US2457853A

US2457853A - Treatment of textiles and composition therefor

Info

Publication number: US2457853A
Application number: US555044A
Authority: US
Inventors: Henry L Van Mater
Original assignee: Nat Lead Co
Current assignee: NL Industries Inc
Priority date: 1944-09-20
Filing date: 1944-09-20
Publication date: 1949-01-04
Anticipated expiration: 1966-01-04

Description

Patented Jan. 4, 1949 TREATMENT OF TEXTILES AND COM- POSITION THEREFOR Henry L. Van Mater, Highland Park, N. J., as-

signor, by mesne assignments, to National Lead Company, New York, N. Y., a corporation of New Jersey No Drawing. Application September 20, 1944, Serial No. 555,044

Claims. 1

The present invention relates to compositions for rendering textile materials water repellent, to water repellent textile materials and to methods of treating textile materials with such compositions. The invention has particular reference to the employment of zirconium compounds for this purpose.

Suggestions have been made heretofore for rendering textile. materials water repellant by employing zirconium compounds as the textile treating agent and, in general, the textile was impregnated with a basic zirconium compound such as the hydrate upon which a soap forming fatty acid was deposited. Such an operation normally required more than one bath and, hence, there was no control of the relative amounts of materials used and, furthermore, where zirconium salts of mineral acids were employed as the starting materials, tendering of the cloth by reason of the high acid content of such salt solutions was usually encountered. In general, such prior treatments are defective in that the cloth was not permanently treated since the precipitated fatty acid was removed by emulsification when washed in soap solutions as in laundering, and by extraction when cleaned with the ordinary dry cleaning solvents.

It is an object of the present invention to pro- I vide a bath composition for treating textile goods, which bath contains controlled and critical amounts of materials.

It is also an object of the invention to provide a textile treating method wherein compounds of zirconium that are relatively inert to dry cleaning solvents and to soap solutions are placed upon textile goods in controlled and desired amounts.

It is a further object of the invention to use relatively non-acidic zirconium compounds for the treatment of textile fibers.

It is also an object of the invention to provide textile treating baths that are relatively stable at ordinary temperatures but which possess a relatively well-defined decomposition point at and above which water repellant zirconium compounds are precipitated on and in the fiber to be treated.

In accordance with the present invention, a solution of the desired concentration oi zirconium salt is made by employing substantially any water soluble zirconium compound. In general, zirconium salts of mineral acids are employed for this purpose. The zirconium salt is then changed to a water soluble double carbonate-by reacting the zirconium salt with a carbonate of and the like.

an alkali metal including ammonium. The resultant solution is mildly alkaline and at room temperatures, and temperatures below about 0., maybe maintained for considerable periods of time with but little decomposition due to loss of carbon dioxide. However, at temperatures above about 0., decomposition of the double carbonate proceeds rapidly and is complete in a matter of a few minutes. The amount of alkali metal carbonate admixed with the soluble zirconium salt is substantially that quantity necessary to produce the double carbonate in accordance with the following reaction wherein zirconium sulfate and ammonium carbonate are the reactants:

The treating composition of the present inven-' tion is made by mixing with the double carbonate an amount of soluble soap sufiicient to react with the double carbonate to produce a zirconium mono fatty acid compound. The soluble soap may be substantially any soluble salt of any of the soap forming higher fatty acids as, for instance, the alkali' metal salts including ammonium of oleic acid, stearic acid, palmitic acid, The resultant solution is a colloidal solution of the double carbonate and soap which may be maintained at room temperatures for several hours without appreciable chemical action 'occuring between the ingredients.

However, when the temperature of the bath is raised, the speed of the reaction is rapidly accelerated and, above about 60 0., carbon dioxide is evolved copiously, and reactionoccurs between the resulting zirconyl ion and the soap to form a basic zirconyl mono fatty acid, a compound insoluble in water and in most organic solvents, particularly those used as dry cleaning solvents. At temperatures at which decomposition occurs, the double carbonate reacts with the soluble salt of the fatty acid in accordance with the following equation where F" represents a fatty acid radical:

It will be noted that all soluble products are either decomposed and removed by heating or it not so decomposed and removed are then removed in the final washing. Thus the insoluble basic zirconyl mono fatty acid compound remains deposited in or on the material so treated.

In accordance with the present invention, therefore, the material to be rendered water repellant is impregnated or padded with the colloidal mixture of soap and soluble double carbonate of zirconium at a temperature below the rapid decomposition point of the mixture. The material, such as textile goods, may be impregnated or padded in any suitable manner although, in general, the goods will be immersed in the solution and excess solution removed by squeezing or centrifuging so that the goods re-' tain sufllcient solution to produce water repellency upon subsequent processing. Thereafter, the impregnated goods are heated in any desirable fashion to a temperature above which rapid decomposition occurs with the formation of zirconyl mono fatty acid. This may be done by treating the goods on hot or calender rolls or by contact with hot air. Thereafter, the goods, having deposited thereon, or having absorbed therein, the precipitated zirconyl mono fatty acid are washed to eliminate soluble by-products and are finally dried and finished in any desirable fashion.

In carrying out the method, certain operating controls must be followed; namely, the impregnation should be carried out below about 50 C. and the goods impregnated with the treating solution should be then heated to a temperature above about 60 C. and preferably to 80 to 100 0. Furthermore, the amount of soluble fatty acid soap employed should be relatively close to one mole of fatty acid soap for each mole of zirconium salt present. If more than one mole of fatty acid salt is used, a precipitate is obtained which is zirconyl mono fatty acid combined with a mole of free fatty acid, which type of compound is not entirely insoluble in dry cleaning solvents as the free fatty acid is extractable from the complex. Where the mole relation is such that substantially less than one mole of fatty acid soap is employed per mole of zirconium salt, the fullest advantages of the present invention are not obtained.

Somewhat better control of the operating procedure is obtained if care is taken with respect to the type or lay-product salts produced, it being preferred that such salts be of the type which readily form supersaturated solutions. Sodium acetate and sodium sulfate are salts of this type. By-product salts, as for instance sodium chloride. show some tendency to precipitate the colloidal mixture by salting out the colloid. In such in-- stances it is advantageous to add an equal mole ratio of ammonium acetate. There is thus formed. from the soluble soap, an ammonium fatty acid and acetate of alkali metal.

The following illustrations will serve to show the application of the method. The concentrations of chemicals are merely by way of illustration since the concentration will depend upon the over-all operating conditions and the type of goods being treated. It will be understood, however, that the manipulative steps of the treatment are substantially the same under all conditions.

- Example N0. 1

56.8 grams of ammonium carbonate are dissolved in 500 ml. of water at room temperature. To the resulting solution is added 40 grams of zirconium sulfate crystals with mechanical stirring. Stirring is continued until the zirconium sulfate is dissolved.

34% grams of sodium oleate are dissolved in 500 ml. of water with heating to approximately 4 C. The soap solution is then cooled to between 40 and 50 C. when it is then mixed with the solution containing the zirconium double car bonate.

The material to be made water repellant is then introduced into the colloidal mixturefor a period of 30 to 60 seconds. It is then freed from excess solution by squeezing or centrifuging andheated either in hot air, to between 80 C. and C., or by hot calendering. The material is then passed into water to dissolve out b'y-product salts, and finally dried.

. Example No. 2

Example No. 3

30 grams of ammonium carbonate are dissolved in a solution made up of 425 ml. of water .and '75 ml. of 5 Normal ammonium hydroxide. 30 grams I of zirconium sulfate crystals are added to the above solution with stirring. Stirring is continued until solution is complete.

24 grams of stearic acid are added to 325 ml. of water and 1'75 ml. of 5 Normal ammonium hydroxide. The mixture is heated until the resulting solution is clear. The solution is then cooled to between 40 and 50 C. and then mixed with the zirconium solution.

The promdure for treatment of the material is the same as in Example 1.

Example No. 4

1%.10 grams of anhydrous sodium carbonate are dissolved in 250 ml. of water. 36.25 grams of zirconium oxychloride are dissolved in 250 m1. of water. The solution containing the zirconium is introduced into the sodium carbonate solution resulting in the precipitation of zirconium carbonate. The precipitate is washed and filtered and to the paste is added 22.15 grams of anhydrous sodium carbonate. This produces resolution of the precipitate to form the double salt of zirconium sodium carbonate. This solution is made up to 500 ml. volume.

34.5 grams of sodium stearate are dissolved in 500 ml. of water with heating and then cooled to between 40 and 50 C. This solution is then mixed with the zirconium solution. 40.9 grams of ammonium acetate is then dissolved in the above colloidal mixture.

The procedure for the treatment of the material to be rendered water repellant is the same as in Example 1.

Example No. 5

ing precipitation of the zirconium. The precipitate is washed and filtered. To the paste is added 25% grams of ammonium carbonate which causes resolution of the precipitate. This solution is made up to 500 ml. volume.

34.2 grams of sodium oleate is dissolved in 500 ml. of hot water which is then cooled to between 40 and 50 C. The soap solution is then added to the zirconium solution. The procedure for the treatment of the material to be rendered water repellant is the same as in Example 1.

The amount of water repellant material added to the goods will depend upon several factors, viz., the type ofgoods being treated, whether light or heavy, whether tight or loosely woven, whether cotton, woolen or mixed goods, the set of the squeeze rolls, etc. In normal operation the goods contain sufhcient material to produce the desired water repellency when finished. Although illustrative concentrations of treating chemicals are given herein, it will be understood that variations may be made therefrom without departing from the scope or spirit of the invention.

The term alkali metal as used in the claims designates the alkali metals and ammonium.

What is claimed is:

1. The method of rendering textile goods water repellant which comprises impregnating the goods with a solution of a soluble double carbonate of zirconium and a soluble soap in amounts to react to form a zirconyl mono fatty acid compound at a temperature below which reaction occurs and thereafter elevating the temperature of the so impregnated goods above 60 C. so that reaction occurs with precipitation of zirconyl mono fatty acid compound.

2. The method of rendering textile goods water I 3. The method of rendering cellulosic fiber material water repellent which comprises impregnating such material with a solution of a soluble alkaline double carbonate of ammonium and zirconium, and soap as reactants at a temperature below 'C. and thereafter elevating the temperature of the so impregnated material above C. to induce reaction with precipitation of zirconyl mono fatty acid compound rendering said material water repellant.

4. A waterproofing composition which comprises an alkaline aqueous solution of a soluble soap, and a soluble double carbonate of a zirconium salt and an alkali metal carbonate, the soap and zirconium salt being present in amounts sufficient to form a zirconyl mono fatty acid compound.

5. A waterproofing composition which comprises an alkaline aqueous solution of a soluble soap, and a soluble double carbonate of a zirconium salt and ammonium carbonate, the soap and zirconium salt being present in amounts sufficient to form a zirconyl mono fatty acid compound.

HENRY L. VAN MATER.

REFERENCES CITED The following references'are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,536,254 White May 5, 1925 2,191,982 Doser et a1. Feb. 27, 1940 2,221,975 Kinzie Nov. 19, 1940 2,252,658 Bigelow Aug. 12, 1941 2,289,316 Myers July '7, 1942 2,328,431 Doser et al Aug. 31, 1943