US3523033A - Pressure wet-fixation of resins in cellulosic fabrics by the action of heat and pressure - Google Patents

Description

United States Patent U.S. Cl. 11765.2 2 Claims ABSTRACT OF THE DISCLOSURE The purpose of this invention is to wet-fix N-methylol resins in cellulosic fabrics by the action of heat and pres sure to produce fabrics capable of resisting wrinkling or mussing throughout a reasonable wear life. Pressure wetfixation is accomplished by either of two methods, a onestep or alternatively a two-step process. The advantage of the two-step padding method over that known in the prior art as wet-fixation is a reduction in the time required to wet-fix the N-methylol resins in the cellulosic fabrics. The other simpler method, the one-step padding method, has the advantage that it eliminates one of the padding, washing and drying steps.

A nonexclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

Because of their poor resiliency, cellulosic textile fabrics tend to become wrinkled in use and acquire a mussed or unplesant appearance. To overcome this objectionable property, it has been the practice to treat or finish cellulosic textiles with the methylol derivatives of organic nitrogen compounds, such as urea, ethyleneurea, guanidine, maleamine, and the like. These agents produce a finished cellulosic fabric that has improved resistance to wrinkling or mussing and give to the fabric the ability to dry smooth after laundering. A serious drawback results since the cellulosic fabrics are damaged during these treatments, thereby reducing the wear life of the treated cellulosic fabrics.

A wet fixation method was devised by Workers of the National Cotton Council and Harris Research Laboratories to overcome damage to the cellulosic fabrics during treatment. In this method of treatment, the cellulosic fabrics are impregnated with a solution which deposits resins inside the wet, swollen cellulosic fiber. This is accomplished by padding an N-methylol resin-mineral acid solution on the fabric, heating the fabric in a closed or semiclosed container for 15 minutes at 180 F., neutralizing in sodium carbonate solution, washing, and drying. The heating re-- sults in deposition of the resin in the fiber in such a manner that it is not removed by washing and so sustains the fibers in a somewhat swollen condition. Subsequent application of a crosslinking catalyst, followed by a hightemperature dry cure, results in only modest loss of fabric strength as compared with conventional pad-dry-cure processing.

According to the developers of the wet-fix process, the important factor in arriving at good strength properties of the finished fabric and high levels of fabric performance, both in resistance to wrinkling and good crease retention, is the use of two resin components. One of these, called a polymer builder, acts to swell the fibers and keeps them in a swollen state (melamine derivatives are 3,523,033 Patented Aug. 4, 1970 particularly effective in this regard); the second component, primarily a crosslinking agent for cotton, contributes only moderately to the swelling of the fiber but enhances wet wrinkle recovery and, once catalyzed and dried, imparts high dry wrinkle recovery to the fabric (dimethyloldihydroxyethylene urea and dimethylol carbamates are good examples of this class).

In mill trials cellulosic fabric is impregnated with the resin solution, made into rolls, sealed, and rotated overnight while wet fixation is taking place. Difficulty has been experienced in achieving good yarn penetration in plant runs. In short, the laboratory procedure of wet-fix is not directly applicable to mill runs; in addition, it requires more steps than the procedures normally used in the prior art to achieve resistance to wrinkling and mussing. Mill runs have not given the desired yarn penetration, nor is the method applicable to continuous processing.

For the purposes of the instant invention, the fabrics used were an x 80 cotton printcloth (3.2 oz./sq. yd.) which was desized, scoured, and bleached; and a white, 7 02., cotton twill from Testfabrics, Inc. (#413).

The press used was a standard hot-head press on which I the time the press was closed could be manually controlled. The air pressure was adjustable, but the steam pressure was constant; however, the steam controlled temperature increased with the length of time that the press was closed.

The properties of the cellulosic fabrics which were finished by the methods of this invention are illustrated in the following discussion and examples. All parts and percentages described are by weight. The degree of wrinkle resistance in the finished textile is shown by the wrinkle recovery angle, determined by the American Society for Testing Materials Test Dl424-56T. The tearing strength of the fabrics is obtained by the Elmendorf method, American Society for Testing Materials Test D1424-63. The Stoll fiex abrasion resistance of the fabrics is determined by the American Society for Testing Materials Test D117 5-64T. The laundry tests with simulated trouser cuffs were evaluated after repeated laundry wash-tumble dry cycles. A four-pound load was washed in 18 gallons of water on a normal laundry cycle set for eight minutes using a wetting agent as detergent. Water temperature control was set for a hot (61 C.) wash and warm rinse. After washing, the cuffs were tumble dried for 30 minutes in a gas-heated dryer at about 60 C. Each cuff was then inspected for abrasive damage. The breakage of either a warp or filling yarn was classified as minor damage. The breakage of both a warp and a filling yarn to form a detectable hole was classified as major damage. Wash-wear ratings were obtained by the Monsanto Overhead Lighting method.

The mechanism by which the resins mentioned produce the wrinkle resistant and smooth drying properties without seriously affecting the wear life of the cellulosic fabric in our new pressure wet-fix process is essentially the same as that described previously for the 'Wet-fix process. That is, N-methylol resins are deposited inside the wet, swollen cellulosic fiber in such a manner that they are not removed by washing, thereby sustaining the fibers in a somewhat swollen condition. However, by reason of the fact that pressure is applied, resin penetration is accomplished in a shorter time; in addition, the N-methylol resins penetrate the fibers evenly, resulting in an even distribution of resin throughout the fabric.

An object of this invention is to provide a method for treating or finishing cellulosic textiles whereby the textile is rendered resistant to wrinkling or mussing during use and will have improved smooth drying properties after laundering without impairing the wear life of the cellulosic fabric. This was accomplished by padding cellulosic fabrics with solutions of the following compositions:

(1) About from 5 to percent solids of a polymer builder of the methylated methylolmelamine type resin from the group consisting of Aerotex 23S, Aerotex M3, and Melrez MF, about from 5 to 10 percent solids of a crosslinking resin, dimethyloldihydroxyethyleneurea (Permafresh 183), and about from 80 to 90 percent water. The solution was adjusted to about from pH 2 to pH 6 with hydrochloric acid and allowed to remain about 30 minutes at room temperature. The solution was adjusted before padding to about from pH 2 to pH 6 with sodium hydroxide, or alternatively.

(2) About 10 percent solids of a polymer builder, hexamethyoxymethylmelamine (Cymel 301) and about 10 percent dimethyloldihydroxyethyleneurea (Permafresh 183), 13.6 percent absolute ethyl alcohol, and 66.4 percent water. The solution was adjusted to a pH of about 6, if necessary and used for padding after thorough mixing at room temperature.

After padding to about 80 percent wet pick-up with the selected treating solution, the fabrics were placed either in plastic bags or between sheets of aluminum foil and pressed in a hot-head press for about from 1 to 4 minutes under about from to 90 p.s.i. pressure with a temperature increase of about from 60 to 120 C., cooled in the container, and after cooling the wet fabrics were washed. After drying, the fabrics were padded with a solution containing about 4 percent magnesium chloride hexahydrate as the catalyst, about 2 percent polyethylene emulsion (Polymul CS81) as the softener, and 94 percent water. The fabrics were dried for about 7 minutes at about 60 Cv in a forced draft oven. The fabrics were either cured in a forced draft oven for about from 3 to 5 minutes at about 160 C. or stored for subsequent curing.

In the earlier experiments aluminum foil was used to seal in the volatile components during pressing; however, plastic bags proved to give a more efficient seal, as the heat softened bag sealed itself under pressure. Since the heat softens the plastic bags during pressing, it is necessary to insulate the bags from the press. A double thickness of cloth on both sides of the plastic bag eliminated this problem. Fabrics removed from the textiles whereby the textile is rendered resistant to wrinkling or mussing during use and will have improved smooth drying properties after laundering without impairing the wear life of the cellulosic fabric. This was accomplished by padding a cellulosic fabric in a solution of the following compositions: about from 5 to 12 percent solids of a polymer builder of the methylated methylolmelamine type resin from the group consisting of Aerotex 23S and Aerotex M3, about from 5 to 12 percent dimethyloldihydroxyethyleneurea (Permafresh 183), about from 4 to 5 percent of a catalyst, magnesium chloride hexahydrate, about from 2 to 3 percent of a softener, polyethylene emulsion (Polymul CS81), and about from 69 to 84 percent water. The solution was at pH 6, and no adjustment was made during treatment of the fabric. After padding to about 80 percent wet pick-up, the fabrics were placed in plastic bags and pressed for about from 3 to 5 minutes under about 27 p.s.i. pressure with a temperature increase of about from 60 to 115 C. On cooling, the heat sealed plastic bags were opened and the wet fabrics were dried about from 5 to 10 minutes at about 60 C. in a forced draft oven. The fabrics can be made into garments or stored for future garment preparation. Curing can be carried out in a forced draft oven at. about 160 C. about from 3 to 5 minutes.

The data in Table I show that the dry (or conditioned) fabrics treated by the pressure wet-fix method are of relatively low wrinkle resistance after the pressure wet-fix step. This is shown with treatment C. The cured fabrics have conditioned wrinlele recovery angle values above those of the controls while the uncured are not improved. Fabrics remaining in the hot-head press for one minute at 88 p.s.i. pressure showed some increase in conditioned wrinkle recovery angle over the valves for the controls; the better conditions appeared to be 3 minutes in the hothead press at 27 p.s.i. pressure. Although fabrics were allowed to remain in the hot-head press for 7 minutes at 27 p.s.i. pressure, the overall properties of the treated fabrics did not improve. Treatment D shows that as the time in the hot-head press increases, the conditioned and wet wrinkle recovery angles increase while the tearing strength and abrasion resistance values decrease. Satisfactory results were obtained at pH 4 but there was no plastic bags were wet and limp while those removed advantage over that obtained at pH 6.

TABLE I.TWO STEP PADDING METHOD OF PRESSURE WET FIXATION ON 80 x 80 COTTON PRINTOLOTH Pressure Time in wet-fix, Cure time Cure, Conditioned Tearing Abrasion resist- Air prespress Temp percent at 160 0. percent WRA (w+f) Wet WRA strength, gins. ance flex cycles Treatment pH sure, p.s.i. (min) add on (min) add-on deg. (w+i) deg. (w.) (w.)

A. Average values of washed samples of Bil-square cotton printcloth, 3.2 oz.lsq.yd., which had been caustic-boiled, bleached, and desized.

B. Average values of unwashed samples of -square cotton printeloth, 3.2 oz./sq.yd., which had been caustic-boiled, bleached and desired.

C. These 80-square cotton fabrics were padded in a solution consisting of Aerotex 238 (a methylated methylolmelamine) (10% solids), Permafresh 183 (a dhnethyloldihydroxyethyleneurea) (10% solids), and water (80%). The solution was adjusted to pH 2 with H01, allow ed to stand 30 minutes at room temperature and adjusted to pH 6 with NaOH before three drops of Triton X- were added to the pad bath per each 100 grams of solution used. A catalyst-softener solution consisting of Mgfrom the aluminum foil were damp and slightly stiff in some cases. The stiifness was removed on washing.

Another object of the invention is to provide a less Gig-EH20 (4% solids), Polymul 05-81 (a polyethylene emulsion) (2% sollds) and water (94%) was padded onto the fabrics that were cured.

D. These Bil-square cotton fabrics were padded with the solution identical as in treatment 0 above with one exception; that is, a fresh supply of Aerotex 238 (a methylated methylolmelamine) was used. There was not any difficulty in adjusting the pH of the pad bath when the fresh Aerotex 235 was used.

E. These ESQ-square cotton fabrics were padded in solutions identical to treatment D with one exception; that is, one half of the resin pad $31Zhfiv5 adjusted to pH 4 before padding. The other half was adjusted The data in Table 11 show that pressure wet-fixation can be accomplished on a heavier fabric of a more complex construction. As in Table I the dry (or conditioned) complex method for treating or finishing cellulosic 75 fabrics treated by the pressure wet-fix method are of relatively low wrinkle resistance until cured. Treatments C and D show, as the length of time that the sealed fabrics remained under pressure was increased, the percent addon, as well as the conditioned and wet wrinkle recovery angles, increased with an accompanying decrease in the tearing strength and flex abrasion. Treatment E proved to be an exception, and no significant differences occurred lower than conditioned wrinkle recovery angles. In the pressure wet-fix method, both the conditioned and wet wrinkle recovery angles are essentially the same.

A comparison of pressure wet-fixed fabrics with those from the wet-fixation method in treatment I shows the former is superior in abrasion resistance at the same level of wrinkle resistance.

TABLE II.TWO STEP PADDING METHOD OF PRESSURE WET-FIXATION ON #413 COTTON TWILL Pressure wet-fix, Cure time Cure, Conditioned Tearing Abrasion resis- Air pres- Time in Temp percent at 160 0. percent WRA (w+f) Wet WRA strength, gms. tance flex cycles Treatment pH sure, p.s.i. press (min) add-on (min.) add-on deg. (w-l-f) deg. (w.) (w.)

A. These values were obtained on a washed sample of #413 twill which is a white cotton twill.

B. These values were obtained on an unwashed sample of #413 twill.

C. These #413 cotton twill fabrics were padded at p.s.i. pressure in a solution consisting of Aerotex 238 (a methylated methylolmelamine) (10% solids), Penuafresh 183 (a. dimethyloldihydroxyethyleneurea) (10% solids) and water (80%). The solution was adjusted to pH 2 with HCl and allowed to stand 30 minutes at room temperature before padding. A catalyst-softener solution consisting of MgClrGHzO (4% solids), Polymul 08-81 (a polyethylene emulsion) (2% solids) and water (94%) was subsequently padded onto the fabrics at 30 p.s.i. pressure.

D. These #413 cotton twill fabrics were padded in solutions identical to those in treatment B; however, the pad pressure was p.s.i., and the pad solution was divided into two equal parts, one being adjusted to pH 4 and the other adjusted to pH 6 with NaOH before padding.

E. The #413 cotton twill fabrics were padded at 20 p.s.i. pressure ina solution consisting of Melrez-MF (a methylated methylol-melamine) (10% solids), Permafresh 183 (a dimethyloldihydroxyethyleneurea) (10% solids) and water (80%). The solution was adjusted to pH 2 with HCl and allowed to stand 15 minutes at room temperature before padding. A catalyst-softener solution consisting of MgCl2-6H2O (4% solids), Polymul 08-81 (a polyethylene emulsion) (2% solids) and water (94%) was padded onto the fabrics at 20 p.s.i. pressure.

when the length of time under pressure was increased. Regardless of the length of time the sealed fabrics were under pressure, their Stoll flex cycles exceeded those of the controls, which indicated an increase in abrasion resistance. Tearing strength values were not significantly altered by variations in time as compared with those of the washed and unwashed controls. In every case the wet wrinkle recovery angle is equal to or exceeds the conditioned wrinkle recovery angle.

The pH of the pad bath has an effect on the final product, but satisfactory results can be obtained over a range of pH 2 to 6 when methylated methylolmelamines, such as Aerotex 23S, Aerotex M-3 and Melrez MF, are used as the polymer builders and a dimethyloldihydroxyethyleneurea, such as Permafresh 183, is used as the crosslinker. When a hexamethoxymethylmelamine such as Cymel 301 is used as the polymer builder and a dimethyloldihydroxyethyleneurea, such as Permafresh 183, is used as the crosslinker it is necessary to have the pad bath at about pH 4 or lower to obtain satisfactory results.

The overall distribution of properties of pressure wetfixed fabrics is better than those produced by treatments well known in the prior art. When a crosslinking resin, catalyst, and softener solution (Treatment H) is padded onto the fabric, dried, and cured, a high conditioned wrinkle recovery angle is obtained. Wet wrinkle recovery angles obtained by this method are usually about 20 F. These #413 cotton twill fabrics were padded at 20 p.s.i. pressure in a solution consisting of Cymel 301 (a hexamethoxyrnethylrnelamine) (10% solids), Permafresh 183 (a dimethyloldihydroxyethyleneurea) (10% solids), absolute ethyl alcohol (13.6%) and water (66.4%). The solution was adjusted to pH 2 with HCl and allowed to stand 30 minutes at room temperature before padding. A catalyst-softener solution consisting of MgOlz-(SHeO (4% solids), Polymul 08-81 (a polyethylene emulsion) (2% solids), and water (94%) was padded onto the fabric at 20 p.s.i. pressure.

G. These #413 cotton twill fabrics were padded in solutions identical to those in treatment E with one exception; that is, after standing at room temperature for 30 minutes, the pad bath was adjusted to pH 6 with N 80H before padding. 4

H. These #413 cotton twill fabrics were padded in a solution consisting of Permafresh 183 (a dimethyloldihydroxyethyleneurea) (18% solids), Zn(NO3)2-6H2O (1% solids) and Polymul 03-81 (1% solids). They were not pressure wet-fixed but were cured in a forced draft oven which is the normal method used in the prior art.

I. These #413 cotton twill fabrics were padded in a solution consisting of Aerotex 238 (a methylated methylolmelamine) (20% solids), Permafresh 183 (a dirnethyloldihydroxyethyleneurea) (20% solids) at pH of 2. These fabrics were fixed by the previously mentioned method of the National Cotton Council. The fabrics were then cured after padding with a catalyst-softener solution composed of Zn(NOa)2-6H2O (0.75% solids) and Polymul 08-81 (1% solids).

Another promising one-step pressure fixation procedure is described by the descriptions and data in Table III. In this method all pad baths were at about pH 6 which is the pH resulting on mixing of the components. The pad rolls were set at 20 p.s.i. which gave about 70 percent wet pickup. All of the fabrics were pressed at about 27 p.s.i. for 3 minutes with a temperature increase of about from 60 C. or 5 minutes with a temperature increase of about from 60 to C. The fabrics were dried for about from 7-10 minutes on removal from the plastic bags. Curing was performed when desired.

This method of pressurewet-fixation produces fabrics with high conditioned and wet wrinkle recovery angles which are of the same magnitude. Wash-wear ratings were not as high as one would expect of fabrics having such high-wrinkle recovery angles. Treatment D was repeated with a green sateen fabric and #413 cotton twill. The wash-wear rating of the #413 twill was 4.2 and the wash-wear rating of the green sateen was 5. The tearing strength of the treated fabrics was reduced slightl from that of the washed and unwashed controls. In most treatments the Stoll flex cycles were greatly reduced; however, they were not lower than the conventional treatment G. Cuff laundering tests point out that the pressure wetfixation method is superior in abrasion resistance to the conventional treatment G as well as the wet-fixation treatment I.

TABLE LIL-ONE STEP PADDING METHOD OF PRESSURE WET-FIXATION ON #413 COTTON TWILL Cure Pressure C ondi- Abrasion W W Rating Cycles Total damage time at wet-fix, tloned Wet Tearing resistance to damage after 30th wash Treat- 160 C. percent add- W RA WRA strength, flex cycles 1st 30th ment (mm on (w+f) (w-i-f) gms.(w.) (w.) wash wash Slight Major Slight Major A B C 3 5. 21 D 3 10. 45 E-l 3 4. 88 E-2 5 4. 77 F-l 3 9. 40 F- 5 9. 15 3. F-3 0. 48 G 7 9. 70 205 4. 2 a. 3 (Hi 7-8 4. 3. 0 15 9. 65 159 4. 2 4. 3 3-3 3-4 4. 0 5. 0 H 1, 3 9. 08 522 4. 2 3. 7 11-15 22-24 4. (l 5. 0

Percent add-on under treatments G and H are based on the weight of the fabrics before curing.

A. These values were obtained on a washed sample of fabric.

B. These values were obtained on an unwashed sample of fabric.

0. These #413 cotton twill fabrics were padded in a solution consisting of Aerotex M-3 (a methylated methylolmelamine) solids), Permafresh 183 (a dimethyloldihydroxy-ethyleneurea) (5% solids), MgClz.6H2O (4% sogidsy)3 Polymul (IS-81 (a polyethylene emulsion) (2% solids), and water 84 a D. These #413 cotton twill fabrics were padded in a solution consisting of Aerotex M-3 (a methylated methylolmelamine) (11.7% solids), Permafresh 133 (a dimethyloldihydroxy-ethyleneurea) (11.7% solids), MgCl'x- GHZO (4.8% solids), Polymul (IS-81 (a polyethylene emulsion) (2.4%

olids) and the remainder water.

E. These #413 cotton twill fabrics were padded in a solution consisting of Aerotex 238 (a methylated methylolmelamine) (5% solids), Permafresh 183 (a dimethyloldihydroxyethyleneurea) (5% solids), MgClzfiH O (4% solidsyL) Polymul 08-81 (a polyethylene emulsion) (2% solids), and Water 84 0 EXAMPLE 1 Wrinkle and abrasion resistant cellulosic fabric is produced in a process whereby 80 x 80 cotton printcloth is padded at 40 p.s.i. pressure in a solution of the following composition: percent solids of a polymer builder of a melamine type resin, methylated methylolmelamine (Aerotex 23S), 10 percent solids of a crosslinking resin, dimethyloldihydroxyethylencurca (Pcrmafresh 183), and 80 percent water. The solution was adjusted to pH 2 with hydrochloric acid and allowed to stand for minutes at room temperature before adjusting to pH 6 with sodium hydroxide before use. Three drops of a wetting agent, alkyl aryl ethylcneoxidc alcohol (Triton X400) were added to the pad bath per each 100 grams of solution. After padding, the fabrics were placed between sheets of aluminum foil which were folded over to form a closed or semiclosed container and pressed in a hot-head press for 1 minute under 88 p.s.i. pressure with a temperature increase of 60 to 92 C. On cooling, the wet fabrics were removed from the aluminum foil containers and washed. After drying, the fabrics weer padded at p.s.i. pressure in a solution containing 4 percent solids of a catalyst, magnesium chloride hcxahydrate, 2 percent solids of a softener, polyethylene emulsion (Polymul C5 81), and 94 percent water. The fabrics were dried for 7 minutes at C. in a forced draft oven. The fabrics were either cured in a forced draft oven for 3 minutes at 160 C. or stored for subsequent curing. Results are given in item 04 of Table I.

EXAMPLE 2 Exactly the same as Example 1, except the fabrics were not padded in the catalyst-softener solution. Results are given in item C-2 of Table 1.

EXAMPLE 3 Exactly the same as Example 1, except the time in the press was 3 minutes with a temperature increase of 60 to 110 C. Results are given in item C-3 of Table I.

EXAMPLE 4 Exactly the same as Example 3, except the fabrics were not padded in the catalyst-softener solution. Results are given in item C-4 of Table EXAMPLE 5 Exactly the same as Example 1, except the fabrics remained in the hot-head press for 3 minutes under 27 F. These #413 cotton twill fabrics were padded in a solution consisting of Aerotex 238 (a methylated methylolmelamine) (10% solids), Permafresh 183 (a dimethyloldihydroxyethyleneurea) (10% solids) ,hIgC12.6H2O (4%t, solidis)a Polymul 08-81 (a polyethylene emulsion) (2% solids), and we. er 7 G. These #413 cotton twill fabrics were padded in a solution consisting of Permafresh 183 (a dimethyloldihydroxyethyleneurea) (18% solids), MgCl2.6H2O (4% solids) and Polymul CS-Sl (a polyethylene emulsion) (2% solids). They were not pressure wet fixed but were dried and cured in a forced draft oven which is the normal method used in the prior art.

H. These #413 cotton twill fabrics were padded in a solution consisting of Aerotex 238 (a methylated methylolmelamine) (20% solids), Permafresh 183 (a dimethyloldihydroxyethyleneurea) (20% solids) at pH of 2. These fabrics were fixed by the previously mentioned method of the National Cotton Council. The fabrics were then cured after padding with a catalyst-softener solution composed of ZH(NO3) 2.61120 (0.75% solids) and Polymul 08-81 (1% solids).

p.s.i. pressure with a temperature increase of 60 to 110 C. Results are given in items 0-5, D-1, and E-3 of Table I.

EXAMPLE 6 Exactly the same as Example 5, except the fabrics were not padded in the catalyst-softener solution. Results are given in item C-6 of Table I.

EXAMPLE 7 Exactly the same as Example 1, except the fabrics remained in the hot-head press for 5 minutes under 27 p.s.i. pressure with a temperature increase of 60 to 115 C. Results are given in items D-2 and 13-4 of Table I.

EXAMPLE 8 Exactly the same as Example 1, except the fabrics remained in the hot-head press for 7 minutes under 27 p.s.i. pressure with a temperature increase of 60 to 122 C. Results are given in item D-3 of Table I.

EXAMPLE 9 Exactly the same as Example 1, except the pad bath was adjusted to pH 4 with sodium hydroxide before use, and the fabrics remained in the hot-head press for 3 minutes under 27 p.s.i. pressure with a temperature increase of 60 to 110 C. Results are given in item E-l of Table I.

EXAMPLE 1O Exactly the same as Example 9, except the fabrics remained in the hot-head press for 5 minutes with a temperature increase of 60 to 115 C. Results are given in item E-Z of Table I.

EXAMPLE 1 1 Exactly the same as Example 1 but with the following exceptions: Style #413 cotton twill (Testfabrics, Inc.) was the fabric used; the pH of the pad bath was allowed to remain at pH 2; the fabrics remained in the hot-head press for 1.5 minutes under 27 p.s.i. pressure with a tempcrature increase of 60 to C. In addition, the pad pressure was 30 p.s.i. in both paddings. Results are given in item 0-1 of Table I1.

EXAMPLE 12 Exactly the same as Example 11, except the fabric remained in the hot-head press for 3 minutes with a temperature increase of 60 to C. Results are given in item C-2 of Table II.

9 EXAMPLE 13 Exactly the same as Example 11, except the fabric remained in the hot-head press for minutes with a temperature increase of 60 to 115 C. Results are given in item C-3 of Table II.

EXAMPLE l4 Exactly the same as Example 11 with the following exceptions: the pH of the pad bath was adjusted to pH 4 with sodium hydroxide before use; the pad pressure was 40 p.s.i. in both paddings; the fabrics remained in the hot-head press for 3 minutes with a temperature in crease from 60 to 110 C. Results are given in item D-l of Table II.

EXAMPLE 15 Exactly the same as Example 14, except the time in the hot-head press was 5 minutes with a temperature increase from 60 to 115 C. Results are given in item D-2 of Table II.

EXAMPLE 16 Exactly the same as Example 14, except the pH of the pad bath was adjusted to pH 6 with sodium hydroxide before use. Results are given in item D-3 of Table II.

EXAMPLE 17 Exactly the same as Example 15, except the pH of the pad bath was adjusted to pH 6 with sodium hydroxide before use. Results are given in item D-4 of Table II.

EXAMPLE 18 Wrinkle and abrasion resistant cellulosic fabric is produced in a process whereby Style #413 cotton twill (Testfabrics, Inc.) was padded at 20 p.s.i. pressure in a solution of the following composition: percent solids of a polymer builder of a melamine type resin, methylated methylolmelamine (Melrez MF), 10 percent solids of a crosslinking resin, dimethyloldihydroxyethyleneurea (Permafresh 183), and 80 percent water. The solution was adjusted to pH 2 with hydrochloric acid and allowed to stand for minutes at room temperature before use. Three drops of a wetting agent, alkyl aryl ethyleneoxide alcohol (Triton X100), were added to the pad bath per each 100 grams of solution. After padding the fabrics were placed in plastic bags, which were self-sealing during pressing. The fabrics were pressed in a hot-head press for 3 minutes under 27 p.s.i. pressure with a temperature increase from 60 to 110 C. On cooling, the wet fabrics were removed from the sealed plastic bags and washed. After drying, the fabrics were padded at p.s.i. pressure in a solution containing 4 percent solids of a catalyst, magnesium chloride hexahydrate, 2 percent solids of a softener, polyethylene emulsion (Polymul CS-81), and 94 percent water. The fabrics were dried for 7 minutes at 60 C. in a forced draft oven. The fabrics were either cured in a forced draft oven for 3 minutes at 160 C. or stored for subsequent curing. Results are given in item E-l of Table II.

EXAMPLE l9 Exactly the same as Example 18, except the time in the hot-head press was 5 minutes and the temperature increase was from 60 to 115 C. Results are given in item E2 of Table II.

EXAMPLE 20 Exactly the same as Example 18, except the pad bath so lution consisted of 10 percent solids of a melamine type resin, hexamethoxymethylmelamine (Cymel 301), 10 percent solids of a crosslinking resin, dimethyloldihydroxyethyleneurea (Permafresh 183), 13.6 percent absolute ethyl alcohol and 66.4 percent water. The solution was adjusted to pH 2 with hydrochloric acid and allowed to stand for 30 minutes at room temperature before use. Results are given in item F of Table II.

10 EXAMPLE 21 Exactly the same as Example 20, except the pad bath was adjusted to pH 6 with sodium hydroxide before use. Results are given in item G of Table II.

EXAMPLE 22 Wrinkle and abrasion resistant cellulosic fabric is produced in a process whereby Style #413 cotton twill (Testfabrics, Inc.) was padded at 20 p.s.i. pressure in a solution of the following composition: 5 percent solids of a polymer builder of a melamine type resin, methylated methylolmelamine (Aerotex M-3), 5 percent solids of a crossliuking resin, dimethyloldihydroxyethyleneurea (Permafresh 183), 4 percent solids of a catalyst, magnesium chloride hexahydrate, 2 percent solids of a softener, polyethylene emulsion (Polymul CS-81), and 84 percent water. Three drops of a wetting agent, alkyl aryl ethyleneoxide alcohol (Triton X), were added to the pad bath per each 100 grams of solution. The solution was padded at about pH 6, which was the pH of the solution without alteration. After padding, the fabrics were placed in plastic bags, which were self-sealing during pressing. The fabrics were pressed in a hot-head press for 3 minutes under 27 p.s.i. pressure with a temperature increase from 60 to C. On cooling, the wet fabrics were removed from the sealed plastic 'bags and dried 5 minutes at 60 C. in a forced draft oven. The fabrics were either cured in a forced draft oven for 3 minutes or stored for subsequent curing. Results are given in item C of Table III.

EXAMPLE 23 Exactly the same as Example 22, except the percentages of the components in the pad both :were: 11.7 percent Aerotex M3 (a methylated methylolmelamine), 11.7 percent Permafresh 183 (a dimethyloldihydroxyethyleneurea), 4.7 percent catalyst, 2.4 percent softener, and 69.5% water. Results are given in item D of Table III.

EXAMPLE 24 Exactly the same as Example 22, except the melamine type resin was methylated methylolmelamine (Aerotex 238). Results are given in item E-l of Table III.

EXAMPLE 25 Exactly the same as Example 24, except the fabric remained in the press for 5 minutes with a temperature increase from 60 to C. Results are given in item E-2 of Table III.

EXAMPLE 26 Exactly the same as Example 22, except for the composition of the pad bath which is of the following composition: 10 percent solids of a polymer builder of a melamine type resin, methylated methylolmelamine (Aerotex 23S), 10 percent solids of a cross-linking resin, dimethyloldihydroxyethyleneurea (Permafresh 183), 4 percent solids of a catalyst, magnesium chloride hexahydrate, 2 percent solids of a softener, polyethylene emulsion (Polymul CS-81), and 74 percent water. Results are given in item F-l of Table III.

EXAMPLE 27 Exactly the same as Example 26, except the fabrics remained in the hot-head press for 5 minutes with a temperature increase from 60 to 115 C. Results are given in item -F2 of Table III.

EXAMPLE 28 Exactly the same as Example 26, except the fabric was washed after drying and was not cured. Results are given in item F-3 of Table III.

We claim:

1. A process for accomplishing the wet-fixation of resins in cellulosic fabrics comprising the following operations carried out in sequence:

(a) padding the cellulosic fabric to a wet pickup of 1 1 about 80 weight percent with an aqueous solution containing about from to weight percent of a methylated methylolmela-mine, and about from 5 to 10 weight percent of dimethyloldehydroxyethyleneurea, said aqueous solution being adjusted prior to 1 2 about 4 weight percent of magnesium chloride hexahydrate, and about 2% by weight of emulsified polyethylene. (b) enrobing the padded cellulosic fabric within a flexible, moisture impervious material,

the padding operation to pH within the range 2 to 6, 5 (0) imposing a positive pressure of from to (b) enrobing the padded cellulosic fabric within a pounds per square inch upon the exterior surfaces flexible, moisture impervious material, of the enrobing material for a period of about from (c) imposing a positive pressure of from 20 to 90 1 to 7 minutes and at a tem erature of about from pounds per square inch upon the exterlor surfaces of 10 60 to C.,

the enrobing material for a period of about from (d) removing the enrobing material from the cellulosic 1 to 7 minutes and at a temperature of about from fabric,

'60 to 120 C., (e) drying and then curing the cellulosic fabric from (d) cooling the enrobed cellulosic fabric, step (d) for a period of from about 3 to 5 minutes (e) removing the em'obing material from the cellulosic 15 at a temperature of about C.

fabric,

(f) Washing and drying the cellulosic fabric, R f r nces C ted (g; paddting (tge washed and dried Icellulosicfabric UNITED STATES PATENTS rom 5 ep =w1 an aqueous so u 1011 con almng about 4% by weight of magnesium chloride hexa- 2O $5.

hydrate and about 2% by weight of emulsified poly- 3o52570 9/1962 3 22;

ethylene, (h) drying and curing the padded cellulosic fabric from g ij step (g) for a period of from about 3 to 5 minutes at 3245831 4/1966 ggp et a 1 5 3 2 Xempemme abmt i 25 313411955 9/1967 'Pyke etal 117 139.4 X

. process for accomplishing the wet-fixation of 3 374 3/1968 cotton 117 139 4 resins in cellulosic fabrics comprising the following operations carried out in sequence: (a) padding the cellulosic fabric to a wet pickup of about 80 weight percent with an aqueous solution containing about from 5 to 10 weight percent of a methylated methylolmelamine, about from 5 to 10 weight percent of dimethyloldihydroxyethyleneurea,

WILLIAM D. MARTIN, Primary Examiner 30 T. G. DAVIS, Assistant Examiner US. Cl. X.R.