[1] [Cross-Reference to Related Applications]
[2] This application claims priority to Korean Patent
10 Application No. 10-2019-0123821, filed on October 7, 2019,
and Korean Patent Application No. 10-2020-0124402, re-filed
on September 5, 2020, based on the priority of the above
patent, in the Korean Intellectual Property Office, the
disclosures of each of which are incorporated herein by
15 reference.
[3] The present invention relates to an ASA-based resin
composition, a molded article including the ASA-based resin
composition, and a method of manufacturing the molded
article. More particularly, the present invention relates
20 to an ASA-based resin composition having excellent
2
colorability and transparency even at a processing thickness
of a predetermined value or more while having excellent
mechanical properties and processability, a molded article
including the ASA-based resin composition, and a method of
manufacturing the molded 5 article. In particular, due to
excellent colorability and transparency thereof, the ASAbased
resin composition may be applied to high value-added
products having non-painting, transparent, high saturation,
or special color properties.
10
【Background Art】
[4] In the case of acrylate compound-styreneacrylonitrile
copolymers (hereinafter referred to as "ASA
resins"), no unstable double bonds are included in a polymer.
15 Due to this feature, ASA resins have excellent weather
resistance, and thus have been used in various fields such
as electrical/electronic parts, construction materials (e.g.,
vinyl siding), extrusion profiles, and automobile parts.
[5] Recently, there is increasing demand for high value20
added outdoor products having non-painting, transparent,
3
high saturation, or special color properties. However, ASA
resins have poor colorability and transparency, and thus use
of ASA resins in manufacture of such products is limited.
Therefore, an ASA resin that meets such market demands needs
5 to be developed.
[6] [Related Art Documents]
[7] [Patent Documents]
[8] (Patent Document 1) KR 2009-0095764 A
10 【Disclosure】
【Technical Problem】
[9] Therefore, the present invention has been made in
view of the above problems, and it is one object of the
present invention to provide an ASA-based resin composition
15 having excellent colorability and transparency even at a
processing thickness of a predetermined value or more while
having excellent mechanical properties and processability, a
molded article including the ASA-based resin composition,
and a method of manufacturing the molded article. In
20 particular, due to excellent colorability and transparency
4
thereof, the ASA-based resin composition may be applied to
high value-added products having non-painting, transparent,
high saturation, or special color properties.
[10] The above and other objects can be accomplished by
the present 5 disclosure described below.
【Technical Solution】
[11] In accordance with one aspect of the present
invention, provided are an ASA-based resin composition
10 including 20 to 47 % by weight of an acrylate-aromatic vinyl
compound-vinyl cyanide compound graft copolymer containing
acrylate rubber having an average particle diameter of 50 to
150 nm as a core; 23 to 55 % by weight of an alkyl
methacrylate-aromatic vinyl compound-vinyl cyanide compound
15 copolymer; and 25 to 45 % by weight of a poly(alkyl
methacrylate) resin, and a molded article including the ASAbased
resin composition.
[12] In accordance with another aspect of the present
invention, provided is a method of manufacturing a molded
20 article, the method including kneading and extruding 20 to
5
47 % by weight of an acrylate-aromatic vinyl compound-vinyl
cyanide compound graft copolymer containing acrylate rubber
having an average particle diameter of 50 to 150 nm as a
core, 23 to 55 % by weight of an alkyl methacrylate-aromatic
vinyl compound-vinyl cyanide 5 compound copolymer, and 25 to
45 % by weight of a poly(alkyl methacrylate) resin under
conditions of 200 to 300 °C and 100 to 500 rpm to prepare a
pellet; and performing sheet molding or injection molding of
the prepared pellet at a molding temperature of 200 to
10 300 °C to manufacture a molded article.
【Advantageous effects】
[13] According to the present invention, an ASA-based
resin composition having excellent colorability and
15 transparency even at a processing thickness of a
predetermined value or more while having excellent
mechanical properties and processability, a molded article
including the ASA resin composition, and a method of
manufacturing the molded article can be provided. In
20 particular, due to excellent colorability and transparency
6
thereof, the ASA-based resin composition can be applied to
high value-added products having non-painting, transparent,
high saturation, or special color properties.
5 【Best mode】
[14] Hereinafter, an ASA-based resin composition, a
molded article including the ASA-based resin composition,
and a method of manufacturing the molded article will be
described in detail.
10 [15] The present inventors confirmed that an ASA-based
resin composition including an acrylate-aromatic vinyl
compound-vinyl cyanide compound graft copolymer, an alkyl
methacrylate-aromatic vinyl compound-vinyl cyanide compound
copolymer, and a poly(alkyl methacrylate) resin in a
15 predetermined content range had excellent colorability and
transparency at a processing thickness of 0.5 T or more
while maintaining mechanical properties and processability
equal or superior to those of conventional ASA resin
compositions. Based on these results, the present inventors
20 conducted further studies to complete the present invention.
7
[16] The ASA-based resin composition of the present
invention includes 20 to 47 % by weight of an acrylatearomatic
vinyl compound-vinyl cyanide compound graft
copolymer containing acrylate rubber having an average
particle diameter of 50 to 150 5 nm as a core, 23 to 55 % by
weight of an alkyl methacrylate-aromatic vinyl compoundvinyl
cyanide compound copolymer, and 25 to 45 % by weight
of a poly(alkyl methacrylate) resin. Within this range, the
ASA resin composition may have excellent mechanical
10 properties and processability and in particular, may have
excellent colorability and transparency even at a processing
thickness of a predetermined value or more. Thus, the ASA
resin composition may be applied to high value-added
products having non-painting, transparent, high saturation,
15 or special color properties.
[17] Hereinafter, each component constituting the
thermoplastic resin composition of the present invention
will be described in detail as follows.
[18] A) Acrylate-aromatic vinyl compound-vinyl cyanide
20 compound graft copolymer
8
[19] For example, the acrylate rubber contained in the
graft copolymer (A) of the present invention may have an
average particle diameter of 50 to 150 nm, preferably 60 to
140 nm, more preferably 70 to 140 nm, still more preferably
80 to 140 nm. Within this 5 range, a prepared thermoplastic
resin composition may have excellent weather resistance,
colorability, impact strength, and surface gloss.
[20] In the present description, average particle
diameter may be measured by dynamic light scattering, and
10 specifically, may be measured as an intensity value using a
Nicomp 380 particle size analyzer (manufacturer: PSS) in a
Gaussian mode.
[21] For example, the graft copolymer (A) may be included
in an amount of 20 to 47 % by weight, preferably 20 to 40 %
15 by weight, more preferably 20 to 35 % by weight, still more
preferably 20 to 30 % by weight. Within this range, balance
between mechanical strength and fluidity may be excellent,
and in particular, transparency, colorability, and weather
resistance may be excellent.
20 [22] For example, the graft copolymer (A) may include 40
9
to 60 % by weight of acrylate rubber, 25 to 45 % by weight
of an aromatic vinyl compound, and 10 to 20 % by weight of a
vinyl cyanide compound. Within this range, weather
resistance, fluidity, tensile strength, and impact strength
5 may be excellent.
[23] As a preferred example, the graft copolymer (A) may
include 45 to 55 % by weight of acrylate rubber, 30 to 50 %
by weight of an aromatic vinyl compound, and 5 to 20 % by
weight of a vinyl cyanide compound. Within this range,
10 weather resistance, fluidity, tensile strength, and impact
strength may be excellent.
[24] As a more preferred example, the graft copolymer (A)
may include 45 to 55 % by weight of acrylate rubber, 30 to
40 % by weight of an aromatic vinyl compound, and 10 to 20 %
15 by weight of a vinyl cyanide compound. Within this range,
weather resistance, fluidity, tensile strength, and impact
strength may be excellent.
[25] In the present description, a polymer including a
compound refers to a polymer prepared by polymerizing the
20 compound, and a unit in the polymerized polymer is derived
10
from the compound.
[26] For example, the acrylate may include one or more
selected from the group consisting of alkyl acrylates
containing an alkyl group having 2 to 8 carbon atoms,
preferably alkyl acrylates containing 5 an alkyl group having
4 to 8 carbon atoms. More preferably, the acrylate is butyl
acrylate or ethylhexyl acrylate.
[27] For example, the aromatic vinyl compound may include
one or more selected from the group consisting of styrene,
10 α-methylstyrene, m-methylstyrene, p-methylstyrene, and ptert-
butylstyrene, preferably styrene.
[28] 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.
[29] For example, the graft copolymer (A) may have a gel
content of less than 90 % by weight, 30 to 90 % by weight,
preferably 50 to 90 % by weight. Within this range,
mechanical properties such as impact strength and flexural
20 strength may be excellent, and weather resistance may be
11
improved.
[30] For example, the graft copolymer (A) may have a
swelling index of 6 to 14, 6 to 12, preferably 6 to 10.
Within this range, mechanical properties such as impact
strength and flexural strength 5 may be excellent, and weather
resistance may be improved.
[31] For example, the graft copolymer (A) may have a
grafting degree of 20 to 80 %, preferably 25 to 60 %, more
preferably 25 to 40 %. Within this range, mechanical
10 properties such as impact strength and flexural strength may
be excellent, and weather resistance may be improved.
[32] In the present description, to measure gel content
and swelling index, acetone is added to 1 g of graft
copolymer powder, stirring is performed at room temperature
15 for 24 hours, centrifugation is performed to obtain a
fraction not dissolved in acetone, and then the fraction is
dried. Then, the weights of the fraction before and after
drying are measured, and gel content and swelling index are
calculated by substituting the weight values into the
20 following equations.
12
[33] * Gel content (%) = [Weight after drying after
centrifugation/sample weight] × 100
[34] * Swelling index= Weight before drying after
centrifugation/Weight after drying after centrifugation
[35] In the present description, 5 to measure grafting
degree, resin latex of a graft polymer is coagulated, washed,
and dried to obtain powdered resin latex, and then 2 g of
the obtained powder is added to 300 ml of acetone, followed
by stirring for 24 hours. Then, the stirred solution is
10 separated using an ultracentrifuge, and then methanol is
added to the separated acetone solution dropwise to obtain a
non-grafted fraction, followed by drying. Thereafter, the
weight of the dried non-grafted fraction is measured, and
grafting degree is calculated by substituting the measured
15 weight value into the following equation.
[36] * Grafting degree (%) = (Weight of grafted monomer
(g) / Weight of rubber (g)) × 100
[37] For example, the graft copolymer (A) may be prepared
by emulsion polymerization. Emulsion polymerization
20 commonly practiced in the art to which the present invention
13
pertains may be used in the present invention without
particular limitation. As a specific example, the graft
copolymer (A) may be prepared by graft-emulsion-polymerizing
an aromatic vinyl monomer and a vinyl cyanide monomer onto
5 alkyl acrylate rubber.
[38] For example, the alkyl acrylate rubber included in
the graft copolymer (A) may be prepared by emulsion
polymerizing alkyl acrylate. As a specific example, the
alkyl acrylate rubber may be prepared by mixing alkyl
10 acrylate, an emulsifier, an initiator, a grafting agent, a
crosslinking agent, an electrolyte, and water and by
emulsion polymerizing the mixture.
[39] For example, the emulsifier is preferably an aqueous
solution having a pH of 3 to 9 and containing an alkyl
15 sulfosuccinate metal salt derivative having 12 to 18 carbon
atoms, or an alkyl sulfuric ester having 12 to 20 carbon
atoms or a sulfonic acid metal salt derivative thereof.
[40] As a specific example, in the aqueous solution
having a pH of 3 to 9 and containing an alkyl sulfosuccinate
20 metal salt derivative having 12 to 18 carbon atoms, the
14
alkyl sulfosuccinate metal salt derivative is preferably
dicyclohexyl sulfosuccinate sodium salt, dihexyl
sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate
sodium salt, di-2-ethylhexyl sulfosuccinate potassium salt,
or di-2-ethylhexyl sulfosuccinate 5 lithium salt, and the
alkyl sulfuric ester having 12 to 20 carbon atoms or the
sulfonic acid metal salt derivative thereof is preferably
sodium lauryl sulfate, sodium dodecyl sulfate, sodium
dodecyl benzene sulfate, sodium octadecyl sulfate, sodium
10 oleic sulfate, potassium dodecyl sulfate, or potassium
octadecyl sulfate.
[41] Based on 100 parts by weight of the alkyl acrylate
rubber, the emulsifier is preferably used in an amount of
0.1 to 1 part by weight.
15 [42] For example, the initiator is preferably an
inorganic or organic peroxide. Specifically, the initiator
is preferably a water-soluble initiator such as potassium
persulfate, sodium persulfate, or ammonium persulfate or a
fat-soluble initiator such as cumene hydroperoxide or
20 benzoyl peroxide.
15
[43] Based on 100 parts by weight of the alkyl acrylate
rubber, the initiator is preferably used in an amount of
0.05 to 0.2 parts by weight.
[44] In the present description, 100 parts by weight of
the alkyl acrylate rubber 5 means the weight of the prepared
alkyl acrylate rubber or the total weight of monomers added
to prepare the alkyl acrylate rubber.
[45] For example, the grafting agent preferably includes
one or more selected from the group consisting of allyl
10 methacrylate, triallyl isocyanurate, triallyl amine, and
diallyl amine, and the grafting agent is preferably used in
an amount of 0.01 to 0.07 parts by weight based on 100 parts
by weight of the alkyl acrylate rubber. Within this range,
the objects of the present invention may be achieved more
15 easily.
[46] For example, the crosslinking agent preferably
includes one or more selected from the group consisting of
ethylene glycol dimethacrylate, diethylene glycol
dimethacrylate, triethylene glycol dimethacrylate, 1,3-
20 butanediol dimethacrylate, 1,6-hexanediol dimethacrylate,
16
neopentyl glycol dimethacrylate, trimethylolpropane
trimethacrylate, and trimethylolmethane triacrylate, and the
crosslinking agent is preferably used in an amount of 0.02
to 0.3 parts by weigh based on 100 parts by weight of the
5 alkyl acrylate rubber.
[47] When the grafting agent and the crosslinking agent
are used, the elasticity of the alkyl acrylate rubber
according to the present invention may be further increased,
thereby further improving physical properties such as impact
10 strength.
[48] The electrolyte preferably includes one or more
selected from the group consisting of NaHCO3, Na2S2O7, and
K2CO3, and the electrolyte is preferably used in an amount
of 0.05 to 0.4 parts by weight based on 100 parts by weight
15 of the alkyl acrylate rubber.
[49] In the present description, water serves as a medium
in which emulsion polymerization is performed, and is
preferably deionized water. The amount of water used may be
appropriately selected according to need.
20 [50] For example, to prepare the alkyl acrylate rubber,
17
the components used to prepare the alkyl acrylate rubber may
be continuously fed into a reactor, or may be fed into a
reactor in a combination of continuous feed and batch feed,
and then emulsion polymerization may be performed under
polymerization conditions commonly 5 known in the art to which
the present invention pertains. In this case, the alkyl
acrylate rubber may be obtained in the form of latex.
[51] For example, immediately after completion of
polymerization, the pH of the alkyl acrylate rubber in the
10 form of latex is preferably 5 to 9, more preferably 6 to 8.
Within this range, the stability of latex may be excellent.
[52] In the present description, pH may be measured using
a pH meter.
[53] The graft copolymer (A) is a graft copolymer
15 prepared by grafting an aromatic vinyl compound-vinyl
cyanide compound copolymer onto a backbone of the alkyl
acrylate rubber polymer. As a specific example, the graft
copolymer (A) may be prepared by mixing the alkyl acrylate
rubber with an aromatic vinyl compound, a vinyl cyanide
20 compound, and polymerization additives as necessary and
18
performing emulsion polymerization.
[54] For example, the polymerization additives may
include a grafting agent and/or a crosslinking agent. In
this case, the grafting agent and the crosslinking agent are
the same as those used 5 to prepare the alkyl acrylate rubber,
and the content of each of the grafting agent and the
crosslinking agent may be determined within the same range
as those used to prepare the alkyl acrylate rubber based on
100 parts by weight of total monomers except for rubber.
10 [55] In the present description, the monomers may include
an alkyl acrylate, an alkyl methacrylate, an aromatic vinyl
compound, and a vinyl cyanide compound.
[56] When emulsion polymerization of the graft copolymer
(A) is performed, in addition to the alkyl acrylate rubber,
15 the aromatic vinyl compound, and the vinyl cyanide compound,
an emulsifier, a polymerization initiator, a molecular
weight modifier, and water commonly used in the art to which
the present invention pertains may be used. In addition,
immediately after completion of emulsion polymerization, the
20 prepared graft copolymer may be obtained in the form of
19
latex.
[57] For example, an aqueous solution containing the
emulsifier may have a pH of 9 to 13, and the emulsifier is
preferably a carboxylic acid metal salt derivative such as a
fatty acid metal salt 5 having 12 to 20 carbon atoms and a
rosin acid metal salt having 12 to 20 carbon atoms.
[58] For example, the fatty acid metal salt having 12 to
20 carbon atoms preferably includes one or more selected
from the group consisting of sodium fatty acid, sodium
10 laurate, sodium oleate, and potassium oleate, and the rosin
acid metal salt having 12 to 20 carbon atoms preferably is
sodium rosinate, potassium rosinate, or a mixture thereof.
[59] For example, the emulsifier is preferably used in an
amount of 1 to 2 parts by weight based on 100 parts by
15 weight of a reaction mixture containing the alkyl acrylate
rubber, the aromatic vinyl compound, and the vinyl cyanide
compound.
[60] For example, the initiator may be the same as that
used to prepare the alkyl acrylate rubber, and is preferably
20 used in an amount of 0.05 to 0.3 parts by weight based on
20
100 parts by weight of the reaction mixture.
[61] For example, the molecular weight modifier may be tdodecylmercaptan,
n-octylmercaptan, or a mixture thereof,
and may be used in an amount of 0.02 to 0.2 parts by weight
based on 100 parts by 5 weight of the reaction mixture.
[62] Water used in the present invention is preferably
deionized water, and may be used in an amount commonly used
in the art to which the present invention pertains.
[63] When graft emulsion polymerization is performed,
10 when the reaction mixture and polymerization additives such
as an emulsifier are fed batchwise, the pH of a
polymerization system rises temporarily, which makes
grafting difficult. In addition, the stability of copolymer
particles decreases, and thus the internal structure of the
15 particles becomes uneven. Accordingly, when the graft
copolymer (A) is prepared through graft emulsion
polymerization, the reaction mixture and polymerization
additives are preferably fed continuously, as a specific
example, are continuously fed for 1 to 10 hours or 1 to 5
20 hours within a total reaction time.
21
[64] It should be noted that polymerization conditions
not described herein are obvious to those skilled in the art
that polymerization conditions generally known in the art
may be appropriately selected.
[65] In the present 5 description, continuous feed is a
feed method that is opposite to batch feed, and means
continuously feeding for a certain period of time or feeding
stepwise within a certain time.
[66] For example, immediately after completion of
10 polymerization, the pH of the graft copolymer (A) in the
form of latex is preferably 8 to 11, more preferably 9 to
10.5. Within this range, the stability of latex may be
excellent.
[67] As a specific example, the graft copolymer latex (A)
15 may be coagulated at a temperature of 80 to 90 °C or 82 to
88 °C under atmospheric pressure using an aqueous calcium
chloride solution, aged at a temperature of more than 90 °C
and less than or equal to 100 °C or a temperature of 92 to
98 °C, dehydrated and washed, and then dried with hot blast
20 at 85 to 95 °C or 88 to 92 °C for 20 minutes to 1 hour or
22
for 30 minutes to 40 minutes to obtain powder.
[68] B) Alkyl methacrylate-aromatic vinyl compound-vinyl
cyanide compound copolymer
[69] Based on the total weight of the ASA resin
composition (A+B+C), the alkyl 5 methacrylate-aromatic vinyl
compound-vinyl cyanide compound copolymer of the present
invention is preferably included in an amount of 23 to 55 %
by weight, more preferably 25 to 50 % by weight, still more
preferably 25 to 45 % by weight, most preferably 30 to 40 %
10 by weight. Within this range, transparency and colorability
may be excellent.
[70] The alkyl methacrylate-aromatic vinyl compound-vinyl
cyanide compound copolymer preferably includes 40 to 90 % by
weight of an alkyl methacrylate, 9 to 40 % by weight of an
15 aromatic vinyl compound, and 1 to 20 % by weight of a vinyl
cyanide compound, more preferably 50 to 85 % by weight of an
alkyl methacrylate, 12 to 35 % by weight of an aromatic
vinyl compound, and 3 to 15 % by weight of a vinyl cyanide
compound, still more preferably 55 to 65 % by weight of an
20 alkyl methacrylate, 25 to 35 % by weight of an aromatic
23
vinyl compound, and 5 to 10 % by weight of a vinyl cyanide
compound. Within this range, transparency and colorability
may be excellent.
[71] For example, the alkyl methacrylate may be an alkyl
methacrylate containing an alkyl 5 group having 1 to 15 carbon
atoms. As a specific example, the alkyl methacrylate may
include one or more selected from the group consisting of
methyl methacrylate, ethyl methacrylate, butyl methacrylate,
2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and
10 lauryl methacrylate, preferably an alkyl methacrylate
containing a chained alkyl group having 1 to 4 carbon atoms,
more preferably methyl methacrylate.
[72] For example, the aromatic vinyl compound may include
one or more selected from the group consisting of styrene,
15 α-methylstyrene, m-methylstyrene, p-methylstyrene, and ptert-
butylstyrene, preferably styrene.
[73] For example, the vinyl cyanide compound may include
one or more selected from the group consisting of
acrylonitrile, methacrylonitrile, ethylacrylonitrile, and
20 isopropylacrylonitrile, preferably acrylonitrile.
24
[74] The alkyl methacrylate-aromatic vinyl compound-vinyl
cyanide compound copolymer preferably has a weight average
molecular weight of 10,000 to 150,000 g/mol, more preferably
40,000 to 120,000 g/mol. Within this range, rubber
dispersion may be increased, 5 thereby improving impact
strength, processability, transparency, and colorability.
[75] In the present description, unless otherwise defined,
when measuring weight average molecular weight, powder is
dissolved in acetone, a sol fraction dissolved in acetone is
10 extracted, and the extracted sol fraction is dissolved in
tetrahydrofuran (THF). Then, weight average molecular
weight is measured through gel permeation chromatography
(GPC). In this case, weight average molecular weight is
obtained as a relative value to a standard polystyrene (PS)
15 specimen.
[76] For example, the alkyl methacrylate-aromatic vinyl
compound-vinyl cyanide compound copolymer may be prepared by
solution polymerization, bulk polymerization, emulsion
polymerization, or suspension polymerization. Solution
20 polymerization, bulk polymerization, emulsion polymerization,
25
and suspension polymerization practiced in the art to which
the present invention pertains may be used in the present
invention without particular limitation.
[77] As a preferred example, to prepare the alkyl
methacrylate-aromatic vinyl 5 compound-vinyl cyanide compound
copolymer, 0.01 to 0.5 parts by weight, preferably 0.02 to
0.15 parts by weight, more preferably 0.02 to 0.1 parts by
weight of each of one or more of an initiator and a
molecular weight modifier may be added to 100 parts by
10 weight in total of an alkyl methacrylate, an aromatic vinyl
compound, and a vinyl cyanide compound in the absence of a
solvent or in a reaction solvent, and then bulk
polymerization or solution polymerization may be performed
in a continuous reactor. In this case, economics may be
15 improved, and residual impurities may be reduced.
[78] Reaction solvents for bulk polymerization or
solution polymerization commonly used in the art to which
the present invention pertains may be used as the reaction
solvent of the present invention without particular
20 limitation. For example, the reaction solvent may be
26
aromatic hydrocarbons. The reaction solvent preferably
includes one or more selected from the group consisting of
toluene, xylene, ethylbenzene, cumene, and tetralin, more
preferably toluene.
[79] Preferably, the weight 5 of the graft copolymer (A) is
not greater than that of the alkyl methacrylate-aromatic
vinyl compound-vinyl cyanide compound copolymer (B). More
preferably, the weight ratio (A:B) of the graft copolymer (A)
to the alkyl methacrylate-aromatic vinyl compound-vinyl
10 cyanide compound copolymer (B) is 1:1 to 1:2.5, more
preferably 1:1 to 1:2. Within this range, balance between
mechanical strength and fluidity may be excellent, and in
particular, transparency, colorability, and weather
resistance may be excellent.
15 [80] C) Poly(alkyl methacrylate) resin
[81] The poly(alkyl methacrylate) resin (C) of the
present invention is preferably included in an amount of 25
to 45 % by weight, more preferably 30 to 45 % by weight,
still more preferably 30 to 40 % by weight. Within this
20 range, transparency and colorability may be greatly improved
27
while maintaining mechanical properties and processability
equal or superior to those of conventional ASA resin
compositions.
[82] For example, the poly(alkyl methacrylate) resin may
be a polymer including an 5 alkyl methacrylate containing an
alkyl group having 1 to 15 carbon atoms.
[83] The alkyl methacrylate preferably includes one or
more selected from the group consisting of methyl
methacrylate, ethyl methacrylate, butyl methacrylate, 2-
10 ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and
lauryl methacrylate, more preferably an alkyl methacrylate
containing a chained alkyl group having 1 to 4 carbon atoms,
still more preferably methyl methacrylate.
[84] The poly(alkyl methacrylate) resin preferably has a
15 weight average molecular weight of 50,000 to 200,000 g/mol,
more preferably 50,000 to 150,000 g/mol, still more
preferably 50,000 to 100,000 g/mol. Within this range,
weather resistance, fluidity, tensile strength, impact
strength, transparency, and colorability may be excellent.
20 [85] For example, the poly(alkyl methacrylate) resin may
28
be prepared by adding a crosslinking agent and an initiator
to monomers including an alkyl methacrylate and performing
bulk polymerization, solution polymerization, suspension
polymerization, or emulsion polymerization, preferably
suspension polymerization 5 or emulsion polymerization.
[86] Initiators commonly used to prepare a poly(alkyl
methacrylate) resin may be used as the initiator of the
present invention. For example, azo-based initiators such
as 2,2'-azobis 2'4-dimethyl-valeronitrile may be used.
10 [87] Materials such as solvents and emulsifiers that must
be added according to each polymerization method or
conditions such as polymerization temperature and
polymerization time that must be changed according to each
polymerization method may be appropriately selected, without
15 particular limitation as necessary, from materials or
conditions commonly used when a poly(alkyl methacrylate)
resin is prepared.
[88] ASA-based resin composition
[89] The ASA-based resin composition of the present
20 invention preferably has a total rubber content of 8 to 23 %
29
by weight, more preferably 10 to 20 % by weight, still more
preferably 10 to 17 % by weight, most preferably 10 to 15 %
by weight. Within this range, mechanical properties may be
excellent, and in particular, weather resistance,
transparency, and 5 colorability may be excellent.
[90] In the present description, an ASA-based resin
refers to an alkyl acrylate-aromatic vinyl compound-vinyl
cyanide compound copolymer.
[91] Based on 100 parts by weight in total of the
10 acrylate-aromatic vinyl compound-vinyl cyanide compound
graft copolymer, the alkyl methacrylate-aromatic vinyl
compound-vinyl cyanide compound copolymer, and the
poly(alkyl methacrylate) resin, the ASA-based resin
composition preferably includes 0.05 to 5 parts by weight of
15 one or more of a lubricant, a heat stabilizer, and a UV
stabilizer. Within this range, the intrinsic properties of
an ASA-based resin composition may be efficiently expressed
without deterioration in the physical properties of the ASA
resin composition.
20 [92] The lubricant is preferably included in an amount of
30
more than 0.3 parts by weight and less than 2 parts by
weight, more preferably 0.5 to 1.9 parts by weight, still
more preferably 0.9 to 1.5 parts by weight. Within this
range, impact strength and fluidity may be excellent.
[93] For example, the lubricant 5 may include one or more
selected from the group consisting of ester-based lubricants,
metal salt-based lubricants, carboxylic acid-based
lubricants, hydrocarbon-based lubricants, and amide-based
lubricant, preferably amide-based lubricants, more
10 preferably stearamide-based lubricants, still more
preferably alkylene bis(stearamide) containing an alkylene
having 1 to 10 carbon atoms. In this case, the intrinsic
properties of a lubricant may be well expressed without
deterioration in the mechanical properties and thermal
15 stability of a resin.
[94] In the present description, the stearamide-based
lubricants may include stearamide and steramid substituents
obtained by substituting at least one hydrogen of stearamide
with another substituent (e.g., a C1 to C10 alkyl group,
20 halogen, etc.).
31
[95] Ester-based lubricants, metal salt-based lubricants,
carboxylic acid-based lubricants, hydrocarbon-based
lubricants, and amide-based lubricant commonly used in the
art to which the present invention pertains may be used in
the present invention 5 without particular limitation.
[96] For example, the heat stabilizer may include 0.01 to
3 parts by weight of each of one or more selected from the
group consisting of amine-based heat stabilizers and
phosphorus-based heat stabilizers. Within this range,
10 thermal stability, transparency, and colorability may be
excellent.
[97] For example, the amine-based heat stabilizers may
include one or more selected from the group consisting of
N,N-di-t-butyl hydroxylamine, N,N-distearyl hydroxylamine
15 (DSHA), N,N-diphenyl hydroxylamine (DPHA), N,N-dibenzyl
hydroxylamine, N,N-benzylphenyl hydroxylamine, N,N-di(2,4-
dimethylphenyl) hydroxylamine, and N,N-naphthyl
hydroxylamine. For example, the amine-based heat stabilizer
may be included in an amount of 0.01 to 3 parts by weight,
20 preferably 0.05 to 2 parts by weight, more preferably 0.1 to
32
1 part by weight. Within this range, thermal stability,
transparency, and colorability may be excellent.
[98] For example, the phosphorus-based heat stabilizers
may include one or more selected from the group consisting
of tris(nonylphenyl) phosphite, 5 tris(2,4-di-t-butylphenyl)
phosphite (TBPP), 2,4,6-tri-tert-butylphenyl-2-butyl-2-
ethyl-1,3-propanediol phosphite, diisodecyl pentaerythritol
diphosphite, distearyl pentaerythritol diphosphite, bis(2,4-
di-t-butylphenyl) pentaerythritol diphosphite (PEP24),
10 bis(2,4-di-cumylphenyl) pentaerythritol diphosphite, and
tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4’-diyl
bisphosphonite. For example, the phosphorus-based heat
stabilizer may be included in an amount of 0.01 to 3 parts
by weight, preferably 0.05 to 2 parts by weight, more
15 preferably 0.1 to 1 part by weight. Within this range,
thermal stability, transparency, and colorability may be
excellent.
[99] For example, the UV stabilizer may include 0.1 to
2.5 parts by weight of one or more selected from the group
20 consisting of benzotriazole-based UV absorbers and HALS33
based UV stabilizers, preferably 0.1 to 2.0 parts by weight
of a benzotriazole-based UV absorber and 0.1 to 2.0 parts by
weight of a HALS-based UV stabilizer, more preferably 0.1 to
1.0 part by weight of a benzotriazole-based UV absorber and
0.1 to 1.0 part by weight 5 of a HALS-based UV stabilizer,
still more preferably 0.2 to 0.7 parts by weight of a
benzotriazole-based UV absorber and 0.2 to 0.7 parts by
weight of a HALS-based UV stabilizer, most preferably 0.3 to
0.6 parts by weight of a benzotriazole-based UV absorber and
10 0.3 to 0.6 parts by weight of a HALS-based UV stabilizer.
Within this range, weather resistance may be greatly
improved without deterioration in impact strength and
fluidity.
[100] For example, the benzotriazole-based UV absorber may
15 be hydroxybenzotriazole, preferably 2-(2'-
hydroxyphenyl)benzotriazole. More preferably, the
benzotriazole-based UV absorber includes one or more
selected from the group consisting of 2-(2'-hydroxy-5'-
methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-
20 hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-
34
hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-
tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tertbutyl-
2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tertbutyl-
2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2-
(3'-sec-butyl-5'-tert-butyl-5 2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-ditert-
amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-
dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tertbutyl-
2'-hydroxy-5'-(2-octyloxy-carbonylethyl)phenyl)-5-
10 chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-
chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-
tert-butyl-2'-hydroxy-5'-(2-
15 methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-
2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-
hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-
methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-
20 (2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-
35
methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-
ylphenol], and transesterification products of 2-[3'-tertbutyl-
5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2Hbenzotriazole
and polyethyleneglycol. In this case, weather
resistance may be greatly improved 5 without deterioration in
impact strength and fluidity.
[101] The HALS-based UV stabilizer preferably includes one
or more selected from the group consisting of 1,1-
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-
10 tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-
4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-
piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-
N-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,
condensation products of 1-(2-hydroxyethyl)-2,2,6,6-
15 tetramethyl-4-hydroxypiperidine and succinic acid, linear or
cyclic condensation products of N,N'-bis(2,2,6,6-
tetramethyl-4-piperidyl)hexamethylene diamine and 4-tertoctylamino-
2,6-di-chloro-1,3,5-triazine, tris(2,2,6,6-
tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-
20 tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate,
36
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-
2,2,6,6-tetramethylpiperidine, linear or cyclic condensation
products of N,N'-bis(2,2,6,6-tetramethyl-4-
piperidyl)hexamethylene diamine 5 and 4-morpholino-2,6-
dichloro-1,3,5-triazine, and reaction products of 7,7,9,9-
tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-
[4,5]decane and epichlorohydrin, more preferably
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacade(bis(2,2,6,6-
10 tetramethyl-4-piperidyl) sebacate), 2-(2H-benzotriazole-2-
yl)-4-(-(1,1,3,3-tetramethylbutyl)phenol(2-(2H-benzotriazol-
2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol), or a mixture
thereof. In this case, weather resistance may be greatly
improved without deterioration in impact strength and
15 fluidity.
[102] When necessary, the ASA-based resin composition may
further include 0.01 to 5 parts by weight, 0.05 to 3 parts
by weight, 0.1 to 2 parts by weight, or 0.5 to 1 part by
weight of one or more additives selected from the group
20 consisting of dyes, pigments, colorants, release agents,
37
antistatic agents, antibacterial agents, processing aids,
metal deactivators, flame retardants, smoke inhibitors,
anti-drip agents, anti-friction agents, and anti-wear agents
based on 100 parts by weight described above. Within this
range, the effects of 5 additives may be well expressed
without deterioration in the intrinsic physical properties
of an ASA resin composition.
[103] The ASA-based resin composition preferably has a
melt index (220 °C, 10 kg) of 8 g/10 min or more, more
10 preferably 8 to 11 g/10 min, still more preferably 9 to 11
g/10 min as measured according to ASTM D1238. Within this
range, balance between impact strength, weather resistance,
and fluidity may be excellent.
[104] The ASA-based resin composition preferably has an
15 Izod impact strength (1/4inch, 23 °C) of 3 kgf·cm/cm2 or
more, more preferably 3 to 8 kgf·cm/cm2, still more
preferably 3 to 4 kgf·cm/cm2 as measured according to ASTM
D256. Within this range, balance between impact strength,
weather resistance, and fluidity may be excellent.
20 [105] For example, the ASA-based resin composition may
38
have a tensile strength (1/8 inch) of 570 kg/cm2 or more,
preferably 570 to 700 kg/cm2, more preferably 580 to 650
kg/cm2, still more preferably 580 to 610 kg/cm2 as measured
according to ASTM 638. Within this range, balance between
impact strength, tensile strength, 5 weather resistance, and
fluidity may be excellent.
[106] For example, the ASA-based resin composition may
have a flexural strength of 850 kg/cm2 or more, preferably
850 to 1,000 kg/cm2, more preferably 860 to 950 kg/cm2,
10 still more preferably 870 to 920 kg/cm2 as measured
according to ASTM 790. Within this range, balance between
impact strength, tensile strength, flexural strength,
weather resistance, and fluidity may be excellent.
[107] The ASA-based resin composition preferably has a
15 surface gloss (45°) of 80 or more, more preferably 85 or
more or 95 or more as measured according to ASTM D528.
Within this range, transparency and colorability may be
excellent, and balance between physical properties may be
good.
20 [108] The ASA-based resin composition preferably has a
39
transparency (haze) of 7 or less, more preferably 6 or less,
still more preferably 5 or less as measured according to
ASTM D1003. Within this range, mechanical properties,
processability, transparency, and colorability may excellent.
[109] The ASA-based resin 5 composition preferably has a
weather resistance (△E) of 1.3 or less, more preferably 1.2
or less as measured using a Weather-Ometer when 6,000 hours
have elapsed according to ASTM J1960. Within this range,
mechanical properties, processability, colorability, and
10 weather resistance may be excellent.
[110] The method of preparing the ASA-based resin
composition preferably includes a step of kneading and
extruding 20 to 47 % by weight of an acrylate-aromatic vinyl
compound-vinyl cyanide compound graft copolymer containing
15 acrylate rubber having an average particle diameter of 50 to
150 nm as a core, 23 to 55 % by weight of an alkyl
methacrylate-aromatic vinyl compound-vinyl cyanide compound
copolymer, and 25 to 45 % by weight of a poly(alkyl
methacrylate) resin under conditions of 200 to 300 °C and
20 100 to 500 rpm to prepare pellets.
40
[111] Extrusion kneaders commonly used in the art to which
the present invention pertains may be used in the step of
kneading and extruding without particular limitation. For
example, a single-screw extruder, a twin-screw extruder, or
a Banbury mixer, preferably 5 a twin-screw extruder may be
used. In this case, compatibility may be excellent due to
uniform dispersion of a composition.
[112] The kneading and extruding are preferably performed
at a barrel temperature (temperature condition) of 210 to
10 300 °C, more preferably 210 to 280 °C, still more preferably
220 to 250 °C. In this case, throughput per unit of time
may be adequate, melt kneading may be sufficiently performed,
and thermal decomposition of a resin component may be
prevented.
15 [113] The kneading and extruding are preferably performed
at a screw speed (rpm) of 150 to 400 rpm, more preferably
100 to 350 rpm, still more preferably 200 to 310 rpm, most
preferably 250 to 350 rpm. In this case, throughput per
unit of time may be adequate, and thus process efficiency
20 may be improved and excessive cutting may be prevented.
41
[114] The method of preparing the ASA resin composition
shares all the technical characteristics of the abovedescribed
ASA-based resin composition. Accordingly,
repeated description thereof will be omitted.
5 [115] Molded article
[116] The molded article of the present invention may be
manufactured using the thermoplastic resin composition of
the present invention. In this case, due to increased
compatibility, mechanical properties, such as impact
10 strength, transparency, and colorability may be excellent.
[117] For example, the molded article may be an extrusion
molded article or an injection molded article. Preferably,
the molded article includes housings for home appliances
such as air conditioners, vacuum cleaners, washing machines,
15 refrigerators, and TV back covers; housings for OA equipment
such as computers, notebooks, monitors, facsimiles,
telephones, copiers, and scanners; automotive parts such as
automotive interior and exterior materials; interior and
exterior materials for construction; materials for toys;
20 leisure products; and interior decoration products, more
42
preferably exterior materials, finishing materials, nonpainted
products, or extrusion profiles. In this case, by
using the thermoplastic resin composition of the present
invention, a product having quality superior to that
required 5 in the market may be provided.
[118] The molded article preferably has a processing
thickness, e.g., surface thickness, of 0.5 T (mm) or more.
[119] Method of manufacturing molded article
[120] Preferably, the method of manufacturing a molded
10 article of the present invention includes a step of kneading
and extruding 20 to 47 % by weight of an acrylate-aromatic
vinyl compound-vinyl cyanide compound graft copolymer
containing acrylate rubber having an average particle
diameter of 50 to 150 nm as a core, 23 to 55 % by weight of
15 an alkyl methacrylate-aromatic vinyl compound-vinyl cyanide
compound copolymer, and 25 to 45 % by weight of a poly(alkyl
methacrylate) resin under conditions of 200 to 300 °C and
100 to 500 rpm to prepare a pellet; and a step of performing
sheet molding or injection molding of the prepared pellet at
20 a molding temperature of 200 to 300 °C to manufacture a
43
molded article. In this case, the molded article may have
excellent colorability and transparency even at a processing
thickness of a predetermined value or more, and thus the
molded article may be applied to high value-added ASA-based
resin products having 5 non-painting, transparent, high
saturation, or special color properties.
[121] As a preferred example, the step of preparing the
molded article may include a step of performing sheet
molding of the prepared pellets at a molding temperature of
10 180 to 300 °C. As a more preferred example, the step of
preparing the molded article may include a step of
performing sheet molding at a molding temperature of 180 to
300 °C under a molding pressure of 50 to 300 kgf/cm2. In
this case, a large molded sheet having excellent
15 transparency and colorability may be easily manufactured.
[122] The molding temperature is preferably 200 to 230 °C,
more preferably 210 to 220 °C. Within this range, a large
molded sheet having excellent transparency and colorability
may be easily manufactured.
20 [123] The molding pressure is preferably 190 to 270
44
kgf/cm2, more preferably 200 to 250 kgf/cm2. Within this
range, a large injection-molded article having high impact
strength may be easily manufactured.
[124] As another preferred example, the step of
manufacturing the molded 5 article may include a step of
injection molding the prepared pellets under conditions of
an injection temperature of 200 to 260 °C, an injection
pressure of 60 to 100 bar, and a holding pressure of 25 to
55 bar. In this case, a large injection-molded article
10 having excellent transparency and colorability may be easily
manufactured.
[125] The injection temperature is preferably 200 to
230 °C, more preferably 210 to 220 °C. Within this range, a
large injection-molded article having excellent transparency
15 and colorability may be easily manufactured.
[126] The injection pressure is preferably 70 to 90 bar,
more preferably 75 to 85 bar. Within this range, a large
injection-molded article having high impact strength may be
easily manufactured.
20 [127] The holding pressure is preferably 30 to 50 bar,
45
more preferably 35 to 45 bar. Within this range, a largearea
injection-molded article having high impact strength
may be easily manufactured.
[128] In describing the thermoplastic resin composition,
the method of preparing the 5 thermoplastic resin composition,
and the molded article according to the present invention,
it should be noted that other conditions or equipment not
explicitly described herein may be appropriately selected
within the range commonly practiced in the art without
10 particular limitation.
[129] Hereinafter, the present invention will be described
in more detail with reference to the following preferred
examples. However, these examples are provided for
illustrative purposes only and should not be construed as
15 limiting the scope and spirit of the present invention. In
addition, it will be apparent to those skilled in the art
that various changes and modifications may be made without
departing from the spirit and scope of the present invention,
and such changes and modifications are also within the scope
20 of the appended claims.
46
[130] [Examples]
[131] Materials used in Examples below are as follows.
[132] A) Graft copolymer (core: 50 % by weight of a
butylacrylate polymer-derived unit having an average
particle diameter of 150 nm, 5 shell: 35 % by weight of a
styrene-derived unit, and 15 % by weight of an
acrylonitrile-derived unit) prepared by emulsion
polymerization
[133] B) SAMMA resin prepared by bulk polymerization: A
10 SAMMA resin was prepared by the following method.
[134] Polymerization was performed at a temperature of
140 °C in a first reactor and polymerization was performed
at a temperature of 150 °C in a second reactor while feeding,
at a rate of 14 L/hr into a 26 L reactor, a polymerization
15 solution prepared by adding 0.02 parts by weight of 1,1-
bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 0.08 parts by
weight of n-dodecyl mercaptan, and 0.1 parts by weight of
Irgacure (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-
dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione) as a
20 hindered phenolic antioxidant to a mixed solution containing
47
20 parts by weight of toluene, 24 parts by weight of styrene,
50 parts by weight of methyl methacrylate, and 6 parts by
weight of acrylonitrile. When polymerization rate reached
about 60 % or more, unreacted monomers and the reaction
medium were removed in a volatilization 5 tank at 215 °C to
prepare a styrene-acrylonitrile-methyl methacrylate (SAMMA)
resin in the form of pellets. The weight average molecular
weight of the prepared SAMMA resin was 70,000 g/mol.
[135] C) PMMA resin prepared by bulk polymerization: A
10 PMMA resin was prepared by the following method.
[136] 100 parts by weight of methyl methacrylate, 200
parts by weight of distilled water, 0.3 parts by weight of
polyvinyl alcohol as a suspending agent, and 2.0 parts by
weight of n-octyl mercaptan were fed into a nitrogen15
substituted reactor batchwise. Then, the temperature inside
the reactor was raised to 80 °C, 0.05 parts by weight of
AIBN as an initiator was added thereto to initiate reaction,
and the temperature inside the reactor was maintained at
80 °C to perform polymerization for 90 minutes. Thereafter,
20 the temperature of the reactor was raised to 110 °C for 30
48
minutes to perform additional polymerization. The obtained
beads were washed using a dehydrator and dried in a
fluidized bed dryer at 80 °C for 2 hours. The weight
average molecular weight of the prepared PMMA resin was
5 100,000 g/mol.
[137] Examples 1 to 5 and Comparative Examples 1 to 6
[138] 1 part by weight of an EBS resin (Sunkoo Co.) as a
lubricant, 0.5 parts by weight of each of SONGNOX 1076 and
SONGNOX 1680 (Songwan Co.) as antioxidants, and 0.5 parts by
10 weight of each of Tinuvin 770 (BASF Co.) and Sunsorb 329
(Sunfine global Co.) as UV stabilizers were added to the
compositions and contents shown in Table 1 below, and the
mixture was kneaded and extruded at 230 °C and 150 rpm in a
twin-screw extruder to prepare pellets. The melt index of
15 the prepared pellets was measured. In addition, a 0.5 T
sheet was prepared using the prepared pellets at a molding
temperature of 220 °C and molding pressure of 200 kgf/cm2.
Surface gloss, Tt, and haze were measured using the prepared
sheet. In addition, the prepared pellets were injected at a
20 molding temperature of 220 °C, an injection pressure of 50
49
bar, and a holding pressure of 35 bar to prepare a specimen
for measuring physical properties. Impact strength, tensile
strength, flexural strength, colorability, and weather
resistance were measured using the prepared specimen.
5 [139] [Test examples]
[140] The properties of the pellets, the sheets, and the
specimens prepared in Examples 1 to 5 and Comparative
Examples 1 to 6 were measured according to the following
methods, and the results are shown in Table 1 below.
10 [141] * Rubber content (% by weight): Rubber content was
measured according to FT-IR.
[142] * Surface gloss (%): Surface gloss was measure at 45°
according to ASTM D528.
[143] * Izod impact strength (kgf·cm/cm): Izod impact
15 strength was measured according to ASTM 256.
[144] * Flexural strength (kgf/cm2): Flexural strength was
measured according to ASTM 790.
[145] * Tensile strength (kgf/cm2): Tensile strength was
measured according to ASTM 638.
20 [146] * Melt index (MI): Melt index was measured using the
50
prepared pellet under conditions of 220 °C and 10 kg
according to ASTM D1238.
[147] * Transparency (light diffusivity and light
transmittance): The haze value and total light transmittance
(Tt) of a 0.5 mm thick sheet 5 were measured according to ASTM
D-1003. Transparency becomes better as the haze value
decreases, whereas transparency becomes better as light
transmittance increases.
[148] * Surface hardness: Surface hardness was measured
10 according to ASTM D785.
[149] * Colorability: The L value of a specimen was
measured using a color difference meter (Color-Eye 7000A, XRite
Co.) in a CIELAB mode. As the L value increases, the
degree to which the color of a white plate located behind
15 the specimen is projected onto the specimen increases, i.e.,
colorability increases.
[150] * Weather resistance (△E): Color was measured using
a weather resistance analyzer (Weather-Ometer) when 6,000
hours have elapsed under the ASTM J1960 conditions, and the
20 measured color was compared with an initial color. A small
51
△E value indicates that the degree of color change is
insignificant. Thus, weather resistance becomes better as
the △E value decreases.
[151] [Table 1]
(Parts by
weight)
Example 1 Example 2 Example 3 Example 4 Example 5
A 30 30 20 40 46
B 40 30 40 30 24
C 30 40 40 30 30
Rubber
content
15 15 10 20 23
Melt
index(MI)
10.7 9.7 15 9 8
Impact
strength
3.5 3.2 2.3 4.3 4.5
Tensile
strength
600 590 650 500 450
Flexural
strength
900 880 960 800 700
Tt 86 88 88 83 83
Haze 5 4 4 6 7
Surface gloss 100 106 105 95 93
Surface
hardness
110 110 109 95 90
Colorability 80 81 80 76 76
Weather
resistance
(△E)
1.1 1.2 1.1 1.6 1.7
5 [152] [Table 2]
(Parts by
weight)
Comparative
Example 1
Comparative
Example 2
Comparative
Example 3
Comparative
Example 4
Comparative
Example 5
Comparative
Example 6
A 30 30 65 10 30 56
B 70 40 15 40 65 20
C - 30 20 50 5 24
Rubber
content
15 15 32.5 5 15 28
Melt
index(MI)
12 12 14 18 16 6
Impact
strength
3.4 3.4 9 2.1 3.5 8.5
Tensile
strength
540 560 380 700 590 420
Flexural
strength
840 860 590 1060 885 660
52
Tt 80 85 82 88 83 84
Haze 17 9.1 10 8 15 9.5
Surface gloss 98 96 75 97 97 90
Surface
hardness
109 105 65 109 105 86
Colorability 75 76 75 78 76 75
Weather
resistance
(△E)
1.4 1.6 2.3 1.5 1.4 1.9
[153] As shown in Tables 1 and 2, it can be confirmed that
compared to Comparative Examples 1 to 6 not according to the
present invention, the ASA resin compositions (Examples 1 to
5) according to the present invention have excellent
transparency (haze), colorability, 5 and weather resistance
while having mechanical strength, such as impact strength
and tensile strength, and processability represented by MI,
which are equal or superior to those of Comparative Examples
1 to 6. In particular, it can be confirmed that Examples 1
10 to 3 having a preferred composition ratio and rubber content
have excellent transparency (haze), colorability, and
weather resistance. Accordingly, it can be confirmed that
the ASA resin composition according to the present invention
has excellent colorability and transparency even at a
15 processing thickness of a predetermined value or more while
maintaining mechanical properties and processability equal
or superior to those of conventional ASA compositions, and
53
thus the ASA resin composition is applicable to high valueadded
products having non-painting, transparent, high
saturation, or special color properties.

WE CLAIMS

An ASA-based resin composition, comprising:
20 to 47 % by weight 5 of an acrylate-aromatic vinyl
compound-vinyl cyanide compound graft copolymer containing
acrylate rubber having an average particle diameter of 50 to
150 nm as a core;
23 to 55 % by weight of an alkyl methacrylate-aromatic
10 vinyl compound-vinyl cyanide compound copolymer; and
25 to 45 % by weight of a poly(alkyl methacrylate)
resin.
【Claim 2】
15 The ASA-based resin composition according to claim 1,
wherein the ASA-based resin composition has a transparency
(haze) of 7 or less as measured according to ASTM D1003.
【Claim 3】
55
The ASA-based resin composition according to claim 1,
wherein the ASA-based resin composition has a total rubber
content of 10 to 23 % by weight.
5 【Claim 4】
The ASA-based resin composition according to claim 1,
wherein the acrylate-aromatic vinyl compound-vinyl cyanide
compound graft copolymer comprises 40 to 60 % by weight of
acrylate rubber, 25 to 45 % by weight of an aromatic vinyl
10 compound, and 10 to 20 % by weight of a vinyl cyanide
compound.
【Claim 5】
The ASA-based resin composition according to claim 1,
15 wherein the alkyl methacrylate-aromatic vinyl compound-vinyl
cyanide compound copolymer comprises 45 to 65 % by weight of
an alkyl methacrylate, 25 to 35 % by weight of an aromatic
vinyl compound, and 10 to 20 % by weight of a vinyl cyanide
compound.
20
56
【Claim 6】
The ASA-based resin composition according to claim 1,
wherein the alkyl methacrylate-aromatic vinyl compound-vinyl
cyanide compound copolymer has a weight average molecular
weight 5 of 10,000 to 150,000 g/mol.
【Claim 7】
The ASA-based resin composition according to claim 1,
wherein the poly(alkyl methacrylate) resin is a polymer
10 comprising an alkyl methacrylate containing an alkyl group
having 1 to 15 carbon atoms.
【Claim 8】
The ASA-based resin composition according to claim 1,
15 wherein the poly(alkyl methacrylate) resin has a weight
average molecular weight of 50,000 to 200,000 g/mol.
【Claim 9】
The ASA-based resin composition according to claim 1,
20 wherein the ASA-based resin composition comprises one or
57
more of a lubricant, a heat stabilizer, and a UV stabilizer
in an amount of 0.05 to 5 parts by weight.
【Claim 10】
A molded article manufactured 5 using the ASA-based
resin composition according to any one of claims 1 to 9.
【Claim 11】
The molded article according to claim 10, wherein the
10 molded article is an exterior material, a finishing
material, a non-painted product, or an extrusion profile.
【Claim 12】
A method of manufacturing a molded article, the method
15 comprising:
kneading and extruding 20 to 47 % by weight of an
acrylate-aromatic vinyl compound-vinyl cyanide compound
graft copolymer containing acrylate rubber having an average
particle diameter of 50 to 150 nm as a core, 23 to 55 % by
20 weight of an alkyl methacrylate-aromatic vinyl compound58
vinyl cyanide compound copolymer, and 25 to 45 % by weight
of a poly(alkyl methacrylate) resin under conditions of 200
to 300 °C and 100 to 500 rpm to prepare a pellet; and
manufacturing a molded article by performing sheet
molding or injection molding 5 of the prepared pellet at a
molding temperature of 200 to 300 °C.
59
【ABSTRACT】
The present invention relates to an ASA resin
composition, a molded article including the ASA resin
composition, and a method of manufacturing the molded
article. More particularly, 5 the present invention relates
to an ASA resin composition including 20 to 47 % by weight
of an acrylate-aromatic vinyl compound-vinyl cyanide
compound graft copolymer containing acrylate rubber having
an average particle diameter of 50 to 150 nm as a core; 23
10 to 55 % by weight of an alkyl methacrylate-aromatic vinyl
compound-vinyl cyanide compound copolymer; and 25 to 45 % by
weight of a poly(alkyl methacrylate) resin, a molded article
including the ASA resin composition, and a method of
manufacturing the molded article.
15 According to the present invention, an ASA resin
composition having excellent colorability and transparency
even at a processing thickness of a predetermined value or
more while having excellent mechanical properties and
processability, a molded article including the ASA resin
20 composition, and a method of manufacturing the molded
60
article may be provided. In particular, due to excellent
colorability and transparency thereof, the ASA resin
composition may be applied to high value-added products
having non-painting, transparent, high saturation, or
5 special color properties.