ABRASION RESISTANT AND FLAME RETARDANT THERMOPLASTIC VULCAN IZATE COMPOSITIONS FIELD OF THE INVENTION

The present invention relates to flame retardant thermoplastic vulcanizate compositions having improved abrasion resistance and strip force. In addition, the invention relates to wire and cable coated with these compositions.

BACKGROUND OF THE INVENTION

Thermoplastic vulcanizates (TPVs) are polymer blend compositions composed of a continuous thermoplastic phase and a dispersed

vulcanized elastomer phase. TPVs combine many desirable

characteristics of crosslinked (i.e. vulcanized) rubbers with certain characteristics of thermoplastic resins. For example, TPVs can be melt processed utilizing thermoplastic resin processing equipment, such as for example extruders. As a result of their excellent tear strength, tensile strength, flex life, chemical resistance and broad end-use temperature ranges, TPVs, especially copolyetherester TPVs such as those described in Int'l. Pat. App. Pub. No. WO 2004/029155, are used in a wide range of applications including manufacture of articles for use in the automotive, wire and cable, fluid power, electrical/electronic, hose and tubing, and appliance fields.

A specific example of the use of such TPVs is in the manufacture of insulating layers for wire and cable applications in the automotive industry. The wire and cable coating not only provides electrical insulation but also imparts mechanical, chemical and physical protection. Because

temperatures in excess of 150°C are often reached in the underhood compartments of automobiles, temperature specifications for wire and cable insulation materials are constantly increasing. Further, in this highly demanding application it is necessary that the insulation material meet additional requirements including flame retardancy, abrasion resistance, thermal resistance and high elongation. Polyvinyl chloride (PVC) is the most widely used material for wire and cable insulation. However, in many instances, PVC is perceived as an environmental threat. It would be desirable to have a halogen-free, high temperature resistant thermoplastic material available as an alternative automotive wire and cable insulation material.

Compositions based on TPVs have been proposed as coatings and covers for wire and cable. Int'l. Pat. App. Pub. No. WO 2008/060549 discloses a non-halogenated flame retardant composition comprising a thermoplastic polyester-based vulcanizate. This flame retardant TPV composition is said to be advantageously used to protect, coat or insulate cables and wires in the automotive industry where an outstanding balance of properties is desired that includes good resistance to environmental conditions, excellent resistance to a variety of fluids (e.g. gasoline, oil, transmission fluid, power steering fluid, radiator fluid, lubricating greases and the like) and flexibility sufficient to enable manipulation and bending of the material without damage or deterioration. Over time, wire and cable coating and insulation mamterials are subjected to friction and abrading forces with the result that articles made of the disclosed non-halogenated flame retardant TPV compositions may be susceptible to damage. In addition to the low abrasion resistance of currently available non- halogenated flame retardant TPV compositions, such as those disclosed in Int'l. Pat. App. Pub. No. WO 2008/060549, the use of such

compositions, which contain phosphinate flame-retardants, has the disadvantage that such compositions adhere so strongly to wire or cable materials that strippability is reduced. As a result, the TPV coating cannot be easily removed either by hand or through use of simple tools. Cable laying operations are thereby rendered more difficult. It would be desirable to have alternative TPV compositions available that do not exhibit such strong adhesion between the insulating layer and wire so that stripping of the insulating layer is easily accomplished and excessive wire and/or insulating layer damage during stripping and installation is avoided.

There is a need for a flame retardant thermoplastic vulcanizate composition that combines good abrasion resistance and good strip characteristics but which also exhibits excellent mechanical properties. SUMMARY OF THE INVENTION

The present invention is directed to a flame retardant composition comprising

A. a thermoplastic vulcanizate composition comprising:

1 . from about 15 to about 75 weight percent of a

continuous phase comprising at least one thermoplastic polyester; and

2. from about 25 to about 85 weight percent of a

dispersed phase comprising at least one peroxide- cured elastomer selected from the group consisting of polyacrylate rubbers,

polymethacrylate rubbers,

polyethylene/polyacrylate rubbers, and

polyethylene/polymethacrylate rubbers; wherein said rubber is dynamically crosslinked with at least one peroxide free radical initiator and at least one organic multiolefinic co-agent;

the weight percentages of the continuous phase and the dispersed phase being based on the total combined weight of the continuous and dispersed phases,

B. from about 1 to about 30 weight percent, based on the total weight of the flame retardant composition, of at least one flame retardant selected from the group consisting of phosphinates of formula I, diphosphinates of formula II, polymers thereof and combinations of two or more thereof

wherein R ¹ and R ² are independently selected from the group consisting of hydrogen, linear or branched C ₁ -C ₆ alkyl groups, and aryl groups; R ³ is a linear or branched Ci-Cio-alkylene group, a C6-Cio-arylene group, a Ce- Cio— alkylarylene or a C ₆ -Ci ₀ -arylalkylene group; M is a metal ion selected from the group of calcium ions, magnesium ions, aluminum ions, zinc ions, and mixtures thereof, m is 2 to 3; n is 1 or 3; and x is 1 or 2 with the proviso that when m is 2, then x and n are each 1 , and when m is 3, x is 2 and n is 3; and

C. from about 0.05 to about 1 .75 weight percent, based on the total weight of the flame retardant composition, of an ultra-high molecular weight polysiloxane.

Further described herein are articles comprising the flame retardant composition of the invention.

Also described herein are wires or cables comprising a coating comprising the flame-retardant composition described herein.

Also described herein are uses of an ultra-high molecular weight polysiloxane as an additive in a flame retardant composition comprising a) the thermoplastic vulcanizate described above and b) the at least one flame retardant described above for improving the abrasion resistance of an insulating layer comprising said composition and the ultra-high molecular weight siloxane.

Also described herein are methods for improving the abrasion resistance of an insulating layer made of a flame retardant composition comprising a) the thermoplastic vulcanizate described above and b) the at least one flame retardant described herein, said method comprising a step of melt blending an ultra-high molecular weight polysiloxane with the thermoplastic vulcanizate and the at least one flame retardant.

DETAILED DESCRIPTION

The following definitions are to be used to interpret the meaning of the terms discussed in the description and recited in the claims.

As used herein, the term "a" refers to one as well as to at least one and is not an article that necessarily limits its referent noun to the singular.

As used herein, the term "about" is intended to mean that the amount or value in question may be the value designated or some other value that is approximately the same. The phrase is intended to convey that similar values promote equivalent results or effects according to the invention

As used herein, the term "(meth)acrylic acid" refers to methacrylic acid and/or acrylic acid; the term "(meth)acrylate" refers to methacrylate and/or acrylate and the term "poly(meth)acrylate refers to polymers derived from the polymerization of methacrylate and/or acrylate

monomers.

As used herein, the term "ultra-high molecular weight polysiloxane" refers to a polysiloxane having a weight average molecular weight (Mw) of at least 100,000, the weight average molecular weight (Mw) being determined by gel permeation chromatography (GPC).

As used herein, the term "thermoplastic polyester" includes thermoplastic polyester elastomers as well as non-elastomeric

thermoplastic polyesters.

As used herein, the term "acrylate rubber" refers to

poly(meth)acrylate or polyethylene/(meth)acrylate rubber.

The abrasion resistant flame retardant compositions of the invention comprise a blend of a melt-processable thermoplastic vulcanizate (TPV) composition, a non-halogenated flame retardant composition and an ultra- high molecular weight polysiloxane composition. The melt-processable TPV is preferably present in an amount of about 70 to about 98 weight percent, the weight percentage being based on the total weight of the flame retardant composition. The non-halogenated flame retardant is present in an amount of from about 1 to about 30 weight percent, or preferably about 2 to about 20 weight percent, or more preferably about 3 to about 15 weight percent, based on the total weight of the flame retardant composition. The ultra-high molecular weight polysiloxane is present in an amount of about 0.05 to about 1 .75 weight percent, the weight percentage being based on the total weight of the flame retardant composition.

The TPV component of the flame retardant composition of the invention is a multi-phase polymer composition. TPVs are blends composed of a thermoplastic continuous phase and a vulcanized elastomer dispersed phase. The dispersed phase is dispersed within and throughout the continuous phase. The term "vulcanizate" and the phrase "vulcanizate rubber" as used herein are intended to be generic to the cured or partially cured, crosslinked or crosslinkable rubber as well as to curable precursors of crosslinked rubber. These terms as used herein include elastomers, gum rubbers and so-called soft vulcanizates as commonly recognized in the art. Melt-processable TPV compositions useful in the present invention are described in U.S. Patent. No.

7,074,857, U.S. Patent Application Publication. No. 2005/084694 and International Patent Application. Publication. No. WO 2004/029155, which are hereby incorporated by reference.

An example of a TPV is disclosed in International Patent Application Publication No. WO 2004/029155, which describes a curable

thermoplastic blend comprising a polyalkylenephthalate polyester polymer or copolymer and a crosslinkable poly(meth)acrylate or

polyethylene/(meth)acrylate vulcanizate rubber in combination with an effective amount of peroxide free-radical initiator and an organic multiolefinic co-agent to crosslink the rubber during extrusion or injection molding of the thermoplastic elastomeric blend. As used herein, the term "organic multiolefinic co-agent" refers to organic co-agents that contain two or more unsaturated double bonds, for example, diethylene glycol diacrylate, diethylene glycol dimethacrylate, N,N'-m-phenylene

dimaleimide, triallylisocyanurate, trimethylolpropane trimethacrylate;

tetraallyloxyethane; triallyl cyanurate; tetramethylene diacrylate and polyethylene glycol dimethacrylate. When the blend composition is melt extruded, the result is a TPV that can be processed in many ways like a thermoplastic, but which has characteristics of a crosslinked rubber. In contrast to conventional vulcanized (thermoset) elastomers, TPVs can reprocessed by injection molding or extrusion.

According to the present invention, the thermoplastic vulcanizate comprises (i) from about 15 to about 75 weight percent, or preferably from about 15 to about 60 weight percent, of at least one thermoplastic polyester that forms a continuous phase; and (ii) from about 25 to about 85 weight percent, or preferably from about 40 to about 85 weight percent of at least one poly(meth)acrylate or polyethylene/(meth)acrylate rubber that forms a dispersed phase, wherein the rubber is dynamically crosslinked with at least one peroxide free radical initiator and at least one organic co-agent having multiple olefinic unsaturated groups, the weight percentage of components (i) and (ii) being based on the total weight of (i) and (ii). Such thermoplastic vulcanizates are described in Int'l. Pat. App. Pub. Nos. WO 2004/029155 and WO 2008/060549.

Preferred thermoplastic polyesters are typically prepared by polymerization of one or more dicarboxylic acids (where herein the term "dicarboxylic acid" also refers to dicarboxylic acid derivatives such as esters) and one or more diols. In preferred polyesters the dicarboxylic acids comprise one or more of terephthalic acid, isophthalic acid, and 2,6- naphthalene dicarboxylic acid, and the diol component comprises one or more of HO(CH ₂ ) _n OH (I); 1 ,4-cyclohexanedimethanol;

HO(CH ₂ CH ₂ O) _m CH ₂ CH ₂ OH (II); and

HO(CH ₂ CH ₂ CH ₂ CH ₂ O) _z CH ₂ CH ₂ CH ₂ CH ₂ OH (III), wherein n is an integer of 2 to 10, m on average is 1 to 4, and z is on average about 7 to about 40. Note that (II) and (III) may be a mixture of compounds in which m and z, respectively, may vary and that since m and z are averages, they need not be integers. Other dicarboxylic acids that may be used to form the thermoplastic polyester include sebacic and adipic acids.

Hydroxycarboxylic acids such as hydroxybenzoic acid may be used as comonomers. Specific preferred polyesters include poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), poly(1 ,4- butylene terephthalate) (PBT), poly(ethylene 2,6-naphthoate), and poly(1 ,4-cyclohexyldimethylene terephthalate) (PCT).

The thermoplastic polyester may be a thermoplastic polyester elastomer, such as a copolyetherester. Useful copolyetheresters are copolymers that have a multiplicity of recurring long-chain ester units and short-chain ester units joined head-to-tail through ester linkages, said long-chain ester units being represented by formula (A):

and said short-chain ester units being represented by formula (B):

wherein

G is a divalent radical remaining after the removal of terminal hydroxyl groups from poly(alkylene oxide)glycols having a number average molecular weight of between about 400 and about 6000, or preferably between about 400 and about 3000; R is a divalent radical remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than about 300; D is a divalent radical remaining after removal of hydroxyl groups from a diol having a molecular weight less than about 250; and wherein said copolyetherester(s) preferably contain from about 15 to about 99 weight percent short-chain ester units and about 1 to about 85 weight percent long-chain ester units, or wherein the copolyetherester(s) more preferably contain from about 20 to about 95 weight percent short-chain ester units and about 5 to about 80 weight percent long-chain ester units.

As used herein, the term "long-chain ester units" as applied to units in a polymer chain refers to the reaction product of a long-chain glycol with a dicarboxylic acid. Suitable long-chain glycols are poly(alkylene oxide) glycols having terminal (or as nearly terminal as possible) hydroxy groups and having a number average molecular weight of from about 400 to about 6000, and preferably from about 600 to about 3000. Preferred poly(alkylene oxide) glycols include poly(tetramethylene oxide) glycol, poly(trimethylene oxide) glycol, poly(propylene oxide) glycol, poly(ethylene oxide) glycol, copolymer glycols of these alkylene oxides, and block copolymers such as ethylene oxide-capped polypropylene oxide) glycol. Mixtures of two or more of these glycols can be used.

As used herein, the term "short-chain ester units" as applied to units in a polymer chain of the copolyetheresters refers to low molecular weight compounds or polymer chain units having molecular weights less than about 550. They are made by reacting a low molecular weight diol or a mixture of diols (molecular weight below about 250) with a dicarboxylic acid to form ester units represented by Formula (B) above.

Included among the low molecular weight diols which react to form short-chain ester units suitable for use for preparing copolyetheresters are acyclic, alicyclic and aromatic dihydroxy compounds. Preferred

compounds are diols with about 2-15 carbon atoms such as ethylene, propylene, isobutylene, tetramethylene, 1 ,4-pentamethylene, 2,2- dimethyltrimethylene, hexamethylene and decamethylene glycols, dihydroxycydohexane, cydohexane dimethanol, resorcinol, hydroquinone, 1 ,5-dihydroxynaphthalene, and the like. Especially preferred diols are aliphatic diols containing 2-8 carbon atoms, and a more preferred diol is 1 ,4-butanediol. Included among the bisphenols which can be used are bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)methane, and bis(p- hydroxyphenyl)propane. Equivalent ester-forming derivatives of diols are also useful (e.g., ethylene oxide or ethylene carbonate can be used in place of ethylene glycol or resorcinol diacetate can be used in place of resorcinol). As used herein, the term "diols" includes equivalent ester- forming derivatives such as those mentioned. However, any molecular weight requirements refer to the corresponding diols, not their derivatives.

Dicarboxylic acids that can react with the foregoing long-chain glycols and low molecular weight diols to produce the copolyetheresters are aliphatic, cycloaliphatic or aromatic dicarboxylic acids of a low molecular weight, i.e. having a molecular weight of less than about 300. The term "dicarboxylic acids" as used herein includes functional equivalents of dicarboxylic acids that have two carboxyl functional groups that perform substantially like dicarboxylic acids in reaction with glycols and diols in forming copolyetherester polymers. These equivalents include esters and ester-forming derivatives such as acid halides and anhydrides. The molecular weight requirement pertains to the acid and not to its equivalent ester or ester-forming derivative. Thus, an ester of a dicarboxylic acid having a molecular weight greater than 300 or a functional equivalent of a dicarboxylic acid having a molecular weight greater than 300 are included provided the corresponding acid has a molecular weight below about 300. The dicarboxylic acids can contain any substituent groups or combinations that do not substantially interfere with the copolyetherester polymer formation and use of the polymer in the compositions of this invention.

The term "aliphatic dicarboxylic acids," as used herein, refers to carboxylic acids having two carboxyl groups each attached to a saturated carbon atom. If the carbon atom to which the carboxyl group is attached is saturated and is in a ring, the acid is cycloaliphatic. Aliphatic or

cycloaliphatic acids having conjugated unsaturation often cannot be used because of homopolymerization. However, some unsaturated acids, such as maleic acid, can be used. Aromatic dicarboxylic acids, as the term is used herein, are dicarboxylic acids having two carboxyl groups each attached to a carbon atom in a carbocyclic aromatic ring structure. It is not necessary that both functional carboxyl groups be attached to the same aromatic ring and where more than one ring is present, the rings can be joined by aliphatic or aromatic divalent radicals or divalent radicals such as -O- or -SO2-.

Representative useful aliphatic and cycloaliphatic acids that can be used include sebacic acid; 1 ,3-cyclohexane dicarboxylic acid; 1 ,4- cyclohexane dicarboxylic acid; adipic acid; glutaric acid; 4-cyclohexane- 1 ,2-dicarboxylic acid; 2-ethylsuberic acid; cyclopentanedicarboxylic acid decahydro-1 ,5-naphthylene dicarboxylic acid; 4,4'-bicyclohexyl

dicarboxylic acid; decahydro-2,6-naphthylene dicarboxylic acid; 4,4'- methylenebis(cyclohexyl) carboxylic acid; and 3,4-furan dicarboxylic acid. Preferred acids are cyclohexanedicarboxylic acids and adipic acid.

Representative aromatic dicarboxylic acids include phthalic, terephthalic and isophthalic acids; bibenzoic acid; substituted dicarboxy compounds with two benzene nuclei such as bis(p- carboxyphenyl)methane; p-oxy-1 ,5-naphthalene dicarboxylic acid; 2,6- naphthalene dicarboxylic acid; 2,7-naphthalene dicarboxylic acid; 4,4'- sulfonyl dibenzoic acid and C1-C12 alkyl and ring substitution derivatives thereof, such as halo, alkoxy, and aryl derivatives. Hydroxyl acids such as p-(beta-hydroxyethoxy)benzoic acid can also be used provided an aromatic dicarboxylic acid is also used.

Aromatic dicarboxylic acids are a preferred class for preparing the copolyetherester polymers useful for this invention. Among the aromatic acids, those with 8-16 carbon atoms are preferred, particularly terephthalic acid alone or with a mixture of phthalic and/or isophthalic acids.

The copolyetheresters preferably comprise about 15 to about 99 weight percent short-chain ester units corresponding to Formula (B) above, the remainder being long-chain ester units corresponding to Formula (A) above. The copolyetheresters more preferably comprise about 20 to about 95 weight percent, and even more preferably about 50 to about 90 weight percent short-chain ester units, where the remainder are long-chain ester units. More preferably, at least about 70% of the groups represented by R in Formulae (A) and (B) above are 1 ,4- phenylene radicals and at least about 70% of the groups represented by D in Formula (B) above are 1 ,4-butylene radicals and the sum of the percentages of R groups which are not 1 ,4-phenylene radicals and D groups that are not 1 ,4-butylene radicals does not exceed 30%. If a second dicarboxylic acid is used to prepare the copolyetherester, isophthalic acid is preferred and if a second low molecular weight diol is used, ethylene glycol, 1 ,3-propanediol, cyclohexanedimethanol, or hexamethylene glycol are preferred.

A blend or mixture of two or more copolyetherester elastomers can be used as the thermoplastic polyester component in the compositions of the invention. The copolyetherester elastomers used in the blend need not come within the values disclosed hereinbefore for the elastomers on an individual basis. However, the blend of two or more copolyetherester elastomers must conform to the values described herein for the

copolyetheresters on a weighted average basis. For example, in a mixture that contains equal amounts of two copolyetherester elastomers, one copolyetherester can contain 60 weight percent short-chain ester units and the other copolyetherester can contain 30 weight percent short-chain ester units for a weighted average of 45 weight percent short-chain ester units.

Preferably, the copolyetherester elastomers used as components in the compositions of the present invention are prepared from monomers comprising (1 ) poly(tetramethylene oxide) glycol, poly(trimethylene oxide) glycol and/or ethylene oxide-capped poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol being preferred; (2) a dicarboxylic acid selected from isophthalic acid, terephthalic acid and mixtures thereof; and (3) a diol selected from 1 ,4-butanediol, 1 ,3-propanediol and mixtures thereof, or are prepared from esters of terephthalic acid, e.g.

dimethylterephthalate, 1 ,4-butanediol and poly(alkylene oxide) glycol. More preferably, the copolyetherester elastomers are prepared from esters of terephthalic acid, e.g. dimethylterephthalate, 1 ,4-butanediol and poly(tetramethylene oxide) glycol.

Examples of suitable copolyetherester elastomers useful as the continuous phase of the thermoplastic vulcanizate component of the compositions of the invention are commercially available under the trademark Hytrel ^® polyetherester elastomers from E. I. du Pont de

Nemours and Company, Wilmington, Delaware.

The acrylate rubber component of the TPV compositions useful in compositions of the invention may be prepared by copolymerizing one or more (meth)acrylate monomers with one or more olefins. A preferred olefin is ethylene. As used herein, the term "crosslinked acrylate rubber" refers to the second component of the TPV component of the flame retardant compositions of the invention. Preferred acrylate rubbers include poly(alkyl (meth)acrylate) rubbers, ethylene/alkyl (meth)acrylate copolymer rubbers and poly(perfluoroalkyl (meth)acrylate) rubbers, and more preferably ethylene/alkyl (meth)acrylate copolymer rubbers where the alkyl group has from 1 to 4 carbons. Preferred ethylene/alkyl

(meth)acrylate copolymers are those derived from less than about 80 weight percent of ethylene and more than about 20 weight percent alkyl (meth)acrylate.

The acrylate rubbers may optionally comprise additional repeat units derived from one or more functionalized comonomers, such as (meth)acrylate glycidyl esters (such as glycidyl methacrylate), maleic acid, maleic acid esters (such as monoethyl maleate) or other comonomers having one or more reactive groups including acid, hydroxyl, epoxy, isocyanates, amine, oxazoline, chloroacetate, or diene functionality. The acrylate rubbers may also be prepared from more than two (meth)acrylate monomers. Examples are acrylate rubbers made by polymerizing ethylene, methyl acrylate, and a second acrylate (such as butyl acrylate).

The melt processible TPV compositions useful in the invention may be prepared by mixing at least one of the above-described thermoplastic polyesters with at least one of the above-described acrylate rubbers in the presence of an organic peroxide free radical initiator and an organic diene (i.e. multiolefinic) co-agent. The resultant composition is then dynamically cured to produce a TPV having a crosslinked disperse phase within a thermoplastic continuous phase.

Suitable free-radical initiators include but are not limited to 2,5- dimethyl-2,5-di-(f-butylperoxy)hexyne-3; i-butyl peroxybenzoate; 2,5- dimethyl-2,5-di-(f-butylperoxy)hexane; dicumyl peroxide; a,a-bis(f- butylperoxy)-2,5-dimethylhexane; and the like and nnixtures thereof.

Suitable organic multiolefinic co-agents include but are not limited to diethylene glycol diacrylate; diethylene glycol dimethacrylate; Ν,Ν'-m- phenylene dimaleimide; triallylisocyanurate; trimethylolpropane

trimethacrylate; tetraallyloxyethane; triallyl cyanurate; tetramethylene diacrylate; polyethylene glycol dimethacrylate; and the like and mixtures thereof.

Thermoplastic vulcanizates used in the present invention may be prepared using processes such as those described in International Patent Publication WO 2004/029155. The actual mixing of components and subsequent dynamic crosslinking may be performed either in a batch mode or a continuous mode using conventional melt blending equipment.

The flame retardant composition described herein comprises at least one flame retardant (also referred to in the art as a flameproofing agent). Flame retardants are used in thermoplastic compositions to suppress, reduce, delay or modify the propagation of a flame through the composition or article made of the flame retardant composition. The at least one flame retardant is preferably present in the insulating

composition described herein in an amount from about 1 to about 30 weight percent, more preferably about 2 to about 20 weight percent, and still more preferably about 3 to about 15 weight percent, the weight percent being based on the total weight of the flame retardant

composition.

Preferably, the at least one flame retardant is a non-halogenated flame retardant and more preferably, it is selected from phosphinates of formula (C), diphosphinates of formula (D), polymers thereof and mixtures thereof:

wherein each of R ¹ and R ² independently is hydrogen, linear C ₁ -C ₆ alkyl groups, branched C ₁ -C ₆ alkyl groups or an aryl group; R ³ is a linear Ci- Cio-alkylene group, a branched Ci-Cio-alkylene group, a C ₆ -C ₁₀ -arylene group, an alkylarylene group or an arylalkylene group; M is a metal ion selected from calcium ion, magnesium ion, aluminum ion, zinc ion or mixtures thereof, m is 2 to 3; n is 1 or 3; and x is 1 or 2 with the proviso that when m is 2, then x and n are each 1 , and when m is 3, x is 2 and n is 3; and optionally comprising condensation products of melamine and/or reaction products of melamine with phosphoric acid and/or reaction products of condensation products of melamine with phosphoric acid and/or comprising a mixture of these.

R ¹ and R ² are preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and/or phenyl. R ³ is preferably methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, or phenylene or naphthylene, or methylphenylene, ethylphenylene, tert-butylphenylene,

methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene, or phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene. M is preferably aluminum or zinc.

Preferred phosphinates are metal salts of organic phosphinates, such as methylethylphosphinat.es and diethylphosphinates. More preferred are aluminum methylethylphosphinate, aluminum

diethylphosphinate, zinc methylethylphosphinate, and zinc

diethylphosphinate. Also preferred are aluminum phosphinate,

magnesium phosphinate, calcium phosphinate, and zinc phosphinate. The flame retardant can have any particle size distribution, as commonly understood and used by those having skill in the art, but preferably it has a particle size (D90 value) of less than or equal to 100 microns and more preferably less than or equal to 20 microns. The D90 value corresponds to a particle size below which 90 weight percent of the particles lie, wherein the particle size distribution is measured by the technique of laser diffraction from a suspension of particles in a solvent as determined using a Mastersizer 2000 particle size analyzer available from Malvern Instruments Ltd. This test method meets the requirements set forth in ISO 13320.

The flame retardant composition according to the present invention comprises an ultra-high molecular weight polysiloxane that is present in a particular concentration. The ultra-high molecular weight polysiloxane has a weight average molecular weight (Mw) of at least 100000, the weight average molecular weight (Mw) being determined by gel permeation chromatography (GPC).

The ultra-high molecular weight polysiloxane is present in the composition according to the present invention in an amount from about 0.05 to about 1 .75 weight percent, the weight percentage being based on the total weight of the flame retardant composition.

An example of a preferred ultra-high molecular weight polysiloxane is an ultra-high molecular weight polysiloxane of formula (E):

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently selected from the group consisting ot alkyl, vinyl, chloroalkyl, fluororalkyl, aminoalkyl, epoxy, chloro, fluoro, or hydroxy groups, and a is 500 or greater, preferably 1000 or greater, more preferably from 1000 to 20000, and still more preferably from 1000 to 15000. Preferably, the ultra-high molecular weight polysiloxane is a polydimethylsiloxane of formula (F), i.e. an ultra-high molecular weight polysiloxane wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ of formula (E) are methyl groups:

wherein R ¹ and R ² are independently alkyl, vinyl, chloroalkyl, aminoalkyl, epoxy, fluororalkyl, chloro, fluoro, or hydroxy groups, and a is 500 or greater, preferably 1000 or greater, more preferably from 1000 to 20000, and still more preferably from 1000 to 15000.

More preferably, the ultra-high molecular weight polysiloxane is a polydimethylsiloxane of formula (G), i.e. an ultra-high molecular weight polysiloxane wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ of formula (E) are methyl groups and wherein R ¹ and R ⁸ of formula (E) are vinyl groups:

wherein a is 1350 or greater.

Even though the molecular weight of ultra-high molecular weight polysiloxanes is ultra-high, the flexibility and free volume of the siloxane chain allow the polymers to exist as fluids with viscosities increasing as molecular weight increases. Ultra-high molecular weight polysiloxanes are not crosslinked, flow like molten polymers and have viscosities in the 10 to 50 million mm ² /s range.

Ultra-high molecular weight polysiloxanes are available in many different forms, e.g., as pure compositions, as compounds, as

concentrates, or as masterbatches. Example of polymers into which the ultra-high molecular weight polysiloxanes can be compounded include polypropylene, polyethylene, polystyrene, polyamides, polyacetal, acrylonitrile-butadiene-styrene (ABS), polyester elastomer and

copolyetherester elastomer. Typically, commercially available

concentrates may contain the ultra-high molecular weight polysiloxane in a concentration ranging from 40 to 70 weight percent; however, any concentration is acceptable for purposes of the invention so long as the desired weight percent in the final product can be achieved.

Examples of suitable ultra-high molecular weight polysiloxanes are MB50-010 sold by Dow Corning Corporation. MB50-010 is a masterbatch of ultra-high molecular weight polysiloxane dispersed in a copolyetherester elastomer that is in a solid dry pellet form.

The compositions of the present invention may further comprise one or more amorphous polymers. In such compositions, the one or more amorphous polymers are preferably present in an amount from about 1 to about 30 weight percent, more preferably from about 10 to about 30 weight percent, and still more preferably from about 15 to about 25 weight percent, the weight percentage being based on the total weight of the flame retardant composition. The one or more amorphous polymers are preferably selected from polycarbonates, polyarylates, amorphous polyester copolymers, poly(methyl methacrylate) ("PMMA"), and mixtures thereof. Amorphous polymers do not crystallize, even upon annealing. Amorphous polymers are characterized by their glass transition

temperature, Tg, which is the temperature at which the polymers are transformed from a glassy state to a rubbery state. More preferably, the one or more amorphous polymers are selected from polycarbonates, polyarylates and mixtures thereof. Polycarbonates are polymers which comprise carbonate linkages. Preferably, polycarbonates used in the present invention are aromatic polycarbonates, i.e. polymers which contain carbonate groups and aromatic moieties in the main polymer chain. Aromatic polycarbonates include homopolycarbonates,

copolycarbonates, copolyestercarbonates and mixtures thereof.

Preferably, the polycarbonates used in the present invention are high molecular weight polymers having a weight average molecular weight (Mw) from at or about 8000 to at or about 200000, the weight average molecular weight (Mw) being determined by gel permeation chromatography (GPC). Polycarbonates are produced by using a dihydroxydiarylalkane as the main starting material, including those wherein the alkane is branched. Such polycarbonates are manufactured by known processes, generally by reaction of a dihydroxy compound and/or a polyhydroxy compound with either phosgene or a diester of carbonic acid. More preferably, the polycarbonates used in the present invention are based on 4,4'-dihydroxy-2,2-diphenylpropane (i.e. bisphenol A, BPA) and are commonly referred to as bisphenol A polycarbonates. Polyarylates are polymers derived from the reaction of a polyhydroxy compound with a polycarboxylic acid compound, preferably from the reaction of one or more dihydroxy compounds with one or more

polycarboxylic acid compounds, and more preferably from the reaction of one or more dihydroxy compounds with one or more dicarboxylic acid compounds. Examples of polyhydroxy compounds include without limitation bisphenols, dihydric phenol ethers, dihydroxyaryl sulfones, dihydroxy benzenes, halo- and alkyl-substituted dihydroxy benzenes. Examples of polycarboxylic acid compounds include without limitation monocyclic aromatic dicarboxylic acids such as for example

benzenedicarboxylic acids including phthalic acid, isophthalic acid, terephthalic acid, o-, m-, and p-phenylenediacetic acids;

bis(carboxyaryl)Ci-6 alkanes; and polycyclic aromatic dicarboxylic acids such as for example diphenic acid and 1 ,4-naphthalic acid. More preferably, the polyarylates used in the present invention are derived from the reaction of 4,4'-dihydroxy-2,2-diphenylpropane (bisphenol A) and a mixture of isophthalic acid and terephthalic acid and still more preferably from the reaction of 4,4'-dihydroxy-2,2-diphenylpropane (bisphenol A) and a 50:50 mixture of isophthalic acid:terephthalic acid.

The flame retardant composition described herein may further comprise one or more heat stabilizers and/or antioxidants and/or metal deactivators (e.g. hydrazines, hydrazides and mixtures thereof).

Preferably, the one or more heat stabilizers and/or antioxidants are selected from diphenylamines, amides, thioesters, phenolic antioxidants, phosphites and mixtures thereof. When used, the heat stabilizers and/or antioxidants are preferably present in an amount of from about 0.01 to about 5 weight percent, or more preferably from about 0.01 to about 3 weight percent, the weight percentage being based on the total weight of the flame retardant composition.

The flame retardant composition described herein may further comprise additional additives such as synergists, colorants, fillers and reinforcing agents, impact modifiers, conductive additives, viscosity modifiers, nucleating agents, plasticizers, drip suppressants, and adhesion modifiers.

Fillers, modifiers and other ingredients described above may be present in the flame retardant composition in amounts and in forms well known in the art, including in the form of so-called nano-materials where at least one of the dimensions of the particles is in the range of 1 to 1000 nm.

The flame retardant compositions are melt-mixed blends, wherein all of the polymeric components are well-dispersed within each other and all of the non-polymeric ingredients are well-dispersed in and bound by the polymer matrix, such that the blend forms a unified whole. Any melt- mixing method may be used to combine the polymeric components and non-polymeric ingredients of the present invention. For example, the polymeric components and non-polymeric ingredients may be added to a melt mixer, such as, for example, a single or twin-screw extruder; a blender; a single or twin-screw kneader; a Haake mixer, a Brabender mixer, a Banbury mixer, or a roll mixer, either simultaneously by a single step addition, or in a stepwise fashion, and then melt-mixed. When adding the polymeric components and non-polymeric ingredients in a stepwise fashion, a portion of the polymeric components and/or non-polymeric ingredients are first added and melt-mixed. The remaining polymeric components and non-polymeric ingredients are subsequently added and the composition is further melt-mixed until a well-blended composition is obtained.

In another aspect, the present invention relates to a method for manufacturing an article by shaping the flame retardant composition of the invention and the article prepared therefrom. By "shaping", it is meant any shaping technique known to those skilled in the art, such as for example extrusion, injection molding, thermoform molding, compression molding, blow molding, rotational molding, melt casting and slush molding.

Preferably, the article is shaped by extrusion.

Due to the combination of high abrasion resistance and strippability, the flame retardant compositions according to the present invention are particularly suited for producing an insulating layer. The flame retardant composition described herein is particularly suited for producing a wire or cable coated with the flame retardant composition and even more particularly for producing a wire or cable useful in automotive applications. Thus, an aspect of the invention is a wire or cable comprising a coating comprising the flame retardant compositions described herein. Indeed, the flame retardant compositions described herein have the particular advantage of combining good chemical and temperature resistance, good abrasion resistance, good strippability and good retention of physical properties, particularly elongation, after long-term heat aging in air at temperatures as high as 150 ^° C. This unique combination of properties makes the compositions of the invention very attractive candidates for use in wire and cable applications and especially in wire and cable

constructions for use in automotive applications. Indeed, wire and cable used in automotive applications is subjected to high temperature and to mechanical abrasion caused by engine vibration and motion of the vehicle during normal use, resulting in deterioration of the wire and cable structures with use and time. Wires and cables may be coated with the flame retardant compositions described herein by processes known in the art such as for example by an extrusion process wherein the flame retardant compositions are extruded over the wires and cables at high speed using a single screw extruder with a tubular die.

The flame retardant compositions described herein combine good abrasion resistance and good strip characteristics while maintaining good mechanical properties. The ultra-high molecular weight polysiloxanes that are described herein are advantageously used as additives to improve abrasion resistance of flame retardant polyester compositions, particularly in the production of insulating layers for wire and cable constructions.

Thus, an aspect of the invention is a use of from about 0.05 to about 1 .75 weight percent, based on the total weight of the flame retardant composition, of an ultra-high molecular weight polysiloxane as additive in a flame retardant composition comprising a) the thermoplastic vulcanizate described herein and b) from about 1 to about 30 weight percent, based on the total weight of the flame retardant composition, of the at least one flame retardant described herein for improving the abrasion resistance of an insulating layer comprising said composition and the ultra-high molecular weight siloxane.

Also described herein is a use of a flame retardant composition comprising a) the thermoplastic vulcanizate composition described herein, b) from about 1 to about 30 weight percent, based on the total weight of the flame retardant composition, of the at least one flame retardant described herein and c) from about 0.05 to about 1 .75 weight percent, based on the total weight of the flame retardant composition, of the ultrahigh molecular weight polysiloxane described herein for manufacturing an abrasion resistant cable or wire, wherein the abrasion resistant cable or wire comprises a coating made of the flame retardant composition. Also described herein is a use of a cable or wire comprising a coating made of a flame retardant composition comprising a) the thermoplastic vulcanizate composition described herein, b) from about 1 to about 30 weight percent, based on the total weight of the flame retardant composition, of the at least one flame retardant described herein and c) from about 0.05 to about 1 .75 weight percent, based on the total weight of the flame retardant composition, of the ultra-high molecular weight polysiloxane described herein in an abrasive environment. As described above, examples of abrasive environments are automotive applications wherein the cable or wire is subjected to high temperature and to mechanical abrasion caused by engine vibration and motion of the vehicle during normal use.

Thus, an aspect of the invention is a use of from about 0.05 to about 1 .75 weight percent, based on the total weight of the flame retardant composition, of an ultra-high molecular weight polysiloxane as an additive in a flame retardant composition comprising a) the thermoplastic vulcanizate described herein and b) from about 1 to about 30 weight percent, based on the total weight of the flame retardant composition, of the at least one flame retardant described herein for improving the abrasion resistance and strip force of an insulating layer comprising said composition and the ultra-high molecular weight siloxane. Also described herein is a use of a flame retardant composition comprising a) the thermoplastic vulcanizate composition described herein, b) from about 1 to about 30 weight percent, based on the total weight of the flame retardant composition, of the at least one flame retardant described herein and c) from about 0.05 to about 1 .75 weight percent, based on the total weight of the flame retardant composition, of the ultra-high molecular weight polysiloxane described herein for manufacturing an abrasion resistant and strippable cable or wire, wherein the abrasion resistant and strippable cable or wire comprises a coating made of the flame retardant

composition.

Thus, an aspect of the invention is a method for improving abrasion resistance of an insulating layer of a wire or cable, the insulating layer comprising a flame retardant composition comprising a) the thermoplastic vulcanizate described herein and b) at least one flame retardant as described herein, said method comprising a step of melt blending the ultra-high molecular weight polysiloxane described herein with the thermoplastic vulcanizate composition and applying said composition to a wire or cable.

Thus, an aspect of the invention is a method for improving abrasion resistance and strip force of an insulating layer of a wire or cable, the insulating layer comprising a flame retardant composition comprising a) the thermoplastic vulcanizate described herein and b) at least one flame retardant as described herein, said method comprising a step of melt blending the ultra-high molecular weight polysiloxane described herein with the thermoplastic vulcanizate composition and applying said composition to a wire or cable.

Preferably, an insulating layer made of the flame retardant composition of the invention possesses a scrape abrasion resistance of at least 100 cycles as measured according to ISO 6722:2002 (paragraph 9.3) using a 7 Newton load and a needle having a diameter of 0.45 mm. More preferably, an insulating layer made of the flame retardant composition described herein possesses a scrape abrasion resistance of at least 100 cycles as measured according to ISO 6722:2002 (paragraph 9.3) using a 7 Newton load and a needle having a diameter of 0.45 mm and possesses a strip force less than 70 N as measured according to ISO 6722:2002.

The invention is further described in the Examples below, which are provided to describe the invention in further detail. These examples, which set forth a preferred mode presently contemplated for carrying out the invention, are intended to illustrate and not to limit the invention.

EXAMPLES

The following materials were used for preparing an insulating composition according to the present invention and a comparative example.

Materials

Thermoplastic vulcanizate (TPV): a vulcanizate blend containing about 50.2 weight percent of a copolyetherester elastomer component and a rubber component, the weight percentage being based on the total weight of the vulcanizate blend. The copolyetherester elastomer comprised about 15.8 weight percent of poly(tetramethylene oxide) having an average molecular weight of about 1000 g/mol as polyether block segments, the weight percentage being based on the total weight of the copolyetherester elastomer, the short chain ester units of the

copolyetherester being polybutylene terephthalate segments. The rubber component was an ethylene methyl acrylate copolymer comprising 62 weight percent of methyl acrylate, the weight percentage being based on the total weight of the copolymer. The rubber was crosslinked using about 3.4 weight percent of 2,5-dimethyl-2,5-di-(t-butylperoxy) hexyne-3 (DYBP) as peroxide curative and about 4.6 weight percent of an organic

multiolefinic co-agent cure system, specifically a diethylene glycol dimethacrylate (DEGDM) cure system using a dynamic vulcanization process in a melt extruder as described in the detailed description and in Intl. Patent Appln. Publn. No. WO 2004/029155.

As required for the manufacturing process and well-known to those skilled in the art, the thermoplastic vulcanizate contained up to 3 weight percent of heat stabilizers, antioxidants and metal deactivators and up to 2 wt percent of a color concentrate. The thermoplastic vulcanizate comprised about 2 weight percent of suitable heat stabilizers and/or antioxidants including diphenylannines, amides, thioesters, phenolic antioxidants and/or phosphites.

Ultra high molecular weight polvsiloxane: MB 50-010, an ultra-high molecular weight polydimethylsiloxane dispersed in a copolyetherester elastomer at a siloxane content of 50 weight percent, available from Dow Corning Corporation. This ultra-high molecular weight

polydimethylsiloxane corresponds to the polydimethylsiloxane of formula (G).

Flame retardant: Exolit® OP935, an aluminum salt of diethylene phosphinate having a D90 max of 7.506 microns, available from Clariant International Ltd.

Comparative additives:

Licolub® WE40P, an ester of montanic acids with multifunctional alcohols, available from Clariant International Ltd.

Tegomer® C-Si2342, an organo-modified siloxane (PDMS with with carboxylated end groups) available from Degussa-Goldschmidt GmbH. Hi-Wax 1 105: MAAH ethylene-propylene wax, available from Mitsui Chemicals, Inc..

Test Methods

Abrasion resistance was determined by the scrape abrasion specification according to ISO 6722:2002 (paragraph 9.3) using a 7 Newton load, a needle having a diameter of 0.45 mm and at a frequency of 55 ±5 cycles/min. Scrape abrasion resistance was measured on copper cables that had been coated with the compositions according to the present invention (E1 -E2) and the comparative compositions (Comparative

Examples C1 -C6) so as to form coated copper wires having a diameter of 1 .65 mm. Coated cables were prepared on a Nextrom 45mm 30:1 L/D pressure extrusion line at a die temperature of 240 ^° C. The compositions were extruded directly on a stranded 7x0.32mm red annealed copper cable of 0.935 mm diameter as the conductive core thus producing a single insulating layer with a wall thickness of 0.35 +-0.3 mm. Results are expressed in numbers of cycles to failure and correspond to the average value of three test specimens.

Strip force measurements were performed according to ISO 6722:2002. The strip force of an insulated wire is the axial force expressed in Newtons required to remove a given length of insulation from the wire, i.e. the force necessary to break the adhesive bond between the insulation and the wire conductor. Strip force measurements were performed on test specimens (coated cables) prepared as described above with respect to the preparation of samples for abrasion resistance testing. Results are expressed in Newtons and correspond to the average value of three test specimens.

Flammabilitv testing was performed according to UL 94 test standard, 20 mm vertical burning test. Test specimens were formed from compositions of the invention (Examples 1 and 2 (E1 -E2)) and from comparative compositions (Comparative Examples C1 -C6) by injection molding the compositions in the form of test bars of dimensions 125 mm long by 13 mm wide by 0.8 mm thick. Before measurement, the test specimens were conditioned for 48 hours at 23°C and 50% relative humidity. According to this procedure test specimens were clamped with the longitudinal axis vertical, so that the lower end of each of the specimens was 300 mm above a horizontal layer of dry absorbent surgical cotton. A burner producing a blue flame 20 mm high was placed such that the flame was applied centrally to the mid-point of the bottom edge of the specimen being tested for 10 seconds. After the application of the flame to the specimen for 10 seconds, the burner was withdrawn from the sample and the after-flame time, ti, was measured. When after-flaming of the test specimen ceased, the burner was again placed under the specimen for an additional 10 seconds. The flame was then withdrawn from the test specimens and the second after-flame time, t ₂ , was measured. Materials are classified according to the test specifications as V-0, V-1 or V-2, based on the behavior of the material during burning, V-2 being the least demanding classification. Examples 1 and 2 (E1 -E2) and Comparative Examples (C1 -C6)

Flame retardant compositions of the invention Examples 1 and 2 (E1 -E2) were prepared as follows. The above-described TPV

composition, flame retardant and ultra-high molecular weight polysiloxane, in the amounts listed in Table 1 were melt blended in a 40 mm twin screw extruder (Berstorff ZE40) operated at a temperature of about 230 ^° C to about 240 ^° C using a screw speed of about 300 rpm, and a throughput of 90-1 10 kg/hour. The melt temperature was approximately 275 ± 10 ^° C. Quantities shown in Table 1 are presented in weight percent on the basis of the total weight of the composition.

The compounded mixture was extruded in the form of laces or strands which were then cooled in a water bath, chopped into granules and placed in sealed aluminum lined bags in order to prevent moisture pick-up.

The compositions of Comparative Examples C1 -C6 were prepared in a similar manner. These comparative compositions did not contain ultra-high molecular weight polysiloxane. Components of the C1 -C6 compositions are shown in Table 1 .

Results of abrasion resistance testing, strip force testing, and flammability testing, performed as described above, are reported in Table 1 .

As indicated in Table 1 , the incorporation of conventional additives (C3-C5) such as lubricants, mold-release agents or surface modifiers in a flame retardant composition (C3-C5) did not produce cables exhibiting a combination of an improved abrasion resistance and improved strip characteristics compared to Comparative Example C2.

The incorporation of 4 wt.% of a masterbatch comprising 50% of an ultra-high molecular weight polysiloxane in a flame retardant composition (C6) did not produce a flame retardant compositions that exhibited a combination of improved abrasion resistance and improved strip characteristics compared to Comparative Example C2. Although the incorporation of 4 wt.% of a masterbatch comprising 50% of an ultra-high molecular weight polysiloxane in a flame retardant composition resulted in production of cables having improved strip characteristics the test specimens exhibited significantly reduced abrasion resistance (17 cycles vs.67 cycles).

The incorporation of 2 wt.% of a masterbatch comprising 50% of an ultra-high molecular weight polysiloxane in a flame retardant composition produced a cable coated with a composition E1 that exhibited a

combination of improved abrasion resistance (83 cycles vs. 67 cycles) and improved strip characteristics compared to C2.

The incorporation of 3 wt.% of a masterbatch comprising 50% of an ultra-high molecular weight polysiloxane in a flame retardant composition produced a cable coated with a composition E2 that exhibited comparative flame retardance performance relative to C1 and a combination of improved abrasion resistance (175 cycles vs. 94 cycles) and improved strip characteristics compared to C1 .