【Technical Field】
[1] [Cross-Reference to Related Applications]
[2] This application claims priority to Korean Patent
Application No. 10-2020-0143292, filed on October 30, 2020,
10 and Korean Patent Application No. 10-2021-0141840, re-filed
on October 22, 2021, based on the priority of the above
patent, in the Korean Intellectual Property Office, the
disclosures of each of which are incorporated herein by
reference.
15 [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
present invention relates to a thermoplastic resin
composition having excellent clutch force, dimensional
20 stability, and colorability by including a base resin
2
including a vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound graft copolymer, an alkyl acrylate
rubber-vinyl cyanide compound-aromatic vinyl compound graft
copolymer, and an aromatic vinyl compound-vinyl cyanide
compound 5 copolymer and a polysiloxane.
【Background Art】
[4] Acrylonitrile-butadiene-styrene resins (hereinafter
referred to as "ABS resins") based on conjugated diene rubber
10 has excellent processability, mechanical properties, and
appearance characteristics, and thus are used in various
fields such as parts of electric/electronic products,
automobiles, small toys, furniture, and building materials.
[5] Meanwhile, since brick toys are manufactured in
15 various colors and shapes, colorability, appearance, and
physical property balance of a certain level or more are
required, and thus brick toys are mainly manufactured using
ABS resins. In addition, since brick toys are played by
children with relatively weak strength, assembling and
20 disassembling of the bricks should be made easily with only
3
the child's strength. The degree of ease in assembling and
disassembling bricks is expressed as "clutch force". As
clutch force decreases, ease in assembling and disassembling
bricks increases. As a technique for improving these
properties, a technique 5 for adding a high-viscosity
polysiloxane is known. In this case, due to decrease in
dimensional stability, clutch force increases as a shape is
deformed over time, making assembly and disassembly difficult,
which may result in injury to a user when bricks are detached.
10 [6] Therefore, it is required to develop a material that
can be used to manufacture bricks of various colors and
shapes and can maintain low clutch force for a long period of
time.
[7] [Related Art Documents]
15 [8] [Patent Documents]
[9] KR 10-0717926 B1
【Disclosure】
【Technical Problem】
20 [10] Therefore, the present invention has been made in
4
view of the above problems, and it is one object of the
present invention to provide a thermoplastic resin
composition exhibiting high colorability and low clutch force
and having excellent clutch force retention due to excellent
dimensional 5 stability against thermal aging.
[11] 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.
10 [12] The above and other objects can be accomplished by
the present invention described below.
【Technical Solution】
[13] In accordance with one aspect of the present
15 invention, provided is a thermoplastic resin composition
including 100 parts by weight of a base resin including a
vinyl cyanide compound-conjugated diene rubber-aromatic vinyl
compound graft copolymer (A), an alkyl acrylate rubber-vinyl
cyanide compound-aromatic vinyl compound graft copolymer (B),
20 and an aromatic vinyl compound-vinyl cyanide compound
5
copolymer (C); and 0.1 to 0.4 parts by weight of a
polysiloxane (D), wherein the graft copolymer (B) has a
grafting degree of 42 % or more and is included in an amount
of 0.1 to 10 % by weight based on 100 % by weight in total of
5 the base resin.
[14]
[15] In addition, the present invention provides a
thermoplastic resin composition including 100 parts by weight
of a base resin including 10 to 50 % by weight of a vinyl
10 cyanide compound-conjugated diene rubber-aromatic vinyl
compound graft copolymer (A), 0.1 to 10 % by weight of an
alkyl acrylate rubber-vinyl cyanide compound-aromatic vinyl
compound graft copolymer (B) having a grafting degree of 42 %
or more, and 40 to 80 % by weight of an aromatic vinyl
15 compound-vinyl cyanide compound copolymer (C) and 0.1 to 0.4
parts by weight of a polysiloxane (D), wherein the
thermoplastic resin composition has a clutch force of 22 N or
less, wherein, when brick specimens including the
thermoplastic resin composition are manufactured and then two
20 of the brick specimens are coupled to each other in an
6
interlocking manner, the clutch force is measured as a
maximum tension required to separate the two brick specimens
coupled to each other by pulling the brick specimens in a
vertical direction at a speed of 10 mm/min using a universal
testing machine 5 (Z010, Zwick Roell Co.).
[16]
[17] Preferably, the thermoplastic resin composition may
have a clutch force of 22 N or less, wherein, when brick
specimens including the thermoplastic resin composition are
10 manufactured and then two of the brick specimens are coupled
to each other in an interlocking manner, the clutch force is
measured as a maximum tension required to separate the two
brick specimens coupled to each other by pulling the brick
specimens in a vertical direction at a speed of 10 mm/min
15 using a universal testing machine (Z010, Zwick Roell Co.).
[18] Preferably, the thermoplastic resin composition may
have a clutch force increase rate of 15 % or less, before and
after performing thermal aging of brick specimens
manufactured by including the thermoplastic resin composition
20 at a temperature of 57 °C for 24 hours, wherein, when the
7
clutch force is measured as a maximum tension required to
separate the two brick specimens coupled to each other by
pulling the brick specimens in a vertical direction at a
speed of 10 mm/min using a universal testing machine (Z010,
5 Zwick Roell Co.).
[19] Preferably, the base resin may include 10 to 50 % by
weight of a vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound graft copolymer (A), 0.1 to 10 % by
weight of an alkyl acrylate rubber-vinyl cyanide compound10
aromatic vinyl compound graft copolymer (B), and 40 to 80 %
by weight of an aromatic vinyl compound-vinyl cyanide
compound copolymer (C).
[20] Preferably, the graft copolymer (A) may include 50 to
80 % by weight of conjugated diene rubber, 5 to 20 % by
15 weight of a vinyl cyanide compound, and 10 to 40 % by weight
of an aromatic vinyl compound.
[21] Preferably, in the copolymer (B), a vinyl cyanide
compound-aromatic vinyl compound copolymer grafted onto alkyl
acrylate rubber may have a weight average molecular weight of
20 166,000 to 250,000 g/mol.
8
[22] Preferably, the graft copolymer (B) may include 30 to
60 % by weight of alkyl (meth)acrylate rubber, 10 to 30 % by
weight of a vinyl cyanide compound, and 15 to 45 % by weight
of an aromatic vinyl compound.
[23] Preferably, the copolymer 5 (C) may include 20 to 40 %
by weight of a vinyl cyanide compound and 60 to 80 % by
weight of an aromatic vinyl compound.
[24] Preferably, the base resin may further include 1 to
12 % by weight of an alkyl methacrylate compound-vinyl
10 cyanide compound-aromatic vinyl compound copolymer (E), and
the copolymer (E) may preferably include 40 to 70 % by weight
of an alkyl methacrylate compound, 20 to 50 % by weight of an
aromatic vinyl compound, and 1 to 20 % by weight of a vinyl
cyanide compound.
15 [25] Preferably, the polysiloxane (D) may have a kinematic
viscosity of 700,000 to 3,000,000 cSt as measured according
to ASTM D-445.
[26] Preferably, the polysiloxane (D) may include one or
more selected from the group consisting of
20 polydimethylsiloxane, polydiphenylsiloxane,
9
polymethylphenylsiloxane, and polymethylhydrogensiloxane.
[27]
[28] In accordance with another aspect of the present
invention, provided is a method of preparing a thermoplastic
resin composition, the 5 method including kneading and
extruding 100 parts by weight of a base resin including a
vinyl cyanide compound-conjugated diene rubber-aromatic vinyl
compound graft copolymer (A), an alkyl acrylate rubber-vinyl
cyanide compound-aromatic vinyl compound graft copolymer (B),
10 and an aromatic vinyl compound-vinyl cyanide compound
copolymer (C) and 0.1 to 0.4 parts by weight of a
polysiloxane (D) at 200 to 280 °C, wherein the graft
copolymer (B) has a grafting degree of 42 % or more and is
included in an amount of 0.1 to 10 % by weight based on 100 %
15 by weight in total of the base resin.
[29]
[30] In accordance with yet another aspect of the present
invention, provided is a molded article including the
thermoplastic resin composition.
20
10
【Advantageous effects】
[31] According to the present invention, by adding a
polysiloxane, in a predetermined content ratio, to a base
resin including a vinyl cyanide compound-conjugated diene
rubber-aromatic vinyl compound 5 graft copolymer (ABS-based
resin), an alkyl acrylate rubber-vinyl cyanide compoundaromatic
vinyl compound graft copolymer (ASA-based resin),
and an aromatic vinyl compound-vinyl cyanide compound
copolymer (SAN-based resin) and adjusting the grafting degree
10 and content of the ASA-based resin within a predetermined
range, the present invention advantageously provides a
thermoplastic resin composition having excellent colorability,
exhibiting low clutch force, and having excellent clutch
force retention at high temperatures due to excellent
15 dimensional stability against thermal aging even including a
high-viscosity polysiloxane; a method of preparing the
thermoplastic resin composition; and a molded article
manufactured using the thermoplastic resin composition.
20 【Description of Drawings】
11
[32] FIGS. 1A to 1C are drawings showing the structure of
a brick specimen of the present invention.
[33] FIGS. 2A to 2D are images for explaining a method of
measuring clutch force according to the present invention.
5
【Best mode】
[34] Hereinafter, a thermoplastic resin composition, a
method of preparing the same, and a molded article including
the same will be described in detail.
10 [35] The present inventors confirmed that, when a
polysiloxane was added in a predetermined content ratio to a
base resin including an ABS-based resin, an ASA-based resin,
and a SAN-based resin, and the grafting degree and content of
the ASA-based resin were adjusted within a predetermined
15 range, in addition to excellent colorability and initial
clutch force characteristics, clutch force retention rate was
greatly improved due to excellent dimensional stability
against thermal aging. Based on these results, the present
inventors conducted further studies to complete the present
20 invention.
12
[36]
[37] The thermoplastic resin composition of the present
invention includes 100 parts by weight of a base resin
including a vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound 5 graft copolymer (A), an alkyl
acrylate rubber-vinyl cyanide compound-aromatic vinyl
compound graft copolymer (B), and an aromatic vinyl compoundvinyl
cyanide compound copolymer (C) and 0.1 to 0.4 parts by
weight of a polysiloxane (D), wherein the graft copolymer (B)
10 has a grafting degree of 42 % or more and is included in an
amount of 0.1 to 10 % by weight based on 100 % by weight in
total of the base resin. In this case, colorability may be
excellent, initial clutch force may be low, and clutch force
retention against thermal aging may be excellent.
15 [38]
[39] In addition, the thermoplastic resin composition of
the present invention includes 100 parts by weight of a base
resin including 10 to 50 % by weight of a vinyl cyanide
compound-conjugated diene rubber-aromatic vinyl compound
20 graft copolymer (A), 0.1 to 10 % by weight of an alkyl
13
acrylate rubber-vinyl cyanide compound-aromatic vinyl
compound graft copolymer (B) having a grafting degree of 42 %
or more, and 40 to 80 % by weight of an aromatic vinyl
compound-vinyl cyanide compound copolymer (C) and 0.1 to 0.4
parts by weight of a 5 polysiloxane (D), wherein the
thermoplastic resin composition has a clutch force of 22 N or
less, wherein the clutch force is measured as a maximum
tension required to separate two brick specimens coupled to
each other by pulling the brick specimens in a vertical
10 direction at a speed of 10 mm/min using a universal testing
machine (Z010, Zwick Roell Co.). In this case, colorability
may be excellent, clutch force may be low, and clutch force
retention against thermal aging may be excellent.
[40]
15 [41] In this description, the composition ratio of a
(co)polymer may mean the content of units constituting the
(co)polymer, or may mean the content of units input during
polymerization of the (co)polymer.
[42]
20 [43] Hereinafter, each component constituting the
14
thermoplastic resin composition of the present invention will
be described in detail.
[44]
[45] (A) Vinyl cyanide compound-conjugated diene rubberaromatic
5 vinyl compound graft copolymer
[46] The vinyl cyanide compound-conjugated diene rubberaromatic
vinyl compound graft copolymer (A) (hereinafter
referred to as "graft copolymer (A)") is preferably included
in an amount of 10 to 50 % by weight, more preferably 15 to
10 47 % by weight, still more preferably 20 to 45 % by weight
based on 100 % by weight in total of the base resin. In this
case, mechanical properties, moldability, and appearance may
be excellent.
[47]
15 [48] For example, the graft copolymer (A) may include 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 aromatic vinyl compound. In this case, mechanical
properties, moldability, appearance, and physical property
20 balance may be excellent.
15
[49] As a preferred example, the graft copolymer (A)
includes 50 to 70 % by weight of conjugated diene rubber, 5
to 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 5 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
resistance and physical property balance may be excellent.
[50]
10 [51] In this description, a polymer including a certain
compound means a polymer prepared by polymerizing the
compound, and a unit in the polymer is derived from the
compound.
[52]
15 [53] For example, the conjugated diene rubber included in
the graft copolymer (A) may have an average particle diameter
of 2,500 to 3,500 Å, preferably 2,600 to 3,400 Å, more
preferably 2,700 to 3,300 Å. Within this range, impact
strength may be excellent without degradation of other
20 properties.
16
[54] In this description, the 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 size analyzer (manufacturer:
PSS) in a Gaussian mode. As 5 a specific measurement example, a
sample is prepared by diluting 0.1 g of latex (TSC: 35 to 50
wt%) 1,000 to 5,000-fold with deionized water or distilled
water, i.e., a sample is diluted appropriately so as not to
deviate significantly from an intensity setpoint of 300 kHz,
10 and is placed in a glass tube. Then, the average particle
diameter of the sample is measured using a flow cell in autodilution
in a measurement mode of dynamic light
scattering/intensity 300 kHz/intensity-weight Gaussian
analysis. At this time, setting values are as follows:
15 temperature: 23 °C; measurement wavelength: 632.8 nm; and
channel width: 10 μsec.
[55]
[56] For example, the graft copolymer (A) may have a
grafting degree of 20 to 50 %, preferably 25 to 45 %, more
20 preferably 30 to 45 %. Within this range, compatibility and
17
moldability may be properly secured, and balance between
other mechanical properties, compatibility, and moldability
may be excellent.
[57] In this description, when measuring grafting degree,
30 g of acetone is added to 0.5 g 5 of dry powder of a graft
polymer, agitation is performed at 210 rpm and room
temperature for 12 hours using a shaker (SKC-6075, Lab
Companion Co.), centrifugation is performed at 18,000 rpm and
0 °C for 3 hours using a centrifuge (Supra R30, Hanil Science
10 Co.) to separate only insoluble matter that is not dissolved
in acetone, and the separated insoluble matter is dried via
forced circulation at 85 °C for 12 hours using a forced
convection oven (OF-12GW, Lab Companion Co.). Then, the
weight of the dried insoluble matter is measured, and
15 grafting degree is calculated by Equation 1 below.
[58] [Equation 1]
[59] Grafting degree (%) = [Weight (g) of grafted monomers
/ Weight (g) of rubber] × 100
[60] In Equation 1, the weight of grafted monomers is a
20 value obtained by subtracting the weight (g) of rubber from
18
the weight of insoluble matter (gel) obtained by dissolving a
graft copolymer in acetone and performing centrifugation, and
the weight (g) of rubber is the weight of rubber components
theoretically included in the graft copolymer powder.
5 [61]
[62] For example, in the graft copolymer (A), the vinyl
cyanide compound-aromatic vinyl compound copolymer grafted
onto the conjugated diene rubber may have a weight average
molecular weight of 50,000 to 110,000 g/mol, preferably
10 60,000 to 100,000 g/mol. Within this range, due to proper
fluidity, processability and impact resistance may be
excellent.
[63] In this description, unless otherwise defined, the
weight average molecular weight may be measured using gel
15 permeation chromatography (GPC, Waters Breeze). As a specific
example, the weight average molecular weight may be measured
using tetrahydrofuran (THF) as an eluate through gel
permeation chromatography (GPC, Waters Breeze). In this case,
weight average molecular weight is obtained as a relative
20 value to a polystyrene (PS) standard sample. As a specific
19
measurement example, the weight average molecular weight may
be measured under conditions of solvent: THF, column
temperature: 40 °C, flow rate: 0.3 ml/min, sample
concentration: 20 mg/ml, injection amount: 5 μl, column model:
1× PLgel 10 μm MiniMix-B (250 5 × 4.6 mm) + 1× PLgel 10 μm
MiniMix-B (250 × 4.6 mm) + 1× PLgel 10 μm MiniMix-B Guard (50
× 4.6 mm), equipment name: Agilent 1200 series system,
refractive index detector: Agilent G1362 RID, RI temperature:
35 °C, data processing: Agilent ChemStation S/W, and test
10 method (Mn, Mw and PDI): OECD TG 118.
[64]
[65] For example, the graft copolymer (A) may be prepared
by a known polymerization method including emulsion
polymerization, suspension polymerization, bulk
15 polymerization, and the like, preferably emulsion
polymerization.
[66] For example, based on 100 parts by weight in total of
the conjugated diene rubber, the aromatic vinyl compound, and
the vinyl cyanide compound included in the graft copolymer
20 (A), the graft copolymer (A) may be prepared by adding,
20
continuously or batchwise, a monomer mixture including 5 to
20 parts by weight of the vinyl cyanide compound and 10 to 40
parts by weight of the aromatic vinyl compound to a mixed
solution containing 50 to 80 parts by weight (based on solids)
of the conjugated diene rubber 5 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 performing polymerization.
[67] As another example, based on 100 parts by weight in
10 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 containing 5 to 20 parts by weight of
the vinyl cyanide compound, 10 to 40 parts by weight of the
15 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
parts by weight of a molecular weight modifier, which are
mixed in a separate mixing apparatus, to 50 to 80 parts by
20 weight (based on solids) of the conjugated diene rubber latex
21
and 60 to 150 parts by weight of deionized water, adding 0.01
to 0.5 parts by weight of an initiator thereto, increasing
temperature to 75 to 80 °C for 30 to 90 minutes to perform
graft polymerization, and terminating graft polymerization at
a polymerization conversion rate 5 of 93 to 99 % by weight. In
this case, impact resistance, mechanical strength, and
moldability may be excellent.
[68] In this description, the polymerization conversion
rate may be defined as the amount (wt%) of monomers converted
10 into a polymer until measurement time based on 100 % of the
total weight of the monomers input until polymerization is
completed. A method of measuring the polymerization
conversion rate is not particularly limited as long as the
method follows this definition. As a specific example, 1.5 g
15 of a prepared (co)polymer latex is dried for 15 minutes in a
hot air dryer set to 150 °C, and the weight of the
(co)polymer latex is measured. Total solids content (TSC) is
calculated by substituting the measured values into Equation
2, and then a polymerization conversion rate is calculated by
20 substituting the total solids content value into Equation 3.
22
In Equation 3, the total weight of added monomers is based on
100 parts by weight.
[69] [Equation 2]
[70]
5 [71] [Equation 3]
[72] Polymerization conversion rate (%)= [Total solids
content (TSC) × (Total weight in sum of added monomer,
deionized water, and subsidiary raw materials) / 100] -
(Weight of added subsidiary raw materials excluding monomers
10 and deionized water)
[73] In Equation 3, the subsidiary raw materials include
an initiator, an emulsifier, and a molecular weight modifier,
and include an electrolyte when the electrolyte is used.
[74]
15 [75] The conjugated diene rubber may include a conjugated
diene compound.
[76] 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-
20 butadiene, 1,3-pentadiene, isoprene, chloroprene, and
Total solids content (TSC; %) =
Weight after drying
Weight before drying
× 100
23
pyrerylene, preferably 1,3-butadiene.
[77] For example, the vinyl cyanide compound may include
one or more selected from the group consisting of
acrylonitrile, methacrylonitrile, ethylacrylonitrile, and
isopropylacrylonitrile, 5 preferably acrylonitrile.
[78] For example, the aromatic vinyl compound may include
one or more selected from the group consisting of styrene, α-
methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl
styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-
10 bromo styrene, p-bromo styrene, m-bromo styrene, ο-chloro
styrene, p-chloro styrene, m-chloro styrene, vinyltoluene,
vinyl xylene, fluorostyrene, and vinyl naphthalene,
preferably one or more selected from the group consisting of
styrene and α-methyl styrene, more preferably styrene. In
15 this case, due to proper fluidity, processability and
mechanical properties such as impact resistance may be
excellent.
[79] In this description, a derivative is a compound
produced by substituting a hydrogen atom or an atomic group
20 of an original compound with another atom or atomic group,
24
for example, refers to a compound produced by substitution
with a halogen or an alkyl group.
[80]
[81] For example, the emulsifier may include one or more
selected from the group consisting 5 of allyl aryl sulfonates,
alkali methyl alkyl sulfonates, sulfonated alkyl esters,
fatty acid soap, and rosin acid alkali salts. In this case,
polymerization stability may be excellent.
[82] For example, the molecular weight modifier may
10 include one or more selected from the group consisting of tdodecyl
mercaptan, n-dodecyl mercaptan, n-octyl mercaptan,
and carbon tetrachloride, preferably t-dodecyl mercaptan.
[83] For example, the initiator may be a water-soluble
persulfuric acid polymerization initiator, a fat-soluble
15 polymerization initiator, or an oxidation-reduction catalyst
system. For example, the water-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
20 polymerization initiator may include one or more selected
25
from the group consisting of cumene hydroperoxide,
diisopropyl benzene hydroperoxide, azobis iso butyronitrile,
t-butyl hydroperoxide, paramethane hydroperoxide, and
benzoylperoxide.
[84] For example, 5 latex prepared by emulsion
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.
10 [85] For example, when the graft copolymer (A) is prepared,
an oxidation-reduction catalyst system is further included.
For example, the oxidation-reduction catalyst system may
include one or more selected from the group consisting of
sodium formaldehyde sulfoxylate, sodium ethylenediamine
15 tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate,
and sodium sulfite. However, the present invention is not
limited thereto, and oxidation-reduction catalyst systems
commonly used when preparing an ABS-based graft copolymer may
be used without particular limitation.
20 [86]
26
[87] In this description, other additives such as
electrolytes, which are not specifically mentioned, may be
appropriately selected when necessary. The other additives
are not particularly limited, and may be selected within a
range generally applied 5 to prepare vinyl cyanide compoundconjugated
diene rubber-aromatic vinyl compound graft
copolymer latex.
[88]
[89] In the method of preparing the graft copolymer, other
10 reaction conditions, such as reaction time, reaction
temperature, pressure, and time of input of reactants, other
than the above-mentioned conditions, may be appropriately
selected and used without particular limitation as long as
the other reaction conditions are commonly used in the art to
15 which the present invention pertains.
[90]
[91] As the graft copolymer (A), commercially available
products may be used as long as the products follow the
definition of the present invention.
20 [92]
27
[93] (B) Alkyl acrylate rubber-vinyl cyanide compoundaromatic
vinyl compound graft copolymer
[94] For example, based on 100 % by weight in total of the
base resin, the alkyl acrylate rubber-vinyl cyanide compoundaromatic
vinyl compound graft 5 copolymer (B) (hereinafter
referred to as "graft copolymer (B)") is included in an
amount of 0.1 to 10 % by weight. Within this range, clutch
force retention against thermal aging of a composition and
colorability may be excellent.
10 [95] As a preferred example, based on 100 % by weight in
total of the base resin, the copolymer (B) may be included in
an amount of 1 to 9 % by weight, more preferably 2 to 8 % by
weight. Within this range, a desired effect may be achieved.
[96]
15 [97] The graft copolymer (B) may have a grafting degree of
42 % or more, preferably 42 to 60 %, more preferably 45 to
55 %. Within this range, clutch force retention against
thermal aging and colorability may be excellent without
degradation of other properties.
20 [98] The grafting degree of the graft copolymer (B) may be
28
measured by the method described for the graft copolymer (A).
[99]
[100] For example, the graft copolymer (B) may include 30
to 60 % by weight of alkyl acrylate rubber, 10 to 30 % by
weight of a vinyl cyanide compound, 5 and 15 to 45 % by weight
of an aromatic vinyl compound, preferably 35 to 60 % by
weight of alkyl acrylate rubber, 10 to 25 % by weight of a
vinyl cyanide compound, and 20 to 40 % by weight of an
aromatic vinyl compound, more preferably 40 to 60 % by weight
10 of alkyl acrylate rubber, 10 to 20 % by weight of a vinyl
cyanide compound, and 25 to 40 % by weight of an aromatic
vinyl compound. Within this range, clutch force retention
against thermal aging and colorability may be excellent
without degradation of other properties.
15 [101]
[102] For example, in the graft copolymer (B), the vinyl
cyanide compound-aromatic vinyl compound copolymer grafted
onto the alkyl acrylate rubber may have a weight average
molecular weight of 166,000 to 250,000 g/mol, preferably
20 170,000 to 230,000 g/mol, more preferably 170,000 to 200,000
29
g/mol. Within this range, clutch force retention against
thermal aging and colorability may be excellent without
degradation of other properties.
[103] In this description, to measure weight average
molecular weight, the copolymer 5 grafted on the rubber may be
separated from the rubber by a separation method commonly
used in the art to which the present invention pertains. For
example, a sol separated by the method of measuring a
grafting degree is dissolved in a THF solvent to prepare a
10 solution, and the solution is filtered using a filter to
obtain a filtrate. The filtrate may be used as a specimen for
measuring weight average molecular weight.
[104]
[105] For example, the alkyl acrylate rubber may have an
15 average particle diameter of 2,000 to 4,000 Å, preferably
2,200 to 3,800 Å, more preferably 2,500 to 3,500 Å. Within
this range, a desired effect may be achieved without reducing
impact resistance.
[106] The average particle diameter of the alkyl acrylate
20 rubber may be measured in the same manner as the conjugated
30
diene rubber.
[107]
[108] For example, the alkyl acrylate may include one or
more selected from the group consisting of alkyl acrylates
having an alkyl group having 2 5 to 8 carbon atoms preferably
one or more selected from the group consisting of alkyl
acrylates having an alkyl group having 4 to 8 carbon atoms,
more preferably butyl acrylate or ethylhexyl acrylate.
[109] For example, the aromatic vinyl compound may include
10 one or more selected from the group consisting of styrene, α-
methylstyrene, m-methylstyrene, p-methylstyrene, and p-tertbutylstyrene,
preferably styrene.
[110] For example, the vinyl cyanide compound may include
one or more selected from the group consisting of
15 acrylonitrile, methacrylonitrile, ethylacrylonitrile, and
isopropylacrylonitrile, preferably acrylonitrile.
[111]
[112] For example, the graft copolymer (B) may be prepared
by emulsion polymerization. In this case, chemical resistance,
20 weather resistance, fluidity, and mechanical strength may be
31
excellent.
[113] Emulsion polymerization methods commonly practiced in
the art to which the present invention pertains may be used
in the present invention without particular limitation. As a
preferred example, emulsion 5 graft polymerization may be used.
[114]
[115] As the graft copolymer (B), commercially available
products may be used as long as the products follows the
definition of the present invention.

【CLAIMS】
【Claim 1】
A thermoplastic resin composition, comprising:
100 parts by weight of 5 a base resin comprising a vinyl
cyanide compound-conjugated diene rubber-aromatic vinyl
compound graft copolymer (A), an alkyl acrylate rubber-vinyl
cyanide compound-aromatic vinyl compound graft copolymer (B),
and an aromatic vinyl compound-vinyl cyanide compound
10 copolymer (C); and 0.1 to 0.4 parts by weight of a
polysiloxane (D),
wherein the graft copolymer (B) has a grafting degree
of 42 % or more and is comprised in an amount of 0.1 to 10 %
by weight based on 100 % by weight in total of the base
15 resin.
【Claim 2】
The thermoplastic resin composition according to claim
1, wherein the thermoplastic resin composition has a clutch
20 force of 22 N or less, wherein the clutch force is measured
63
as a maximum tension required to separate two brick specimens
coupled to each other by pulling the brick specimens in a
vertical direction at a speed of 10 mm/min using a universal
testing machine (Z010, Zwick Roell Co.).
5
【Claim 3】
The thermoplastic resin composition according to claim
1, wherein the thermoplastic resin composition has a clutch
force increase rate of 15 % or less before and after
10 performing thermal aging of brick specimens at a temperature
of 57 °C for 24 hours, wherein the clutch force is measured
as a maximum tension required to separate two brick specimens
coupled to each other by pulling the brick specimens in a
vertical direction at a speed of 10 mm/min using a universal
15 testing machine (Z010, Zwick Roell Co.).
【Claim 4】
The thermoplastic resin composition according to claim
1, wherein the base resin comprises 10 to 50 % by weight of
20 the vinyl cyanide compound-conjugated diene rubber-aromatic
64
vinyl compound graft copolymer (A), 0.1 to 10 % by weight of
the alkyl acrylate rubber-vinyl cyanide compound-aromatic
vinyl compound graft copolymer (B), and 40 to 80 % by weight
of the aromatic vinyl compound-vinyl cyanide compound
5 copolymer (C).
【Claim 5】
The thermoplastic resin composition according to claim
1, wherein the graft copolymer (A) comprises 50 to 80 % by
10 weight of conjugated diene rubber, 5 to 20 % by weight of a
vinyl cyanide compound, and 10 to 40 % by weight of an
aromatic vinyl compound.
【Claim 6】
15 The thermoplastic resin composition according to claim
1, wherein, in the copolymer (B), a vinyl cyanide compoundaromatic
vinyl compound copolymer grafted onto alkyl acrylate
rubber has a weight average molecular weight of 166,000 to
250,000 g/mol.
20
65
【Claim 7】
The thermoplastic resin composition according to claim
1, wherein the graft copolymer (B) comprises 30 to 60 % by
weight of alkyl acrylate rubber, 10 to 30 % by weight of a
vinyl cyanide compound, 5 and 15 to 45 % by weight of an
aromatic vinyl compound.
【Claim 8】
The thermoplastic resin composition according to claim
10 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.
【Claim 9】
15 The thermoplastic resin composition according to claim
4, wherein the base resin further comprises 1 to 12 % by
weight of an alkyl methacrylate compound-vinyl cyanide
compound-aromatic vinyl compound copolymer (E).
20 【Claim 10】
66
The thermoplastic resin composition according to claim
9, wherein the copolymer (E) comprises 40 to 70 % by weight
of an alkyl methacrylate compound, 1 to 20 % by weight of a
vinyl cyanide compound, and 20 to 50 % by weight of an
5 aromatic vinyl compound.
【Claim 11】
The thermoplastic resin composition according to claim
1, wherein the polysiloxane (D) has a kinematic viscosity of
10 700,000 to 3,000,000 cSt as measured according to ASTM D-445.
【Claim 12】
The thermoplastic resin composition according to claim
1, wherein the polysiloxane (D) comprises one or more
15 selected from the group consisting of polydimethylsiloxane,
polydiphenylsiloxane, polymethylphenylsiloxane, and
polymethylhydrogensiloxane.
【Claim 13】
67
A method of preparing a thermoplastic resin
composition, comprising a step of kneading and extruding 100
parts by weight of a base resin comprising a vinyl cyanide
compound-conjugated diene rubber-aromatic vinyl compound
graft copolymer (A), an alkyl 5 acrylate rubber-vinyl cyanide
compound-aromatic vinyl compound graft copolymer (B), and an
aromatic vinyl compound-vinyl cyanide compound copolymer (C)
and 0.1 to 0.4 parts by weight of a polysiloxane (D) at 200
to 280 °C, wherein the graft copolymer (B) has a grafting
10 degree of 42 % or more and is comprised in an amount of 0.1
to 10 % by weight based on 100 % by weight in total of the
base resin.
【Claim 14】
15 A molded article, comprising the thermoplastic resin
composition according to any one of claims 1 to 12.