【Technical Field】
[1] [Cross-Reference to Related Application]
[2] This application claims priority to Korean Patent
Application No. 10-2020-0128800, filed on October 06, 2020 in
10 the Korean Intellectual Property Office, the disclosure of
which is incorporated herein by reference.
[3] The present invention relates to a thermoplastic
resin composition, a method of preparing the same, and a
molded article including the same. More particularly, the
15 present invention relates to a thermoplastic resin
composition prepared by adding a recycled vinyl cyanide
compound-conjugated diene rubber-aromatic vinyl compound
copolymer and a recycled polycarbonate resin to a composition
including a vinyl cyanide compound-conjugated diene rubber20
aromatic vinyl compound graft copolymer, an α-methyl styrene2
vinyl cyanide compound-aromatic vinyl compound copolymer, and
an aromatic vinyl compound-vinyl cyanide compound copolymer
according to a specific composition ratio. Due to this
compositional feature, the thermoplastic resin composition of
the present invention includes 5 a recycled resin while
maintaining mechanical properties. In addition, the heat
resistance and chemical resistance of the thermoplastic resin
composition may be greatly improved.
10 【Background Art】
[4] Acrylonitrile-butadiene-styrene resins (hereinafter
referred to as "ABS resins") based on conjugated diene rubber
have excellent processability, mechanical properties, and
appearance, and thus have been used in various fields, such
15 as parts of electrical and electronic products, automobiles,
small toys, furniture, and building materials.
[5] Meanwhile, as interest in the environment is growing
worldwide, regulations are being strengthened to reduce
carbon dioxide emissions. In particular, in recent years,
20 environmental pollution due to increased use of plastics has
3
emerged as a serious problem. Accordingly, regulations at a
manufacturing stage, such as mandatory use of recycled resins,
are being strengthened mainly in the United States.
Accordingly, a manufacturer must add more than a certain
amount of recycled resin when 5 manufacturing a resin molded
product. In addition, an eco-friendly grade is given
according to the content of recycled resin.
[6] However, since a recycled resin has already been
processed, the recycled resin contains additives such as
10 colorants, lubricants, and release agents, and the like. In
addition, the properties of a recycled resin are already
changed through high-temperature processing. Thus, as the
content of a recycled resin is increased, physical properties
are inevitably deteriorated compared to that of an existing
15 resin. In particular, a product including a recycled resin
may not have sufficient chemical resistance to organic
solvents, detergents, or fragrances used in a post-processing
process when manufacturing a molded article, so that cracks
or breakage may occur. Due to these problems, it is difficult
20 to commercialize a product including a recycled resin.
4
[7]
[8] [Related Art Documents]
[9] [Patent Documents]
[10] KR 2016-0144185 A
5
【Disclosure】
【Technical Problem】
[11] Therefore, the present invention has been made in
view of the above problems, and it is one object of the
10 present invention to provide a thermoplastic resin
composition having excellent heat resistance and chemical
resistance while maintaining mechanical properties and
physical properties, such as moldability, equal to those of a
conventional ABS-based resin.
15 [12] It is another object of the present invention to
provide a method of preparing the thermoplastic resin
composition and a molded article manufactured using the
thermoplastic resin composition.
[13] The above and other objects can be accomplished by
20 the present invention described below.
5
【Technical Solution】
[14] In accordance with one aspect of the present
invention, provided is a thermoplastic resin composition
including 10 to 40 % by weight 5 of a vinyl cyanide compoundconjugated
diene rubber-aromatic vinyl compound graft
copolymer (A), 10 to 40 % by weight of an α-methyl styrenevinyl
cyanide compound-aromatic vinyl compound copolymer (B),
5 to 30 % by weight of an aromatic vinyl compound-vinyl
10 cyanide compound copolymer (C), 10 to 30 % by weight of a
recycled vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound copolymer (D), and 25 to 50 % by
weight of a recycled polycarbonate resin (E), wherein a
weight ratio of the copolymer (B) to the copolymer (C) is
15 1.3:1 to 3.0:1.
[15] As another example, the present invention provides a
thermoplastic resin composition including 10 to 40 % by
weight of a vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound graft copolymer (A), 10 to 40 % by
20 weight of an α-methyl styrene-vinyl cyanide compound-aromatic
6
vinyl compound copolymer (B), 5 to 30 % by weight of an
aromatic vinyl compound-vinyl cyanide compound copolymer (C),
10 to 30 % by weight of a recycled vinyl cyanide compoundconjugated
diene rubber-aromatic vinyl compound copolymer (D),
and 25 to 50 % by weight of 5 a recycled polycarbonate resin
(E), wherein, when a specimen having a size of 200 mm × 12.7
mm × 3.2 mm is fixed to a curved jig having a strain of 1.1 %,
1 cc of thinner is applied thereto, and then time at which
cracks occur on a surface of the specimen is measured, the
10 thermoplastic resin composition has a chemical resistance of
600 seconds or more.
[16] In accordance with another aspect of the present
invention, provided is a method of preparing a thermoplastic
resin composition, the method including a step of kneading
15 and extruding 10 to 40 % by weight of a vinyl cyanide
compound-conjugated diene rubber-aromatic vinyl compound
graft copolymer (A), 10 to 40 % by weight of an α-methyl
styrene-vinyl cyanide compound-aromatic vinyl compound
copolymer (B), 5 to 30 % by weight of an aromatic vinyl
20 compound-vinyl cyanide compound copolymer (C), 10 to 30 % by
7
weight of a recycled vinyl cyanide compound-conjugated diene
rubber-aromatic vinyl compound copolymer (D), and 25 to 50 %
by weight of a recycled polycarbonate resin (E) at 200 to
280 °C, wherein a weight ratio of the copolymer (B) to the
5 copolymer (C) is 1.3:1 to 3.0:1.
[17] As another example, the present invention provides a
method of preparing a thermoplastic resin composition, the
method including kneading and extruding 10 to 40 % by weight
of a vinyl cyanide compound-conjugated diene rubber-aromatic
10 vinyl compound graft copolymer (A), 10 to 40 % by weight of
an α-methyl styrene-vinyl cyanide compound-aromatic vinyl
compound copolymer (B), 5 to 30 % by weight of an aromatic
vinyl compound-vinyl cyanide compound copolymer (C), 10 to
30 % by weight of a recycled vinyl cyanide compound15
conjugated diene rubber-aromatic vinyl compound copolymer (D),
and 25 to 50 % by weight of a recycled polycarbonate resin (E)
at 200 to 280 °C, wherein, when a specimen having a size of
200 mm × 12.7 mm × 3.2 mm is fixed to a curved jig having a
strain of 1.1 %, 1 cc of thinner is applied thereto, and then
20 time at which cracks occur on a surface of the specimen is
8
measured, the thermoplastic resin composition has a chemical
resistance of 600 seconds or more.
[18] In accordance with yet another aspect of the present
invention, provided is a molded article including the
5 thermoplastic resin composition.
【Advantageous effects】
[19] By including a recycled vinyl cyanide compoundconjugated
diene rubber-aromatic vinyl compound graft
10 copolymer (hereinafter referred to as "ABS-based resin") and
a recycled polycarbonate (PC)-based resin in predetermined
contents and by adjusting a composition ratio to include an
alpha-methylstyrene-vinyl cyanide compound copolymer (heatresistant
SAN-based resin) and a vinyl cyanide compound15
aromatic vinyl compound copolymer (SAN-based resin) in a
specific weight ratio, the present invention advantageously
provides a recycled thermoplastic resin composition having
excellent mechanical properties, moldability, heat resistance,
and chemical resistance while containing an excess of a
20 recycled resin; a method of preparing the recycled
9
thermoplastic resin composition; and a molded article
manufactured using the recycled thermoplastic resin
composition.
5 【Description of Drawings】
[20] FIG. 1 shows the chemical resistance test results of
Examples according to the present invention and Comparative
Examples.
10 【Best mode】
[21] Hereinafter, the thermoplastic resin composition of
the present invention will be described in detail.
[22] The present inventors confirmed that, when a
predetermined amount of a recycled PC-based resin was added
15 to a recycled thermoplastic resin composition including a
recycled ABS-based resin, and a heat-resistant SAN-based
resin and a general SAN-based resin were included in a
specific weight ratio, the intrinsic physical properties of
the ABS-based resin were maintained and heat resistance and
20 chemical resistance were improved even though an excess of a
10
recycled resin was included. Based on these results, the
present inventors conducted further studies to complete the
present invention.
[23]
[24] The thermoplastic resin 5 composition of the present
invention includes 10 to 40 % by weight of a vinyl cyanide
compound-conjugated diene rubber-aromatic vinyl compound
graft copolymer (A), 10 to 40 % by weight of an α-methyl
styrene-vinyl cyanide compound-aromatic vinyl compound
10 copolymer (B), 5 to 30 % by weight of an aromatic vinyl
compound-vinyl cyanide compound copolymer (C), 10 to 30 % by
weight of a recycled vinyl cyanide compound-conjugated diene
rubber-aromatic vinyl compound copolymer (D), and 25 to 50 %
by weight of a recycled polycarbonate resin (E), wherein the
15 weight ratio of the copolymer (B) to the copolymer (C) is
1.3:1 to 3.0:1. In this case, mechanical properties,
moldability, heat resistance, and chemical resistance may be
excellent while an excess of a recycled resin is included.
[25]
20 [26] As another example, the thermoplastic resin
11
composition of the present invention includes 10 to 40 % by
weight of a vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound graft copolymer (A), 10 to 40 % by
weight of an α-methyl styrene-vinyl cyanide compound-aromatic
vinyl compound copolymer (5 B), 5 to 30 % by weight of an
aromatic vinyl compound-vinyl cyanide compound copolymer (C),
10 to 30 % by weight of a recycled vinyl cyanide compoundconjugated
diene rubber-aromatic vinyl compound copolymer (D),
and 25 to 50 % by weight of a recycled polycarbonate resin
10 (E), wherein, when a specimen having a size of 200 mm × 12.7
mm × 3.2 mm is fixed to a curved jig having a strain of 1.1 %,
1 cc of thinner is applied thereto, and then time at which
cracks occur on the surface of the specimen is measured, the
thermoplastic resin composition has a chemical resistance of
15 600 seconds or more. In this case, mechanical properties,
moldability, heat resistance, and chemical resistance may be
excellent while an excess of a recycled resin is included.
[27]
[28] In this description, the composition ratio of a
20 (co)polymer may mean the content of units constituting the
12
(co)polymer, or may mean the content of units input during
polymerization of the (co)polymer.
[29]
[30] Hereinafter, each component constituting the
thermoplastic resin composition 5 of the present invention will
be described in detail.
[31]
[32] (A) Vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound graft copolymer
10 [33] The vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound graft copolymer (A) (hereinafter
referred to as "graft copolymer (A)") is included in the
thermoplastic resin composition in an amount of 10 to 40 % by
weight. In this case, mechanical properties, moldability, and
15 appearance may be excellent. As a preferred example, based on
a total weight of the composition, the graft copolymer (A)
may be included in an amount of 15 to 40 % by weight, more
preferably 17 to 35 % by weight. Within this range,
mechanical properties, moldability, appearance, and physical
20 property balance may be excellent.
13
[34] For example, the graft copolymer (A) may include 50
to 80 % by weight of conjugated diene rubber comprising a
conjugated diene compound, 5 to 20 % by weight of a vinyl
cyanide compound, and 10 to 40 % by weight of an aromatic
vinyl compound. In this 5 case, mechanical properties,
moldability, appearance, and physical property balance may be
excellent.
[35] As a preferred example, the graft copolymer (A) may
include 50 to 70 % by weight of conjugated diene rubber, 5 to
10 15 % by weight of a vinyl cyanide compound, and 20 to 40 % by
weight of an aromatic vinyl compound, more preferably 55 to
65 % by weight of conjugated diene rubber, 10 to 15 % by
weight of a vinyl cyanide compound, and 20 to 30 % by weight
of an aromatic vinyl compound. Within this range, impact
15 resistance and physical property balance may be excellent.
[36] For example, an average particle diameter of the
conjugated diene rubber included in the graft copolymer (A)
may be 2,000 to 5,000 Å, preferably 2,000 to 4,000 Å, more
preferably 2,500 to 3,500 Å. Within this range, impact
20 strength may be excellent without deterioration in other
14
physical properties.
[37] In this description, average particle diameter of the
conjugated diene rubber may be measured by dynamic light
scattering, and specifically, may be measured as an intensity
value using a Nicomp 380 particle 5 size analyzer (manufacturer:
PSS) in a Gaussian mode.
[38]
[39] For example, the graft copolymer (A) may have a
grafting degree of 20 to 70 %, preferably 20 to 55 %, more
10 preferably 20 to 45 %. Within this range, appropriate
compatibility and moldability may be secured, and balance
between compatibility, moldability, and other mechanical
properties may be excellent.
[40] In this description, to measure grafting degree,
15 graft (co)polymer latex is coagulated, washed, and dried to
obtain powder, and then 1 g of the obtained powder is added
to 30 ml of acetone, followed by stirring for 24 hours. Then,
the stirred solution is centrifuged at 14,000 rpm for 4 hours
using an ultracentrifuge to obtain insoluble matter, and the
20 insoluble matter is dried at 85 °C for 4 hours. Then, the
15
weight of the dried insoluble matter is measured, and
grafting degree is calculated by substituting the measured
value into Equation 1 below.
[41] [Equation 1]
[42] Grafting degree (%) = [{Weight 5 (g) of dried insoluble
matter - weight (g) of rubber added during graft
polymerization} / weight (g) of rubber added during graft
polymerization] × 100
[43] The drying may proceed until there is no further
10 change in weight.
[44]
[45] For example, the graft copolymer (A) may have a
weight average molecular weight of 500,000 to 1,000,000 g/mol,
preferably 650,000 to 900,000 g/mol. Within this range, due
15 to proper fluidity, excellent processability and impact
resistance may be secured.
[46] In this description, weight average molecular weight
may be measured at 40 °C using tetrahydrofuran (THF) as a
solvent using a gel permeation chromatograph (GPC) filled
20 with porous silica as a column packing material. In this case,
16
weight average molecular weight is obtained as a relative
value to a polystyrene (PS) standard sample.
[47]
[48] For example, the graft copolymer (A) may be prepared
by a known polymerization 5 method including emulsion
polymerization, suspension polymerization, bulk
polymerization, and the like, preferably emulsion
polymerization.
[49] For example, based on 100 parts by weight in total of
10 the conjugated diene rubber, the aromatic vinyl compound, and
the vinyl cyanide compound included in the graft copolymer,
the graft copolymer (A) may be prepared by adding,
continuously or batchwise, a monomer mixture including 5 to
20 parts by weight of the vinyl cyanide compound and 10 to 40
15 parts by weight of the aromatic vinyl compound to a mixed
solution containing 50 to 80 parts by weight (based on solids)
of conjugated diene rubber latex, 0.1 to 5 parts by weight of
an emulsifier, 0.1 to 3 parts by weight of a molecular weight
modifier, and 0.05 to 1 part by weight of an initiator and
20 then performing polymerization.
17
[50] As another example, based on 100 parts by weight in
total of the conjugated diene rubber, the aromatic vinyl
compound, and the vinyl cyanide compound, the graft copolymer
(A) may be prepared by adding, at 65 to 75 °C for 2 to 4
hours, a mixed solution including 5 5 to 20 parts by weight of
the vinyl cyanide compound, 10 to 40 parts by weight of the
aromatic vinyl compound, 10 to 50 parts by weight of
deionized water, 0.09 to 1.5 parts by weight of an initiator,
0.1 to 2 parts by weight of an emulsifier, and 0.05 to 1.5
10 parts by weight of a molecular weight modifier, which has
been mixed in a separate mixing device, to 50 to 80 parts by
weight (based on solids) of conjugated diene rubber latex and
60 to 150 parts by weight of deionized water; adding 0.01 to
0.5 parts by weight of an initiator thereto; raising
15 temperature to 75 to 80 °C for 30 to 90 minutes; and
terminating graft polymerization at a polymerization
conversion rate of 93 to 99 % by weight. In this case, impact
resistance, mechanical strength, and moldability may be
excellent.
20 [51] In this description, based on 100 % of the total
18
weight of monomers input until polymerization is completed,
polymerization conversion rate may be defined as % by weight
of the monomers converted into a polymer until measurement
time. A method of measuring polymerization conversion rate is
not particularly limited as 5 long as the method follows this
definition. As a specific example, after drying 1.5 g of
prepared (co)polymer latex in a hot air dryer at 150 °C for
15 minutes, the weight of the dried latex is measured, and
total solids content (TSC) is calculated by Equation 2 below.
10 Then, polymerization conversion rate is calculated by
substituting the total solids content value into Equation 3
below. In Equation 3, the total weight of added monomers is
given as 100 parts by weight.
[52] [Equation 2]
15 [53] Total solids content (TSC; %) = (Weight after drying
/ Weight before drying) × 100
[54] [Equation 3]
[55] Polymerization conversion rate (%) = [Total solids
content (TSC) × (Total weight of added monomers, deionized
20 water, and subsidiary raw materials) / 100] - (Weight of
19
added subsidiary raw materials other than monomers and
deionized water)
[56] In Equation 3, subsidiary raw materials include an
initiator, an emulsifier, and a molecular weight modifier,
and include an electrolyte 5 when the electrolyte is used.
[57]
[58] For example, the conjugated diene compound may
include one or more selected from the group consisting of
1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-
10 butadiene, 1,3-pentadiene, isoprene, chloroprene, and
pyrerylene.
[59] For example, the vinyl cyanide compound may include
one or more selected from the group consisting of
acrylonitrile, methacrylonitrile, ethylacrylonitrile, and
15 isopropylacrylonitrile, preferably acrylonitrile.
[60] For example, the aromatic vinyl compound may include
one or more selected from the group consisting of styrene, α-
methyl styrene, ο-methyl styrene, p-methyl styrene, m-methyl
styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-
20 bromostyrene, p-bromostyrene, m-bromostyrene, ο-chlorostyrene,
20
p-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene,
fluorostyrene, and vinylnaphthalene, preferably one or more
selected from the group consisting of styrene and α-methyl
styrene, more preferably styrene. In this case, due to proper
fluidity, processability and 5 mechanical properties, such as
impact resistance, may be excellent.
[61] In this description, the derivative is a compound
produced by substituting a hydrogen atom or an atomic group
of an original compound with another atom or atomic group,
10 for example, refers to a compound produced by substitution
with a halogen or an alkyl group.
[62]
[63] For example, the emulsifier may include one or more
selected from the group consisting of allyl aryl sulfonates,
15 alkali methyl alkyl sulfonates, sulfonated alkyl esters,
fatty acid soap, and rosin acid alkali salts. In this case,
polymerization stability may be excellent.
[64] For example, the molecular weight modifier may
include one or more selected from the group consisting of t20
dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan,
21
and carbon tetrachloride, preferably t-dodecyl mercaptan.
[65] For example, the initiator may be a water-soluble
persulfuric acid polymerization initiator, a fat-soluble
polymerization initiator, or an oxidation-reduction catalyst
system. For example, the water-5 soluble persulfuric acid
polymerization initiator may include one or more selected
from the group consisting of potassium persulfate, sodium
persulfate, and ammonium persulfate, and the fat-soluble
polymerization initiator may include one or more selected
10 from the group consisting of cumene hydroperoxide,
diisopropyl benzene hydroperoxide, azobis iso butyronitrile,
t-butyl hydroperoxide, paramethane hydroperoxide, and
benzoylperoxide.
[66] For example, latex prepared by emulsion
15 polymerization may be coagulated using a coagulant such as
sulfuric acid, MgSO4, CaCl2, or Al2(SO4)3, and then the
coagulated latex may be aged, dehydrated, and dried to obtain
powdered latex.
[67] For example, when the graft copolymer (A) is prepared,
20 an oxidation-reduction catalyst may be further included. For
22
example, the oxidation-reduction catalyst may include one or
more selected from the group consisting of sodium
formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate,
ferrous sulfate, dextrose, sodium pyrrolate, and sodium
sulfite, without being limited 5 thereto. Oxidation-reduction
catalysts commonly used when ABS-based graft copolymers are
prepared may be used in the present invention, without
particular limitation.
[68]
10 [69] Other additives such as electrolytes and the like not
specifically mentioned in the present description may be
appropriately selected when necessary. The additives may be
used within a range commonly applied in the preparation of
vinyl cyanide compound-conjugated diene rubber-aromatic vinyl
15 compound graft copolymer latex, without particular limitation.
[70]
[71] In the method of preparing the graft copolymer, other
reaction conditions, such as reaction time, reaction
temperature, pressure, and time of input of reactants, other
20 than the above-mentioned conditions, may be appropriately
23
selected and used without particular limitation as long as
the other reaction conditions are commonly used in the art to
which the present invention pertains.
[72]
[73] (B) α-methyl styrene-5 vinyl cyanide compound-aromatic
vinyl compound copolymer
[74] Based on a total weight of the thermoplastic resin
composition, the α-methyl styrene-vinyl cyanide compoundaromatic
vinyl compound copolymer (B) (hereinafter referred
10 to as "copolymer (B)") is included in an amount of 10 to 40 %
by weight. In this case, heat resistance and mechanical
properties may be excellent. As a preferred example, based on
100 % by weight in total of the thermoplastic resin
composition, the copolymer (B) may be included in an amount
15 of 10 to 35 % by weight, more preferably 15 to 35 % by weight.
Within this range, heat resistance may be excellent without
deterioration of appearance.
[75]
[76] For example, the copolymer (B) may include 50 to 80 %
20 by weight of α-methyl styrene, 10 to 30 % by weight of a
24
vinyl cyanide compound, and 5 to 25 % by weight of an
aromatic vinyl compound excluding α-methyl styrene,
preferably 50 to 75 % by weight of α-methyl styrene, 15 to
30 % by weight of a vinyl cyanide compound, and 5 to 25 % by
weight of an aromatic vinyl 5 compound excluding α-methyl
styrene, more preferably 55 to 75 % by weight of α-methyl
styrene, 15 to 25 % by weight of a vinyl cyanide compound,
and 5 to 20 % by weight of an aromatic vinyl compound
excluding α-methyl styrene. Within this range, heat
10 resistance may be excellent without deterioration in other
physical properties.
[77] For example, the copolymer (B) may have a weight
average molecular weight of 80,000 to 200,000 g/mol,
preferably 80,000 to 150,000 g/mol. Within this range, a
15 desired effect may be sufficiently obtained.
[78] For example, the copolymer (B) may have a glass
transition temperature (Tg) of 100 to 140 °C, preferably 110
to 130 °C. Within this range, heat resistance may be
excellent without deterioration in other physical properties.
20 [79] In this description, glass transition temperature (Tg)
25
may be measured at a temperature increase rate of 10 °C/min
using a Pyris 6 DSC (Perkin Elmer Co.).
[80]
[81] Preparation methods commonly used in the art to which
the present invention pertains 5 may be used as a method of
preparing the copolymer (B), without particular limitation.
As specific example, the method of preparing the copolymer (B)
may include a step of adding 0.05 to 0.5 parts by weight of a
polyfunctional initiator to 100 parts by weight of a monomer
10 mixture containing 50 to 80 % by weight of α-methyl styrene,
10 to 30 % by weight of a vinyl cyanide compound, and 5 to
25 % by weight of an aromatic vinyl compound excluding α-
methyl styrene and performing polymerization. In this case,
polymerization may be suspension polymerization, emulsion
15 polymerization, solution polymerization, or bulk
polymerization, preferably bulk polymerization. In this case,
heat resistance and fluidity may be excellent.
[82] Commercially available products may be used as the
copolymer (B) as long as the commercially available products
20 follow the definition of the present invention.
26
[83]
[84] (C) Aromatic vinyl compound-vinyl cyanide compound
copolymer
[85] Based on a total weight of the thermoplastic resin
composition, the aromatic 5 vinyl compound-vinyl cyanide
compound copolymer (C) (hereinafter referred to as "copolymer
(C)") is included in an amount of 5 to 30 % by weight. In
this case, mechanical properties, moldability, and appearance
may be excellent. As a preferred example, based on 100 % by
10 weight in total of the thermoplastic resin composition, the
copolymer (C) may be included in an amount of 5 to 25 % by
weight, more preferably 5 to 20 % by weight. Within this
range, chemical resistance, mechanical properties,
moldability, appearance, and physical property balance may be
15 excellent.
[86]
[87] For example, the copolymer (C) may include 20 to 40 %
by weight of a vinyl cyanide compound and 60 to 80 % by
weight of an aromatic vinyl compound excluding α-methyl
20 styrene, preferably 20 to 35 % by weight of a vinyl cyanide
27
compound and 65 to 80 % by weight of an aromatic vinyl
compound, more preferably 23 to 33 % by weight of a vinyl
cyanide compound and 67 to 77 % by weight of an aromatic
vinyl compound. Within this range, due to proper fluidity,
5 moldability may be excellent.
[88] For example, the aromatic vinyl compound included in
the copolymer (C) may include one or more selected from the
group consisting of styrene, ethyl styrene, ο-bromostyrene,
p-bromostyrene, m-bromostyrene, ο-chlorostyrene, p10
chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene,
fluorostyrene, and vinylnaphthalene, preferably styrene.
[89] For example, the vinyl cyanide compound may include
one or more selected from the group consisting of
acrylonitrile, methacrylonitrile, ethylacrylonitrile, and
15 isopropylacrylonitrile, preferably acrylonitrile.
[90]
[91] For example, the copolymer (C) may further include 0
to 30 % by weight, preferably 1 to 20 % by weight, more
preferably 5 to 10 % by weight of one or more selected from
20 the group consisting of an unsaturated carboxylic acid, an
28
anhydride of an unsaturated carboxylic acid, and a maleimidebased
monomer. As such, when a comonomer is included when a
copolymer is polymerized, heat resistance and processability
may be excellent.
[92] For example, the unsaturated 5 carboxylic acid may
include one or more selected from the group consisting of
maleic acid, acrylic acid, and methacrylic acid, the
anhydride of an unsaturated carboxylic acid may be an
anhydride of the unsaturated carboxylic acid, and the
10 maleimide-based monomer may be maleimide N-substituted with
an alkyl group having 1 to 5 carbon atoms or an aryl group
having 6 to 10 carbon atoms, as a specific example, N-phenyl
maleimide, maleimide, or a mixture thereof.
[93]
15 [94] For example, the copolymer (C) may have a weight
average molecular weight of 70,000 to 200,000 g/mol,
preferably 80,000 to 180,000 g/mol, more preferably 90,000 to
160,000 g/mol. Within this range, chemical resistance,
processability, and physical property balance may be
20 excellent.
29
[95]
[96] The aromatic vinyl compound-vinyl cyanide compound
copolymer (C) may be prepared by emulsion polymerization,
suspension polymerization, bulk polymerization, or continuous
bulk polymerization, preferably 5 emulsion polymerization or
suspension polymerization.
[97]
[98] Commercially available products may be used as the
copolymer (C) as long as the commercially available products
10 follow the definition of the present invention.

【Claim 1】
A thermoplastic resin composition, comprising:
10 to 40 % by weight 5 of a vinyl cyanide compoundconjugated
diene rubber-aromatic vinyl compound graft
copolymer (A);
10 to 40 % by weight of an α-methyl styrene-vinyl
cyanide compound-aromatic vinyl compound copolymer (B);
10 5 to 30 % by weight of an aromatic vinyl compound-vinyl
cyanide compound copolymer (C);
10 to 30 % by weight of a recycled vinyl cyanide
compound-conjugated diene rubber-aromatic vinyl compound
copolymer (D); and
15 25 to 50 % by weight of a recycled polycarbonate resin
(E),
wherein a weight ratio of the copolymer (B) to the
copolymer (C) is 1.3:1 to 3.0:1.
20 【Claim 2】
53
The thermoplastic resin composition according to claim
1, wherein, when a specimen having a size of 200 mm × 12.7 mm
× 3.2 mm is fixed to a curved jig having a strain of 1.1 %, 1
cc of thinner is applied thereto, and then time at which
cracks occur on a surface 5 of the specimen is measured, the
thermoplastic resin composition has a chemical resistance of
600 seconds or more.
【Claim 3】
10 The thermoplastic resin composition according to claim
1, wherein a sum of weights of the copolymer (D) and the
resin (E) is 50 % by weight or more based on a total weight
of the thermoplastic resin composition.
15 【Claim 4】
The thermoplastic resin composition according to claim
1, wherein the graft copolymer (A) comprises 50 to 80 % by
weight of conjugated diene rubber, 5 to 20 % by weight of a
vinyl cyanide compound, and 10 to 40 % by weight of an
20 aromatic vinyl compound.
54
【Claim 5】
The thermoplastic resin composition according to claim
4, wherein the conjugated diene rubber has an average
particle 5 diameter of 2,000 to 5,000 Å.
【Claim 6】
The thermoplastic resin composition according to claim
1, wherein the graft copolymer (A) has a weight average
10 molecular weight of 500,000 to 1,000,000 g/mol.
【Claim 7】
The thermoplastic resin composition according to claim
1, wherein the copolymer (B) comprises 50 to 80 % by weight
15 of α-methyl styrene, 10 to 30 % by weight of a vinyl cyanide
compound, and 5 to 25 % by weight of an aromatic vinyl
compound excluding α-methyl styrene.
【Claim 8】
55
The thermoplastic resin composition according to claim
1, wherein the copolymer (C) comprises 20 to 40 % by weight
of a vinyl cyanide compound and 60 to 80 % by weight of an
aromatic vinyl compound.
5
【Claim 9】
The thermoplastic resin composition according to claim
1, wherein the copolymer (D) has a glass transition
temperature of 90 to 150 °C.
10
【Claim 10】
The thermoplastic resin composition according to claim
1, wherein the copolymer (D) has a melt index of 10 g/10 min
or more as measured at 220 °C under a load of 10 kg according
15 to ASTM D1238.
【Claim 11】
The thermoplastic resin composition according to claim
1, wherein the resin (E) comprises one or more selected from
20 the group consisting of a linear polycarbonate resin, a
56
branched polycarbonate resin, and a polyester carbonate
copolymer resin.
【Claim 12】
The thermoplastic resin 5 composition according to claim
1, wherein the resin (E) has a melt index of 10 g/10 min or
more as measured at 300 °C under a load of 1.2 kg according
to ASTM D1238.
10 【Claim 13】
The thermoplastic resin composition according to claim
1, wherein the resin (E) has an Izod impact strength of 60
kg·cm/cm or more as measured under 1/8" thickness conditions
according to ASTM D256.
15
【Claim 14】
The thermoplastic resin composition according to claim
1, wherein the thermoplastic resin composition has a heat
deflection temperature of 100 °C or higher as measured
20 according to ASTM D648-7.
57
【Claim 15】
The thermoplastic resin composition according to claim
1, wherein the thermoplastic resin composition has a melt
index of 8.0 g/10 min or more 5 as measured at 220 °C under a
load of 10 kg according to ASTM D1238.
【Claim 16】
A method of preparing a thermoplastic resin
10 composition, comprising kneading and extruding 10 to 40 % by
weight of a vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound graft copolymer (A), 10 to 40 % by
weight of an α-methyl styrene-vinyl cyanide compound-aromatic
vinyl compound copolymer (B), 5 to 30 % by weight of an
15 aromatic vinyl compound-vinyl cyanide compound copolymer (C),
10 to 30 % by weight of a recycled vinyl cyanide compoundconjugated
diene rubber-aromatic vinyl compound copolymer
(D), and 25 to 50 % by weight of a recycled polycarbonate
resin (E) at 200 to 280 °C,
58
wherein a weight ratio of the copolymer (B) to the
copolymer (C) is 1.3:1 to 3.0:1.
【Claim 17】
A molded article, comprising 5 the thermoplastic resin
composition according to any one of claims 1 to 15.