US3378397A - Highly alkylolated textile finishing composition and process for treating textile fabric therewith - Google Patents

Description

United States Patent 3,378,397 HIGHLY ALKYLOLATED TEXTILE FKNISHING COMPOSlTlON AND PROCESS F83 TREAT- ING TEXTILE FABRIC THEREWITH Michael A. Silvestri and Herman B. Goldstein, Cranston, and Gerhard E. Sprenger, Ashaw'ay, ILL, assignors to Sun Chemical Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Apr. 9, 1964, Ser. No. 358,652 18 Claims. (Cl. 117-139.4)

ABSTRACT OF THE DISCLOSURE The reaction of compounds having at least one active hydrogen atom attached to the nitrogen atom of an amino or an amido group included therein with formaldehyde at a pH of at least 10.5, the highly alkylolated compositions produced by said reaction, a textile fabric treated with said compositions and a process for treating a textile fabric with said compositions.

This invention relates to modified nitrogen compounds, particularly to a process for modifying nitrogen containing compounds and to the treatment of textile materials with the modified nitrogen containing compounds. More particularly, the present invention relates to a novel process for preparing alkylol derivatives of nitrogen containing compounds.

Heretofore, the products obtained from the alkylolation of nitrogen compounds such as melamine, urea and cyclic urea with formaldehyde under slightly alkaline conditions thave been applied to cellulosic fabrics, such as cotton, for the purpose of imparting crush-resistance and reduced shrinkage in laundering. However, fabrics treated with these condensates have a tendency to pick up chlorine during bleaching operations using chlorine, such as those using it in the form of a hypochlorite. On ironing the fabrics that have been bleached in this manner, severe discoloration and/ or loss in tensile and/ or tear strengths have generally resulted. In those cases where severe discoloration is encountered, the treatment with these condensates is unsuitable when a white fabric is ultimately desired. In some cases, as much as 90 percent loss is encountered as a result of the action of heat as in ironing on fabrics treated with these condensates and bleached with chlorine.

Even textile fabrics treated with partially alkylolated nitrogen containing compounds are somewhat inferior with respect to the measure of wrinkle recovery after laundering, as well as with respect to the tensile strength of the finished fabric after laundering.

Heretofore it has been the practice to alkylolate nitrogen compounds with the requisite amount of an aldehyde under neutral or slightly alkaline conditions.

It was assumed that the rate and extent of alkylolation was dependent on the temperature and the stoichiometry of the reaction. However, it has been found, that an even more potent factor in the alkylolation is the basicity of the system. Furthermore, it has been found that certain nitrogeneous compounds and in particular the carbamides, may be more fully alkylolated when the system is operated at excess basicity.

It has been found that the more fully alkylolated products when applied to cellulosic fabrics such as cotton impart chlorine resistance to the treated fabrics thereby resulting in a decrease in the loss in tensile strength and/or tear strength. Furthermore, it has been found that fabrics treated with the fully alkylolated products are very durable to laundering and are both crush-resistant and shrink-resistant.

ice

It is an object of this invention to provide an improved method for alkylolating nitrogen compounds.

Another object of this invention is to provide a method for carrying out chemical reactions involving formaldehyde as one of the reactants.

Another object of this invention is to provide a method for carrying out chemical reactions involving formaldehyde and a nitrogen compound.

Still another object of this invention is the preparation of a clear stable liquid product having good shelf stability.

Still another object of this invention is the preparation of a fully alkylolated composition.

Still another object of the present invention is to provide a composition which when applied to cellulose acetate, nylon, or other hydrophobic fibers, will produce a stiffening effect with excellent resiliency.

Still another object of the present invention is to provide a composition which when applied to textile material shows excellent resistance to degradation when the fabric is subjected to chlorine containing bleach.

A still further object of the present invention is to provide a composition which when applied to textile material imparts creaseresistance, shrinkage control, Wash-wear properties and resiliency.

A still further object of the present invention is to provide a textile treating composition containing highly alkylolated nitrogen containing compounds.

These and still further objects will be apparent from the ensuing description of the invention.

The above objects may be accomplished in accordance with the present invention by reacting nitrogen containing compounds with formaldehyde or substances which split off formaldehyde in a highly basic system at elevated temperatures to produce alkylol derivatives of nitrogen containing compounds.

Some of the more prominent alkylolated nitrogen containing compounds which may be employed in the treatment of textile fabrics are the carbamides and the s-triazines. Examples of the s-triazines are polyalkylol-s-triazines and more preferably polymethylol-s-triazines.

The reaction of formaldehyde with the nitrogen containing compounds can be carried out smoothly in a highly alkaline system, preferably in alkaline system having a pH of at least 10, and more preferably a pH of at least 10.5 and above. The alkalizing agent may be an inorganic alkaline material selected from the group consisting of alkali metal hydroxides such as sodium and potassium hydroxide, alkaline-earth metal hydroxides such as calcium hydroxide and the like. Although there does not appear to be any advantage in doing so, it appears possible to add part of the necessary alkali at the beginning of the reaction, and then continue to add alkali as the reaction proceeds. Similarly, there does not appear to be any advantage in adding any more alkali than is necessary to obtain a pH of about 10.5. If excess alkali is added, it may be consumed in the Cannizzaro reaction.

The reaction temperature employed in the alkylolation reaction is not critical and may be adequately chosen from a temperature ranging from about 20 C. to the reflux temperature of the reaction mixture, but in order that the reaction mixture may proceed smoothly, a temperature range of from about 40 to C. is preferred. The reaction time is correlated with the reaction temperature. In case the reaction temperature is from 60 to 90 C., the reaction is substantially completed in about 3 to 6 hours.

The reaction of formaldehyde or substances which split off formaldehyde with nitrogen containing compounds may be carried out in the absence of a solvent; however, water may be employed as a reaction medium,

but other solvents such as alcohols, particularly the lower alkanols having from 1 to 6 carbon atoms such as methanol and ethanol may also be employed. The amount of lower alkanol employed may range up to about one mol of alkanol per mol of formaldehyde and more preferably about 0.5 mol of alkanol per mol of formaldehyde. Other conventional organic solvents may also be employed as the reaction medium in this invention. However, from an economical point of view, Water is the preferred reaction medium.

As the molar ratio of formaldehyde to nitrogen containing compound is concerned, it is usual to employ 0.8 to 1.2 mols of the former for each active hydrogen atom attached to the amino or amido nitrogen of the latter, and more preferably to employ 1.0 mol of the formaldehyde for each active hydrogen atom attached to the amino or amido nitrogen of the nitrogen containing compound.

Instead of using single nitrogen containing compounds from among the reaction components in the process of the invention, it will be understood that mixtures of two or more such compounds may be employed. For example, it is within the contemplation of this invention to co-react melamine and urea with formaldehyde, with a melamine: urea ratio of 1 mol of melamine per 100 mols of urea to 10 mols of melamine per mol of urea.

Nitrogen containing compounds which are suitable for use in the process of this invention are for example watersoluble formaldehyde reactable nitrogen containing compounds which have amino or amido groups and consist of nitrogen, hydrogen, carbon and which in some instances also include oxygen and sulfur atoms. Urea, thiourea, melamine, aceto guanidine, acetamide, formamide, dicyandiamide, di-succicamide, methylcarbamate, tris (carbamoyl-ethyl) amine, and acetylenediurea are examples of such compounds.

The alkylolation of the nitrogen containing compounds with formaldehyde may be carried out by either a batch or a continuous system. That is, in the latter case, the nitrogen containing compounds and the formaldehyde or substance which splits off 3. formaldehyde may be continuously introduced into the same reaction vessel at the supplying ratio of 1.5 to 2.2 mols of formaldehyde per amino or amido group in the nitrogen containing compound. The contents of the reaction vessel are then heated with sufficient agitation and controlled at an alkalinity of about a pH of 10.5. After a certain period of time the reaction mixture is taken out continuously through such means as an over-flowing system and the mixture thus discharged is cooled to obtain the object alkylol derivatives of the nitrogen containing compounds. According to the continuous manufacturing method, it is quite possible to obtain the object product more efiiciently than with the batch system. The reaction time in the continuous process is again determined in correlation with the employed reaction temperature.

The compositions of this invention may be applied to cellulose textile material such as regenerated cellulose or cotton fabric by any of the Well known techniques as for example, spraying, dipping, immersing, padding and the like in such amounts as to apply from between 2 and 20 percent and in some instances higher amounts of the composition of this invention, based on the dry weight of the fabric. When the alkylolated compounds are employed in padding baths for the treatment of textile materials, the compounds are diluted with an aqueous solvent to form a padding bath concentration of about 2 percent to about 35 percent solids by weight, preferably from about 5 to percent solids by weight. The compounds of this invention are also useful on fabrics comprising synthetic fibers, or blends of synthetic fibers with cellulosic fibers.

Within certain limits, the amount of compound applied depends on the particular type of fabric being treated. Thus in treating fabric consisting of cotton fibers, a solids concentration of from 2 to about percent,

preferably from about 3 to 10 percent of the compound based on the dry weight of the fabric are utilized. In treating regenerated cellulose a 5 to 20 percent solids concentration based on the dry weight of the fabric is generally used.

Generally, the composition is applied with a curing catalyst or accelerator. The catalyst or curing accelerator employed, preferably in the aqueous treating, impregnating or finishing composition, may consist of the type comprising free acid or latent acid salts, and the like. The concentration of catalyst employed may range from between about 0.1 to about 25 percent or higher, based on the weight of resin solids and depending upon the particular type of catalyst employed. Thus, for example, from between about 0.1 to about 10 percent of a free acid, such as maleic acid, tartaric acid, oxalic acid and the like may be employed, while in the case of salts such as magnesium chloride, zinc chloride, zinc nitrate, zinc fluorborate, ammonium sulfate, mono-ammonium phosphate, aluminum chloride, the hydrochloride of ethanolamine, the hydrochloride of 2-amino-2-methyl-1-propanol, amounts of between about 5 and 25 percent have been successfully employed. In all instances, the concentration of the catalyst is based on the weight of resin solids employed.

Following the application of the treating composition to the textile fabric, it is then subjected to drying and curing operations to effect the desired improved properties. The drying and curing operations may be carried out in a single step or in separate steps. The temperature in which drying and curing operations are effected vary widely and are influenced to some extent by the type of catalyst employed. Normally, the temperature range extends from about F. to about 450 F. or even higher. Generally, the time of drying and/ or curing operations is inversely proportional to the temperature employed and of course is influenced by whether or not separate or combined drying and curing steps are employed.

Normally, when drying and curing is carried out in a combined step, a time of from about 1 minute to 10 minutes may be employed at temperatures from about 450 F. to 250 F. respectively. When the fabric has been dried preliminary to curing, curing time from 5 minutes to A minute at temperatures of 250 F. to 450 P. respectively, have been successfully employed.

As stated above, the products of this invention are usually applied to textiles in conjunction with a catalyst. In addition to the catalyst, it is customary to include a suitable textile softener or other finishing agent which may provide an additional desirable effect. Among the softeners contemplated are silicone dispersions, polyethylene dispersions, fatty esters of glycerine, polyethylene glycol, etc. Also materials such as water repelling agents, flameproofing agents, stiffening agents, fluorescent brighteners, etc, may be employed with the compounds of this invention in the treatment of fabric materials. Likewise, appropriate classes of dyestuffs may be incorporated in the treating bath so as to permit simultaneous dyeing and finishing in a single treatment. Among the dyestuffs most suitable for this type of simultaneous dyeing and finishing are the reactive dyestuffs which are based on cyanuric chloride, but other dyes may also be used in this manner.

It was also found that when compounds of this invention were applied to viscose or cotton, a permanent mechanical deformation of the fabric could be obtained. The deformation may be accomplished by impregnating the cloth with the compound together with an appropriate catalyst, and then partially drying the cloth, and then passing the cloth through a suitable calender in which the steel roll has an engraving. After the calendering, the fabric may then be cured, and the deformation imparted by the calender was found to be permanent and durable to laundering.

By a suitable modification of the instant process, the products of this invention may be employed to provide extremely high levels of wash-wear properties on cotton fabrics. Such very high levels of wash-wear properties were evidenced by dry crease recovery values of 260 C. (total of warp and filling), when the cloth was tested dry as well as when the cloth was tested wet.

The following illustrative embodiments are given merely to further describe the invention, but are not to be understood as limiting our invention solely thereto. The parts of the reactants are parts by weight.

Example (A) Approximately 311 parts of dimethyl formamide and 689 parts of formalin (37%) were charged to a reaction vessel. Approximately 10 parts of sodium hydroxide (50%) were added to the reaction mixture to adjust the pH to about 10.6. The mixture was agitated and heated to a temperature of about 60 C. and maintained at this temperature for a period of hours. The percent of unreacted formaldehyde was determined at the end of each hour. Approximately 0.4 percent of the formaldehyde and reacted.

Example (B) Example (A) was repeated except the pH of the mixture was adjusted to a pH of 9.0. At the end of the 5 hour reaction period, approximately 0.4 percent of the formaldehyde had reacted.

Example (C) 362 parts of dimethyl formamide and 638 parts of methyl formcel (46.5% formaldehyde) were charged to a reaction vessel. Approximately parts of sodium hydroxide (50%) were added to the reaction mixture to adjust the pH to about 10.7. The mixture was agitated and heated to a temperature of about 60 C. and maintained at this temperature for a period of 5 hours. Approximately 0.9 percent of the formaldehyde had reacted at the end of the 5 hour reaction period.

Example (D) Example (C) was repeated except the pH of the mixture was adjusted to a pH of 9.0. At the end of the 5 hour reaction period, it was determined that 0.7 percent of the formaldehyde had reacted.

Examples (A), (B), (C) and (D) above show that dimethylformamide and formaldehyde do not interact in either an aqueous or methanol system and that essentially none of the formaldehyde was being consumed in an unforeseen manner.

The following examples, namely, Examples I(B), II(B), III(B), IV(B), V(B), VI(B), VII(B), VIII(B) and IX(B) are included to show the ettects obtained when alkylolation is conducted according to the prior art, and

as such, are not illustrative of the specific embodiments of this invention.

Example I(A) A vessel was charged with 156 parts of urea and 844 parts of formalin (37%). Approximately 10 parts of sodium hydroxide (50%) were added to the mixture.

to adjust the initial pH to about 10.5. The mixture was heated to about 80 C. with agitation and after 3 hours the percent of unreacted formaldehyde amounted to less than (35%).

Example I(B) 6 Example II(A) Example I(A) was repeated except potassium hydroxide was substituted for sodium hydroxide At the end of the 5 hour period, approximately 69 percent of the formaldehyde had reacted.

Example d-l-(B) Example I(B) was repeated except potassium hydroxide (45%) was substituted for sodium hydroxide (50%). At the end of the 5 hour reaction period, again only approximately percent of the formaldehyde had reacted.

Exarnple III(A) A vessel was charged with 189 parts of urea and 811 parts of methyl formcel (46.5% formaldehyde). Approximately 10 parts of sodium hydroxide (50%) were added to the mixture to adjust the initial pH to about 10.7. The mixture was heated to a temperature of between and C. with agitation and the percent of unreacted formaldehyde determined at the end of each hour. At the end of a 5 hour reaction period, approximately 69 percent of the formaldehyde had reacted.

Example H'IOB) Example III(A) was repeated except the pH of the mixture was adjusted to a pH of 9.0 with sodium hydroxide (50%). At the end of the 5 hour reaction period, approximately 61 percent of the formaldehyde had reacted.

Example IV(A) A reactor was charged with 218 parts of formamide and 782 parts of formalin (37%). Approximately 10 parts of sodium hydroxide (50%) were added to the mixture to adjust the initial pH to about 10.6. The mixture was heated to about 60 C. with agitation and the percent of unreacted formaldehyde determined at the end of each hour. At the end of a 5 hour reaction period, approximately 82 percent of the formaldehyde had reacted.

Example IV (B) Example -IV (A) was repeated except the pH of the mixture was adjusted to a pH of 9.0 with sodium hydroxide (50%). At the end of the 5 hour reaction period, approximately 27.6 percent of the formaldehyde had reacted.

Example V(A) Example IV(A) was repeated except potasium hydroxide (45%) was substituted for sodium hydroxide (50%). Approximately 82 percent of the form-aldehyde had I acted at the end of a 5 hour reaction period.

Example V(B) Example IV(B) was repeated except potassium hydroxide (45%) was substituted for sodium hydroxide (50%). Approximately 25 percent of the formaldehyde had reacted at the end of a 5 hour reaction period.

Example II(A) Approximately 259 parts or form-amide and 741 parts of methyl tomncel (46.5% formaldehyde) were charged into a reactor. Approximately 10 parts of sodium hydroxide (50%) were added to the mixture to adjust the initial pH to about 10.7. The mixture was agitated and heated to a temperature of about 60 C. and the percent of unreacted formaldehyde determined at the end of each hour. It was determined that approximately 70 percent of the formaldehyde had reacted in three hours.

Example VI(B) Example VI-(A) was repeated except the pH of the mixture was adjusted to a pH of 9.0 with sodium hydroxide (50%). Approximately 13 percent of the formaldehyde had reacted at the end of the 5 hour reaction period.

7 Example VTI(-A) Example V=II(A) was repeated except the pH of the mixture was adjusted to a pH of 9.0 with sodium hydroxide (50%). At the end of 5 hours, approximately 10 percent of the formaldehyde had reacted.

8 Example X 78 parts of melamine, 620 parts of water and 302 parts of .formalin (37%) were charged to a reaction vessel. Approximately 10 parts of sodium hydroxide (50%) were added to the mixture to adjust the pH to about 10.7. The mixture was agitated and heated to a temperature of about 90 C. The percent of unreacted formaldehyde was determined at the end of each hour. Approximately 60 mrcent of the formaldehyde had reacted within a 3 hour reaction period.

The following table illustrates the results obtained in Examples 1 through X wherein a nitrogen containing compound is reacted with formaldehyde or a substance which yields formaldehyde in a highly alkaline system having a pH above 10.5 in comparison to an alkaline system having a pH of approximately 9.0.

TABLE I M01 Ratio Initial Percent Nitrogen Temp percent Formal- Example Reactants Compound: Base Solvent pH 0. Free Fordehyde Formaldemalde Reactcd hyde hyde (5 hr.)

1:2 NaOH Water 10.6 60 25. 5 0.4 1:2 NaO ..do--. 9. 60 25. 0 1:2 NaOEL... Methanol 10.7 60 29.7 0.9 1:2 NJOH 9.0 60 29.7 0.7 1:4 NaOH. Wate 10. 5 80 31. 2 66. 8 1:4 NaOH 9.0 80 31.2 59.9 1:4 KOH 10. 5 80 31. 2 68.8 1:4 OH 9. 0 80 31. 2 60.3 1:4 10. 7 85-90 37.7 08.8 1:4 9.0 85-90 37.7 61.3 Fcrmamide 1:2 0.6 60 29. 0 81. 9 1:2 9.0 00 29.0 27.6 1 :2 0. 6 60 29. 0 82. 3 1 :2 9. 0 60 29. 0 24. 5 1:2 0. 7 60 34. 5 69. 7 1:2 NuOH do 8.0 60 34.5 13.0 1:2 NaOH. Watch.-- 10.6 60 27.1 60.3 1 :2 H d 9. 0 60 27. 1 0. 6 1:2 0.5 60 31.9 49.7 1 :2 9. O 60 31. 9 6. 0 1:6 0. 6 7274 21. 7 60. 6 1:6 9. 0 72-74 21. 7 49. 8 1:6 0.7 90 11.2 59.4

Percent of formaldehyde reacted after 3 hours.

Example VIII(A) 314 parts of acetamide and 686 parts of methyl xformcel (46.5% formaldehyde) were charged to a reactor. Approximately 10 parts of sodium hydroxide were added to the mixture to adjust the pH to 10.5. The mixture was agitated and "heated to a temperature of C. The percent of unreaeted {formaldehyde was determined at the end of each hour. Approximately 50 percent of the formaldehyde had reacted within the 5 hour reaction period.

Example VIII(B) Example V111(A) was repeated except the pH of the mixture was adjusted to a pH of 9.0. Approximately 6 percent of the formaldehyde had reacted over a 5 hour period.

Example IX(A) Example IX(A) was repeated except the pH of the mixture was adjusted "to a pH of 9.0. Approximately 50 percent of the formaldehyde had reacted over a 5 hour period.

It is readily seen that formalin or methyl formcel do not react with dimethyl formamide and that formaldehyde was not being consumed in an unforseen manner.

Also it can readily be seen that under a highly alkaline system, (pH of 10.5 or above), the rate and extent of alkylolation is increased in comparison to the normal alkylolation conditions.

Example XI 330 parts of paraformaldehyde (91%), 209 parts of methanol, 130.5 parts urea, 27.4 parts of melamine and 6.9 parts of caustic soda (50%) were added to a reactor. When this mixture is made, there is an appreciable exotherm, and then the mixture is heated further to -90 C. and held at that point until the free formaldehyde content does not drop appreciably further. When the resulting product is cooled, it is an essentially clear solution of good storage stability. If desired, the slight turbidity due to undissolved paraformaldehyde may be eliminated by filtration. Approximately 15 parts of the product of this example were dissolved in 84 parts of water to which 1 part of zinc nitrate was added, and cotton cloth was impregnated with this solution. The treated cotton cloth, after curing, exhibited excellent shrinkage control, high crease recovery, and the finish was not appreciably affected by laundering in the presence of chlorine containing bleach.

Example XII 257 parts of paraformaldehyde (91%), 162.5 parts methanol, 101.5 parts urea, 64.1 parts melamine, and 5.9 parts of caustic soda (50%) were charged into a reaction vessel. After heating as indicated in Example XI, the resulting product was diluted by the addition of 409 parts of water. The resulting product can be applied to a cotton-polyester blend in the same manner described under Example XI, and the treated cloth showed excellent shrinkage control, crease recovery properties, and chlorine resistance. In spite of the presence of the melamine in this treatment, the fabric did not discolor on exposure to bleach as would be typical of an ordinary melamine formaldehyde resin made by previously known methylolation reactions.

Example XIII 502 parts of paraformaldehyde (91%), 162.5 parts methanol, 101.5 parts urea, 205.5 parts melamine, and 10.7 parts of caustic soda (50%) were charged to a reacting vessel. The product was heated and then cooled padder rolls to provide a wet pick up of approximately 70 to 80 percent. The fabric was then dried and cured at a temperature ranging from 180 F. to about 450 F.

In Table II, the values reported and tests referred to were obtained as follows:

Crease recovery values are total for warp plus fill, using AATCC Tentative Test method 66-1959t.

Chlorine resistance performed by AATCC Tentative Test method 92-19581 and wash-wear performed by AATCC Tentative Test method 88-19602 using Test #411 (spin-line dried) and using low angle illumination and three dimensional standards.

The Hydrolysis Wash (HW) is performed with a very alkaline built soap at 160 F. for 30 minutes. In the final as indicated in Example XI. The resulting product was 15 rmse Zmc 511100 flPonde 1S Included sour a clear stable liquid after it was filtered. 500 parts of water The SW Wash 15 Performed accordmg to AATCC Test were added to the finished product to prepare a material methodwhich was suitable for treating of textiles. When 100 parts The HL Wash 15 Pfirfofmed ill a regular automatic of this product were diluted with 830 parts of water, and household Washer using a household detergent, and Washthen 30 parts of magnesium chloride crystals were added, 20 ing at 140 F.

a fabric comprising a blend of cotton and polynosic rayon Table II shows the results of the tests run on the fabrics may be treated with this solution by impregnation foltreated as described in Examples XV through XXIX.

TABLE II Crease Recovery Wash-N-Wcar Percent Tensile Loss Reactants (mol Ratio) (W & F) Spin-Line Dry AATCC Chlorination Example Formaldehyde Methanol Urea Melamine Catalyst Initial 5 SW 5 KW 1 HL 1 HL 1 HL Initial 5 SW 5 HW 5 S W 5 H17 4. 6 3. 1. 0 0. 1 Zn(NOs)z 297 265 245 3. 8 4. 0 3. 4 17. 6 45. 1 66. 6 4. 6 3. 0 1. 0 0. 3 Dig C12.... 283 245 2. 2. 9 23. 3 67. 1 4. 6 3. 0 1. 0 0. 5 280 231 204 3. 4 3. 6 l. 8 37. 0 88. 8 91. 8 4. 6 3.0 1. 0 0. 75 269 224 190 2. 6 2. 2 1.7 20. 7 9i. 0 93. 8 5. 0 3. 0 1. 0 0. 1 284 268 229 4. 1 3. 8 3. 5 14. 8 26. 6 62. 5 5. 0 3. 0 1. O 0. 3 285 246 212 2. 3 3. 7 2. 0 32. 4 63. 4 84. 2 5. 0 3. 0 1. 0 0. 5 267 245 224 2. 3 2.0 1.6 28. 0 75. 0 77. 9 5. 0 3. 0 1. 0 0.75 270 236 173 4.0 3. 5 3.8 6. 5 73. 6 87. 2 6. 0 3. 0 1. 0 0.1 314 276 240 3.8 4.0 3. 5 12.5 33. 3 60. 6 6. 0 3. 0 1. 0 0.75 274 200 260 3. 8 3. 7 3. 2 9. 5 26. 6 86. 7 7. 0 3. 0 1. 0 0. 1 300 278 247 4. 0 4. 0 3. 2 13. 7 16. 2 57. 5 7.0 3. 0 1. 0 0. 75 283 257 209 3. 8 3.8 3. 5 5. 0 24. 4 80. 3 8. 0 3. 0 l. 0 0. 75 284 238 212 4. 0 3. 8 3. 8 13. 3 23. 5 69. l 9. 0 3. 0 I. 0 1. 0 281 244 254 4. 0 4. 0 4. 2 12. 5 22. 5 51. 3 10. 0 3. 0 l. 0 1. 0 282 255 220 3. 7 3. 8 4.1 0. 0 2. 3 47. 8

lowed by drying and curing at 150 C. for 5 minutes. The resulting treated cloth has excellent crease recovery properties, was shrinkage resistant, and when laundered in the presence of bleach, it does not discolor nor does it lose strength.

Example XIV 360.8 parts of paraformaldehyde (91%), 290 parts methanol, 109.5 parts urea, 230 parts melamine, and 10 parts of caustic soda, (50%) were charged to a reactor. This product was then heated and cooled as indicated in Example XI. The resulting product was a clear, stable liquid after filtration. parts of this product was diluted with 75 parts of water, and then 5 parts of a solution of Z-amino-Z-methyl-l-propanol hydrochloride were added, it formed a solution suitable for treating textiles. For example if a nylon marquisette fabric was impregnated with solution and the impregnated fabric was dried and cured, the resulting treated cloth was found to have an attractive, stiff, resilient finish.

Examples XV to XXIX In each of these examples, the formaldehyde or material which yields formaldehyde, urea, melamine and methanol were added to a reaction vessel in the ratio as shown in the Table II herein. To this mixture was added approximately one percent by weight of a caustic soda. The reaction mixture was brought to reflux temperature, 85-90 C. over a 30 to 45 minute period of time and held at this temperature for 2 hours. The reaction product was cooled to 25 C. and diluted with water to reduce the total solids content to between 30 and 33 percent.

A solution, containing approximately 6 percent by weight, of the highly alkylolated compound and a suitable catalyst were applied to a cotton broadcloth. The excess solution was squeezed off by passing the cloth through Surprisingly it was found that the degree and rate of alkylolation of the nitrogen containing compounds were enhanced in a highly alkaline system. Also the products obtained from the highly alkaline system were considerably more stable than the products made under prior reaction conditions.

Furthermore these highly alkylolated products will impart a durable finish on fabrics when cured with an acid or latent acid catalyst. It has also been found that the overall performances of these products such as crease recovery, wash-n-wear and chlorine resistance may be further modified to enhance one particular property by either varying the ratio of the respective nitrogen containing compounds in the mixture or by varying the catalyst system.

Also the products of this invention will impart crease resistance and shrinkage control when applied to textile fabrics. Textile fabrics treated with these compositions are resistant to discoloration due to heat, show excellent resistance to degradation when subjected to a chlorine containing bleach and are durable through a number of launderings.

Cellulose acetate, nylon and other synthetic hydrophobic fibers exhibit a highly desirable stiffening effect and excellent resiliency when treated with the alkylolated products described herein.

We claim as our invention:

1. A process for preparing a highly alkylolated textile finishing composition which comprises reacting a compound having at least one active hydrogen atom attached to the nitrogen atom of a member selected from the group consisting of amino and amide groups contained in said compound with from 0.8 to 1.2 mols of formaldehyde for each of said active hydrogen atoms at a pH of at least 10.5.

2. The process according to claim 1 wherein the compound is carbamide.

3. The process of claim 1 wherein the compound is an s-triazine.

4. The process according to claim 1 wherein the compound is a mixture of a carbamide and an s-triazine.

5. The process according to claim 1 wherein said compound has at least two active hydrogen atoms attached to said nitrogen atom.

6. The process according to claim 5 wherein the compound is a carbamide.

7. The process according to claim 5 wherein the reaction is conducted in the presence of a solvent.

8. The process according to claim 7 wherein the solvent is a lower alkanol.

9. The process according to claim 7 wherein the solvent is water.

10. A process for preparing a highly alkylolated textile finishing composition which comprises reacting a mixture of compounds each of which has at least one active hydrogen atom attached to the nitrogen atom of a member selected from the group consisting of amino and amido groups contained in said compound with from 0.8 to 1.2 mols of formaldehyde for each of said active hydrogen atoms at a pH of at least 10.5.

11. The process according to claim 10 wherein each of said compounds have at least two active hydrogen atoms attached to said nitrogen atom and wherein the reaction is conducted in the presence of a solvent.

12. The process for preparing a highly alkylolated textile finishing composition which comprises reacting a mixture of melamine and urea with one mol of formaldehyde for each active hydrogen atom contained in the amino and amido groups in said melamine and urea at a pH of at least 10.5 and in the presence of a lower alkanol solvent.

13. The process for preparing a highly alkylolated textile finishing composition which comprises reacting a mixture of melamine and urea with one mol of formaldehyde for each active hydrogen atom contained in the amino and amido groups in said melamine and urea at a pH of at least 10.5 and in the presence of water.

14. A textile finishing composition consisting essentially of an aqueous solution containing from 2 to by weight of said solution of a highly alkylolated composition obtained by reacting a compound having at least one active hydrogen atom attached to the nitrogen atom of a member selected from the group consisting of amino and amido groups contained in said compounds with from 0.8 to 1.2 mols of formaldehyde for each of said hydrogen atoms at a pH of at least 10.5 and in presence of a catalyst selected from the group consisting of maleic acid, tartaric acid, oxalic acid, zinc chloride, zinc nitrate, magnesium chloride and a hydrochloride of 2-amino-2- methyl-l-propanol.

15. The textile finishing composition of claim 14 wherein said compound is a carbamide.

16. A textile finishing composition consisting essentially of an aqueous solution containing from 2 to 35% by weight of said solution of a highly alkylolated composition obtained by reacting a mixture of melamine and urea with one mol of formaldehyde for each active hydrogen atom contained in the amino and amido groups in said melamine and urea at a pH of at least 10.5 and in presence of a catalyst selected from the group consisting of maleic acid, tartaric acid, oxalic acid, zinc chloride, zinc nitrate, magnesium chloride and a hydrochloride of 2- amino-Z-methyl-l-propanol.

17. The process for treating a textile fabric which comprises applying to said fabric an essentially aqueous medium containing an at least partially water soluble product obtained by reacting an compound having at least one active hydrogen atom attached to the nitrogen atom of a member selected from the group consisting of amino and amido groups contained in said compound with from 0.8 to 1.2 mols of formaldehyde for each of said active hydrogen atoms at a pH of at least 10.5 and in presence of an acid acting catalyst, and thereafter curing said product to a water insoluble state at a temperature of from F. to 450 F.

18. A process for treating a textile fabric which comprises applying to said fabric an essentially aqueous medium containing an at least partially water soluble product obtained by reacting a mixture of melamine and urea with from 0.8 to 1.2 mols of formaldehyde for each active hydrogen atom attached to the nitrogen atoms of said melamine and urea at a pH of at least 10.5 and in presence of an acid acting catalyst, drying said treated fabric at a temperature of at least 180 F. and thereafter curing said product to a water insoluble state at a temperature of from 200 F. to 450 F.

References Cited UNITED STATES PATENTS 2,529,856 11/1950 West et a1 26067.6 2,684,347 7/ 1954 Nickerson 260-676 X 2,690,404 9/ 1954 Spangler et al 11756 2,804,402 8/ 1957 Williams 117139.4 ..2,950,553 8/1960 Hurwitz ll7-139.4 X 3,211,805 10/1965 Herbes et al. 1l7-139.4 X 2,797,206 6/1957 Suen et al. 260-675 2,825,710 3/1958 Etzel 117l39.4 3,043,719 7/1962 Burr et a1. 117-1394 WILLIAM D. MARTIN, Primary Examiner.

T. G. DAVIS, Assistant Examiner.