaniline, acrylamide, and methacrylamide,
without being limited thereto. The ethylenically unsaturated
monomer may be present in an amount of about 30 wt % or less,
preferably about 1 wt % to about 20 wt %, more preferably about 2
wt % to about 15 wt % in the vinyl-based compound (d2).
[0086] (E) Aromatic Vinyl Resin Copolymerized with
Alkyl(meth)acrylate
[0087] The (E) aromatic vinyl resin copolymerized with an
alkyl(meth)acrylate may a copolymer of an alkyl(meth)acrylate and
an aromatic vinyl-based compound.
[0088] Preferably, the (E) aromatic vinyl resin copolymerized with
an alkyl(meth)acrylate is a copolymer of an alkyl(meth)acrylate, an
aromatic vinyl compound and a vinyl cyanide compound. Here, the (E)
aromatic vinyl resin copolymerized with an alkyl(meth)acrylate is
preferably a copolymer of about 5 wt % to about 50 wt % of the
alkyl(meth)acrylate, about 30 wt % to about 80 wt % of the aromatic
vinyl compound and about 10 wt % to about 40 wt % of the vinyl
cyanide compound. More preferably, the alkyl(meth)acrylate is
present in an amount of about 10 wt % to about 30 wt %, most
preferably in an amount of about 15 wt % to about 20 wt % in the
copolymer.
[0089] The alkyl(meth)acrylate is a C.sub.1 to C.sub.10
alkyl(meth)acrylate. For example, the alkyl(meth)acrylate may be
methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl
methacrylate, methyl acrylate, ethyl acrylate, and the like.
[0090] Examples of the aromatic vinyl monomer (aromatic vinyl
compound) may include styrene, .alpha.-methyl styrene,
.beta.-methyl styrene, p-methyl styrene, p-t-butyl styrene, ethyl
styrene, vinyl xylene, monochlorostyrene, dichlorostyrene,
dibromostyrene, and vinyl naphthalene, without being limited
thereto. Styrene is most preferable. These aromatic vinyl monomers
may be used alone or as mixtures thereof.
[0091] Examples of the vinyl cyanide monomer (vinyl cyanide
compound) may include acrylonitrile, methacrylonitrile, and
ethacrylonitrile, without being limited thereto. These aromatic
vinyl monomers may be used alone or as mixtures thereof.
Thereamong, acrylonitrile is preferable.
[0092] The (E) aromatic vinyl resin copolymerized with an
alkyl(meth)acrylate may have a weight average molecular weight from
about 80,000 g/mol to about 200,000 g/mol, preferably from about
120,000 g/mol to about 160,000 g/mol. Within this range, the
thermoplastic resin has excellent compatibility and mechanical
properties.
[0093] The (E) aromatic vinyl resin copolymerized with an
alkyl(meth)acrylate may be present in an amount of about 6 wt % to
about 12 wt %, preferably about 8 wt % to about 10 wt %. Within
this range, the thermoplastic resin composition exhibits excellent
heat resistance and surface roughness, and has good property
balance between flowability and impact strength.
[0094] In the present invention, the weight average molecular
weight was measured by gel permeation chromatography GPC (Model No.
GPC-16) under conditions of Table 1.
TABLE-US-00001 TABLE 1 Detector: Differential Refractive Index
Detector (RI-8020, Sensitivity: 32, Tosoh Corporation), UV
Absorbance Detector (2487, Wavelength: 215 nm, Sensitivity: 0.2
AUFS, Waters Co., Ltd.)), Column: TSKgel GMHXL (two), G2500HXL
(one) (S/N M0052, M0051, N0010, 7.8 mm .times. 30 cm, Tosoh
Corporation), Solvent: Tetrahydrofuran, Flow rate: 1.0 mL/min,
Column temperature: 35.degree. C., Sample: [Concentration] about
0.2% [Filtration] filtered through a 0.45 .mu.m filter. Input:
0.200 mL, Reference sample: Mono-dispersed polystyrene
[0095] The thermoplastic resin composition of the present invention
may further include typical additives such as lubricants, impact
modifiers, dyes, pigments, release agents, dispersants,
anti-dripping agents, weather stabilizers, inorganic fillers,
inorganic fibers, and the like.
[0096] The thermoplastic resin composition of the present invention
may be prepared by any method known in the art. For example, the
thermoplastic resin composition may be prepared in pellet form by
mixing the components of the thermoplastic resin composition and
the additives, followed by melt-extrusion using an extruder.
[0097] Another aspect of the present invention relates to a molded
product prepared by molding the thermoplastic resin
composition.
[0098] In one embodiment, the molded product is molded using the
thermoplastic resin composition and may have an average surface
roughness (Ra) from about 10 nm to about 62 nm as measured using an
optical profiler (NT1100). For example, the molded product may have
a metal layer formed on a surface thereof. The metal layer may
include nickel, chromium, aluminum, gold, silver, platinum, copper,
lead, tin, or alloys thereof. Preferably, the metal layer is formed
of aluminum or aluminum alloys. Preferably, the molded product is
applied to housings for automobile lamps.
Mode for Invention
[0099] Next, the present invention will be better understood from
the following examples and comparative examples. It should be
understood that these examples are provided for illustration only
and are not to be construed in any way as limiting the scope of the
invention.
[0100] Descriptions of details apparent to those skilled in the art
will be omitted.
EXAMPLES
[0101] Components of thermoplastic resin compositions of the
following examples and comparative examples were as follows.
[0102] (A) Rubber-modified aromatic vinyl graft copolymer resin: A
mixture of g-ABS (manufactured by Cheil Industries Inc., product
name: Starex CHT) and SAN (manufactured by Cheil Industries Inc.,
product name: HF-5661) was used.
[0103] (B) Polyester resin: Recycled PET (manufactured by Samyang
Co., Ltd., product name: Recycled PET Bottle Flakes) was used.
[0104] (C) Maleimide-based polymer: PMI (manufactured by DENKA Co.,
Ltd., product name: MS-NI) was used.
[0105] (D) Aromatic vinyl compound-vinyl cyanide compound copolymer
resin containing a functional group capable of reacting with
polyester (GMA-SAN): To a mixture of 120 parts by weight of
deionized water and 100 parts by weight of a monomer mixture, which
consists of 0.5 parts by weight of glycidyl methacrylate, 70.5
parts by weight of styrene and 29 parts by weight of acrylonitrile,
0.2 parts by weight of azobisisobutyronitrile, 0.4 parts by weight
of tricalcium phosphate and 0.2 parts by weight of a
mercaptan-based chain transfer agent were added, heated from room
temperature to 80.degree. C. over 60 minutes, and maintained at
this temperature for 180 minutes, thereby preparing an
epoxy-containing styrene-acrylonitrile copolymer resin (GMA-SAN).
Then, the obtained copolymer resin was washed with water,
dehydrated and dried to form epoxy-containing styrene-acrylonitrile
copolymer resin (GMA-SAN) powder to be used in the examples and
comparative examples.
[0106] (E) Aromatic vinyl resin copolymerized with
alkyl(meth)acrylate: To a mixture of 120 parts by weight of
deionized water and 100 parts by weight of a monomer mixture, which
consists of 74 parts by weight of methyl methacrylate, 21 parts by
weight of styrene and 5 parts by weight of acrylonitrile, 0.2 parts
by weight of azobisisobutyronitrile, 0.4 parts by weight of
tricalcium phosphate and 0.2 parts by weight of a mercaptan-based
chain transfer agent were added, heated from room temperature to
80.degree. C. over 60 minutes, and maintained at this temperature
for 180 minutes, thereby preparing a methyl
methacrylate-styrene-acrylonitrile copolymer resin (MSAN). Then,
the obtained copolymer resin was washed with water, dehydrated and
dried to form methyl methacrylate-styrene-acrylonitrile copolymer
resin (MSAN) powder to be used in the examples and comparative
examples.
Examples 1 to 3 and Comparative Examples 1 to 3
[0107] The respective components were added in amounts as listed in
the following Table 2, followed by extrusion molding using a
twin-screw extruder at 250.degree. C., thereby preparing
thermoplastic resin compositions in pellet form. The prepared
pellets were subjected to injection molding (LGH 140N) at
250.degree. C. to prepare specimens.
TABLE-US-00002 TABLE 2 Comparative Example Example 1 2 3 1 2 3 (A)
ABS g-ABS 24 24 24 24 24 24 (A) ABS SAN 36 33 30 42 39 27 (B) PET
12 12 12 12 12 12 (C) PMI 14 14 14 14 14 14 (D) GMA-SAN 8 8 8 8 8 8
(E) MSAN 6 9 12 0 3 15 Surface 60.17 56.82 58.47 68.16 63.88 67.08
roughness (nm) HDT (.degree. C.) 97.9 98.6 97.0 94.3 95.4 96.4
Unit: wt %
[0108] <Property Evaluation>
[0109] 1. Surface roughness: Average surface roughness was measured
on an area of 2.4 mm.times.1.9 mm using an optical profiler (Veeco
Co., Ltd., NT1100) (unit: nm).
[0110] 2. Heat deflection temperature (HDT): HDT was measured in
accordance with ASTM D 648. Evaluation was performed by applying a
load of 18.5 kg/cm.sup.2 to a 1/4-inch thick specimen. Results were
evaluated according to an average of five specimens.
[0111] As shown in Table 2, it could be seen that the thermoplastic
resin compositions prepared in Examples 1 to 3 exhibited high heat
deflection temperature and excellent surface roughness, whereas the
thermoplastic resin compositions prepared in Comparative Examples 1
to 3 had lower surface roughness and heat deflection temperature
than those of the examples.
[0112] Although some embodiments have been disclosed herein, it
should be understood by those skilled in the art that these
embodiments are provided by way of illustration only, and that
various modifications, changes, and alterations can be made without
departing from the spirit and scope of the invention. Therefore,
these examples are not to be construed in any way as limiting the
present invention.
* * * * *