CA1322825C - Waxless polyvinyl alcohol size composition - Google Patents

Abstract

ABSTRACT
An aqueous waxless size composition for textile yarn comprising in an aqueous solution (a) 100 parts polyvinyl alcohol and (b). 2-6 parts ethylene oxide-propylene oxide surfactant which has a surface tension less than 49 dynes/cm, preferably between about 40 to 48 dynes/cm, as a 0.1% aqueous solution at 25°C, and desirably d foaming number less than about 20 (ml foam/g solution)°F as a 7%
aqueous polyvinyl alcohol solution containing 4 parts surfactant per 100 parts polyvinyl alcohol.

Description

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WAXLESS POLYVINYL ALCOHOI. SIZE COMPOSITION
TECHNICAL FIELD
The invention relates to sizing textile yarn with aqueous polyvinyl a:lcohol compos:itions.
BACKGROUND OF THF INVENTI.ON
Siæing of textile fibers with polyvlnyl alcohol (PVOH) is woll known ~n the art. PVOII with a degree Oe hydrolysis in the range Oe 87 to 100 mole% has proven effectivQ in practice as a sizing agent.
Essentially all textile warp size compositions for spun yarns contain a hydrophobic waxy material, such as hydrogenated tallow wax in order to impart lubricity during weaving and to lessen hoth sticking to the drying cans and build-up during slashing.
In addition, such waxes are difficult to remove from the woven product prior to finishing. Special solvent extraction steps are sometimes used or finishing mills must accept a high percentage of second quality. Frequently wax spots left on the cloth result in dye defects.
Moreover, finishing mills are interested in lowering the temperature of the aqueous size removal systems which causes further removal problems with wax.
Further, foaming problems during sizing are observed whenever the degree of hydrolysis of the polyvinyl alcohol is below 99% and such problems increase with decreasing hydrolysis level. The presence of foam leads to uneven sizing with the result being a decrease in weaving efficiency. Foaming can be ~liminated through the use of superhydrolyzed PVOH (degree of hydrolysis 99-100%) or by the use of defoamers.
The use of superhydrolyzed PVOH in sizing operations, however, imparts other problems such a brittleness of the sizing film which in turn leads to excessive shedding and reduced weaving efficiency. The film properties and adhesion to the fibers can be increased through the addition of polyacrylates, polyesters, polyglycerols and the like.
The film properties and the adhesion to the fibers of partially hydrolyzed PVOH (hydrolysis 85-96 mole%) are superior to those exhibited ~. -` i ~`, ' 8 2 ~

by superllydrolyze(l I'VOII. Further, the deslzlng can be accompllshed at a lower te~)erdtllre, dllo to dccrease(l crystalllnlty of the PVOII, leadlng to an cnertJy savlngs. Fodmlng durlng the slzlng operatlon, however, has to a ~re.lt exten~ prevente(l partlally hy(lrolyzed PVOII l~rades from pene-tratlng thc slzlrl~J market desplte the above advantages.
The foamlng of aqueous slzlng compos~tlons con-talnlng partlally hydrolyzed PVOII can, ln many operatlons, be successfully overcome through the addltlon oF defoamers such as*Collold 69~, 693 or 513, ~rew Y-281, *Nopco NXZ L,*Foammaster Vl. defoamers or certaln e-thylene oxlde-propylene oxlde adducts wlth a hlyh level of propylene oxlde. ~lowever, the pres-ence of a hydrophoblc waxy materlal ln the typ1cal aqueous slzlng compo-s1-tlons wlll have a pronounce(l and detrlmen-tal efFect on the performance of -the above-~entloned defoamers. Thus, the foam1ng problem has, to a great exten-t, excluded PVOli products havlng a lower degree of hydrolysls from use ln s1zlng composltlons desplte the mentloned advantages.
Japanese Patent Publlcatlon No. 47-45634 dlscloses a method for warp slzlng polyamlde synthetlc flber whlch comprlses treatlng synthetl'c poly-amlde flber wlth a warp-slzlng composltlon comprlslng PVOH, a hlghly hydroscoplc anlonlc surfactant and a nonlonlc surfactant whlch ls low-foamlng polypropylene glycol-e~hylene ox1de adduct and~or monoester thereof. Example l (test 2) shows, ln the absence of the anlonlc component, there ls deslzlng 1n the weavlng operatlon.
U.S. 4,389,506 dlscloses a process fo'r the preparatlon of a sub-

2~ stantlally dust-free PVOH powder comprlslng contact1ng the PVOH wlth about 0.5 to 4% polyg'lycol. Th1s document states that block copolymers contalnlng the const1tuents of polyethylene glycol w1th propylene oxlde 1n whlch the oxyethylene content predomlnates (more than 50%) are, to a lesser extent, sultable as long as the end-use propertles of the PVOH are not adversely affected. Composltlon B ln Example I shows PVOH plus 1%
* Pluronlc F98 surfactant.
U.S. 4,428,751 dlscloses a process for the wet process1ng of text11e materlals whlch comprlses applylng to the textlle materlal an aqueous textlle-treatlng 11quor containlng a textlle-treatlng component 1n an amount suff1clent to prov1de a deslred eFfect on the textlle materlal, * Tr~de Marks .
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~J2~21i and further containing in an amount sufficient to provide foam control properties, a foam control agent of the formula n c~o (c~ O~CII~-)~C ,~lz where y is 0 or 1; m and n are both independently an integer from 0 to 30 with the proviso that the sum of y ~ m ~ n must be at least 1; a and b are independently an integer from 1 to 7; R is a Cl -C40 aliphatic group; ~1 is a C1 -Cl6 alkyl group, a C1 -C7 alkoxy group or a C3-C8 alkoxy alkyl group; and Z is hydrogen, halogQn, phosphate or phosphite.
South African Patent 712671 discloses a jute sizing composi-tion which comprises a dilute aqueous solution of PVOH which hasbeen hydrolyzed to at least about 85% and a water soluble glycol selected from the group consisting of polyethylene glycol and polypropylene glycol.
U.S. 3,634,295 discloses a sizing composition for man-made yarns comprising a PVOH and a polyacrylic acid.
U.S. 3,304,785 discloses aqueous solution~ of PVOH con-taining amylose and/or amylitol of low molecular weight for sizing paper and textile fibers.
U.S. 4,222,922 discloses a warp size for filament yarn consisting essentially of PVOH, alkylphenoxy (or cresoxy) ethoxyethyl dimethylbenzyl ammonium chloride and a plasticizer such as glycerol or urea.
U.S. 4,251,403 discloses a warp size for filament yarn consisting essentially of PVOH, urea and mono- and di-saccharides, such as sucrose.
U.S. 4,309,510 discloses a sizing composition consistlng ofa PVOH and 1-30 wt% of an amine oxide.
U.S. 4,383,063 discloses a PVOH based sizing solution con-taining a small amount of quaternary (e.g. dialkyldimethyl) ammonium salt or guaternary imidazolinium salt additives.
U.S. 4,399,245 discloses a sizing composition consisting substantially of PVOH and polyglycerol.
SUMMARY OF THE INVENTION
The present invention provides a waxless sizing composition :

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~2g~r consis~ing essentially of (a) 100 parts PVOH, and (b) 2 to 6 parts ethylene oxide-propylene o~ide surfactant having a surface tension less than about ~9 dynes/cm at 25C in a 0.1% water solution.
In a preferred embodiment the ethylene oxide-propylene oxide sur~actant has a ~oaming number less than about 20 (ml foam F/g so.lution) as a 7~ aqueous PVOH solution containing 4 parts ~0 s~lrEactant per 100 parts PVOH.
The sizing composition is utilized as an aqueous solution at about 2 to 20 wt%~
The addition of certain ethylene oxide-propylene oxide surfactants according to the invention to a PVOH sizing com-position advantageously provides a waxless size that affordslubricity during weaving and easy release of the sized yarn from the drying drum as provided by a wax containing PVOH-size compositions, but also affords low shedding during the weaving operation, high weaving efficiency and, particularly, easy desizing. These advantages are obtained when the siziny composition is used for cotton-containing textile yarn. No significant advantages are observed for all polyester synthetic textile yarn.
The percentage decrease in hairiness resulting from the use of an ethylene oxide-propylene oxide surfactant in the PVOH size will depend upon the degree of hydrolysis and the molecular weight of the PVOH. The use of such surfactants according to the present invention at 4 wt% tbased on PVOH) in an B% aqueous PVOH
sizing composition, the PVOH having about a 1700 degree of poly-merization and being 87-90 mole% hydrolyzed, will provide at least about 55% decrease in hairiness compared to unsized 50/50 polyester/cotton spun yarn.
It is believed that the presence of the ethylene oxide-propylene oxide surfactant provides improved encapsulation and penetration of the yarns~ Thus a size film having greater strength and lower shedding due to increased adhesion and uniformity is achieved. The hairiness of the yarn is often taken as a measure of these qualities. The improved ' ~, .
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~ ~22~25 adhes10n 1s surpr~slng ln vlew of U.S. 3,598,883 whlch teaches that poly-oxyethylene and polyoxymethylene may affect the adhes1ve abll1ty of PVOH.
Another embod1ment of the lnvent10n ls a textlle process for treat-1ng yarn wh~ch comprlses passlng the yarn through an aqueous s1ze solutlon S accordlng to the lnventlon, remov1ng excess slze solut10n from the yarn, dry1ng the s1zed yarn, splltt1ng the yarn, wlnd1ng the yarn, weav1ng the yarn and remov1ng the s1ze from the woven product.

DETAILED DESCRIPTION OF THE INVENTION
; lO Accord1ng to the 1nventlon the s~zlng compos~t10n cons1sts essen-t1ally of the follow1ng components:
~ a) a PVOH wh1ch preferably 1s 85-g9~ mole~ hydrolyzed and has a vlscos1ty rang1ng from about 3 to about 60 mPas (cps) as a 4% aque-ous solut10n at 20~C, and (b) 2-6 wt% ethylene ox1de-propylene ox1de surfactant based on PVOH, the surfactant hav1ng a surface tenslon less than 49 dynes/cm and preferably between 40 and 48 dynes/cm measured at 25C 1n a 0.1% -aqueous solutlon.
The s1zlng compos1t10ns accord~ng to the 1nvent10n are waxless, 1.e.
the composltlons do not conta1n a hydrophob1c waxy mater1al as 1s cus-tomary 1n the art, but prov1de the advantages of a wax-conta1n1ng s~z1ng compos1t10n. Furthermore, an10n1c surfactants are not needed.
Defoamers known to the art 1n the cus~omary amounts may be added 1f foam1ng of the aqueous slz1ng compo;lt10ns presents a problem. However~
in a preferred embod1ment certa1n ethylene ox1de-propylene o~lde sur-factants wh1ch afford reduced foam~ng are used. Such ethylene ox~de-propylene ox1de surfactants have a foam1ng number less than about 20 (ml foam F/g solut10n) as a 7% aqueous PVO~ solut10n conta1n1ng 4 parts surfactant per lOO parts PVOH.
~u1table polyvlnyl alcohols for use in the s1zlng compos1t10n 1n-clude fully hydrolyzed PVOH's (98-99~ mole% hydrolyzed) such as produced by methanolys1s of polyv~nyl acetate homopolymers, and copolymers o~
vlnyl alcohol and methyl methacrylate at least 99.5 mole% hydrolyzed cons1st1ng of 94-98% v1nyl alcohol and 2-6 wt~ methyl methacrylate as ~ 3 disclosed in U.S. 3,689,469. Suitable partially hydrolyzed PVOH's are those that are about 85 to 97 mole% hydrolyzed although material which is at least about 78 mole% hydrolyzed may also be used. Partially hydrolyzed PVOH is preferred.
The sthylene oxide-propylene oxide surfactant is used pre-ferably in an amount rangincj~ Erom 3 to 5 wt%, and most desirably

3.5-4.5 wt~, based on polyvinyl alcohol. If less than about 2%
~thylene ox.ide-propylene oxide surfactant is used, the percentage decrease in hairiness falls off dramatically, and at 1% or less sticking to the drying drum becomes a problem. ~t more than 6%
ethylene oxide-propylene oxide surfactant the percentage decrease in hairiness starts to fall off and integrity of the size film deteriorates because of the incompatibility of the two polvmers.
Illustrative of suitable ethylene oxide~propylene oxide surfactants are those having the following formulas:
~o(c2~ o)y(c3~l6o)x(c24)y and ~l(oc2~l4)y(oc3~l6)x \ (C3~l60~x(c2~4o)y~
/ NCH2CN2N \ Il ~1(c2H4)y(oc3H6)x , (C3H60)X(C2~40)yH
where x and y are integers and are selected such that the oxy-propylene groups constitute at least 900 molecular weight of the compound and the oxyethylene groups constitute 10 to 90 wt% of the compound. Surfactants according to the first formula are condensates of ethylene oxide with hydrophobic bases formed by condensing propylene oxide with propylene glycol. Such sur-factants are sold commercially under the trademark Pluronic by BASF Wyandotte Corp. Surfactants according to the second formula are compounds formed by the addition of propylene oxide to ethylenediamine followed by the addition of ethylene oxide and are sold commercially under the trademark Tetronic by BASF
- Wyandotte Corp.
In addition, ethylene oxide-propylene oxide surfactants according to the above formulas in which the ethylene oxide and propylene oxide units are reversed have also been found suitable.
Such reverse ethylene oxide-propylene oxide surfactants are also ,,~j;~

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available from BASF Wyandotte Corp.
Monoesters of the above surfactants with C1-C1B carboxylic acids are contemplated as being functional, or operative, equi-valents in this invention.
Ethylene oxide-propylene oxide surfactants having a surface tension less than 49 dynes/cm afford greater strength and lower shedding (reduced hairiness) when used in an aqueous PVOH-waxless composition. However, it is preferred to use such surfactants 10having a surface tension bet.ween about 40 and 48, especially 43 to 47, and urther, those with a foaming number of less than 20, preferably less than 15 and most preferably below 10, because foam control is superior and defoamers may not be needed.
The following technique is used to determine the foaming 15number, i.e. the degree of foami.ng of an aqueous size solution.
The aqueous size solution contains 7% PVOH (based on water) having a DP of about 1700 and a degree of hydrolysis of about 87-89 mole% and 4% ethylene oxide-propylene oxide (EO-PO) surfactant (based on PVOH).
20The aqueous si~e solution (400 g) is placed in a 1 liter beaker, equilibrated at the desired temperature and stirred at 1000 rpm for one hour using a 2.25 inch 45 pitched turbine placed in the center of the beaker 0.75 inch below the liquid surface. The mixture is then transferred to a 1 liter graduated 25cylinder and the weight as well as volume of the foamed size is recorded. The foaming is calculated according to the following formulas:
Foam Density (g/ml~ = weiqht PVOH size solution (q) foam volume (ml) ml foam/g = (l~Foam Density Foam Density The foaming is measured at 140F, 150F, 170F and 190F, thus covering the normal operating range of a sizing operation.
35When ml foam/g is plotted against temperature, the area below the curve from 140 to 190F is the foaming number, the measure of the foaming behaviour of the size solution. The smaller the area, the lower the foaming number, and the lower the foaming tendency.
The PVOH-containing size composition of the present inven-40tion will be used as an aqueous solution in the textile industry ..
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Thus an a~ueous size solution will generally have a solids content from about 2 to about 20 wt~, preferably about 5 to 15 wt%, or 2 ~o 7 wt~ if the yarn is double~dipped.
Any means and method for physically mixing the components in an aqueo-ls medium can be used. Preferably the PVO~I and the ethylene oxide propylene oxide surfactant are simply added to the cooking kettle containing water (heated). ThQ surfactant ma~ be physically mixed with the PVOH or spra~ed on the PVO~ as a liquid ~0 or solut.ion to yield a solids procluct for subsequent dissolving in water.
Starch is often blended with PVOH in sizing compositions.
Similarly, the present size composition can also contain common textile warp size starch. The sizing composition can also be modified with other materials for specific textile uses as is customary in sizing applications.
The temperature of the aqueous size solution should be between 50C (122F) and 93C (200F), preferably between 60C
(140F) and 88C (190F) in the sizing operation. Either single or multiple size boxes containing the aqueo~ls size solution may be used as is well known in the art. After removal of excess size solution by passage between squeeze rolls, the sized yarn is dried by contact with multiple drying cans heated to a temperature of about 100 to 175C, split by stationary lease rods, and wound as a weaving beam. The slashing operation is conduc~ed at speeds of 10 to 100 meters/min.
Advantageous properties of the size composition include no build-up on drying cans, clean splitting at the lease bars ` without breakage of ends or filaments, easy separation of the sized yarns when entering into the loom harness, and reduced foaming in the size box when the preferred ethylene oxide-propylene oxide surfactants are used.
Weaving may be performed with conventional shuttle looms, air-jet looms, rapier looms or shuttleless weaving machines.
Beneficial characteristics are production of first class cloth, loom efficiency, absence of loom fouling by shedding and very easy desizing. During finishing the size is removed by scouring with hot water. The size is easily removed . ~
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g -especlally ln the case of partlally hydrolyzed PVO~I by uslng a moderate water temperature of 50 to 70C. There ~s no need for a speclal solvent extractlon step slnce there 15 no hard-to-remove wax ln -the slzlng compo-sltlon. Thus wax spots on the cloth resultlng In dye defects are absent.
The lIse oF IVOII/ethylene oxl(Ie-propylene oxlde surfactant waxless slze coIllposltlons accor(Ilng to the present lnventlon for cotton-contalnlng tex-tlle yarn aFfor(Is s~Irprtsln~ly hl~Jh weavlng efflclency and decreased shed-dlng ~ rlnt~ weav~ng. The weavIng efflc~ency ls essentlally Ident1cal to that obtalned us~ng a conventlonal PVO~I/tallow wax composltlon. Cotton-contalnlng textiIe yarns lnclude comblnatlons of synthet1c flbers such as for example polyesters and polyamldes wl-th at least 10%~ preferably at least 35/~ cotton flbers or all-cotton yarns.
The followlng examples are glven for the purpose of lllustratlng the present lnven-tlon. All parts and percentages are by welght unless other-wlse speclfled.
The halrlness was measured uslng a Shlrley Yarn lIalrlness Meter~
* Wlnder Model 4 connected to an*Epson ~IX-20 computer. The total yarn length used ln the measurements was 50 meters. The 50 meter sample was prepared by knottlng together yarns of 1.5-2 meter length ln order to obtaln a representatlve sample of the slzed warp.
The penetratlon and encapsulatlon data was obtalned by embeddlng the slzed yarns ln*Uersamld 9~0 polyamlde preparlng a mlcrotome cross sectlon of ll-12 mlcrons thlckness treatlng thls wlth a toluene/lsopropanol mlx-ture followed by exposure to an lod1ne solutlon. The prepared cross-sec-tlon was then placed ln a mlcroscope 1n order to obtaln a 35 mm plcture by whlch the penetrat10n and encapsulatlon was ~e-termlned. ~he PVOH contaln-1ng areas appeared as the dark colored areas.

EXAMPLE l Th1s Example presents the foamlng numbers whlch were determlned for a number of e-thylene oxlde-propylene oxlde (EO-PO) surfactants havlng a sur-face tens10n ranging from 3~ to 50.4 dynes/cm followlng the prevlously descr1bed procedure.
Run 1 was a control us~ng the aqueous waxless PVOH slze compos1t10n wlthout a surfactant. Runs 2~-16 employed ln add1tlon an ethylene ox1de-propylene ox1de surfactant. The data ls presented in Table I.

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rhe datd ln rable l demonstrates the lmportance of surface tenslon and foamlng nulllber for achlevlny Poam control. It can be seen that Runs 2 5-7 9-13 and 16 provldetl surprlslrlg foam contral. Runs 3 ~ 8 l~ and lS ln whlch the surfact(lnt had a foamlng number ~reater tllan 20 S demonstrated only sllght lf any foamlng control.

FX~MI'LE 2 Slze solutlons were prepared by slurrylng 20.4 kg of*WS-53 polyvlnyl alcohol from ~lr Products and Chemlcals Inc. (degree of polymer1zat1On about 1700; degree of hydrolysls about ~7-90 mole%) and 0.804 kg of ethylene oxlde-propylene ox1de surfactant 1nto la3 kg of wa-ter. A solu tlon was formed by lnJectlng steam lnto the aqueous mlx-ture under stlr-rlng untll a temperature of 98C was reached. The flnal solut1On sollds was measured once the mlxture had been added to the slze box. The slze eomposltlon was applled to 50/5Q polyester/cotton spun yarns havlng a yarn count of 24.5 uslng a conventlonal commerclal slasher. The halr-lness of the unslzed yarn was 33.4 halrs/meter. The yarn speed durlng slashlng was 12 yards per mlnute and the temperature 1n tlle slze box was at 82C (180F).
The obtalned slzed yarn propertles are shown ln Table II. The results show that the E0-PO compound's surface tenslon has a great 1n-fluence upon the halrlness. A % decrease 1n halrlness of less than 5S%
ls not acceptable slnce lt 1s not s1gnlficànt enough to reduce shedd1ng 2s and weav1ng lneff1c1ency. Runs 20-26 showed an acceptable decrease 1n ha1rlness.

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Slze solutlons were prepared as descrlbed ln Example 2 wlth the ex-ceptlon that the ethylene oxlde-propyle~e oxlde (EO-PO) surfactant content based on PVO~ WAS varled from 2.0 wt% to a.o wt~. The EO-PO compound used was Pluron1c 25Ra surfactant obtalned from BASF Wyandotte. The results 1n Table III lndlcate that the optlmum ratlo of EO-PO surfactant to PVOH ~s between 0.025 and 0.07. Hlgher amounts of EO-PO block copolymers severely weaken the slze fllm.

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- 15 _ EX~MPLE 4 _ _ ___ Slze solutlons were prepare(I by slurrylng 26.5 kg of*WS-42 polyvlnyl aIcohol from ~Ir Iro(lucts and Chemlcals Inc. ~tIegree of polymerlzatlon about 900; dQJree of hytlrolysls about 95-97 mole%) and 1.06 kg of an ethylcne oxl(Ie--I)ropylene oxlde surfactant lnto 177 kg of water. A solu-tlon was formed by InJectlng steam lnto the aqueous mlxture under st1rr1ng until a temperature of 9CC was reached. The slash1ng condltlons and yarn used were as descr1bed 1n Example 2. The obtalned s1zed yarn proper-t1es shown In Iable IV lndlcate that the maxlmum decrease ln halrlness occurs lf the surface tenslon of thc E0-P0 addltlve ls malntalned ln the 40-4~i dynes/cm range.

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~13 2 h EXAMPlE 5 Sl~e solutlons WQre prepared as descrlbetI ln Example 2 wlth the ex-ceptlon Or the I'VOII whlcII ln thls case wa~ ~INOL 325 polyvlnyl alcohol of Alr I'roducts and CheInlcals Inc. havlng a degree of polymerlzatlon of about 1700 and a tIegree of hytIrolysls of 97.5 99 mole%. 1'he data shown In Table V Indlcate that the decrease In halrlness ls llttle lnfluenced by the surface tenslon of the addltlve In the range lnvestlgated when a substantlally fully hydrolyzed polyvlnyl alcohol Is used.

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EXAMP_E 6 ~ slze solutlon was prepared as descrlhe(l ln Example ~. Ilowever, the PVOII use(l In thls exanlple was*r-66 obtalned from OuPont and belleved to be a PVOII/Inetllyl methacrylate copolymer. lhe addltlve used was l'luronlc 25R~ surfactant. The halrlness was wlthln the uncertalnty l(lentlcal to that obtallled whellever WS-~2 polyvlllyl alcohol was used as shown ln Example ~.

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A slze solutlon was prepared by slurry1ng 159 kg (350 lbs.) of PVOH
(DP of 1700, degree of hydrolysls 87-89~.), 6.4 kg (14 lbs.) of an ethylene oxlde-propylene oxlde adduct lnto 1325 kg of H20. A solutlon was formed by lnJectlng steam lnto the slze solutlon, under stlrr1ng untll d temperature of 82C (180F) was reached. The flnal solut10n sollds was 9X. Thls materlal was used to slze a 65/35 polyester/cotton spun yarn employlng a conventlonal slasher. The yarn speed was 86 yards/mln., slze box temperature 82C (180F) and squeeze roll pressure lO 15 ps19. Weav1ng of the slashed yarn was accompllshed us1ng a Schulzer a~r ~et loom. The obtalned results are shown ln Table VII.

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~3~8~ ~3 The res-llts in Table VII compare the weaving efficiency and hairiness of traditionally sized warps where hydrogenated tallow wax was used to impart lubricity (Run 38), to those ~Runs 39 and 40) obtained using a waxless formulation according to the inven-tion. Table VII clearly indicates the ob~ained weaving ~ffi-ciency imparted by the ethylQne-p~opylene ox.ide adducts is essentially the same as that o~ the tallow ~ax. Such weaving e~iclency when coupled with low foaming, lubricity and easier ~0 desizin~ in the absence of a wax is recognized by the industry as a significant improvement.
The ethylene oxide-propylene oxide surfactants which have a surface tension between about ~0 and 48 dynes/cm and a foaming number less than about 20 prevent build-up on the drying cans by depositing a thin liquid film on the dryer drums thus preventing direct contact between the PVOH coated fibers and the can. In addition to the fact that the interfacial tension of the sur-factant is lowe~ than that of PVOH, the phase separation between PVOH and the surfactant leads to a deposit O:e surfactant on the surface of the fi.ber which provides lubricity. The surfactant, furthermore, works as a wetting agent promoting good penetration and complete encapsulation of the yarns, thus producing a size film having greater strength and lower shedding due to increased adhesion and uniformity. The size composition according to the invention takes advantage of the excellent size properties inherent to partially hydrolyzed polyvinyl alcohols, thus permitting the elimination of additives such as polyacrylates, polyesters, polyglycerols and the like as needed in the case of fully hydrolyzed poly~inyl alcohols.
ST~TEMENT OF INDUSTRIAL APPLICATION
The invention provides an agueous waxless polyvinyl alcohol-containing size composition which affords a high weaving effi-ciency acceptable hairiness, very easy desizing when used in conjunction with cotton-containing textile yarn.

, ~

Claims (19)

1. THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
   PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
   
   l. A waxless sizing composition consisting essentially of (a) 100 parts polyvinyl alcohol, and (b) 2-6 parts ethylene oxide-propylene oxide surfactant having a surface tension less than 49 dynes/cm measured at 25°C
   in a 0.1% aqueous solution, said surfactant being represented by one of the following formulas:
   HO(C2H4O)y(C3H6O)x(C2H4O)y I
   
   and II
   
   where x and y are integers and are selected such that the oxy-propylene groups constitute at least 900 molecular weight of the surfactant and the oxyethylene groups constitute 10-90 wt% of the surfactant, or the above formulas in which the ethylene oxide and propylene oxide units are reversed.
2. 2. The sizing composition of claim 1, in which the poly-vinyl alcohol is at least 78 mole% hydrolyzed and has a viscosity of about 3-60 cps as a 4% aqueous solution at 20°C.
3. 3. The sizing composition of claim 2, in which the poly-vinyl alcohol is 85-97 mole% hydrolyzed.
4. 4. The sizing composition of claim 1, in which the sur-factant has a surface tension between 40 and 48 dynes/cm and a foaming member less than about 20 as a 7% aqueous polyvinyl alcohol solution containing 4 parts surfactant per 100 parts polyvinyl alcohol.
5. 5. The sizing composition of claim 1, in which the sur-factant has a surface tension between 43 and 47 dynes/cm.
6. 6. The sizing composition of claim 4, in which the sur-factant has a foaming number less than 15.
7. 7. The sizing composition of claim 4, in which the sur-factant has a foaming number less than 10.
8. 8. A waxless sizing composition consisting essentially of (a) 100 parts polyvinyl alcohol which is at least 85 mole%
   hydrolyzed and has a viscosity of about 3-60 cps as a 4-% aqueous solution at 20°C, and (b) 3-5 parts ethylene oxide-propylene oxide surfactant having a surface tension ranging from 40-48 dynes/cm measured at 25°C and a 0.1% aqueous solution, the surfactant being represen-ted by one of the following formulas:
   
   HO(C2H4O)y(C3H6O)x(C2H4O)yH I
   
   and II
   
   where x and y are integers and are selected such that the oxy-propylene groups constitute at least 900 molecular weight of the surfactant and the oxyethylene groups constitute 10-90 wt% of the surfactant, or the above formulas in which the ethylene oxide and propylene oxide units are reversed.
9. 9. The sizing composition of claim 8, in which the surfac-tant has a foaming number less than about 15 as a 7% aqueous polyvinyl alcohol solution containing 4 parts surfactant per 100 parts polyvinyl alcohol.
10. 10. The sizing composition of claim 8, in which the poly-vinyl alcohol is 85-97 mole% hydrolyzed.
11. 11. The sizing composition OF claim 8, in which the poly-vinyl alcohol is 87-89 mole% hydrolyzed.
12. 12. A waxless sizing composition consisting essentially of (a) 100 parts polyvinyl alcohol which is 87-89 mole% hydro-lyzed and has a viscosity of about 3-60 cps in a 4% aqueous solu-tion at 20°C, and (b) 3.5-4.5 parts ethylene oxide-propylene oxide surfactant having a surface tension ranging from 40-48 dynes/cm measured at 25°C and a 0.1% aqueous solution, and a foaming number less than about 20 as a 7% aqueous polyvinyl alcohol solution containing 4 parts surfactant per 100 parts polyvinyl alcohol, said surfac-tant being represented by one of the following formulas:
    
    HO(C2H4O)y(C3H6O)x(C2H4O)yH I
    and II
    
    where x and y are integers and are selected such that the oxy-propylene groups constitute at least 900 molecular weight of the surfactant and the oxyethylene groups constitute 10-90 wt% of the surfactant, or the above formulas in which the ethylene oxide and propylene oxide units are reversed.
13. 13. An aqueous sizing composition containing from 2 to 20 wt% of the sizing composition of claim 1.
14. 14. An aqueous sizing composition containing from 2 to 20 wt% of the sizing composition of claim 8.
15. 15. An aqueous sizing composition containing from 2 to 20 wt% of the sizing composition of claim 12.
16. 16. A textile process which comprises passing a cotton-containing textile yarn through an aqueous size composition of claim 13, removing excess size solution from the yarn, drying the sized yarn, splitting the yarn, winding as a weaving beam, weav-ing the yarn and removing the size from the woven product by scouring with hot water.
17. 17. A textile process which comprises passing a cotton-containing textile yarn through an aqueous size composition of claim 14, removing excess size solution from the yarn, drying the sized yarn, splitting the yarn, winding as a weaving beam, weav-ing the yarn and removing the size from the woven product by scouring with hot water.
18. 18. A textile process which comprises passing a cotton-containing textile yarn through an aqueous size composition of claim 15, removing excess size solution from the yarn, drying the sized yarn, splitting the yarn, winding as a weaving beam, weav-ing the yarn and removing the size from the woven product by scouring with hot water.
19. 19. A composite comprising a cotton-containing textile yarn having a coating of a size composition of claim 1.