US3503794A - Sizing of textile filament and yarn with mixture of hydroxy polymer and hydrolyzed starch - Google Patents

Description

United States Patent M SIZING 0F TEXTILE FILAMENT AND YARN WITH MIXTURE OF HYDROXY POLYMER AND HY- DROLYZED STARCH Donald D. Donermeyer, Springfield, and Robert A. Isaksen, East Longmeadow, Mass., assignors to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Apr. 25, 1967, Ser. No. 633,367

Int. Cl. D06m 11/00 US. Cl. 117-l39.5 4 Claims ABSTRACT OF THE DISCLOSURE The application describes the sizing of textile filaments and yarns with a hydroxy-containing polymer system containing up to about 75 weight percent of a non-crystalline starch hydrolyze having a dextrose equivalent of from about 13 to about 38. The sized filaments and yarns exhibit improved processing and weaving efficiency.

BACKGROUND OF THE INVENTION This invention relates to the sizing of textile filaments and yarns.

Many filaments and yarns both of natural and synthetic materials require a protective coating to prevent breakage thereof during weaving and processing operations. The protective coatings are known as sizes and the application of them to the filaments and yarns is known as sizing. The size must not only protect the filaments and yarns from snags, pulled threads and breakage but must also adhere so as not to accumulate on the weaving equipment. Moreover, the size must be capable of being readily removable prior to the dyeing of the woven fabric. Hydroxy-containing polymers, such as polyvinyl alcohol and related polymers are desirable as textile sizes. However, such polymers are not entirely satisfactory sizes formers. Thus, much industrial elfort has been expended in the modification of hydroxy-containing polymers to improve their capability for use as sizes. Various additives have been proposed for modifying hydroxy-containing polymers such as boric acid, metal salts, urea, starches and sugars. Such additives are not completely satisfactory in obtaining sizing compositions of hydroxy-containing polymers because of incompatibility in either solution form or solid form or both. Also, either the expense of the additives has made their use with hydroxy-containing polymers commercially prohibitive or the additives have enhanced one property of the polymer at the sacrifice of another desirable property. Heretofore, again because of compatibility problems, the additives for hydroxy-containing polymers have been limited to low quantities of addition or low level of extension. It is, of course, desirable to extend hydroxy-containing polymers at high levels for economic reasons.

In the sizing of textile filaments and yarns, the size is applied from a solution and then dried to a solid thereby requiring compatibility of the additive with the hydroxycontaining polymer both in solution form and in solid form. Additives such as starch and low molecular weight saccharides are dissolvable or dispersible in hot water but exhibit retrogradation with crystallization upon cooling. Thus, when such materials are used as extenders for polyvinyl alcohol as a size, the retrogradation of the materials on cooling or during film formation yields twophase films having poor mechanical and physical properties.

SUMMARY This invention is directed to the sizing of textile filaments and yarns with a particular hydroxyl-containing polymer size system and to improved filaments and yarns sized with such system.

Accordingly, typical objects of this invention are to provide (1)novel sized textile filaments and yarns, (2) sized textile filaments and yarns having a combination of improved processing properties, and (3) a process for sizing textile filaments and yarns.

Other objects, aspects and advantages of this invention will become apparent to those skilled in the art upon further study of this disclosure in the appended claims.

In accordance with this invention, an improved process for sizing textile filaments and yarns is provided which comprises applying thereto a coating of a composition containing a water-soluble hydroxy-containing polymer and 2575 weight percent, based on the weight of said polymer, of a particular starch hydrolyzate. The improved textile filaments and yarns of this invention comprise said yarns sized with a composition comprising a water soluble hydroxy-containing polymer and 25-75 weight percent based on the weight of said polymer of a particular starch hydrolyzate.

The particular starch hydrolyzates employed in the composition useful in this invention are non-crystalline and can be formed from any starch. The corn starch derivatives are presently preferred because of their commercial availability. The hydrolysis of corn starch to convert starch to dextrose is well known and is carried out by use of acid alone or by use of acid intially followed by enzyme hydrolysis. However, the conversion reaction may be regulated to produce intermediate hydrolyzates containing various amounts of intermediate products in the chemical path from starch to dextrose. The characteristics of a porduct as a hydrolyzate is expressed by a DB. number which is the ratio of dextrose equivalent, or in other words, of reducing sugars, to the total dry substance of the hydrolyzate. Completely hydrolyzed corn starch is corn sugar or dextrose which has a 100 DE. The commercial intermediate hydrolyzates of corn starch are termed dextrins 13D.E.), malto-dextrins (13 to 28D.E.), and corn syrups (28 and higher DE). The corn syrups are further classed by degree of conversion, i.e. low (28 to 38D.E.), regular (38 to 48D.E.), intermediate (48 to 58D.E.), high (58 to 68D.E.) and extra high (68 and higher D.E.). Relative to colloidal starch, the hydrolyzates are non-colloidal compounds of small molecular size and are of such character that they may be dried to a powder. The starch hydrolyzates compatible with hydroxy-containing polymer compositions useful in this invention are those termed malto-dextrins and low conversion corn syrups, i.e. having a DB ranging from about 13 to about 38.

The hydroxy-containing polymers employed in the compositions useful in this invention include the polymeric materials having a viscosity determined from a 4% aqueous solution at 20 C. up to about 200 centipoises and containing a plurality of recurring hydroxy groups either in the form of the alcohol or partially esterified alcohol.

More specifically, one group of hydroxy-containing polymers employed in the composition useful in this invention are the (A) water soluble homopolymers of vinyl esters which are from to and preferably from 87 to 99% hydrolyzed; (B) water soluble hydrolyzed copolymers of at least 50 weight percent of a vinyl ester and up to 50 weight percent of an ethylenically unsaturated material copolymerizable therewith, such as ethylene, propylene, acrylates, vinyl chloride, maleates, fumarates, and the like or mixtures thereof; and (C) physical blends of (A) and (B). Examples of suitable hydroxy-containing polymers are polyvinyl alcohol, par- Corn Syrups and Sugars, 3rd ed., 1965, Corn Industries Research Foundation, Inc., p. 15.

tially hydrolyzed polyvinyl acetate, partially hydrolyzed polyvinyl propionate, partially hydrolyzed polyvinyl butyrate, partially hydrolyzed polyvinyl stearate, partially hydrolyzed polyvinyl trifluoroacetate, and the like; partially hydrolyzed copolymers of vinyl acetate with ethylene, vinyl chloride, or acrylonitrile, and the like. Polyvinyl alcohol is the presently preferred polymer.

Other extenders and plasticizers for hydroxy-containing polymers, such as boric acid, urea, glycerine, and the like, may be present in combination with the particular starch hydrolyzates set forth above in the composition useful in this invention. When a combination of extenders is employed, the particular starch hydrolyzates should comprise at least about 60%, by weight, of the total quantity of extenders employed which should not exceed about 75% by weight of the composition.

The polyhydroxy-containing polymers and particular starch hydrolyzates useful in this invention are combined by slurrying them in water and then heating the slurry to dissolve the polymer and hydrolyzate. Water is the preferred medium for dissolving the polymer and hydrolyzate to form the sizing solution, however, it is to be understood that any medium capable of slurrying and/ or dissolving the polymer and hydrolyzate and useful in sizing applications can be equally employed.

The sizing of textile filaments and yarns is obtained in accordance with this invention by applying to the filaments and yarns a solution, preferably aqueous solution of a water soluble hydroxy-containing polymer and up to about 75 weight percent, preferably 25 to 75 weight percent, of a starch hydrolyzate having a DB of from about 13 to about 38, based on the weight of the polymer. Any quantity of polymer and hydrolyzate can be present in the solution, however, generally not more than 25%, based upon solids, will be used and preferably only 2 to 10% need be used to obtain satisfactory results. The sizing solution is applied to the filaments and/or yarns in amounts of 1-20 weight percent based upon the weight of the filaments and/ or yarns. The application of the sizing solution to the textile filaments of yarns can be accomplished in any suitable manner such as spraying, brushing, immersion, and the like. Preferably, the filaments or yarns are drawn through a bath of the sizing tolution, passed hmlgh squeeze rolls to remove excess) solution and tl/e'n dried.

The following examples are set forth to describe more fully the practice of this invention and the particular materials, quantities and conditions described should not be considered as limitations upon the inventive concept and scope thereof disclosed herein. Where parts are mentioned in this disclosure, they are parts by weight unless otherwise specified.

EXAMPLE I Fifty-five parts of polyvinyl alcohol (89% hydrolyzed) and 45 parts of corn starch hydrolyzate having a D.E. of 24 are slurried in 900 parts of water. The polyvinyl alcohol and hydrolyzate are dissolved by heating the slurry at 85 C. for 15 minutes. The solution is designated as textile sizing solution 1. A second solution, designated textile sizing solution 2, is prepared by dissolving sufiicient 89% hydrolyzed polyvinyl alcohol in water to provide a 7% solids solution. A third solution, designated textile sizing solution 3, is prepared by dissolving parts of 89% hydrolyzed polyvinyl alcohol, 130 parts of starch and 13 parts of an acrylic binder in 900 parts of water to provide a 15% solids solution. To each of these solutions is added 5 weight percent of a waxy lubricant.

Textile yarn (Warp 5,900 ends of 65/35 polyester/cotton yarn 50/1) is sized separately with each of the sizing solutions prepared above and is processed on a commercial can slasher having an internal steam pressure of 35 pounds per square inch. The size box temperature is maintained at 170 F. for solutions 1 and 2 and at 200 F. for solution 3, and the squeeze roll is held at a total pressure of 1200 pounds. Each of the separately sized warps is tested for slasher performance and weaving performance.

The yarn sized with textile sizing solution 1, having an applied total solids of 13 /2 weight percent based on the weight of the yarn, is cleanly and easily separated at the split rods with little or no shedding and only a single leasing is required. At start up, breakage of only 1 Warp end occurs. The sizing solution in the size box remains homogeneous throughout the operation and exhibits no tendency to form a surface skin. The sized yarn is subsequently woven on a commercial loom. The loom operates at a weaving elficiency of about with approximately only 0.5 Warp stops per hour. (Warp stops result when a breakage of the sized yarn occurs.)

The same grade of Warp yarn sized with textile sizing solution 2, having an applied total solids of 10 weight percent based on the weight of the yarn, is separated with difficulty at the split rods but with little or no shedding. At start up, breakage of 5 to 11 warp ends occur and a double leasing is required. The sizing solution forms a surface skin during intermittent operations and must be replaced to allow continued operation of the slasher. The sized yarn is subsequently woven on a commercial loom. The weaving efiiciency is about the same as that for yarn sized with solution 1. However, about 10% polyvinyl alcohol was applied to the yarn from solution 2, compared with 7% polyvinylalcohol applied from solution 1.

The above described sequence of operations is repeated using textile sizing solution 3 except that the starch requires a cook period of at least 1 hour to form the solution. The sizing solution exhibits similar tendency to form a skin or film as that described in connection with sizing solution 2. The sized yarn, having an applied total solids of 22 weight percent based on the weight of the yarn, is separated easily but exhibits excessive shedding. At start up, breakage of 5 to 10 Warp ends occurs. Subsequent weaving of the sized yarn on a commercial loom exhibits a weaving efficiency of 93% With about 1.5 warp stops per hour.

This example clearly shows that the yarn sized in accordance with this invention, solution 1, performs much better than unmodified hydrolyzed polyvinyl alcohol, solution 2, or a conventional size, solution 3, in solution compatibility, slashing, and weaving efliciency.

EXAMPLE II Nine pounds of polyvinyl alcohol (89% hydrolyzed), 8 pounds of corn starch hydrolyzate having a DB of 22, 1 pound of glycerine and 3 pounds of a lubricant are slurried in gallons of water. The slurry is heated at 85 C. for 20 minutes and then the solution is stored at F. This solution is designated as sizing solution 1. A second solution is prepared in like manner using 18 pounds of polyvinyl alcohol (89% hydrolyzed) having a viscosity of 50 centipoises and 3 pounds of a lubricant. A third solution is prepared in a like manner using 18 pounds of polyvinyl alcohol (89% hydrolyzed) having a viscosity of 5 centipoises and 3 pounds of a lubricant. A fourth solution is prepared in a like manner using 24 pounds of gelatin, 6 pounds of a lubricant, 1 pound of a penetrant and 100 gallons of water by heating at 850 C. for 20 minutes.

Textile yarn (warp 3000 ends of /40/2 (denier/filaments/ turns per inch) (filament rayon) is sized separately with each of the sizing solutions prepared above and is run on a commercial 9 can slasher having an internal steam pressure of 30 psi. The size box temperature is maintained at IDS-110 F. and the squeeze roll is held at a total pressure of 1400 lbs. Each of the separately sized yarns is tested for slasher performance and Weaving performance.

The yarn sized with solution 1, having an applied total solids of 1.7 weight percent based on the weight of the yarns, is cleanly and easily separated at the split rods with little or no shedding and only a single leasing is required. The sizing solution in the size box remains homogeneous throughout the operation and exhibits no tendency to form a surface skin. The yarn is subsequently woven on a commercial loom. The loom operates at a weaving efficiency of about 94% with the result of only 3% fabric seconds.

The yarn sized with solution 2 is difficult to separate at the split rods and causes severe yarn breakage. The sizing solution in the size box forms a surface skin which must be continually removed to allow operation of the slasher. It is impossible to obtain yarn which is usable on the looms due to excess breakage of the yarn on the slasher.

The yarn sized with solution 3, having an applied total solids of 1.7 weight percent based on the weight of the yarn, is separated with difficulty at the split rods. The yarn is subsequently Woven on a commercial loom. The loom operates at a weaving efiiciency of about 93% with 4% fabric seconds.

The yarn sized with solution 4, having an applied total solids of 3.2 weight percent is woven on a commercial loom at a weaving efficiency of 94% with 3% fabric seconds. Although yarn sized with solution 4 gave the same weaving efliciency as yarn sized in accordance with this invention, solution 1, almost twice the quantity of solution 4 size was applied to the yarn to obtain such weaving efiiciency as was the quantity of solution 1 size.

This example clearly shows that the yarn sized in accordance with this invention, solution 1, performs much better than unmodified hydrolyzed polyvinyl alcohols, solutions 2 and 3, or a conventional size, solution for, in solution compatibility, slashing, weaving efilciency and/or quantity of size required on the yarn. Also, the yarn sized with solution 1 possesses finishing properties such as receptivity to dyes superior to yarn sized with the conventional sizes.

Various modifications will be apparent to those skilled in the art from the preceding disclosure which may be made in or to the composition disclosed and which will not depart from the spirit and scope thereof.

What is claimed is:

1. Textile filaments and yarns containing a size of an admixture comprising a water-soluble hydroxy-containing polymer and a non-crystalline starch hydrolyzate having a dextrose equivalent value of from about 13 to about 38; said hydrolyzate comprising from about 25% to about by weight based upon the weight of the water-soluble hydroxy-containing polymer; the admixture of watersoluble hydroxy-containing polymer and non-crystalline starch hydrolyzate being present in an amount of from about 1% to about 20% solids by weight based upon the weight of the filament and/ or yarn.

2. The article of claim 1 wherein said size comprises 2-10 weight percent based on the weight of the filaments and yarns.

3. The article of claim 1 wherein said polymer is a vinyl ester homopolymer which is 87-99% hydrolyzed and has a viscosity of up to 200 centipoises determined at 20 C. from a 4% aqueous solution of said polymer.

4. The article of claim 3 wherein said polymer is polyvinyl alcohol and has a viscosity of 15-200 centipoises.

References Cited UNITED STATES PATENTS 2,743,194 4/1956 Berner et al 1l7139.5

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US. Cl. X.R. 117161