GB2520358A - A heel counter or toe puff - Google Patents

Abstract

A heel counter or a toe puff formed of a composite material comprising a polymer component and a non-polymeric additive, wherein the composite material has a dielectric loss tangent of more than 0.05 and the non-polymeric additive increases the dielectric loss tangent of the composite material. The non-polymeric additive may be a metallic powder or carbon black. The addition of the conductive additive to a polymer can improve the electrical and thermal properties of the polymer and will improve its susceptibility to microwave heating. Counters or puffs are rigid and generally formed of resilient polymeric materials which give structure and strength to the heel or toe of the shoe. Susceptibility to microwaves means that the structures can be heated quickly prior to moulding.

Description

Intellectual Property Office Applicacion Nc,. (lB 320430.0 RTM Date: IS May 2014 The following terms are registered trade marks and should he rcad as such wherever they occur in this document: Cabot Inlelleclual Property Office is an operaling name of the Pateni Office www.ipo.gov.uk A Heel Counter or Toe Puff

Field of Envebtion

The present invention relates to the manufacture of for twear. In particular, the present invention provides heel counters and toe puffs that are made of an improved material.

The improved material makes the heel counters and toe puffs more susceptible to microwave heating and imprOves their thermal and mechanical properties.. This may be beneficial as microwave heating can be used to heat heel counters and toe puffs much more rapidly andefficiently than current heating methods.

Background of Invention

Many items of footwear contain heel counters and/pr toe puffs. Heel counters are generally formed of resilient polymeric materials that are formed into a suitable shape and provide structure, strength and protection to the heel region of the footwear Toe a5 puffs are also generally formed of resilient polymeric rnate.ri]s that are formed into a suitable shape and provide structure., strength and protection to the toe region of the footwear. A major function of both heel counters and toe puffs is to stiffen the relevant part of the footwear.

It s often necussary to heat both heel c!=ounters and toe puffs dunng manufactuie of footwear In particular, this is done during, oç immediately before, a moulding stage when the heel counter o.r toe puff is moulded into the desired shape. This is because the materials used to form heel counters and toe puffs are necessarily rigid at room temperature and it is necessary to. heat the materials to make them fk xible enough to mould.

Generally, heel counters and toe puffs are heated and moukied insitu, That is, heel counters and toe puffs are heated when they form part of at least partially formed piece of footwear In particular, the heel counters and toe puffs may heated at the same time as other components of the fbotwear, such as leather or synthetic upper layers. For example, a heel counter of a sports shoe may be heated whilst fixed to a polyurethane foam upper layer. This may be problematic as, while it is necessary to heat the heel counter or toe puff to high temperature in order for it to be moulded, it may riot benefrc;al to heat the other components of the footwear 2' lurther, after heating ft'i' necessary to cool a unter crtoe puff in oider to ensute shape Min1n. Heattg other components: of the foSr hinders the cooling process due to heat retained In those cornponenttA relat&J Issue is that the presenoe.

S Oft ercOmponeAti will stow cortduefnie heating Of a heel counter ortoepuff and iris leceasry to heat those otherS components. tQ tethperat*4té$ higher than the desired temperature QPthaQQl4flte; orpuff In order'to heat the cqurterorpuftsufflSntly eurrentiy, heel counters ace heated using a back pal" moulding mactine. These to ttathMes utilise' ether heatid air and/or heated moulds to heat the,,ceunter and:a'wo pait' rrioiiid to Mould the Courtbt into: a, suitable shapt Tho heel ôOutdOy' Is head to' between gq°c an4 90°C dependipg upOn The spao inatSrial froth *111th they, are :fpn,,,':. if ihe mould W heatedMe, pafts of mould are gereraHy formed of metal and.

arehealed' to between: 0Q and 15C, $eel eguritem and toe puffs re heated, by is inserting the apprOate component' Into the mould pressing the pars: of 0, mSd, tt" ether and he' iig Th" k' ;ponents lot between SO and, 40 secords.. Aftr eating the components are removed from the moukiing machine' and ae cooled at a,coollng $$ion It Is desirable to gØl the cOmpopGñts to 20°C. However1 not only the heel ninter That Is heed, the cooling pro,s is re}$$',, stow A typical cooling o,oyde only lasts 30 seconds and 11*. is insufficient to reach thetarg&:temperature of kThereiorejhe components are generally riotco,,lqd fle optimum empe!atwe but ternain bead.

As wifi be readily apprec1a4, the,cUrflsitmetho o dk'pert moulding has a,aun'iber zs of laws, Components other' than the heel,couhteit are heated during the "mbulding which is not" desirable, Addiflcnafly and, as:5, result it is difficuJi to rapidly cOol The counters: after heating. Ebially. the whole process is refative'iys1ow taking a rryinutS to' heat and cool an: IndMdusJ ta* part., in light;of'thls: It would be benetictaJ to. have an' aPparatUs End ittethod that' Would allow,more dàcted and quicker heating of the courttev'wlth lesS' heating of the othet' corrponentS. Toe; pd moulding Is oartled,*ut fri i very i,Srnar,neránd'tPesat$ problems aS applicable totheir rnouithnç..

In Ught of the abe: problem; a method of heating toe pJff,, and heel coflers, microwave heattng has' been propo, :,. This method ie'tb, ,su!jectofa, separate 1n4' related invention and is the subjectm.atter of.a UK patent application entitled A Heel Counter and/or Toe Puff Heatar" that was filed by Texon Management Ltd on the same day as this application.. fri orderfor the proposed method to be beneficial its necessary that a heel counter or toe puff is formed of a material that will heat rapidly when s exposed to microwaves.

In order for the method of microwave heating to be benefiral it is necessary that the heel counter ot'toe puff being heated is suitable for microwave heating. In particular, R is necessary that the materials from which the counters or puffs are formed have a to high microwave absorption, Microwave absorption within a mater'al is primarily determined by the dielectric loss, tangent (tanj of the material; .A matedal may he considered to have a suitably high dielectilo loss, tangent for microwave heating if it has a loss tangent of 005 or higher is Some materials that are currently used for heel counters and toe puffs do have a suitably high dielecthc loss tangent.. For example, a polymer belend of TRU (65%) and PMMA (35%) has a dielectric loss tangent of 0 1 arid is suitable for microwave heating In this material it is the TPU that contnbutes to microwave heating However, many current m.atertals do not have a suitably high dielectric loss tangent. In fact, most low cost composites cu rently used for heel counters and toe puffs do not contain TPU and are not midrowave receptive i.e. they have a dielectric loss tangent less, than 005.

These blends.include but are not limited to composites of PET, PP and EVA.

Although some.curreht materials do. have a suitably high microwave absorption, they zs were not designed to do so and, as a result their microwave absorptiv'ty is not optmised Further, many current materials are not suitable for microwave heating but have material properties that may be better suited for a given item of footwear than materials that are suitable for microwave heating In light of this there is a need for heel counters or toe puffs that are formed of materials that are modified from e.isting matenals to make them optimal for microwave heating

Summary of Invention

The present invention provides a heel counter or toe puff formed of a composite i,later:al comprising a polymer component and a non-polymeric additive, wherein the QorflpQsite:r,ateial has a dielectric loss tangent of more than.0.05 aid the non-pqlymertc additive increases: the dielectric ioastdnqentof the composite material The propoff Ion thio oisin*dc dditi requited to athieve an approprjate dlelecjyc S tangent is dependent an the conductlvfty of the additive. The non-polymeric additive maybe arnetaflic pow4erwnha cpnvctlvlwartpan. 1*6 snrt anittie composite.

may cg*an Q.O1*t% to tSM% at the metallic powder;. Al emailvely, the fort-pcrymeucaddftlve may have t conduttM otbetween 100 and ib,®O.Stn' and the compoSe. may contain more thai twt% of the nonolymetit additive. enerally, if to the non-potymeulo additive is arnetaflk pwder much SmailerarnouMsofte additive are Pessaw; This is due t th c. giea*èr otductLvJt of metalbe powder as compared tot eater a 4thtSs WIth lower conducti:iIty The present invention lé advantagezrna as the addftion ta tonductive additive to a, is pOlytne r can improve theelict4caf and themiai properties of the polymer. in partiwlar, edding eor&cM additives to p*ty erg can hictease the electrical and Thermal conductivity and rOdu' stheepeclIIche&t cipa:cd OflhittU1t1fl9 compb&w,,ated4 It will aI$o Increase: the dieteqtt css tangei*ofthe,rnateiiaj+ ALa rés$t, adding the additive to::a pólymerwitl Ibnprgve its susceptiblUty:to n*rov,, ye beatipg. Therefore1 a.

heel courger or toe puff formed of a polymer that has a aiitable additive added tb ft will be better tufted to mltrowsve heating and will be advantageous if me heelcounter or toe puff is fbrnied using miaUie heat. AS It has nev r previously been proposed to microwave heat: bee! courtters Or to pUffs addihg CofldutiVe additives Ms never pre ouly been considered to be beneficial: The pmferred jmount ngrt-poiyrnedccompo nent that any particular heel pujtr or o pull accdIg to the present invention contains will be dependent upon ffi polymer thet it u: to make the ounS or puL the specific nonrpohpttedt tothPoM or cotpoheMs that are used, the microwave heater that is used to heat t the ôgunter or puff SM the power & which the heater ii bpetatBd. Further, itwill also depend onthaeffectoflhenon-polymeric componénton the material pfbpèidesofthe polymer; For any sp*cifio composite: ft yjill ba necessary to have a balance be$en tile impioed suitability for Merowave heating that Is gained by adding The non-poiymericcomponent and arty potentially negative eflettb the matedsi properties of the polymer. This.baince wifi determine the ideal amount of. non-polymeric component that the composite should contaip. It is believed that, the skilled person will be able to readily determine the ideal quantity of non-polymeric component fQr any specific composite using routine expenm'entation.

S

in some embodiments of the'invention the composite may co'ntan at east 1wt% of a non-polymeric additive with a conductivity belween 100 and 10000 Srm1. Such additives include, but are not limited to, metal oxides, zeoi'ites (alurninosilicates) and fibre materials, Examples of aultabie. metal oxides include, but are' not limited to, zinc ox'de cobalt oxide and nickel nydroxide The non-polymeric additive may comprise only' one metal oxide or it may contaip a mix of metal okides. Examples of suitable fibre materials include but are not limited to! e-glas's and carbon flbre (including graphite). The non-polymeric additive may comprise only one suitable fibre material or it may contain a mix of fibre materials Furthermore, th non-polymeric additive may is contain a mix of metal oxides, zeolites and fibre materials or only metal oxides or only zeolites or only fibre materials.

The non-polymeric additive may also comprise metallic particles. f'metaliic particles are used it may be preferable that the nonpoiymeric additive comprises less than iwt'% of the composite materiaL Preferably metallic particles should only' b.c used in circumstances where uniform mixing of nanoparticulate metallic particles and the polymer can be achieved.

Although the non-polymeric component of the present invention may be any of the materials listed above or a mix thereof,, it may be generally preferable that the non polymeric component of the present fr'vention is carbon black. If the non-polymeric component is carbon black it is preferable that it comprises at least 2wt% of the composite material Generally, in these embodiments it is preferred that the non-polymeric component is formed solely of carbon black. However, it is possible' for the non-p,olymeri'c component to be formed of a mixture of carbon black and any of the non-polymeric components set out above In some embodiments of the present where the aesthetic appearance (particularly colour) of the heel counter or toe puff is important it may be preferable fot the non-rolytNftdffive to ct" pdse cabOñ black and a tol ur neUtraksing a ditive. Cqipur fleutra (Sing additives' fflckid9 but are tot!k:,it** zinoqxieort* or chalk, In such.

ec$dk,,abe proportipn of carbon blatk wHite attredto accquflt'fprtheS,edrc ProPel". of the gqloq, ne4n,Iisihg additive. Per example, if the oIour,peutEalising S aødftSIszih oxide the' amount of c',th,,. Sack; may be reduced from the amount requiied if' only parSon black it used as,, both additIves will tontdbute to thicrd*ae.

sorpMy.

ri black is the prefented nop*polyreric addtWe die to its ready and low cct 19 avaiat,iity,, pwtia4ariy in plymer asc, maserkatches. Further,, a large body of existing research l validated the' USS of cethon btnqk as a polymer additive to' improve thermal and rnecfanlcil properties of a cømposlternatedal.

If the polymer cbntalnsless thafl'2% carbon black it Is beheve4 thavtheéffEcti of'thé carbor bl will not b,e $UfflbiE'ht to significantly improve the su!ceptt'1hW to r*rowa,,,e heatk,,g of'the polyrner; However, it Is to he qnderstood' that 2% Is the.

:m113 ryuirn amount of carbon brick ap ing to the present invention and It whO be rneralfr preferable tar the polymer to ontain more carbon b:Md. In some *t'dirnentt of the, ptesert Ivwentton it may e advantageous that the polymer o coirpilses at least 5% carboh black In' sothé, effibOdiffiet it May be 9" aqt9,"uS that'the,pqlyrne!' comprisesat least 10% caibon black, As tor any other' noripq,,,erig component The' preferredH, ,, ou,nt ct carbon b!aøc,,that any particular' heel,xunter or toe putf"aording to, the pn,liventi will be Sperideilt upon' the porirner that is used to make the. counter orpuft, the. microwave heater that is used to,heat'the coUnter'Or puff'and the power atwS th"heater'ts c*perated, Ftitthar, it will also dSsnd sthe efteot ofthécàrboP black Onto maten'al properties of the polymer: It is believed that: the skilled person, wilt be able to readily 4eWmne the ideal quantity 0 qathon black for any specific polymer t$ing routine au axporimetion. It Is currently believed' that:"Jt Si not generally be adantageous for a poly'rner'to comprIse more than 2O, ca'rbon'bjack.

Catbon bIack can be added to a polymer to forth aS I'oou,nter or toe puft"attcwthng b the present lne''tIOp In any marAer that would be Bppirtenttothe person,ikilIed In 7.

the ar.However,. it may be preferable that the carbon black component of the polymer is addeo to the polymer by adding carbon back masterbatch PE2772 to tne polymer PE2772 contains approximately 47.5% carbon black, the remainder being a carrier polymer.. The suitable polymer carrier and the polymers to which PE2772 can be S added wHI be w&l known to the person skiUed in the art, Carbon black can be added using any suUabl polymer carrier, for example polypropylene. The choice of how carbon black is added will be dependent upon the properties and oomposltiQn of the polymer to which the carbon black s added The polymer of a heel counter or toe puff according to the present invention may be any polymer that is suitatle for forming.a heel counter or* toe puff and to which carbon black can be readily added..

the polymer of a heel counter or toe puff of the present invention may be a sandwich is product formed of larninatet Any such sandwich product may or may not be impregnated with a latex. In one embodiment, the polymer may comprise outer layers of polyester (PET) and an inner layer of ethylene-vinyl acetate (EVA), recycled polypropylene (P.P) and recycled low density polyethylene (LDPE). The inner layer may comprise 30 50% EVA and 20-40% of PP and LDPE U has been found that is most advantageous to add 9-10% carbon black to this polymer, preferably by adding 1.9-21% PE2772. The carbon black component replaces the LOPE component of the polymer, whilst maintain the EVA and PP components. It has also been found tht it is advantageous to increase the proportion of EVA when adding the carbon black masterbatch. This can be done by using PP6331 as the carbon black masterbatch m additive. The effect of increasing varying the amOunt of EVA in the polymer using this carbon black masternatch is illustrated in Figure 3 and is described below Alternatitely the polymer of a hee' counter or toe puff of the present invention may comprise thermoplastic polyurethane (TPU) and ground recycled polyester terphthalate (PET). It has been found that 5 most advantageous to add 6-7% carbon black to this polymer preferably by addIng 12-14% PE2772, As a further alternative the polymer of the present invention maybe a mixture of TPU, EVA and an ethylerie/methacrylic (E/MAA copolymer. This polymer (excluding any carbon black component) may comprise 40-50% TPU, 30-40% EVA and 15-20% EIMAAA. It has been tound that is most advantageous Ia add 4-5:5% carbOn black to this polymer. preferably by adding 9-11% .PE2772.

s Alternatively the polymer may be a mixture of TPU and poly(methyl methacrylato) (PMMA) This polymer excluding any carbon black component, may comprise 60- 70% TPU and 3O4O% PMMA. t has been found that most advantageous to.. add 4- 55% carbon black to this polymer, preferably by adding 0-1% Pt2772 Further features and advantages, of the present invention, will be apparent from the description of the preferred embodiments set out below and illustrated in the Figures, Drawirig Figure 1 is a graph shawL g the effect of adding carbon black to the rnicrcwave heating i.s of a polymer used to form a heel counter according to the present invention.; Figure 2 is a second graph showing the same effect for a shorter period of heating; and Figure 3 i.s a graph showing the effect of varying the composition cf a polymer used to fcrm a heel counter according to the present invention.

Figure 1 shawsthe temperature rise of a varietyof polymers (1, 2, 3., 4,5, 6, 7) when subjected to 15s of microwave heating at 700W in a single-mode cavity. The three materials (1 2, 3) on the left do not contain any carbon black. The four materials (4, 5, 6, 7) on the right contain increasing amounts of carboh black. Specifically, from left to ñght they contain 2% PE27T12, 5% PE2772, 10% FF2772 and 15% FF2772 approximately 1% carbon black, 25% carbon black. 5% carbon black and *5% carbon black) The material (3) immeaiately to the left of these four materials 4, 5 6, 7) formed of exactly the same material and is formed in exactly the same manner as the four materials (4, 5, 6, 7) but c.ontaina rio Carbon black. All of these materials (3, 4, 5, &, 7) are sintered and are a mixture of 60-70% TPU and 30-40% PMMA, excluding any carbon black component. The rñaterial on the left (1) is 40-50% TPU, 30-40% EVA and 15-20% E/MAAA and is not sintered. The second material from the left 2) has a. different composition.

As can be readily seen from Figure 1, the temperature rise from microwave heating increases as The carbon black content of the intered material curnpnsing 60-70% TPU and 30-40% PMMA (3, 4. .5. 6, 7): increases, The biggest increase is obtained by increasng the carbon black content from 2 5% to 5% and when the content is s increased from 5% to 7.5% a much smaller increase.is obtained. Increasing the carbon black content from.0% to 5% Increases the temperature rise resultirg from the microwave heating from approximately 52°C to aproximateIy t1.8C. This is clearly heneficiai f microwave heating is used when forming a heel counter made of this materiaL Increasing the carbon black content from 5% to 7,5% increases the io temperature rise resufting from the microwave heating from approximately 118°C to approximately 1WC.. ln some cases this small aditignl rise may be benefidal.

However, in most cases it is expected that detrimental effects to the material properties of the polymer caused by adding the additional 25.% carbon black will Outweigh any benefit gained from the small increase in susceptibility to micrOwave heating. As a is result, it is believed that in most. situations it will be preferable to add approximately 5% carbon black to this material (3, 4, 5! 6, 7).

Theheating of four of the same materials (3, 5. 6, 7) is shown in Egure 2. in this Figure the temperature rise of the materials is measured when subjected to only Ss of micrc wave heating at 700W in a single-mode cavity. Again: it can be seer that addihg carbon black increases the temperature rise of the material (3, 5, 6, 7). The more carbon black that the material 3, 5, ft 7) contains, the greater the temperature rEse In this shorter heating the temperature rise gained by increasing the carbon black content from 5% to 7.5% is more significant. Thus, for materials that will undergo shorter heating and require lower temperature rises Xless than 60°C) it may be.. preferable that the material contains approximately 7.5% carbon black. Thi.s is an example cf.how the specific heating apparatus and conditions may affect the choice of the best material for a heel counter or toe puff according io the present nvent:on and in particu'ar the best carbon black content.. 30.

Figure 3 shows the temperature rise of four composite materials that could be used to from heel counters according to the present invention. All four materials have been subject to the same amount df microwave heating in the same cavity. The composition *1.0 of the tout materials is 8$ out in the Figure. This lgure Shows That: Increasing the ØrOpoition of fllA In the polyrper a. sing: carbon masterbatch PPS:3i imrovestbe swpJbWty of fltTOWIVe hntIn Of the polymer. In particular, the first rnSriai contains 10% PP, 4Q%EVA, 30% 1bPS and 20%. P06331. The secnd mateS s replaces the 30% LOPE With. an additional 3OPA EVA. This lthproves the j,iaterlaVs Sttsoaptlbilfty of mItiwave heating. The thkd material rp!aoesihe 10% PP of the first material an addltiorS 10% PP6331, gaip this imp.vea the materiaPs susceptthilit'jto microwave hting The fóh material replaces the 30% LOPE f the thltd material with, 30% EVA Again, Wa Unproxes the material's suscepitbitit to ntrowave heatlrtg. ii.

Claims (6)

1. Claims A heel counter or toe puff formed of a composite material comprising a polymer component and a non-polymeric additive, wherein the composite material has a S dielectric loss tn9ent of more than 0.05 and the non-polymeric additive increases the dielectric ass tangent of the corflposite material.
2. 2. A heel counter or toe puff according to claim 1 wherein the non-polymeric additive comprises a metallic powder with a conductivitygreater than 1O°Snt1 and the to composite contains between O.Olwt% and O.5wt% of the metallic powder.
3. 3. A heel counter or toe puff according to claim I comprising at least iwt% of the non-polymerw addthve with a conductivity between 100 and 10000 Sm as 4. A heel counter or toe puff according to claim 3 wherein, the additive comprises a metal oxide, a zeoflte or a fibre material.5. A heel counter or toe puff according to claim 4, wherein the non-polymeric a dditive comprises a metal oxide and comprises zinc oxide, cobalt oxide, nickel o hydroxide, a zeoftte, era mix of any thereof.E. A heel counter according to claim 4, wherein the non-polymeric additive comprises e-glass, carbon fibre, graphite ora mix of any thereof.7 A heel counter or toe puff according to claim 3, wherein the non-polymeric component is carbon black.S. A heel counter or toe puff according to claim 7, comprising at least 2wt% carbon black.9. A heel counter or toe puff accordirg to claim 8 comprising at least 5wt% carbon black.UlOb.A heel cOtntet at toe pqff apcc.r4ing to qkjm. c, ,pflSirg at least lflwt% carP°p black.IlL. Apeel counter ortoe.pufraccrclfrg W,anyot:ciólms Ito tø,wherein thecarbon s. black cornpon:ent of the composlte:matevial is. Obtained by addthg C ibot catbohblacii mastetbatch PE2772 to:tfie polynier.12 Albeel counter qrtaepffaccordpg to any preelng claim wherein thepotyrner Is a sandwich prodvettórmed of laminates. toit Ktiest counter r toe puff atorthng to asty prneding ciiIffi wheieit, the polytier is irnpreflE Si Sex.:14 A hee counter or toe prjff according to Sirn. 12 or claim 13, wherein the is pqjyrnarcorpprises ou erlayersptpqiyester(PET)artdEn hner layer of ethyfer*vinyl aSate (F A) rec cled poly pyter,e (PP) and recycled low density potyethylene It A:heei courtt br toe puff acccrding to dat 14, tterein the iriher layer g omprises:3Q-5C% Wtand W-4Q%; of PP and LOPE.* A heel counter r be puff accorag to annf claims? to 11, whereIn the poIymere1ornpflsesthermoplispolyureThane (WV) nrtd ground recyited polyester Ietephttlalate (PET).17. Abel counter or toe 1 aObótflh1r to släI wtie rein the polyr er äompriseS 4% carbon black.18. Ahe& caunteror toe puff sccordMgt* anyofclalcns no i:j, whereinthe 3D polymer cotnp:dies a: rnhtture at TM.), ethylene vinyl acetate (EVA) and an ethyl4rekfl ethaayiic (E(MM) cDpoiyrsr.1:$. A heel counter oft pyffçcqr4g t{n t8,Whereh the p lyfl*ttmprls$ 404P% TPU, $O4Q%EVAand 152Q%EJMM.20. A heel counter or toe puffaccorcung to cLaim 19, wher&n the polymer cmprees 4-55% carbon black.21 A heel counter or toe puff according to any of claims 7 to 11, whee'n the polymer comprises a mixture ci ThU and poly(meffylmethacrylate) (PMMA).22, A heel counteror toe puff according to claim 21, wherein the polymer, excluding any carbon black component, may compise 60-70% IPU and 3O-40% PMMA.23. A heel counte or toe puff accorthng to claim 22, whecein the polymer comprises 4-5.5% carbon black.Amendments to the claims have been filed as follows.Claims 14 1. A heel counter or toe puff formed of a composite material comprising a polymer component and a non-polymeric additive, wherein the composite material has a s dielectric loss tangent of more than 0.05 and the non-polymeric additive increases the dielectric loss tangent of the composite material and, wherein the composite comprises at least 1 wt% of the non-polymeric additive with a conductivity between 100 and 105000 Sm-1 and the non-polymeric additive comprises a metal oxide or a zeolite or a fibre material.2. A heel counter or toe puff according to claim 1, wherein the non-polymeric additive comprises a metal oxide and comprises zinc oxide, cobalt oxide, nickel hydroxide, a zeolite, or a mix of any thereof.is 3. A heel counter according to claim 1, wherein the non-polymeric additive comprises e-glass, carbon fibre, graphite or a mix of any thereof.
4. 4. A heel counter or toe puff acbording to any preceding claim wherein the polymer is a sandwich product formed of laminates.
5. 5. A heel counter or toe puff according to any preceding claim, wherein the cc polymer is impregnated with latex.
6. 6. A heel counter or toe puff according to claim 4 or claim 5, wherein the polymer 0000 25 comprises outer layers of polyester (PET) and an inner layer of ethylene-vinyl acetate (EVA), recycled polypropylene (PP) and recycled low density polyethylene (LDPE).C. n 0U7. A heel counter or toe puff according to claim 6, wherein the inner layer comprises 30-50% EVA and 20-40% of PP and LDPE.