TEXTILE WARP SIZE

Abstract: Warp sizing compositions and starch derivatives useful therefore are provided. The compositions strengthen and pro­ tect warp yarns as well as render textile lubricants uniformly dispersible thereon. The compositions additionally facilitate ef­ ficient lubricant removal during desizing. The starch deriva­ tives are hydrophobic starch ether or ester derivatives wherein the ether or ester substituent comprises a saturated or unsat­ urated hydrocarbon chain of at least 5 carbon atoms.

Description: The present invention is directed to a warp sizing composition comprising water, a hydrophobic starch derivative, wherein the starch substituent comprises a hydrocarbon chain with 5 carbon atoms and a lubricant, and to an improved process for the warp sizing of textile yarns comprising passing the yarns through a sizing composition of the type containing water, a starch derivative, and a lubricant. GB-A-1 444 498 refers to an aqueous size for glass fibres comprising an isoalkanoic starch ester having a substituted or unsubstituted isoalkyl radical of from 3 to 5 carbon atoms inclusive and an unctuous material from the group consisting of vegetable waxes, animal waxes, mineral waxes, synthetic waxes, fats and gelled oils, wherein an effective amount of the starch ester is present as swollen but unburst starch granules for preventing migration of the unctuous material during drying. This size for glass fibres has the advantage, as for example, greater ease of burn off. J. Gordon Cook "Handbook of Textile Fibres", 5th edition, part II, pages 652/653 describes a particular sizing method. According to this method glass marbles are molten in a furnace. During the manufacture of the filaments out of the melt a size is sprayed on the filaments. The filaments are then transferred into a strand. As used herein "warp" is an inclusive term which refers to the lengthwise running yarns in a woven fabric. A warp sizing material is any substance which is applied to the warp yarns for the basic purpose of strengthening and protecting the yarns from abrasion, usually as a result of its adhesive, film-forming action. Warp sizes provide stiffness and smoothness to fibers which facilitate decreased incidents of entanglement and breakage during the weaving operation while also providing abrasion resistance to the fibers to avoid breakage and injury during handling. The warp sizing, or slashing as it is often called, of textile yarns consists in the impregnation of these yarns with a sizing solution or dispersion. This is followed by removal of the excess sizing by passage of the wet yarns through a set of squeeze rolls followed by drying. Warp sizing is carried out on a slashing machine consisting of a creel which generally holds one or more section beams. These section beams usually contain from 200-500 yarn ends. The yarn ends from several of these section beams are brought together so as to form a sheet of yarn with about 1500-8000 ends. This sheet then enters the size box wherein it is guided through the sizing solution and through one or more sets of squeeze rolls, so as to remove the surplus size which then falls back into the size box. Drying is accomplished by passing the yarn through a heated chamber or over the surface of internally heated drying cylinders. The dried yarn is then separated by means of horizontal split rods into sections corresponding to those of the original section beams. The yarn is then almost immediately recombined by being passed through a vertical comb and thereupon onto a take-up beam referred to as a loom beam. This loom beam holds the yarn until such time as it is used in the weaving process. One of the primary functions of the disclosed sizing process is to aid in the reduction of loom abrasion. To do this, the sizing must exert a film forming action, with the resultant film having the ability to resist the abrasive action of the various machine parts that come in contact with the yarns as well as the rubbing together of the individual yarns themselves. Typical film-forming substances used as warp size materials have included starches, dextrins, glues, flours, gums, gelatin, cellulosics (e.g., carboxymethyl cellulose), polyvinyl alcohol, and polyacrylic acid. Many factors including the type and composition of fibers to be sized, construction, and count (weight per unit length) will determine which sizing materials or combination thereof should be employed. Aqueous dispersions of starch and starch derivatives have been employed in the warp sizing of many natural, synthetic, or blended fibers. See, for example, the warp sizes of US-A- 2,946,705 employing starch amine derivatives; 3,650,787 and 3,673,171 employing amphoteric and oxyalkylated amphoteric starches; and 4,421,566 employing high amylose, cationic fluidity starch derivatives. Lubricants are also conventionally employed in warp size compositions to improve weaving performance. The lubricants aid in reducing yarn-to-yarn and loom-to-yarn friction. Additionally they are noted to provide lubrication to loom parts during the later steps of the weaving process. Sizing compositions which evenly disperse the lubricants are particularly preferred as uniform lubricant distribution will help provide optimum weaving performance. The ability to improve loom efficiency (where 100% = no loom stops) by an amount of as little as 1% to 2% would be recognized in the field as a significant improvement. Many varieties of fats, oils, and waxes obtained from various animal, vegetable, mineral, or synthetic sources have been advantageously used for such lubrication in typical amounts ranging from 0.5 to 10%, based upon the weight of the film-forming substance. Mill waxes which generally comprise tallow and hydrogenated tallow glycerides are typically employed as size lubricants. Although the presence of size is necessary to make a yarn weave satisfactorily, it is equally true that complete removal of the size is an essential prerequisite to successful finishing. Therefore, in most cases subsequent to weaving, the woven textile must be desized in order to avoid interference of the size with finishing processes such as, for example, bleaching, dyeing, printing, and water repellancy treatment. Depending on the size composition employed, desizing is accomplished by one or more steps including the following: enzymatic or oxidative degradation, high temperature washing, steaming, caustic scouring, and solvent or surfactant treatment. Although the film-forming portion of the size composition will normally be completely removed by the above methods, removability of the lubricant is significantly more difficult, often requiring expensive and time consuming removal techniques. It has been estimated that only approximately 25-30% of conventional size waxes on fabric are saponified or converted to water-soluble materials which are then removable. The remainder is not totally soluble and thus ends up on the fabric in the form of resist spots which are especially noticable after dyeing as exhibited by uneven dye penetration. Therefore, while uniform distribution of lubricant will result in the best weaving performance, its removal is also important for the textile finisher who, even if unable to remove it all, can achieve a condition which may permit a more regular and even appearance after dyeing. Due to the current use of high speed air jet looms (with fill yarn insertion rates of 400-650 per minute as compared to 170-240 per minute for conventional looms), greater amounts of lubricants are sometimes employed to combat increased yarn stress encountered during weaving. With these higher quantities, lubricant removal, always a major cause for concern, is now aggravated. With respect to the above prior art therefore there is a need for a warp sizing composition capable of forming a uniform film upon warp yarns to sufficiently strengthen and protect them during conventional and high speed weaving, capable of uniformly dispersing the textile lubricant in quantities equal to or greater than the amounts conventionally used on the warp yarns, and capable of more lubricant removal after weaving, by the use of inexpensive, less time-consuming removal methods. The present invention provides a warp sizing composition comprising water, a hydrophobic starch derivative, wherein the starch substituent comprises a hydrocarbon chain with 5 carbon atoms and a lubricant, which is characterized by the presence, as the hydrophobic starch derivative, of a starch ether or ester, wherein the ether or ester substituent comprises a saturated or unsaturated hydrocarbon chain of at least 5 carbon atoms, preferably less than 22 carbon atoms, and the presence of about 3 to 50 %, preferably 5 to 20%, of a lubricant, based on the weight of the starch derivative. This warp sizing composition preferably comprises 100 parts of the water and 2 to 40 parts of the starch derivative. In a preferred embodinent, starch succinates prepared by reacting a fluidity corn starch base with 1-10% octenyl succinic anhydride provide excellent weavability as well as uniform lubricant dispersion upon textile fibres. During desizing, the starch derivatives as well as the lubricant employed may be easily removed. Other film-forming substances in addition to the starch derivative herein may be added to the warp size composition. In one embodiment, the warp size composition additionally comprises the synthetic resin polyvinyl alcohol, in equivalent amounts to the starch derivative. The present invention also provides an improved process for the warp sizing of textile yarns comprising passing the yarns through a sizing composition of the type containing water, a starch derivative, and a lubricant, which is characterized by applying to the yarns after the fibres have been manufactured the sizing composition according to the present invention. The applicable starch bases which may be used in the preparation of the warp sizing derivatives herein include any amylaceous substance such as untreated starch, as well as starch derivatives including dextrinized, hydrolyzed, oxidized, esterified and etherified starches still retaining amylaceous material. The starches may be derived from any sources including, for example, corn, high amylose corn, wheat, potato, tapioca, waxy maize, sago or rice. Starch flours may also be used as a starch source. By the term "hydrophobic starch" is meant a starch ether or ester derivative wherein the ether or ester substituent comprises a saturated or unsaturated hydrocarbon chain of at least 5 carbon atoms. It should be understood that the hydrocarbon chain may contain some branching. However, it is preferred, to employ those starch derivatives wherein the hydrocarbon chain is unbranched. It should also be understood that the ether or ester substituent may contain other groups in addition to the hydrocarbon chain as long as such groups do not interfere with the hydrophobic properties of the substituent. A suitable class of reagents for preparing the half-acid starch esters useful herein include substituted cyclic dicarboxylic acid anhydrides such as those described in US-A 2,661,349 having the structure wherein R is a dimethylene or trimethylene radical and A' comprises a hydrocarbon chain of at least 5, preferably 5-14, carbon atoms. The substituted cyclic dicarboxylic acid anhydrides falling within the above structural formula are the substituted succinic and glutaric acid anhydrides. In addition to the hydrocarbon chain substituent other substituent groups such as sulfonic acid or lower alkyl which would not affect sizing performance may be present. Another suitable class of reagents for preparing starch ester warp sizing derivatives useful herein include the imidazolides or N,N'-disubstituted imidazolium salts of carboxylic or sulfonic acids, such as those described in US-E- 28,809 which is a reissue of US-A- 3,720,663 and US-A- 4,020,272, having the general formula wherein Z is or -SO₂-, A comprises a hydrocarbon chain of at least 5, preferably 5 to 14, carbon atoms, R¹ is H or C₁-C₄ alkyl, R² is C₁-C₄ alkyl, and X- is an anion. A third class of reagents useful herein include the etherifying reagents described in US-A- 2,876,217 comprising the reaction product of an epihalohydrin with a tertiary amine having the structure wherein R³ and R⁴ are independantly H or a C₁-C₄ alkyl and A² comprises a hydrocarbon chain of at least 5, preferably 5 to 14, carbon atoms. The starch etherification or esterification reactions may be conducted by a number of techniques known in the art and discussed in the literature employing, for example, an aqueous reaction medium, an organic solvent medium, or a dry heat reaction technique. For a discussion of such techniques see R. L. Whistler, Methods in Carbohydrate Chemistry, Vol. IV, 1964, pp. 279-311; R.L. Whistler et al., Starch: Chemistry and Technology, Second Edition, 1984, pp. 311-366; and R. Davidson and N. Sittig, Water-Soluble Resins, 2nd Ed., 1968, Chapter 2. The warp sizing starch derivatives herein are preferably prepared employing an aqueous reaction medium at temperatures between 20° and 45°C. For use in the warp sizing process, the starch derivatives may be produced either in gelatinized or ungelatinized form. The advantage of having the derivative in ungelatinized form is that it may be filtered, washed, dried and conveyed to the mill in the form of a dry powder. When employing the cyclic dicarboxylic acid anhydride reagents, starch is preferably treated in granular form with the reagents in an aqueous alkali medium at a pH not lower than 7 nor higher than 11. This may be accomplished by suspending the starch in water, to which has been added (either before or after the addition of the starch) sufficient base such as alkali metal hydroxide, alkaline earth hydroxide, quaternary ammonium hydroxide, or the like, to maintain the mixture in an alkaline state during the reaction. The required amount of the reagent is then added, agitation being maintained until the desired reaction is complete. Heat may be applied, if desired, in order to speed the reaction; however, if heat is used, temperatures of less than about 40°C should be maintained. In a preferred method, the alkali and the anhydride reagent are added concurrently to the starch slurry, regulating the rate of flow of each of these materials so that the pH of the slurry remains preferably between 8 and 11. Due to the greater hydrophobic nature of certain of the substituted cyclic dicarboxylic acid anhydride reagents useful herein (i.e., those having C₁₀ or higher substituents), the reagents react with starch in only minor amounts in standard aqueous reactions. In order to improve the starch reaction efficiency, starch is reacted with the hydrophobic reagent under standard aqueous conditions in the presence of at least 5%, preferably 7-15% (based on the weight of the reagent), of a water-soluble organic quaternary salt which is employed as a phase transfer agent. The organic salts, of which trioctylmethyl ammonium chloride and tricaprylmethyl ammonium chloride are preferably employed, are described in US-A 3,992,432. The proportion of etherifying or esterifying reagent used will vary with the particular reagent chosen (since they naturally vary in reactivity and reaction efficiency), and the degree of substitution desired. Thus, substantial improvements in warp sizing efficiency have been achieved by using a starch derivative made with 1% of the reagent, based on the weight of the starch. Preferred ranges are on the order of 1 to 5%. Warp sizing compositions must necessarily be resistant towards congealing in aqueous dispersion. This brings about improved work-ability of the sizing in the slasher, more uniform application and less gelling and lumping, thus leading to a reduction in the clogging of size lines and mechanical breakdowns. It has been observed that some of the etherifying and esterifying reagents useful herein which possess linear chain hydrocarbon substituents containing 12 or more carbon atoms render starches capable in aqueous dispersion of forming high viscosity complexes with amylose at temperatures above 70°C. Sizing compositions are typically applied at temperatures ranging between 75° and 98°C. In order to avoid application problems, it may therefore be necessary to maintain the warp sizing composition at a temperature above that which the starch derivative is known to complex. When employing waxy starch derivatives (composed primarily of amylopectin), no complex formation is exhibited at high temperatures. It has been discovered that the viscosity increases due to complex formation can also be eliminated by employing derivatives of converted starch bases, prepared by conventional acid conversion, enzyme hydrolysis, or oxidation procedures, which have been sufficiently converted depending upon the starch base and the hydrophobic derivatization employed. For example, the tetradecenyl succinate of corn starch will form complexes at high temperatures; however, an acid hydrolyzed corn starch base having a water fluidity (WF) of at least 40 which is treated with the same succinic anhydride reagent will not exhibit any detrimental effects due to complex formation and thus is useful at all typical application temperatures. In practice, it has been found that the hydrophobic starch derivatives can be most effectively used as warp sizing agents when dispersed in water in amounts ranging from 2 to 40 parts of the derivative per hundred parts of water. The precise amounts of the starch employed vary depending upon the weaving equipment, the fabric construction (i.e., the style) and the type of fiber being treated. The lubricants employed in the warp size composition may be selected from a wide variety of known synthetic and natural fats, oils, and waxes typically used to reduce friction during weaving. Preferred lubricants include vegetable and mineral oils and tallow. As with the starch derivatives, the amount of lubricant employed will vary depending mainly upon the weaving equipment and fiber to be lubricated. Typical amounts range between 0.5 to 15%, based on starch concentration. Larger amounts have not typically been employed due to the difficulties experienced when attempts are made to provide uniform lubricant distribution during sizing and acceptable lubricant removal during desizing. However, by employing the starch derivatives described herein, larger amounts of lubricant (i.e. 20 to 50%) may be employed due to the improved lubricant distribution and removability facilitated by the derivatives. In addition to the hydrophobic starch derivatives and lubricants employed in the present invention, other conventional warp size additives such as softeners, acrylic and polyester binders, anti-static agents and mildew preventatives may also be used in conventional amounts. Since many materials used as additives offer both a lubricating and a softening effect, lubricants are sometimes mistakenly referred to as softeners and vice versa. However, softeners (i.e., glycerine and soaps) are used to give a soft handle to the warp and the size film and to decrease the film brittleness through a plasticizing effect. Other film-forming substances may also be employed in addition to the hydrophobic starch derivatives, if desired. Suitable substances for use herein would include, for example, polyvinyl alcohol, carboxymethyl cellulose, and polyacrylic acid. If employed, such film forming substances are preferably present in amounts less than or equal to that of the hydrophobic starch. The warp sizes produced herein are useful in the conventional sizing of any natural, synthetic or blended fiber as, for example, cotton, polyester, wool, nylons, rayons and glass fibers. In the examples which follow, all parts and percentages are given by weight and all temperatures are in degrees Fahrenheit (Celsius). The wax removeability of the warp sizes herein was qualitatively evaluated employing the following test procedure: Dye Receptivity Test An aqueous slurry comprising 8.8% of the starch derivative to be tested and 1.8% mill wax (20% wax based on starch) is cooked in a boiling water bath for 30 minutes in order to form a uniform dispersion. The wax employed is North Wax 686 (hydrogenated tallow) obtained from North Chemical Co. of Marietta, Ga. To obtain 10% by weight of the size on fabric, a 12 x 12 in. (0.305 x 0.305 m.) piece of 65/35 polyester/cotton fabric is saturated in the dispersion then run through a laboratory padder (manufactured by L & W Machine Works of Rock Hill, South Carolina) for extraction at a pressure setting of 20. Thereafter, the fabric is dried in a forced draft oven at 270°F (132°C) for three minutes. The fabric is desized by soaking the piece in an enzyme solution consisting of 2 parts enzyme (Super Exsize TX-2H obtained from Premier Malt of Peoria, Illinois), 0.75 parts surfactant (Triton RX-100 obtained from Rohm and Haas of Philadelphia, Pennsylvania), and 97.25 parts water at 160°F (71°C) for fifteen minutes. The fabric is then padder extracted, rinsed with water at 185-190°F (85-88°C) for ten minutes and washed with cold tap water for 3 minutes, then padder extracted again. Thereafter, the fabric is dried on a pin frame at 300°F (149°C) for three minutes. The fabric is finally scorched with an AATCC Scorch Tester (obtained from Atlas Electric Devices Co. of Chicago, Illinois) at 425°F (218°C) for 1 minute in order to exaggerate the effects of fabric dye absorbancy caused by the presence of any residual wax. The dye solution employed is an aqueous solution comprising 0.3% acetic acid and 0.1% Sevron Brill Red 4G (obtained from Plyam Chemical, of Queens Village, New York). The desized fabric is immersed in the dye solution which is maintained at 70-75°F (21-24°C) for 5 seconds then rinsed under cold tap water for approximately 15 seconds. The uniformity of dye receptivity on fabric is a qualitative measure of wax removal. It is understood that the deeper and more uniform the dye penetration, the more complete the wax removal during desizing. EXAMPLE 1 This example illustrates a laboratory procedure for preparing a converted half-acid ester starch succinate derivative useful herein. About 100 parts corn starch are slurried in 150 parts water followed by 0.55 parts of reagent-grade, concentrated hydrochloric acid. The temperature of the slurry is raised to 125°F (52°C) and the mixture is allowed to react with constant stirring for 16 hours. Thereafter, the pH of the hydrolyzed starch slurry is adjusted to 4.5 with sodium carbonate. After cooling the slurry to room temperature, the pH is adjusted to 7.5 by the addition of dilute sodium hydroxide (3%). A total of 1 part octenyl succinic acid anhydride (OSA) reagent is added slowly to the agitated starch slurry with the pH maintained at 7.5 by the metered addition of the dilute sodium hydroxide. After the reaction is complete, the pH is adjusted to about 5.5 with dilute hydrochloric acid (3:1). The starch is thereafter recovered by filtration, washed three times with water and air dried. The product will have an approximate water fluidity (WF) of 40 and carboxyl content of about 0.8%. EXAMPLE 2 This example demonstrates the use of the product of the invention in an 11 can conventional pressure slasher on a polyester/cotton blend. A starch succinate made as in Example 1 was used to size 26/1 yarns for a 65/35 polyester/cotton poplin fabric of 96 x 60 construction. Size A was prepared consisting of 45.36 kg. (100 lb.) of a starch succinate having a WF of 40 and made according to Example 1 with 1% OSA (based on starch solids); 6.35 kg (14 lb) mill wax; 45.36 kg (100 lb) polyvinyl alcohol; 36.29 kg (80 lb) 25% aqueous polyester binder and 568 l (150 gal) water. Application using a slasher at a pressure gauge reading of 1.1 kg/m² (15 psi) resulted in a size content of 15.0%. For comparative purposes, conventional Size B for this style consisting of 45.36 kg (100 lb) fluidity corn starch (WF 20); 6.35 kg (14 lb) mill wax; 45.36 kg (100 lb) polyvinyl alcohol; 36.29 (80 lb) 25% aqueous polyester binder and 644 l . (170 gal) water, resulting in a size content of 14.1% was also tested. The warp yarns were woven on a conventional Draper X-3 loom at a rate of 178 yarn insertions per minute. Weaving efficiency with Size A was superior to comparative Size B as measured by loom efficiency (97-98% as opposed to 95-96%). Use of Warp Size A also resulted in less shedding at the bust rods (i.e., lease rods and on the loom) in comparison to Size B. The reduced shedding improves loom cleanliness and results in higher quality fabrics. Moreover, desizing and wax removal from the fabric woven with Size A was satisfactorily facilitated with only a standard enzyme technique while the fabric woven employing Size B required a solvent desize in order to provide satisfactory wax removal. EXAMPLE 3 Size formulations C-E were prepared and evaluated as in Example 2 on 26/1 yarns for a 65/35 polyester cotton fabric of 96 x 60 construction. The size formulations in addition to size content and weaving efficiency data may be found in Table I. From the above results it can be seen that all three formulations provided excellent weaving efficiency. In a like manner, starches may be reacted with other suitable substituted dicarboxylic acid anhydrides such as those listed below and employed in warp sizing compositions with similar results expected: pentyl succinic anhydride pentenyl succinic anhydride hexyl succinic anhydride octyl succinic anhydride nonenyl succinic anhydride decyl succinic anhydride decenyl succinic anhydride dodecyl succinic anhydride dodecenyl succinic anhydride tetradecyl succinic anhydride tetradecenyl succinic anhydride hexadecyl succinic anhydride hexadecenyl succinic anhydride octadecyl succinic anhydride 3-methyl-hexenyl succinic anhydride EXAMPLE 4 This example demonstrates the use of the present invention on a high speed loom. A starch succinate made as in Example 1 was used to size 35/1 yarns for a 50/50 polyester/cotton fabric of 74 x 54 construction (printcloth). Size F was prepared consisting of 90.12 kg (200 lb) of a starch succinate having a WF of 40 and made according to Example 1 with 1% OSA (based on starch solids); 13.61 kg (30 lb) mill wax; 90.12 (200 lb) polyvinyl alcohol; and 890 l (235 gal) water. Comparative Size G, another conventional size for this style, was prepared with 79.38 kg. (175 lb) acetylated fluidity corn starch (WF 50) starch reacted with 4% acetic anhydride as described in US-A- 2,461,139; 11.34 kg (25 lb) mill wax; 79.38 kg (175 lb) polyvinyl alcohol; 31.75 kg (70 lb) 50% aqueous polyester binder and 890 l (235 gal) water. The sizes were applied to warp yarns which were woven on a Ruti high speed air jet loom run at a rate of 450 yarn insertions per minute. The size content and weaving efficiency data of the yarns may be found in Table II. EXAMPLE 5 This example illustrates a laboratory study of the wax removeability of the size compositions of the present invention by observing the dye receptivity of enzyme-desized fabric which had been impregnated with size compositions containing 20% wax (based on starch content). Starch succinate derivatives were prepared as described in Example 1 by treating a fluidity corn starch (40 WF) with 1,3,5, or 10% OSA, based on starch solids. As an indication of reaction efficiency, the starch half acid esters were evaluated by carboxyl titration and found to contain 0.85, 2.96, 3.74, and 6.42% carboxyl groups, respectively. Size dispersions containing mill wax were prepared and evaluated according to the Dye Receptivity Test procedure (described above) employing the starch succinate derivatives and a comparative fluidity corn starch (WF 40). The desized fabrics which had been treated with the starch succinate dispersions were all similar in appearance after dyeing. The fabrics treated with these sizes were more uniformly dyed and had significantly deeper dye penetration in comparison to the fabric treated with the comparative starch size. This indicates the wax of the size formulations containing the starch succinate derivatives was more effectively removed during desizing. EXAMPLE 6 This example illustrates the effect of the starch derivatives herein to facilitate the removal of larger quantities of wax by comparing two sizing compositions containing 50% wax (based on starch content). The starch succinate derivatives of Example 5 prepared from 40 WF corn starch and 1 or 3% OSA (based on starch solids) were evaluated by the Dye Receptivity Test as above except the size dispersions each contained 8.8% starch and 4.4% mill wax (as opposed to 1.8% wax). Dye penetration of the desized fabric which had been treated with the size containing the 3% OSA starch derivative was significantly deeper than the fabric treated with size containing the less substituted starch derivative. The results indicate that when larger amounts of wax are employed in a size formulation, more highly substituted starch succinate derivatives will facilitate better wax removal during desizing. EXAMPLE 7 This example illustrates the effect of the starch derivatives herein to facilitate the removal of paraffin, another typical lubricant employed in warp size formulations. Size dispersions were prepared and evaluated as described in the procedure for the Dye Receptivity Test with the exception that paraffin was employed at levels of 10 and 20% based on starch solids instead of the mill wax. Dispersions were prepared with the OSA starch of Example 1 and a comparative fluidity corn starch (WF 40). In order to thoroughly disperse the paraffin, the size compositions were continuously agitated during cooking. The desized fabric which had been treated with OSA starch and 10 or 20% paraffin were quite similar in appearance, both exhibiting excellent dye penetration indicative of complete and near complete paraffin removal, respectively. With 10% paraffin, the comparative starch size provided slighly inferior paraffin removal to that of the OSA starch size containing 20% paraffin. The comparative starch size containing 20% paraffin, however, was drastically inferior with the desized fabric containing numerous resist spots. EXAMPLE 8 Starch succinate derivatives were prepared as described in Example 1 by treating a fluidity corn starch (41 WF) with 3% pentenyl succinic anhydride or 3% hexenyl succinic anhydride, based on starch solids. Fabrics treated with size dispersions containing the starch derivatives and 20% wax (based on starch content) were evaluated by the Dye Receptivity Test. Fabric treated with a comparative fluidity corn starch (WF 40) was also evaluated. The desized fabrics which had been treated with the dispersions containing the starch succinate derivatives were similar in appearance after dyeing. The uniformity and depth of dye penetration were significantly better than that exhibited by the desized fabric which had been treated with the comparative fluidity starch dispersion. EXAMPLE 9 This example demonstrates the ability of another starch derivative suitable for use in warp size compositions to provide improved wax removability during desizing. Unhydrolyzed waxy maize starch was reacted with 5 or 10% tetradecenyl succinic anhydride (TDSA) as described in Example 1 in the presence of 0.7 parts (based on starch solids) of tricaprylmethyl ammonium chloride phase transfer agent at a pH of 8 instead of 7.5. Size dispersions containing mill wax were prepared and evaluated by the Dye Receptivity Test employing the TDSA derivatives and two comparative fluidity corn starches having WF's of 20 and 40. The desized fabrics which had been treated with the TDSA derivatives had significantly deeper dye penetration (with the fabric treated with more highly substituted TDSA derivative having the darkest color). The results indicate that superior wax removal was achieved with the sizes containing the TDSA starches. EXAMPLE 10 This example illustrates the improved wax removability provided by starch derivatives suitable for use in warp size compositions which are prepared by additionally treating conventional sizing starches with a long hydrocarbon chain substituted succinic anhydride. A. An acetylated fluidity corn starch described in Example 4 was prepared. A portion of this starch was additionally treated with 3% OSA. Sizing compositions containing the two starches were compared for wax removability by the Dye Receptivity Test. More uniform dye penetration of the fabric treated with the OSA derivatized starch was observed indicating the hydrophobic derivatization facilitated improved wax removability. B. Another conventional starch employed as a warp size was prepared by reacting high amylose corn starch (containing approximately 50% amylose) with 6% diethylaminoethylchloride hydrochloride as described in US-A- 2,876,217 (cited previously). A portion of this starch was additionally treated with 3% OSA. Sizing compositions containing the two starches were also compared as above. The fabric treated with the OSA derivatized starch was observed to have deeper dye penetration indicating the hydrophobic derivatization provided improved wax removal during desizing. EXAMPLE 11 Starch ester derivatives, prepared employing N,N'-disubstituted imidazolium salts of long hydrocarbon chain carboxylic acids are also suitable for use in warp sizing compositions. This example demonstrates the ability of these derivatives to facilitate improved wax removal during desizing. Corn starch was acid hydrolyzed to a WF of 41 then reacted with 5 or 10% N-decanoyl-N'-methylimidazolium chloride (based on starch solids) employing a procedure described in US-A- 4,020,272 (cited previously). The procedure comprised slurrying 100 parts corn starch (as is) in 150 parts water at pH 8 and then slowly adding the reagent to the slurry. The reaction was conducted for 2 to 3 hours at room temperature while maintaining the pH at 8 as described in Example 1. When the reaction is complete, the pH of the slurry was adjusted to 4 with 3:1 hydrochloric acid. The starch ester derivatives were recovered by fitration, washed three times with water having a pH of about 4, and air dried. Size dispersions containing the ester derivatives and mill wax were evaluated by the Dye Receptivity Test and compared to a similar dispersion containing an underivatized fluidity corn starch (WF 40). Dye penetration of the fabrics treated with the starch ester derivatives was deeper in comparison to the fabric treated with the underivatized corn starch size. Dye uniformity of the fabric treated with the more highly substituted starch ester was also noted to be by far the best of the series. The results indicate that the hydrophobic starch esters are useful in facilitating wax removal during desizing. Other suitable esterifying reagents which may be employed in the preparation of starch derivatives useful in warp size compositions with similar effectiveness expected include, for example, the N,N'-disubstituted imadazolium salts of the following acids: hexanoic acid 2-ethylhexanoic acid caprylic acid lauric acid myristic acid palmitic acid. EXAMPLE 12 Starch ether derivatives, prepared by employing long hydrocarbon chain quaternary amine epoxide reagents, are suitable for use in warp sizing compositions. This example demonstrates the ability of these derivatives to also provide improved wax removability during desizing. Corn starch was acid hydrolyzed to a WF of 41 then reacted with 5 or 10% dimethylglycidyl-N-dodecyl ammonium chloride (based on starch solids) employing the procedure described in US-A- 2,876,271 (cited previously). The procedure comprised slurrying 100 parts starch (as is) in 150 parts water containing 40 parts sodium sulfate and 3 parts sodium hydroxide. The reagent was added and the mixture was agitated for 16 hours at 104°F (40°C). Thereafter the pH was adjusted to 3 with 3:1 hydrochloric acid. The starch ethers were filtered (methanol was added to aid in the filtration), then washed three times with water having a pH of about 3, and air dried. Size dispersions containing mill wax were prepared and evaluated by the Dye Receptivity Test employing the starch ether derivatives and a comparative underivatized fluidity corn starch (WF 40). The dye penetration of the desized fabric which had been treated with the less substituted starch ether derivative was poorer than that of the fabric treated with the underivatized corn starch size. Dye penetration and uniformity of the fabric treated with the more highly substituted starch ether, however, was far superior to that exhibited by the comparative sample. The results indicate that although both starch ether derivatives are useful in warp sizing compositions, in order to facilitate sufficient wax removal (when employing high concentrations of about 20% based on starch), the more highly substituted starch ether is preferably employed. In a like manner, starches may be reacted with other substituted quaternary amine epoxide reagents and employed in warp size compositions with similar effectiveness expected. Suitable reagents include, for example, the reaction products of epihalohydrins with one of the long chain tertiary amines listed below: pentyldimethylamine hexyldimethylamine octyldimethylamine 2-ethylhexyldimethylamine nonyldimethylamine decyldimethylamine decenyldimethylamine dodecenyldimethylamine tetradecyldimethylamine tetradecenyldimethylamine hexadecyldimethylamine hexadecenyldimethylamine octadecyldimethylamine octadecenyldimethylamine. didecylmethylamine Summarizing, a warp sizing composition and a process for the use thereof are provided whereby the composition is capable of strengthening and protecting warp yarns to withstand loom abrasion as well as facilitating uniform textile lubricant dispersion onto the warp yarns and providing efficient lubricant removal during desizing.

Claims: A warp sizing composition comprising water, a hydrophobic starch derivative, wherein the starch substituent comprises a hydrocarbon chain with 5 carbon atoms and a lubricant, characterized by the presence, as the hydrophobic starch derivative, of a starch ether or ester wherein the ether or ester substituent comprises a saturated or unsaturated hydrocarbon chain of at least 5 carbon atoms and the presence of about 3 to 50% of the lubricant, based on the weight of the hydrophobic starch derivative. The warp sizing composition of Claim 1, wherein 100 parts of the water and 2 to 40 parts of the starch derivative are present. The warp sizing composition of Claim 2, wherein the lubricant is selected from the group consisting of tallow, hydrogenated tallow, and paraffin present in amounts of 5 to 20%, based on the weight of the starch derivative. The warp sizing composition of Claim 2, wherein the lubricant is present in amounts of 11-50%, based on the weight of the starch derivative. The warp sizing composition of Claims 3 or 4, wherein the hydrophobic starch ester is the ester reaction product of starch and an imidazolide or N,N'-disubstituted imidazolium salt of a carboxylic or sulfonic acid containing the hydrocarbon chain or the half-acid ester reaction product of starch and a substituted cyclic dicarboxylic acid anhydride containing the hydrocarbon chain. The warp sizing composition of Claims 3 or 4, wherein the hydrophobic starch ether is the reaction product of starch and an etherifying reagent, the reagent being the reaction product of an epihalohydrin and a tertiary amine containing the hydrocarbon chain. The warp sizing composition of Claims 5 or 6, wherein the hydrocarbon chain contains 5 to 14 carbon atoms. The warp sizing composition of Claim 5 or 6, wherein the starch is selected from the group consisting of waxy maize, corn starch, high amylose corn starch, the converted products thereof, and the derivatized products thereof wherein the derivatization employs an ionic or nonionic etherifying or esterifying reagent other than the reagent containing the at least 5 carbon hydrocarbon chain. The warp sizing composition of Claim 5, wherein the hydrophobic starch ester is a half-acid ester prepared with octenyl succinic acid anhydride. Process for the warp sizing of textile yarns comprising passing the yarns through a sizing composition of the type containing water, a starch derivative, and a lubricant, characterized by applying to the yarns after the fibers have been manufactured the sizing composition according to at least one of the preceeding claims.

Inventors: HASULY, MICHAEL J., TRZASKO, PETER T.
Applicants: NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CORPORATION
Application year: 1986
Main classification: D06M15
IPC codes: D06M13, D06M15, C08L3, C08B31