CA1085122A - Sheath-core filament with antistatic core - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Antistatic filaments are comprised of a fiber-forming polymeric sheath and a fine core of a conductive polymer having a second order glass transition temperature of less than 25°C. Preferred core polymers are N-alkyl polycarbonamides, aliphatic polyesters and polyetheresters.
The filaments are spun by careful metering of the core poly-mer into the fiber-forming sheath polymer at the spinneret.

Description

~s~

Antistatic components in filaments can be included in Just the core of a sheath-core bicomponent ~ilament as shown in Japanese Application Publication 47-24176/1972 to E. Hayashi and T. Manabe, published July 41 1972; Br.
1,237,589 and U.S. 3,329,557. Such modified cores generally comprise ~rom 15 to 50~ of the filament. Other references such as U.S. 3,~16,183 and U.S. 37558,419 show concentrating the antistatic component in the ~ilament sheath. Each approach has its own limitations. The dispersion technique taught in Br. 1~237,589 and U.S. 3,329,557 encounters problems with some higher melting synthetic flber-~orming polymers such as polyamides of bis(4-aminocyclohexyl) methane and dodecanedioic acidJ described in U.S. 3,393~210, which use melt-spinning temperatures as high as 340C. At such high temperatures the antistatic modi~iers tend to thermally decompose, or to react with, to over disperse in or to become dissolved in the molten fiber-forming polymer prior to spinnlng. Thus, the search has continued for synthetic filaments and ~ibers having adequate antistatic properties with a minimum sacrifice of physicalJ chemical, aesthetic and performance properties.
The invention is an antistatic filamerlt of a synthetic linear fiber-~orming polymer having a polymeric antistatic core wherein the ~iber-forming polymer comprises a sheath and the core comprises 10 percent or less of the filament volume, the core consisting essentially of a low T~ conductive polymer as represented by a Tg (NMR) o~
less than 25C. and a log Rs of less than 10. The core polymer is pre~erably selected ~rom the group consisting of N-alkyl polycarbonamides, aliphatic polyesters and polyether-esters. Normally, the core should comprise at least 0.2 ?'1 ~8S~L22 ~ercent clf the f$1amen~ by volum~ an~ 2 to ~ perc~n~ i~
particu:Lar~y pre~crre~
The in~rention lnclud~ a proce~s P~r the pre~
tion oP the abo~r~ d~scribed anti~t~lc :~il~en~ ~er01n the c~re ~olymer is m~tored propo:~ior~lly ~ ~ con~inuous ~tream into the cor~ r~gion o~ ~ ~tream o~ th~ ~iber-~o~ng polymor imm~ tel~ prior to ~pinr~ng t~ ~pro~rld~ a v~l~e o~
10 perccnt or l~s of the tota~ ~amen~ ~tre~n. ~ sxtrud~d mon~s ha~ng a co~inuous cor~ consi~tlng ~s~tia:Lly oP
10 the conduc~ pol~mer a~ then quenche~ and collcct~d,.
Becau~e of thelr low ~!g~ h0 cor~ polym~r~ ar~
g@nerally much mor~ ~luid ~ no~l fib~r 8pi~n&; te~E)era-tures, ~or exu~ 225 to 34OC., ln c~ar~on to th~ mel~
viscosilties o~ the f~ber-~vrr~ng polym~rs. I~ rge di~p~rity b~t~en ~hc melt v~sco~ o~ tha Mb~r~orming and the core polym~r~ r~quir~s ce~ain p:r~DC~88 ~reCalXii~10n8 in spinnine ~ e~s of thi~ e~ion to m~ter aecurat~ly ~uch a low vi~co~t~r co~po~ t ~uch a low rela~iv~ ~rol uni~orm~y to a pluralitg o:~ ~il~en~O
~0 ~ ~ o~ the core i~ e3@ecially facillt~t~d 1~
th~ polgmor has an inhQr@n~ co~lty o~ at least abou~ O.l, and prefe:~bly at lea~t abo~ O~5O
Core spi~nlne a#sociat~d wil5h thi~ i~v~ roquire~ ;
a ~i~neret-p~ek~sembly aesigned t~ produc~ suf~cie~t pre~-~ure arop in ~he distribution and met~r pl~te zg~oæ to æue~s~-:eull;~r gpin a pl~r~3~ty ~ ~rm ~i~mo~ ap~13~rg t~ æ
lr~sert~ (in pl~ce o~ llled hole~) or thir~ narrow che-~els ~ormed in ver~ thi~ ~a~dt~L~he~ m~er pl~s i~ g the ipl~ eckr~tte ~,SO 3,~66~'~'o3, pr~id~ the cox~
3O xa~d~d to d~trib~t~ th~ c~re polymer ~i~o~ to Ithe ~,, 353i ~;~

8plnn~r~t cap~llarl~s. T~ latt~r technique i8 a more le and pre:f'err~d method. Caplllary tliblng in~rt~
wlth O.û8x2 ~nd 0.2xlO ~m in~3ld~ diam~ter~ an~ nglth~ are u~e~. ~e meter pl~Lt~ may bo ~s ~hln Z3L8 fro~ 0.025 to 0025 mm. T~ese ~echnlque~ ~or metering the cor~ polym~r co~pled with the pl~teau ~p~nneret techn~quo as de~c~lbed in the Kllian patent, U.S~ 2,936,482 caLn be ~d ~ucces~ulJy to control th~ ~low and locati~n of th~ cora polymer to pr~duce ~llamen~s o~ the in~e~tion. ~peeial care mu~t also be taken 10 to m~chine pack partæ su~clently pr~ci~ely to pro~nt l~
age o~ the low visco~ity core polymcr.
~ he low ten~peratures ~uitable ~or handling th~
low Tg core polymer avold the need Por a 3crew~ er commonly used ln ~ico~ponent ~pinnin~s. A he~tea hopper pre~suri~ed with an inert gas 3u~h a~ ~trogen can b~
conn~eted to a meter pu~ ~or ~orwarding the pol~er to the ~p1n~; machine,.
~ he ~ynthetic polymers used ~or th~ sh~a~h o* ~he filam~ts o~ the in~ tion ~re flber-~orming polymer~ ~uch 20 a~ pol~des, polye~ter6 and pol~le~in~. A~ suitabl~
polga~des ~or the sheo,th th~re 1~ mention~d poly-w-but~id~, poly-w-caproamlde, poly-w-do~ecanoa~de, poly(h~m~hylene adipamid~), poly(hexamethylene sebacamide), poly~hexE~e~hyl~ne dodeca~ e)> the polyamide ~ bi~(4~inoc~10he:~yl) ~thane or bi~(~nt~cy~lohe~yl)~hane ari~ dod@caneaioic acid, poly(p-~ylyle~e a~pa~e)" poly(p-gylylene d~decanedio~
as w~ll as copolymer~ ~rom approp~la~ely chos~n lact~ or corre~ponding w-amin~3acîd~9 diamille~ ana dibasîc ~cids o~
the ~3~ve homo~olym0rs. A~ other dlb~ic acid~ uæ~ful ~.or 3~ pr~p~:~ng copo~ , th~re m~y be n~n~lone~ l~oph~hallc

2~

ac~d, t~rephthalic acld and hexahy~ t~r~ph~h~lic aci~.
Poly~ters u~eful in the ~h~ath lnc~ude poly-(ethylene terephthalate), poly(trimethylen~ terephthalate), pol~r(tetramethylene t~r2ph~ha1ate) ~ poly( athylen~
terephth~Llate/i~opi~halate) (85/15) 9 poly(ethylene ter~pht~alate hex~hydrot~rephthalat~ ) ( 90/10 ), poly( hexa -hydro~-xy~ylene tereph~halate), tereph~th~late copolye~ter~
cont~ining an aliphatlc dica~DoxyL1~ acid con~tltuenlt ~ es~eeially t~reph~h~late/ad~pate and ter 3phth~1ate/glllta~ate copolyest;er~) and ter~phthalate copoly~sters containing a branched-chain gly~ol con~tituent (~specially elthylene/2,2-dimethylpropylene terephthalate copoly~ster~ of 5-sul~ol~Gphthalic acld, d~methyl ~ter, ~uch a~ ~h~e sodium and potas~ium salt~ may also be wed in prepar~rlg.
sui~able co~olyester3. Prer~bly the polyester wlll be a terephthalate polyester con~prising at least 85 mole percent ethylene terephthalate polymer units.
Pol~olefine such a~ polyethylene ~nd poly~r~pyl~ne alao may be en~ployed a~ the 8heathO
For core polymer~, ~he N~lk~ polyc~rbonamid~
contain terti~ry am~de gro~p~ a~ an in~egral pa~t o~ the polymer chain as described in Brl, l,237,5890 q~hey m~y be homopolymer~ or copolymers frcm N-alkyl and N,N~ialkyl-~ub~tit~d diamines or N~alkyl amino-c~rboxyllc acids~ ~he copolgmer~ may corltaln minor amoun~ of corr~spo~aing :
un~u~atituted ~ni~eæ. At lea81t 35,~, pr~eI~ably 50~, of the ~ .
polymer~h~ln ~ide ~lnkages shoul~ b~ N-sub~itut~d with an alkyl gro~pO Suit~bl~ al~yl group~ are th~e co~aiLni~
~rom 1 to 18J pre~er~bly 2 to 10 carbon atom~9 or cyc:Loa~yl ~ :~
30 gr~ co~l;alnl~g 3 to 8 carborl atom~. Alkyl g~o~p~ o~ 2 ~:

3~ 5~L~Z

4 carbon atoms are e~pecially pre~erre~. ~o~lly, ~he N-alkyl polycarbonamld~ c~polym~r ~hould contain no more th~n about 15 mole perc~nt o~ amide gro~ rom a non-~ubstituted, diprimary diamin~. }Iigher conc~n~rations o~
such dlamine~ tend to reduc~ to an un~ati~s*actory degree the antlstatic ef~ecti~reness o~ the polymer, Suitable N-~ub~ti tuted ~iamine~ are the N~ono- and N,N7-diL~u~stltu~d diamines contai~ng from about 2 to 18 and pr~rablgg 2 to 12 carbon ~to~s in the alkylene gr0~p,. Suita~le alipl~.tlc IO d1Lcar~oxylic aci~ are tho~e contalnlng from about 1 to 189 preferably, 4 to 12 carbon at~ms in the alkylenQ group.
S~m0 ~uitable N~ y~ted diamine~ for U8~9 in the preparation of the N-alkyl polycarbon~midcs are ~,N~-diethyl-, -dilsobutyl~ n~butyl-J ~dih~xyl-, -diheptyl-, ~decyl-and -di~tearyl- ethylene, propylene, tetr~methylene, hexa-methylene, nonamethylene ana decamethylene diaDqin~ and the mono-N~ cyl derivatives c)~ th¢se dl~ne~.
Some suitable dlcarboxyllc acids ~or use in the preparati~n o~ the N-a~Xyl polycarbo~d~s are ~ucci~c, 20 glu~aric, adipic, pimellc, ~ ~c, az21aic9 seba~lc, dod~-c~nedlo~c and hlgher dicarbox~rlic acid~ and also such acid~
as N-N~ W-carboxyal~yl)piperazine.
Som~ s~itable ~-alkyl ~mino-carboxylic acid~, or th~ir ami~e-~o:cming d~ a~re~, which carl be use~ to prepare ~table ~alkyl polycarbo~de~ ~or thi8 i~ntio~ e-re ~ethyl-, -eth~l ~9 -l~obu~yl-~ n~butyl-, -hexyl-~"
~ecyl~ 3tC~g ll~i~tearlc a~d w~ o-sl;ear~c acidsO
~ om~ sui~able ~lkyl polycarbon~idLe~ are tho~e pr~pared u~lng N,~ diethyl-he~meth~ene~ u~yl-3~ he~m~thylene or ~gNI~di n-~utyl-hex~methylene dia~e ana _ 5 _ ~5~Z;~

adlpic, azel~lc or dodec~edioic acid.
~ h~ N-alkyl pol~carbonan~d~ may con~ai~l oth~r s~ibstituents~ ~unctlonal gro~p~J copolyme!ri~ ~nka~ or end-gro~p~ than thos~ mention~d herein pl~ded æuch modi~-cation~ do not in~er~ere wlth th~ ~equired p:t~pertie~ ll;h~reof a~ ci~ied.
qh~ N~lkyl polycarbon~mides h~.~re ~ ~ol~cular W~ig}lt greater than 1500 as determlned by vapor pre~ure o~m~:~et correP~ponding to an i~erent ~ cosl1;y 1~1 m~*~ar~sol ~P
10 ~r~a~er than about Ool~ q~he molecular weigh~ b~ rl~gulateli to ths desirQd d~gr~e for proc~ s ænd per~o~Dan¢e b;y polymerization con~ltion~ and by th~ u~e of ~i~co~ity stabilizers. Particularly ~uitable sts,bili~er~ ~re mollo-~unctional carboxylic ac~d cont0.ining ~rom 2 to ~6 c~rbon ~tom~ and morlo~unctlorlal prlmar~r an~ ~con~ary ~nes co~ining alkyl g~p~ with from 1 to 18 ca~n ~tom~.
Sultabl~ ~tabi~zers are ~c~tic, p:~pionic3 bu~y~ ~Ller~c"
p1vAlle, ~ nthic, pel~rgonic" decano~c, ~ri8tic9 palnitic"
aric, benzoic~ cyclohexane carbo~ cidl8 and ~ ~orthg , 20 and nu~no- ~nd d~tearyl A~lne~.
Sultable po~yether~sters are dl~ s~a in Br.
Pat~lt 1,176,,~48 a~d U.S. 3,655,821 and additional ~oly-ether~ter con~positlon~ are ai~clo~ed in the e~ple~ o~
thi8 ~nven~io~. ~r~i~erably the Pol~eth~r~t~r wLll be pre$iare~ from a poly(ethyl~n~ ether)glycol harlng ~ molecular :~
weight fr~m abou~ 2~0 to 2000 an~ at l~a3t o~e dibasic acid that i~ a ~aturat~ aliphatic ~ib~sic acîd having at le~ia8E;
99 preferably 9 ~ 2D c~rbon atoms or ar~ lc ~a~id~ ~ueh ~ :~
a~ ~er~phthalic, ~soph~halic s,nd their e~ter ~02~ming 30 derivative~<, . . .

;22 ~ rhe cor~ pol~e~ter~ can be prepared ~om a~p~tic glycol~ ~ving 2 to g carbon atoms and ali.p}~tic ~lba~lc acld~, or their estar-~orming der:i~rativesg ha~ing 4 to 36 c~rbon atomff. I~nor amounts o~ aromatle dLiba~ic acidL~9 or th~ir ester-~o~ning der~u~atives, may be u~ed in ~on~uncti~Dn with the al~ph~tic di~a~lc acld~. It should be noted, however~
that exces~ive arvmatic ch~rac~er ~n th~ polym~r wll~ be ~flec~ed in an incr~ase in log R8, AR suitable reacta~nt~ ~
~or pre~a~ng these polge~tgrs ~her~ m~y b~ mentloned 10 ethyl~ne glycol, 1,3-pro~all~3d~ butane~iol, 1S6-he~n~ol~ 2,2~m~thyl~1,3~r~a~ediol, 2~n~thyl 2-ethyl-1,3-propanediol, 2,2-diethyl~193-propanetiiol, 2,2,4~
methylhexanedlol, 2J49~-trlmethylh0xansdi~1, glutaric acid, 8UCCirliC acid, adip~c acld, ~odecarlediolc acid, 2-m~thyl-2-propyl-1,3-pro~n0dioic aci~, azelsic aci~, tereph~halic acl~, dimer aci~ an~ ~h~ir es~er forming ~na ~de-*~ng derivative~ .
~ he polyme~c antista~ ~an be laade more c~nauctive by the a~ lon of a polym~r-~ol~le t~tr~yl pho~phoz~n 20 salt~ q~his i~ pa~tlcul~rl~ u~e~ th thc aliphatic poly-ester~. Pre~erably the alkyl ero~ps atta~hed to the ph~-phoru~ atom will ha~e a to~al Or at least ~6 carbs:~n atom~
to in~rea~e the~r hydro~?ho~clty ar~d thu~ reduce the~r t~ndency to be~ e~ cted w~en in ~ ct ~ h an ~qll~ou~
medium, F~:>r thls r~a~n ~al~s ~uch a~ ths:~se corl~air~inLg t~ bu~ylphosphoni~n a~â bu~yl~rioctylph~ph~n cati~n~
are pre~r~ed.
~ r ~igr~ca~ in~ ~en~ on~e~ y l~h~
phQ~phs~u~n ~al~ æh~ be ~pr~e~ in the pol~mer an~
30 ~ a c~nce~t~tion of ~t lea~t OoOl mol p~r~en~, N~r~ll;y, no more th~n abou~ 30 mol p~rcen~ w~ll be de~lred.
me pho~honi~n ~ may be inco~po~at~d irltl3 th~
polgmers by any conve~ellt m~ uch as by mlx:ln~ ~ither ~rom ~olution or dir~ctly wlth the polymer ~n a fluld ~ta~e, or lt may contre~sn~ly be added during the pol~ne~lzatlon; o~
the polymer~
E~r optimum anti~tat~c e~ct, i-t ~ pre~erred thE~t the pho3p~0nium ~alt be pre~3nk 1~ a ~u~:E'iclent cn~
centratlon ~o provide a log R~ Of` 1~ han 8 ~or th~ core 1~ polgm~r.
As suitabl~ p}l~ph~nlum salt~ for usa in ~ inven-tion there n~y be mentioned in add~tion to tho~e o~ the eau~le~ belo~, tetrabutylpho~pho~n toluenesul~o~te, di-(m~thyltricyclohexylpho~phonium~ ~aphthalen~ o~ste, benzyltrlphe~rlphosphonium tolueneæul~onLteJ trioct~ yl- -pho~ph~nium x~ylene~ onate, tetr~oetylphosphonium phenyl-pho~phinate, tetrabu~ylphosphQnlum dime~hypho~p~te~ di tmethyltribenzylpho~phoni~) phen~rlp~phonal;e, methyl~
tolyl~ho~phonium benzoate, a~d ethyltriphenylpho~honi~
20 stearate. Wh~n u~ed i~ an N-alkyl polycarbon~L~e, th~
carbon~ a~t~che~ ts~ the phospho~um pho~phorous atom mu~t be alk~leIle.
Bra~chillg age~s~ ~.e., ~olymer reactan~ having more tha~ t~ ~unc~ional gro~p~, may be addell ~en il~
desir~d tc increase th~ e~ity o~ the a~ ta~ic p~lgmer~ AB ~t~1e bra~ch~ng ag~ there m~T be men~i~ne~ p3n~e71itic ~lar~drideJ, trime~l~;srlol pr~a~
p~nt~erythritol a~d bis-(he~un~hylen~)tria~
The p~lyms~e an~i~tzLt core ~h0~ eQ~it~e leæs il5.~2 t~n abolrt 10~, preferably fr~m abou~ 0~.2~ to ~b~ut 10% o~
~he volume o~ the ~l~ment. Core~ greater than a~ou~ 10~
~ecQntu~te problem~ ~æociated with E~ ing" par~icularl~r where iiber cros~-~ection~ are n~ round, such ~ trilobal, and con~Lb~e exc~ ly tt3 ~iber pro~erty dillxtlon by phy~ic~l di~ cament o~ the ~ber p~lyme:r by th~ antiL~t~t,.
Anti~tatic ~ilamen~ y be co~blned ~th u~modifi~d ~:il~e~ to give arl~istatic ya~.
The c~ndu~tiv~ polym~rs u~ed in the ln~en~ L h~re a 10 ~1ui81-ke molecular m~bility at nox~al a~bîent ter~ ures as reflected by halring a glas~ tra~ltiorL t~perature o~
le~ th~n 25C. A~ desc~bed her~in, the gla~ transltlon te~p~rature 1~ determine~ u~ uclear magnet~c re~o~nce techniqu~3. Such glass transition ten~per~ture~ can l~e approx~ ated b~ using le~33 co~plicated techn~que~ such a~
~fIerenti~l thermal analysi~ for conven:ieIlceO ~ch material~ are readlly ~nd permanen:tly de~ e when stresse~ and vary in th~ir phy~lcal nature ~rom rlibb~ry ~c~po~itlo~s to low melting soltds and llquideO The~ ~re 20 no~ suitable ~or ro~ng useiu:L textile îilamen~s b~
thernselve~ .
For texturing ~eea yar~8 wherein the sheath is stib~ect to damage un~er ~he severe t~uring co~ditions e~ploy2d ~uch as m~y exi~ in f~lse-l~wist te.xturinK ~pera-tion~g the l~wer ra~ge Or leæs tha~ 6~: cc~re i.8 prer~rre~.
Th~ ant~sta~;ic ~ctirity pro~d by the~ t~c f~la~e~lt~ may be e~lua~ed by a nun~er of me~suremeEr~ he ~lame~t~ may be comrerted to ~b~c, all~ the ~tic pe~ity det~:~Lned by meaæu~L~g the am~unt e~ alr~ct; ~u:rren~
30 thE~t pa~seæ ~hrou~h the ~bric at a t~ rature o~ 22C.. and 1~5~L22 26~ rel~Ltive h~Ldity. The ohm~ per ~uare ~mlt o:e area o~
~bric 3ur~acc 1~ d~te~ ed ac~o:rding to ~h~ AATCC ~eth~d, 76-59 ('ITechnical P~nu~l of the ~AT~CI', tlrolu~ 41, 1965, page~ B-1~38). ~L~ value, given a~ log R, i~ th~ l~ga~thum to the b~e 10 of the ~bric r~ tance in ohm~ p~r ~quare,.
~i~her ~raluea ~Lndi~ate a greater l;~n~lenc~ to ~c~u~re a~d ret~:ln an electro~ta~ic c}~rge. Thl~ method pro~Lde~ ~ ~
approx:lmat~ me~re of ~tat~c prop~n~ity. Th~ log r~ of the :eilament~, ~ch tak~ ln~o accoun~ rence~ in total ya~
0 c:ro88-8ec~ion arld pe~ts more ~ccur~e cr3n~pari son~
obtalned fr~m the e~ ion: .
log rho (~ilament) ~ loe R (~b~lc) - log ~9 x :105 D) ~ log (Pd) whers 1) 1~ the den~lty of the pol~7merg P ~8 the nwliber of pick~
(yarn end~) per ce}~timeter i~ th~ ~bric and d i~ the lto~
~enier of each pick. In the ~2a~1es, the ~llo~ng valu~ o~
D are u~ed~ or 66 poly~d~ or 612 po~L~de; ~0 ~or the poly~ide f~om bîst4~mi~ocycloh~xyl)methane a~d 12- ~ :
aeld, 1.4 ~r polyethy~ne tere~halatea and ~09 ~r pu3.g-20 pr~ylene~
m~ (Pd~ value, w~ch g:~re~ ~he amoun~ ~f yarn in the ~bric" i8 mult~plled by the percent or the con~lucti~re ~en~ in a yarEl bu~le to obta~ the loe~ rh~ ~orl;ea ~or the c~n~u~ti~re ~ nts ~
Fibers ~ch prDduc~ ~ log rho ~lue o~ th~n 11 ~re con~iaer~d tl~ ~re acce~?tabl~ ~tl~a~ic properties.
For ca~p~t~, the ~tic pr~e~ity of the ~i sts.tlc f~ e~ ~ar~ d~te~n~d by u~ing th~ filame~t~ :
to make a c~pe~ an~ measu~i~g; the electr~st~tie ~ ;Ag~
3~ buil~ ~ o:n a perso~ n a ~ecti~l1 o:e the caxpe~
o~ 21C. azld ~0% reïati~e humidit~. Thi~ mea~suremerlt .

11~85~;22 erred to as the Shuf~le Te~t. ~he proc~dur~ for ~he Shu~le Te~t i~ de~c~bad ir~ AATCC T~t Method 134-196 with c~nge~ adopted by the ~p~t & ~ug ~n~tituteJ
: S~pt~ber3 1971.
Static propen~lty o~ the filament~ o ~n b~
dete~i~d b~ a m~a~uremen~ of dec~ing tim~ i~ a pr~cedure referred to as the S~il Te~t. The &~1 'Eest u~e~ h~rein ~ measu~e~ the ~eve:rity and duration o~ ~arment cli~ag dl,le 1;~ ~
~tatic ~nder si~ulated u8e ~on~tion~. ~ thi~ ~e~t, static 10 is induced in a g~rmellt, w~ich m~y be a ~ , a ~kirt or a ~Ire~s~ ~orn o~rer cotton brle~ by a techPlcian, ~y rulJ~bing a~ain~t a ~abric held between two ~e:rtieal pole~. A p~ly (ethyl~ne terl3phthalate) ~b:ric i~ us~d ~ith n po1~yamide ga:rment and a poly(hexam~hylene ad~p~de) i;abric i3 used ~ith a pol~ster gs,rme~t. l~he time t~k~n for the garments to uncling (or decling) ~ile b~ing w~ durlng walkl~g arourld the r~om i8 dete~ned. me ro~m i~ main~ain~d at 21~C and 20% relative humidi~y. ~he deeling t~e i~ th~
time in mi~ute~ reqt~ired ~or the ~armen~ to be Judged eom-20 ~ortab~e ~ith n~ dete~table cling ~rom sta~ic charge~. mere~ult3 c~ ly ~re r~o~ed a;Pter a nu~er of "C'~ h~
~th t;he g~xment~ containing the ~n~istat~c ~laments having decllng l;ime~ less than 10 minutes and pr~erably le~ an 2 mi~ute~.
~e~ the ~abr~c~ are given a n~i2mber ~f` "home~l :
wash-d~ cy~les i~ a tu~ble Wa8hillg machi~e wlth a ;~
ay~hetic deterg~nt in wa~er at 38C., ~p~lr~e~ a~
t~mble~r~ed at 770~ hey are re~arr~d ~o ~518 being "C~
~shed.
3~ The ~c~:eie r~ ta~ce, R8, o~ the ary ~er-,.; :

. . , . .- , Pree) pol~merlc an~i~ta~ i~ d~ermlned at xoom t~pe~ure.
~rhe polym~r i~ d~ed ~ 100C. ~n ~n oven at æ, pre~ure le~
th~ 50 torr Por at l~a~t 12 hour~. The cell ~ed ~r th~
m~a~ure~nent~ con~lst~ o* a ~Pyrex" har~ Ig~ tube of 2 ~ 0.25 mm. in~ide di~meter and 8 mm. o~s~de di~E~met~r. Th~ t~e i~
f~lle~ by ~ucki~g ~31tell core polymer i~t~ the tube rrOm a mel~ pper wire eleetrode~ ar~ ertl3d thr~ bber end-eAp~ at e~c}~ end o~ th~ tube to &~ve a 33 ~m~ electr~de sep~
a~ati~n and the ev;rrer~.iG tran~3mitted thro~h the ~a~le ~t a 10 ps~en~ial ~fference o~ 2~0 ~ s DC i~ r~corded u~ing, a ~ ~:
Beckma~ Vibr~ s Re~d M~el 1051 ~croa~etcrO ~pecif~
resi~ta~ce i8 c~lculated ~rom the eq~tion:
Rs (o~m8) -~he cell con~tan~ Kc i~ dete~nined by u~i~g a liqu:~d oi~ know~
specl~c resi~tance. ~he value~ r~ported herei~ u~ed 7.63 X
10 2 a~ the c~ll con~ or cor~ven~nce, ~h~ R$ ~alue i~
rted æ~ it~ log1Q ~alue.. q~h~ lower ~h~ l~g Rs v~lue, the higher i~ the cond~ctîvity o~ th~ ple.
2~ ~he p~ en~ core in ~he ~il~ i~ ca~culat~d rr~
th~ peree~b o~ ~he ¢:roos-~ee~ional ~rea o~ the ~lamen~ 0cc~pied by l;he ~o~ erlal. 9~he core m~y be ce~ltrally loc~d,~
center and o~ y ~h~pe, Th~ cro~-section~l a~ea ~s co~e-niently detexml~ed by pho~ographing a cros~-sect1o~ o~ the ~ilament ~der a micro~c~pe ~t a kn~ ic~ti~n of 50 to 1500X an~ ~ete~r~g the percent c~re fr3m mea~ure~ne~ the photoeraph. I~ th~ ca~e of irre~r~tle~, th~ a~erage of 5 to 10 aetermina~ion~ i~ u~ed.
F~r ~u~d ~ e2~s with ~un~ cor~s, th~
30 per¢en~ eore G~}l al~o be deter~ned by ph~ogr~phirig the - ~2 -, ; , .
~-.' , ' '. ~ ' ' .
, i~lamen~ in a longitud~l ~ie~O imm~r~d in a med~ ha~ng a refractive ~ndex clo~ly m~tchlng the r~sfractlve index bf the ~Llamen~, and me~su~ng the :ei.l~menlt ~nd th~ cor~
~eter~ E~nd c~lcula~ g ~he p~rc~n~ cclrl~.
The Tg (~m) i~ th~ t~pera~ure ~b~re ~:ich th0re i~ a ra~id rise in the ~R n~rrow peak a~d the pgak r~io wlth an increase ln te~e~ture. The r~ p~; ~klo i~ ~
determined ~rom the N~ bx~adline ~3p@Cl~rlm~ mea~ d ~t a gi~en te~pe~ture on the d~ polymer (e.gS,3 dried a~ 125C., 10 ~r 15 minute~ in dry ni~rog~n~ in an ~I;~o~phere o~ dry nltrog~n u~ing a radlo iregu~nc~ of 56.4 megacycle~ a~ a~
at~enu~tion setting o~ 17 decibels ~rlth a ~ dulatl0n ~tude o~ one gauss. ~he N~R ~pectrum i~ mea~u:red usi.rlg the nuclear magrletic re~or~nce equipment o~ Varlan Al!380Ciate~9 Model V - ~302 Dual Pu~po~e ~pectr~meter and their high ten~perature pr~be inse:~, M~de~ ~oO ~t_ 4331 r~L. The NM:R
spectr~gram a~ a g:lve~ te~?er~ture ~hl~w~ a broad ab~o~?t~o "hun~ upon which i~ s~pe~n~po~ed a very narrow peak. The deri~ re cur~e o~ the sp~¢t~gram is recordea b~ the 2~ ~:pe~tr~meter, "peak r~tlo" mea~ureme~ts are m~de orl ~his curve. The heigh~ o~ the narrow peak dl~lded by the hei~t of the ~'hu~pH gives the ~'peak ra~o"7 ~8 dc~cribe~ tn . Polymer ~cience Pa~ CJ Pol~mer Sy~po~t~, No. 3, pp. 3-8 (1963). ~e ~recisi~:n o~ thi~ peak rati~ ~ete~ al;ion is abo~t ~ 0.2 and the ~g ~) is ab~ut ~ 5~C.
The rela~ive ~ co~ity ~ ~he polyamid~ ~er-mi~e~ by m~s~ the ra~iLo o~ the rlow time in a ~risc~m~er of a ?olymer so3.u~ion rel~lti~e to the ~l~w time Or the ~ol~e~
by it~ measured in ~he ~e UI2it5 at 25C. ~le~s ol;her 30 w~se ~pec~flea the po~ relativ~ vlsco~it~ is d~texmine~
~ 13 .. ~.

.
.. ~ , . .. .

usin~ a~ 8.1~;~ by ~eighl;~ ba~ed on total weigh~, ~olu~lon 1 a 90~ b~ W~ightr b~sed on total w~ , aqu~ous ~e acla ~olution.
Inher~n~ ~sco~ityJ ~ i8 d~3~e~ned :er~m the ~?re~ion:

~er~ n is the ~sco~ty of a dllut~ ~olu~lon o~ the polym~r in m-cre~ol divlded by the ~i~c~ity o~ ol in kh.e ~
units and ~t the same t~n~perature and C i8 the concentration 10 o~ ~he ~lu~e ~ol~t~on in gr~ o~ pvl~Qr per lOO ~. o~
~olution. In the ex~les, the ter~?~mtur~ used i~ 25C. ~ .
and the ~lue o~ C u~ed i~ 0,.5.
m~ relati~e ~ ¢o~i~y of the polye~ter~ i~ de~er- ::
mined tunle~s indtcated other~rlse) by m~asuring th~ r~tio o~
the ~i~co~ity o~ a ~ol~ n con~aining 4.75% by wei~ht or the p~lymer, ~n he~fluor~tsopr~a~ol co~t~i}~ng lOO p~rt~ per millio~, by v~ e, o~ eonc~r~tra~ea ~ urlc a~ t~ the ~iseosi~y ~ th~ hex~ roi~oprQ~anol ~ c acid solY@n~
me~ured in th~ same u~ts a~ 25 0.0~C. :~
~ h~ proc~ures and ~ th~t ~llo~ ll per- .
cen~ge~ except ~?~r~en~ core ,~re ~y w~ , b~ed ~n tatal ~ :
ht, unle~s ind~c~ted o~herwi~eO Pereen~ core i~ by vol~ae.
E~E I
Thl~ ex~l~ demo}lstrates suitabl~ polyether~lter ~ ::
core polymer~ ~f the ~nve~rtlon and the use o~ oll~ a~ ~ c~
in poly~ter ~ilamea~ o:e the iIl~en~ion.

P~lyether-ester A :1B prepared by ch~r~ a stlll w~th 29513 gra~as of' poly(~thyl~ ether)glys~l h~g ~
3~ a~rer$ge m~lecular wei~ 5 ~S~æ ox~ poly~ hyl~rle - 14 _ .. ~ .

.

ethor) glycol ~ng an average m~lecul~r wei~h~ of 6009 4000 gra~ o~ dimethylter~phth~ e, 2480 grams o~ eth~l~ne g~ycol~
300 grams of 1,3,5-t~meth~rl-2~4~,6-~ri-(3,5(diterti~rybut~
4-hydroxybe~yl) benzene ~ntioxidant, and 14.0 gm~. o~ tetra-butyl titanate cat~lyst. The ten~perature of the ~till 1~
rai~ed tQ 210C. aI~d about 130û gram~ of methanol i8 remo~sd by distill~tioIl. The batch ~ therl tran~ rred to an ~uto-clave at 220C. ~ich has b~en purged ~ith ni~rogen. An agitalior i8 opsrated at 15-30 ~pm., ~he p:res~ure is reclue~d to less th~n 2 torr iEl 45 min~es a~ the ten~erai;ure iE~
raised to 260C. during this perlod. ~he batch is helcl ~t a pre~ ure o~ less than 2 torr ~or 4 to 6 hours~ The pres-~ure is then brought to a~mo~heri¢ wlth nitrogen ~nd the batch is cooled to 220C. and extruded urlder a bls,~ike~ o~
nitrogen. Prope:~ies s,re shown in Tabl~ I.
Polyether-ester B is prepared, ln a 22-kilogram vacuum a~;ocla~e equ~pped with a stirre~ an~ a st~ll, by e~ter exchange between 1778 gram~ o~ ai(2-hydroxyeth~rl) tere~?h~ e an~ 3241 gram~ of a 50/5~ molar r~io mi~ure o~
2~ 4 a~ 6~o molec~lar weigh~ poly(ethylene ether) glycol w:l I;h 0.7 milliliter o~ ~e~rabu~yl titax~ate ~a~a~y~. Trimethylol ane, 70 g~9, iS u~ed a~ ~ brarlchi:ng a~ to incr~a~e vi~cosity 2nd 7.7 grAms of 1,3,5-t~lmethyl-2,4,6~ (3,5-ditert~arybutyl~-hydro~:ybe~) benz~nc an~ioxldant ls ~d t~ enhaIl~e the~ tab~lity. l~e materials are chargsd to the 8't'tll~ the te~pe~ture r~ised to 210C~,I a~d then t~ns- -f'erred to th~ a~toclaYe ~nd p~lyme~*ze~ ~r 5 h~ur~ at 260CJ
~nd at a press~e ffl 1 t~rr. ~he ~gita~or i~ ~3pexa~e~ at 30 ~pm., P~ly~ther~ter ~ i~ prepared using the n~mb~r of :

i~S~

g~;m8 of the ~ die~t~ peci~ied in T~ble I, along ~:lth 1 millilit~r o~ tet~butyl titar~te, whi~h are char@ed to 2 stalnle~ ~teel autoclave. q~e a~tocla~e 1.8 h~ed to 18~Co under nitrogen then e~acu~ted ~o 1.e~ t~n 10 torr and heat~d to 240C. The agitator i0 B~'t at 8 ~m while 6.5 cubic ~et per hour (51 cc.~ecl,) r~tr~gen 1~ bubbled t~rough the mi~ture ~r a~ded ~i~aWon~, A~ter 2 hour~ at 24~C~ the t~pe~ ure i~ ed to 260C. ~c~r a 4 hour p~rloa a~d the nltroæe:~ b~ibble nOw r~duced to 1 culbic roOt 10 per h~ (8 cc./~ec.). Th~ bat~h 1~ ~hen ex~ruded ~naler nitrogen pre~sure a~ter cooltng to 110C. Pr~erti~ are sho~ n ~abl~ ~.
Poly~ther~r D i~ de by the fol:Lowir~g pr~-cedure: q~wo hund:red g~8 oi~ po~y~hylene ~ther)e;lycol hatring an ave~ge mo~cular wel~h~ o~ 200, 214 gram~ o:P
d~decanedioic ~cid, 6.6 gram~ of p~rromellitic diar~urdride, 0.2 gram p~oluene ~ o~i~ acld alidl 1 gxam 133,5-trlmethyl-?,4~6~ (3,~-ditertiary butyl-4-hydr~xgbenzyl)b~ ne are placed in a 5Q0 mil~liter fl~s~ fitted with a ~eam-~acketed 20 reflw~ conden~er and a ~ ofr c~ndenser. Ai~er pl2rgi~g ~4ith n~tr~ge~ the m~terial3 are heated to approximaltel~ 130C.
and then ra~ed to 225C. a~ about 40~. per hour. iracuum i8 then applied at 0.2-0.5 torr and th¢ te~perature increa~2d to 265C. and held :~or about 2 hour~ il the polymer o~ity i~ 1~0 poi~e as mea~ured ~n ~he ~ k wi~h ~ ro~a~
ing ~i~dle ~isco~eter. Pr~per~ie~ are sho~ in ~bla I.
Polyether~t~r E i~ prepared ~r~qn 218 gr~s o~
dodeca~e~ ic ac~d,~ 200 gr~n~ o~ pol;r~s~hyle~e ether)glycol o~ 2G0 a~r~ge mQle~ r wei~ht~ 6.6 g~ams o~ pyr~m~llitlc 3~ ~ar2hydrlde (b~a~ching agen~), and 0,,4 gram o~ p~t~luene-,, 8Ul:~O~liC acid ~catalyst 3 . The~e .ingre~Lien~ a:re comblnedin a 50û~o:111iliter ~lask ~tted with a ~te~m-~acket~d~
r~flux conden~er a~d a ~ake-o~f cond~n~er. The mixtu:r~
is purged ~th nitrogen and i~ he~ed ~ 250C. ~r 2 hour~ under an ~tmosphere o~ ~t~gen. It ~B then h~a~d ~t 2~GC. ~or 1.5 hc~ur~ at a pres3u:Ee o~ 0002 to 0.5 torr~
In 5 separ~te r~n~, tetra~ but~l pho~p~onium d~phenyl-phosphinate i~ mlxed wi~h the polymer at lOO~C., an~ the mix~ure i~ d~ed ovexni~ 100C. i~ ~ ~acu~n ov~.
~he phoE~phon~um ~a~t dl~ eæ co~pletely i~ the poly~ex~0 ~he amoant~ o~ pho~phc)x~n sal~ wed a}~d ~he con~uctlvitie~
o~ the g~y (25%) pol~mer~ are ~ho~ in T~ble II. The Tg (~SMR) are les~ thEm 25C.
The tetr~-n~utylph~sphonit~ phenylph~ph:L~te i~ obts.ined ~ ollo~. To a Bu~3~pex~ion Df~ 43.6 ~;ram~ o~
dighenylpho~phinic acid in 300 mllliliters o~ illed water i~ adde~ a solution of 8,0 ~ o~ ~vdi~m hyd3~x:~de ln 20~ -mill~liters o~ er and the mlxture ~t$rredl, Th~ acld di~solve~ wl~r., To the re~ g $ol~ion i~ a~lded a solution o~ 59 g~m8 0~ tetra-n-b~ylphospho~um chlo~
in abou~ 200 n~lliliters o~ ~illed water. ~rhe reaetivn mix~ure 18 ~tlrred ~or hal~ an hour and 1~3 then ~x~racted with about 500 millili~0rs o~ chloro~orm. m~ extract i~ dr~ed over a~rou~ ~a2S~4 and th~ c~lor~rm 1~ th~
di~tilled. A ~gh~ro~ v~eou~ liquid rema:3n~ is ~ :
dr~d o~ernight a~ 800a~, On cooli~g~ tet~ n-~u~yl phos~
pho~um dlphe~ylpho~ ate ~epara~e~ aæ whit~ crystal~

?

T~IE I
~ A B C D
Inher~n~ co~ity 1~,04 0.98 0.93 lo~ Rs9.6 8.4 8.8 8.1 Polymer na~ure ~ubbery Gulmng Rubbery G~
( ~,7 2~ C ~
c~y~t~line) Tg (~) C. ~,25 -41* ~5 -25 :~redien~
D~,l _ - 847 -10 PEG2 ~o PE~ 600 _ _ _ _ E~IP3 - - 100 l oxidant _ ~ 50 *By di~erentlal thermal ~ly~8.
~`
(1) I)i(2-hydroxye~hyl)ter~ph~ te (2~ Poly(~hylene ether)glycol a~rerage molecular w~i~t (3) 2-ethyl-2-hydroxymethyl-1~,3-3pr~ anediol (4) 1~3,5-~r~me~hyl-2~96-~r~-(3~5-ditertlarybu~yl~4-h~dr~xybenzyl)benzene --~

~8 _ ~5 ~L~ I~
Phosphonium Sal~t~ ;
Rlm Mol % ~ Log Rs 0.21 6.88 II 0.~ 6.54 III 0.63 6.36 1.04 6~
~T 2.08 5,.~4 - Non~ 8.1 10 * Mole~ O:e pho~phonium 1OI1 per 100 mol~ o~ all carb~x~late cs~pon~ in the polym~r Polyether-eæte~ B is ~pun a~ 3.4% core ~ poly (eth~ene ~erephthalate) ya~ llaments ~t abo~ 290C. ~he core ~ntistatlc polymer and ~ber ~he~th polymer ar~ pu~ped to ~e~?arate char~er~ ~n a melt ~pir~i~ p~ek a~s~ibly ~er~ they ~ach pa~s through a ~ilter medi~. m~ eor~ polymer l~ve~ the er me~um ~ en~er~ a pæ~sag~ w~lch ~eed~ ev0xa~ sqeter eha~el~ in a 0.075 mm. thick plal;e. ~e chan~ are ~05 r~
20 wide~ 9 mm. l~n~s a:~ld the ~hiek~ o~ th~ pla~e. ~ ne~r I;he ~ore eq~hslly ~nd uni~ormly to holes ~ch del~rer th~ cor~
polym~r to a posl~ion ~ htly~ ~paced above ~pinneret s~ ices ;:
(0.375 ~mO dia. x 1.1 mmO lo:~g) t~3 e~ch of ~ch the ~h~a~h ~lymer ls l~t~ra?l~r d~livere~ u~d~r ~ii:'o~m pre~s~ f:~m all to rorm ~ c~al poly~er ~low whers the core m~er-~al i~ isely e~ered in the ~hes~h poly~ he ~oly (et~ylene ter~h~ e) ~heath pcly~er ha~ a rel~ti~re ~ si~
a~ a~o~ 22 axld con~;ai~s 0~3% Ti~2. qh~ 34 ~mer~ and i8 ~Ira~l tQ a de~er o~ . The ys.~ i~
30 te~Et~rea9 knitted lntv ~b~c~ hed and t~t~dlD D~ng 19 - . - .
: ~ .

. , , times of 2.5 and 0.1 n~n. are obtained a~te:r 5 a~d 30 "C"
w~she~ respecl;ivelyl, l~MPLE II
___ 9~ple demon~tr~e~ su~table N-alky~ poly-car~on~de~ core polymer~ ~ u~e of ~o~e o~ th~m in ~lamer~t~ o~ a pol~de Or bi~(4~n~cyclohexyl)metha~e and dodecanealoic acid ~or which thi~ inve~tion i8 partic~ rl~r use*u3.

The pr~cedure ~or the p~paration of th~ lkgl poly~rbor~de antista~s i~ ~e~cribed belo~ for the poly-amldes o~ ~le II~. An au~oclave i~ char~d ~th the nun~er o~ g~n~ o~ the ~ngredlen~ ~pecii~led in T~ble III, purged with nitro~n and hea~ed to 215C. ~r three hours at a pre~sure not greater tha~ 300 pounds per ~q~ar~ lnch (21.1 kil~Qgram8 por ~uare cerltimeter) ~ge. ~he autl~la~ :
i8 pr~vided with a~ ~gitat~r ~ch ope~e~ at a ~eed of 6 t~ 8 ~pm. ~rhe pres~ure iæ reduced to a~ms3~phe~c o~er a period ~f 6~ minu~es while khe ~e~perature 1~ rai~ed to 295Oa. The pr~sure is then re~uced t~ leæ~ than 10 t~rr ~:
over a 30~ntxte p~riod ~ h~ld there ~r 3 ho~rs a;~
300 ~ 5C~, Ihe pre~ur~ i3 b:ro~ht to ~mo~pher~c N~h }~trogen, the pol~mer cooled a~d th~n extru~d a~ 200-220C.
u~der a ~ ke~ o~ ~troge~. P~lymer pro~er~ies are g:~ve~
Ta~ polymer~ h~ve a Tg (~) o~ le~ th~n 25C.

20 _ - -U~
o o .~C qS ~ (f) ~V3 ~ ; ~::
X l~ ~ 9 ' , '' V ~ :

H~ i N

o o ;~

o~

¦ ~ 8 o z;
~ tf) ~ m ~ "

P~ ~ ..

:~ /
: ~
u~

::
~ ~ o~ ~ l 0~ ~ ~

a~
O ~ ~ N
i h O I I I P' i P~ W
~ql h ~ O

~;~
:: ~ o ~ ~
~ CO~D ~ ' o ~

`~

3S~;~2 Tetra-n-butylphosphonium Phenylphosphinate Pr~paratlon ( Salt A ~
A ~olution o~ 147.5 g~amB 0~ t~tra-n-bu~ylpho~-pho~i~nn chloride :ln 1 liter o~ 2B alcohol is ~tirred in a 3-liter round~bottom flask fltted wlth ~ re~lux conden~er snd a heating mantl~. Tc~ it i 5 added a ~olu~ion o~ gO
grams o~ potassium phenylphosphinate in 500 ml. of 2B alcohol.
A white preeipita~ ~eparates l~media~ely. q~he mixl;ure i~
rerlwc~a ~or 2 hours ar~d i8 then cooled to room ten~p~rat~r~, 10 and i~ ere~. Sol~e~t i~ remo~red ~rom th~ ~iltrate wlth a rQtatory evapo mtor. The pho~phonium !~alt remains behind a~ ~n oil.
Polya~ide D i~ prepared by ~harglng an autoclaYe w~th 2412 grams of N,~'-diethylhex~meth~lene diamane and dodecanedioic acid ~altt 51,6 grams o~ N,N~-die~hylhexa-methyle~e dlamin~, 5 gr~m8 0~ bo~ic acid, 16 ~rams o~ ~ormic acld, 2.15 gr~m~ bi~-he~methylene triamine and 4 gr~m8 0 pot~Rsium phenylpho~phi~te. Th~ auto~ e i~ purged w th nitrogen and heated at 215C. ~or 2 hour~ under 20 150 pound~ per ~quare ~nch (10.5 kilogrQm~ per ~qu~re cent~meter) gage with an agitator ~peed of 6 to 8 rpm.
The au~oclave pressure 1~ reduc0~ to atmo~pherlc and the tempe~ature raised to ~30C. A 81~w blee~ Or nitrogen i~
establi~hed ~or 30 mi~u~es. Te~ra-n-butylph~phonlum dl-phenylpho~phln~te 125 gr~m8 ls added in ~olten form at about 120C. thr~ugh a close~ pre~sure hop~er~ me batch tem~erature ed to 300C. and the batch i~ held under ~ preR~ure o~
leæ~ th~n 2 torr ror 2 h~ur~. The ag~ator i8 tur~ed o~f an~
tha pre~sure 1~ ~rought to atmosphex~ wlth nltrog~O ~he 30 pol~mer i~ ex~ruded at 275C~ und~r ~ blanket Or nitrogen.
The gummy (a~^25~.) polymer cQntai~ 4.15 ~ole % ~ the - 23 - ~ :

., ~. .. . :

lQ~35~22 phosphonium 8alt ha~3 a. relatlve vi~c08ity oi~ 66~ZJ a lQg R~
o:~ 6.9 ~nd T~3 (NMR) o~ <25~Ct (e~ti~aated).

A serqe~ o~ r, 34~ n~ t~lobal sheath-core ;~rarns iB prepared using the poly~r~de ~:rom the sal~ o~ bi~(4-amlnocyclohexyl) meth~ne (con~airllng about 70% Or the trans-tran~ 3tereoi~0mer) and ~dodecanediolc ~cid for the shea~h and v~rlou~ ~unt~ o~ Pol;yamides A and B
as the co~e~, The yarn~ ar~ woven a~ i;h~ lnF, in ~a~ Lc~.
The log R ~ralues of the ~abri~s ~re then dete:~nad a~ter the ~ab~c~ ~re ~coured, bleached and given 50 "C"
washe~.
q~he percen~ core and ~ilameNt log rho ~ralu~ ~re ~hown ~n T~ble V:
~rE V
Percent Core ~, . .
Polya~mide A
9.7 9-~
Polyamide B
2.5 g.4 9.2 Polyamid~ D ls spun a~ 3.3~ core a~ wlth Polyamide B
where the gheath polym~r i~ the s~me a~ that for Polyamlde B.
The appara~u~ ~or ~rmirlg the ~hea~h c~r~ ~ilamerst~ i~ e~@n-t~ally a~ in Ex~pl~ I except tha~ ~ap~llary ttiblllg îRl~eYrl;~
o~ 0.08 mm. in~ide diame~er alld 2 m~ ng~h are u~ed i~ tel~y b~low the filt~r medi~n ~or the core polg~er to meter the cvre to wh~re the sheath polymer is in~roduc~d. ~he splnni~g te~?erature iæ ~bout 325C. The yarn is ~overl a5 th~ rilling - 24 _ .

~s~

in a ~ric ~ch a:~ter 30 "C" ~ hes h~ a log R of` 12.6 corre~ponaing to a log rho of lO,~.
EXAMPI E III
~le ~on~trate~ th~ use o~ N~lkyl poly-~arbon~nide~ as a core in ~l~ment~ o~ po.ly~hex~thylen~ :
adipamide) .

me pr~cedure for th~ pr~paration o:E the N~lkyl polycarbonami~e antis~t~ i~ described below :Eor the poly-10 amide~ o~ Table VI. An au~ocla~e i~ eh~r~sed ~dth the ~lumber~3~ gr~m~ oi~ ~Ae i~gredie~ts ~peci~ied in Table ~,~ purged with nitr~g~n and heated ~c~ 215~C. ~or three hour~ at a pressure not greater than 300 p~und~ p~r square inch (21.1 kllograms per square centimeter) gage. ~he aultoclave is prov:ided wlth an agitator ~ch ~p~xate~ at a ~peed o~ 6 to 8 rpm.
l~he pressure is rsauced to atm~spheric over a perioR Or 60 min~es b~ile the te~erature ~3 rai~e~ to 295C~, The pressure i~ then re~ucea to les~ th~n 10 torr o~rer a 3~-minute pe~od ~d is held there ~or 3 hc)ur~ a~ 300 ~ 5C. : !
20 ~he pressure is brou~h~ tQ ~;mo~he~lc ~11th ~trog~:n, thepolymer cooled aIid then extrucle~l ~ 295C. ~der a b3~r~ke~
o~ gen. PoI~mer pro~ex~ties are gi~ren in T~ble ~II.

.. . . . . .

;il22 ~ .rl Ir~ ~3 N

~ C~
~!.., ~
h ~ N N 0~
~C¢

C~

~1 ~
~ ~ a~ ~
0 ~ ~ :
p~ ~

I
~lo l I V

h ¦ h ,~

rl ~ I
,' ~ ~

.' ~
~ 1~1 ~1 :

S~ : : .: .

..~ ~':.' . ~ ' `` ', , .:: , ,: , . . , ., , , . ~ " ~ ;: - , a~
A yarn o~ conc~tric ~heath-core ~ nen~ :ls prepared using poly~he~amethylene adipam:lde) ~or ~h~ ~h~ath and 10% Polyamide A ~or the core. The ~pi~ng ass~m~ly i~
a~ wlth E~L~1e II except the caplllary tublng inserts ha~e 0,.2 ~Dn. inælde dia~ne~er and ~re 10 7mnO long. The spinnlng te~peratu:re i8 286C. me ya:~n contain~ 13 ~l~nen:t~
and is drawn to a de~er o~ 40. Two o~ the ya~n~ are plied and used to prepare a w~en ~b~c th~t i~ ~ou~d to ha~re a log 10 rho o~ 9~5 a:E~ter a 60~nlnute b~ f in di6tilled water.
Another po:r~ion o* the yarn is used ln n~king trlcot half-sLips which are found to ha~re a decling time o~ 0.3 mlnu~e~ in the sail test con~pared to greater than 10 minutes ~or ælip~ oP ur~nodified poly(he~uneth~lene ad~pamide).
A carpe~ yarn o~ concentric sheath-core ~l~ments is prepared ~ing poly(hexamet;h~lene adlp~de) ~or the ~heath and 9% Polyamide B ~r ~he core. The y~n c~ntain~ 26 ~ t~
and is arawn to a de~ier o~ about 500. ~he ~laments h~ve a log rho o~ 9.9. In the shu~le testy ~he charge build ~
20 i5 fou~d to be 7 kilovol~ c~ pare~ to 20 kilo~rolt~ for an ur~nod~iied poly(hexameth~Jlene adipam1d~) yarn.
E~l IE ~
The e~ea~le demonstr;~tes the use o~ arl alip~atlc polyester core conta~ning a dl~solved phosphoni~n sul~Dna~e in p~ ide ~ilament~.
Te~ b~yl pho~ph~nium xglen~ ~te i~
prepared aæ ~llows: a fflixture o~ 370 graJn~ sodlwn xyle~e sul~3na~e ~ 00 m:L. wat~r ls stlrre~ a~d heat0d u~til c~pl0te dt~:solutlorl o~ the ~lf'ona~e~ then 50~ gr~m~ tetra-~-30 butyl ph~sph~ni~n chlor~d~ dded. A:eter co~ple~e . . - 2~ -2:~

olution o.f the chl~r:Lde, the rea~tion mixture :~ cool~d and the pho~phonitnn ~ onate ~eparat~ a~ a ligh~ ~llow iscou~ l~quid. It i3 drled a~ <100 torr s,nd 60C. ove~ t.
A still ~ B c~rg~d ~th 11, 700 g~ o* dlmethyl ~ 1ate, 2250 gr~n~ o:P ~,Z~imethyl-lD3~pr~pane~ol, 13~
gram~ o~ the pho~phoxli~m sul~onate, 100 g~ o~ 2-ethyl-2-h~droxym~th~l-153-~ropaned~ol~, 4 gra~ o~ ~dlum ac~t~e t~Lh;s~dr~te, 11.2 gr~ o~ mar~ aceliatle ta~rahydrateg 7.7 gr~m~ of antimony o:~:Lde3 and 620û g~ of ethyl~l~e glycol6 10 The ter~per~ture o~ the ~till i~ raise~ to 230C. and abou~
2700 grams o~ methan~l s,nd abo~t 1000 gr~æ of ethylene glycol arQ remored by ~stillation. ~he b~tch iq then tran~*erred to an autocla~ ~t 230C. which ~a~ been purged with rli1;rogen and 8.3 ml. o~ 85%, by w~ , pho~p~oric acid i~ added. me autoclave is equipped ~ith an agit~tor which is opera~ed ~t 30 rpm. The pre~sur~ is r~u~e~ to le~s tha~a 2 torr ~or 4-5 hour~ at ~70C. The pressure i~ tll~ brou~ o 309 ~logram~ ~-per ~quare centimeter ~ge ~rith heli~n a~d the poly3~r extruded under ~ bla~ket o~ nitrogen. 5rhe lnherent vi~c~lty i~ o.87~, 20 log R3 ~.8 a~d Tg (~) les~ tl~ 25C. (estim~ed) ~r the g~ny ~olymer.
The polyester is spun as a 4% core ln r~ ~;8 to ~Lve a 3~ nt ya:~n of 150 der~ier. ~ heath i~ a polg~ide a~ in E~le II~ ~he ~pinnere~ a~nibly 'LB e~en~
tlall~ a~ in Ex~?le I except tl~ meter pla~e f;lt~knes~
0.025 ~m. and th~ c~a:~el~ are ~)~25 X 9 mm. The spl~n~
~e~perature is abou~ 325C. T~e i~e~l~s h~e a log rh~ o~
9 . 3 ~"' ~,' ~ 29 - ~

., .
. . .

Claims (14)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An antistatic sheath-core filament having a log rho of less than 11, comprising a sheath of synthetic linear fiber-forming polymer and a polymeric antistatic core wherein the core comprises between 0.2 and 10% of the filament volume and consists essentially of a low Tg, con-ductive polymer having a Tg (NMR) of less than 25°C and a log Rs of less than 10.

2. The filament of Claim 1 wherein the core polymer is selected from the group consisting of N-alkyl polycarbon-amides, aliphatic polyesters and polyether-esters.

3. The filament of Claim 1 wherein said core com-prises at least 0.5 percent of the filament volume.

4. The filament of Claim 1 wherein the core com-prlses from 2 to 6 percent of the filament volume.

5. The filament of Claim 1 wherein the fiber-forming sheath polymer is a polycarbonamide.

6. The filament of Claim 5 wherein the polyamide of the sheath is a polymer of bis(4-aminocyclohexyl) methane and a linear aliphatic dicarboxylic acid containing from 12 to 14 carbon atoms.

7. The filament of Claim 6 wherein the core poly-mer is an N-alkyl polycarbonamide.

8. The filament of Claim 6 wherein the core poly-mer is an antistatic aliphatic polyester.

9. The filament of Claim 1 wherein the fiber-forming sheath polymer is a polyester.

10. The filament of Claim 9 wherein the core polymer is a polyether-ester.

11. The filament of Claim 1 wherein the fiber-forming sheath polymer is a polyolefin.

12. The filament of Claim 11 wherein the core polymer is an aliphatic polyester containing a dissolved phosphonium salt.

13. The filament of Claim 11 wherein the core polymer is a polyether-ester.

14. A filament of Claim 1 wherein the core polymer contains branched molecular chains.