US3573971A - Process of making permanent-press fabrics and garments - Google Patents

Abstract

A PROCESS FOR TREATING FABRICS TO PROVIDE PERMANENTPRESS PLEATS, CREASES, ETC., WHILE MAINTAINING SOFT "HAND" AND GOOD COLOR FASTNESS, WHICH COMPRISES APPLYING A SPECIFIC TREATING COMPOSITION TO THE FABRIC, THEN PRESSING IN THE PLEATS, CREASES OR THE LIKE, SEWING THE FABRIC INTO A GARMENT OR THE LIKE WHEN SO DESIRED, AND THEN CURING THE COMPOSITION IN SITU. THE SPECIFIC COMPOSITION IS FORMED BY REACTING AN AQUEOUS FORMALDEHYDE-UREA SOLUTION WITH UREA UNDER ALKALINE CONDITIONS, HEATING THE MIXTURE TO A PREDETERMINED TEMPERATURE, ADDING AN ALCOHOL AT ACIDIC PH, HEATING AGAIN TO A PREDETERMINED TEMPERATURE, NEUTRALIZING THE PH OF THE MIXTURE, STRIPPING OFF THE VOLATILE MATTER, AND THEN ADDING A LOWERALKYLCARBAMATE TO THE RESIDUE AND REACTING FURTHER AT AN ALKALINE PH AT A PREDETERMINED TEMPERATURE FOR A PERIOD SUFFICIENT TO CAUSE THE REACTION TO GO TO COMPLETION. THE ESSENTIAL STEP IN THIS PROCESS IS THE ADDITION OF THE LOWERALKYLCARBAMATES AS THE LAST STEP. THE TERM "LOWERALKYLCARBAMATE" INCLUDES NOT ONLY UNSUBSTITUTED ALKYLS BUT SUCH SUBSTITUTED LOWER ALKYLS AS METHOXY AND HYDROXYLOWERALKYL.

Description

United States Patent 3,573,971 PROCESS OF MAKING PERMANENT-PRESS FABRICS AND GARMENTS Sidney Cohen, Hillsdale, Thaddeus A. Gulakowski, Ridgefield, and Phillip Adams, Murray Hill, N.J., assignors to Millmaster Onyx Corporation, New York, N.Y. No Drawing. Continuation of application Ser. No. 688,327, Dec. 6, 1967. This application Nov. 14, 1969, Ser. No. 877,017

Int. Cl. D06m /54 US. Cl. 117-139.5 1 Claim ABSTRACT OF THE DISCLOSURE A process for treating fabrics to provide permanentpress pleats, creases, etc., while maintaining soft hand and good color fastness, which. comprises applying a specific treating composition to the fabric, then pressing in the pleats, creases or the like, sewing the fabric into a garment or the like when so desired, and then curing the composition in situ. The specific composition is formed by reacting an aqueous formaldehyde-urea solution with urea under alkaline conditions, heating the mixture to a predetermined temperature, adding an alcohol at acidic pH, heating again to a predetermined temperature, neutralizing the pH of the mixture, stripping 06 the volatile matter, and then adding a loweralkylcarbamate to the residue and reacting further at an alkaline pH at a predetermined temperature for a period sufiicient to cause the reaction to go to completion. The essential step in this process is the addition of the loweralkylcarbamates as the last step. The term loweralkylcarbamate includes not only unsubstituted alkyls but such substituted lower alkyls as methoxy and hydroxyloweralkyl.

This is a continuation of co-pending application Ser. No. 688,327, .filed Dec. 6, 1967, now Pat. No. 3,497,471.

This invention relates to the treatment of fabrics, particularly of the wash-wear type, and of garments made therefrom, wherein, even after repeated launderings or dry cleaning, pleats, creases, or the like, applied to the fabrics during the process of manufacturing, are retained, whereas, wrinkles, creases, etc., appearing in the fabrics or garments after the completion of manufacture are removed during laundering or dry-cleaning.

The particular process in which the present invention is utilized is the so-called delayed-cure process wherein the treating composition, containing a resin finish, is applied to the fabric prior to its being made up into a garment, but wherein the composition is not cured until the garment has been completed and the required pleats, creases, or the like have been formed.

Heretofore, in delayed-cure processing, it was the general practice to employ as the resin finish either (a) a dimethylol-dihydroxyethyleneurea condensation product made from glyoxal, formaldehyde and urea, or (b) a uron-resin formed by the reaction of urea, Formalin, paraforrnaldehyde and methanol, most frequently employed in the crude (undistilled) form, or (c) a so-called uron type resin formed by the reaction of a formaldehyde-urea-solution and urea.

The aforementioned processes, however, had various disadvantages in accordance with the particular resin finish used. One such disadvantage was the excessive amount of obnoxious formaldehyde fumes in the uncured (and, often, even in the cured) fabrics because of the excessive amount of free formaldehyde present. This was particularly true of the so-called uron type resin. In order to avoid these fumes, it was necessary to repeatedly add water to the composition and to vacuum-distill-off this water and formaldehyde between each water addition.

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This continued heating, however, had the effect of forming appreciable amounts of undesirable polymerized resin which, in turn, produced a harsh, boardlike" effect on the hand of the treated fabric, especially, when the fabric contained synthetic fibers, such as nylon, polyester, Acrilan, acrylic fibers, and the like. The present process eliminates this necessity of repeated water-addition and distillation.

Another disadvantage of many of the prior processes was that the ratio of bound formaldehyde to urea in the resin, especially in the dimethylol-dihydroxyethyleneurea type resin, was undesirably low, i.e., no more than about 2: 1. The greater the crosslinking effect caused by the reaction of the OH groups of cellulosic materials and bound formaldehyde, the better the wash-wear performance. In the present process, the resin finish has a ratio of bound formaldehyde to urea which is, generally, greater than 2.5: 1.

Another great disadvantage of most prior processes was the yellowing that occurred when white or light- 4 colored fabrics were cured. An important advantage of the present process is that it completely eliminates this yellowing effect while simultaneously retaining all the advantages of the prior type processes such as satisfactory tensile strength, tear strength, flex abrasion strength and wrinkle recovery. At the same time, the present process also provides a greatly improved (softer) hand.

The present process further provides high stability of the treated, but uncured fabrics, even when drying has been carried to extremely low moisture levels.

In accordance with the present invention, the essence of the improvement resides in the preparation of a uron type resin wherein, after the volatile matter has been stripped-off in vacuo, a solution of alkylcarbamate is added to the residue. Further reaction is then permitted to take place between the residue and the alkylcarbamate. The product resulting from this reaction is utilized as the resin finish in the present process.

The term alkyl carbamate, as used herein, includes both unsubstituted alkyl groups and such substituted alkyls as methoxyalkyl and hydroxyalkyl. The alkyl is also preferably a lower alkyl such as methyl, ethyl, propyl, and isopropyl.

The following examples illustrate the present invention, with no intent, however, to limit the invention except as claimed:

EXAMPLE 1 Into a closed, agitated and jacketed reactor, equipped with vacuum distillation means, was charged the followmg:

Components: Parts by weight U.F.- concentrate (an aqueous mixture containing, by Weight, 60% formaldehyde and 25 %ureamanufactured by Allied Chemical Co.) 3,330

Urea (solid) 120 Aqueous NaOH, 25% strength (or sufiicient to bring the pH of the mixture to about 10.5) 17 This mixture may be heated to a temperature of between about 50 to C. for from about 1 to 3 hours. In this case, it was heated, with agitation, to the preferred temperature of about 7080 C. for about 2 hours, after which 1,500 parts by weight methanol and 75 parts by weight 20 B. HCl were added, to bring the pH to between about 4.0-5.0.

The mixture was then heated under reflux (about 85 C.), and with agitation, for about 40 minutes (although the time may vary between about 15 minutes to 1 hour), after which it was neutralized and brought to a pH of about 8.5 with 25% caustic soda (about parts by weight).

The volatile matter was then stripped off in vacuo (at about 28 inches) until the residue assayed about 70% by weight of dry solids.

To the residue was then added an 80% by weight solution of methoxyethylcarbamate in an'amount equivalent to about 6% by weight, of the resin in the residue (although about 4 to 8% by weight may be used). The pH was then adjusted to about 10.0 and the reaction was then continued at about 50 C. for two hours.

At the end of the two hour period, the pH was adjusted to about 8.0 and the mixture was filtered.

Analysis of the final product revealed a total active content of 82% by weight, consisting of 77% by weight of dry solids and 4.9% by weight of free formaldehyde. The ratio of bound formaldehyde to urea was 2.71:1.

EXAMPLE 2 A number of separate runs of the same process were carried out as in Example 1 and using the same components and proportions except that in each of these runs a different material was substituted for the methoxyethylcarbamate. These substituted materials were as follows: (a) methylcarbamate, (b) ethylcarbamate, (c) propylcarbamate, (d) isopropylcarbamate, (e) methoxypropylcarbamate, (f) methoxyisopropylcarbamate, (g) hydroxyethylcarbamate, and (h) hydroxypropylcarbamate.

EXAMPLE 3 Into the same reactor as in Example 1 were charged the following: 3

Components: Parts by weight U.F.-85 concentrate 3,300 Urea 94 Aqueous NaOH, 25% strength (or suflicient to bring the pH of the mixture to about 10.5) 10 The mixture was heated, with agitation, to 210 F. After minutes, a vacuum of about 28 inches was drawn and as much water as possible (about 525 parts by weight) was distilled off. The mixture was then cooled to 90 F. and the vacuum was released.

There were then added about 1,650 parts by weight methanol and about 85 parts by weight 'B. HCl.

After about 40 minutes, the mixture was neutralized and brought to a pH of about 8.0 with about 100 parts by weight of 25 NaOH, and the mixture was then vacuum stripped. At this time, the free formaldehyde content was about 12% by weight relative to the Weight of the finished product which had a solids content of about 70% by weight. About 100 parts by weight of water was added, and the mixture was again vacuum-stripped under agitation. Five repetitions were required to obtain the required result as shown by analysis which revealed a total activity of about 81.3% by weight, of which solids constituted 76.5% and free formaldehyde 4.8%. The ratio of bound formaldehyde to urea was 2.05:1. The pH was then adjusted to about 8.0 and the mitxure was filtered for clarification.

(B) The crude uron was then distilled in vacuo at about 1 mm. pressure. The main cut assayed 98% by Weight as dimethyloluron dimethyl ether.

(C) A portion of this distillate was then shaken 'with activated carbon and filtered for the purpose of decolorization.

In order to determine the relative softness or hand of fabrics treated with the present composition and those treated with prior type compositions, tests were run as in the following examples:

EXAMPLE 5 A /35 polyester/cotton poplin fabric, a 15/ 10 rayon acetate/nylon fabric, and a 50/35/15 Acrilan/ rayon/ acetate fabric were padded with the following bath:

Bath composition: Parts by weight Product of Example 1 12.0

Mixed zinc-magnesium catalyst 5.5 40% active, reactive acrylic resin 2.5 Water 80.0

The term 40% active refers to the concentration of the resin in the product, while the term reactive means capable of cross-linking.

The samples were dried for 2 minutes at 250 F. and then cured for 10 minutes, at 340 F.

EXAMPLE 6 The same type fabrics as in Example 5 were treated by 0 padding in the same bath as in Example 5 except that the product of Example 3 was substituted for the product of Example 1. These samples were then dried and cured in the same manner as in Example 5.

EXAMPLE 7 The treated samples of Examples 5 and 6 were evaluated for hand with the following ratings.

In order to determine color fastness and crease angle recovery, various tests were made, as in the following examples:

EXAMPLE 8 White cotton broadcloth, and white 65/ 35 polyester cotton shirting were treated by padding in baths containing respectively the products of Examples 1 and 3 at the 16% level and the products of Examples 4A, 4B and 4C at the 12% level. Zinc nitrate catalyst was used in each case. All the samples were dried for 1 /2 minutes at 260 F. and then cured at 340 F. for 15 minutes. Evaluation tests were limited to crease-angle recovery and discoloration after cure. In no case were either optical brighteners or tints used in order that actual color changes could be observed. The results were as follows:

TABLE 1 B. White 65/35 polyester/cotton A. White cotton broadcloth shirting EXAMPLE 4 (A) A crude dimethyloluron dimethyl ether was prepared from urea, Formalin, paraformaldehyde and methanol by the method described in U.S. Pat. No. 3,089,859. It contained 71% by weight of the uron.

The crease angle recovery was obtained by means of the Monsanto crease angle recovery method (Method CCC Tl9lB-52l2) hereinafter further discussed.

The fabrics made in accordance wtih the present invention (Ex. 1) are shown to be clearly superior to each of the other fabrics with regard to color fastness while the crease angle recovery was superior in every instance except one.

EXAMPLE 9 The following fabrics were padded on a one-dip, onenip, two rubber-roll padder at 40 tons pressure, at 80- 90 -F. utilizing the following bath composition:

(a) White, 100% cotton duck.

(b) Multicolor floral print, 100% cotton duck.

(e) White, 100% cotton sateen.

(d) Multicolor floral print, 100% cotton sateen.

(e) Natural, 50% polyester/50% cotton hopsacking.

The bath composition was as follows:

Bath composition: Parts by weight The term active has the same meaning as in Example 5.

The samples were dried at 280 F. in a 45 foot gas-fired entirely-housed clip frame. The cotton sateens were run at 28 yards per minute, the cotton ducks and the hopsacking at 25 yards per minute.

The sensitized (treated, but uncured) fabrics were then pressed on a Prosperity Press, Model #249MU, at 300 F. and medium pressure, programmed at seconds steam, 15 seconds bake, and 5 seconds vacuum. The cotton fabrics were cured for 15 minutes at 325 F. while the polyester/ cotton fabric was cured for minutes at 340 F.

EXAMPLE 10 Samples of the same fabrics as in Example 9 were padded in the same manner as in that example and under the same conditions, except that the following bath was used:

40% active, reactive acrylic resin emulsion 2.0 30% active polyethylene emulsion 4.0 Zinc-nitrate catalyst 4.0 Water 68.0

The terms active and reactive have the same meaning as in Example 5.

The samples were dried in the same manner as in Example 9, except that the sateens were run at 30 yards per minute and the ducks and hopsacking at 28 yards per minute.

Pressing was carried out in the same manner as in Example 9. The cotton fabrics were cured for 10 minutes at 320 F. and the hopsacking for 10 minutes at 340 F.

Here, too, neither optical brighteners nor tints were used in order that actual color changes could be readily observed.

In color fastness tests it was observed that the white fabrics treated with the composition of Example 9, when compared with untreated samples of the same fabrics, showed either no discoloration at all or just a very faint, hardly noticeable yellowing. The same fabrics treated with the composition of Example 10, on the other hand, showed deep discoloration in every instance, this discoloration ranging from pale but quite noticeable yellow to almost brown.

The colored fabrics treated in accordance with Example 9 showed no observable change of tint, whereas, the fabrics treated in accordance with Example 10 showed marked discoloration wherein the reds acquired a bluish to purplish cast, oranges and greens turned muddy, and blues became greenish.

The improved hand and color fastness of the fabrics treated in accordance with the present invention should also retain such desirable characteristics as satisfactory smoothness, tensile strength, tear strength and flex abrasion, as compared with fabrics treated in accordance with the commonly used prior processes. It Was found that fabrics treated in accordance with the present invention were, in most cases, at least as good and, in many cases, better than those fabrics treated in accordance with prior processes.

The testing methods used for these purposes were as follows:

(A) From the Federal Specification, Textile Test Methods:

(l) Tear strengthmethod CCC-T-19lB-5132 (2) Flex abrasion resistanceMethod CCC-T- 19113-5300 (3) Monsanto crease angle recovery Method CCC-T-19 1B-52l2 (B) From the 1964 Technical Manual of the American Association of Textile Chemists and Colorists:

(1) Crease retention ratingAATCC Method No.

(2) Wash/Wear ratingAATCC Method No. 88-

(3) Flat frosting abrasionUnoflicial tentative method, not yet printed.

(C) From the Westinghouse Electric Corporations Manual, Standard Home Laundering at 140 F. the Westinghouse Laundromat:

(1) Shrinkage, percent (D) From the American Society for Testing Materials,

ASTM Standards on Textile Materials:

(1) Tensile strength, grab method Method All of the samples of the fabrics treated in Examples 9 and 10 were evaluated for smoothness, crease retention and shrinkage after one and five washings. The 100% cotton ducks and the white 100% cotton sateen were tested for tensile strength, tear strength, flex abrasion and wrinkle recovery. The three printed fabrics were tested for flat frosting abrasion. The following tables record the results. Unfinished material was used as the Control for the purpose of comparison. Wrinkle recovery was recorded as the sum of warp and fill recoveries in degrees:

TABLE 2 A. 100% cotton duck-multicolor floral print B. 100% cotton duck-white C. 100% cotton sateen-white Example 9 Example 10 Example 9 Example 10 Example 9 Example 10 Control treatment treatment Control treatment treatment Control treatment treatment Test Warp Fill Warp Fill Warp Fill Warp Fill Warp Fill Warp Fill Warp Fill Warp Fill Warp Fill Tensile strength (lbs) 108 54 83 30 72 25 111 69 36 64 27 47 88 36 50 34 39 Tear strength, grams 1, 696 1,408 2, 568 800 2, 176 736 1, 952 1,696 2,016 960 1, 824 640 1, 216 864 1,024 704 736 512 Flex abrasion, cycles.... 270 154 351 161 177 82 164 86 287 101 91 34 214 454 457 496 20 41 Wrinkle recovery, total W & F 163 277 279 169 293 287 143 294 298 The following table is based on the Flat Frosting Abrasion Test utilizing 2.5 lb. head load and 1,200 cycles:

The wash/wear, shrinkage and crease retention characteristics of the fabrics of Examples 9 and 10 are listed in the following table:

TABLE 4 The completed garment was, thereafter, laundered in a washing machine, at 140 F., using Tide detergent, for a full machine cycle, after which it was tumble-dried. The garment retained its pleats unwrinkled, and the seams remained unpuckered.

Obviously, many modifications of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that within the scope of the appended claim, the invention may be practiced otherwise than as specifically described.

The invention claimed is:

1. A fabric impregnated with a bath containing, as the active ingredients, a catalyst and a composition made by reacting an aqueous formaldehyde-urea mixture wherein Crease Percent shrinkreten- W ash/wear age, W tion Treatment, 1 and 5 Fabric example 1 wash 5 wash 1 wash 5 wash wash Red cream 9 5.0 5.0 0. 5/0. 0. /0. 0 5 Cotton duck. 5.0 5.0 0. 5/1. 0 0. 5/1. 0 5 White cotton (in 9 4. 4 4. 1 0. 5/0. 5 1. 0/0. 5 5 10 4. 5 4. 3 0.5/0.0 0.5/0.5 5 White 9 4. 5 4. 1 0.0/0. 5 0. 5/1. 0 5 Cotton sateen 10 4. 5 4. 1 0.0/0. 5 0. 0/0. 5 5 Blue/ Green- 9 5.0 4. 7 0. 0/0. 0 0. 5/0. 5 5 Cotton sateen 10 5. 0 4. 7 0. 5/0. 5 0. 5/0. 5 5 Red/Green 9 5. 0 5.0 O. 0/0. 5 0. 5/1. 0 5 Cotton sateen 10 5. 0 5. 0 0. 0/1. 0 0. 0/1. 0 5 Poly/cotton hopsacking 9 4. 7 4. 3 0. 5/0. 5 1. 0/0. 5 5 10 4. 5 4. 3 1. 0/0. 0 1.0/0. 5 5

The above table indicates that the wash/ wear, shrinkage and crease retention of the fabrics treated in accordance with the present invention (Ex. 9) are, generally, as good as those treated in accordance with prior processes.

In order to determine the storage characteristics of the fabrics treated in accordance with the present invention, the following test was run, as in the following example:

EXAMPLE 1 l cured and treated as above. It was found that the performance of these fabrics was substantially the same as those of Example 9.

The following example illustrates the use of the present invention in making a garment:

EXAMPLE 12 A 75/15/10 rayon/acetate/nylon fabric treated in the manner of Example 5 except that the curing step was omitted was cut and sewn into a dress, the dress was finished and pressed, with pleats being pressed into place. It was then hung on a rack and introduced into a curing oven where it was cured at 320 F. for 10 minutes, thereby setting the pleats.

the amount of formaldehyde exceeds the amount of urea, with urea at a temperature of about 4090 C. for about 1 to 3 hours, while maintaining the pH of the mixture greater than 10.0, to form methylolated urea and its low polymers, then adding an amount of a lower aliphatic alcohol in excess of the amount required to etherify the methylol groups on the acid side, while maintaining the pH at about 4.0-5.0 by the addition of an acid, thereafter agitating the mixture at reflux temperature for about 15 to 60 minutes, followed by neutralization and the addition of an alkali to bring the pH to about 8.5 thereafter stripping 01f the volatile matter, then adding an amount of lower-alkylcarbamate wherein the alkyl contains less than 4 carbon atoms, equivalent to about 4.0 to 8.0% by weight of the solids content of the residue, and adjusting the mixture to a pH of about 10.0 while maintaining the mixture at a temperature and for a time sufiicient to substantially complete the reaction between said residue and the loweralkylcarbamate.

References Cited UNITED STATES PATENTS 2,950,553 8/1960 Hurwitz 117139.4X 2,974,432 3/1961 Warnock et al. 117-l39.4X 3,138,802 6/1964 Getchell 117143X 3,268,915 8/1966 Warnock et al. 117l39.4X

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