US3402989A - Cellulose modification with solution comprising a methylolated carbamate and a methylolated triazone - Google Patents

Description

United States Patent CELLULOSE MODIFICATION WITH SOLUTION COMPRISING A METHYLOLATED CARBAMATE AND A METHYLOLATED TRIAZONE William B. Canter, Danville, Va., and Roger N. Suiter,

Syracuse, N.Y., assignors to Dan River Mills, Incorporated, Danville, Va., a corporation of Virginia No Drawing. Filed June 9, 1964, Ser. No. 373,831

12 Claims. (Cl. 8-116.3)

This invention relates to novel crease-proofing compositions and methods for crease-proofing cellulosic fabrics therewith.

Alkyl N,N-di-methylolcarbamates, such-as methyl and ethyl N,N-dimethylolcarbamates, have been heretofore employed for the purpose of crease-proofing cellulosic fabrics. In addition, condensates of formaldehyde and triazones having the formula:

wherein R is alkyl or hydroxyalkyl having 1 to 4 carbon atoms have also been employed for crease-proofing cellulosic textiles. The above triazone condensates may contain from 0 to 1.0 mole parts of urea formaldehyde condensate based on the combined urea in said urea formaldehyde condensate per mole part of triazone formaldehyde condensate and still be operable in the present invention as will be apparent in the examples.

The above-mentioned carbamates have been limited in their application in that, in order to avoid undue damage due to chlorine retention, it is necessary to employ acid catalysts such as zinc nitrate. The use of such acid catalysts with the c-arbamates causes damage to various sensitive dyes such as Blue BF (Vat Blue 6-, Color Index #693325), thereby limiting the use of such carbamates to undyed fabrics or fabrics carrying dyes which are not affected.

The use of formaldehyde-triazone condensates such as those mentioned above to produce crease-resistance has been found to give rise to undesirable odors. In addition, while the crease-resistance of the fabrics treated with formaldehyde-triazone condensates as well as the carbamates is adequate for many purposes, there is still room for improvement. Similarly, the tear and tensile strengths of fabrics treated with carbamates alone could stand improvement. There is also room for improvement in lessening the degree of damage due to chlorine retention in the use of formaldehyde-triazone condensates for crease-proofing and in improving the appearance ratings of such fabrics.

The present invention is based on the discovery that carbamates of the type described above can be employed with strong acid catalysts such as zinc nitrate to impart crease-resistance to cellulosic fabrics dyed with such sensitive dyes as Blue BF when used in admixture with a formaldehyde-triazone condensate of the type described above. It has also been found that such mixtures of a formaldehyde-triazone condensate and carbamate considerably reduce the odor which ordinarily would be produced by employment of the formaldehyde-triazone condensate alone. Still in addition, it has been found that such mixtures provide improved crease-resistance over that produced by the carbamates or formaldehyde-triazone ice condensates each employed alone as crease-proofing chemicals. In addition, it has been discovered that such mixtures, when applied to cellulosic fabrics and cured thereon, provide much less damage due to retained chlorine than in the case of formaldehyde-triazone condensates employed alOne and much improved appearance ratings over the case where formaldehyde-triazlone condensates alone are employed. It has been further discovered that the mixtures, when applied to cellulosic textiles and cured thereon, result in considerably improved tear and tensile strengths in the textile as compared with textiles treated with carbamates alone.

The relative amounts of formaldehyde-triazone condensates and carbamates employed in the novel mixtures of the present invention can vary widely and preferably range from 0.05 to 1.5 weight parts of the formaldehydetriaz-one condensate per weight part of the carbamate. The mixtures are advantageously employed in aqueous solution. The solids content of total crease-proofing chemical, i.e., carbamate and formaldehyde-triazone condensate, in the aqueous treating solution can vary over a wide range and preferably would not extend below 2 per cent nor above percent. The aqueous treating solution can also contain other ingredients such as softeners, wetting agents and the like in addition to a suitable curing catalyst such as zinc nitrate, magnesium chloride, isopropanolamine hydrochloride, or mixtures thereof, and the like.

The aqueous treating solutions are applied to the cellulosic fabric and conventional techniques such as padding can be employed. The pick-up on the fabric can also vary over a wide range, e.g., wet pick-ups of 50 to percent based on the weight of the fabric.

After application to the fabric the crease-proofing chemicals thus carried by the fabric are cured under suitable curing conditions such as at a curing temperature of 250 to 360 F. for 5 minutes to 1 minute. If desired, the fabric can be dried after application of the treating solution and prior to curing. While air drying at ambient temperatures can be employed, it is preferred and more expeditious to dry at elevated temperatures.

The fabric to be treated may be prepared in any desired manner such as by singeing, desizing, bleaching, and other operations prior to impregnating with the creaseproofing chemical and novel catalyst according to the present invention. Substantially any type of cellulosic fabric can be treated according to this invention. For example, 100 percent cotton woven fabrics, cottonsynthetic fiber blends, 100 percent rayon, rayon-synthetic fiber blends, rayon-cotton blends, all can be treated in accordance with this invention to provide the advantages set forth hereinabove.

The following examples are presented. Unless otherwise specified, the percentages and parts set forth in the examples are by weight and the temperatures set forth are in degrees Fahrenheit. The crease-resistance values were determined by the Monsanto Crease Recovery Test (A.A.T.C.C. Tentative Test Method 66-1959T). Reflectance values were determined on a Hunter Model D-40 Reflectometer using a blue filter.

Example 1 An aqueous treating solution was prepared containing 14 percent of a 57 percent solids aqueous solution of methyl N,N dimethylolcarbamate; 2.5 percent of a catalyst solution containing 36.4 percent solids of zinc nitrate and sodium hypophosphite in a weight ratio of 3.72 parts zinc nitrate per part sodium hyphosphite and 0.2 percent of a nonionic wetting agent and designated Composition A.

A second aqueous treating solution was prepared containing 10.5 percent of a 57 percent solids aqueous solution of methyl N,N-dimethylolcarbamate; 3.5 percent of a 47.4 percent solids aqueous solution of a N,N' dimethylol 5 hydroxyethyl tetrahydro s triazone-2 in a ratio of 60 mole percent of said triazone and 40 mole percent of dimethylol urea and containing 5 percent excess formaldehyde; 2.5 percent of the above-mentioned catalyst solution of zinc nitrate and sodium hypophosphite and 0.2 percent of a nonionic wetting agent and was designated Composition B.

Compositions A and B were separately applied to 100 percent cotton fabric by padding to a 68 percent wet pick-up based on the weight of fabric. The fabric in each case had been dyed with Blue BF as identified hereinbefore in the conventional manner. The impregnated fabric was oven dried at 300 F. for 56 seconds and then cured at 340 F. for 70 seconds.

The fabric treated with Composition A showed a severe color change from the desired blue to a green shade. The fabric treated with Composition B showed no detectable shade change. The physical properties of the fabrics so treated are given below:

Composition A Composition B Composition B contained 0.166 part of said triazone per part of said carbamate.

Example 2 An aqueous treating solution was prepared containing 14 percent of a 57 percent solids aqueous solution of methyl N,N dimethylolcarbamate; 2.5 percent of the catalyst solution used in Example 1 and 0.2 percent of a nonionic wetting agent and designated as Composition C.

A second aqueous treating solution was prepared containing 12.3 percent of a 57 percent solids aqueous solution of methyl N,N dimethylolcarbamate; 1.7 percent of a 69 percent solids aqueous solution of (a) 84 mole percent N,N dimethylol 5 ethyltetrahydro striazone-Z and (b) 16 mole percent dimethylol urea with 5 percent excess formaldehyde; 2.5 percent of the catalyst solution described in Example 1 and 0.2 percent of a nonionic wetting agent and was designated as Composition D.

Compositions C and D were individually applied to cotton fabric which was dyed with Blue BF as identified hereinbefore. The application was performed in the same manner as described in Example 1 and the impregnated fabric was dried and cured in the manner set forth in Example 1. The fabric treated with Composition C underwent a severe color change and presented a green shad rather than the original blue shade. Composition D produced little, if any, noticeable color change. Composition D contained 0.116 part of said triazone per part of said carbamate.

Example 3 Three yards of cotton cloth were padded through an aqueous solution containing 130 pounds of a 43 percent solids aqueous solution of a resin mixture of (a) 70 mole percent 011 N,N dimethylol 5 hydroxyethyltetrahydro S triazone 2 and (b) 30 mole percent of di methylolurea, 20 percent excess formaldehyde and sodium phosphate; 80 pounds of a 53 percent solids aqueous solution of methyl N,N dimethylolcarbamate containing a 35 percent excess formaldehyde; pounds of an aqueous solution containing 25 percent magnesium chloride and 25 percent Zinc nitrate; 40 pounds of a 25 percent solids aqueous emulsion of polyethylene as a softener; 20 pounds of an acetic acid salt of a condensate of stearic acid and aminoethyl ethanolamine as an additional softener; 20 pounds of a 10 percent aqueous solution of polyvinylalcohol and 3 pounds of a nonionic wetting agent. Approximately 70 percent of the treating solution based on the weight of fabric was picked up by the fabric. The treated fabric was thereafter dried at about 250 F. and cured for 70 seconds at 340 F. Thereafter, the cured fabric was washed and Sanforized. The thus treated fabric was then tested and found to have a filling tensile strength by the Grab method of 39, a filling tear strength by the Trapezoid method of 2.6, a crease resistance of 273 and a percent damage due to retained chlorine of 5 percent (as determined by A.A.T.C.C. Standard Test Method 92-1962) and a wash and wear appearance rating of 4 to 5 (A.A.T.C.C. Tentative Test Method 88-1960). The treating bath contained a total of 0.945 part of the above-identified triazone per part of the above-identified carbamate.

Example 4 Three yards of cotton fabric were impregnated at 150 F. with an aqueous solution containing 9 percent of a 43 percent solids aqueous solution of a resin mixture of (a) 70 mole percent of N,N dimethylol 5 hydroxyethyltetrahydro S triazone 2 and (b) 30 mole percent of dimethylolurea, 20 percent excess formaldehyde and sodium phosphate; 9 percent of a 53 percent solids aqueous solution of methyl N,N dimethylolcarbamate containing a 35 percent excess formaldehyde; 3.4 percent of a percent solids aqueous solution of magnesium chloride hexahydrate; 3 percent of a 25 percent solids aqueous emulsion of polyethylene as a softener; 1.5 percent of an acetic acid salt of a condensate of stearic acid and aminoethyl ethanolamine as an additional softener; 1.5 percent of a 10 percent aqueous solution of polyvinylalcohol and 0.3 percent of a nonionic wetting agent. The treating solution contained a total of 0.568 part of the above-identified triazone per part of the above-identified carbamate. The fabric was dried at 250 F. and then cured at 340 F. for seconds. It was then washed and Sanforized.

The thus treated fabric had considerably less odor than cloth treated with a similar composition with the exception that the 9 percent of the 53 percent solids carbamate solution was replaced by the 43 percent solids solution of the triazone and dimethylolurea as described in detail above, thus giving a total of 18 percent of said 43 percent solids aqeuous solution.

Example 5 Treating solution E was prepared containing 18 percent of a 53 percent solids aqueous solution of methyl N,N dimethylolcarbamate containing a 35 percent excess formaldehyde; 3 percent of a 40 percent solids aqueous emulsion of polyethylene as a softener; 3.25 percent of an aqueous solution containing 25 percent magnesium chloride hexahydrate and 15 percent of isopropanolarnine hydrochloride; and 0.2 percent of a nonionic wetting agent. Composition F was prepared from the same ingredients except that instead of 18 percent of the 53 percent solids solution of carbamate as described above, 14 percent was employed, and, in addition, 5 percent of a 43 percent solids aqueous solution of a resin mixture of (a) 70 mole percent of N,N-dimethylol-S-hydroxyethyltetra hydro-S-triazone-Z and (b) 30 mole percent of dimethylolurea, 20 percent excess formaldehyde and sodium phosphate was included.

Compositions E and F were applied to cotton fabric to a wet pick-up of about 70 percent, the fabric then was Example 1. The fabric treated in Composition E underwent a severe color change and presented a green shade rather than the original blue shade. Composition H produced little, if any, noticeable color change. Composition Composition E Composition F Orig. 1 cw 5 cw. cw Orig. 1 cw 5 cw. 10 cw Crease resistance 280 Filling tensile. Filling tear 1. 4 Reflectance:

Initial 80. 5

Suter scorch 75. 3 Appearance:

Spin dry 4. 5

Tumble dry 5 Percent tensile loss C12 retained... 5

It is noted that the crease resistance, tensil and tear strengths, reflectance values and appearance ratings for the fabric treated with Composition F was at least as good as if not better than fabric treated with Composition E. In addition, the degree of damage due to chlorine retention for the fabric treated with Composition F was substantially better than that for the fabric treated with Composition E. The crease resistance, filling tensile and tear strengths, reflectance, wash and wear appearance ratings and damage due to retained chlorine were all determined by the test methods previously identified.

Composition F contained a total of 0.203 part of the above-identified triazone per part of the above-identified carbamate. Similar comparative results are obtained by treating cotton fabric with the same solution wherein, however, there is contained 0.258 part of the above-identified triazone per part of the above-identified carbamate. In addition, similar results were obtained from compositions similar to that of Composition F wherein, however, there was contained 0.756 part of the above-identified triazone per part of the above-identified carbamate.

Similar comparative results are obtained when, in place of the 43 percent solids solution identified above, there is substituted a 47.4 percent aqueous solution of a resin mixture containing (a) approximately 60 mole percent of N,N dimethylol-S-hydroxyethyltetrahydro-S-triazone-Z and (b) 40 mole percent of dimethylolurea and 5 percent excess formaldehyde wherein, for example, there is present 0.563 part of said triazone per part of the aboveidentified carbamate.

The foregoing description is intended for purposes of illustration only and not as a limitation on the scope of this invention inasmuch as obvious equivalents and modifications will be apparent to those skilled in the art without departing from the scope of the invention.

Example 6 An aqueous treating solution was prepared containing 14 percent of a 57 percent solids aqueous solution of methyl N,N-dimethylolcarbamate; 2.5 percent of the catalyst solution used in Example 1 and 0.2 percent of a nonionic wetting agent and designated as Composition G.

A second aqueous treating solution was prepared containing 11.9 percent of a 57 percent solids aqueous solution of methyl N,N-dimethylolcarbamat-e; 2.1 percent of a 69 percent solids aqueous solution of N,N-dimethylol- H contained 0.214 part of said triazone per part of said carbamate.

What is claimed is:

1. Novel composition for treating cellulosic fabrics comprising an aqueous solution containing an alkyl N,N- dimethylol-carbamate wherein said alkyl group contains 1 to 4 carbon atoms and 0.05 to 1.5 weight parts of a condensate of formaldehyde and a triazone of the formula:

wherein R is selected from the class consisting of alkyl or hydroxyalkyl having 1 to 4 carbon atoms per weight part of said alkyl N,N-dimethylolcarbamate.

2. Composition as claimed in claim 1 wherein said alkyl N,N-dimethylolcarbamate is methyl N,N-dimethylolcarbamate.

3. Composition as claimed in claim 2 wherein said condensate is N,N-dimethylol 5 ethyl-tetrahydro-s-trialone-2.

4. Composition as claimed in claim 2 wherein said condensate is N,N'-dimethylol-5-hydroxyethyl-tetrahydro-striazone-2.

5. Composition as claimed in claim 3 wherein said composition also contains N,N'-dimethylol urea.

6. Composition as claimed in claim 4 wherein said composition also contains N,N'-dimethylolurea.

7. Method of treating cellulosic fabric comprising the steps of applying to said fabric an aqueous solution containing crease-proofing chemicals comprising an alkyl N,N-dimethylolcarbamate wherein said alkyl group contains l to 4 carbon atoms and 0.05 to 1.5 weight parts of a condensate of formaldehyde and a triazone of the formula:

wherein R is selected from the class consisting of alkyl or hydroxyalkyl having 1 to 4 carbon atoms per weight part of said N,N-dimethylolcarbamate; and thereafter heating said fabric to dry and cure said crease-proofing chemicals.

8. Method as claimed in claim 7 wherein said alkyl N,N-dimethylolcarbamate is methyl N,N-dimethylolcarbamate.

:8 9. Method as claimed in claim 8 wherein said con- 12. Composition as claimed in claim 10 wherein said densate is- N,N dimethylol 5 ethyl tetrahydro scomposition also contains N,N-dimethylol urea.

triaz0ne-2.

10. Method as claimed in claim 8 wherein said con- No references cited. dcnsate is N,N'-dimethyl0l-5-hydroxyethyl-tetrahydro-s- 5 triaZone 2 NORMAN G. TORCHIN, Primary Examiner.

11. Method as claimed in claim 9 wherein saidcomposi- CANNON, Assistant Examiner tion also contains N,N-dimethyl0l urea.

Claims (2)

1. NOVEL COMPOSITION FOR TREATING CELLULOSIC FABRICS COMPRISING AN AQUEOUS SOLUTION CONTAINING AN ALKYL N,NDIMETHYLOL-CARBAMATE WHEREIN SAID ALKYL GROUP CONTAINS 1 TO 4 CARBON ATOMS AND 0.05 TO 1.5 WEIGHT PARTS OF A CONDENSATE OF FORMALDEHYDE AND A TRIAZONE OF THE FORMULA:

7. METHOD OF TREATING CELLULOSIC FABRIC COMPRISING THE STEPS OF APPLYING TO SAID FABRIC AN AQUEOUS SOLUTION CONTAINING CREASE-PROOFING CHEMICALS COMPRISING AN ALKYL N,N-DIMETHYLOLCARBAMATE WHEREIN SAID ALKYL GROUP CONTAINS 1 TO 4 CARBON ATOMS AND 0.05 TO 1.5 WEIGHT PARTS OF A CONDENSATE OF FORMALDEHYDE AND A TRIAZONE OF THE FORMULA: