US2412832A - Textile material and method of preparing it - Google Patents

Description

STABILIZATION DATA Fonnulae on Percent by Weight Buis shrinkage 1n 5 washes Artnr stabilizing Process:

Filed Oct 30 1945 17, 1946. E. c. PFEFFER, JR., ETAL TEXTILE MATERIAL AND METHOD OF PREPARING IT t Mezza/072; .Zi/mm1 177.27; J7:

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hof Aunt. suphnndu 2.25"/ya 50% Aut-u suplhlendsu 2x2 '1*'111 llvn 92x70 Count. 2.7 oflyd Patented Dee. 17, 1946 TEXTILE MATERIAL AND METHOD OF PREPARING IT Edward C. Pfeffer, Jr., and Jack Epelberg, Troy, N. Y., assignors to Cluett, Peabody & Co., Inc., -l Troy, N. Y., a corporation of New York Application Gctober 30, 1943, Seiiai No. 508,368

8 Claims.

and Epelberg, Serial No. 495,620, vfiled July 21,

The term textile material as herein employed ls intended to include filaments, bers, staple or yarns, whether in the finished state or at some intermediate stage in the production thereof. 'I'he term also includes fabrics whether knitted, Woven or felted, as Well as garments or other articles made from such fabrics.

A principal object of the present invention is to provide textile material, for instance of any of the classes just above enumerated-for more specic example a woven fabricwhich possesses even better stability with respect to dimensional shrinkage, together with equal or better-resistance to crushing than the material disclosed in the aforesaid application as well as other advantages of the latter material and which, if desired, may have a very soft hand and ne draping qualities. A further object is to provide a novel method of preparing textile material of this improved character. Other and further objects and advantages of the invention will be pointed out in the following more detaileddescription and by reference to the annexed drawing which consists of a, table showing the characteristics of the fabric of the present invention as compared with those of untreated fabric and of fabric which has been treated in accordance with the procedure of the aforesaid application.

In'the above application it was pointed out that customary previous modes of stabilizing and crushproong textile materials had involved the use of solutions or suspensions of intermediate condensation products of synthetic resins or resin components either with or without a plasticizer, and forming and` curing the resin in situ, and that such resinous substances as had commonly been employed (phenol formaldehyde, urea formaldehyde, and melamine formaldehyde, etc.)

when used alone possess many disadvantages whichI substantially lessen their field of usefulness. For example, some of them have or emit during curing an exceedingly disagreeable odor or irritating or toxic fumes necessitating special and extensive precautions in their use; in some instances the disagreeable odor is persistent in or develops in the fabric after finishing; some of these resinous type materials cause permanent discoloration or browning of the fabric so that they are not `applicable to white material; some of them make the constituent flbers of the fabric tender thereby reducing the tensile strength of the fabric; and some of them are unduly expensive, particularly when employed in the large amounts sufficient effectively to provide crease resistance as well as dimensional stability.

The aforesaid application further disclosed, as a wholly novel concept, the employment of a dialdehyde, glyoxal CHO also known as oxalic aldehyde, or ethanedial as a, stabilizing and crushproong medium in substitution for the formaldehyde theretofore employed, and pointed out substantial advantages for the glyoxal as compared with the -materials which had previously been employed, for example the fact that the glyoxal may be or in fact must be used in low concentrations, for example from 0.6% to 4.65% by weight in the treating bath, whereas such prior materials as urea formaldehyde condensation products must be use-d in concentrations of from 6% to 8% for stabilization and from 14% to 16% for creaseproong.

Further, it was noted that glyoxal does not emit disagreeable fumes during curing; it does not substantially tender the textile material or make it brittle, when used in the concentrations requisite for stabilization or l crushproong; it does not discolor or brown the textile material to any harmful degree; it may readily be applied without necessitating special equipment, and it has little odor in solution of a strength suitable for its intended use. i

It was also noted that th glyoxal is applied to the fabric in water solution but it does not exist as the above compound when in water solution since it hvdrates to form a compound known 3 as tetrahydroxydioxane, which has the following structural formula:

When the water in which this material is dis-A solved is evaporated and further heat is applied, the material readily dehydrates yielding glyoxal as shown by the following formula:

nonc/ \cnor1 While we do not definitely know the exact action which occurs when cellulose in association with glyoxal is heated. we believe that a reaction takes place in consequence of which the cellulose of the individual fibers of the fabric is at least partially converted into a reaction product which may be termed dicellulose diacetal or cellulose glyoxal, as may be preferred, such product being of the long-chain, high molecular weight type, but with cross-linkages making it more stable than the formaldehyde resins.

We have now discovered that whereas glyoxal alone (or in association with a catalyzer accelerator) in these low concentrations provides a degree of stabilization and crushprooflng comparable with the results obtained by the use of larger amounts of the formaldehyde condensation products previously employed, unexpectedly better results are obtainable by associating with the glyoxal one or more amino-aldehyde waterdispersible resinous condensation products, for y example urea or melamine formaldehyde, but employing such resinous condensation products in amounts far too small (except in association with the glyoxal) to accomplish either stabilization or crushproofing. Further, Wholly unexpectedly it has been discovered that when thus used in association*y the stabilizing effect of the combined resin and glyoxal is even greater than that of the equivalent amount of either material alone and that damage to the fabric is less than might result from an equivalent amount of either the glyoxal or the resin condensation product by itself.

For certain purposes, for instance in the manufacture of mens sport shirts, it is desirable that the fabric be very soft and possess excellent draping qualities or in other words that it should have a very soft hand, although this characteristic is not normally possessed by most fabrics made from synthetic fibers. 'It has further been discoveredthat when the glyoxal and resin are thus used in association, as above suggested, a very soft hand or feel may be imparted to the fabric by including in the treating bath a cationactive softener, for example one of the quaternary ammonium compounds.

As described in the aforesaid application, it is found desirable, in order to hasten the action and to avoid overheating of certain types of fabric, to employ an acid catalyst to facilitate the reaction between the glyoxal and the ce1- lulose of the fiber. Among such catalysts may be mentioned oxalic acid, ammonium chloride, ammonium sulphate, and ammonium nitrate. Oxalic acid is highly satisfactory since vits use avoids the development of any substantial color during heat treatment.

As illustrative. without limitation of the scope of the invention, the following suggestions as to reagent strengths .and conditions of treatment are cited, it beingnoted that in accordance with the present invention substantially the same amount of glyoxal and catalyst are employed as disclosed in the above application, the resinous material being in addition thereto.

1. Amount of glyoxal:

15 to 120 cubic cms. of 30% glyoxal solution per liter of treating bath, or approximately .6 to 4.65% weight in the treating bath.

2. Type of catalyst:

Acid-reacting, such as organic acids or salts of inorganic acids or organic acids which produce an acid effect. 3. Amount of catalyst:

1/8 to 4 gms. per liter of treating bath, or approximately .0125 to .40% by weight of treating bath.

4. Amount of resin:

12 to 50 gms. of 100% condensation product per liter of treating bath or approximately 1 to 5% by Weight of the treating bath.

5. Amount of softener, if used:

Approximately 1% by weight of treating bath.

6. Baking temperature: 212 F. to 350 F. 7. Baking time:

2 minutes to 40 minutes.

Obviously the baking temperature and the baking time are inversely related.

Certain condensation products (now obtainable from the Reichhold Chemicals, Inc., and from the American Cyanamid Company, respectively) which are useful in the practice of the present invention but which as yet have no established chemical names, are herein for convenience referred to as Beckamine P-364 and Aerotex M-3, and are herein identified and defined respectively as follows:

Beckamine P-364 is a water-dispersible condensation product of urea formaldehyde. Its preparation is fully described in copending application Serial No. 540,883, filed June 17, 1944. and assigned to Reichhold Chemicals, Inc., Boston, Massachusetts, from which this reagent may be obtained.

Aerotex M-3 is a methylated methylol-mel- 1amine and may be prepared substantially as folows:

Formula-960 parts by Weight of formalin (37% by Weight CHzO) and 252 parts by Weight of melamine are charged into a reaction vessel fitted with an agitator, thermometer, and reflux condenser and arranged so that it can be placed under a vacuum and heated. The contents of the reaction vessel are heated for one-half hour to a temperature of 62 C. and the pH adjusted to 7.5 with 2 normal NaOH. After heating for another one-half hour, a vacuum of 28 inches of mercury is applied and the mixture concentrated by removal of water. After 40 minutes heating at approximately 54 C. the heat and vacuum are removed and there is added 1000 parts by weight of methyl alcohol containing enough 2 normal HaPO4 to neutralize the 2 nory mal NaOH added previously. The mixture at a pH of 6.4 is then heated to distill off an azeotropic mixture of methanol and water, anhydrous methanol being continuously added to replace the distillate. After heating in this way for glyoxal by tolerate 100 partsof toluol and the resin is, considered dried. It is then concentrated under a vacuum of 28 inches oi' mercury to a solids' con- 6. Exmru 2 p .A plain weave, 60% spun viscose rayon and 40% acetate rayon fabric in the greige made oi' blended 30/2-19 Z turns in the singles and 13 8 turns in The process loss is 1.3 inches warp, none in the filling.

Creuse resistance per yard in the Per cent 45 Untreated Treated 85 75 Treated tent of approximately 50%- The methylated 5 the ply in both warp and filling yarns is desized, methylol-melamine thus prepared may be dis' scoured, and dried on the tenter frame. The loss persed in water to a concentration of 10% resin on the above operation if, 2.25 inches per yard solids. corresponding to 6.2%. The white. pure finished Hereinafter, when Beckamine P-364 and Aero fabric has a count of 65 x 4g, and a Weight of 6,5 '18X M3 are referred t0 it 1S understood that 10 oz. per yard. This fabric is then passed through these terms designate the products above de' an impregnating Solution containing cc. of scribed respectively, or the equivalents thereof. glycxal solution (at 30.2% glyoxal content by The IOUOWIDE Special examples are given as u weight), 3 grams of oxalic acid, and 45 .grams of lustrtive 0f the application 0f the Present novel a water-dispersible condensation product of urea process as a practical matter in materials 0f dif- 16 formaldehyde (producedby Reichholdchemicals ferent types. Inc. and designated as P-364 Beckamine) per EXAMPLE 1 liter of solution. This urea formaldehyde product is condensed to a molecular weight such that A plain weave, 100% spun viscose rayon fabric it is completely dispersible in` water in a very in the greige, made of 28/1 warp and 14/1 iilling 20 finely divided state, but is not sufficiently soluble yarns of spun viscose rayon staple fiber is deto produce a clear solution. On a weight persized, scoured and dried on the tenter frame. centage basis this solution contains 2.25% gly- The white, pure finished fabric has a count of oxal, 0.296% oxalic acid, and 3.36% urea formal- 66 x 41 and a weight of 4 oz. per yard. This dehyde reaction product by weight. After the fabric is then passed through an impregnating fabric is passed through this solution and is well solution containing 60 cubic centimeters of glywetted out, it is squeezed to remove excess soluoxal solution (0f 30.2% glyOXal @Ontent by tion and is then dried on a tenter frame in air weight) 3 grams of oxalic acid, and 45 grams of at around 180 F. to' dimensions before imprega water dispersible condensation product of urea nating. The dried fabric is then cured in a tenter formaldehyde (produced by Reichhold Chemicals 30 frame oven or loop dryer oven in circulating Inc. and designated as P-364 Beckamine) per air at '280 F. for 8 minutes, after which it is liter of solution. This urea formaldehyde product soaped, rinsed and dried t'o the original pure is condensed to a molecular weight such that it is finish fabric dimensions on a tenter frame. The -completely dispersible in water in a very finely resulting fabric is white, free from any odor, firm divided state, but is not sufficiently soluble to and resilient, with greatly improved resistance to produce a clear solution. On a weight percentage shrinkage on washing, which effect is permanent basis this solution contains 2.25% glyoxal, 0.296% to washing, and hasv improved resistance to creasoxalic acid, and 3.36% urea formaldehyde reacing and crushing. A comparison of these propertion product by weight. After the fabric is passed ties of the untreated pure finish fabric and of through this solution and is well wetted out, it is 40 the treated fabric is shown below. 'I'he .table squeezed to remove excess solution and is then shows only the warp shrinkage. The llingv dried on a, tenter frame in air at around 180 F. shrinkage is always much lower in the untreated to dimensions. before impregnating. The dried fabric and is also satisfactorily controlled. The 'fabric is then cured in a tenter oven or loop dryer tensile strength and abrasion resistance of the oven in circulating air at 280 F. for 8 minutes, 45 fabric are not appreciably affected by the process. after which it is soaped, rinsed, and dried to the original pure finish fabric dimensions on a tenter shrinkage 0n washing. inches per 216ml frame. The resulting fabric is white, free from o o any odor, rm and resilient with greatly improved l [5 modified rayon washes-mildnsigai solution at 100 -120 F. for 30 resistance to shrinkage on washing, which effect is permanent to washing, and has improved resistance to creasing and crushing. A comparison washes Wim) wrm Wrp Wrp Wgm of these properties of the untreated pure finish fabric and of the treated fabric is shown below. untreated 3.5 3.9 4,43 4.25 4.20 The tensile strength and abrasion resistance of Treated 0 -1 -1 2 -1 the fabric are not appreciably affected by the process l l Denotes a gain.

Shrink-age on washing, inches per yard [5 modified rayon washes-mild soap solution at 100-l20 F. for 30 min.]

Warp Filling Warp Filling Warp Filling Warp Filling Warp Filling Washes 1 2 a 4 5 untreated 6.10 1.27 ara 1.50 7.13 1.47 7.03 1.30 7.2; 1.27 Treated 0 .1 0.2 .1 .1 .2 .1 .2 .1 .2

'I'he process loss is .9 inch per yard in the warp.

Crease resistance [Percentage recovery in one min. from a 180 fold formed under standard conditions] Per cent Untreated 7 Exmrns 3 A 2 x 2 twill, 70% spun viscose rayon and 30% spun acetate rayon fabric in the greige, made of blended /2-15 Z turns in the singles and 8 8 turns in the ply in both warp and filling yarns is desized, scoured and dried on the tenter frame. The loss on the above operation is 0.98 inch per yard corresponding to 2.7%. The white, pure finished fabric has a count of 56 x 47, and a weight of 8.8 oz. per yard. This fabric is then passed through an impregnating solution containing 60 cubic centimeters of glyoxal solution (of 30.2% glyoxal content by weight) 3 grams of oxalic acid and 40 cubic centimeters of a watersoluble. thermosetting alkyl urea formaldehyde condensation product (manufactured by Sharples Chemicals Company) per liter of solution. On a weight percentage basis this solution contains 2.25% glyoxal, .296% oxalic acid and 1.95% alkyl urea formaldehyde reaction product by weight. After the fabric is passed through this solution and is well wetted out, it is squeezed to remove excess solution and is then dried on a tenter frame in air at around 180 F. to dimensions before'impregnating. The dried fabric is then cured in a tenter oven or loop dryer oven in circulating air at 280 F. for 8 minutes, after which itis soaped, rinsed and dried to the original pure finish fabric dimensions on a tenter frame. The resulting fabric is white, free from any odor, firm and resilient, with greatly improved resistance to shrinkage on washing, which effect is permanent to washing, and has improved resistance to creasing and crushing, A comparison of these properties of the untreated pure finish fabric and of the' oxal, 2.98% voxalic acidv and 3.0% Aerotex M3 by weight. After the fabric is passed through this solution and is well wetted out. it is squeezed to remove excess solution and is then dried on a tenter frame in air at` around 180 F. to dimensions before impregnating. The dried fabric is then cured in a tenter oven or loop dryer oven in circulating air at 280 F. for 8 minutes, after which it is soaped, rinsed and dried to the original pure finish fabric dimensions on a tenter frame. The resulting fabric is white, free from odor, firm and resilient, with greatly improved resistance to shrinkage on washing, which effect is permanent to washing, and has improved resistance to creasing and crushing. A comparison of these properties of the untreated. Dure finish fabric and of the treated fabric is shown below.

The table shows only the warp shrinkage. The filling shrinkage is always much lower in the untreated fabric, and is also satisfactorily controlled. The tensile strength and abrasion resistance of the fabric are not appreciably aHected by the process.

Shrinkage on washing, inches per yard [5 modified rayon washes-mili?) soipl solution at 100-lm F. for

The process loss is .6 inch per yard in the warp.

. Grease resistance [Percentage recovery in one minute from a 180 fold formed under standard conditions] treated fabric is shown below. The tensile Per cent strength and abrasion resistance of the fabric are Untreated notappreciably affected by the process. Treated 60 shrinkage on washing, inches per yard [5 modiilcd rayon washes-mild soap solution at l00120 F. for 30 min.]

Warp Filling Warp Filling Warp Filling Warp Filling Warp Filling washes 1 2 3 4 5 Untreated 4 2.25 .a 2.11 .26 3.55 .4s 3.6 .se 3.91 .es Treated .1 `1 .1 0 O 0 .2 .l .2 0

The process loss is .8 inch per yard in the warp, EXAMPLE 5 I and .5 inch per yard in the filling.

Crease resistance [Percentage recovery in one min. from a 180 fold formed under standard conditions] Per cent Untreated 80 Treated 90 EXAMPLE 4 A 100% plain woven filament viscose rayon fabric made of 98 denier warp and 152 denier filling yarns, with a count of 92 x 70 and weighing 2.7 oz, per yard is desized, scoured and dried on the tenter frame. The loss in the above operation is .1 inch per yard correspondingto .3%. 'I'he white. pure finished fabric is passed through an above operation is 0.56 inch per yard corrcspond` ing to 1.6%. The white, pure finished fabric has a count of 69 x 55 and a weight of 4.7 oz. per yard. This fabric is then passed through animpregnating solution containing 60 cubic centi- Y meters of glyoxal solution (of 30.2% glyoxal conand 1.56% Aerotex M3 by weight.

tent by weight), 3 grams of oxalic acid, 30 grams of the water-dispersible urea formaldehyde condensation product designated as P364 Beckamine and 20 grams of the water-soluble melamine formaldehyde reaction product known as Aerotex M3, per liter of solution. On a weight percentage basis this solution contains 2.25% glyoxal, .296% oxalic acid, 2.24% P-364 Beckamine After the fabric is passed through this solution and is well wetted out, it is squeezed to remove excess solution and is then dried on a tenter frame in air at around F. to dimensions before impregnating. The dried fabric is then cured in a tenter oven or loop dryer oven in circulating air at 280 F. for 8 minutes, after which it is soaped, rinsed, and dried to the original pure finish fabric dimensions on a tenter frame. The resulting fabric is white, free from odor, firm and resilient, with greatly improved resistance to shrinkage on washing, which effect is permanent to washing, and has improved resistance to creasing and crushing. A comparison of these properties of the untreated pure finish fabric and of the treated fabric is shown below. The table shows only the warp shrinkage. The filling shrinkage is always much lower in the untreated fabric, and is also satisfactorily controlled. 'I'he tensile strength and abrasion resistance of the fabric are not appreciably affected by the process.

Shrinkage on washing, inches per yard modified rayon washes-mild soa solution at 100l20 F.

[Percentage recovery in one min. from a 180 fold formed under standard conditions] Per cent Untreated 50 Treated 80 EXAMPLE 6 A plain weave, 100% spun viscose rayon fabric in the greige, made of 28/1 warp and 14/1 filling yarns of spun rayon viscose rayon staple fiber is desized, scoured, and dried on the tenter frame. The white,pure finished fabric has a count of 66 X 41 and a weight of 4 oz. per yard. This fabric is then passed through an impregnating solution containing 60 cubic centimeters of glyoxal solution (of 30.2% glyoxal content by weight), 3 grams of oxalic acid, 45 grams of a water-dispersible condensation product of urea formaldehyde (produced by Reichhold Chemicals Inc., and designated as P-364 Beckamine), and 10 grams of NOPCO 1322-X neutralized with .5 gram oxaiic acid. NOPCO 1322-X belongs to the class of quaternary ammonium compounds referred to as cation-active softeners. On a weight percentage basis this solution contains 2.25% glyoxal, 0.346% oxalic acid, 3.36% urea formaldehyde reaction product, and 0.976% NOPCO 1322-X by weight. After the fabric is passed through this solution and is well wetted out, it is squeezed to remove excess solution and is then dried on a tenter frame in air at around 180 F. to dimensions before impregnating. The dried fabric is then cured in a tenter oven or loop dryer oven in circulating air at 280 F. for 8 minutes after which it is soaped, rinsed and dried to the original pure nish fabric dimensions on a tenter frame. The resulting fabric is white, free from odor, soft and resilient, with greatly improved resistance to shrinkage on washing, which effect is permanent to washing, and has improved resistance to creasing and crushing. A comparison of these properties of the untreated pure nish fabric and of the treated fabric is shown below. The table shows only the warp shrinkage. The lling shrinkage is always much shrinkage on washing, inches per yard [5 modified rayon washes-mild soa solution at 100120 F. for 30 min.

` Warp Warp Warp Warp Warp Washes 1 2 3 4 Untreated 6. 10 6. 53 7. 13 7. O3 7. 2i Treated 0 1 D l 1 4The process loss is 1.3inches per yard in th warp.

Crease resistance [Percentage recovery in one min. from l fold formed under standard conditions] Per cent 45 Untreated Treated EXAMPLE 7 A plain weave, spun viscose rayon fabric in the greige, made of 28/1 warp and 14/1 lling yarns of spun viscose rayon staple fiber is desized, scoured and dried on a tenter frame. The white, pure finished fabric has a count of 66 x 41 and a weight of 4 oz. per yard. 'Ihis fabric is then passed through an impregnating solution containing 60 cubic centimeters of glyoxal solution (of 30.2% glyoxal content by weight) 3 grams of oxalic acid, 45 grams of water-dispersible urea formaldehyde condensation product known as P-364 Beckamine, and 6 grams of the quaternary ammonium salt, octa decyl oxymethyl pyridiniumv chloride per liter of solution. On a weight percentage basis this solution contains 2.25% glyoxal, 0.296% oxalic acid, 3.36% urea formaldehyde reaction product and 0.56% quartemary compound by weight. After the fabric is passed through this solution and is well wetted out, it is squeezed to remove excess solution and is then dried on a tenter frame in air at around F. to dimensions before impregnating. The dried fabric is then cured in a tenter oven or loop dryer oven in circulating air at 280 F. for 8 minutes, after which it is soaped. rinsed and dried to the original pure finish fabric dimensions on a tenter frame. The resulting fabric is white, free from any odor, soft and resilient, with greatly improved resistance to shrinkage on washing. which effect is permanent to washing, and has improved resistance to creasing and crushing. The fabric is found to be water-repellent and retains most of its wa.- ter repellency through at least five launderings. A comparison of these properties of the untreated pure nish fabric and of the treated fabric is shown below. The table shows only the 'warp shrinkage. The filling shrinkage is always much lower in the untreated fabric, and is also satisfactorily controlled. The tensile strength and abrasion resistance of the fabric are not appreciably affected by the process.

Shrinkage on washing, inches per yard l', modified rayon washes-mild soa solution at l00120 F. for 30 min.

' The process loss is 1.5 inches per yard in the warp.

Crease resistance [Percentage recovery in one min. from a 180 fold formed under standard conditions] Per cent Untreated 45 Treated 95 -conversion of the cellulose. Apparently the same actiontakes place when the glyoxal is employed in association with a resin.

It is our belief that when cellulose bers are treated with a thermosetting resinous compound there is a ydefinite reaction between the cellulose and the resinous material and that some further condensation of the resinous material with itself also takes place during the curing operation.

We base our belief (with reference to the autocondensation of the resinous material) upon the fact that an increase inV wet strength of the fabric is observed when compared with the results produced by reacting the cellulose material wtih glyoxal alone. Apparently the combined treatment of cellulose fibers with glyoxal and a resinous material is to produce a fiber consisting in part of a reaction product of cellulose and glyoxal and in part of a reaction product of cellulose and the resinous material, with the resinous material in a more highly condensed state after curing than it was originally. Whatever actually takes place in the cellulose fiber when subjected to the combined treatment-with glyoxal and the thermosetting resin, it is certain that the physical characteristics of the fiber are thereby modified.

For ready comparison ofthe results obtained by the present invention with those obtained by prior usual methods of stabilization by the employment of resins alone, or bythe use of glyoxal alone as described in the aforementioned application, reference may be had to the table shown in the drawing. In this table. column A indicates usual losses in scouring; columnB the shrinkage of normal -(untreated) fabric during five standard laundry washings; column 1 indicates the shrinkage losses in fabrics which have been treated with glyoxal alone; column 3 shows the losses in fabric treated with resin alone: and co1- vumn 2 indicates losses in fabric treated with glyoxal together with a small mount of resinous condensation product.`

In each of the columns B and 1 'to 3 inclusive, :there is a subcolumn headed %5 and a second subcolumn headed %15. The column headed "%5 represents the total shrinkage of the treated fabric in iivemodiiied washes without any process or working loss allowed. The column headed %15" represents the difference in the measurements of the abrio between the first and fth wash, or in ther words, the progressive shrinkage between the first wash and the fifth wash. For example, if a fabric shows 3% shrinkase in the first wash and it still shows 3% shrinkage after the fifth Wash, the %15 shrinkage is 0.

The table shows that the addition of a small quantity of resin to the glyoxal produces better stabilization than results from the use of glyoxal alone. For instance, the results obtained in column 2 are in most instances considerably better than those obtained in column l.

12 The mixed process in which both glyoxal and resinous material are employed not only prol duces dimensional stability but also crushresistance. However, it is important to note -that the crush resistance is apparentlyproduced solely by the glyoxal since there is not sumcient resin to have any appreciable effect on crush resistance.

It will be observed that in no case is the quantity of resin employed in association with .the glyoxal even as much as 50% of the resin required when resin alone is used for stabilization.

It is also to be emphasized, as indicated by the above specific examples, that the resin in association with the glyoxal not only produces dimensional stability but also crush resistance. However, the crush resistance must be attributed to the glyoxal since there is not. suiiicient resin to produce crush resistance, it being notedthat for effective crush resistance it is necessary when using resin alone to employ even more than the 8% shown in column 6, in fact to employ 14% or more of the resin.

To illustrate .the neutral effect of the resin upon crease resistance, when used in the small percentages of the present invention, a fabric like that of Example 1 above described was stabilized using two different formulae as follows:

1. 60 cc. of glyoxal (30.2%) per liter, 3 grams of oxalic acid per liter.

2. 60 cc. of glyoxal (30.2%) per liter, 45 grams of P-364 Beckamine (75% resin content) per liter, 3 grams of oxalic acid per liter.

The following table shows the wash stability results obtained with these two treatments, with a working loss of 1.4 inches.

Warp shrinkage-5 modified washes washes 1 I 2 s 4 5 Untreated fabric 6. l 6. 5 7. l 7. 0 7. 2 Treated [abrio:

The following table shows the results with these same two treatments regarding tensile strength, crease resistance and abrasion resistance.

Thus while the addition of the small quantity of resin in accordance with the present invention does'improve shrinkage control or dimensional stability and in some cases may improve the finish of the fabric, it apparently contributes nothing substantial to the crush resistance of .the fabric. i.

As indicated in the above specific examples,

various types of resinous condensation product maybe used, among them the reaction product of urea and formaldehyde, known as dimethylol urea. Among the other resinous materials which are useful for the purpose is P-364 Beckamine. This is a reaction product of urea and formaldehyde in which the reaction or condensation is carried to the point where the material no longer forms a clear solution in water but actually forms an extremely fine dispersion. In fact, this product of urea and substituted urea with formaldehyde. The material is deflnitely film forming and produces a stable solution in water.

Another useful resin is Aerotex M3, a watersoluble reaction product of low molecular weight of melamine and formaldehyde. It is water-soluble and the solution is quite stable on storage. It appears to be i'llm forming from water solution to a certain degree.

It is also to be observed as indicated vin the above specific examples, that more than one resin may be used in association with the glyoxal in the treating bath, but in any event the total quantity of resinous material is quite low, in fact substantiallyless than one-half the amount of resinous material which `would be lrequired for stabilization if no glyoxal were employed. For best results it appears that substantially the same limiting quantities of glyoxal should be used as when glyoxal is employed alone, while the quantity of resinous material would appear to be within a range of from 1% to 5% of the solution by weight.

When it is desired to impart a. soft hand or feel to the fabric a cation-active softener is added to the treating bath in an amount approximately 1% by weight of the bath.

The term cation-active as used in the present sense, simply means that the active part of the molecule in these compounds is the cation rather than the anion, as is usual with many of the present finishing agents and dyes. Most cation-active compounds may be considered as derived from ammonium hydroxide NH4OH where one or more of the Hs are replaced by complex organic radicals. One type includes the quaternary ammonium compounds. Some are relatively simple while others are extremely complex products containing nitrogenous bases, such as pyridine, quinoline, acridine replacing the Hs in the NH4 group. The possibilities in new compounds of this type seem unlimited.

'I'he empirical formula of the pyridinium compounds can be represented by R-coNH-cHz-Ndem-x wherein R stands for an alkyl radical containing not less than 8 C atoms.

The group N(tert) represents the molecule of a tertiary base such as trimethylamine or pyridine.

X represents the acidic radical, preferably of a weak acid as typified by acetic or formic.

Mode of synthesis Heat together an acylamidomethylol compound, for instance stearoamidomethanol with a salt of pyridine corresponding to the iinal salt desired, for instance pyridine hydrochloride in anexcess of the free base.

Reaction proceeds according to the following equation:

R-CONH-ClIzOH H-N-X The above synthesis does not apply where the acid radical selected for X is the radical of a weak acid, for instanceacetic or formic. For wealr acid as acetic R-CONH-CHr-O-COCH: N -4 R-CONH-CHaiD-COOH:

While certain examples have hereinabove been given as illustrative of the utility of this invention, we consider it to be applicable to a wide variety of textile materials including fibers, yarns and fabric of (1) Regenerated cellulose a-Viscose b-Cuprammonium c-Saponified acetate (2) Cotton cellulose (3) Mixtures-Major part cellulose a-Viscose-acetate b-Viscose-aralac (casein) c-Viscose-soya bean protein d-Viscose-peanut protein e-Viscose-Wool i f-Viscose-cotton (4) Spun and iilament yarns.

It is to be understood that the above are merely by way of example and not by Way of limitation, and that the invention is inclusive of all modifications and equivalents falling within the terms of the appended claims.

1. The method of stabilizing regenerated cellulose textile material which comprises as steps impregnating the material with an aqueous glyoxal solution containing between 0.6% and 4.65% by weight of glyoxal, an acid catalyst and an amino-formaldehyde thermosetting resinous condensation product in amount between 1% and 5% of the solution by weight, removing the material from the solution, and baking the material at a temperature between 212 F. and 350 F.

2. The method of stabilizing textile fabric predominantly of yarns of regenerated cellulose which comprises as steps immersing the fabric in an aqueous solution containing glyoxal. approximately in the amount of 0.6% to 4.65% by weight in the treating solution, an amino-formaldehyde thermosetting resinous condensation product in total amount between 1% and 5% by vweight of the solution, and oxalic'acid, expressing excess nasse 3. The method of stabilizing textile fabric predominantly of yarns of viscose rayon Iwhich comprises as steps immersing `said fabric in a water solution `containing between 0.6% and 4.65% by weight of glyoxal, between 1% and 5% by weight of an amino-formaldehyde thermosetting resinous water-dispersible condensation product,A and between 0.0125% and 0.40% weight, until it is thoroughly wet, extracting excess liquid, drying the fabric, and baking the fabric to react the glyoxal with the cellulose of the yarn. L

4. 'I'he method of stabilizing textile fabric predominantly of yarns of. regenerated cellulose which comprises as steps immersing said fabric in an aqueous treating medium containing from 15 to 120 cc. of an approximately 30% glyoxal solution (30.2% glyoxal by weight) and from 20 to 50 grams of a Water-dispersible urea-formaldehyde condensation product per liter of solution acid catalyst by and an acid catalyst, until it is thoroughly wet, drying the fabric,- baking it at a temperature between 212 F. and 350 F. for a period of from two minutes to forty minutes, thereby to react the cellulose of the yarns with the glyoxal, and washing, rinsing and drying the fabric.

5. As a new article of manufacture, the product producedvaccording tothe method set forth in claim 1.

,6. As a new article of-manufacture, the product produced according to the method set forth in-claim 2.

7. As a new article of manufacture, the product produced according to the method set forth

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