CA1193404A - Hot melt size and yarns sized therewith - Google Patents

Abstract

HOT MELT SIZE AND YARNS SIZED THEREWITH

ABSTRACT OF THE DISCLOSURE

Non-aqueous, water-soluble, quick setting sizing compositions suitable for application as a melt to textile yarns, and for later removal by solvent or aqueous means, characterized by substantial amounts of hydrogenated tallow-type triglyceride wax, are disclosed. The compositions include preferably a 50 :50 weight mixture of a specific class of 80/20 ethylene/ acrylic acid copolymers intimately blended with an equal amount of the wax. A fatty acid amide may be included in an amount up to about 7 weight percent of the composition or from 1 to 9 weight percent sebacic acid or dodecanedioic acid, and the amount of copolymer reduced accordingly. The compositions may contain up to 62 weight percent of the wax, and rigidify at ambient temperatures.

Description

HCT MEr.:r SIZE AND YARNS SIZED THE~EWITH

BACKGROUND OF THE INVENTION

This invention relates to the hot melt sizing of textile warp yarns, mor~ specifically to a novel class of non-aqueous warp s.izes which are applied to yarn in the form of a melt.

For s~me years it has been re~ogni2ed that a system fo~ melt sizing of warp yarn~ would offer many advantages. At the sizing symposium of September 9-12, 1974 ;n Budapest, Hungary (Melliand l~extilberichte, Engtish EdiJcion, April 1975, p~ 262), it was observed, with respect to 5i zing machine~ and sizes~ "All problems related with drying (energy cost~, error sourc~s) can be avoidedr if sizing agents can ~e used which rigidi~y at room temperature. At present there is no satisf actory and practical solution; but it is probable that melt ~izes will be impor~an~ in the future." Both before and since that time ongoing ;20 research on melt sizes and melt sizing methods and apparatus has led to the development and patenting of a number of new size composition~. Various deficiencies~ principally economic in nature, have never~heless limited the commercial acceptability of these ~izes.

U.S~ Patent No. 3,466,717 descrihes a method and apparatus f or si zing warp yarns, in which size i~ applied within a ~izing chambe~

provided with a vat containing a quick~solidifying ~ lten size whose predominant component is wax.

Exemplified f or application in thi~ apparatus i~ a molten size made with hardened castor oil, ~

ethylhexyl acrylate~ and benzoyl peroxide" one of a n~nber o~ sizes described in ~apanese Patent Publication No. 14280/196'j. More broadlyt the latter publication descril:~es certain classes of polymers or copolymers soLuble in specified types of wax, capable of application to yarns by mPlt means. Three facts in ~h:is publication are particularly significant in the context of the present invention. The first is its emPhasis upon high c~mpat;bility of its various simple or mixed polymer components wi th its wax components~ The second is that at least 20 percent of a hydro-phobic vinyl monomer, such as 2-ethylhexyl acrylate, must be present in its polymeric component if compatibility with ~he wax is to be achieved. The third is tha~ a substantial portion of an ester of a hydrox~carbo~ylic acid, such as found in hydrogenated castor oil or esters of hydroxyacids such as tartaric acid, must be present. A minimum of 40 percent of this special kind oE hydroxy ester wax is required as a component in ~he size compositions described in the Japanese patent }?ublication.
Corollary ~o these f acts is the publica-tion's insistence on a 60 percent maximum o hydrogena~ed ~allow in the wax component itself r which latter serves as solvent for the polymeric canponentL More specifically, the document' s examples show no size composition cc~ntainin~ in excess of 24 percent of h~ydrogenated tallow. The 3~ Japanese pa~en~ publicat;on clearly does no~
con~emplate ~he use of high proportions, i~ e. t in the order o 5û percent, o~ readily available hydrogenated ~allow in a melt size c~mposition.
U.S . Patent 4,136, Q~9 describes melt sizes made rom a pol~neric blend of high mol ecular weight w.ith low molecular weight ethylen~"~-unsa~curated carboxylic acid copol~mers, such, for ex~lple, as bLends of high with low molecular weight ethylene/acrylic acid 5 copolymers~ These melt b:lLends are employed as sizes either alone or in c~njunction with 0-50 persent of one or more C5--C12 dicarboxylic acids or with 0-30 percent, preferably S-20 percent, of wax, Eatty acid, or mon~glyceride. With regard to the wax component, the patent mak~s no mention of animal or vegetable wax. ~scher-Tropsch or predominantly hydrocarbon waxes, the only classes of wax identified by name, are represented a~ only a minor substituent in a single example~ at a level of 2.5 percent, in conjunction with 17.5 percent of a monoglyceride.
It is thereEore an object of the present invention to provide a melt size containing substantially more hydrogena~ed tallow or equivalent trigl~ceride wax than hitherto tolerable in ~extile melt sizes.
It is further object of that present invention to provide a mel~ size that is removable from fahric b~ ei~her aqueous or organic solv~nt extraction or scouring means~
It is a further objec~ of the present invezltîon to provide a melt size exhibitlng minimal smolcing and f uming during hot mel t application to yarn.
It is a further object of this invention to provide a melt size giving superior weaving throu~h the enhanced abrasion resistance and fiberlaydown of staple yarns to which it has been appl i ed .

The~e and other ohjects will ~ apparellt from the fol.lowing deta;led description o:E our inve nti on.

S UMMA RY OF T HE I NVE NT ION

According to the present invention approximately e~al wei7ht amounts oiE ully hydrogenated tallow-type triglyceride ~ax and a specific ethylene/acr~2rlic acid copolymer are melted together to form a superior textile melt size. Optionally, ~he lower limit of the copol~mer content may be further reduced to as low as about 35 percent by weight by incorporation of from about one to seven percent of a hydro'genated tallow amide or o~her fatty acid amid~, thereby lS further increasing the tallow-type comp~nent.
Another embodiment of ~he invention incorporates from about one to about nine percent o~ seba~ic acid or dodecaned;oic acid into blends of va~ious proportions of copolyrner and wax~.
Unlike more complex melt size maxtures from the art~ neither highly specific polymQr blends nor low contents of inexpensive hydro~
genated triglyceride wax are required to insure good sizing pe~fQrmance. The unexpected advantages of the melts of the present invention are thus achieved wi~hout loss of either performance or economic meritO
~Iydrogenated tallow, the preerred ~riglyceride wax of ~he invention~ has long been kno~n, and the art sugge~ts that its potential merit as a melt size oomponent has evidently been recognized for many years. Nonetheles~ its utilization in high prop~rtion~ in a melt s;ze in conjunction with a simple and con~nercially availabl.e polymer represents a surprising and con~nerci ally important aclvance i n the melt si zing oE textile warp yarns.

DETAILED DESC:RIPTION OF THE INVENTION

The hot melt size compositions o:E the pr es en t i nv ent ion canpr is e pr ef e ra bl y an ess en-tially two component melt hlend of about 42 to 5 weight percent of subs~antially 80/20 ethylene/
10 acrylic acid copolymer in conjurlction with about 58 to 42 weight percent of f ully hydrogenated tallow-type triglS~ceride wax wherein optionally ~he copolymer content may be reduced to as little as about 35 weight percent by incorporation of one to seven percent of C16_2~ fatty acid am~de or one to n i ne pe r ce n t of s a bac i s or dod ec aned i oi c ac i d, and wherein the copol~ner has a standard melt flow rate value of 250-550 when determined by ANSI/ASTM
D 1238-79 at Cundition D. Thus in its broadest aspect the melt sizes o the present invention canprise~ two- or three-c~mponen~ melt blends of abou~ 35 to ~8 weight percent o, ethylene/acrylic acid copol~ner and about 62 to 47 weight percent of a fully hydrogenated triglyceride such as hydrog~nated tallow, together with f ran 0 up to about '7 weight percent of a C16-C~O ~atty acide amide or fr~m 0 up to about 9 percent of sebacic aci d or dod ec aned i oi c ac i d.
In the preferred tw~component si zes we have found that composition ranges of about ~5 to 55 weight percent of substantY all~ 80~0 ethylene/
acrylic acid and about 55 to 45 percent o:E
hydrogena'ced ~rigl~ceride give the best reslllts, !3 ~ 3 ~

w i th opt i mwn mel s i zi ng pr ope r ti es be i ng cen te red around substantial:Ly 50 :50 weight proportions of these components. ~[~he preferred triglyceride is t all ow.
In the 3-componen~ embodimen~ of ~he invention, the content of ethylene/acrylic acid copolylller in the size may be r~duced below about 45 percent, to as low as about 35 percent, without si~nificant loss o~ sized yarn perEormance. The melt si ze of this embodiment comprises about 35 to 45 percent, preferably about 38 to 42 percent, of substantially 80/20 ethylene/acrylic a~id copol~ner, about 62 to 54 percent, pref erably about 60 to 56 percentt of hydrogenated triglycer-ide~ and about 1 to 7 percent, pref erably about 2 to 5 percent, of fatty acid amide. Incorporation of the amide appears to increase ~he miscibility rarlge of the copolymer and hydrogenated triglycer-ider thereby permitting the use of less copolymer in the melt si ze The o~mpositions of the present invention canprising 40 ~o 55 percent ethylene/acrylic acid copolymer, 55 to 40 percent hydrogena~ced trigly-ceride wax, and 1 to 9 percent sebacic acid c:r dodecanedioic acid exhibit an expanded range of melt compatibility such that they can ~ mel~ed and applied to ~7arn at significantly lower temperatures~ i.e~,, up to around 50F lower, than the two componen~ copolymer/tallow blends~
3Q Increa~ed cc~npati bi lity is closel~ associated with temperature rise, and the capacit~ Eor decreased tempe rat ure witho ut c~mpon en t se p~ rat i.on of ~ he melt is particularly advantageous, The blends con~:aining sebacic acid or dodecanedioic acid further exhibit greatly improved resistance to ~moking at melt temperatur~e, only part of this res ist ance se~mi ng to be at ~r i butabl e to thei r lower melting and applicat:ion tempera~ures. They also appear to have increased thermal stability, 5 canpared to the bl ends of lthe inven~ior~
containirlg either s:>f the acids. For maxim~n }:enefit from these property advantage~, preferred ccmpositions of this tyE~e are those contalning 4 to 7 percent sebacic acid or dodecanedioic acid in colljunction with approximately 50:50 prop~rtions of copolymer and hydrogenated triglyceride. As an alternat;ve various mixtures of sebacic and dodecanedioic acid together consti~u~ing the total 1-9 percent component rnay be used.
:L5 The low molecular weight ethylenefacrylic acid copol5~mers employed in the me~ t sizes of the present inven'cion are themselves well known and commerci al~ ~ ava i 1 abl e mate ri al s . ~hey may be made by methods disclosed in U.SO Patents 3,52û,861 and 4, 515, 317 or less preferably be precipitated from emulsion form as in U. S . Patent 3, 436, 363 . Polymers conta;ning substantially B0~20 weight prop~rtions of ethylerle to acrylic acid are bes'c suited to ~che sizes o the present invention. Canmercial Polymers of this type are defined in terms of both composgtic>n and melt viscx>sity, which latter is e~spressed herein as determined by ANSI/ASTM Test Method D 1238 7~ at C<:ndition D. Pol~mers having a melt flow rate value of 250-550 gr~ms per ~en minutes according to this ~tandard test are useful in our invention~ with a po~ ymer havin~ a melt value of ab~ut 30n bein~ preferrec9O

'~1 ~Y~ r;~

~ Iydrogena'ced or hardenecl tallow .i~ a wi del y ava i 1 abl e by- pr odu ct of t he meat- pac ki ng industry made principally by hydrogenation of beef tallow. As such it is pr;.ncipally compri~ed o:f 5 glycer~l tristearate, with lesser inclusions of mixed ~lycerides of C~ ?0 saturated fatty acids. Principally because of its currently f avora bl e pr i ce and ava i 1 abi li ty, whak is conventionally kno~n as "f ully hydrogenated" beef tallow (iodine number less than one ) is the preferred triglyceride o:E the inven~ion. Other fully hydrogenated triglyceridesr for example those derived from oils and fats such as soybean oilr cottonseed oil, peanut oil~ palm oil, lard, 1~ and tallow~ f rom shee p, goat, and other animal so ur ces, wo ul d al so be at tr ac t i ve i n t he pre s ent invention should they become economically c~mpeti~ive. Reference is made to ~he ~able of campositions of cc~Tunon vegetable and animal fa~s and oils in Xirk~Othmer, Encyclopedia of Chemical TechnologY, Vol. 6, pages 142-1~4 11951). Therein it may be noted that the large majority of land-based vegetable and animal fats and oils canprise glyceride~ 85-95% of whose fatty acid consituents c~nprise C~ 3 saturated and unsaturated acids.
When fully hydrogenat~d~ these acids are converted essen~cia~ly ~o stearic, palmitic, and myristic aci ds, ~ he re s ul ti ng tr i gl yce r i de~ h avi ng thus becane essentially identical to ully hydro~enated ~eef tallvw mixtures of these various waxes can also be used.
Expressly excluded from the category of triglycerides of the invention is castor wax, the fully hydrogenated derivati~ of castor oil.
B~au~e o:E the very high propor~ion of rici noleic acid in castor oil, castor wax, with .its corres-pondingly high content of 12-hydrox~stearlc acid moieties, is unsuitable for use as a major canponent in the melt si zes of the invention.
The fatty a~id amides, also commercially known as hydrogenated tallow amides, and co~nonly made by reaction of free acids or hydrogenated tallow with a~noni a, are typically mi xtures o:E
C~ ~_2~ acid amides, principally stearamide. More chemically specifi~ fatty acide amides may of ~ourse be employed in ~he invention, but will na~urally be more expensive.
Besides the named components, minor amounts of other agents s uch as tracer dyes, anti oxi dants, and the li ke may be added t~ lthe si zes of the invention, as desi red.
Although other means may alternatively be employed, the methods and apparatus of U.SO
Reissue Patent 29,287 are preEerred for applying these si zes; the disdosure of this reissue pa~ent is hereby incorporated by ref erence to the extent tha'c it may ~e usefu3 in describing ~he use of the melt size ~ompositions of our invention.
Typically a predetermined amount o~ hydrogenated tallow is melted while being heated to near smoking ~emperatureJ and ~he ethylene/acrylic acid copolymer is added gradually with stirring until mixing is ccmplete, Next the fatty acid amide or dicarb~xylic acid, i~ i~ is to be employed, is stirred in, and the melt is then poured into suitably dimensioned pans or trays and allowed to cool to solid blocks or si ze. Rapid cooling is desirable, ~o minimiæe ~omponent separation~ As described in the reissu~ pa~ent, a si ze block is 3S then pushed against and into the groov~s o a t~ r!~

heated applicator roll, typically at 350-400F, from which grooves size is taken up as the yarn passes tangentially or alc>ng an arc of the turning rollO Further detail~; will ~ fo md in the sub~equent examples of the invention.
Desizing can be ef f ected by either conventional alkaline aqueous sco ur s or or gani c solvents, a~ with mixtures of petroleum solvents and methanol as de~cribed in our U.S. Patent No, 4,253,840~ dated March 3, 1981.
Our experience has shown that in the field of melt si~ing there exists a fine balance between the need for relatively high melting and application temperatures, to help insure rapid size solidification on the yarn, and the desire to prevent or at least minimi ze the t~rldency f or the hot si ze to f ~ne, smoke~ and perhaps to thicken or gel on the applicator roll. Within the pref erred application range of 350-400F for the sizes of the present invention, a general preference for the indicated upper limit e xists ~ so long as the ~izing operation is proceeding smoothl y and without periodic temporary shutdowns for adj ust-ments, yarn breaks, and the like. At about 400F
the size is les~ vis~ous and flows more freely onto the yarn than at 350~. Although the tendency to fuming and ~moking is naturally greater at the higher temperature, within the entire range i~ is minimal, much better than the applicants have observed with ot~er ~igh melting sizes.
The lower end of the preferred applica-tion temperature range offers greater protection against fuming and smoking, and in particular it markedly redu~es the rate of thermall~-induced ?~

reac~ion~ which otherwi~e migh~ ad ~o g~lli ng or other prema~ure ~olis3ification Qf ~he s~ ze at the lp~int of applicationD ~leall:in~ ~he applicator roll at atx:)ut 350F i5 thu~ preferred a~ s~ar~p times and at o~her times s~here ~schedul ed delays migh cause m~lten 5i ze tc> remain longer ~han des~ red on the applicatc)r roll., It is appli~::antg~ belief that the unusually high s:ontent of hydrogenated ~allow in their si~es is to a ac~ns~derable degree re~ponsibae f OE ~he outstanding si zing perfDrmance whi~h has been o~seFved~
lout wis~l;ng ~hat the limit~ of ~heir inventiorl be bounded thereby exc:ept as defined in the appended ~laimsy app~icants believe that a certain aeSl ra ble mar gi nal ; ncc~npati bi lity with each other of the e:s~mpc)nents t~f ~heir ~izes may underlie g~e merits of their inventiorl. This incompatiblity i~ partlclllarly manifest at the 2û upper percentage leYel~ o~ tallow, i. e." abC)Y2 abc~ut 55 percent tallow, most c:~vis~usly ~n the ~wo-component sizesO
For the mc~st part, prior art teach~ngs relatin~ to melt ~izing appear to advc>e~a'c~ high degree~ ~ oc~mpat~b~lity of the compc~nents of the meltr one Wittl the otherO This is parl:icularly evident in ~he a~rementloned JaFane~;e Publication l~o~ 14280~19 65. ~?plic ant~7 on the other hand, - have ~ucceeded in inventing a limited range of 3~ ~i zes where the mellt~ bec~ne m;sci ble ~nly at near their ap~ication temperatures and ~ubse~ently rapidly revert t~ incc;mpat~ bility as they be~in 'co cool and ~et on the yarn.
The cnpo~lt~onal parameter~ of our invention have been esta~lished in ~iew ~f lthe .,~

perf ormance characteristics of our mel~ si zes~
~ased upon our observations and date it appears that above about 60 weight perc:ent of e thyl ene/ ~ r yl i c ac i d co pol ym er, havi ng the prescribed 250 550 melt flow ra~e value, the compatibility of the molten components is if anything excessive.. In any case the melt has become so viscous at arld above this hiyh percentage of po:lymPr as to be almost unusable as a melt size. In a two-~mponent melt system, when the polymer con tent drops belcw about 4 O weight percent, the compatibility in the mol~en state is insufficient, leading to erratic and uneven si zing performanceO The lower limit of copolyT er content may be somewhat extended, i. e., to about 35 weight percent~ by incorporation of small amounts of f atty acid amides without upsetting the precarious balance of the high-tallow melts. It is believed ~hat ~he ~allow serves within a few degrees of the app~ ication temperature as a dispersant for the polymer, but as cooling begins, enough phase se parati on occur s that the yarn becomes coated with a size film having a higher polymer con~ent and more strength and flexibility than would be expect~d of s uch a high total tallow content if all the tallow had remained in a single blend ph as e on coolin g .
A signiicant merit of the present invention which is thought to be related to the limited compatibility of th~ size components is that the size yarn perform~ so well in the loom.
Its lack of ten~ency to build up deposits c:n heddles and other loom parts i~ uncommonly good, especially in a sîze with such high wax content.
This characteristi c, which applicants associate l3 with lack of taclcines~ of the si zed yarn over wider than usual temperature ranges, is far more significant in a yarn si zing context than mere measurements of size ~ilm strengths and 5 elongations, Probably because of their unusually high resistance o tackiness, the si zes of the present invention can be applied ~;uccessf ully at much higher add-on than most melt sizes, without 10 adve rse ef f ect upon ei ther s i zi ng or weavi ng perf ormance. The af orementioned ~apanese patent publication, for example, describes doubling, weaviny, knitting, etc. difficulties encountered when application of its sizes exceeded 4 weight percent., The si zes of the present invention have been applied successf ully to yarns of various ~ype~ and dimensions in amounts ranging f r~m 8 to 18 percenl:. Lower add-ons can be applied to less demanding yarns ~chan the hairy spun yarns which have mostly been tested in the course of the invention. Losm perf ormance has been superior.
D~SSCRIPTION OF THE PREE~ D EMBaDIMENTS

In the examples which folLow, several test~ are now described that we consider simpler and more rapid than actual weavingl. Many of these tests were employed to evaluate and screen candidat~ melt sizes of the presen~ .invention. As f or the melt si ~e c~nposition preparation :Eor ;nitial laboratory screening, small samples of 80/20 e~h~lene/acrylic acid copolymer; having an indicated standard melt flow ra~e value ~hereinafter reerred to as S~), as determined by AN~ I/ASTM D 1 23 8 -7 9 at C ond i ti on D, we re mel t-1~

blended with designated ~lounts of hydrogenated tallow and tallow amide~ Typically, for a 50~50 blend, a 30 gram portion of the copol~ner was melted, into it was stirred 30 gm of hydrogenated tallow, and the melt was observed for clarity at 400F~ The melt was then poured into a 0.5 x 0.75 x 7-inch Teflon mold and allowed to cOQl. Larger-scale samples may be prepared .in essentiall~ ~he s ~un e wa y.
Brookfield viscosity measurements - A
simple measurement useful in screening the sizes Of the invention is the Brookfield vis~osity, and more particularly the calculated coefficient of variation ~COV) of a succession of Brookfield ~odel LVF) viscosity measur~ments on the same melt. For these determinations a 10-gm portion of the molded size stick is melted in a constant-temperature ~ath, and the visoosity i~ measured at 400~F, with a No. 4 spindle, at 60 rpmO Ten successive measurements are taken, and then analyzed ~o determine their CW~ Since the melts were known to gel if held molten overnight~ it was recognized that the v~scosity was moderately time-dependent hence the measurements were taken as rapidly as possible, at about 30 seconds each.
For preliminary screening of the various size campo~itions on yarn, size was applied to six ends of yarn by urging an end of the molded size stick against a 6~groove labora~ory model of the melt applicator roll of the type described in U.S.
~eissue Pa~ent 29,287. The roll, heated at 400F, wa~ turned at lO rpm in the direction o ~arn travel while the yarns, travelins at 330 yards per minute ~pm) unless otherwi~e indicated, were passed through ~he grooves at the top of the ~.5 roll. Tension in grams on the yarn during sizing was measured with a conven~cional ~ensicmeter.
Abrasion ~est - As a screening means for estimating the relative res istance oE the 5i zed 5 yarns to abrasion in a shuttle loom, a rapid abrasion test was applied to mcst of the test specimens. The device used consists of a verticall~moun~ed heddle eye affixed to the top of a short rod, the bottom of ~7hich rod is in turn danped to the shaft of a hori zontally-mounted air cyl i nd er. The thr ust of the cyl i nd er is controlled to impart a hori zontal reciprocating motion, 4 inches in each direction along a straight line, to the heddle eye. A~ve and parallel to the path of the cylinde~ shaft9 and about one inch below the bottom of the heddle eye hole, are fixed a yarn cl~p and a 1/8-inch rod, clamp and rod being ten inches apar~ with the heddle eye between theqn. E~ch yarn sample, for testing~ is fixed in the cl~npr passed through the heddle eye, and hung over the rod with a gO-gm weight attached ~o put tension on the yarn. Thus, at the midpoint of the 4-inch heddle eye stro3ce, ~he yarn f orms an isosceles triangle, one inch hi gh, wi th the 10 inch li ne beJcween yarn cl amp and drape rod~, Better ~co simulate ~he action of a loom, the pi ane o the heddl e eye i5 set about 20 away f rom normal to the yarn line, a~ heddles are set in a loom. The devi ce operates at a rate of about 150 reciprocatiorls per minute~ A coun~er reco rds the n~ be r of rec i procat i ons .
In ~he abrasisn apparatus as described, the 90-gn weight on ~he yarnr generally intended to app~oximate the tension in a loom, makes the 35 test a very rig~rou~ one. Each co~ted recipro-3~
:l6 catis:~n or stroke of the heddle eye comprises a trip over and back to the starting point~ The operator watches the yarn very caref ully as testing begins, and when ~:he yarn begins to 5 deteriorate, which with a poor size is practically at once~ the co-mter readi.ng is recorded. If the n~n~r of steokes to break are desi redr the device continues until the yarn breaks. At least 20 specimens of each yarn are tested to reach an average~ which typically is in the 3. 0 to 5. 0 range for a "goo~" yarn. Steokes-t~break for such yarns are in the r~nge of 200~250.
Deterioration is judged to represent a point, considerably short of formation of fuzæ balls, where the roughe~up and hairy yarn surf aces of adjacent yarns in a warp would be li kely to cause intr~warp f riction and snagging under the action of a loom. The 90-gm weight, with its attendant low but imprecise test nunber s, has been retained in ~he in~erest of ~Feed and effici~ncy in screening out likely failures among a large number of samples. Good correlation has been o~served be~ween a relatively high rating in the ~ces~ and actual performance in a commercial loom~
~i ze build-up - An~ther test f or screening the potential of melt sizes to perform well in a loan involved estimating the tendency of the si~e to build ~p on loom parts. The apparatus canprise~ a 1/8 x 12-inch stainless steel rod, mounted essentially horia~ntal (bowed 0.5 inch in six ~oward the cen~er ) on a recipLc)ca~ing wooden pl a~f ormt where by a 4-inch movement of the rod in each direction along its a~is is produced. A
thermocouple is at~ached to the bottom of the rod alt its center, for the purpose of determining tempera~ure changes in the rod. On each side of the rod, parallel to it and 7 inches away, is mo un t ed a 0. S - i n ch al umi n um ba r . Th e c en te r of the rod ~ises 1.5 inches above the plane oE the 5 two bars. Ou~side and sligh~ly below the bars are twc) beams for supplying and ~aking up a test warp of ya rn s .
For a f ull test of yarn on this apparatus, gn ends of melt-si zed yarn are beaned to provi de about 30 yards of warp. The warp is fed up over the first al um~num bar, across the stainless steel rod and the second bar, and downward through a 4.5-inch camb to the tak~up be~m, ~der a tension of 100-110 gm/end supplied by braking w~ights hung Er~n the feed beam. The warp i5 drawn across the apparatus at about ten yards per hour. Meanwhlle the rod rubs acrs:~ss ~che bottom of the warp at about 150 reciprocations per minu~e. Friction of the warp on ~che ~est rod is judged by recording the rs3d temperature, which typically rises f rom room temperature to about 105~1~ during tes~ing of an efective size, to as high as 125~ with a mar gi nal or poor si ze. Other evi dence o~ poor s i xe pe rf ormance is lateral or rolling action of the warp, whi~h indicates its sticking or seizing on the rod, in which event the test usually is terminated earl y. When a given warp survive~ the passage o~ its full 3Q yards, ~he rod is carefully exan~ined for evidence of size s~icking to it, and if none is found, "no deposit"
is recorded and the si ~e is re~arded as a car~idate for a full weaving test. Note is talcen of the possi ble presence of loose dust on the wooden pla~form~ as an indication of the dusting potenti al of ~:he 6i ze in a loom.

1~

Melt separation - Besides the c>bservations, as noted herein, o degree o meît ha ziness at 400F, another evaluation of l:he degree of homogeneity of l:he melts was also 5 employed in some instances. This involved o bs e r vi ng the a ppr o xi mat e tem pe ra t ure o~ mel t cc~patibility of the blends, defined as th1~ poin~
where a stirred melt no longer exhibits evidence of stringiness, l~ps, swollen blobs~ or the like in the molten fluid wh~n the stirrer is raised and lowered out of and into the melt. I t is also characteristic of ~his tempera~ure poin~ that below it the wax canponent tends to separate into a floating layer on top of the copolymer when stirring is discontinued. Above this temEerature the melt blend~ though still somewhat hazy in appearance, exhi bits no ~ uch c~mponent la~rs .
The following examples refer to the abov~described tests; unless otherwise indicated all parts and percentages are by weight. In the appended claims the total weight percentages of ~he indicated components is 100%. When included a canponent is present in at least an amount of 0.1 we i ght pe rce nt .
~xampl e Equal portion~ of hydrogenated tallow and 80/20 ethylene/acrylic acid (EAA) copol~mer haviny an SMFR of 500 were mel ed together. The Brookfi~ld viscosity of the size was 825-850 cps~ 5 ize add-on to 25~1 65/35 polyester/cotton yarn with ~he l~inch groc ved roll at 400~F was 15,7 percent, the sizing oFeration being smooth throughout~ On the abrasion ~ester the ~si zed yarn gave a favorable reading of 5. 2 strnlces to deterioration; 202 strokes to break. On the size build-up tester, the sized warp went the entire 30 yards, and there was no deposit on the test rod at the end of the test~
Example 2 With a 50/50 melt: size similar ~o that of Example 1, except that the c~opol~ner had an SMFR
of 300, the si ze level on polyester/cotts~n yarn was l~ . 2 percent, and the abrasion test reading was 6 O 8 strokes to deteri oration. The si zed warp rated l1no deposit" in the build-up test.
Exam ple 3 A series of screening exE~eriments em pl oyi ng 30 0 SMF R EAA c~ pol ym e r i n mel t cambination with varying weight propor'cions of hydrogenated tallow were carried out according to the general procedure of Example l. The resul~s after size preparation, application to polyester/cotton yarn9 and testing as hereinbef ore detai~ ed are given in Table l.

EAA/Tallow ~elt Application to Pol yester/Cotton Yarn B r~ kf ~Ld Vi~ ty EZ~A~allow A~ra~ awSizing A~cn P~rasicn wt. ratio ~; % Tensi.on96 Str~kes 40/'60* 3301~.7 ~2 1~.2 3.~
45/5~ 720l.9 37 17.3 ~. 0 50/~ 1050l. 5 4~ 16 .l 4.9 55/~5 ï4a~ 2.1 4~ 8 ~.7 50/40* l~ 3 45 ~.9 *no~ according ~ ~he invention ~o These data ~how ~.hat the mi ~ range E~A/tallow ratios give results indicating essentially iden~ically favorable performance characteristics. At the high-~polymer 60/40 ratio, however, two faults begin to ~nerge. One is evident from the data, which show that the viscosity is hi~her ~han desirable, and that this is caus ing undue yarn tens ion dur i ng the si zi ng operation. The other fault is less obvious. From these and similar experiments we have learned to be s us pi ci o us o:E s i zes -- o ut:s i d e the cl aim ed scope of the invention -- where melt comp~nents appear to be overly canpatible. In ~he series of Table 1 ~he fi0/40 ~A~tallow composition is the only one where the melt was completely clear at 400F~ the others being more or less cloudy or haz~ at this temperatur-o. This o~erved haziness appears to be a sign of the marginal oompatibility which evidently leads to superior melt-si zing performance. Associated with the high ccmpatibility o:E the 60/~0 EA~/tallow melt is a lower than average coefficient of variation in succes~ive Brookfield viscosity meæur~nents.
At the top of ~he table, the 40/60 E~A/tallow cambination ~also m~t according to the in~ention) s~fers from an oppo~ite fault, ex~nplified in its excessive COV of 12.7. 5uch a high lPvel of vaxiation in thP successive Brookfield measurements is indicative of a very r~n- ~i form mel t and of poor misci bi li ty of the canponents~ Not only was this high-tallow cc~T position excessively hazy at 400F in c~mparison with ~he other mel ts, but on close examination it wa~ apparent that the melt was di st i nc~ 1 y non- un i orm, wi th vi s i bl e evi dences of i ns uf :Ei ci en tl y d is pe r s ed pol yme r .
The data and observations indicate that f or the two-ccmponent melts of the invention there 5 exists a plateau of favor,able sizing properties between about 55/45 an~ 45/55 weight proportions of EAA to tallow, centering on approximately 50/50 proportions .
Exampl e 4 In a f urther series of screening experiments it was fo~d that the lower limit of E:AA con ten t i n th e EAA/ t allow canpos ition s co ul d be lowered somewhat by resort to a 3-a~mponen~
ccmposition7 i. e.~ by adding a small proportion of fatt:y acid amide, thereby e}tending the miscibility range shown in Table 1. The procedure was that of Example 1, usin~? 300 SMFR EAA
copolymer. Af ~er the copolyrner was s~irred into molten hydrogenated tallow, prescribed amo~ts of hydrogenated tallow amide were then stirred in at about 400F, and si~e ~ticks were prepared as before. E2~perimental results are given in Ta~le

2. For purposes of comparison, the results for the 40/60 EAA/tallow run of Table 1 are a:lso included. The results in Table 2 are based on a fi xed copolymer content of 40 percent.

TP~B LE 2 EAA/'r al 1 ow/Ami de M el t Appl i cat i on to P ol yeste r/Co t ton Ya rn ~ EAA F i xed at 4 0 Pe r c ent Br~kf;~Ld E~aLlow/ Visoosity ATnide A~,erage 0V Siz~ng A~a~ Abrasicn wt. ratio ~ ~6 Tension % S trokes 40/6û/0* 3:0 12.7 32 14. 2 3.6 40,~58~8/1~2 5~0 3~,8 32 13.~ 3.3 40/57.6/æ4 470 3.3 33 13.~ 300 ~3~6.4/3.6 440 201 34 16.0 ~.2 4~/55.2/4.~ 4103~2 34 12~ 3.7 40/~0~/6 460 3.1 25 17.7 ~.9 ~0/~o~/804* 3703.1 27 1~.~ 3.2 *not according ~o the in~7ention For these 40 percent EAA canpositions a:~ntaining hydrogenated tallow amide, the results clearly show that the excessive incampat;bility probl ems associ ated wi th the 40/6 0 EA~/hydrogenated tallow si ze o:E Table 1 have been largely eliminated. Throughout the range of these

3-ccmponent campositions the data are entirely sati5f actory and the degree of incompati bi li ty~ as measured by the C9V, is within the requirements for a melt size. The only observed limitation was that a tendency toward excessive br.itt~eness and dust i ng wa~ obs erved i n t he com pos i ti ons containing 696 and 8.4% hydrogenated tallow amide.
Exam~?1 e 5 The range of oompositions evaluated in ~3xample 4 was ex~ended by lowering the E~A content to 35 percent, and then to 30 percent. The results are shown in Table 3.

~3 ~ ~ V

TABI,E 3 E~A/rrallow/~mide Melt Application to Pol~ester/Cotton Yarn (E~,~ a~ 3S and 30 percerlt) ~~ rookfield 5 ~A~ ow/ isco6ity ide A~rage CW Sizing A~a~ Pbrasi~n ratio ~ % Ter~;ion % Strokes 35/61~4/306 ~1 ~3, 2 30 14.1 3.1 35~5g/6 300 4.7 29 15,.5 3~5 3t3/66.4/3.6* ZIL0 606 28 1~.8 2.3 30/64/!6* 1806~,6 ~3 18.6 2.6 *not according to the invention These data shs:)w that ~he content of e~hylene/a~rylic acid copolymer can be reduc~d below 40 percent, but 'cha~ below abou~ 35 perc~t the COV clearly ir~dicates excessive incompati-bility in ~he cambinations. Additionally, at 30 percent copolymer content, the abrasion resistance 20 Of the si zes is i nadequate.
Ex~mpl e 6 In a aommercial scal~up of the warp si zing of ~S/l 65/35 polyester/cot~orl, 400 ends oE
yarn were sized on a 600-groove melt applicator roll, with ~he roll temperature at 350-3hO~F~ the 25 roll speed at 11,5 rpn, and the bl~k f eed rate a~
about one inch E~er m~nute~, The yarn speed was 380 yEm, and the si ze add-on averaged about 13 ~rcent. The slze was a 50/50 melt blend of 3~0 SMFR 8 0~70 ethyl ene~ a~r yl i c ac; d copol ~nner wi t:h 30 hydrogenated tallow, in the f orm of ~ocks 7/~-inch thi ck. The yarn was ~aken up on section beams until each of ten beams contained 3200 yards of sî zed yarn. The section beams were then rewound onto two Sul zer loom beams, each contai ning 3992 warp ends.
The beams were mc~mted on a doubl~warp Sul zer loom f or weaving of 1 20-i nch sheeting fabric. The ~7eaving performance, }:ased on the num~r of warp stops and on loom efficiencies~ was campared with weaving of other conventionally aqueo~ si zed warp weaving the same sty:Le in the same weave area. The hot-m,olt-sized warp averaged only 46.3% of the war~related loo~n stops of the conventional warpsV arxl its loom ef~iciency was about 5~ higher 'chan those of the conventionally-s i zed war ps .
Exampl e 7 A melt blend composed of 45% of 300 SMFR
80 /2 û et h~l en e/ acr yli c aci d co pol yme r~ 4 8%
hydrogenated tallcsw, arx~ 7~ sebacic acid was heated until the melt became c~npatible, as defined above7 at about 280F, a tem~erature about 70F lower than the tempera~ures generally o bs er ved f or a va r i et y of pr o por ti ons of co pol ym e r and tallow i n the 2-conponent ~i zes of the invention. The size was preliminarily screened by application to yarn as i n Example 1J at a level of 12.596D On the abrasion tester the sized yarn gave favorable re~ults, comp~rable to those of the 2-comporlent sizes of the invention~
Exanple 8 ~ similar mel~ blend of S0% cop~y3ner, 46% hydrogenated tallow, and 4~6 sebacic acid also becane c:~mpati b:Le a~ about ~80~F, The most promi~ing pro~rty observed with this mel t was its surprising res istance ~o gelation on long h eatin 9~ Wh en B roo kf i. eld Vi5CC)S i t y meas urem en ts were taken (No. 4 spindle; at 60 r~m) on a melt hel~ at 350F, the 1700 cps starting viscosity had risen only to 2:~50 cps after 24 hours, and ~o 5000 5 cps af ter 4 8 ho ur s .
Exampl e 9 Another mel t bl end, composed of 47 .5~6 copol~ner, 47% hydrogenated tallow, and 5u 5 sebacic acidf alSQ became compatible a~: akou~
28ûF. In the Brookfield viscosity test of Example 8 the starting viscosity of 1200 cps rose t~ 1~50 cps in 24 hours~ to 2500 cps in 48 hours, and to 5300 cps in 90 hours, still without gelation appearing. C~npared to tests with s;milar compositic:)ns less the di}:~asic acid, such lcng resis~ance to thermal degradation was most une xpected .
Example 10 A melt blend of 3296 copolymer, 599~
?0 hyd~ogena ed tallow, arx3 ~% sebacic acid bec3me cornpat i bl e somewhat late r, at 3û 0 F, but a f i ~Jn cast f ram the melt was judged ~oo brittle to indica~e utility as a melt size.
Exam ple 11 A melt blend of 47. 596 copolymer" d~7%
hydrogenated ~allow, and 5O5% dodecanedioic acid became campati ble at 280F~ ar~d showed res istance to gelatin aomparable to th~ melts o Examples 8 and 9. Under ~he conditic~ns of Example 8, except that the melt ~emperature was 360~, ~he initial Rroc: kfield viscosity of 1326 cps rose ~o only 1598 cps in 24 hours, to 1748 cps in 32 hour~, and to 28g4 cps in 56 hours. On the Instron tes~er, samples taken from a 3.5 mil film cast fr~n a f resh melt of this canposition gave an average tensile strength measur~nent of 954 ps i and an elongation-to-break o 430%, values comparable to others f rom the best si zes of the invention.
Although especially sui~able for the 5 si zing of polyester/cotton yarns, the melt si æes oE the in~ention are also suited to the si~ing of o~her natural and synthetic yarns, s uch as 100%
COttO;I, 100% wool, wool~c~ttonp wool~polyester, and other s.
This ;nvention may be embodied in other f orms or carried out in other ways without departing fr~m the spirit or essen~ial characteristics thereof. The preserlt eqnbodiments are thus illustrati~7e, the scope of our invention 15 being i ndicated ~y the appended cl aims and the e~i val ents embraced there i n.

- Z7 ~

SUPPLEMENTARY DISCLOSURE

In the main disclosure reference is made that from 1 to 9 weight percent of sebacic acid or dodecane-dioic acid may be added to the textile melt size compo-sition. It has now been found that these two acids maybe added to the textile melt size composition in an amount up to 14 weight percent.
The following examples refer to the above-described tests; unless otherwise indicated all parts and percentages are by weight. In the appended claims the total weight percentage of the indicated components is 100~. When included a component is present in at least an amount of 0.1 weight percent.
Example 12 In view of the undesirable brittleness of the film of Example 10, a melt blend was prepared from 35.0%
of 30Q S~R 80/20 ethylene/acrylic acid copolymer, 54.5 hydrogenated tallow, and 10.5% sebacic acid. In the Brookfield viscosity test, designed to evaluate the resistance to gelation on long heating, the size of this example showed unusually promising laboratory test results, even after 48 hours at 365F, which is much longer than would be required in practice.
Essentially identical laboratory evaluation results were obtained when the sebacic acid component was substituted by an equal weight of dodecanedioic ' ~

- 2~ -acid. Warp yarn (26/1 65/35 polyester/cotton~ sized with about 8~ o the product wove well on a Ruti air-jet loom. The same yarn sized at a 9~ level wove well on a Suzler missile loom.
Example 13 Raising the copolymer content to 3B.0%, in conjunction with 53.0% hydrogenated tallow and 9.0~
dodecanedioic acid, produced a melt size composi~ion exhibiting no more than the usual insignifi~ant increase in Brookfield viscosity after 24 hours of heating at 365F. An observed slight loss of resistance after longer heating at this temperature was thought of no practical significance. The product was judged to be as good a melt size as the superior product of Example 12.
Example 14 A ~urther upward adjustment of the cop~l~ner content to 39.0%, along with 51.0% hydrogenated tallow and 10.0~ dodecanedioic acid, produced a size which tested essentially the same as that of Example 13.
20. Applied in the laboratory at levels of 8 to 10 percent to several yarns of varying hairiness, the composition once more proved an effective warp si~e, perhaps better than that of Example l~,for sizing the hairier yarns because of bettex fiber-laying capability, afforded by its higher polymer content.

1.~
3't 3~

- 29 -~

Exampl.e 15 :[n thi.s example the percentages of both co-polymer and dicarboxylic acid were raised still further, .namely to 40.35% copolymer, 47.55% tallow, and 12.1%
dodecanedioic acid. The resistance of the product -to long heating, specifically for 48 hours at 365F, was nearly as good as that of the superior product of Example 12, and its overall properties made it look generally favorable as a size candidate. However, when the product was viewed from a practical standpoint, no advantages sufficient to justify the higher content of the more expensive components were foundO Further, it was felt that the upper limit for the content of di-carboxylic acid was being approached; i.e., that using much. more of it would make the size components too compatible with each other.
Example 16 A further increase in copolymer content to 42.0~, in conjunction with 4~.5% hydrogenated tallow and 8.5% dodecanedioic acid, produced a size of the in-vention generally comparable with t~ose of the o-ther examples.

Claims (19)

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

1. A quick setting, non-aqueous, water-extractable textile melt size composition comprising an intimate mixture of about 42 to about 58 weight percent of substantially 80/20 ethylene/acrylic acid copolymer, about 58 to about 42 weight percent of a wax derived by full hydrogenation of animal and plant tallows and oils, excluding castor wax, said size capable of being applied as a melt to textile yarns, with quick setting when exposed to ambient conditions, and capable of being removed from the yarns by aqueous or alkali extraction.

2. The size of Claim 1 in which the copolymer has a standard melt flow rate value of about 250 to 550 when determined by ANSI/ASTM D 1238-79 at Condition D.

3. The size of Claim 1 in which the amount of copolymer is from about 45 to about 55 weight percent and the amount of wax is about 55 to about 45 weight percent.

4. A yarn sized with the composition of Claim 1.

5. The sized yarn of Claim 4 in which the yarn contains polyester, rayon, a blend of polyester and rayon, cotton, a blend of polyester and cotton, poly-propylene, wool or glass.

6. A quick-setting, non-aqueous, water-extractable textile melt size composition comprising an intimate mixture of about 35 to about 45 weight percent of substantially 80/20 ethylene/acrylic acid copolymer, about 62 to about 54 weight percent of a wax derived by full hydrogenation of animal and plant tallows and oils, excluding castor wax, and from about 1 to about 7 weight percent of a fatty acid amide, said size capable of being applied as a melt to textile yarns, with quick setting when exposed to ambient conditions, and capable of being removed from the yarns by aqueous or alkali extraction.

7. The size of Claim 6 in which the copolymer has a standard melt flow rate value of about 250 to 550 when determined by ANSI/ASTM D 1238-79 at Condition D.

8. The size of Claim 6 in which the amount of copolymer is from about 38 to about 42 weight percent, the amount of wax is from about 60 to about 56 weight percent, and the amount of amide is about 2 to about 5 weight percent.

9. A yarn sized with the composition of Claim 6.

10. The sized yarn of Claim 9 in which the yarn contains polyester, rayon, a blend of polyester and rayon, cotton, a blend of polyester and cotton, poly-propylene, wool or glass.

11. In a process for sizing textile yarns by applying a size composition to textile yarn, the improvement comprising using, as said size composition, a quick-setting, non-aqueous, water-extractable textile melt size composition comprising an intimate admixture of about 42 to about 58 weight percent of substantially 80/20 ethylene/acrylic acid copolymer together with about 58 to 42 weight percent of a wax derived by full hydrogenation of animal and plant tallows and oils, excluding castor wax, and applying the size composition to the textile yarn as a melt, wherein the size compo-sition is characterized by a rapid setup and absence of tackiness when the sized yarn is led away from the point of application of the size composition to the yarn, the size composition being capable of removal from the textile yarn by aqueous extraction media.

12. In a process for sizing textile yarns by applying a size composition to textile yarn, the improvement comprising using, as said size composition, a quick-setting, non-aqueous, water-extractable textile melt size composition comprising an intimate admixture of about 35 to about 45 weight percent of substantially 80/20 ethylene/acrylic acid copolymer together with about 62 to about 54 weight percent of a wax derived by full hydrogenation of animal and plant tallows and oils, excluding castor wax, and from about 1 to about 7 weight percent of a fatty acid amide and applying the size composition to the textile yarn as a melt, wherein the size composition is characterized by a rapid setup and absence of tackiness when the sized yarn is led away from the point of application of the size composition to the yarn, the size composition being capable of removal from the textile yarn by aqueous extraction media.

CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE

13. A quick-setting, non-aqueous, water-extractable textile melt size composition comprising an intimate mixture of about 35 to about 50 weight percent of substantially 80/20 ethylene/acrylic acid copolymer, about 60 to about 40 weight percent of a wax derived by full hydrogenation of animal and plant tallows and oils, excluding castor wax, and from about 1 to about 14 weight percent of sebacic acid or dodecanedioic acid, said size capable of being applied as a melt to textile yarns, with quick setting when exposed to ambient con-ditions, and capable of being removed from the yarns by aqueous or alkali extraction.

14. The size of Claim 13 in which the co-polymer has a standard melt flow rate value of about 250 to 550 when determined by ANSI/ASTM D 1238-79 at Condition D.

15. The size of Claim 13 in which the amount of copolymer is from about 37 to about 48 weight percent, the amount of wax is from about 55 to about 42 weight percent, and the amount of sebacic or dodecane-dioic acid is from about 4 to about 11 weight percent.

16. A yarn sized with the composition of Claim 13.

17. The sized yarn of Claim 16 in which the yarn contains polyester, rayon, a blend of polyester and rayon, cotton, a blend of polyester and cotton, poly-propylene, wool or glass.

18. In a process for sizing textile yarns by applying a size composition to textile yarn, the improvement comprising using, as said size composition, a quick-setting, non-aqueous, water-extractable textile melt size composition comprising an intimate admixture of about 35 to about 50 weight percent of substantially 80/20 ethylene/acrylic acid copolymer, about 60 to about 40 weight percent of a wax derived by full hydrogenation of animal and plant tallows and oils, excluding castor wax, and from about 1 to about 14 weight percent of sebacic acid or dodecanedioic acid and applying the size composition to the textile yarn as a melt, wherein the size composition is characterized by a rapid setup and absence of tackiness when the sized yarn is led away from the point of application of the size composition to the yarn, the size composition being capable of removal from the textile yarn by aqueous extraction media.

19. A quick-setting, non-aqueous, water-extractable textile melt size composition comprising an intimate mixture of (a) about 35 to about 58 weight percent of sub-stantially 80/20 ethylene/acrylic acid copolymer, (b) about 40 to about 62 weight percent of a wax derived by full hydrogenation of animal and plant tallows and oils, excluding castor wax, (c) 0 to about 14 weight percent of sebacic acid or dodecanedioic acid, and (d) 0 to about 7 weight percent of a fatty acid amide, with the proviso that (1) when compounds (c) and (d) are absent the amount of (a) varies from about 42 to about 58 weight percent and the amount of (b) varies from about 58 to about 42 weight percent;
(2) when compound (c) is absent, the amount of (a) varies from about 35 to about 45 weight percent, the amount of compound (b) varies from about 54 to about 62 weight percent and the amount of compound (d) varies from about 1 to about 7 weight percent; and 36.

(3) when compound (d) is absent, the amount of (a) varies from about 35 to about 50 weight percent, the amount of (b) varies from about 40 to about 60 weight percent and the amount of (c) varies from about 1 to about 14 weight percent, said size capable of being applied as a melt to textile yarns, with quick setting when exposed to ambient con-ditions, and capable of being removed from the yarns by aqueous or alkali extraction.

37.