WO 2006/104811 PCT/US2006/010462
FLAME RETARDANT THERMOPLASTIC COMPOSITION AND ARTICLES
COMPRISING THE SAME
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation in part of U.S. Patent Application Serial No.
11/091,277 filed on March 28, 2005 which is a continuation in part of U.S. Patent
Application Serial No. 10/881,818 filed on June 29, 2004, which claims priority to
U.S. Provisional Patent Application Serial No. 60/651,470, filed on April 1, 2004, all
of which are incorporated by reference herein.
BACKGROUND OF INVENTION
The disclosure relates to flame retardant additive compositions, In particular, the
invention relates to flame retardant additive compositions useful in a variety of
thermoplastics.
A wide variety of applications require flame retardant thermoplastic compositions, In
addition to being flame retardant, the thermoplastic compositions must often meet a
range of criteria ranging from physical performance to appearance to environmental
impact. In recent years there has been an increasing trend to employ phosphates as the
flame retardant in order to meet many or all of these criteria. While the use of
phosphates has been successful in many instances, highly flammable compositions
have continued to be problematic. Highly flammable thermoplastic compositions
frequently require high levels of phosphate flame retardants to obtain the desired level
of flame retardancy but high levels of phosphate flame retardants can result in
objectionable physical properties such as plate-out and migration. Plate out and
migration refer to the movement of solid and liquid component to the surface of the
article as evidenced in some cases by a powdery or tacky feel to the surface. Other
flame retardants such as magnesium hydroxide and aluminum trihydrate are known
but at high levels frequently have a negative impact on physical properties.
Accordingly there remains a need in the art for a flame retardant composition that
provides excellent flame retardance to thermoplastic compositions and has little or no
negative impact on the physical properties of the thermoplastic composition.
1

WO 2006/104811 PCT/US2006/010462
BRIEF DESCRIPTION OF THE INVENTION
The above described needs are addressed by a flame retardant thermoplastic
composition comprises:
a poly(arylene ether);
an impact modifier;
a polyolefin;
a phosphoric acid salt selected from the group consisting of melamine phosphate,
melamine pyrophosphate, melamine orthophosphate, diammonium phosphate,
monoammonium phosphate, phosphoric acid amide, melamine polyphosphate,
ammonium polyphosphate, polyphosphoric acid amide, and combinations of two or
more of the foregoing;
a metal hydroxide; and
an organic phosphate wherein the amount of phosphoric acid salt by weight is greater
than or equal to the amount of organic phosphate by weight.
In another embodiment, a flame retardant thermoplastic composition comprises:
a poly(arylene ether);
an impact modifier;
a polyolefin;
7 to 20 weight percent of a phosphoric acid salt selected from the group consisting of
melamine phosphate, melamine pyrophosphate, melamine orthophosphate,
diammonium phosphate, monoammonium phosphate, phosphoric acid amide,
melamine polyphosphate, ammonium polyphosphate, polyphosphoric acid amide, and
combinations of two or more of the foregoing;
4 to 15 weight percent of a metal hydroxide; and
2

WO 2006/104811 PCT/US2006/010462
3 to 11 weight percent of an organic phosphate wherein weight percent is with respect
to the combined weight of the poly(arylene ether), impact modifier, polyolefin,
phosphoric acid salt, metal hydroxide and organic phosphate.
In another embodiment, electrical wire comprises:
a conductor, and
a covering disposed over the conductor wherein the covering comprises:
a flame retardant thermoplastic composition comprises:
a poly(arylene ether);
an impact modifier;
a polyolefin;
a phosphoric acid salt selected from the group consisting of melamine phosphate,
melamine pyrophosphate, melamine orthophosphate, diammonium phosphate,
monoammonium phosphate, phosphoric acid amide, melamine polyphosphate,
ammonium polyphosphate, polyphosphoric acid amide, and combinations of two or
more of the foregoing;
a metal hydroxide; and
an organic phosphate wherein the amount of phosphoric acid salt by weight is greater
than or equal to the amount of organic phosphate by weight.
In another embodiment, electrical wire comprises:
a conductor, and
a covering disposed over the conductor wherein the covering comprises:
a flame retardant thermoplastic composition comprises:
a poly(arylene ether);
3

WO 2006/104811 PCT/US2006/010462
an impact modifier;
a polyolefin;
7 to 20 weight percent of a phosphoric acid salt selected from the group consisting of
melamine phosphate, melamine pyrophosphate, melamine orthophosphate,
diammonium phosphate, monoarnmonium phosphate, phosphoric acid amide,
melamine polyphosphate, ammonium polyphosphate, polyphosphoric acid amide, and
combinations of two or more of the foregoing;
4 to 15 weight percent of a metal hydroxide; and
3 to 11 weight percent of an organic phosphate wherein weight percent is with respect
to the combined weight of the poly(arylene ether), impact modifier, polyolefin,
phosphoric acid salt, metal hydroxide and organic phosphate.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic representation of a cross-section of electrical wire.
Figures 2 and 3 are perspective views of an electrical wire having multiple layers.
Figure 4 is a perspective view of a jacketed wire.
DETAILED DESCRIPTION
The flame retardant additive composition comprises a phosphoric acid salt selected
from the group consisting of melamine phosphate, melamine pyrophosphate,
melamine orthophosphate, ammonium phosphate, phosphoric acid amide, melamine
polyphosphate, ammonium polyphosphate, polyphosphoric acid amide and
combinations of two or more of the foregoing; a metal hydroxide; and an organic
phosphate. The flame retardant additive composition has the advantage of providing
excellent flame retardance at lower levels of organic phosphate than organic
phosphate alone, thus decreasing or eliminating plate-out and migration in
thermoplastic compositions. The flame retardant additive composition can be used
with a wide range of thermoplastics and combinations of thermoplastics to decrease
4

WO 2006/104811 PCT/US2006/010462
the flammability of the thermoplastic and to yield flame retardant thermoplastic
compositions.
In one embodiment the flame retardant additive composition consists essentially of a
phosphoric acid salt selected from the group consisting of melamine phosphate,
melamine pyrophosphate, melamine orthophosphate, ammonium phosphate,
phosphoric acid amide, melamine polyphosphate, ammonium polyphosphate,
polyphosphoric acid amide and combinations of two or more of the foregoing; a metal
hydroxide; and an organic phosphate. "Consisting essentially of as used herein
allows the inclusion of additional components as long as those additional components
do not materially affect the basic and novel characteristics of the flame retardant
additive, such as the ability to provide the same or greater level of flame retardance to
a mermoplastic composition at lower levels of organic phosphate than organic
phosphate alone and/or being essentially free (containing less than 0.05 weight
percent, or, more specifically less than 0.005 weight percent, based on the combined
weight of phosphoric acid salt, metal hydroxide and organic phosphate) of chlorine
and bromine.
In another embodiment the flame retardant additive composition consists of a
phosphoric acid salt selected from the group consisting of melamine phosphate,
melamine pyrophosphate, melamine orthophosphate, monoammonium phosphate,
diammonium phosphate, phosphoric acid amide, melamine polyphosphate,
ammonium polyphosphate, polyphosphoric acid amide, and combinations of two or
more of the foregoing; a metal hydroxide; and an organic phosphate.
As mentioned above, the phosphoric acid salt can be selected from the group
consisting of melamine phosphate (for example, CAS No. 20208-95-1), melamine
pyrophosphate (for example, CAS No. 15541-60-3), melamine orthophosphate (for
example, CAS No. 20208-95-1), monoammonium phosphate (for example, CAS No.
7722-76-1), diammonium phosphate (for example, CAS No. 7783-28-0), phosphoric
acid amide (for example, CAS No. 680-31-9), melamine polyphosphate (for example,
CAS No. 218768-84-4 or 56386-64-2), ammonium polyphosphate (for example, CAS
No. 68333-79-9), polyphosphoric acid amide and combinations of two or more of the
5

WO 2006/104811 PCT/US2006/010462
foregoing phosphoric acid salts. The phosphoric acid salt can be surface coated with
one or more of compounds selected from melamine monomer, melamine resin,
modified melamine resin, guanamine resin, epoxy resin, phenol resin, urethane resin,
urea resin, silicone resin, and the like. The identity of the surface coating, when
present, is typically chosen based upon the identity of the thermoplastic components
of the fire retardant thermoplastic composition. In one embodiment the phosphoric
acid salt comprises melamine polyphosphate.
Phosphoric acid salts are commercially available or can be synthesized by the reaction
of a phosphoric acid with the corresponding amine containing compound as is taught
in the art.
The phosphoric acid salt can be present in the flame retardant additive composition in
an amount of 10 to 40 weight percent, based on the combined weight of phosphoric
acid salt, metal hydroxide and organic phosphate. Within this range the phosphoric
acid salt can be present in an amount greater than or equal to 12, or, more specifically,
greater than or equal to 14, or, even more specifically, greater than or equal to 16
weight percent based on the combined weight of phosphoric acid salt, metal hydroxide
and organic phosphate. Also within this range the phosphoric acid salt can be present
in an amount less than or equal to 35, or, more specifically, less than or equal to 30,
or, even more specifically, less than or equal to 28 weight percent based on the
combined weight of phosphoric acid salt, metal hydroxide and organic phosphate.
In one embodiment, the phosphoric acid salt can be present in the flame retardant
additive composition in an amount of 30 to 60 weight percent, based on the combined
weight of phosphoric acid salt, metal hydroxide and organic phosphate. Within this
range the phosphoric acid salt can be present in an amount greater than or equal to 32,
or, more specifically, greater than or equal to 34, or, even more specifically, greater
than or equal to 36 weight percent based on the combined weight of phosphoric acid
salt, metal hydroxide and organic phosphate. Also within this range the phosphoric
acid salt can be present in an amount less than or equal to 57, or, more specifically,
less than or equal to 55 weight percent based on the combined weight of phosphoric
acid salt, metal hydroxide and organic phosphate.
6

WO 2006/104811 PCT/US2006/010462
Suitable metal hydroxides include all those capable of providing fire retardance, as
well as combinations thereof. The metal hydroxide can be chosen to have
substantially no decomposition during processing of the fire additive composition
and/or flame retardant thermoplastic composition. Substantially no decomposition is
defined herein as amounts of decomposition that do not prevent the fire retardant
additive composition from providing the desired level of fire retardance. Exemplary
metal hydroxides include, but are not limited to, magnesium hydroxide (for example,
CAS No. 1309-42-8), aluminum hydroxide (for example, CAS No. 21645-51-2),
cobalt hydroxide (for example, CAS No. 21041-93-0) and combinations of two or
more of the foregoing. In one embodiment, the metal hydroxide comprises
magnesium hydroxide. In some embodiments the metal hydroxide has an average
particle size less than or equal to 10 micrometers and/or a purity greater than or equal
to 90 weight percent. In some embodiments it is desirable for the metal hydroxide to
contain substantially no water, i.e. a weight loss of less than 1 weight percent upon
drying at 120°C for 1 hour. In some embodiments the metal hydroxide can be coated,
for example, with stearic acid or other fatty acid.
The metal hydroxide can be present in the flame retardant additive composition in an
amount of 10 to 45 weight percent, based on the combined weight of phosphoric acid
salt, metal hydroxide and organic phosphate. Within this range the metal hydroxide
can be present in an amount greater than or equal to 12, or, more specifically, greater
than or equal to 14, or, even more specifically, greater than or equal to 16 weight
percent based on the combined weight of phosphoric acid salt, metal hydroxide and
organic phosphate. Also within this range the metal hydroxide can be present in an
amount less than or equal to 40, or, more specifically, less than or equal to 37, or,
even more specifically, less than or equal to 35 weight percent based on the combined
weight of phosphoric acid salt, metal hydroxide and organic phosphate.
In one embodiment the weight ratio of metal hydroxide to phosphoric acid salt is
greater than or equal to 0.8, or, more specifically, greater than or equal to 1.0.
In another embodiment, the weight ratio of metal hydroxide to phosphoric acid salt is
0.3 to 0.8.
7

WO 2006/104811 PCT/US2006/010462
The organic phosphate can be an aromatic phosphate compound of the formula (IX):

where each R is independently an alkyl, cycloalkyl, aryl, alkyl substituted aryl,
halogen substituted aryl, aryl substituted alkyl, halogen, or a combination of any of the
foregoing, provided at least one R is aryl or alkyl substituted aryl.
Examples include phenyl bisdodecyl phosphate, phenylbisneopentyl phosphate,
phenyl-bis (3,5,5'-tri-methyl-hexyl phosphate), ethyldiphenyl phosphate, 2-ethyl-
hexyldi(p-tolyl) phosphate, bis-(2-ethylhexyl) p-tolylphosphate, tritolyl phosphate,
bis-(2-ethylhexyl) phenyl phosphate, tri-(nonylphenyl) phosphate, di (dodecyl) p-tolyl
phosphate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, 2-
chloroethyldiphenyl phosphate, p-tolyl bis(2,5,5r-trimethylhexyl) phosphate, 2-
ethylhexyldiphenyl phosphate, and the like. In one embodiment the phosphate is one
in which each R is aryl and/or alkyl substituted aryl, such as triphenyl phosphate and
tris(alkyl phenyl) phosphate.
Alternatively, the organic phosphate can be a di- or polyfunctional compound or
polymer having the formula (X), (XI), or (XII) below:


WO 2006/104811 PCT/US2006/010462

including mixtures thereof, in which R1, R3 and R5 are, independently, hydrocarbon;
R2, R4, R6 and R7 are, independently, hydrocarbon or hydrocarbonoxy; X1, X2 and X3
are, independently, halogen; m and r are 0 or integers from 1 to 4, and n and p are
from 1 to 30.
Examples include the bis diphenyl phosphates of resorcinol, hydroquinone and
bisphenol-A, respectively, or their polymeric counterparts.
Methods for the preparation of the aforementioned di- and polyfunctional aromatic
phosphates are described in British Patent No. 2,043,083.
Exemplary organic phosphates include, but are not limited to, phosphates containing
substituted phenyl groups, phosphates based upon resorcinol such as, for example,
resorcinol bis-diphenylphosphate, as well as those based upon bis-phenols such as, for
example, bis-phenol A bis-diphenylphosphate. In one embodiment, the organic
phosphate is selected from tris(butyl phenyl) phosphate (for example, CAS No.
89492-23-9, and 78-33-1), resorcinol bis-diphenylphosphate (for example, CAS No.
57583-54-7), bis-phenol A bis-diphenylphosphate (for example, CAS No. 181028-79-
5), triphenyl phosphate (for example, CAS No. 115-86-6), tris(isopropyl phenyl)
phosphate (for example, CAS No. CAS No. 68937-41-7) and mixtures of two or more
of the foregoing.
The organic phosphate can be present in the flame retardant additive composition in
an amount of 15 to 80 weight percent, based on the total weight of the flame retardant
additive composition. Within this range the organic phosphate can be present in an
amount greater than or equal to 25, or, more specifically, greater than or equal to 30,
9

WO 2006/104811 PCT/US2006/010462
or more specifically, greater than or equal to 35 based on the total weight of the flame
retardant additive composition. Also within this range the organic phosphate can be
present in an amount less than or equal to 75, more specifically, less than or equal to
70, or, even more specifically, less than or equal to 65 based on the total weight of the
flame retardant additive composition.
In one embodiment, the organic phosphate can be present in the flame retardant
additive composition in an amount of 9 to 45 weight percent, based on the total weight
of the flame retardant additive composition. Within this range the organic phosphate
can be present in an amount greater than or equal to 10 weight percent based on the
total weight of the flame retardant additive composition. Also within this range the
organic phosphate can be present in an amount less than or equal to 43, or, more
specifically, less than or equal to 41 weight percent based on the total weight of the
flame retardant additive composition.
In one embodiment when the weight ratio of metal hydroxide to phosphoric acid salt
is greater than 0.8 the fire retardant additive composition can comprise 5 to 30 mole
percent (mol%) phosphorous, 23 to 79 mol% nitrogen, and 7 to 68 mol% metal
hydroxide, based on the total moles of phosphorous, nitrogen and metal hydroxide.
Within the preceding range the phosphorous can be present in an amount greater than
or equal to 6 mol%, or, more specifically, in an amount greater than or equal to 10
mol%. Also within the preceding range the phosphorous can be present in an amount
less than or equal to 28 mol%, or, more specifically in an amount less than or equal to
24 mol%.
Within the preceding range the nitrogen can be present in an amount greater than or
equal to 30 mol%, or, more specifically, in an amount greater than or equal to 40
mol%. Also within the preceding range the nitrogen containing can be present in an
amount less than or equal to 70 mol%, or, more specifically in an amount less than or
equal to 60 mol%.
Within the preceding range the metal hydroxide can be present in an amount greater
than or equal to 15 mol%, or, more specifically, in an amount greater than or equal to
10

WO 2006/104811 PCT/US2006/010462
20 mol%. Also within the preceding range the metal hydroxide can be present in an
amount less than or equal to 55 mol%, or, more specifically in an amount less than or
equal to 45 mol%.
The components of the flame retardant additive composition can be mixed together to
form an additive composition. Alternatively, as discussed in detail below, the
components can be blended with a thermoplastic to form a masterbatch or added
individually, simultaneously, sequentially or a combination thereof, to the
thermoplastic composition during or after its formation.
The flame retardant thermoplastic composition comprises a thermoplastic resin in
addition to the flame retardant additive composition. The thermoplastic resin can be
selected from the group consisting of poly(arylene ether); poly(arylene ether) blends;
styrenic polymers and copolymers and their blends; polyolefin; polyolefin blends;
polyethers and their blends; and polyamides and their blends. Exemplary poly(arylene
ether) blends include compatibilized poly(arylene ether)/polyamide blends;
poly(arylene ether)/polyolefin blends such as poly(arylene ether)/olefinic
thermoplastics vulcanizates, poly(arylene ether)/ethylene-propylene rubber, and
poly(arylene/ether)/EPDM; poly(arylene ether)/styrenic polymer or copolymer blends;
impact modified poly(arylene ether) blends; and poly(arylene ether)/thermoplastic
polyurethane blends. A flame retardant thermoplastic composition is herein defined
as a thermoplastic composition having, according to the procedure of Underwriter's
Laboratory Bulletin 94 entitled "Tests for Flammability of Plastic Materials, UL94"
(UL94) at a thickness of 3.2 millimeters, a V2 rating or better. In one embodiment the
flame retardant thermoplastic composition has a VI rating or better. In another
embodiment the flame retardant thermoplastic composition has a V0 rating.
In one embodiment the thermoplastic resin comprises poly(arylene ether) and an
impact modifier. The thermoplastic resin may additionally comprise a polyolefin. In
this embodiment the phosphoric acid salt may also be melem polyphosphate or melam
polyphosphate.
In one embodiment, the flame retardant thermoplastic composition has a Durometer
hardness (Shore A), as determined by ASTM D 2240 measured on a specimen having
11

WO 2006/104811 PCT/US2006/010462
a 3 millimeter thickness, greater than or equal to 60. The Shore A hardness can be
greater than or equal to 65 or greater than or equal to 70. The composition may have a
Shore D hardness, as determined by ASTM D 2240 measured on a specimen having a
3 millimeter thickness, of 20 to 60. Within this range the Shore D hardness can be
greater than or equal to 23 or greater than or equal to 26. Also within this range the
Shore D hardness can be less than or equal to 55 or less then or equal to 50.
In some embodiments flame retardant thermoplastic composition has a flexural
modulus, as determined by ASTM D790 using bars with a thickness of 6.4
millimeters (mm), of less than or equal to 1172 megapascals (MPa). The flexural
modulus can be less than or equal to 517 MPa or less than or equal to 482 MPa. A
flame retardant thermoplastic composition with the above described Shore A and
flexural modulus finds use in a variety of applications requiring a flexible material,
particularly wire coating and film, tubes, ducts, electrical insulator, insulation barrier,
insulation breaker plate, wall paper, pipe and other applications where the
combination of flame retardance, softness and flexibility are required.
In one embodiment an electrical wire comprises a covering disposed over a conductor.
The covering comprises the fire retardant thermoplastic composition. The electrical
wire may additionally comprise an adhesion promoting layer disposed between the
electrically conductive wire and the thermoplastic composition.
In one embodiment the flame retardant thermoplastic composition is applied to the
conductor by a suitable method such as extrusion coating to form an electrical wire.
For example, a coating extruder equipped with a screw, crosshead, breaker plate,
distributor, nipple, and die can be used. The melted thermoplastic composition forms
a covering disposed over a circumference of the conductor. Extrusion coating may
employ a single taper die, a double taper die, other appropriate die or combination of
dies to position the conductor centrally and avoid die lip build up.
In one embodiment the covering has a thickness of 0.1 mm to 1.0 mm.
hi some embodiments it may be useful to dry the flame retardant thermoplastic
composition before extrusion coating the wire. Exemplary drying conditions are 60-
12

WO 2006/104811 PCT/US2006/010462
90°C for 2-20 hours. In one embodiment, drying conditions are 7O-85°C for 3-8
hours. Additionally, the flame retardant thermoplastic composition may be filtered
prior to applying it to the conductive wire, typically through a filter having a mesh
size of 30-300. In one embodiment the diameters of the openings in the filter are 175
micrometers to 74 micrometers. A color concentrate or masterbatch may be added to
the flame retardant thermoplastic composition prior to extrusion coating. When a
color concentrate is used it is typically present in an amount less than or equal to 5
weight percent, based on the total weight of the flame retardant thermoplastic
composition. As appreciated by one of skill in the art, the color of the flame retardant
thermoplastic composition prior to the addition of color concentrate may impact the
final color achieved and in some cases it may be advantageous to employ a bleaching
agent and/or color stabilization agents. Bleaching agents and color stabilization
agents are known in the art and are commercially available.
The processing temperature during extrusion coating is generally less than or equal to
320°C, or, more specifically, less than or equal to 300°C, or, more specifically, less
than or equal to 280°C. The processing temperature is greater than or equal to 200°C.
Additionally the processing temperature is greater than or equal to the softening
temperature of the poly(arylene ether).
hi one embodiment the processing temperature during extrusion coating is generally
less than or equal to 290°C, or, more specifically, less than or equal to 280°C, or,
more specifically, less than or equal to 270°C. The processing temperature is greater
than or equal to 200°C. Additionally the processing temperature is greater than or
equal to the softening temperature of the poly(arylene ether).
After extrusion coating the coated wire may be cooled using a water bath, water spray,
air jets or a combination comprising one or more of the foregoing cooling methods.
Exemplary water bath temperatures are 5 to 80°C, or, in some embodiments 5 to
60°C. After cooling the coated wire is wound onto a spool or like device, typically at
a speed of 50 meters per minute (m/min) to 500 m/min, or, more specifically 50
m/min to 300 m/min.
13

WO 2006/104811 PCT/US2006/010462
In one embodiment the composition is applied to a conductor having one or more
intervening layers between the conductor and the covering to form a covering
disposed over the conductor. For instance, an optional adhesion promoting layer may
be disposed between the conductor and covering. In another example the conductor
may be coated with a metal deactivator prior to applying the covering. In another
example the intervening layer comprises a thermoplastic or thermoset composition
that, in some cases, is foamed.
The conductor may comprise a single strand or a plurality of strands. In some cases, a
plurality of strands may be bundled, twisted, braided, or a combination of the
foregoing to form a conductor. Additionally, the conductor may have various shapes
such as round or oblong. Suitable conductors include, but are not limited to, copper
wire, aluminum wire, lead wire, and wires of alloys comprising one or more of the
foregoing metals. The conductor may also be coated with, e.g., tin or silver.
A cross-section of an exemplary electrical wire is seen in Figure 1. Figure 1 shows a
covering, 4, disposed over a conductor, 2. In one embodiment, the covering, 4,
comprises a foamed thermoplastic composition. Perspective views of exemplary
electrical wires are shown in Figures 2 and 3. Figure 2 shows a covering, 4, disposed
over a conductor, 2, comprising a plurality of strands and an optional additional layer,
6, disposed over the covering, 4, and the conductor, 2. In one embodiment, the
covering, 4, comprises a foamed thermoplastic composition. Conductor, 2, can also
comprise a unitary conductor. Figure 3 shows a covering, 4, disposed over a unitary
conductor, 2, and an intervening layer, 6. In one embodiment, the intervening layer, 6,
comprises a foamed composition. Conductor, 2, can also comprise a plurality of
strands. In addition, the covering described herein may be used to form a jacket
surrounding two or more electrical wires wherein the electrical wires comprise a
covering disposed over a conductor. Figure 4 shows a jacket, 8, disposed over a
plurality of covered conductors (electrical wires), 10.
In one embodiment the coating of the coated wire has tensile strength greater than or
equal to 10 MegaPascals (Mpa) and ultimate elongation greater than or equal to 100%
as determined by UL1581. The coated wire can also have flame resistance of VW-1.
14

WO 2006/104811 PCT/US2006/010462
The coated wire is useful for low voltage applications such as direct current electrical
cords, USB cable, audio/visual cable and the like.
In some embodiments the flame retardant thermoplastic composition may have a
tensile strength greater than or equal to 7.0 megapascals and a tensile elongation
greater than or equal to 100%, or, more specifically, greater than or equal to 110%, or,
even more specifically, greater than or equal to 120%. Tensile strength and elongation
are both determined by ASTM D638 on Type I specimens having a thickness of 3.2
millimeters.
In some embodiments the flame retardant thermoplastic composition may have a
tensile strength greater than or equal to 7.0 megapascals and a tensile elongation
greater than or equal to 40%, or, more specifically, greater than or equal to 45%, or,
even more specifically, greater than or equal to 50%. Tensile strength and elongation
are both determined by ASTM D638 on Type I specimens having a thickness of 3.2
millimeters.
As used herein, a "poly(arylene ether)" comprises a plurality of structural units of the
formula (I):

wherein for each structural unit, each Q1 and Q2 is independently hydrogen, primary or
secondary lower alkyl (e.g., an alkyl containing 1 to 7 carbon atoms), phenyl,
haloalkyl, aminoalkyl, alkenylalkyl, alkynylalkyl, hydrocarbonoxy, and aryl. In some
embodiments, each Q1 is independently alkyl or phenyl, for example, C1-4 alkyl, and
each Q2 is independently hydrogen or methyl. The poly(arylene ether) may comprise
molecules having aminoalkyl-containing end group(s), typically located in an ortho
position to the hydroxy group. Also frequently present are tetramethyl
diphenylquinone (TMDQ) end groups, typically obtained from reaction mixtures in
which tetramethyl diphenylquinone by-product is present.
15

WO 2006/104811 PCT/US2006/010462
The poly(arylene ether) can be in the form of a homopolymer; a copolymer; a graft
copolymer; an ionomer; or a block copolymer; as well as combinations comprising at
least one of the foregoing. Poly(arylene ether) includes polyphenylene ether
comprising 2,6-dimethyl-l,4-phenylene ether units optionally in combination with
2,3,6-trimethyl-l,4-phenylene ether units.
The poly(arylene ether) can be prepared by the oxidative coupling of
monohydroxyaromatic compound(s) such as 2,6-xylenol and/or 2,3,6-trimethylphenol.
Catalyst systems are generally employed for such coupling; they can contain heavy
metal compound(s) such as a copper, manganese or cobalt compound, usually in
combination with various other materials such as a secondary amine, tertiary amine,
halide or combination of two or more of the foregoing.
In one embodiment, the poly(arylene ether) comprises a capped poly(arylene ether).
The terminal hydroxy groups can be inactivated by capping with an inactivating
capping agent via an acylation reaction, for example. The capping agent chosen is
desirably one that results in a less reactive poly(arylene ether) thereby reducing or
preventing crosslinking of the polymer chains and the formation of gels or black
specks during processing at elevated temperatures. Suitable capping agents include,
for example, esters of salicylic acid, anthranilic acid, or a substituted derivative
thereof, and the like; esters of salicylic acid, and especially salicylic carbonate and
linear polysalicylates, are preferred. As used herein, the term "ester of salicylic acid"
includes compounds in which the carboxy group, the hydroxy group, or both have
been esterified. Suitable salicylates include, for example, aryl salicylates such as
phenyl salicylate, acetylsalicylic acid, salicylic carbonate, and polysalicylates,
including both linear polysalicylates and cyclic compounds such as disalicylide and
trisalicylide. The preferred capping agents are salicylic carbonate and the
polysalicylates, especially linear polysalicylates. When capped, the poly(arylene
ether) can be capped to any desirable extent up to 80 percent, more specifically up to
90 percent, and even more specifically up to 100 percent of the hydroxy groups are
capped. Suitable capped poly(arylene ether) and their preparation are described in
United States Pat. Nos. 4,760,118 to White et al. and 6,306,978 to Braat et al.
16

WO 2006/104811 PCT/US2006/010462
Capping poly(arylene ether) with polysalicylate is also believed to reduce the amount
of aminoalkyl terminated groups present in the poly(arylene ether) chain. The
aminoalkyl groups are the result of oxidative coupling reactions that employ amines in
the process to produce the poly(arylene ether). The aminoalkyl group, ortho to the
terminal hydroxy group of the poly(arylene ether), can be susceptible to
decomposition at high temperatures. The decomposition is believed to result in the
regeneration of primary or secondary amine and the production of a quinone methide
end group, which may in turn generate a 2,6-dialkyl-l-hydroxyphenyl end group.
Capping of poly(arylene ether) containing aminoalkyl groups with polysalicylate is
believed to remove such amino groups to result in a capped terminal hydroxy group of
the polymer chain and the formation of 2-hydroxy-N,N-alkylbenzamine
(salicylamide). The removal of the amino group and the capping provides a
poly(arylene ether) that is more stable to high temperatures, thereby resulting in fewer
degradative products, such as gels or black specks, during processing of the
poly(controlled distribution arylene ether).
The poly(arylene ether) can be functionalized with a polyfunctional compound such as
a polycarboxylic acid or those compounds having in the molecule both (a) a carbon-
carbon double bond or a carbon-carbon triple bond and b) at least one carboxylic acid,
anhydride, amide, ester, imide, amino, epoxy, orthoester, or hydroxy group. Examples
of such polyfunctional compounds include maleic acid, maleic anhydride, fumaric
acid, and citric acid.
The poly(arylene ether) can have a number average molecular weight of 3,000 to
40,000 grams per mole (g/mol) and a weight average molecular weight of 5,000 to
80,000 g/mol, as determined by gel permeation chromatography using monodisperse
polystyrene standards, a styrene divinyl benzene gel at 40°C and samples having a
concentration of 1 milligram per milliliter of chloroform. The poly(arylene ether) or
combination of poly(arylene ether)s has an initial intrinsic viscosity greater than or
equal to 0.35 dl/g, as measured in chloroform at 25°C. Initial intrinsic viscosity is
defined as the intrinsic viscosity of the poly(arylene ether) prior to melt mixing with
the other components of the composition. As understood by one of ordinary skill in
the art the viscosity of the poly(arylene ether) may be up to 30% higher after melt
17

WO 2006/104811 PCT/US2006/010462
mixing. The percentage of increase can be calculated by (final intrinsic viscosity after
melt mixing - initial intrinsic viscosity before melt mixing)/initial intrinsic viscosity
before melt mixing. Determining an exact ratio, when two initial intrinsic viscosities
are used, will depend somewhat on the exact intrinsic viscosities of the poly(arylene
ether) used and the ultimate physical properties that are desired.
The poly(arylene ether) may have a hydroxy end group content of less than or equal to
6300 parts per million based on the total weight of the poly(arylene ether) (ppm) as
determined by Fourier Transform Infrared Spectrometry (FTIR). In one embodiment
the poly(arylene ether) may have a hydroxy end group content of less than or equal to
3000 ppm, or, more specifically, less than or equal to 1500 ppm, or, even more
specifically, less than or equal to 500 ppm.
The poly(arylene ether) can be substantially free of visible particulate impurities. In
one embodiment, the poly(arylene ether) is substantially free of particulate impurities
greater than 15 micrometers. As used herein, the term "substantially free of visible
particulate impurities" means that a ten gram sample of the poly(arylene ether)
dissolved in fifty milliliters of chloroform (CHCI3) exhibits fewer than 5 visible
specks when viewed in a light box. Particles visible to the naked eye are typically
those greater than 40 micrometers in diameter. As used herein, the term
"substantially free of particulate impurities greater than 15 micrometers" means that
of a forty gram sample of poly(arylene ether) dissolved in 400 milliliters of CHC13, the
number of particulates per gram having a size of 15 micrometers is less than 50, as
measured by a Pacific Instruments ABS2 analyzer based on the average of five
samples of twenty milliliter quantities of the dissolved poly(arylene ether) that is
allowed to flow through the analyzer at a flow rate of one milliliter per minute (plus or
minus five percent).
In one embodiment the poly(arylene ether) can be present in the flame retardant
thermoplastic composition in an amount of 5 to 65 weight percent, based on the total
weight of the flame retardant thermoplastic composition. Within this range the
poly(arylene ether) can be present in an amount greater than or equal to 10, or, more
specifically, greater than or equal to 15 weight percent, or, even more specifically,
18

WO 2006/104811 PCT/US2006/010462
greater than or equal to 17 weight percent, based on the total weight of the flame
retardant thermoplastic composition. Also within this range the poly(arylene ether)
can be present in an amount less than or equal to 50, or, more specifically, less than or
equal to 45, or, even more specifically, less than or equal to 40 weight percent based
on the total weight of the flame retardant thermoplastic composition.
Particularly suitable thermoplastic impact modifiers are block copolymers, for
example, A-B diblock copolymers and A-B-A triblock copolymers having of one or
two alkenyl aromatic blocks A, which are typically styrene blocks or blocks of a
copolymer of styrene and one or more 1,3-cyclodienes such as 1,3-cyclohexadiene,
and a rubber block, B, which can be a polymer or copolymer block resulting from the
polymerization of a conjugated diene such as butadiene, a 1,3-cyclodiene such as 1,3-
cyclohexadiene or a combination of conjugated dienes or a copolymer block resulting
from the copolymerization of a conjugated diene and an alkenyl aromatic compound.
The copolymer block itself can be a block copolymer. The repeating units resulting
from the polymerization of the conjugated dienes can be partially or completely
hydrogenated. After a repeating unit resulting from the polymerization of a
conjugated diene has been hydrogenated the repeating unit may be described as an
alkene unit. Each occurrence of alkenyl aromatic block A may have a molecular
weight which is the same or different than other occurrences of alkenyl aromatic block
A. Similarly each occurrence of rubber block B may have a molecular weight which
is the same or different than other occurrences rubber block B.
Exemplary A-B and A-B-A copolymers include, but are not limited to, polystyrene-
polybutadiene, polystyrene-poly(ethylene-propylene), polystyrene-polyisoprene,
poly(a-methylstyrene)-polybutadiene, polystyrene-polybutadiene-polystyrene (SBS),
polystyrene-poly(ethylene-propylene)-polystyrene, polystyrene-poly(ethylene-
butylene)-polystyrene, polystyrene-(ethylene-butylene/styrene copolymer)-
polystyrene, polystyrene-polyisoprene-polystyrene, and poly(alpha-methylstyrene)-
polybutadiene-poly(alpha-methylstyrene), as well as the selectively hydrogenated
versions thereof, and the like. Mixtures of the aforementioned block copolymers are
also useful. Such A-B and A-B-A block copolymers are available commercially from
a number of sources, including Phillips Petroleum under the trademark SOLPRENE,
19

WO 2006/104811 PCT/US2006/010462
Kraton Polymers Ltd. under the trademark KRATON, Dexco under the trademark
VECTOR, and Kuraray under the trademark SEPTON.
In one embodiment the impact modifier comprises impact modifiers having varying
amounts of alkenyl aromatic units. For example a combination of a polystyrene-
poly(ethylene-butylene)-polystyrene having a polystyrene content of 10 weight percent
to 20 weight percent, based on the total weight of the block copolymer and a
polystyrene-poly(ethylene-butylene)-polystyrene having a polystyrene content of 25
weight percent to 50 weight percent, based on the total weight of the block copolymer.
In one embodiment the impact modifier comprises a block copolymer having (A) one
or more blocks comprising repeating alkenyl aromatic units and (C) one or more
blocks that is a controlled distribution copolymer block. Block A may further
comprise alkene units having 2 to 15 carbons as long as the quantity of alkenyl
aromatic units exceeds the quantity of alkene units.
In one embodiment the impact modifier comprises two block copolymers, one of
which is a block copolymer comprising a controlled distribution copolymer block.
A controlled distribution copolymer is a copolymer of alkenyl aromatic units and
alkylene units having 2 to 15 carbons such as ethylene, propylene, butylene or
combinations of two or more of the foregoing. The C block may comprise some
unsaturated carbon-carbon bonds. "Controlled distribution copolymer block" refers to
a molecular structure having the following attributes: (1) terminal regions adjacent to
A blocks that are rich in (i.e., having a greater than an average amount of) alkylene
units; (2) one or more regions not adjacent to the A blocks that are rich in (i.e., having
a greater than average amount of) alkenyl aromatic units; and (3) an overall structure
having relatively low alkenyl aromatic blockiness.
For the purposes hereof, "rich in" is defined as greater than the average amount,
preferably at least 5% greater than the average amount.
Low blockiness can be shown by either the presence of only a single glass transition
temperature (Tg) for the copolymer block, when analyzed using differential scanning
20

WO 2006/104811 PCT/US2006/010462
calorimetry ("DSC") thermal methods or via mechanical methods, or shown by proton
nuclear magnetic resonance ("H-NMR") methods.
The term "alkenyl aromatic blockiness", as measured by those skilled in the art using
proton NMR (H-NMR), is defined to be the proportion of alkenyl aromatic units in
the polymer having two nearest alkenyl aromatic neighbors on the polymer chain to
the total number of alkenyl aromatic units. The alkenyl aromatic blockiness can be
determined after using H-NMR to measure two experimental quantities. First, the
total number of alkenyl aromatic units (i.e. arbitrary instrument units which cancel out
when ratioed) is determined by integrating the total aromatic signal in the H-NMR
spectrum from 7.5 to 6.2 ppm and dividing this quantity by the number of aromatic
hydrogens on each aromatic ring (5 in the case of styrene). Second, the blocky alkenyl
aromatic units are determined by integrating that portion of the aromatic signal in the
H-NMR spectrum from the signal minimum between 6.88 and 6.80 to 6.2 ppm and
dividing this quantity by 2 to account for the 2 ortho hydrogens on each blocky aryl
alkylene aromatic ring. The assignment of this signal to the two ortho hydrogens on
the rings of the alkenyl aromatic units which have two alkenyl aromatic nearest
neighbors was reported in F. A. Bovey, High Resolution NMR of Macromolecules
(Academic Press, New York and London, 1972), chapter 6. The alkenyl aromatic
blockiness is simply the percentage of blocky alkenyl aromatic units to total alkenyl
aromatic units: Blocky %=100 times (Blocky Styrene Units/Total Styrene Units).
The potential for blockiness can also be inferred from measurement of the UV-visible
absorbance at a wavelength range suitable for the detection of polystyryllithium end
groups during the polymerization of the C block. A sharp and substantial increase in
this value is indicative of a substantial increase in polystyryllithium chain ends. This
will only occur if the conjugated diene concentration drops below the level necessary,
typically a concentration of 0.1% wt of diene, to maintain controlled distribution
polymerization. Any alkenyl aromatic monomer that is present at this point will add
in a blocky fashion.
21

WO 2006/104811 PCT/US2006/010462
In one embodiment the blocky % is less than or equal to 40. In one embodiment, the
block copolymer has an alkenyl aromatic content of ten weight percent to forty weight
percent, and the blocky % is less than or equal to 10 but greater than 0.
In one embodiment the block copolymer comprises an alkenyl aromatic/alkylene
controlled distribution copolymer block, wherein the proportion of alkenyl aromatic
units increases gradually to a maximum near the middle or center of the block and
then decreases gradually until the opposite end of the polymer block is reached.
In one embodiment the first 15 to 25% and the last 15 to 85% of the alkenyl aromatic
/alkylene controlled distribution copolymer block are alkylene rich, with the
remainder considered to be alkenyl aromatic rich. The term "alkylene rich" means that
the region has a measurably higher ratio of alkylene to alkenyl aromatic than the
center region. For the controlled distribution copolymer block the weight percent of
alkenyl aromatic in each controlled distribution copolymer block can be 10 weight
percent to 75 weight percent, or more specifically 15 weight percent to 50 weight
percent, based on the total weight of the controlled distribution copolymer block.
Anionic, solution copolymerization to form the controlled distribution copolymers can
be carried out using known methods and materials. In general, the copolymerization
is attained anionically, using known selections of adjunct materials, including
polymerization initiators, solvents, promoters, and structure modifiers, but as a key
feature, in the presence of a distribution agent. An exemplary distribution agent is a
non-chelating ether. Examples of such ether compounds are cyclic ethers such as
tetrahydrofuran and tetrahydropyrane and aliphatic monoethers such as diethyl ether
and dibutyl ether. Production of block copolymers comprising a controlled
distribution copolymer block is taught in United States Patent Application No.
2003/0176582.
One feature of the impact modifier comprising an alkenyl aromatic block and a
controlled distribution copolymer block is that it can have two or more Tg's, the lower
being the single Tg of the controlled distribution copolymer block. The controlled
distribution copolymer block Tg is typically greater than or equal to -60 °C, or, more
specifically, greater than or equal to -40°C. The controlled distribution copolymer
22

WO 2006/104811 PCT/US2006/010462
block Tg is typically less than or equal to +30°C, or, even more specifically, less than
or equal to +10 °C. The second Tg, that of the alkenyl aromatic block, is +80 ° C to
+110°C, or, more specifically, +80 °C to +105 °C.
Each A block may have an average molecular weight of 3,000 to 60,000 g/mol and
each C block may have an average molecular weight of 30,000 to 300,000 g/mol as
determined by gel permeation chromatography using polystyrene standards. The total
amount of alkenyl aromatic units is 15 to 75 weight percent, based on the total weight
of the block copolymer. Exemplary block copolymers are further disclosed in U.S.
Patent Applications Nos. 2003/181584, 2003/0176582, and 2004/0138371 and are
commercially available from Kraton Polymers under the trademark KRATON.
Exemplary grades are A-RP6936 and A-RP6935.
In one embodiment, the impact modifier can be functionalized in a number of ways.
One way is by treatment with an unsaturated monomer having one or more functional
groups or their derivatives, such as carboxylic acid groups and their salts, anhydrides,
esters, imide groups, amide groups, and acid chlorides. Exemplary monomers include
maleic anhydride, maleic acid, fumaric acid, and their derivatives. A further
description of functionalizing such block copolymers can be found in U.S. Patent No.
4,578,429 and in U.S. Pat. No. 5,506,299. In another manner, the impact modifier can
be functionalized by grafting silicon or boron containing compounds to the polymer as
taught in U.S. Patent No. 4,882,384. In still another manner, the impact modifier can
be contacted with an alkoxy-silane compound to form a silane-modified block
copolymer. In yet another manner, the impact modifier can be functionalized by
grafting at least one ethylene oxide molecule to the polymer as taught in U.S. Patent
No. 4,898,914, or by reacting the polymer with carbon dioxide as taught in U.S. Patent
No. 4,970,265. Still further, the impact modifier can be metallated as taught in U.S.
Patent Nos. 5,206,300 and 5,276,101, wherein the polymer is contacted with an alkali
metal alkyl, such as a lithium alkyl. And still further, the impact modifier can be
functionalized by grafting sulfonic groups to the polymer as taught in U.S. Patent No.
5,516,831.
23

WO 2006/104811 PCT/US2006/010462
In some embodiments the impact modifier is present in an amount sufficient to attain
a combination of softness (as described above by Shore A and Shore D) and flexural
modulus (as described above). The impact modifier can be present in the flame
retardant thermoplastic composition in an amount of 5 to 55 weight percent, based on
the total weight of the flame retardant thermoplastic composition. Within this range
the impact modifier can be present in an amount greater than or equal to 8, or, more
specifically, greater than or equal to 12, or, even more specifically, greater than or
equal to 15 weight percent based on the total weight of the flame retardant
thermoplastic composition. Also within this range the impact modifier can be present
in an amount less than or equal to 50, or, more specifically, less than or equal to 46,
or, even more specifically, less than or equal to 42 weight percent based on the total
weight of the flame retardant thermoplastic composition.
The flame retardant thermoplastic composition may optionally comprise a polyolefin.
Polyolefins which can be included are of the general structure: CnH2n and include, for
example, polyethylene, polybutene, polypropylene, polyisobutylene, and combinations
of one or more of the foregoing, with preferred homopolymers being polybutene,
polyethylene, LDPE (low density polyethylene), LLDPE (linear low density
polyethylene), HDPE (high density polyethylene), MDPE (medium density
polyethylene), polypropylene, and combinations of two or more of the foregoing.
Polyolefin resins of this general structure and methods for their preparation are well
known in the art and are described for example in U.S. Patent Nos. 2,933,480,
3,093,621, 3,211,709, 3,646,168, 3,790,519, 3,884,993, 3,894,999, 4,059,654,
4,166,055 and 4,584,334.
Copolymers of polyolefins may also be used such as copolymers of ethylene and alpha
olefins having three to twelve carbons or functionalized alpha olefins having three to
twelve carbons. Exemplary alpha olefins include propylene and 4-methylpentene-l,
1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and 3-hexene etc.
Exemplary functionalized alpha olefins include olefins such as ethylene functionalized
with vinyl acetate, ethylene functionalized with acrylate and ethylene functionalized
with substituted acrylate groups. Copolymers of ethylene and C3-C10 monoolefins and
non-conjugated dienes, herein referred to as EPDM copolymers, are also suitable.
24

WO 2006/104811 PCT/US2006/010462
Examples of suitable C3-C10 monoolefins for EPDM copolymers include propylene,
1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene and 3-hexene. Suitable
dienes include 1,4 hexadiene and monocylic and polycyclic dienes. Mole ratios of
ethylene to other C3-C10 monoolefin monomers can range from 95:5 to 5:95 with
diene units being present in the amount of from 0.1 to 10 mol%. EPDM copolymers
can be functionalized with an acyl group or electrophilic group for grafting onto the
polyphenylene ether as disclosed in U.S. Patent No. 5,258,455.
In one embodiment the flame retardant thermoplastic composition comprises a liquid
polyolefin, or, more specifically, a liquid polybutene. "Liquid" as used herein with
reference to a polyolefin is defined as having a viscosity less than or equal to 700
centiStokes (cSt), or, more specifically, less than or equal to 300 cSt, as determined by
ASTM D445 at 100°C. The viscosity of the polyolefin is greater than or equal to
70cSt as determined by ASTM D445 at 100°C.
The polyolefin, when used, can be present in the flame retardant thermoplastic
composition in an amount of 2 to 50 weight percent, based on the total weight of the
flame retardant thermoplastic composition. Within this range the polyolefin can be
present in an amount greater than or equal to 2, or, more specifically, greater than or
equal to 5, or, even more specifically, greater than or equal to 7 weight percent based
on the total weight of the flame retardant thermoplastic composition. Also within this
range the polyolefin can be present in an amount less than or equal to 40, or, more
specifically, less than or equal to 30, or, even more specifically, less than or equal to
25 weight percent based on the total weight of the flame retardant thermoplastic
composition.
The flame retardant thermoplastic composition may optionally comprise a
poly(alkenyl aromatic) resin. The term "poly(alkenyl aromatic) resin" as used herein
includes polymers prepared by methods known in the art including bulk, suspension,
and emulsion polymerization, which contain at least 25% by weight of structural units
derived from an alkenyl aromatic monomer of the formula
25

WO 2006/104811 PCT/US2006/010462

wherein R1 is hydrogen, C1-C8 alkyl, or halogen; Z1 is vinyl, halogen or C1-C8 alkyl;
and p is 0 to 5. Preferred alkenyl aromatic monomers include styrene, chlorostyrene,
and vinyltoluene. The poly(alkenyl aromatic) resins include homopolymers of an
alkenyl aromatic monomer; non-elastomeric random, radial and tapered block
copolymers of an alkenyl aromatic monomer, such as styrene, with one or more
different monomers such as acrylonitrile, butadiene, alpha-methylstyrene,
ethylvinylbenzene, divinylbenzene and maleic anhydride; and rubber-modified
poly(alkenyl aromatic) resins comprising blends and/or grafts of a rubber modifier and
a homopolymer of an alkenyl aromatic monomer (as described above), wherein the
rubber modifier can be a polymerization product of at least one C4-C10 nonaromatic
diene monomer, such as butadiene or isoprene, and wherein the rubber-modified
poly(alkenyl aromatic) resin comprises 98 to 70 weight percent of the homopolymer
of an alkenyl aromatic monomer and 2 to 30 weight percent of the rubber modifier.
Rubber-modified polystyrenes are also known as high-impact polystyrenes or HIPS.
In one embodiment the rubber-modified poly(alkenyl aromatic) resin comprises 88 to
94 weight percent of the homopolymer of an alkenyl aromatic monomer and 6 to 12
weight percent of the rubber modifier.
The composition may comprise the poly(alkenyl aromatic) resin, when present, in an
amount of 1 to 46 weight percent, based on the total weight of the flame retardant
thermoplastic composition. Within this range the poly(alkenyl aromatic) resin can be
present in an amount greater than or equal to 2, or, more specifically, greater than or
equal to 4, or, even more specifically, greater than or equal to 6 weight percent based
on the total weight of the flame retardant thermoplastic composition. Also within this
range the poly(alkenyl aromatic) resin can be present in an amount less than or equal
to 25, or, more specifically, less than or equal to 20, or, even more specifically, less
26

WO 2006/104811 PCT/US2006/010462
than or equal to 15 weight percent based on the total weight of the flame retardant
thermoplastic composition.
In general the fire retardant thermoplastic composition comprises the fire retardant
additive composition in an amount sufficient to attain a V2 rating or better at a
thickness of 3.2 millimeters according to UL94. The fire retardant thermoplastic
composition may comprise the fire retardant additive in an amount of 15 to 45 weight
percent, based on the total weight of the thermoplastic composition. Within this range
the fire retardant additive composition can be present in an amount greater than or
equal to 18, or, more specifically, greater than or equal to 20, or, even more
specifically, greater than or equal to 23 weight percent based on the total weight of the
flame retardant thermoplastic composition. Also within this range the fire retardant
additive composition can be present in an amount less than or equal to 40, or, more
specifically, less than or equal to 35, or, even more specifically, less than or equal to
32 weight percent based on the total weight of the flame retardant thermoplastic
composition.
Additionally, the fire retardant thermoplastic composition may optionally also contain
various additives, for example antioxidants, such as organophosphites, including
tris(nonyl-phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-
butylphenyl)pentaerythritol diphosphite or distearyl pentaerythritol diphosphite,
alkylated monophenols, polyphenols and alkylated reaction products of polyphenols
with dienes, such as, for example, tetrakis[methylene(3,5-di-tert-butyl-4-
hydroxyhydrocinnamate)] methane, 2,4-di-tert-butylphenyl phosphite, butylated
reaction products of para-cresol and dicyclopentadiene, alkylated hydroquinones,
hydroxylated thiodiphenyl ethers, alkylidene-bisphenols, benzyl compounds, esters of
beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydric or
polyhydric alcohols, esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic
acid with monohydric or polyhydric alcohols, esters of thioalkyl or thioaryl
compounds, such as, for example, distearylthiopropionate, dilaurylthiopropionate,
ditridecylthiodipropionate, amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-
propionic acid; fillers and reinforcing agents, such as silicates, TiO2, fibers, glass
fibers (including continuous and chopped fibers), carbon black, graphite, calcium
27

WO 2006/104811 PCT/US2006/010462
carbonate, talc, and mica; mold release agents; UV absorbers; stabilizers such as light
stabilizers and others; lubricants; plasticizers; pigments; dyes; colorants; anti-static
agents; and blowing agents.
In some embodiments it is desirable to make fire retardant thermoplastic compositions
in a variety of colors. One method of achieving this is to manufacture the fire
retardant thermoplastic composition in a single color and then modify the color by
using a color concentrate which comprises a resin with a dye or colorant in a
concentration significantly higher than that found in the final composition. In some
embodiments it may be necessary to adjust the composition of the single color fire
retardant thermoplastic composition to accomodate the later inclusion of the color
masterbatch to achieve a final colored fire retardant thermoplastic composition having
the amounts of components as described above.
The flame retardant thermoplastic composition is blended under conditions
appropriate to the formation of an intimate blend. The components are combined and
mixed, using equipment such as an extruder or kneader, typically at a temperature
sufficient to allow melt mixing without substantial decomposition of any of the
components. In one embodiment components can be blended in a twin screw extruder
at a temperature of 200°C to 300°C. If using, for example, a 53 millimeter twin screw
extruder the screw speed can be 200 to 600 rotations per minute (rpm).
In one embodiment the phosphoric acid salt, metal hydroxide and organic phosphate
are blended with a thermoplastic either at a temperature above the melt temperature of
the thermoplastic (melt mixing) or at a temperature below the melt temperature of the
thermoplastic to form a masterbatch. The masterbatch can then be melt mixed with
the components of the flame retardant composition. The masterbatch can be added
initially or after some mixing of the components of flame retardant composition.
In another embodiment the phosphoric acid salt, metal hydroxide and organic
phosphate are premixed, without thermoplastic, to form a flame retardant additive
mixture. The flame retardant additive mixture can be added at any point along the
formation of the flame retardant thermoplastic composition such as at the beginning of
the melt mixing of the thermoplastic or during the melt mixing of the thermoplastic.
28

WO 2006/104811 PCT/US2006/010462
Alternatively the flame retardant additive mixture can be melt mixed with a pelletized
thermoplastic blend.
In another embodiment the phosphoric acid salt, metal hydroxide, and organic
phosphate are added directly to the components of the thermoplastic composition.
They can be added together or separately and at any point during melt mixing
provided the composition is sufficiently melt mixed to disperse the flame retardant
additive composition components.
In one embodiment a fire retardant additive masterbatch comprises 30 to 70 of the
flame retardant additive composition and 30 to 70 of a diluent material. The diluent
material can be a solid or liquid and may serve as a binder for the fire retardant
additive composition. While the identity of the diluent is not crucial the choice of
diluent material is typically made with consideration of the resin or resins the
masterbatch is to be combined with. For example if the masterbatch is to be
combined with poly(arylene ether) the choices for the diluent material could include
poly(arylene ether) or a material compatible with poly(arylene ether) such as
polystyrene, polyolefin as described above, or impact modifier as described above.
In some embodiments the flame retardant thermoplastic composition is essentially
free of compounds having a functional group reactive to an active hydrogen atom such
as compounds having a functional group selected from a cyclic ether group (e.g., an
epoxy group), an acid anhydride group, an isocyanate group, an oxazoline group, an
oxazine group, or a carbodiimide group. The flame retardant thermoplastic
composition may also be free of fluorine-containing oligomers, and/or silicone-series
resins such as poly(organosiloxane). In the absence of compounds having a functional
group reactive to an active hydrogen atom, fluorine-containing oligomers, and/or
silicone-series resins the flame retardant composition retains hydrolysis resistance.
Hydrolysis resistance can be determined by injection molding the composition into a
test piece for ISO tensile test and carrying out the PCT test (measurement conditions:
121° C.xl00% RH, 2 atmospheres, and 24 hours). The tensile strengths before and
after PCT test are measured, and the retention (%) of the tensile strength is an index of
hydrolysis resistance. The composition typically retains 75% to 100% of tensile
29

WO 2006/104811 PCT/US2006/010462
strength. Within this range the composition can retain greater than or equal to 80% of
tensile strength, or, more specifically, greater than or equal to 85% of the tensile
strength.
"Essentially free" as used herein means that the composition contains less than 1
weight percent, or, more specifically, less than 0.5 weight percent, or, even more
specifically, less than 0.05 weight percent, based on the total weight of the
composition.
The compositions are further illustrated by the following non-limiting examples.
EXAMPLES
The following examples employed the materials listed in Table 1. All weight percents
employed in the examples are based on the weight of the entire composition except
where stated.
Table 1.

Component Description/Supplier
PPE Poly(phenylene ether) having an
intrinsic viscosity of 0.46g/dl when
measured in chloroform at 25°C
SEBSI Polystyrene-poly(ethylene-butylene)-
polystyrene having a polystyrene content
of 13 weight percent that is
commercially available from Kraton
Polymers Ltd under the tradename
Kraton G1657.
30

WO 2006/104811 PCT/US2006/010462

SEBS II Polystyrene-poly(ethylene-butylene)-
polystyrene having a polystyrene content
of 30 weight percent that is
commercially available from Kraton
Polymers Ltd under the tradename
Kraton G1650.
SEBS III Polystyrene-poly(ethylene-butylene-
styrene)-polystyrene having 39%
polystyrene content and commercially
available from Kraton Polymers Ltd
under the tradename Kraton A, grade
RP 6936.
SEBS IV Polystyrene-poly(ethylene-butylene)-
polystyrene having a polystyrene content
of 30 weight percent that is
commercially available from Kraton
Polymers Ltd under the tradename
Kraton G1652.
SEBS V Blend of polys tyrene-poly(ethylene-
butylene)-polystyrene, a copolymer of
ethylene-propylene and mineral oil that
is commercially available from
Sumitomo Chemical under the
tradename SB-2400.
LLDPE Linear low density polyethylene
commercially available from Nippon
Unicar Co. Ltd under the tradename
NUCG5381.
31

WO 2006/104811PCT/US2006/010462

Polybutene I Polybutene having a viscosity of 200-235 cSt at a temperature of 100°C,commercially available from BPChemical under the tradename Indopol,grade H100.
Polybutene II Polybutene having a viscosity of 100-115 cSt at a temperature of 100°Ccommercially available from BPChemical under the tradename Indopol,grade H50.
RDP Resorcinol bis-diphenylphosphatecommercially available from GreatLakes Chemical Co. Ltd. under the tradename of Reofos RDP.
MPP Melamine polyphosphate commerciallyavailable from Ciba Specialty ChemicalCo. Ltd under the tradename Melapur200.
MP Melamine pyrophosphate commerciallyavailable from Budenheil under thetradename Budit 311MPP.
Mg(OH)2 Magnesium hydroxide commerciallyavailable from Kyowa ChemicalIndustry Co. Ltd. under the trade nameof Kisuma 5A.
BTPP Butylated triphenyl phosphatecommercially available from AkzoNobel Chemical Inc. under the
32

WO 2006/104811PCT/US2006/010462

tradename Phosflex 71B.
TPP Triphenyl phosphate commerciallyavailable from Akzo Nobel ChemicalInc. under the tradename Phosflex TPP.
BPADP Bisphenol A bis-diphenylphosphatecommercially available from AkzoNobel Chemicals Inc under thetradename of Fyroflex BDP.
LDPE Low density polyethylene commerciallyavailable from Nippon Unicar Co. Ltdunder the tradename NUC8042.
EVA Ethylene-vinyl acetate copolymercommercially available from DupontMitsui Polymers Co Ltd under thetradename Elvaloy A710.
EEA Ethylene-ethyl acrylate copolymercommercially available from NipponUnicar Co. Ltd under the tradenameNUC8451.
EXAMPLES 1-9
A thermoplastic composition containing 38.5 weight percent PPE, 26.9 weight percent
SEBS I, 25.6 weight percent LLDPE and 9.0 weight percent polybutene, based on the
total weight of thermoplastics was melt mixed with RDP, MPP, and Mg(OH)2 in the
amounts shown in Table 2. The amounts of RDP, MPP and Mg(OH)2 amounts are
shown in parts per hundred parts of thermoplastic composition (PPE + SEBS I +
LLDPE + polybutene). The composition was molded into 3.2 millimeter bars for
33

WO 2006/104811 PCT/US2006/010462
flammability testing. Flammability tests were performed following the procedure of
Underwriter's Laboratory Bulletin 94 entitled "Tests for Flammability of Plastic
Materials, UL94". Each bar that extinguished was ignited twice. According to this
procedure, the materials were classified as either HB, V0, VI or V2 on the basis of the
test results obtained for five samples. The criteria for each of these flammability
classifications according to UL94, are, briefly, as follows.
HB: In a 5 inch sample, placed so that the long axis of the sample is parallel to the
flame, the rate of burn of the sample is less than 3 inches per minute, and the flames
should be extinguished before 4 inches of sample are burned.
V0: In a sample placed so that its long axis is parallel to the flame, the average period
of flaming and/or smoldering after removing the igniting flame should not exceed five
seconds and none of the vertically placed samples should produce drips of burning
particles which ignite absorbent cotton.
VI: In a sample placed so that its long axis is parallel to the flame, the average period
of flaming and/or smoldering after removing the igniting flame should not exceed
twenty-five seconds and none of the vertically placed samples should produce drips of
burning particles which ignite absorbent cotton.
V2: In a sample placed so that its long axis is parallel to the flame, the average period
of flaming and/or smoldering after removing the igniting flame should not exceed
twenty-five seconds and the vertically placed samples produce drips of burning
particles which ignite cotton.
Results are shown in Table 2. Burn time is the sum of the amounts of time the bar
burned each time it was lit. "Burn" indicates that the bar did not self-extinguish.
"NA" in the UL94 rating column means that the sample did not fall within the
parameters of any of the UL94 ratings.
34

WO 2006/104811PCT/US2006/010462

Table 2.

Example RDP MPP Mg(OH)2 Burn time UL94 rating
1* 19.3 19.3 0 Burn NA
2 19.3 19.3 8.3 5.5 VO
3 19.3 19.3 13.9 1.5 vo
4* 27.7 16.6 0 Burn NA
5 27.7 11.1 8.3 3.8 VO
6* 24.9 0 12.5 Burn NA
7* 0 27.7 8.3 Burn NA
8* 23.8 19.1 0 Burn NA
9* 22.2 19.4 0 Burn NA
* Comparative Example
Examples 1-9 demonstrate that all three components of the flame retardant additive
composition are required for flame retardance. Examples 1, 4, 8, and 9 all lack
magnesium hydroxide and none of these samples self-extinguished. Example 6
lacked melamine polyphosphate and did not self extinguish. Example 7 lacked
resorcinol diphosphate and it too did not self extinguish. The fact that all three
components of the fire retardant additive composition are required indicates an
unexpected synergistic relationship between the three components.
EXAMPLES 10-15
A thermoplastic composition containing 42.6 weight percent PPE, 32.0 weight percent
SEBS I, 21.4 weight percent LLDPE and 4.0 weight percent polybutene, based on the
total weight of thermoplastics, was melt mixed with BTPP, RDP, MPP, and Mg(OH)2
in the amounts shown in Table 3. BTPP, RDP, MPP, and Mg(OH)2 amounts are in
35

WO 2006/104811 PCT/US2006/010462
parts per hundred parts of thermoplastic composition (PPE + SEBS I + LLDPE +
polybutene). The composition was molded into 3.2 millimeter bars for flammability
testing and tested as described in Examples 1-9.
Table 3.

Example BTPP RDP MPP Mg(OH)2 Burn time UL94rating
10 3.9 19.3 11.4 7.7 5.2 VO
11 0 19.3 11.4 7.7 17.4 VI
12 0 24.4 12.8 7.7 2.9 VO
13 0 25.7 7.7 7.7 1.9 VO
14 6.4 19.3 11.4 11.4 24.2 VI
15 10.3 15.4 1.1 10.3 8.8 VO
Examples 10-15 demonstrate that combinations of organic phosphate are useful in the
flame retardant additive composition and that excellent flame retardance (VI and V0)
can be achieved with the fire retardant additive composition.
EXAMPLES 16-19
26 weight percent PPE, 25 weight percent SEBS I, 15.0 weight percent polyethylene
copolymer (as shown in Table 4) and 2 weight percent polybutene, based on the total
weight of the composition, were melt mixed with BTPP, RDP, MPP, and Mg(OH)2 in
the amounts shown in Table 4. BTPP, RDP, MPP, and Mg(OH)2 amounts are shown
in weight percent, based on the total weight of the composition. The compositions
were molded into 2.0 millimeter bars for flammability testing and tested as described
in Examples 1-9. In Example 19 one out of 10 burns caused dripping at 20 seconds,
which resulted in a V2 rating.
36

WO 2006/104811 PCT/US2006/010462
Table 4.

Example PEcopolymer BTPP RDP MPP Mg(OH)2 Burntime UL94rating
16 LDPE 8.0 12.0 5.0 7.0 3.4 VO
17 LLDPE 8.0 12.0 5.0 7.0 9.5 VI
18 EEA 8.0 12.0 5.0 7.0 3.1 VO
19 EVA 8.0 12.0 5.0 7.0 12.3 V2
Examples 16-19 demonstrate that compositions containing a significant amount of
polyolefin and comprising a variety of polyethylene copolymers can attain a V2 rating
or better using the flame retardant additive composition.
EXAMPLE 20
26 weight percent PPE, 25 weight percent SEBS I, 15.0 weight percent EEA and 2
weight percent polybutene were melt mixed with 8.0 weight percent BTPP, 12.0
weight percent RDP, 5.0 weight percent melamine cyanurate, and 7 weight percent
Mg(OH)2, where all weight percents are based on the total weight of the composition.
The composition was molded into 2.0 millimeter bars for flammability testing and
tested as described in Examples 1-9. The composition did not self extinguish
indicating that phosphoric acid salt cannot be replaced by a nitrogen containing
compound free of phosphorous, further confirming the surprising synergistic
relationship between the three components of the fire retardant additive composition.
37

WO 2006/104811 PCT/US2006/010462
EXAMPLES 21-33
Compositions according to the formulations shown in Table 5 were made and tested
for tensile strength and elongation according to ASTM D 638, flexural modulus
according to ASTM D790 and shore A hardness according to ASTM D2240.
Formulation amounts are in weight percent based on the total weight of the
compositions. Tensile strength values are in megapascals (MPa) and tensile
elongation values are in percent. Flexural modulus values are in MPa.
The compositions were molded into 2.0 millimeter bars for flammability testing and
tested as described in Examples 1-9. Results are shown in Table 6.
Table 5

Example PPE SEBS] SEBSH LLDPE EEA LDPE PB MPP Mg(OH)2 BTPP RDP
21 25.2 29.1 ~ 13.6 ~ 2.9 4.9 6.8 7.8 9.7
22 25.9 23.5 3.0 14.3 2.7 5.4 7.0 7.1 10.7
23 25.0 25.5 3.8 10.6 2.9 5.3 7.7 7.7 11.5
24 25.2 26.2 1.9 14.6 2.9 4.9 5.8 8.7 9.7
25 25.2 26.2 1.9 2.9 14.6 4.9 5.8 8.7 9.7
26 25.2 28.2 — 17.5 ~ 5.3 5.3 8.7 9.7
27 30.8 21.5 15.0 --- 2.8 5.6 5.6 18.7
28 26.1 23.4 " 17.1 " " 2.7 8.1 4.5 4.5 13.5
29 32.0 35.0 5.0 -- 5.0 6.0 17.0
30 35.0 20.0 17.0 5.0 6.0 17.0
38

WO 2006/104811 PCT/US2006/010462

31 35.0 22.0 10.0 - 5.0 - - 5.0 6.0 17.0
32 26.0 27.0 14.0 2.0 5.0 6.0 9.0 11.0
33 25.1 28.2 14.6 _ 2.9 4.9 6.8 7.8 9.7
Table 6.

Example TensileStrength (MPa) TensileElongation(%) FlexuralModulus(MPa) DurometerHardness(Shore A) UL 94V Rating
21 8.7 173 81 82 VI
22 12.4 179 257 88 VI
23 11.3 192 246 88 VI
24 11.0 187 150 85 vo
25 11.2 175 214 89 vo
26 10.7 164 196 87 VI
27 13.9 114 328 92 VI
28 9.5 155 161 88 VI
29 14.3 175 310 91 VI
30 17.6 103 530 95 vo
31 18.1 105 666 97 vo
32 13.4 163 322 91 vo
33 9.0 170 102 83 VI
39

WO 2006/104811 PCT/US2006/010462
The data in Table 6 demonstrates that the fire retardant thermoplastic composition can
obtain a surprising combination of physical properties, namely softness, flexibility and
tensile strength as well as flame retardance, without the use of halogenated flame
retardants. None of Examples 21-33 exhibited plate out or migration by visual
inspection.
Additionally Examples 22, 23 and 33 were tested for viscosity using a capillary
viscometer having a length to diameter ratio of 10. Viscosity values are in Pascal
seconds (Pa s). Data for Example 22 is shown in Table 7. Data for Example 23 is
shown in Table 8. Data for Example 33 is shown in Table 9.
Table 7

\. Shear rate (s-1)
10 100 1,000 4,000 10,000
Temperature N.
210°C 2584 1002 293 134 81
230°C 2031 650 199 90 53
250°C 826 474 143 70 40

WO 2006/104811 PCT/US2006/010462
Table 8

Shear rate (s-1)Temperature 10 100 1,000 4,000 10,000
210°C 2022 959 283 128 73
230°C 2189 632 196 88 50
250°C 1608 453 139 68 40
Table 9

Shear rate (s-1)Temperature 10 100 1,000 4,000 10,000
210°C 1988 750 237 113 71
230°C 1384 534 175 83 50
250°C 1001 373 126 63 38
The data in Tables 7-9 demonstrate that the compositions have excellent
processability, particularly for extrusion processes.
EXAMPLES 34-37
Compositions according to the formulations shown in Table 10 were made and tested
for tensile strength and elongation according to ASTM D 638, flexural modulus
41

WO 2006/104811 PCT/US2006/010462
according to ASTM D790 and shore A hardness according to ASTM D2240.
Formulation amounts are in weight percent based on the total weight of the
composition. Tensile strength values are in megapascals (MPa) and tensile elongation
values are in percent. Flexural modulus values are in MPa.
The compositions were molded into 3.2 millimeter bars for flammability testing and
tested as described in Examples 1-9. Results are shown in Table 11.
Table 10.

Example PPE SEBSin EEA LLDPE PB MPP Mg(OH)2 RDP
34 19.0 30.0 -- 19.0 6.0 5.0 6.0 15.0
35 25.8 28.3 12.9 5.3 4.8 5.7 17.2
36 23.0 31.1 12.9 5.3 4.8 5.7 17.2
37 25.8 31.1 10.1 5.3 4.8 5.7 17.2
Table 11.

Example TensileStrength (MPa) TensileElongation(%) FlexuralModulus(MPa) DurometerHardness(Shore A) UL 94V Rating
34 13.8 292 210- 89 VI
35 15.8 227 306 92 VO
36 13.5 279 235 89 VO
37 15.9 224 290 91 VO
42

WO 2006/104811 PCT/US2006/010462
Examples 34 through 37 demonstrate flame retardant thermoplastic materials having
an excellent combination of properties, notably high values for tensile elongation
indicating materials having a resistance to breakage under stress such as stress exerted
by pulling. The flame retardant thermoplastic materials also demonstrate a
combination of softness (as demonstrated by the Shore A values), good flame
resistance, tensile strength, and flexural modulus.
EXAMPLES 38-42
Examples 38 through 42 demonstrate the wire properties made from flame retardant
thermoplastic compositions of 38 through 42. Compositions according to the
formulations shown in Table 12 were made and tested for tensile strength and
elongation according to ASTM D 638, flexural modulus according to ASTM D790
and shore A hardness according to ASTM D2240. Formulation amounts are in weight
percent based on the total weight of the composition. Tensile strength values are in
megapascals (MPa) and tensile elongation values are in percent. Flexural modulus
values are in MPa. The compositions were molded into 3.2 millimeter bars for
flammability testing and tested as described in Examples 1-9. Results are shown in
Table 13. Copper wire having a cross sectional area of 0.75 square millimeters was
extrusion coated with the compositions of Examples 38-42. The coating had a
thickness of 0.6 millimeters. The coating was tested for tensile strength and ultimate
elongation according to UL 1581 and the entire wire was tested for flame retardance
according to UL 1581.
43

WO 2006/104811 PCT/US2006/010462
Table 12.

Example PPE SEBSI SEBSIV SEBSm EEA LLDPE PB MPP Mg(OH)2 RDP
38 20.0 29.0 18.0 7.0 5.0 6.0 15.0
39 29.0 5.0 27.0 10.0 " 6.5 4.0 4.5 14.0
40 31.7 26.2 ~ ** 13.4 2.0 5.4 5.4 15.8
41 35.3 28.7 3.9 3.9 2.9 4.0 4.6 16.7
42 30.5 11.0 20.0 6.5 6.0 5.0 5.0 16.0
Table 13.

Example TensileStrength(MPa) TensileElongation(%) FlexuralModulus(MPa) DurometerHardness(Shore A) UL94VRating Coating TensileStrength (MPa) UltimateElongation(%) UL1581VW-1
38 13.5 245 195 89 VI 14.7 260 Pass
39 13.4 170 117 84 V2 21.0 245 Pass
40 14.2 125 210 89 VO 16.4 134 Pass
41 16.5 110 300 91 VO 20.0 165 Pass
42 15.0 120 227 90 VO 18.9 193 Pass
44

WO 2006/104811 PCT/US2006/010462
EXAMPLES 43-60
Compositions according to the formulations shown in Table 14 were made and tested
for tensile strength and elongation according to ASTM D 638, flexural modulus
according to ASTM D790 and Shore A hardness according to ASTM D2240. The
compositions also contained 1.7% weight percent of stabilizers and additives.
Formulation amounts are in weight percent based on the total weight of the
composition. Tensile strength values are in megapascals (MPa) and tensile elongation
values are in percent. Flexural modulus values are in MPa. The compositions were
molded into 3.2 millimeter bars for flammability testing and tested as described in
Examples 1-9. Results are shown in Table 14. In addition electrical wires were made
using the compositions of Examples 43-61. The conductor was a 20 x 0.12 millimeter
copper conductor and the covering had a thickness of approximately 0.7 millimeters.
The covering was tested for tensile strength (in MPa) and ultimate elongation (in %)
according to UL 1581 and the entire wire was tested for flame retardance according to
UL 1581. Some examples were also tested for heat deformation according to UL
1581 at 121°C and 250 grams. Heat deformation values are in percentage. Migration
was determined by putting two electrical wires in between two plates made of
polystyrene or two plates made of ABS to form a stack. Prior to placing the electrical
wires between the plates the wires were visually inspected to verify that they were free
of dust or other obvious contamination. A 500 gram weight was placed on top of the
stack to form a weighted stack. The weighted stack was then put into an oven at 60°C.
After 48 hours at 60°C, the stack was removed from the oven and disassembled. The
surface of the plates that was in contact with the wires was visually inspected for
marks left by the wires during the test.
45

46
WO 2006/104811 PCT/US2006/010462


47
WO 2006/104811 PCT7US2006/010462


WO 2006/104811 PCT/US2006/010462
As can be seen from the foregoing examples compositions having an amount of
organic phosphate greater than the amount of phosphoric acid salt (Examples 57-60)
show good flame retardance but also demonstrate migration against polystyrene and
migration against ABS. In contrast examples having an amount of phosphoric acid
salt greater than or equal to organic phosphate demonstrate little or no migration.
While the invention has been described with reference to various embodiments, it will
be understood by those skilled in the art that various changes can be made and
equivalents can be substituted for elements thereof without departing from the scope
of the invention. In addition, many modifications can be made to adapt a particular
situation or material to the teachings of the invention without departing from essential
scope thereof. Therefore, it is intended that the invention not be limited to the
particular embodiment disclosed as the best mode contemplated for carrying out this
invention, but that the invention will include all embodiments falling within the scope
of the appended claims.
All cited patents are incorporated by reference herein.
48

WO 2006/104811 PCT/US2006/010462
CLAMS:
1. A flame retardant thermoplastic composition comprising:
a poly(arylene ether);
an impact modifier;
a polyolefin;
a phosphoric acid salt selected from the group consisting of melamine phosphate,
melamine pyrophosphate, melamine orthophosphate, diammonium phosphate,
monoammonium phosphate, phosphoric acid amide, melamine polyphosphate,
ammonium polyphosphate, polyphosphoric acid amide, and combinations of two or
more of the foregoing;
a metal hydroxide; and
an organic phosphate wherein the amount of phosphoric acid salt by weight is greater
than or equal to the amount of organic phosphate by weight.
2. The composition of Claim 1 wherein the phosphoric acid salt is present in an
amount of 30 to 60 weight percent, the metal hydroxide is present in an amount of 10
to 45 weight percent and the organic phosphate is present in an amount of 9 to 45
weight percent, all based on the combined weight of the phosphoric acid salt, metal
hydroxide and organic phosphate.
3. The composition of Claim 1 wherein the organic phosphate is selected from
the group consisting of tris(butyl phenyl) phosphate, resorcinol bis-
diphenylphosphate, bis-phenol A bis-diphenylphosphate, triphenyl phosphate,
tris(isopropyl phenyl) phosphate, and combinations of two or more of the foregoing;
the phosphoric acid salt is selected from the group consisting of melamine
polyphosphate, melamine pyrophosphate and a combination of melamine
polyphosphate and melamine pyrophosphate; and the metal hydroxide is selected from
the group consisting of magnesium hydroxide, aluminum hydroxide, cobalt hydroxide
and combinations of two or more of the foregoing.
49

WO 2006/104811 PCT/US2006/010462
4. The composition of Claim 1 wherein the polyolefin is a liquid polyolefin.
5. The composition of Claim 1 wherein the impact modifier comprises a
combination of a first block copolymer having a polystyrene content of 10 weight
percent to 20 weight percent based on the total weight of the first block copolymer
and a second block copolymer having a styrene content of 25 weight percent to 50
weight percent based on the total weight of the second block copolymer.
6. The composition of Claim 1 wherein the impact modifier comprises a block
copolymer comprising an aryl alkylene block and a controlled distribution copolymer
block.
7. The composition of Claim 1, wherein the weight ratio of metal hydroxide to
phosphoric acid salt is 0.3 to 0.8.
8. The composition of Claim 1, wherein the composition has a Shore A hardness
greater than or equal to 60 when determined by ASTM D 2240 using a specimen
having a 3 millimeter thickness.
9. A flame retardant thermoplastic composition comprising:
a poly(arylene ether);
an impact modifier;
a polyolefin;
7 to 20 weight percent of a phosphoric acid salt selected from the group consisting of
melamine phosphate, melamine pyrophosphate, melamine orthophosphate,
diammonium phosphate, monoammonium phosphate, phosphoric acid amide,
melamine polyphosphate, ammonium polyphosphate, polyphosphoric acid amide, and
combinations of two or more of the foregoing;
4 to 15 weight percent of a metal hydroxide; and
50

WO 2006/104811 PCT/US2006/010462
3 to 11 weight percent of an organic phosphate wherein weight percent is with respect
to the combined weight of the poly(arylene ether), impact modifier, polyolefin,
phosphoric acid salt, metal hydroxide and organic phosphate.
10. The flame retardant thermoplastic composition of Claim 9 wherein the organic
phosphate is selected from the group consisting of tris(butyl phenyl) phosphate,
resorcinol bis-diphenylphosphate, bis-phenol A bis-diphenylphosphate, triphenyl
phosphate, tris(isopropyl phenyl) phosphate and mixtures of two or more of the
foregoing organic phosphates; the phosphoric acid salt is selected from the group
consisting of melamine polyphosphate, melamine pyrophosphate or a combination of
melamine polyphosphate and melamine pyrophosphate; and the metal hydroxide
comprises magnesium hydroxide, aluminum hydroxide, cobalt hydroxide and
combinations of two or more of the foregoing metal hydroxides.
11. The composition of Claim 9 wherein the metal hydroxide comprises
magnesium hydroxide.
12. The composition of Claim 9 wherein the impact modifier comprises a
combination of a first block copolymer having a polystyrene content of 10 weight
percent to 20 weight percent based on the total weight of the first block copolymer
and a second block copolymer having a styrene content of 25 weight percent to 50
weight percent based on the total weight of the second block copolymer.
13. The composition of Claim 7 wherein the impact modifier comprises a block
copolymer comprising an aryl alkylene block and a controlled distribution copolymer
block.
14. A flame retardant thermoplastic composition comprising:
a poly(arylene ether);
an impact modifier;
a liquid polyolefin;
51

WO 2006/104811 PCT/US2006/010462
7 to 20 weight percent of a phosphoric acid salt selected from the group consisting of
melamine phosphate, melamine pyrophosphate, melamine orthophosphate,
diammonium phosphate, monoammonium phosphate, phosphoric acid amide,
melamine polyphosphate, ammonium polyphosphate, polyphosphoric acid amide, and
combinations of two or more of the foregoing;
4 to 15 weight percent of a metal hydroxide; and
3 to 11 weight percent of an organic phosphate wherein weight percent is with respect
to the combined weight of the poly(arylene ether), impact modifier, polyolefin,
phosphoric acid salt, metal hydroxide and organic phosphate and
the amount of phosphoric acid salt by weight is greater than or equal to the amount of
organic phosphate by weight.
15. An electrical wire comprising:
a conductor, and
a covering disposed over the conductor wherein the covering comprises:
a flame retardant thermoplastic composition comprises:
a poly(arylene ether);
an impact modifier;
a polyolefin;
a phosphoric acid salt selected from the group consisting of melamine phosphate,
melamine pyrophosphate, melamine orthophosphate, diammonium phosphate,
monoammonium phosphate, phosphoric acid amide, melamine polyphosphate,
ammonium polyphosphate, polyphosphoric acid amide, and combinations of two or
more of the foregoing;
a metal hydroxide; and
52

WO 2006/104811 PCT/US2006/010462
an organic phosphate wherein the amount of phosphoric acid salt by weight is greater
than or equal to the amount of organic phosphate by weight.
16. An electrical wire comprising:
a conductor, and
a covering disposed over the conductor wherein the covering comprises:
a flame retardant thermoplastic composition comprises:
a poly(arylene ether);
an impact modifier;
a polyolefin;
7 to 25 weight percent of a phosphoric acid salt selected from the group consisting of
melamine phosphate, melamine pyrophosphate, melamine orthophosphate,
diammonium phosphate, monoammonium phosphate, phosphoric acid amide,
melamine polyphosphate, ammonium polyphosphate, polyphosphoric acid amide, and
combinations of two or more of the foregoing;
4 to 15 weight percent of a metal hydroxide; and
3 to 11 weight percent of an organic phosphate wherein weight percent is with respect
to the combined weight of the poly(arylene ether), impact modifier, polyolefin,
phosphoric acid salt, metal hydroxide and organic phosphate.

A flame retardant thermoplastic composition comprises: a poly(arylene ether); an impact
modifier; a polyolefin; and phosphoric acid salt selected from the group consisting of
melamine phosphate, melamine pyrophosphate, melamine orthophosphate,
diammonium phosphate, monoarnmoniurn phosphate, phosphoric acid amide,
melamine polyphosphate, ammonium polyphosphate, polyphosphoric acid amide, and
combinations of two or more of the foregoing; a metal hydroxide; and an organic
phosphate wherein the amount of phosphoric acid salt by weight is greater than or
equal to the amount of organic phosphate by weight. The flame retardant composition is
may be used in the production of electrical wires.