[TECHNICAL FIELD]
Cross-reference to Related Applications
[0001] This application claims the benefit of Korean Patent
Application No. 10-2020-0139933, filed on October 27, 2020,
in the Korean Intellectual Property Office, the disclosure of
10 which is incorporated herein in its entirety by reference.
Technical Field
[0002] The present invention relates to a resin composition,
and more particularly, to a flame retardant resin composition
15 enabling self-charring without containing a charring agent,
and a molded article formed therefrom.
BACKGROUND ART
[0003] Acrylonitrile-butadiene-styrene (ABS) copolymers are
20 prepared by graft-copolymerizing styrene and acrylonitrile
onto butadiene rubber polymers. ABS copolymers are superior
in impact resistance, chemical resistance, thermal stability,
coloring properties, fatigue resistance, rigidity, and
processability to conventional high-impact polystyrene (HIPS),
25 and thus used in interior and exterior materials for vehicles,
2
office equipment, parts for various electrical/electronic
products, or toys.
[0004] Meanwhile, resins used in areas exposed to fire risks
need to meet flame retardant standards required in the areas.
5 However, ABS copolymers are not flame retardant themselves,
and thus, there have been proposals for methods of mixing flame
retardants with ABS copolymers to ensure safety against fire
by meeting the flame retardant standards.
[0005] In this case, halogen-based flame retardants,
10 phosphorus-based flame retardants, nitrogen-based flame
retardants, and hydroxide-based flame retardants may be used
as the flame retardants, and among these flame retardants, the
halogen-based flame retardants are beneficial in that the flame
retardants provide high flame retardant efficiency and
15 maintain the mechanical properties of resins, but the halogenbased
flame retardants have limitations in that the flame
retardants are decomposed upon processing and cause halogen
gas, which is highly hazardous to human health and the
environment. Accordingly, recently there has been a growing
20 need for no halogen-containing, that is, halogen-free flame
retardant resins.
[0006] Against this backdrop, it is suggested to use not
halogen-based flame retardants, but non-halogen-based flame
retardants such as phosphorus-based flame retardants,
25 nitrogen-based flame retardants, and hydroxide-based flame
3
retardants, in particular, phosphorus-based flame retardants,
and these phosphorus-based flame retardants impart flame
retardancy through gas phase reactions by phosphate, and solid
phase reactions by formation of char such as C-P-O(N).
5 [0007] Although resins having a carbon main backbone, such as
polycarbonate resins, easily form char through phosphorusbased
flame retardants, making the phosphorus-based flame
retardants easy to be applicable, but ABS copolymers alone are
not able to form char through phosphorus-based flame retardants,
10 thereby requiring charring agents. However, the charring
agents are high-priced to have reduced price competitiveness,
thereby causing a decrease in productivity.
[0008] [Related Art Document]
[0009] [Patent Document]
15 [0010] (Patent Document 1) KR10-1411825B1
DISCLOSURE OF THE INVENTION
TECHNICAL PROBLEM
[0011] The present invention has been devised to overcome
20 limitations of the related art, and in a flame retardant resin
composition including a graft copolymer such as an ABS
copolymer, there is provided a resin composition capable of
both ensuring flame retardancy and thermal stability without
adding a charring agent by applying a phosphorus-based flame
25 retardant composition enabling self-charring through a flame
4
retardant.
[0012] In addition, the present invention provides a molded
article molded from the resin composition.
5 TECHNICAL SOLUTION
[0013] To solve the tasks, the present invention provides a
resin composition including 25 to 50 parts by weight of a
phosphorus-based flame retardant composition, with respect to
100 parts by weight of a base resin including a graft copolymer
10 containing a rubber polymer, and a styrene-based copolymer,
wherein the phosphorus-based flame retardant composition
includes 30 wt% to 70 wt% of Mn+(diethylphosphinate)-
n (M is a
metal having an oxidation number of 2 to 5, and n is an integer
selected from 2 to 5) and 30 wt% to 70 wt% of ammonium
15 polyphosphate.
[0014] In addition, the present invention provides a molded
article molded from the resin composition.
ADVANTAGEOUS EFFECTS
20 [0015] A resin composition according to the present invention
enables self-charring from a phosphorus-based flame retardant
composition, and thus contains no charring agents but has
excellent flame retardancy and thermal stability.
25 BRIEF DESCRIPTION OF THE DRAWINGS
5
[0016] FIG. 1 is an image of aluminum diethylphosphinate
particles in which M is aluminum (Al) in
Mn+(diethylphosphinate)-
n according to an embodiment of the
present invention, taken using a scanning electron microscope.
5 [0017] FIG. 2 is an image of ammonium polyphosphate particles
according to an embodiment of the present invention, taken
using a scanning electron microscope.
[0018] FIG. 3 is an image of a surface after burning a resin
composition according to Example 2 of the present invention,
10 taken using a scanning electron microscope.
[0019] FIG. 4 is a graph schematically showing the tendency
of flame retardancy according to the amounts of phosphorusbased
flame retardant compositions according to Examples 1 to
3 and Comparative Example 1 of the present invention.
15 [0020] FIG. 5 is a graph schematically showing the tendency
of flame retardancy according to the composition of phosphorusbased
flame retardant compositions according to Example 2 and
Comparative Examples 2 to 5 of the present invention.
20 BEST MODE FOR CARRYING OUT THE INVENTION
[0021] Hereinafter, the present invention will be described
in detail to aid in understanding of the present invention.
[0022] It will be understood that words or terms used in the
description and claims of the present invention shall not be
25 construed as being limited to having the meaning defined in
6
commonly used dictionaries. It will be further understood
that the words or terms should be interpreted as having
meanings that are consistent with their meanings in the context
of the relevant art and the technical idea of the invention,
5 based on the principle that an inventor may properly define
the meaning of the words or terms to best explain the
invention.
[0023] The term “monomer unit” as used herein may refer to a
component, a structure, or a material itself resulting from
10 each monomer, and specifically, may refer to a repeating unit
constituted in a polymer when monomers to be added participate
in a polymerization reaction upon polymerizing the polymer.
[0024] The term “composition,” as used herein includes
reaction products and decomposition products formed from
15 materials of the composition as well as a mixture of materials
including the composition.
[0025] The present invention provides a resin composition,
specifically, a flame retardant resin composition.
20 [0026] According to an embodiment of the present invention,
the resin composition may include 25 to 50 parts by weight of
a phosphorus-based flame retardant composition, with respect
to 100 parts by weight of a base resin including a graft
copolymer containing a rubber polymer and a styrene-based
25 copolymer, wherein the phosphorus-based flame retardant
7
composition may include 30 wt% to 70 wt% of
Mn+(diethylphosphinate)-
n (M is a metal having an oxidation
number of 2 to 5, and n is an integer selected from 2 to 5)
and 30 wt% to 70 wt% of ammonium polyphosphate.
5 [0027] According to an embodiment of the present invention,
the graft copolymer may be part of the base resin of the resin
composition, and may be a resin for imparting basic physical
properties to the resin composition.
[0028] According to an embodiment of the present invention,
10 the graft copolymer may include a rubber polymer, an aromatic
vinyl-based monomer unit, and a vinyl cyan-based monomer unit.
As a specific example, the rubber polymer may be a conjugated
diene-based polymer, and the conjugated diene-based polymer
may be prepared through polymerization of a conjugated diene15
based monomer to include a conjugated diene-based monomer unit,
and as a more specific example, the conjugated diene-based
polymer may be prepared through emulsion polymerization of a
conjugated diene-based monomer, making it easy to control an
average particle size of the conjugated diene-based polymer in
20 this case, and a conjugated diene-based polymer suitable for
desired mechanical properties may thus be used.
[0029] According to an embodiment of the present invention,
a conjugated diene-based monomer for forming a conjugated
diene-based monomer unit of the conjugated diene-based polymer
25 may be at least one selected from the group consisting of 1,3-
8
butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-
1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene, and more
specifically, may be 1,3-butadiene.
[0030] According to an embodiment of the present invention,
5 the graft copolymer may result from graft polymerization of an
aromatic vinyl-based monomer unit and a vinyl cyan-based
monomer unit onto a rubber polymer. Accordingly, the graft
copolymer may include the rubber polymer, and the aromatic
vinylic monomer unit and the vinyl cyan-based monomer unit
10 grafted onto the rubber polymer, and may include both an
aromatic vinyl-based monomer unit and a vinyl cyan-based
monomer unit that are not grafted onto the rubber polymer in
a portion where a graft layer of the graft copolymer is formed
according to graft polymerization conditions. In this case,
15 the graft polymerization may be performed through emulsion
polymerization or bulk polymerization.
[0031] According to an embodiment of the present invention,
an aromatic vinyl-based monomer for forming an aromatic vinylbased
monomer unit of the graft copolymer may be at least one
20 selected from the group consisting of styrene, α-
methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-
propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(pmethylphenyl)
styrene, and 1-vinyl-5-hexylnaphthalene, and as
a specific example, may be styrene.
25 [0032] According to an embodiment of the present invention,
9
a vinyl cyan-based monomer for forming a vinyl cyan-based
monomer unit of the graft copolymer may be at least one
selected from the group consisting of acrylonitrile,
methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and
5 α-chloroacrylonitrile, and as a specific example, may be
acrylonitrile.
[0033] According to an embodiment of the present invention,
the graft copolymer may include 40 wt% to 90 wt% of a rubber
polymer, 5 wt% to 50 wt% of an aromatic vinyl-based monomer
10 unit, and 1 wt% to 30 wt% of a vinyl cyan-based monomer unit,
and, as a specific example, may include 50 wt% to 80 wt% or 50
wt% to 70 wt% of a rubber polymer, 10 wt% to 40 wt% or 10 wt%
to 30 wt% of an aromatic vinyl-based monomer unit, and 1 wt%
to 20 wt% or 5 wt% to 15 wt% of a vinyl cyan-based monomer
15 unit, and within this range, the mechanical properties of the
resin composition are possibly secured.
[0034] According to an embodiment of the present invention,
the styrene-based copolymer may be part of the base resin of
the resin composition, and may be a matrix resin.
20 [0035] According to an embodiment of the present invention,
the styrene-based copolymer may include an aromatic vinylbased
monomer unit and a vinyl cyan-based monomer unit, and,
as a specific example, may be prepared through emulsion
polymerization or bulk polymerization of an aromatic vinyl25
based monomer and a vinyl cyan-based monomer.
10
[0036] According to an embodiment of the present invention,
an aromatic vinyl-based monomer for forming an aromatic vinylbased
monomer unit of the styrene-based copolymer may be at
least one selected from the group consisting of styrene, α-
5 methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-
propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(pmethylphenyl)
styrene, and 1-vinyl-5-hexylnaphthalene, and as
a specific example, may be styrene.
[0037] According to an embodiment of the present invention,
10 a vinyl cyan-based monomer for forming a vinyl cyan-based
monomer unit of the styrene-based copolymer may be at least
one selected from the group consisting of acrylonitrile,
methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and
α-chloroacrylonitrile, and as a specific example, may be
15 acrylonitrile.
[0038] According to an embodiment of the present invention,
the styrene-based copolymer may include 10 wt% to 90 wt% of an
aromatic vinyl-based monomer unit and 10 wt% to 90 wt% of a
vinyl cyan-based monomer unit, and as a specific example
20 thereof, may include 20 wt% to 80 wt% or 30 wt% to 70 wt% of
an aromatic vinyl-based monomer unit and 20 wt% to 80 wt% or
30 wt% to 70 wt% of a vinyl cyan-based monomer unit, and within
this range, the graft copolymer has excellent dispersibility,
and thus have excellent mechanical properties and physical
25 property balance.
11
[0039] According to an embodiment of the present invention,
the base resin may include 10 wt% to 50 wt% of a graft copolymer
and 50 wt% to 90 wt% of a styrene-based copolymer, and as a
specific example, may include 10 wt% to 40 wt% or 20 wt% to 40
5 wt% of a graft copolymer and 60 wt% to 90 wt% or 60 wt% to 80
wt% of a styrene-based copolymer, and within this range, the
base resin provide excellent mechanical properties. In
addition, the graft copolymer and the styrene-based copolymer
each include an aromatic vinyl-based monomer unit and a vinyl
10 cyan-based monomer unit, and when the types of the aromatic
vinyl-based monomer unit and the vinyl cyan-based monomer unit
forming each copolymer are the same, the units are mixed and
dispersed as the same component in an extrusion process of a
resin composition, and thus in an actual resin composition and
15 a molded article molded therefrom, a rubber polymer may be
present in a dispersed form in a matrix formed of the aromatic
vinyl-based monomer unit and the vinyl cyan-based monomer unit.
Therefore, the amount of each of the graft copolymer and the
styrene-based copolymer in the base resin may be identified
20 from a total amount of the aromatic vinyl-based monomer unit
and the vinyl cyan-based monomer unit, and the amount of the
rubber polymer in the base resin.
[0040] As described above, unlike the graft copolymer and the
styrene-based copolymer according to the present invention, a
25 resin having a carbon main backbone, such as a polycarbonate
12
resin, easily forms char through a phosphorus-based flame
retardant, making the phosphorus-based flame retardant easy to
be applicable, but for the graft copolymer according to the
present invention, the graft copolymer alone is not able to
5 form char through a phosphorus-based flame retardant, thereby
requiring a charring agent. However, the addition of a
charring agent may deteriorate the thermal stability of the
graft copolymer, and particularly, the charring agent is highpriced
to have reduced price competitiveness, causing a
10 decrease in productivity.
[0041] Meanwhile, the base resin according to the present
invention is designed not to require a charring agent,
particularly a carbon-based charring agent. Accordingly, the
base resin may further include an additional resin component
15 for imparting other properties as needed, in addition to the
graft copolymer and the styrene-based copolymer, but in this
case, the additional resin component does not indicate a
carbon-based charring agent.
[0042] According to an embodiment of the present invention,
20 in a resin that is not able to directly form char through a
phosphorus-based flame retardant, such as the base resin, the
phosphorus-based flame retardant composition may enable
charring for the base resin without adding a charring agent,
particularly a carbon-based charring agent, thereby imparting
25 flame retardancy.
13
[0043] According to an embodiment of the present invention,
the phosphorus-based flame retardant composition may include
Mn+(diethylphosphinate)-
n (M is a metal having an oxidation
number of 2 to 5, and n is an integer selected from 2 to 5)
5 and ammonium polyphosphate. It is known that, in this case,
Mn+(diethylphosphinate)-
n above (M is a metal having an
oxidation number of 2 to 5, and n is an integer selected from
2 to 5) may be used as one type of phosphorus-based flame
retardant, and also the ammonium polyphosphate may be used as
10 one type of flame retardant synergist or flame retardant aid.
However, in the related art, forming char is not achievable
using a graft copolymer and/or a styrene-based copolymer
together with a phosphorus-based flame retardant, and thus, in
order to substantially apply a phosphorus-based flame
15 retardant to a base resin including a graft copolymer,
particularly an ABS copolymer as in the present invention, as
described above, it was required to include a carbon-based
charring agent such as a polyester resin or the like, which is
capable of forming char with a phosphorus-based flame
20 retardant. In addition, even when both the carbon-based
charring agent and the phosphorus-based flame retardant are
included, char is not sufficiently formed depending on the
type of carbon-based charring agent and phosphorus-based flame
retardant, thereby failing to obtain flame retardancy, and
25 accordingly, using a flame-retardant synergist or a flame
14
retardant aid has been suggested, but even in such a case,
when a charring agent, a phosphorus-based flame retardant, and
a flame retardant synergist are not suitably induced in
combination, char is not easily formed, and thus, flame
5 retardancy is not achieved.
[0044] On the other hand, a phosphorus-based flame retardant
composition according to the present invention satisfies a
predetermined composition in a resin composition with respect
to a base resin, and when included in a predetermined amount,
10 self-charring is achievable and when exposed to flames or fire,
thereby imparting flame retardancy to the resin composition.
That is, a resin composition of the present invention including
the phosphorus-based flame retardant composition according to
the present invention may form char without adding a charring
15 agent when exposed to flames or fire. As a specific example,
when the resin composition is exposed to flames or fire,
polyphosphate derived from ammonium polyphosphate of the
phosphorus-based flame retardant composition, and metal ions
(Mn+) derived from Mn+(diethylphosphinate)-
n may form
20 metallosupramolecular.
[0045] As a more specific example, when M is aluminum (Al),
metallosupramolecular may be formed through a reaction as in
Scheme 1 below, and in this case, the formed
metallosupramolecular may be char.
25 [0046] [Scheme 1]
15
[0047] In this case, according to an embodiment of the present
invention, in order to form metallosupramolecular through the
reaction as in Scheme 1, it is important to control the
composition of Mn+(diethylphosphinate)-
5 n (M is a metal having
an oxidation number of 2 to 5, and n is an integer selected
from 2 to 5) and ammonium polyphosphate. According to an
embodiment of the present invention, the phosphorus-based
flame retardant composition may include 30 wt% to 70 wt% of
Mn+(diethylphosphinate)-
10 n (M is a metal having an oxidation
number of 2 to 5, and n is an integer selected from 2 to 5),
and 30 wt% to 70 wt% of ammonium polyphosphate, and as a
specific example, may include 40 wt% to 60 wt% or 45 wt% to 55
wt% of Mn+(diethylphosphinate)-
n (M is a metal having an
15 oxidation number of 2 to 5, and n is an integer selected from
2 to 5) and 40 wt% to 60 wt% or 45 wt% to 55 wt% of ammonium
polyphosphate, and when the resin composition is exposed to
16
flames or fire within this range, flame retardancy through
self-charring is achievable at a maximum level.
[0048] In addition, even when the metallosupramolecular is
formed through the reaction as in Scheme 1, if an absolute
5 amount of metallosupramolecular is not sufficiently secured,
the base resin is not entirely covered even with the formed
char, and accordingly, flame retardancy is not achievable, and
thus, securing the absolute amount of the phosphorus-based
flame retardant composition itself is critical. Accordingly,
10 the resin composition according to the present invention may
include 25 to 50 parts by weight, 25 to 45 parts by weight, or
28 to 40 parts by weight of the phosphorus-based flame
retardant composition, with respect to 100 parts by weight of
the base resin, and within this range, deterioration in
15 mechanical properties of the resin composition may be
prevented, and flame retardancy may be achieved at a maximum
level.
[0049] According to an embodiment of the present invention,
Mn+(diethylphosphinate)-
n above (M is a metal having an
20 oxidation number of 2 to 5, and n is an integer selected from
2 to 5) is a phosphorus-based flame retardant that may include
metal ions having an oxidation number of 2 to 5. In this case,
when the metal ions are monovalent, the reaction as in Scheme
1 is not induced when the resin composition is exposed to
25 flames or fire, and thus the metal ions are required to be
17
metal ions having at least an oxidation number of 2.
[0050] According to an embodiment of the present invention,
M above may be a metal having an oxidation number of 2 to 5,
and specifically, may be a white metal having an oxidation
5 number of 2 to 5, and more specifically, may be at least one
selected from the group consisting of zinc (Zn), tin (Sn),
calcium (Ca), magnesium (Mg), aluminum (Al), scandium (Sc),
cerium (Ce), zirconium (Zr), hafnium (Hf), antimony (Sb), and
tantalum (Ta).
10 [0051] According to an embodiment of the present invention,
the higher the oxidation number of the metal, the more the
reaction between the metal ions and ammonium polyphosphate as
shown in Scheme 1, making self-charring easy, and accordingly,
M above may be a metal having an oxidation number of 3 to 5,
15 specifically, may be a white metal having an oxidation number
of 3 to 5, and more specifically, may be at least one selected
from the group consisting of tin (Sn), aluminum (Al), scandium
(Sc), cerium (Ce), zirconium (Zr), hafnium (Hf), antimony (Sb),
and tantalum (Ta).
20 [0052] According to an embodiment of the present invention,
the resin composition may include the base resin and the
phosphorus-based flame retardant composition, and thus have a
flame retardant rating of V-1 or higher according to UL-94 V
Test. In this case, in the flame retardancy test by UL-94 V
25 Test, specimens are directly exposed to flames, and thus, even
18
when the resin composition has the same composition, the
thinner the specimens, the harder to ensure flame retardancy,
and the thicker the specimens, the greater the flame
retardancy. Accordingly, in order for the resin composition
5 to sufficiently secure flame retardancy, flame retardancy
needs to be high even at a thin state, and according to an
embodiment of the present invention, the resin composition may
have a flame retardant rating of V-1 or higher at a thickness
of 1.5 mm according to UL-94 V Test. In this case, "V-1 or
10 higher" indicates that ratings of V-0 and V-1 are included.
[0053] According to an embodiment of the present invention,
the resin composition may have a flame retardant rating of V-
0 at a thickness of 2.0 mm, 2.5 mm, and 3.0 mm according to
UL-94 V Test.
15
[0054] In addition, the present invention provides a molded
article molded from the resin composition.
[0055] According to an embodiment of the present invention,
the molded article may be extruded and injection molded from
20 the resin composition, and may be applied to product groups
requiring both mechanical properties and flame retardancy, and
specific examples may be interior and exterior materials for
vehicles, office equipment, and parts for various
electrical/electronic products.
25
19
[0056] Hereinafter, embodiments of the present invention will
be described in detail to make sure that those skilled in the
art easily implement the present invention. However, the
present invention may be modified into other various forms,
5 and is not limited to the embodiments described herein.
Examples and Comparative Examples
[0057] The following components in an amount indicated in
Tables 1 and 2 were mixed with a lubricant and a stabilizer to
10 prepare a resin composition.
[0058] (1) Base resin: ABS resin (DP270 from LG Chem) as a
graft copolymer and SAN resin (90HR from LG Chem) as a styrenebased
copolymer were mixed in the amounts indicated in the
tables.
[0059] (2-1) Mn+(diethylphosphinate)-
15 n: Aluminum
diethylphosphinate (Al DEP), OP1240 from Clariant
[0060] (2-2) Mn+(diethylphosphinate)-
n: Zinc
diethylphosphinate (Zn DEP), OP950 from Clariant
[0061] (3) Ammonium polyphosphate (APP): APP from LS Chem
20
Experimental examples
[0062] Resin compositions prepared in Examples and
Comparative Examples were extruded at 220 °C using a twinscrew
extruder to prepare pellets, and then specimens were
25 injected at 210 °C, and flame retardancy and heat deflection
20
temperature were measured through the following method and are
shown in Table 1.
[0063] In addition, particles of aluminum diethylphosphinate
in a phosphorus-based flame retardant composition blended in
5 the resin composition were taken using a scanning electron
microscope and are shown in FIG. 1; particles of ammonium
polyphosphate were taken using with a scanning electron
microscope and are shown in FIG. 2; a surface of the resin
composition according to Example 2 after burning was taken
10 using a scanning electron microscope and is shown in FIG 3;
and results of element analysis of a surface of the resin
composition according to Example 2 after burning, using EDS
(Energy Dispersive X-ray Spectroscopy) are shown in Table 2
below.
15
[0064] * Flame retardancy (UL-94 V Test, Vertical Burning
Test): for specimens having a thickness of 1.5 mm, 2.0 mm, 2.5
mm, and 3.0 mm, according to standard measurement UL-94,
ratings for each specimen by thickness were divided into V-0,
20 V-1 and V-2 and indicated, and the tendency of flame retardancy
according to the amounts and composition of the phosphorusbased
flame retardant compositions are schematically shown in
FIGS. 4 and 5.
[0065] * Heat Deflection Temperature (°C): for specimens of 5
25 inch X 1/2 inch X 1/4 inch, according to ASTM D648, conditions
21
were set to a core load of 1.82 MPa and a heating temperature
of 2 °C/min in oil bath to measure temperatures at which the
specimens were deflected by 0.01 inch.
5 [0066] 【Table 1】
Item Examples Comparative Examples
1 2 3 1 2 3 4 5
Graft
copolymer
(Part
s by
weigh
t)
30 30 30 30 30 30 30 30
Styrenebased
copolymer
(Part
s by
weigh
t)
70 70 70 70 70 70 70 70
Al DEP (Part
s by
weigh
t)
14 17 20 11 3 10 24 31
APP (Part
s by
weigh
t)
14 17 20 11 31 24 10 3
Flame
retardancy
(Thickness)
1.5 mm V-1 V-0 V-0 NG NG NG NG NG
2.0 mm V-0 V-0 V-0 V-2 V-2 V-2 V-0 V-1
2.5 mm V-0 V-0 V-0 V-2 V-2 V-1 V-0 V-1
3.0 mm V-0 V-0 V-0 V-1 V-1 V-1 V-0 V-0
Heat
deflection
temperature
(°C) 87.
4
88.
3
88.
9
86.
6
84.
0
86.
1
88.
7
90.
2
[0067] 【Table 2】
Element Weight% Atomic%
C 62.63 72.56
O: 25.72 22.37
22
Al 1.37 0.71
P 10.28 4.36
Totals 100.00 100.00
[0068] As shown in Table 1 above, it was confirmed that, for
a base resin including a graft copolymer and a styrene-based
copolymer, the resin composition according to the present
5 invention enabled self-charring only through the composition
of a phosphorus-based flame retardant composition including a
phosphorus-based flame retardant without adding a carbon-based
charring agent (see FIGS. 1 to 3), thereby ensuring a flame
retardant rating of V-1 or higher, that is, V-1 and V-0 even
10 at a thickness of 1.5 mm according to UL-94 V Test. In
particular, it was confirmed that when the thicknesses of the
resin composition specimens increased to 2.0 mm, 2.5 mm, and
3.0 mm, it was easier to secure flame retardancy, and thus V-
0 was secured for all of Examples. It is considered that when
15 the resin composition according to the present invention was
exposed to flames or fire, polyphosphate derived from ammonium
polyphosphate and metal ions (Mn+) derived from
Mn+(diethylphosphinate)-
n formed metallosupramolecular (see
FIG. 3 and Table 2), and thus such flame retardancy was
20 achieved.
[0069] In addition, it was confirmed that when the amount of
Mn+(diethylphosphinate)-
n included in the phosphorus-based
flame retardant composition increased, the thermal deflection
23
temperature of the resin composition rose, thereby improving
thermal stability. This is, it is considered that in a resin
composition including a graft copolymer as a thermoplastic
resin, that is, an ABS resin, thermal stability is a property
5 determined by the ABS resin, which is a graft copolymer of a
base resin, and a SAN resin, which is a styrene-based
copolymer, but the thermal stability results from the thermal
property improvements obtained when the metal ions Mn+ of
Mn+(diethylphosphinate)-
n react with the graft copolymer by heat
10 applied to the resin composition in an extrusion process.
[0070] Meanwhile, it was confirmed that in Comparative
Example 1 where the composition of the phosphorus-based flame
retardant composition is satisfied but the amount is not
sufficient, self-charring is not sufficiently done, and thus
15 flame retardancy was not secured at a thickness of 1.5 mm, and
only V-1 was secured at a thickness of 3.0 mm at best even
when the thickness of the specimen was increased (see FIG. 4).
[0071] In addition, it was confirmed that in Comparative
Examples 2 to 5 where the composition of the phosphorus-based
20 flame retardant composition is apart from the composition
defined in the present invention even with the sufficient
amount of the phosphorus-based flame retardant composition,
when the resin composition is exposed to flames or fire, the
ratio for forming metallosupramolecular from
Mn+(diethylphosphinate)-
25 n and ammonium polyphosphate was not
24
secured, and accordingly, self-charring was not sufficiently
done, and thus flame retardancy was not achieved at a thickness
of 1.5 mm, and flame retardancy was achieved only at least at
a thickness of 2.0 mm.
5
[0072] These results confirmed that the resin composition
according to the present invention enables self-charring from
the phosphorus-based flame retardant composition, and thus has
excellent flame retardancy and thermal stability without 10 adding a charring agent.

CLAIMS
1. A resin composition comprising:
25 to 50 parts by weight of a phosphorus-based flame
5 retardant composition, with respect to 100 parts by weight of
a base resin including a graft copolymer containing a rubber
polymer, and a styrene-based copolymer,
wherein the phosphorus-based flame retardant composition
includes 30 wt% to 70 wt% of Mn+(diethylphosphinate)-
n (M is a
10 metal having an oxidation number of 2 to 5, and n is an integer
selected from 2 to 5) and 30 wt% to 70 wt% of ammonium
polyphosphate.
2. The resin composition of claim 1, wherein the graft
15 copolymer comprises a rubber polymer, an aromatic vinyl-based
monomer unit, and a vinyl cyan-based monomer unit.
3. The resin composition of claim 1, wherein the styrenebased
copolymer comprises an aromatic vinyl-based monomer unit
20 and a vinyl cyan-based monomer unit.
4. The resin composition of claim 1, wherein the resin
composition comprises 28 to 40 parts by weight of a phosphorusbased
flame retardant composition, with respect to 100 parts
25 by weight of the base resin.
26
5. The resin composition of claim 1, wherein the phosphorusbased
flame retardant composition comprises 40 wt% to 60 wt%
of Mn+(diethylphosphinate)-
n (M is a metal having an oxidation
number 5 of 2 to 5, and n is an integer selected from 2 to 5)
and 40 wt% to 60 wt% of ammonium polyphosphate.
6. The resin composition of claim 1, wherein M above is at
least one selected from the group consisting of zinc (Zn), tin
10 (Sn), calcium (Ca), magnesium (Mg), aluminum (Al), scandium
(Sc), cerium (Ce), zirconium (Zr), hafnium (Hf), antimony (Sb),
and tantalum (Ta).
7. The resin composition of claim 1, wherein M above is at
15 least one selected from the group consisting of tin (Sn),
aluminum (Al), scandium (Sc), cerium (Ce), zirconium (Zr),
hafnium (Hf), antimony (Sb), and tantalum (Ta).
8. The resin composition of claim 1, wherein the resin
20 composition forms char without containing carbon-based
charring agents when exposed to flames or fire.
9. The resin composition of claim 1, wherein when the resin
composition is exposed to flames or fire, polyphosphate derived
25 from ammonium polyphosphate and metal ions (Mn+) derived from
27
Mn+(diethylphosphinate)-
n form metallosupramolecular.
10. The resin composition of claim 1, wherein the resin
composition has a flame retardant rating of V-1 or higher at
5 a thickness of 1.5 mm according to UL-94 V Test.
11. A molded article molded from the resin composition
according to any one of claims 1 to 10.