CA1199152A - Process for imparting lubricity and hydrophilicity to synthetic fibers and fabrics - Google Patents

Abstract

PROCESS FOR IMPARTING LUBRICITY TO FIBERFILL FIBER

Abstract Process for imparting lubricity and hydrophilicity to synthetic fibers and fabrics which comprises applying a graft copolymer of an N-(oxymethyl)-acrylamide and a poly(oxyalkylene) to the surface of the fiber or fabric and crosslinking the graft copolymer on said surface in the presence of an acid catalyst.

Description

PR~CESS FOR IMPARTING LUBRICITY ~ND
HYDROPHXLICITY TO SYNTHETIC FIBERS AND FABRICS

~echnical Field Thi6 inYen~ion pertain~ ~o the art of applying polymeric fini~hes to textile ~iber6 and fabric6.
Background of the Invention Unfinished polyes~er fiberfill fibers exhibi~ fiber ficroop and a rough hand due ~o high interfiber riction. It i6 known in the art that a silicone finish will lower interfiber friction and t~ereby make polye~ter fiberfill fiber6 accep~able for comm~rcial U8eS where fiber ~croop can be a problem. For example, Dacron~ Hollofil II, available from E. I. du Pont de Nemours, is finished with a silicone which lowers the interfiber fric~ion associated ~ith fiberfill fibers and t~ereby impart~
a 60f~, down~ e handO However, 6ilicone fini~he6 advers21y affect the flammability and latex bondabili~y of polyester fiberfill ribers.
The unblended polye6ter fabric6 produced for the garment indu~try are hydrophobic~ This lead6 to two problemfi in the use of a polye6~er fabric. Hydrophobic fabric~ ase not ea~ily treated in an aqueou6 medium unle6s a surfactant is added ~o aid in wettin~ the f~bric. Even more impor~antly, garmen~s made ~rom ~ polyester f2bric do not readily ab60rb perspiration from ~he 6kin of the wearer.
Thi~ impart~ a hot or clammy feel ~o t~e polye~ter garment w~ic~ leads to con~umer discomort and in ~urn ~o consumer resistance of polyester fabric6=

D-13,~21 5r~

It would be advantacJeous ~o develop a durable hydrophilic fini~h or a polyeæter fabric.
It is a1~o known in the ar~ of fabric fini6hin~ ~hat a ero~linkable organic ~olymer, when ~pplied ~o a ~ynthetic fabric, w111 provide various u6eful propertie~, e.g., r~duction of ~he eta~ic electricity a~ociated with such abrics. For example, U.S. Patent ~,213,0~3 ~o Kendrick disclo6e~
that an anti6~atic compo~ition of a croæ~linkable terpolymer of: (1) 5~ to ~0% v glycidyl m~thacrylate; (Z) 35% ~o s5~ of an alkali ~e~al 6alt of a 6tyrene sulfonate and S3) ~5~ to ~08 o methoxypoly~ethylene glycol) methacrylate whe.rein the poly(ethylene glycol) chain ha6 a molecular weig~t from 250 to S00, will reduce the static electrici~y of a ~ynthetic fabr}c ~hen applied aæ 2 fini~h. Freneh Patent No. 1,~27,787 discioses tha~
a copolymer of: (1) from 2~ to ~0% of ~n ethy~lenically un6aturated epoxid~ or a corresponding ~ethylol compound: with (2) from ga~ to ao% of an e~te!r of an ethylenically unsatura~ed carboxylic acicl and an alkylphenoxy polyet~ylene glycol, will reduce the 'stat1c electricity or ~ynthe~ic fabric~
when applied to said fabrics as a fabri~ fini~h.
swi~6 Pa~en~ No. 513,28Z diselo6eæ that a copolymer co~po~ed of: (1) from 80~ to 90~ of an e~ter o an alkyl polyethylene glycol haviny an alkyl refiidue Wit~l 1 to ~ carbon atom6 and an average molecular weight of from 300 So 1000 and an ethylenically un~aturated polmeri~able carboxylic acid; ~z) 5~ ~o 10% of a e~he.riied N-methylolamide of an ethyleni~ally unsaturated ~olymeri~able carboxylic D-13,321 ~eid, and (3~ 5D4 ~0 10~ o an ethylenically un~a~ura~ed ~oly~e~izable compound ~ontalni~ at least one acid group ~apable of impartin~ ~olubility i~ water, e.g. acrylic acid, ~ill reduce ~he ~ta~1c eles~ricity a~sociated ~th a ~ynthetic fabric ~nd ~nhance ~e ~oil release properties of ~Duch a fabric.
Summ~rv of ~he Inven~ion In accordanee ~it~ ~he ~r~sent inventio~D
it has been found ~ha~ the proce6~ ~hich ~omp~i~e6 ~a~ trea~ing ~ibe~6 and f~bric~ ~it~ a ~ea~
eompo~ition, Bolution or disper6ion co~taining:
(i) at least about .001~ by ~olution weight or neat composition ~elgh~ o~ an acid ~atalyst, a~d (ii) rom about .1~ to ~bout 15~ by ~olution ~ei~ or ~eat compoEition weig~ o~ a graf~. ~opolymer pr~pared by grafti~g to a poly(oxyalkylene) ~ro~ a~ou~ .5~ to about ~0~ ~y graf~ copolymer weiqht of an N-(Qxymethyl)-~crylamide having the for~ul~:
~1 R3 C ~ ~ C ~ ~Hz - ~ - R~

1 R2 ~3 and R4 are hydrogen or ~onovalent ~ydrocarbon radical~ ~ontaining from 1 to abou~ 6 car~on 3~0m6 each and may be tha ~ame or differ~, and a ~oly~oxy~lkylene) o t~e formul~:
~ ~ t(0C~H~ R ~ a ~erein R5 i.~ a ~ydrocaEbo~ radical ~av~n~ a valence o~ cl ~nd ~one~ning u~ ~o abou~ 21 carbo~

~-~3~321 Lt3f~d ~toms, a is an integer having values betwee~ 1 and 4. ~ is an oxygen, nitrogen or sulfur a~om~ ~6 i8 a hydrogen atom or hydroearbon radical containing up to about ~ carbon ~toms and may contain hydroxyl, amino or ~ercap~yl group~ an lnteger fr~m ~ to 4~ and z i5 an integer having a ~alue fro~ 2 to dbOUt 800, and ~ b) drying and curing ~aid treated ~iber at bet~een about 100C and about 170C, which imparts to the fiber a durable fini~h which increa6es the lubricity of the fiber manifefited by a lowering of interfiber friction wiC~ou~ adver~ely affectin5l the flammability or the latex bondabil1ty of the flber.
In a particular embodi~ent of ~he invention, the poly(oxyalkylene) preferably ha the formula:
R5[(oc2H~)x(oc3H~)y~R ]a wherein y i~3 an integer from 2 ~o about 5000, and ~he other designation~ are a~ above. T~e grat copolyme.r produced rom 8UC~ poly(oxyalkylenes) imparts the property of hydrophilicity to the fabric as manifested by a decrease in ~he time nece~ary to wet the Eabric.
Th~e graft copolymers useful in the presen~
invention ~ay be prepared as described in copending U.S. application Serial No. 307,211 fil~d September 30, 19~1.

Details of the Invention Graft copolymers useful in the presen~
inven~ion having an N-(oxyme~hyl3 acrylamide graft~d Lr~

onLo a poly(oxyalkylerl~) compound are prepared ~y a ~ethod ~hich compri~es ~dding an N-(oxyme~hyl) deriYatiYe of acrylamide monomer as hereinafter more fully de6cribed ~nd a ~uitable cataly~t to an agitated bath of the poly(oxyalkylene), whereby all of ~aid components are in~imately admixed at a temper.ature at which reaction occurs, and ~aintaining ~aid te~perature until said graft copolymer of acryl~mide deriva~ive on poly~alkylene oxide) i~ obtained.
In general~ ~he poly(oxyalkylene) compounds of this invention contain oxyethylene, oxypropylene, oxybutylene groups or both oxyethylene group~ and hîgher oxyalkylene group6 such a~ oxypropylene and oxybutylene groups, either in random or block distribution in their molecules, and have molecular weig~ts (number averaqe~ in the range of about 100 to about 35,000, and, preferably, in the range of abou~ 1,500 to about 4~003O The~e ~oly~oxyalkylene) compounds may be ~ade by processe6 well known in the art by reac~ing a~ alkylene oxide or mixtures of alkylene oxides with an aliphatic co~pound, which may be saturated or contain some aliphatic unsaturation, having from one up to a6 many as four active hydrogen atoms, 6uch a6 wa~er, monohydroxylic alcohol~ such as ethanol~ propanol, and allyl alcohol dihydroxylic alcohols such a~ ethylene glycol and ~onoethylether o~ glycerine trihydroxylic alcohol6 such a8 glycerine and trimethylolpropane and te~rahydroxylic alcohol~
~uch a~ ~orbitol~ E6peclally preferFed acti~e hydrogen compound6 are allyl alcohol and glycerine.

9-13,321 The ~oly(oxyalkylene) ~roduc~ o~ 8UC~ reac~on~
will ha~e lineaE or ~ranched oxyalkylene or ~ixed oxyalkylene chaing, and ~uch ~hai~ ~111 t@r~ina~8 ~i~h hyd~o~yl grou~ lChough ~he ~oly(oxyal~ylene~) may be hydro~yl ~ar~inaeed, 80~e or all of ~he~e hydroxyl grou~ may be etherifi~d by reaotion ~i~ a dialkyl ~ulfaC@ ~uc~ a~ die~yl sulfate or an alkyl halid~ such ~ e~hyl chlorider These ~er~inal ~ydroxyl grou~s may al~o be e~herified ~ith alkyl~halohydrin~ such a~ 2-chloro ethansl. This ~ill yield a ~oly~oxyalkylene) t~at ha6 a terminal hydrsxyl grou~, ~h~ch ~ preferred becau~e of i~ ~bility ~o ~onden6e ~ith t~e N-(oxymethyl) functionality that i~ ~ntroduced into ~he poly~oxyalkylene) ~o facll~tate cros~linking of ~e poly(oxyal~ylene) chains.
The grating monomer~ em~loyed ~n ~reparing ~he copolymer3 u~eful ~n ~e pre~nt i~ve~tion are sub~tituted acrylar~ide monomer~ ~aYi~9 t~e formula Rl ~3 0 ~ 1 11 C ~. C - C - NHCH20~R
~2 w~erein ~, R2, ~3 and R4 may b~ the a~me or different and ara ~ydrogen atoms or a ~onoval~nt ~ydrocar~on radicals con~aining from 1 to about carbon atom6. Th~6e acrylamide deriva~e ~onomer~
arc generally homo~olymerizable monomer~ vit~ a react1v~, cros~-llnkable ~endent ~rou~ or grou~.
Illustrat~v~ ~uitable monomer~ ar~ met~oxyDet~yl acEyla~d~, e~hyoxymethyl acrylam~de~ N-buto~ymet~yl aerylamide, allyloxy~e~hyl acryla~d@~

~-13,32 39~ . S ~

N-bu~oxymethacryl~mide and prefera~ly~
N-methylolacrylamide and N-(i60-butoxymethyl)-acrylamide.
A grafting catalyst i~ employed ~hich is a ~ree-radical initiator. The choice of ~uch ini~ia~or is not narrowly critical, a~ any one oP a ~ide varie~y of known inorganic or organic initiator6 of free-radical polymerization ~ay be used. The choice of initiator will generally depend on the pareicular combination of reac~ants fEom whic~ the graft copolymer will be prepared. ~or example, if a given grafting monomer will ~elf-condense at the grafting reaction temperature neces~ary for a given catalyst, ~hen the reaction mixture will form an unde6ireable gel i.e. the graft copolymer ~ill cure before applica~ion to the fiber. Therefore, a cataly~t must be cho~en such that t~e grating reaction temperature will no~
cause the graf~ing momomeE ~elf-conden6e. Exemplary 9f ~ui~able ini~iators are azobisi60butyronitrile hydroperoxide~ 6uch a6 ~-butyl peroxypivalate, di ~butyl pero~ide, and t-bu~yl perbenzoate, peroxycarbonate~; 6uch as diethyl peroxydicarbonate and diisopropyl peroxycarbonate: and per6ulfates ~uch as pota~ium and ~odium persulfates.
Homogeneous graft copolymers useful in the present invention which are Rubs~antially free ~contain less than 2 percent by weigh~) of in601uble homopolymerized acrylamide derivative may be prepared by methods known in ~he ar~ but preerably are prepared by charging the reactan~s in ~wo 6eparate feed ~treams, advantageou61y in gradual D-13,321 and~or i~cremen~al amount~, one of whic~ con~ist~ Qf the graftiny monomer and a ~econd con~isting of the free-radical gra~ting ini~iator. Either of ~he reactant~ may be ~ixed ~i~h a por~ion of the poly~oxyalkylene) compound prior to feeding ~hem to the redction zone when doing 60 facilitate6 the gradual or incremental feedlng ~hereof to the reaction mix~ure. The amount of acrylamide derivative added to the polymeriza~ion reaetor ~one i5 not critical and may be varied over a ~ide range. The preferred range iB from about 6% ~o about 12~ by weight of poly(oxyal~ylene). In general, ~owever, up to about 70 percent by weight, and preferably from about .5 percen~ by ~eig~t ~o about ~0 percent by ~eight based on ~he total weight of poly~alkylene oxide) compound~ ifi charged.
T~e temperature~ at which the graft reac2ion may be carried out may vary over a ~ide range and depend, in general, upon ~he combina~ion of reactant~ to be u~ed in the reaction and the cataly6t chosen to cataly2e the graft reaction. For example, when organic free-radical grafting initiators are employed, ~ temperature 6ufficient to activate the ini~iator, to abou~ 160C, can be u~ed in the grafting reacting, and preferably, a tempera~ure in the range from about 70C to about 100C. ~here employing inorganic free-radical initiator~, a temperature from about above the free~ing point of the solvent to about 65~C may be employed. Reaction temperature~ abo~e 160C lead to gelling of t~e reac~ion mixture and ~ould be avoided.

D-13,321 Incremental and/or gradual addi~ion of the two ~eparate reactant feed ~treams coupled with efficient agitation of the poly(oxyalkyl~ne~
compound in the reaction zone constituts6 the mo~t i~portant technique for producing the ~ra~t copolymer6 u6eful in ~he pre6ent invention. Thi6 me~hod iB particularly important in large ~cale or commercial operation~, not only or preparing the desired homogenous graft compolymer, but al~o to facilitate! handling and storage of the monomer and the free radical initiator.
The qrafting reaction i~ preferably carried out in bulk without the UBe of a solven~. If de6ired, however, a solvent may be u~ed which is iner~ to ~he reactan~s. Suitable ~olvents include benzene, t:oluene, terCiary-butylbenzene, heptane, hexane, or octane, and mixture~ thereof, and water.
l'he preferred graft copolymers are made from a po].y(oxyethylene-co-oxypropylene) copolymer of molecu].ar weight in the ra~ge of 3~0 ~/mol to gOOo g/mo]. and ~hich are a~ least about 40~ ethylene oxide monomer by weight of t~e polymer. The upper limit i~ no~ crltical a6 longer chain polymers have been founcl to impart better lubricity however, the hig~ visco~ity o very high molecular ~eight poly(oxya]Lkylenes) may make the use o~ such polymer6 dificult. The preferred poly(oxyalkylenes) have been ~rea1:ed ~ith a sufficien~ amount of N-me~hylo'L-acrylamide or N-(isobutoxymethyl)-acrylamide in a ~rafting reaction such tha~ at lea~t an a~erage of 1 l/Z N-(oxymethyl)-acrylamide~
molecule6 are graftPd onto each poly(oxyalkylene~

D-13,321 3aa~

lt) --~olecule and most preferably an average of from 3 to 6 N-(oxymelhyl)-acrylamide molecules per ~oly(oxyalkylene) molecule.
All optional compGnent oP the treating ~olution ir~ an antioxidant ~hat ~ill inhibit the degradatioll o the poly(oxyal~ylene) ~olymer ~hereby improving ~he durability of the "fiber ini6h."
Such antioxidant~ are ~ell ~nown in the ar~ of s~abilizin,~ poly(oxyalkylenes) and may include any number of .antioxidant compound~0 E6pecially suitable are hindered phenolic eompounds ~uch a~
Bisphenol .~, BHA and BHT. The amount of 6uch ~n antioxidant i8 not critical and generally ranges fxom about 1~ to abou~ 3% by weight of the ~rea~ing compo6ition or solution.
The grat copolymer iB then mixed with an acid eatalyst and applied to the fiber or fabrie to be trea~ed.
Although the various examples ~iven herein are directed to the practice o the in~tant inven~ion with fiberfill ~iber6, i~ i6 ~elieved that the inst3n.t invention will impart lubricity to any ~ynt~etic fiber, e.g., 3 ~extile ~iber. It i8 ~0 be under6tood that the phrase "fiberfill fiber~
intended t.o IDean any non-woven bating or fiber mat.
Although all the exampleB BhOwn herein are directed to carded polye~ter fibers, i~ i~ to be expected ~hat non-carded~ non-polyester ~iber~ will exhibit simil2r propertie6 when treat2d by ~he process Gf ~he instan~ inven~ion. In addition to She Hollof;l-E~08 fiber~ available ~ro~ E. I. du Po~ de Nemour6 that are exemQllied herein, other fiberfill ~-130321 t~

fiber~, 6UC~ a~ ~he round, ~olid fiber a~ailable from Hoech~;t, are u~eul in the instant invention, Similarly~ ~he process of the in6tan~
inventioa i~ exe~plified hereinafter by the ~pplication of the ~raft copollImer to lOOS polyester fabric6 made from polyethylene tereph~halate.
Examples oi 6uitable polye6ter fabries are ~odel, a regi6~ered ~rademark of Ea~tman ~odak, and Dacron, a regi6tered trademark of E.I. du Pont de Nemour~.
However, it i~ to be understood that the procesc of the in~tan~ invention i~ not l~imited So polyester fabric~. It i~ believed that substantial ~ydrop~ilicity ~ould be imparted to other textile fabric~, e.g. nylon, ~ynthe~ic/natural fiber blends, etc.
The choice of acid catalyst 6uitable for use in the invention is not critical and may depend on ~uch consider2tion6 as economic or toxicological factor6. Any acid that will lower ~e p~
6uficiently ~o make the solution ~eakly acidie ~ill ca~alyze the cro~linking of t~e grat copolymer on the fabric surface. Examples of acid cataly~t6 include inorganic acids such as hydrochloric, hydrobromic, sulfuric and nitric acids: organic acids ~uch as carboxylic acidsi phenol6, alkyl and aryl ~ulonic acid~, and the like. Lewi6 acids, ~uc~ a~ æine fluoroborate and the li~e, ~ill al60 catalyæe the ~raf~ copolymer cross-linking on ~he surface of t~e fabric. An acid catalyst that i~
particularly ~uitable for u~e in the in~ant inven~ion is citric acid becau6e of it~ commercial availabili~y and non-toxicity. In a mo~t ~referred D-13,321 embodiment, the acid cataly~ cho~en i~ water soluble because an aqueous solutlon i6 a convenient medium with which to apply ~he qraft copolymer ~o the fiber.
The graft copolymer and acid cataly6~ ~ay be applied as a neat compo6ition or a solu~ion. Any 601Yent ~hich will di~solve t~e graf t copolymer may be u6ed. 5uitable ~olvent6 include water, alcohol, ketone~. e6ter6 or mixture6 ~hereof that ~ill di~solve the graft copolymer and the acid cataly~t.
When ~ater is u6ed a6 the 601vent, a functional additive such as an anionic or nonionic ~urfactan~
may be added to acilitate the initial wetting of the fiber. In a highly preferred embodiment, ~he graft copolymer and acid cataly~t are added to ~a~er to form a treatment ~olution that is from lJ23 to 15S by 601ution weight of graft copolymer and .001 ~o 2~ by solution ~eight o an acid cataly~.
I'he solu~ion may be applied in any manner ~a~ is effective to we~ the fiber or fabric with ~he solu~ion. I the fiber or fabric is depo~ited in a bat~ containing the treatment ~olution, the residence time in the bath need only be ~o long as to 3110w sub6tantial wetting by the ~olution. The addition of we~ting agents ~uch as fiurfactants will reduce the necessary re6idenee time. Other functional add;tive~ ~uch a~ colorants, sizing agents, etc., may al60 be added to the treating bath alony with a surfactant. The ~emperature o ~he treatment ~olution i8 not critical 80 long ~s it i6 ~a~ntainecl below ~he ternperature that will cro~8-link the grafC copolymer in solution with the ~- 1 3 , 3 ~2 1 3 ~

~cid ca~alyst. ~he ~reated 1ber or 4abric i~ then hea~ed at a t~mperature and for a period of time aufficient to dry it and cure the graf~ copolymer on ~he fi~er or fabric surface. Generally, a Pew minute. in an oven at bet-~een about 100C and about 170C is 6ufficient ts cure ~he graft copolymer and remove any exces~3 æolvent taken up by ~he fabric in ~re3tmen~, but the actual time and tempera~ure nece;sary will depend primarily upon the catal~st ~nd solvent chosen.
Th~ dried, treated fiber or fabric is ~en ready for further processing ~ith the graft copolymer cros~-linked on the surace of th2 fiber or fabric as a durable, lubricating and ~ydrophilic fiber fini;h. Any residual acid catalys~ may be removed by further proces6ing, which may include a simple rin;ing procedure.
T~i6 invention is urtAer described in the Examples which follow. These examples are intended ~o be illu~rative of specific embodimen~s of t~is invention and are not intended in any ~ay to limit the scope of t~e invention. All parts and percent.age, are by weight unless otherwise specified.
Examples 1 6 2 raft Copol~mer Preparation Example l ~ . four-neck, round-bottom glas; flask, fit~.ed ~ith a mechanical stirrer, t~ermometer, water co~den;er, two 250 inch dropping funnels nitrogen ~ource, and nitrogen outlet~ wa6 charged ~i~h 1~.3 D-13,371 . r~

gms of an allyl-~ar~ed e~hylene oxide/propylene oxide copolym2r ~40/60 by weig~t.) having a visco6ity of ~50 SUS (Second~, Univer6al, Saybolt). One dropping unnel ~as chargecl with ~.3 g~ of N-(isobutcxymethyl)-acrylamide (IB~) and ehe other was charged wieh 20.3 gm~ of ethyl aceta~e and 1.3 gm8 of Z,2 azobis-(Z-methylplopionitrile). The 1a6k con~ent~ were heated to 80 with an electrical heating mantle and the flask wa6 purged wi~h dry nitrogen. The IBMA and e~hylacetate Z,2-azobi~ -methylpropionitrile) ware added ~imultaneously and drop~ise over a period of one hour at a rate which kept the reaction mixture between 80 and 83~C. Afeer addition of the IBM~
and ethyl acetateJ2,2-azobis (2-methylpropionitrile) wa6 co~ple~ed, ~he fla6k and it6 content6 were heated to RO~C for three additional hour~ and then allowecl ~o cool to room temperature. Any re~aining unreacted IBMA wa~ removed by vacuum stripping along with ~he ethyl aceta~ u~ed ~o in~roduce the acid catalyst. The graft copolymer obtained thereby i~ a clear, pour2ble liguid that is added to water to make ~he fabric treating aolution or may be applied to the fabric as a neat compo~ition with t~e acid ca~aly6t.
~xample 2 ~ , ~50 ml three neck round bottom flask eguipped ~ith a ~tirrer was u~ed in thi~ exampl2.
To ~hi6 reac~or wa~ charged lZ0 gram~ of di6tilled water, 0.cl gram of sodium biearbonate, 0.5 gram of ~odium ~ulgi~e and 0.5 qram of ~odium per~ulfate.
After di6~,01ution of the salt6 wa6 completed ~y D-13,321 ~5 -~tirrinq, 1'i.3 ~ram~ (0~0059 ~ole) of the ~oly(oxydlkylend2) ~olymer u~ed in Example 1 were added and ~he resulting ~olutio~ was ~ooled ~o 0~ ~dO
5~C. A 4a ~er~ent aq~eou~ ~olu~lon o N-me~hylolacryla~ide containi~ 7.~ gram d~O.O3~
mole) ~2~.6 weight -Qercent of the total ~har-Je'J with 5.0 gram~ additional water wa~ ~dded drop~ise ~o the reaction ~ixtufe over a period of 1~ ~inu~e~. ~f~er addit:ion of all reactant~ ~as comple~edd the reaction ~oixtur~ ~as ~irred or an additional 45 ~inute6 w~ile ~daintaining t~e temperature a~ 03 ~5 5C~ and th~en the reaction mixture ~as allo~ed to ~arm to room temperaeure.
T~is crude reaction mixture may then be diluted to Eorm a treatins ~olution u~on ~he addition of a ~olvent ~nd a ~u~table acid ~atalyst.
Lubrici~y Te~ting Th~ ~ample~ ~e~ed in examples 3-7were prepared by ~adding the aqueou6 fini~hing compo~i~ion on~o carded Hollofil-~08, a round, hollow, pol~yefiter f1berfill iber available rom E.I. du Pont de Nemours. T~e a~ount of fini~h taken up ~as controlled BUCh that t~e Hollofil-BOB takes up l~s own ~weight ln aqueou~ finish. Thi~ 100~
~ick-~ of fini~h on the fiberfill tran61ated in~o a ~ercen~ by ~weigh~ of finish on ~he fiberfill ~qual to t~e ~ercPnt by wei~h~ of finish in ~olution, l.e~, a 13 graf~ copslymer f~ni~hing ~olu2isn yielded a fini~hed Hollof~ 0~ ~ample tha2 i~ 1~ by ~eigh~ of graf~ copolyme~ finish.
The ~ini6hed ~ibera were ~hen dried at ~he ~e~pera~ure indicated and ~or the time ~ndic~ted in the following e~amples.

5.~

T~le ~reated ~amRles were then allo~ed to condition or three days by maintainin~ them i~ a con6tant enYiron~ent of 50~ relative humidi~y and 70~F. The samplee wera then ~e~ted for lu~ricity aceording eo a "Staple Pad Friction" technique. In this 'cechn:ique, a weigh~ed sled i 6 pulled acro6s a fiber ~ample by an ~nstron Model 1000 available from Ins~ron Co:cp., Canton, ~A. The "Staple Pad Fric~ionll i6 displayed in grams by the Infitron and the Staple Pad Friction (hereinafter referred to SPF~ Index is compu~ed by dividing the Staple Pad Friction in gram~ by ~he 61ed weight in gram~.
T~ te6t ~e durability of the graft copolymer finish, the samples as indicated ~ere wa6hed for 10 min. in a solution of 2.~5 gm~ of AATCC Detergent ~124 held at 70~C. T~e samples were then rinsed with deionized water at room ~e~perature ana were allo~ed to recondition in a constant environment as hereinbefore des~ribed.
Example 3 This i~ a control for Examples 4-6 in which untreated Hollofil-808 exhibited an SPF of .40. ~he re6ults of Examples 3-6 are tabulated in Table I.
Example 4 This i~ a comparative example in which a 1%
solution of 2 ungrafted allyl-star~ed ethylene oxide/propylene oxide (~0~60 by weight) with a vi~c06ity o 2700 5US ~Seconds, Univer6al, Saybolt) and an average molecular weight of 3700 g/mol ~a~
paaded on~;o a carded Hollof 1-00B sample as he~einat~r described and tested 38 herein before D~13,321 ~3~

- 17 _ described. The SFF for ~uch an ~ngrafted ~ample was .36 befo~e ~a~hing.

S
~ hi6 i~ a comparative example wherein no cat31yst was used to cure the grat copolymer. The procedure o~ Example 4 ~a6 followed with the exception ~Chat the graft copolymer was compo~ed of 26 . 6 gms by weight of N-( isobu~oxym2thyl)-acrylamide graf~ed onto an allyl-~tar~ed Q~hylene oxide/propylene oxide (40/60 by weig~t) ~ith a vi~co~i~.y of ~50 SUS and an sverage molecular weight of 1900 g/mol. ~o catalyst was, however, added to ~he fini6hing 501ution. The ~reated ~ollofil-80~
fiber exhibited an SPF of .30 before washing and and SPF of .39 after wa~hing.
Exam~le 6 This i~ a preferred example wherein 7.5 gms of a graft copolymer composed of 12~ by weight of polymer of N-(isobutoxymethyl) acrylamide grafted on~o the poly(oxyalkylene) of Example 4, 7.5 gms of citric acid and .15 9 of ~isphenol A were di~solved in enough deionized water to orm 750 gms of fini6hing solution. 5am~1es of Hollofil-80~ were treated and tested as hereinbefore described to yield ~n 5PF Index of .27 after curing for 10 min.
at 150C but before washing, and an SPF of .2g after washing ~s ~ereinbefore de6cri~ed.
Example 7 - ~'his is a preferred example wherei~ 7.4 gms of a gr2ft copolymer ~ompo6ed of 12 ,321.

N- t ~obutoxyJ~e~hyl 1 -acrylan~ide grated onto a ~lyoerol-sta.rted ethylene oxide~r~flene ox~de (l~JB6 by weight~ ~th a Y3.5:Co6i~Ly o~E 360 SUS and an avera~e molecular weight o~ 4741 ~mol was d~persed in 750 gms o:E flnis}liny to whieh was al~o added .75 9TG of ethGxylated nonyl~heIIol, Tergitol (TM) NP-40 available from Unio~ ~:arbide Ccr~orat~ on (as a surfa~tane to di ~jperBe ~he nearly ~n~oluble gragt ~:opolym~r~ .5 gmg ~f citric acid and .15 ~ o~
Bisphenol ~ T~ procedure o applic~iorl as~a ~e~ti~g of l:xam~le 5 ~hen yield an 5P~ before wa6hing o . 26 and an SPF af eer wa~hlslg of , 29 .
TABLE I
5P~
EO~P0 Be f o r ~ Af S ~ r Example ~Q~ Catal st ~ia~hln~ ~a~
3 '.None ~o~e .40 .
4 ~@O~PO- None . 36 ~700 5US~
S l@~/PO~ . 3 450 SUS~
:2 6 . 6 ~; I B~
6 ]EO/PO- Citr~ c 2700 SUS~ Aeid . 2~ . ~9 :12 3 IB~
7 EO~PO~ rlc 36~) SUS~ ~ci~ 6 o29 12~ IBM~
~ Afi mora ~ully de~orlbed i~ the eorre~pondi~g ~:xampl T~bl~ I ill~stxa~e~ th~3t a durabl~
f ~ber~ ini~ ~LB o~a~ned by ~he ~rae~iee o~ ~e p~e~ellt ~rentiQn w~eh ~gni~i~antly lo~er~ t~e n t ~ es .r ~ n a s r~ ~ e ~ ~ ~ e d ~ D ~ y 3 ~ 3 2 1 Hydro~hilicity ~e6tin~
The 100% polye~ter fabric ~amples te~ed in the following example~, B-19, were treated by immer~in~ them in a bath containing a solution of 5 graft ~opol.ymeræ by weigh~ along with .15~ para-toulene ~ul.fonic ~cid ~s a cataly~t and .1~ Tergitol T~N-6, a non-ionic surfac~ant available from Union Carbide Corporation, to aid we~ting in treatment.
The fabric wa~ weighed before im~er6i~n, immer6ed, retrieved and ~hen pre6~ed in a ~athis ~wo-bowl ~ertical Lclbora~ory Padder, type VF, ~ith a pad ~res~ure of 1 bar and a roller 6peed of S rpm. The resulting weight of the wet, treated fabric indicated el wet pickup of treating 601ution of ~0%
to 70~ by weight of the fabric. These wet 6amples were then placed upon a ra~e and dried in a ~a~hi6 Laboratory Dryin~ and Curing Apparatus, type LTF, for Z minu~e6 at 165C. The curing of ~he graft copolymer occurred during this drying cycle.
The 6amples were ~hen conditioned and te6~ed for ~ettability in accordance with AATCC Te~t Method 39~:L977 promulgated by the American A~ociation of Textile Chemis~ and Colori6t~ for the evalual:ion of wet~bility of fabric. The reading~ ~herefrom are expres6ed in the average time in ~econd6 needed vi~ibly to wet the te~ted fabric with a drol? of water. The ~horter the average we~ting time, ~he more hydrophilie iB ~he fabric.
The 6amplel; were then laundered in aceordanee with AATCC Te6t Method 130-1977 the number of time~
indicated :ln Table II.

~-13,3~1 1 1~3~ ~3~

-- zo --The AATCC Standard Detergent 124 wa6 used in an amount of about 140 gram6 in a ~4 wa6h load wit~ a wa6h;ng ~emperture of about 120F and a rinse temperature of about 105F~ The laundered samples ~ere then reconditioned in accordance with AATCC
Test ~ethod ~g-1977 for re-te~ting.
Table II ~et~ for~h the nature of ~he graft copolymer applied to the fabric, the initial wettability of the ~amples and the wettability after five standard laundering~.

D-13,321 ~q~

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13, 32:L

- ~2 -The data ~how that 6ignifieant durable hydrophilici~y i6 obtained wi~h N-me~hylol-acrylamide graf~ copolymers ~nd that superior dusable hydrophilicity i~ obtained with ~-~isobutoxy-methyl)~acrylamide graft polymers. The data a1BO
~how that the structure and func~tionality of the graft eopolymer is not critical within the claimed range6 of s~ructure and functionality o the polyether precursor.
The data in Table III set orth the nature of the graf~ copolymers applied ~o the 100%
polyester fabrie tested in example~ 20-24 along with the wettabili~y re6ult~ after 5, 10, 15 and Z0 standard launderings. The ~reatment process of example6 20-24 is otherwi6e identical to the treatment process described for example6 8-19.

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13, :321 5~

- 2~ -Th~ data in Tablc III 6how that ~x~ended durabili~y of hydrophilici~y ifi achieved for the obutoxymethyl)-acrylamide ~raft copolymer of the pre~ent invention regardle66 of the structure or functionali~y of ~he graft copolymer wi~hin ~hose ~hown in Table III.
The data in Table IV set forth the eEfect of a cataly6t on ~he cro~-linking of the graf~
copolymer on ~he ~ur~ace of the ~reated fabric. The graft copolymer i6 the ~ame a~ that d~6cribed in Example 23 and ~he treatment process ~as identical with the excep~ion of the varied catalyst type and concentra~ion.
T~BLE IV
~ ettability Example Ca~aly~t Concentration ~6ec) After 5 __ ~wt. ~ Laundering~
25 None - ~300 ~6 para-~oluene 6ulfonic acid.Z~ 4 27 2inc 1uoroborate 1.4~ 11 ~ rhe data in Table IV illu~rate the need for a Lewis ~cid catalyst, but that t~e choice of cataly~t i6 not cr~tical.
~ rhe data in Table V illus~rate the e~fect of solution concentration of the graft copolymer of Example 23 in the treatment bathO The other treatment proce~ condi~ion~ were identical to those of example~ 8-19.

D-13,321 ~ 25 ~

TABLE V
Wet~ability after IBMA Grat Launderiny6 Copolymer Concentra~ion (~ac) Example (wt ~) _5~ 10~ 15 ~8 - 300 3QO ~00 2~ 1 25 45 ~8 2 18 ~2 The data show that although increasing hydrophilicity i~ imparted by incr~a~ed solution concentra~ions, a~ littl~ a~ 1~ graft copolymer in solution impart6 subfitantial hydrophilicity to the fabric test~d~

D-13,321

Claims (25)

1 A process to impart lubricity and hydrophilicity to fibers or fabric which comprises:
(a) treating said fibers or fabric with a neat composition, solution or dispersion containing:
(i) at least about .001% by solution or dispersion weight or neat composition weight of an acid catalyst, (ii) from about .1% to about 15%
by solution or dispersion weight or neat composition weight of a graft copolymer prepared by grafting to a poly(oxyalkylene) from about .5% to about 50% by polymer weight of an N-(oxymethyl) acrylamide of the formula:

wherein one or more R1, R2, R3, and R4 are hydrogen or monovalent hydrocarbon radicals containing from 1 to about 6 carbon atoms each and the poly(oxyalkylene) is of the formula:
R5 [(OCnH2n)zXR6] a wherein R5 is a hydrocarbon radical having d valence of a and containing up to about 21 carbon atoms, a is an integers having values between 1 and 4, X is an oxygen, nitrogen or sulfur atom, R6 is a hydrogen atom or hydrocarbon radical containing up to about 6 carbon atoms and may contain hydroxyl, amino or mercaptyl groups, n is an integer from 2 to 4 and z is an integer from 2 to about 800, and (b) drying and curing said treated fiber or fabric.

2. The process of claim 1 wherein said substituted N-methylol derivative of acrylamide is N-(isobutoxymethyl) acrylamide.

3. The process of claims 1 wherein said poly-(oxyalkylene) is made by reacting an alkylene oxide, or mixtures thereof, with an aliphatic compound which is saturated or contains aliphatic unsaturation and which con-tains from one to four active hydrogen atoms.

4. The process of claims 1 wherein the poly-(oxyalkylene) is poly(oxyethylene), poly(oxypropylene) or mixtures or copolymers thereof.

5. The process of claims 1 wherein the poly-(oxyalkylene) is poly(oxyethylene-co-oxypropylene) monoallyl ether, containing 40 percent oxyethylene/60 percent oxy-propylene.

6. The process of claim 1 wherein the acid catalyst is citric acid.

7. The process of claim 1 wherein the acid catalyst is acetic acid.

8. The process of claims 1 wherein the hydro-carbon radical R5 is selected from the group of allyl, butyl, and glyceryl radicals.

9. The process of claims 1 wherein R6 is a hydrogen atom.

10. The process of claims 1 wherein z is between about 40 and about 135.

11. The process of claims 1 wherein bis-phenol is added to the treatment solution.

12. The process of claims 1 wherein the curing temperature is between 100°C and 170°C.

13. The process of claim 1 wherein the curing temperature is about 140°C.

14 The process of claim 1 wherein the fiber treated is a fiberfill fiber.

15. A process to impart hydrophilicity to fibers or fabric which comprises:
(a) treating said fiber or fabric with a neat composition, solution or dispersion containing:
(i) at least about .001% by solution weight or neat composition weight of an acid catalyst, and (ii) from about .1% to about 15% by solution weight or a neat composition of a graft copolymer prepared by grafting an N-(oxymethyl)-acrylamide to a poly (oxyalkylene) the poly(oxyalkylene) being of the formula R5[(OC2H4)x(OC3H6)yOR6]a wherein R5 is a hydrocarbon radical having a valence of a and containing up to about 21 carbon atoms, a is an integer having a value between 1 and 4, R6 is a hydrogen atom to hydrocarbon radical containing up to about 6 carbon atoms and x is an integer having a value from about 2 to about 5000, and y is an integer having a value from about zero to about 5000, the N-(oxymethyl)-acrylamide having the formula wherein R1, R2, R3 and R4 are hydrogen or monovalent hydro-carbon radicals containing from 1 to 6 carbon atoms each and may be the same or different, the poly(oxyalkylene) being present in an amount of about 0.5% to about 50%
by weight of the graft copolymer, and (b) drying said treated fibers or fabric.

16. The process of Claim 15 wherein said N-methylol derivative of acrylamide is N-(isobutoxymethyl) acrylamide.

17. The process of Claim 15 wherein said poly-(oxyalkylene) is poly(oxyethylene-co-oxypropylene) monoallyl ether, containing 40 percent oxyethylene and 60 percent oxypropylene.

18. The process of claim 15 wherein the acid catalyst is citric acid.

19. The process of claim 15 wherein the acid catalyst is acetic acid.

20. The process of claim 15 wherein the acid catalyst is p-toluene sulfonic acid.

21. The process of claim 15 wherein the acid catalyst is zinc fluoroborate.

22. The process of claim 15 wherein R5 is selected from the group of allyl, butyl and glyceryl radicals.

23. The process of claim 15 wherein R6 is hydrogen.

24. The process of claim 15 wherein z is between about 40 and about 135.

25. The process of claim 15 wherein the fibers or fabric material is polyester.