US2495845A

US2495845A - Textile sizing composition

Info

Publication number: US2495845A
Application number: US716878A
Authority: US
Inventors: George D Jefferson; Richard D Fine
Original assignee: Atlas Powder Co
Current assignee: Atlas Powder Co
Priority date: 1946-12-17
Filing date: 1946-12-17
Publication date: 1950-01-31
Anticipated expiration: 1967-01-31

Description

Patented Jan. 31, 1950 TEXTILE SIZING COMPOSITION George D. Jefferson, Kennett Square, Pa., and

Richard D. to Atlas Powder Fine,- Merchantville, N. 1., assignorl Company. Wilmington, Del, a corporation of Delaware No Drawing. Application December 17, 1946. Serial No. 716.878

" 13 Ell-hill.- (Cl. 260-285) The present invention relates to a textile sis:

ing composition.

An object of the invention is to provide a composition which is particularly useful for sizing nylon yarn preparatory to a knitting operation.

Another object is to provide an improved sizing composition of'the type comprising boric acid and a water-sensitive polyvinyl e A further object is' to provide iirdry form and readily water-dispersible a sizing composition comprising boric acid and a water-sensitive polyvinyl resin.

Another object is to provide a sizing composition, particularly for nylon yarns, which combines the known valuable properties of a boric acid-water-sensitive polyvinyl resin size with new properties of lubricity, improved water resistance and improved yarn protection.

The above and other objects will become apparent in the course of the following description of the invention.

The present invention-will be described particularly in relation to the field of manufacture of full fashioned hosiery from nylon yarns since it is in this field that thecom'position has been found to have outstanding utility. The compositions of the invention are however useful in other textile manufacturing operations in which yarns of nylon, vinyl polymers, rayon, cellulose esters, cotton, silk, wool or the like are em,- ployed.

Nylon yarns have been found to present a number of technical problems to textilemanufacturers and particularly tomanufacturers of full fashioned hosiery. Among the problems are tendencies for the yarn'to elongate and slip during knitting, making control of stitch and fabric length diflicult, and a tendency for the fiat knitted fabric to curl at'the' edges, makingthe necessary seaming operation of the sheer fabric difficult. Some of these problems are solved by the use of the boric acid-water-sensitive polyvinyl resin sizes described, for example, in-Patent Number 2,324,601 to spanagel. '--"Ihe combination of boric acid and water-sensitive polyvinyl resin is also referred to in the artas borated vinyl resin and borated polyvinyl alcohol (PVA). Sizes of this type produce a coating on the yarn which is sufiiciently adhesive to reduce to 'a' substantial degree the objectionable tendencies to elongate and slip during knitting. 'The-boatlng'also stiffens the yarn and thus minimizes'the curling of the selvages. There are howeverseveral objections to the heretofore known forms of these sizes. The borated vinyl resin coating on the yarn is quite water-sensitive whereby itftakes up water, softens and becomes subject to stripping, which is objectionable mainly because itv fouls the knitting machines. The borated vinyl resin coating does not adequately lubricate the yarn and a separate yarn oiling operation is customarily required to protect the yarn and to assist good stitch formation and the maintenance of uniform tension. Another objection to the berated vinyl resin sizes is that they must be compounded in water in a critical manner and from the separate ingredients and they must, therefore, either be distributed as solutions or made up from the components at the place of use. A dry mixture of boric acid and, for example, polyvinyl alcohol is not readily dispersible in water presumably because the boric acid dissolves first and the polyvinyl alcohol will not disperse smoothly in the boric acid solution.

To overcome one or more of the objections to the simple boric acid-polyvinyl resin sizes there have been numerous proposals in the art to add various types of ingredients for modifying the characteristics of the resinous coating or to add special properties. Until the present invention, however, no way was known to overcome these objections without introducing further dimculties, such as increasing the water-sensitivity of the coating where the suggested additions are watersoluble. Many of the proposals in the art for the addition of water-insoluble substances are of little or no use either by reason of inability to introduce the suggested ingredients into aqueous solutions of boric acid and the vinyl resins, or by reason of the loss of useful properties of the resin size when the necessary dispersing agents or soivents are employed to include such ingredients.

In accordance with the present invention a textile sizing composition is provided which comprises as active ingredients 2. water-sensitive polyvinyl resin, boric acid, a. water-insoluble scourable waxy material (hereinafter referred to as a wax) which is incompatible with the resin, and a non-ionic water-soluble emulsifier for dispersing .the wax in an aqueous solution of the resin and boric acid. This composition has been found to have a number of unique properties. In the first place the known beneficial properties of the borated vinyl resin composition are retained as to stiffening the yarn, anchoring the stitches during knitting, and imparting snag resistance to the knitted products. Secondly, on the sized yarn the scourable wax is found to be incorporated into the sizing coating heterogenouslv and is found on the surface of the coating andin places where the boric acid resin coating is broken. This action of the water-insoluble scourable wax imparts lubrication to the yarn without altering perceptibly the film characteristics of the borated ,vinvl resin, reduces the watersensitivity of the berated vinyl resin composition. and gives greater protection to the yarn during knitting and subsequent operations. A third and very important property of this new composition is that it can be prepared in the form of a dry 3 mixture which can be manufactured to exact specifications on a large scale and distributed to users for dispersion in water for application to the yarn. In the dispersion of the dry composition no difllculty is experienced in getting the borated vinyl resin into solution in the water. This is believed to be due to the coating of the vinyl resin particles with the scourablewax and emulsifier which in turn prevents lumping of the vinyl resin when added to water.

The water-sensitive polyvinyl resins useful as yarn size ingredients are the hydroxylated resins described in the said patent to Spanagel. The preferred resins are the commercial polyvinyl alcohols produced by hydrolyzing poylvinyl acetate, especially the low viscosity members of this group. These commercial polyvinyl alcohols may contain some residual acetate radicals. Higher viscosity poylvinyl alcohols can be used only in dilute solutions but these can be used advantageously where sizing is accomplished by multiple coating.

The scourable waxes that can :be used are water-insoluble materials that are incompatible with the water-sensitive vinyl resins and that have a waxy consistency at temperatures to which a yarn is subjected during knitting, weaving or other intended operation. The waxes must be scourable, that is, they must be sufliciently hydrophilic to be readily dispersible in water either alone or at least in the presence of a mild scouring agent, such as soap, to permit ready removal from the yarn at the end of the manufacturing operation. Preferred scourable waxes are those selected from the class consisting of (1) partial esters of neutral polyhydroxylic organic compounds, with from 2 to 6 carbon atoms, and saturated fatty acids with from 16 to 30 carbon atoms; (2) diesters of hexldes and saturated fatty acids with from 16 to 30 carbon atoms; (3) waterinsoluble esters of polyoxyalkylene ethers of neutral polyhydroxylic organic compounds with from 2 to 6 carbon atoms, and saturated fatty acids with from 16 to 30 carbon atoms; and (4) waterinsoluble polyoxyalkylene ethers of partial esters of neutral polyhydroxylic organic compounds with from 2 to 6 carbon atoms, and saturated fatty acids with from 16 to 30 carbon atoms. Specific esters of group (1) are the ethylene glycol, propylene glycol, glycerol, erythritol, pentaerythritol, diglycerol, hexitol, hexitan, and hexide, partial esters of palmitic, stearic, margaric, camaubic, montanic and melissic acids or mixtures of such acids. The preferred partial esters are the hexitan monoesters, especially sorbitan monopalmitate and sorbitan monostearate. Specific esters of group (2) are sorbide and mannide diesters of the named fatty acids, preferably sorbide or mannide dipalmitate or distearate. Specific esters of group (3) are the 16 to 30 carbon atom fatty acids, tetra-, penta-, and hexaesters of a polyoxyethylene ether of sorbitol with an average of 6 oxyethylene groups per molecule of sorbitol, the tetra and 'penta esters of the corresponding polyoxyethylene ether of glucose, and the esters of the corresponding polyoxypropylene ether of sorbitol or of glucose. Specific ether-esters of group (4) are the polyoxyethylene ethers of hexitan mono-, di-, and triesters of fatty acids with from 16 to 30 carbon atoms wherein the number of oxyethylene groups is insufiicient to render the ethers water-soluble, as for example, the polyoxyethylene ethers of sorbitan tristearate wherein there is an average of 16 oxyethylene groups per molecule of sorbitan 4 tristearate. The polyoxypropylene ethers of hexitan fatty acid partial esters are further members of group (4) The class of scourable waxes that can be used according to the invention comprises waxes with a considerable variation in melting points, film hardness and dispersibility. The most desirable waxes from the standpoint of melting point and film hardness are relatively diiilcult to disperse in water with the borated polyvinyl resin and therefore require a large amount of water-soluble dispersing agents to produce satisfactory dispersions. The dispersing agents have a tendency to soften and weaken the'sizing coating when used in large proportionso that it is desirable to keep the proportion of dispersing agent as low as possible. It has been found possible to reduce materially, by 50% in some cases, the requirement for watersoluble dispersing agent by employing as the scourable wax a mixture of two or more members of the class of which one is a high melting, difficulty dispersible, hard wax and another is a more readily dispersible wax. All of the scourable waxes in the mixture are valuable textile waxes and it is possible to formulate a mixture with optimum textile improving qualities and minimum requirement for the water-soluble dispersing agent.

The water-soluble emulsifier for emulsifying the scourable wax in the boric acid-polyvinyl resin solution is a non-ionic organic compound, or preferably a mixture of such compounds, with an aliphatic hydrocarbon portion of 10 to 18 carbon atoms and a polyoxyethylene portion containing a sufficient number of oxyethylene groups to render the compound water-soluble. The linkage between the long chain hydrocarbon portion and the polyoxyethylene portion of the emulsifier may be direct or indirect, as for example of the ester type, RCOO(C2H4O) 11H, as where the hydrocarbon chain (R) is derived from a long chain fatty acid; of the ether type, RO(C2H40)nH, as where the hydrocarbon chain (R) is derived from a long chain fatty alcohol; or of the type wherein the hydrocarbon portion and the polyoxyethylene portion are both chemically linked through oxygen to a neutral organic coupling compound with from 3 to 6 carbon atoms. Emulsifiers of the last named type are exemplified by compounds of the types RCOQCsHtO (C2H40)nH and ROCaHaO (C2H40)nH, the CsHcO coupling portion being derived from propylene glycol or propylene oxide. The coupling radical may also be derived from a polyhydric alcohol, with 3 or more hydroxyl groups such as glycerol, hexitols and hexitans. and in such cases the emulsifier may contain more than one long' hydrocarbon radical and/or more than one polyoxyethylene chain. It will be apparent to those skilled in the art that emulsifiers of the class contemplated by the invention can be prepared in various ways. It will also be apparent that, as in the case of most emulsifiers, more efficient products result from the use of mixtures of related compounds such as occur in the production of emulsifiers from commercial grades of material and by the use of processes which produce not only the nominal reaction product but also quantities of related by-products. For example, the emulsifier for use in the preferred composition according to the invention, has the hydrocarbon radical derived from commercial lauric acid which contains, in addition to lauric acid, quantities of fatty acids of lower and higher molecular weights. The polyoxyethylene portion of the preferred emulsifier is introduced by reaction of ethylene v propylene glycol and commercial lauric acid in oxide and a monoester of the proportion of mols of ethylene oxide per mol of the monoester. This ethylene oxide reaction produces a wide distribution of compounds having different polyoxyethylene chain lengths. As understood by the art the number of oxyethylene groups required to obtain water-solubility for compounds containinglong chain hydrocarbon groups varies with the length, nature (saturated, unsaturated, hydroxylated, etc.) and number of such groups.

The sizing compositions according to the invention can be considered conveniently to be composed of a boric acid-water sensitive polyvinyl resin portion and a wax portion, the wax portion containing the scourable wax and the emulsifier. The relative proportions of the boric acid-resin portion and the wax portion may :be varied within wide limits to obtain properties ranging from maximum stiffering, where the wax is at a minimum, to maximum lubrication where the wax is at a maximum. The boric acid-resin portion and the wax portion can be mixed in virtually any proportions and aqueous dispersions of useful stability prepared. The viscosity of the aqueous dispersions increases as the wax content increases and this viscosity constitutes a limiting factor in many uses. The concentration of solids in the dispersion. can be varied to keep viscosity in a preferred range for some uses. For use in nylon yarn knitting sizes the ratio is preferably kept in the range 4.3 to 1.3 parts by weight of 'borated vinyl resin to 1 part of the wax portion. The optimum ratio is 2.3 parts borated vinyl resin to 1 part wax for presently accepted sizing and knitting techniques in the manufacture of full fashioned nylon hosiery.

The usual proportions of boric acid and watersensitive polyvinyl resin can be employed in the present invention. It is known and is described for example in the patent to Spanagel Number 2,324,601 that these proportions can be varied to produce difierent characteristics of water resistance, hardness, etc. In general proportions of 5 to 25% by weight boric acid based on resin are suitable. Some of the water-sensitive polyvinyl resins will not tolerate as much as 25% boric acid, as described by Spanagel, but the determination of this factor is very simple to one skilled in this art. The limit of tolerance of a particular resin for boric acid can be established by adding various amounts of boric acid to an aqueous solution or dispersion of the resin and observing the quantity of boric acid that results in precipitation or gelling of the resin. The upper limit of tolerance of the resin for boric acid is the largest amount that can be added without causing preci-pitation or gelling. In the preferred form of the present invention the resin is a polyvinyl alcohol with a saponification number of about 140,

.a viscosity of 4 to 6 centipoises in 4% aqueous solution at C., and prepared by partially hydrolyzing polyvinyl acetate. With this resin the preferred proportions of boric acid are 20 to by weight of the resin.

In the wax portion the relative amounts of scourable wax and emulsifier must be such that the wax will be emulsified in the solution produced by dissolving the boric acid and the resin in water and so that the resulting emulsion will be sufii-ciently stable to permit proper application to the yarn. For a sizing composition to be used on nylon yarn for hosiery manufacture the quantity of emulsifier should be kept to a minimum due to the softening effect of the emulsifier on the wax portion or the sizing coating. Furthermore the wax portion of the size should be formulated to have a melting point sufliclently high to insure that the wax will be solid under conditions of use. The preferred sizing composition employs a wax portion (scourable wax+emulslfier) with a melting point of about 37 C. as determined by a suitable modification oi the "Standard Method of Test for Melting Point of Petrolatum, A. S. T. M. designation D 127-30.

In the preferred sizing composition of the invention the wax portion contains as the waterinsoluble scourable wax a mixture of a hexltan monostearate, or monopalmitate, and a polyoxyethylene ether of a hexltan tristearate in which there is an average of 16 oxyethylene groups per molecule of hexltan tristearate. This waxy poly- 'oxyethylene ether is more readily water-dispersible than the hexltan monostearate or palmitate and assists in its eanulsification thereby reducing the amount of emulsifier required. The emulsifier in the preferred composition is a polyoxy-= ethylene ether of propylene glycol monolaurate in which there is an average of 15 oxyethylene groups per molecule of propylene glycol monolau'rate. The specifically preferred composition for this wax portion of the size is 50% hexitan monostearate, or monopalmitate, 25% polyoxyethylene ether of hexitan tristearate (16 oxyethylene groups per molecule of hexltan tristearate) and 25% polyoxyethylene ether of propylene glycol monolaurate (15 oxyethylene groups per molecule of propylene glycol monolaurate) This specific composition is preferred because it gives sizing emulsions of excellent stability and the wax portion has a melting point of about 37 C. which insures that the sizing coating will be solid under normal conditions for yarn processing. The preferred composition of the wax po tion of the size is susceptible of variation withi the ranges of 40 to 50% hexitan monostearate, or monopalmitate, 22.5 to 33% polyoxyethylene ether of hexitan tristearate (16 oxyethylene groups per molecule of hexltan tristearate), and 22.5 to 33% polyoxyethylene ether of propylene glycol monolaurate 15 oxyethylene groups per molecule propylene glycol monolaurate), the total amounts constituting The following specific examples illustrate the preparation and use of sizing compositions in accordance with the invention.

Example 1 The following materials were heated together in a steam-jacketed kettle to a temperature of 50 to 60 C. and stirred until melted and thoroughly mixed;

Pounds Sorbitan monopalmitate 50 Polyoxyethylene ether of sorbltan tristearate containing .an average of 16 oxyethylene groups per molecule of sorbltan tristearate 25 Polyoxyethylene ether of propylene glycol monolaurate containing an average of 15 oxyethylene groups per molecule of propylene glycol monolaurate 25 The mixture was then allowed to cool to room temperature.

In a separate container 95.5 lbs. of an aqueous solution of boric acid and polyvinyl alcohol were prepared as follows: 7.64 lbs. of the polyvinyl alcohol were added to 55.73'lbs. of cold water with continuous stirring, and, after the polyvinyl alcohol was dispersed, the temperature was raised to 70 C. Separately 1.53 lbs. of boric acid were dissolved with warming in 30.6 lbs. water. Both solutions were cooled to 30 C. and the boric acid solution was added with stirring to the polyvinyl alcohol solution. The polyvinyl alcohol used was prepared by partially saponifying polyvinyl acetate and the product had a saponification number .of 140 and a viscosity of 4 to 6 centipoises in a 4% aqueous solution at 20 C. The solution so prepared was heated with stirring to a temperature of 65 C. and to it were added 4.5 lbs. of the wax and emulsifier mixture prepared as in the preceding paragraph. The resulting dispersion of the wax in the solution was then cooled to 26 C. while continuing the stirring and the viscosity of the dispersion was adjusted to 120 seconds (Saybolt Universal at 78 F.) by the addition of water.

The above described dispersion was applied to yarn by a single sizing technique in which the yarn was wound from a spool or pirn over a sizing roll onto a drum. A 30-denier 10-filament 30-turn polyhexamethylene adipamide yarn was sized by passing it at a speed of 750 yards perminute over a rotating size roll dipping into a trough containing the size dispersion. The speed of the size roll was adjusted to 9.0 R. P. M. and the angle of contact of the yarn with the size roll was 5". Sizing was done at a room tempera ture of 78 F. and at an observed relative humidity of About 5.0 to 5.5% of the size solids were applied based on the weight of the yarn. After drying and aging, the yarn was coned without the application of oil or any other material. The sized yarn was found to knit well on a fullfashioned hosiery knitting machine and the size adhered-well to the yarn even under conditions of high relative humidity. The size was found to be readily removable by washing in hot water which preferably contains a mild scouring agent.

Example 2 A water-dispersible dry composition containing ingredients corresponding to'those described in Example 1 was prepared in the following manner.

A No. 3 Lancaster mixer was charged with 13.7 lbs. of 'finely powdered boric acid and 68.5 lbs. of the poylvinyl alcohol described in Example 1. These ingredients were milled together in the mixer until intimately mixed and then 35.9 lbs. of molten wax and emulsifier mixture, prepared as in Example 1, were added at a temperature of 45 C. Mixing continued until the mass was of uniform consistency and after cooling to-25 to 30 C. the charge was transferred to a Stokes Granulator in which it was granulated through a U. S. S. No. 10 wire screen. The resultant product was collected and packaged.

A yarn sizing dispersion of the granular mixture prepared as described was made by gradually adding 12.5 lbs. of the granular mixture to 87.5 lbs. of water heated to 65 C. with gentle stirring during the addition. The gentle stirring was continuedas the dispersion was cooled to 26 C. Thereafter, the viscosity of the dispersion was adjusted to 120 seconds (Saybolt Universal at 78 F.) by the addition of water. The dispersion was used in sizing a nylon yarn in the manner described in Example 1 and the yarn was knitted into full-fashioned hosiery with the same very successful results.

Example 3 A yarn sizing dispersion was prepared and used as described in Example 1 with the variation that, in place of sorbitan monopalmitate in the wax and emulsifier mixture of Example 1, sorbitan monostearate was substituted in the same proportion. The dispersion was prepared as readily as in Example 1 and exhibited the same advantages on application to the yarn and in the subsequent manufacture of hosiery from the sized yarn.

Example 4 A yarn sizing dispersion was prepared as described in Example 1 with the variation that the wax and emulsifier mixtures of Example 1 was replaced by a mixture of sorbitan monopalmitate and polyoxyethylene ether of propylene glycol monolaurate containing an average of 15 oxyethy1ene groups per molecule of propylene glycol Eat sample 5 A dispersible dry composition was prepared with the ingredients described in Example 2 but the proportions were varied in the following manner.

The Lancaster mixer was charged with 12.5 lbs. of finely powdered boric acid and 68.5 lbs. of the polyvinyl alcohol. When these ingredients were intimately mixed 37 lbs. of the wax-emulsifier mixture were added in a molten condition at a temperature of 45 C. This composition was granulated and screened as in Example 2. The composition was dispersed in water to form a sizing composition as in Example 2 and the resulting dispersion was applied to nylon yarn. Subsequently the sized yarn was knitted into fullfashioned hosiery with excellent results. The size of this example'has a lower proportion of boric acid to polyvinyl alcohol and also a higher proportion of wax to polyvinyl alcohol the effect of which is to reduce slightly the stiffness of the sizing coating described in Example 2.

The dry sizing composition containing the borated vinyl resin, the scourable wax and the emulsifier can be prepared in any of the proportions and with any of the specific ingredients described above. This composition can be made up to precise specifications on a large scale and is avaluable article of commerce. The user of the composition has only to disperse it in water, adjust vicosity if necessary for his purpose, and apply it to his yarn or fabric.

The wax portion of the size is also a valuable article of commerce and can be prepared in alarge scale using any of the proportions and ingredients described. The resulting wax is preferred by users who desire to make up their own borated vinyl resin compositions or to vary the proportions of borated resin to wax.

The composition of the invention can of course be modified non-essentially by including coloring matters or the like. In the application of the sizes to yarns many variations can be made. Anchor coatings of tannic acid or other substances can be used if desired but no such coatings have been found necessary up to the present time. Sizing may precede twisting of the yarns or may follow twisting or both.

In the course of the preceding description the terms solution, soluble, and dissolving have been used with reference to high molecular weight organic compounds such as polyvinyl alcohol and polyoxyethylene derivatives but in accordance with the usual understanding in the art these terms are employed to designate apparent solution recognizing that true molecular dispersion is not achieved in many instances. Also, the terms polyhydric and "polyhydroxylic are employed in the sense of more than one hydroxyl group.

It will be apparent that many variations can be made without departing from the scope of the invention which is defined in the appended claims.

What is claimed is:

1. A textile sizing composition comprising a water-sensitive hydroxylic polyvinyl resin; boric acid; a water-insoluble scourable wax which is incompatible with said resin and which consists of a compound selected from the class consisting of (1) partial esters of neutral polyhydroxylic organic compounds with from 2 to 6 carbon atoms and saturated fatty acids with from 16 to 30 carbon atoms, 2) diesters of hexides and saturated fatty acids with from 16 to 30 carbon atoms, (3) water-insoluble esters of polyoxyalkylene ethers of neutral polyhydroxylic compounds with from 2 to 6 carbon atoms, and saturated fatty acids with from 16 to 30 carbon atoms, and (4) water-insoluble polyoxyalkylene ethers of partial esters of neutral polyhydroxylic organic compounds with from 2 to 6 carbon atoms, and saturated fatty acids with from 16 to 30 carbon atoms;

and a non-ionic water-soluble emulsifier for emulsifying said wax in an aqueous solution of said resin and said boric acid, said emulsifier consisting of an organic compound with an aliphatic hydrocarbon portion with from 16 to 18 carbon atoms and a polyoxyethylene portion containing a sufficient number of oxyethylene groups to render the compound water-soluble.

2. A textile sizing composition comprising polyvinyl alcohol; boric acid; a water-insoluble scourable wax which is incompatible with said resin and which consists of a mixture of a hexitan monopalmitate. and a waxy water-insoluble polyoxyethylene ether of a hexitan tristearate; and a water-soluble polyoxyethylene ether of propylene glycol monolaurate as an emulsifier for emulsifying said scourable wax in an aqueous solution of said polyvinyl alcohol and said boric acid.

3. A textile sizing composition comprising polyvinyl alcohol; boric acid; a scourable wax mixture containing a major proportion of a hexitan monopalmitate, and a minor proportion of a polyoxyethylene ether of a hexitan tristearate wherein there is an average of about 16 oxyethylene groups per molecule of hexitan tristearate: and a polyoxyethylene ether of propylene glycol monolaurate wherein there is an average of about 15 oxyethylene groups per molecule of propylene glycol monolaurate as an emulsifier for emulsifying said scourable wax mixture in an aqueous solution of said polyvinyl alcohol and said boric acid.

4. A composition for dispersion in an aqueous solution of polyvinyl alcohol and boric acid to produce a textile sizing medium, said composition consisting essentially of from 40 to 50% of a hexitan monopalmitate, from 22.5 to 33% of a polyoxyethylene ether of a hexitan tristearate wherein there is an average of about 16 oxyethylene groups per molecule of hexitan tristearate, and

10 from 22.5 to 33% of polyoxyethylene ether of propylene glycol monolaurate wherein there is an average of about oxyethylene groups per molecule of propylene monolaurate, the total amounts constituting 100%.

5. A dry composition adapted for mixture with water to produce a textile sizing medium, said composition comprising an intimate mixture of a water-sensitive hydroxylic polyvinyl resin; boric acid; a water-insoluble scourable wax which is incompatible with said resin and which consists a compound selected from the class consisting of (1) partial esters of neutral polyhydroxylic organic compounds with from 2 to 6 carbon atoms and fatty acids with from 16 to carbon atoms, (2) diesters of hexides and saturated fatty acids with from 16 to 30 carbon atoms, (3) water-insoluble esters of polyoxyalkylene ethers of neutral polyhydroxylic compounds with from 2 to 6 carbon atoms, and saturated fatty acids with from 16 to 30 carbon atoms, and (4) water-insoluble polyoxyalkylene ethers of partial esters of neutral polyhydroxylic organic compounds with from 2 to 6 carbon atoms, and saturated fatty acids with from 16 to 30 carbon atoms; and a non-ionic wa ter-soluble emulsifier for emulsifying said wax in an aqueous solution of said resin and said boric acid, said emulsifier consisting of a compound with an aliphatic hydrocarbon portion with from 10 to 18 carbon atoms and a polyoxyethylene portion containing a sufficient number of oxyethylene groups to render the compound water-soluble.

6. A dry composition adapted for mixture with water to produce a textile sizing medium, said composition comprising polyvinyl alcohol: boric acid; a water-insoluble scourable wax which is incompatible with said polyvinyl alcohol and which consists of a mixture of a hexitan monopalmitate. and a waxy water-insoluble polyoxyethylene ether of a hexitan tristearate; and a water-soluble polyoxyethylene ether of propylene glycol monolaurate as an emulsifier for emulsifying said scourable wax in an equeous solution of said polyvinyl alcohol and said boric acid.

7. A dry composition adapted for mixture with water to produce a textile sizing medium, said composition comprising polyvinyl alcohol; boric acid; a scourable wax mixture containing a major proportion of a hexitan monopalmitate, and a minor proportion of a polyoxyethylene ether of a hexitan tristearate wherein there is an average of about 16 oxyethylene groups per molecule of hexitan tristearate; and a polyoxyethylene ether of propyleneglycol monolaurate wherein there is an average of about '15 oxyethylene groups per molecule of propylene glycol monolaurate as an emulsifier for emulsifying said scourable wax mixture in an aqueous solution of said polyvinyl alcohol and said boric acid.

8. A dry composition adapted for mixture with water to produce a textile sizing medium, said composition comprising from 4.3 to 1.3 parts by weight of a polyvinyl alcohol and boric acid mixture; and 1 part by weight of a mixture consisting of from 40 to of a hexitan monopalmitate, from 22.5 to 33% of a polyoxyethylene ether of a hexitan tristearate wherein there is an average of about 16 oxyethylene groups per molecule of hexitan tristearate, and from 22.5 to 33% of a polyoxyethylene ether of propylene glycol monolaurate wherein there is an average of about 15 oxyethylene groups per molecule of propylene 11 glycol monolaurate, the total of the percentages of a mixture of about 50% sorbitan monopalmitate, about 25% polyoxyethyle'ne ether of sorbitan tristearate wherein there is an average of about 16 oxyethylene groups per molecule of sorbitan tristearate, and about 25% polyoxyethylene ether of propylene glycol monolaurate wherein there is an average of about oxyethylene groups per molecule of propylene glycol monolaurate.

10. A textile sizing composition comprising P lyvinyl alcohol; boric acid; a water-insoluble scourable wax which is incompatible with said resin and which consists of a mixture of a herdtan monostea'rate and a waxy water-insoluble polyoxyethylene ether of a hexitan tristearate; and a water-soluble polyoxyethylene ether of propylene glycol monolaurate as an emulsifier for emulsifying said scourable wax in an aqueous solution of said polyvinyl alcohol and said boric acid.

11. A composition for dispersion in an aqueous solution of polyvinyl alcohol and boric acid to produce a textile sizing medium, said composition consisting essentially of from 40 to 50% of a hexitan monostearate from 22.5 to 33% of a polyoxyethylene ether of a hexitan tristearate wherein there is an average of about 16 oxyethylene groups per molecule of hexitan tristearate, and 40 an average of about 15 oxysthylene groups per molecule of propylene monolaurate, the total amount constituting 100%.

12. A dry composition adapted for mixture with water to produce a textile sizing medium. said composition comprising polyvinyl alcohol; boric acid; a water-insoluble scourable wax which is incompatible with said polyvinyl alcohol and which consists of a mixture of a hexitan monostearate and a waxy water-insoluble polyoxyethylene ether or a hexitan tristearate; and a water-soluble polyoxyethylene ether of propylene glycol monolaurate as an emulsifier for emulsifying said scourable wax in an aqueous solution of said polyvinyl alcohol and said boric acid.

13. A dry composition adapted for mixture with water to produce a textile sizing medium, said composition comprising from 4.3 to 1.3 parts by weight of a polyvinyl alcohol and boric acid mixture; and 1 part by weight of a mixture consisting of from to of a hexitan monostearate, from 22.5 to 33% of a polvoxyethylene ether of a. hexitan tristearate wherein there is an average of about 16 oxyethylene groups per molecule of hexitan tristearate, and from 22.5 to 33% of a polyoxyethylene' ether of propylene glycol monolauratewherein there is an average of about 15 oxyethylenegroups per molecule of propylene glycol monolaurate, the total of the percentages constituting GEORGE D. JEFFERSON. RICHARD D. FINE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,297,135 Davis et al. Sept. 29, 1942 2,300,074 Strain Oct. 27, 1942

Claims

1. A TEXTILE SIZING COMPOSITION COMPRISING A WATER-SENSITIVE HYDROXYLIC POLYVINYL RESIN; BORIC ACID; A WATER-INSOLUBLE SCOURABLE WAX WHICH IS INCOMPATIBLE WITH SAID RESIN AND WHICH CONSISTS OF A COMPOUND SELECTED FROM THE CLASS CONSISTING OF (1) PARTIAL ESTERS OF NEUTRAL POLYHYDROXYLIC ORGANIC COMPOUNDS WITH FROM 2 TO 6 CARBON ATOMS AND SATURATED FATTY ACIDS WITH FROM 16 TO 30 CARBON ATOMS, (2) DIESTERS OF HEXIDES AND SATURATED FATTY ACIDS WITH FROM 16 TO 30 CARBON ATOMS, (3) WATER-INSOLUBLE ESTERS OF POLYOXYALKYLENE ETHERS OF NEUTRAL POLYHYDROXYLIC COMPOUNDS WITH FROM 2 TO 6 CARBON ATOMS, AND SATURATED FATTY ACIDS WITH FROM 16 TO 30 CARBON ATOMS, AND (4) WATER-INSOLUBLE POLYOXYALKYLENE ETHERS OF PARTIAL ESTERS OF NEUTRAL POLYHYDROXYLIC ORGANIC COMPOUNDS WITH FROM 2 TO 6 CARBON ATOMS, AND SATURATED FATTY ACIDS WITH FROM 16 TO 30 CARBON ATOMS; AND A NON-IONIC WATER-SOLUBLE EMULSIFIER FOR EMULSIFYING SAID WAX IN AN AQUEOUS SOLUTION OF SAID RESIN AND SAID BORIC ACID, SAID EMULSIFIER CONSISTING OF AN ORGANIC COMPOUND WITH AN ALIPHATIC HYDROCARBON PORTION WITH FROM 10 TO 18 CARBON ATOMS AND A POLYOXYETHYLENE PORTION CONTAINING A SUFFICIENT NUMBER OF OXYETHYLENE GROUPS TO RENDER THE COMPOUND WATER-SOLUBLE.