US3323939A - Process for imparting rot and wrinkle resistant finish to a cellulosic textile material and the resulting textile - Google Patents

Description

United States Patent 3,323,939 PROCESS FOR IMPARTING ROT AND WRINKLE RESISTANT FINISH TO A CELLULOSIC TEX- ;EE MATERIAL AND THE RESULTING TEX- William Julius Van Loo, Jr., Middlesex, N.J., assignor to American Cyanamid Company, Stamford, Conn., a corporation of Maine No Drawing. Filed Mar. 9, 1964, Ser. No. 350,533 13 Claims. (Cl. 117-76) The present invention relates to processes for imp-roving the wrinkle resistant properties of textile materials and to the textile materials so finished. More particularly the invention relates to processes for treating textile materials whereby they are made both crease resistant and rot resistant.

The primary object of the invention is accomplished by treating cellulosic textile materials, which have previously been treated for rot resistance by a wet steam process, with a non-aqueous solution of a difunctional compound and heat curing the thus treated material. This finishing treatment imparts both a crease resistance and a rot resistance to the textile material without seriously affecting the tensile strength of the material.

It is known that cellulosic textile materials can be treated with hardenable aminoplasts to render the materials resistant to the attack of microorganisms. However, while a degree of rot resistance is obtained from these resins, it is accomplished by a loss in the tensile strength of the materials. In US. Patent No. 2,763,574 there is described a wet steam process for treating materials with these hardenable aminoplasts whereby rot resistance is imparted to the textiles without loss of fabric strength. This wet steam process will be more fully described in a later paragraph. While this type of treatment, as described in the above-identified patent, imparts rot resistance to the textiles, it does not impart any other improvements in the major physical properties desired in fabrics such as wrinkle resistance or wrinkle recovery.

It is also known that cellulose-containing textile material can be treated with creaseproofing resins to impart wrinkle recovery properties to the material. These creaseproofing resins are generally applied to fabrics free from sizes or other finishes, and while they improve the wrinkle recovery properties of the fabric, there is always suffered a loss in tensile strength. Such creaseproofing resins, like those of the hardenable aminoplasts, are applied to the materials in a water-soluble state and then dried and cured. However, while a fabric which has been finished with these resins is characterized by improved wrinkle resistance, the effect of the curing of the resin whereby cross-linking of the fibers is effected results in reducing the tensile strength of the material.

The inventor has found that by treating the textile materials with -a resin capable of imparting rot resistance to the material by the wet steam process and then subsequently treating it with a difunctional compound from a non-aqueous solution and heat curing the same, that creaseproofing properties are imparted to the textile without the use of a creaseproofing resin.

When creaseproofing resins are normally applied to textiles from aqueous solutions, the fibers swell so that the resin can cross-link and react with the fibers during curing, thereby giving it crease resistance. However, the difunctional compounds used in this invention are water insoluble or water reactive and thus are not applicable from an aqueous solution. It will be appreciated that the application of the difnnctional compound from nonaqueous solutions will not produce fiber swelling, and without fiber swelling the compounds normally would not be expected to impart any wrinkle recovery properties to 3,323,939 Patented June 6, 1967 ice the materials. In addition, if the materials were treated with these compounds from non-aqueous solutions there would be excessive discoloration and loss in tensile strength of the materials.

However, the inventor has found that if these same non-aqueous solutions of the difunctional compounds are applied to a cellulosic material which has previously been treated for rot resistance by the wet steam process an unexpected result is obtained. It is found that crease resistant properties are imparted to the material without any substantial loss in the rot resistant properties given to the material by the resin treatment or in the tensile strength of the material.

The wet steam process as described in US. Patent No. 2,763,574 is essentially a process wherein the hardenable aminoplast is cured on the fabric in the presence of about 45% of the water in the original impregnating aqueous resin solution. By' fixing the aminoplast with little or no drying of the impregnated fibrous material, tensile strength properties are retained. The inventor pretreats the cellulosic textile materials with hardenable aminoplasts by this wet steam process. This process used by the inventor involves applying to the fabric by any convenient method an aqueous solution of the aminoplast resin containing a curing catalyst. The fabric is then rolled up tightly on a dowel, rod or shell and placed in a suitable container of a size such that very little free space exists. The container is closed but is fitted with a small opening to allow for the release of potential pressure build-up but insufiiciently large to allow for the significant escape of moisture. In the examples which follow, the complete assembly was then placed in an oven at 210 F. and allowed to remain for 2.5 hours. The assembly is then removed and the fabric unrolled and allowed to dry at room temperature. As can be seen from the reference patent, there are other ways of elfecting affixation of the aminoplast in the presence of moisture without substantial drying and these are well within the scope of this invention.

Suitable hardenable aminoplasts which can be used to pretreat the fabric by the wet steam process include condensations of formaldehyde with compounds such as urea, thiourea, cyanamide, dicyandiamide, biguanide, melamine, formoguanamine, acetoguauamine and so forth, including their alkyl and acyl compounds. Particularly suitable are the water-soluble condensation products of melamine and formaldehyde and in particular the methylol or methoxymethyl derivatives of melamine. These include various compounds as methylated methylol melamines, such as hexa(methoxymethyl)melamine and the preferred dimethylol melamine.

Advantageously, curing catalysts are added to the solutions of the resins, and suitable catalysts include diacetin, monochlorohydrin, dichlorohydrin, glycol ethyl etheracetate, glycol methyl ether acetate and the like, with the preferred catalyst being diacetin.

These resins are applied in their aqueous solutions by the wet steam process as previously described through general methods of application such as spraying, dipping, immersion or padding. Generally the resins are applied in an amount of from 1 to 30% resin solids based on the weight of the fabric and generally included is a curing catalyst amounting from 2 to 25% based on the weight of the resin. When properly processed, the treated textile material will show approximately or higher of the initial amount of resin applied remaining after boiling for 30 minutes in water. The amount of resin fixation is determined by nitrogen analysis.

The cellulosic textile materials which can be used include cotton, rayon, linen, hemp, jute or the like. They may be present in combination with up to 50% of other natural or synthetic fibers 'such as wool, acetate, nylon, polyester fibers such as Dacron, acrylic fibers such as Creslan, Orlon, Acrilan and the like. Preferably, the textile material is a formed woven cotton fabric.

The difunctional compounds used in the second step of this two-step process refers to those types of compounds having two functional or reactive groups attached to a divalent radical. These compounds may be used in combination with a suitable catalyst. Examples of difunctional compounds contemplated in this invention include those represented by the following general formula:

whereinX can represent hydrogen or halogen and R can be (CH with n an integer from zero to 12, arylene or lower alkylarylene. This formula includes such specific compounds as oxalyl chloride, succinyl chloride, glutaryl chloride, pimelyl chloride, succinaldehyde, pimelaldehyde, terephthaloyl chloride, terephthalaldehyde, S-methylisophthaloyl chloride and S-methylisophthalaldehyde.

Other suitable difunctional compounds include compounds which contain two functional or reactive halomethyl groups and in particular chloromethyl groups per molecule. The divalent radical to which these reactive groups may be attached includes oxygen and residues of lower alkylene ethers, lower dialkylene polyethers, alkylenediamine and substituted alkylenediamines, alkyl'enediamides. and substituted alkylenediamides, urea, imidazolidones, pyrimidinones, uron, triazones, triaminotriazines, diaminodiazines, and diurein. Examples of these chloromethyl ethers include such compounds as chloromethyl ether, 1,2-ethylene bis(chloromethyl ether), bis(chloromethyl ether) of diethylene glycol, 1,2-propylene bis(chloromethyl ether), N,N'-di(chloromethyl)propylene-l,3- diamine, N,N-di(chloromethyl)succinamide, N,N-di (chloromethyl)urea, N,N' di(chloromethyl)imidazolidone-2, N,N-di(chloromethyl)pyrimidinOne-Z, N,N'-di (chloromethyl)uron, N N -di(chloromethyl) N -(betahydroxyethyl)tetrahydrotriazone-Z, N,N'-di(chloromethyl)melamine, N,N'-di(chloromethyl)acetoguanamine or N,N',N,N"'-tetra (chloromethyl) acetylenediurein.

Also suitable for this invention are compounds which contain two aziridinyl groups per molecule. Such compounds are characterized by the following formula:

R20 X C l\ 320 i \CRH wherein R may be hydrogen or lower alkyl and X may be oxygen or sulfur and Ycan be another aziridinyl group, a. lower alkyl substituted aziridinyl group, aryl or lower alkylether. Examples of these include such compounds as tris(aziridinyl)phosphine oxide, tris(aziridinyl)phosphine sulfide, tris(Z-methylaziridinyl)phosphine oxide, phenylbis(2-methylaziridinyl)phosphine oxide, or ethoxy-bis(2- methylaziridinyl)phosphine oxide. 4

Certain compounds which are water insoluble and contain at least two reactive alkylol or alkoxyalkyl groups are also suitable for this invention. These compounds include the methylol or alkoxymethyl derivatives of alkylene diamides of more than six carbon atoms. For example, N,N'-dimethylolazelaamide. Also suitable are the ethoxymethyl or higher alkoxymethyl derivatives of urea and uron. For example, N,N' bis(n-propoxymethyl)urea and N,N'-bis(n-propoxymethyl)uron. In addition, the water insoluble higher alkoxymethyl derivatives of triamino triazines are suitable difunctional agents. This includes among other compounds N,N',N"-tris(n-butoxymethyl) N,N-dimethylol melamine.

The catalysts which may be advantageously used with these heat curable difunctional compounds may be metal salts such as the chlorides and nitrates of magnesium, zinc and aluminum. Amine and alkanolamine salts such 4. as ethanolamine hydrochloride may also be employed as catalysts. I V v I Since these difunctional compounds are water insoluble or water reactive, they can only be applied from nonaqueous solvent solutions. Suitable solvents which can be used and which are compatible with the catalysts used, if any, include such solvents as acetone, methyl ethyl ketone, benzene, toluene and the like.

These difunctional compounds which are applied .in the form of non-aqueous solution are usually applied in an amount of from 1 to 30% based on the weight of the fabric. The catalyst used, if any, is usually from about .5% to about 40% based onthe compound solids.

After the material is treated with these difunctional compounds, it is usually dried at about 150 to 400 F.

for anywhere from .25 to 3.0 minutes. It is then cured at about 250 to 500 F. for anywhere from .5 to 3.0 minutes. Since, in general, time and temperature are inversely proportional, i.e., as the time increases, the temperature may be lowered and as the time decreases, the temperature may be elevated, wide limits of time and temperature can be employed.

The non-aqueous solution of the difunctional compound may be applied by any convenient means such as spraying, dipping, immersion or padding. The preferred method is by padding through a microset padder.

By combining this wet steam process for applying a. rot resistant or pre-treatment resin to a textile with a subsequent treatment of a non-aqueous solution of a difunctional compound and heat curing the same, new and unexpected results are obtained. The subsequent examples will show that if these cellulosic materials are treated merely with a hardenable aminoplast resin by the wet steam process as described in US. Patent No. 2,763,574, the materials have rot resistance and no loss in tensile strength, but no wrinkle recovery. However, the results also show that if these materials which have been pretreated by the wet steam-process are subsequently treated with a difunctional compound, they show good wrinkleresistance without substantial loss in the tensile strength or the rot resistance properties previously obtained. This improvement in the wrinkle resistant properties of the textile materials is accomplished by the applicationof these difunctional compounds which by themselves would give to the textile materials no wrinkle resistant properties. Thus the inventor has found that the wrinkle resistant properties of textiles may be greatly enhanced without a substantial loss of tensile strength by treating them with two separate treatments which by themselves would not impart to the textiles any wrinkle resistant properties. Because of this treatment there is obtained a combined rot resistant and wrinkle resistant finish for cellulosic textile material.

The following examples illustrate the invention.

Example 1 Cotton percale x 80) was treated with 10% solids of dimethylol melamine containing 10% diacetin (on weight of resin) as a catalyst by the wet steam process previously described. The wet fixation time was 2.5 hours and the percent resin fixation was determined by nitrogen analysis. Initially the treated fabric had a nitrogen content of 3.95% and after boiling for 30 minutes in water, it was 2.1 1% indicating that 54% of the resin was fixed to the fabric.

The nitrogen content indicates that sufiicient resin has been afiixed to the cotton material to assure rot resistance as at least 2% nitrogen is all that is necessary to obtain a rot resistant cellulosic material.

The wrinkle recovery of the fabric was measured on a Monsanto Wrinkle Recovery Tester and the'values are reported in degrees, following the tentative test method of 66-1956 described on page 158 of the 1957 Technical Manual and Year Book of the American Association of Textile Chemists and Colorists, vol. 33.

The tensile strength was measured on a Scott Tester according to ASTM standards.

The results of the tests run on the fabrics indicated that untreated cotton fabric had a wrinkle recovery of 168 degrees and a tensile strength of 91 pounds. The cotton fabric which had been treated with dimethylol melamine by the wet steam process had a wrinkle recovery of 171 degrees and a tensile strength of 91 pounds. While the fabric has rot resistance, the treatment has given the fabric no wrinkle resistance and has not adversely affected its tensile strength.

Example 2 A sample of a fabric wet steam treated as in Example 1 was subsequently treated with 5% solids based on the weight of the fabric of succinyl chloride from an acetone solution through a microset padder. The thus treated material was dried for 2 minutes at 225 F. and cured for 1.5 minutes at 350 F. in a circulating hot air oven. The fabric was then tested for wrinkle recovery and tensile strength by the test methods outlined in Example 1. Results indicated that the fabric now had a wrinkle recovery of 238 degrees with a tensile strength of 62 pounds.

While an application of succinyl chloride alone to the material would have destroyed it and given it no wrinkle recovery, the results indicate that when used in combination with the wet steam pretreatment, good wrinkle recovery properties are obtained over those which had been merely pretreated as shown in Example 1. The results also show that the tensile strength of the material is not affected too adversely. When other acid chlorides such as oxalyl chloride, glutaryl chloride or pimelyl chloride are substituted for the succinyl chloride or in mixture with it, good wrinkle recovery properties are also obtained.

Example 3 A sample of the fabric wet steam treated as in Example 1 was treated with an aqueous solution of .7% based on the weight of the fabric of magnesium chloride as a suitable catalyst for the difunctional compound through a microset padder. The thus treated fabric was dried for 2 minutes at 225 F. in a circulating hot air oven. The fabric was then treated with a 5% solution of terephthalaldehyde in acetone through a microset padder. After obtaining a wet pickup of 100%, the fabric was dried for 2 minutes at 225 F. and cured for 1.5 minutes at 350 F. in a circulating hot air oven.

The fabric was then tested for its wrinkle recovery and tensile strength by the test methods of Example 1. The results indicated that the fabric now had a wrinkle recovery of 246 degrees with a tensile strength of 68 pounds. The results here indicate that when terephthalaldehyde is used in combination with an aminoplast resin which has been applied by the wet steam process, that good wrinkle recovery properties are obtained.

When other aldehydes such as succinaldehyde, pimealdehyde, S-methylisophthalaldehyde are substituted for the terephthalaldehyde or in mixture with it, good wrinkle recovery properties are also obtained.

Example 4 A sample of the fabric treated by the wet steam process as described in Example 1 was treated with 5% solids based on the weight of the fabric of terephthaloyl chloride in an acetone solution through a microset padder. The thus treated fabric was dried for 2 minutes at 225 F. in a circulating hot air oven, and cured for 1.5 minutes at 350 F.

The fabric was then tested for its wrinkle recovery and tensile strength by the test methods of Example 1. The results indicated that the fabric had a wrinkle recovery of 238 degrees and a tensile strength of 64 pounds. These results indicate that when terephthaloyl chloride is used in combination with the rot resistant aminoplast resin applied by the wet steam process, that the material has obtained good wrinkle recovery properties without a great loss in tensile strength.

When S-methylisophthaloyl chloride was substituted for terephthaloyl chloride or in mixture with it, good wrinkle recovery properties were also obtained.

It will be appreciated that at any stage in the abovedescribed process other textile finishing agents and auxiliaries may be employed, such as softeners, lubricants, brighteners, odors, and the like.

I claim:

7 1. A process for imparting to cellulose containing textile materials rot and wrinkle resistance with minimum tensile strength losses, which comprises treating the material with an aqueous impregnating solution of a melamine formaldehyde resin in an amount of from 1 to about 30% based on the weight of the material which contains a curing catalyst, curing said resin impregnated material in the presence of water, subsequently applying to said treated material a non-aqueous solution of a member of the group consisting of water insoluble and water reactive difunctional compounds in an amount from 1 to about 30% based on the Weight of the material of said difunctional compounds and heat curing the thus treated material.

2. A process for importing to cellulose containing textile materials rot and wrinkle resistance with minimum tensile strength losses, which comprises treating the material with an aqueous impregnating solution of a melamine formaldehyde resin containing a curing catalyst so as to apply from 1 to 30% of said resin based on the weight of the material, curing said resin impregnated material in the presence of water, subsequently applying to said material a non-aqueous solution of from 1 to 30% based on the weight of the material of a difunctional compound of the following formula:

where X is a member of the group consisting of halogen and hydrogen and R is a member of the group consisting of (CH with n an integer from zero to 12, arylene or lower alkylarylene and heat curing the thus treated material.

3. A process according to claim 2 wherein the melamine formaldehyde resin is applied in an amount of from 1 to about 30% based on the weight of the material and the difunctional compound is applied in an amount of from 1 to 30% based on the weight of the material.

4. A process according to claim 3 wherein the difunctional compound is succinylchloride.

5. A process according to claim 3 wherein the difunctional compound is terephthalaldehyde.

6. A process according to claim 3 wherein the difunctional compound is terephthaloyl chloride.

7. A process for imparting to cellulose containing textile materials rot and wrinkle resistance with minimum tensile strength losses, which comprises treating the material with an aqueous impregnating solution of dimethylol melamine with a curing catalyst so as to apply from 1 to 30% of said dimethylol melamine to said materials curing said resin impregnated material in the presence of water, subsequently applying to said material a non-aqueous solution of succinyl chloride so as to apply from 1 to 30% of said chloride to the material and heat curing the thus treated material.

8. A rot and wrinkle resistant cellulose containing textile material having thereon from 1 to 30% based on the weight of the material of a wet cured melamine formaldehyde resin and from 1 to 30% based on the weight of the material of a dry cured member of the group consisting of water insoluble and water reactive difunctional compounds.

9. A rot and wrinkle resistant cellulose containing textile material having thereon from 1 to 30% based on the the following formula:

X-CRCX wherein X is a member of the group consisting of halogen .and hydrogen and R is a member of the group consisting of (CH with m an integer from Zero to 12, arylene or lower alkylarylene. v

10. A textile material according to claim 9 wherein the difunctional compound is'succinyl chloride.

11. A textile material according to claim 9 wherein the difunctional compound is terephthaloyl chloride.

12. A textile material according to claim 9 wherein the difunctional compound is terephthalaldehyde.

13. A rot and wrinkle resistant cellulose containing textile material having thereon a'dimethylolmalamine resin cured in the presence of Water and a dry cured nonaqueous solution of. succinyl chloride.

References Cited UNITED STATES PATENTS 'WILLIAM D. MARTIN, Primary Examiner;

T. G. DAVIS, Assistant Examiner.

Dedication 3,323,939. -Mlliam Julius Van Loo, Jr.. Middlesex, NJ. PROCESS FOR IMPARTING ROT AND WRINKLE RESISTANT FINISH TO A CELLULOSIC TEXTILE MATERIAL AND THE RESULTING TEXTILE. Patent dated June 6, 1967. Dedication filed Mar. 4, 1983, by the asaignee, American Cyanamid Co.

Hereby dedicates the remaining term of said patent to the Public.

[Oflicial Gazette May 31, 1983.]

Claims (1)

1. A PROCESS FOR IMPARTING TO CELLULOSE CONTAINING TEXTILE MATERIALS ROT AND WRINKLE RESISTANCE WITH MINIMUM TENSILE STRENGTH LOSES, WHICH COMPRISES TREATING THE MATERIAL WITH AN AQUEOUS IMPREGNATING SOLUTION OF A MELAMINE FORMALDEHYDE RESIN IN AN AMOUNT OF FROM 1 TO ABOUT 30% BASED ON THE WEIGHT OF THE MATERIAL WHICH CONTAINS A CURING CATALYST, CURING SAID RESIN IMPREGNATED MATERIAL IN THE PRESENCE OF WATER, SUBSEQUENTLY APPLYING TO SAID TREATED MATERIAL A NON-AQUEOUS SOLUTION OF A MEMBER OF THE GROUP CONSISTING OF WATER INSOLUBLE AND WATER REACTIVE DIFUNCTIONAL COMPOUNDS IN AN AMOUNT FROM 1 TO ABOUT 30% BASED ON THE WEIGHT OF THE MATERIAL OF SAID DIFUNCTIONAL COMPOUNDS AND HEAT CURING THE THUS TREATED MATERIAL.