US2320279A - Detergent composition - Google Patents

Description

Patented May 25, 1943 DETERGENT COMPOSITION Varton Mardiras Kalusdian, New York, N. Y., as-

signor to The Mathieson Alkali Works, Inc., New York, N. Y., a. corporation of Virginia No Drawing. Application March 24, 1938, Serial No. 197,867

16 Claims.

Thi invention relates to improved detergent compositions, and more particularly to substantially dry stable salt mixtures having improved characteristics which are useful as detergents. The invention also includes the aqueous solutions formed by dissolving the compositions of the invention in water.

The new and improved compositions of the present invention are salt mixtures containing a solid calcium hypochlorite of high purity, sodium carbonate, and a synthetic organic detergent salt hereinafter more fully described. An acid salt such as, for example, sodium bicarbonate may advantageously be incorporated in this mixture if it is desired to reduce the alkalinity when a large proportion of sodium carbonate is present in the mixture. The product of my invention provides a dry stable detergent mixture readily soluble in water which is of special value in cleaning operations, for example, in rug cleaning where strong detergent and wetting action is required while at the same time any chemical action with the material being cleaned must be avoided. The mixture of the present invention also possesses valuable disinfecting and germicidal properties.

It has previously been proposed to employ mix- 1 tures of a stable calcium hypochlorite and soda ash as a cleansing and Wagent. The dry stable mixture of e present invention possesses important advantages over such a mixture, particularly in operations where soap would normally be employed either preceding or following the use of such a hypochlorite-soda ash mixture. As an example of an application of the mixture of my invention under these conditions may be mentioned operations such as rug cleaning wherein the present salt mixtures possess important advantages such as increased wetting power as well as high detergency. The use and advantage upwards of 60%. The free lime content is preferably maintained at a low value. The calcium hypochlorite referred to herein as useful in my product is not to be confused with the conventional bleaching powder or chlorinated lime from which it differs materially, both as to chemical constitution and in its exceptionally high content of available chlorine. As examples storage of hypochlorite compositions containing of calcium hypochlorite products suitable for use in the composition of the present invention may be mentioned the products whose preparation is described in United States Patents Nos. 1,481,039, 1,481,040, 1,713,650, 1,713,654, 1,713,668 and 1,713,669. The term calcium hypochlorite as used herein refers to a product having the properties just described. The high stability which such a hypochlorite product possesses is particu larly advantageous in the mixed product of the present invention since it permits storage for considerable periods of time without decomposition. Its stability is due in part to its low content of calcium chloride, which at most should not exceed about 10% of the hypochlorite product and preferably should not exceed 2%3%. When this salt which is very hygroscopic is present in substantial amount, it not only makes the product diflicult to keep dry, but it also decreases the stability of the product due to the hydrolysis occasioned by the absorbed water.

The materials above referred to broadly as synthetic organic detergent salts may include a wide variety of organic compounds having strong detergent and wetting action. The organic or non-polar groups of these detergent compounds include a wide variety of organic groups. In addition to carbon, hydrogen and oxygen, these groups may contain sulfur or nitrogen, or other elements commonly associated with them in organic compounds. Such groups include saturated, or unsaturated hydrocarbons, ethers, thioethers, primary and secondary alcohols, thioalcohols, ketones, thioketones, and esters. These groups may furthermore contain aromatic or heterocyclic ring structures. The polar groups contained in the detergents used in my invention are more limited in number. They are in most cases r 1 f sulfur or phosphorous; the sulfur containing acid groups occurring usually as sulfate or sulfonate.

The cations which form the salts with the acid groups in these compounds include the alkali metals, the alkaline earth metals and the am-" monium inn. 'T, e ammonium ion may also constitute the salt forming ion as, for example, in

a quaternary ammonium salt. The non-polar groups mentioned above usually form anions in solution, but the non-polar groups in quaternary ammonium compounds form cations in solutions. Salts of sulfated higher alcohols are generally useful as detergents in the herein described mixtures. An example of another class of satisfactory detergent compounds are the salts of sulfonated long chain compounds. These are distinguished from the referred to sulfates by the fact that the sulfonic group is attached directly to a hydrocarbon group, whereas the alcohol sulfates are in reality sulfuric acid esters of the alcohols. Specific examples of synthetic organic detergent salts useful in the composition of my invention are as ogiumlamidsulfate, sodium laur l W W 5 51mm ethylene methyl la uramide sulfonate, and p l l amm nium chl de.

' Soaps react alkaline in water solution and form insoluble compounds with the alkaline earth metals. Under the same conditions the water soluble detergents of the present invention do not form such insoluble compounds. They produce substantially neutral aqueous solutions, apparently owing to the fact that their solubilizing groups are more strongly acidic than the carboxyl group in soap with the result that their metallic salts are more nearly neutral. These detergent compounds therefore do not contain the carboxyl group as such, but may contain it in a muzzled form, for example as an ester grouping. By the phrase synthetic organic detergent salt as used in this application and in the claims, I refer to a detergent compound of the above referred to type, and I intend to exclude organic compounds which may be classified as soaps which give a strong alkaline reaction in aqueous solution and which precipitate insoluble compounds with the alkaline earth metals.

I have found that a calcium hypochlorite having the above-described stable properties may be mixed with Web and a synthetic organic detergent salt 0 e class described above to produce a dry mixture having high stability and improved properties. A stable hypochlorite composition is thus provided which does not lose its available chlorine on standing, and in which the stability of the organic detergent component is not impaired. It will be apparent that the organic detergent salt and the other components of the mixture should be substantially dry before being intimately admixed with the calcium hypochlorite by any means suitable for comminuting and admixing solid chemical substances.

The relative proportions in which the various components are present in the salt mixtures of the present invention may vary over wide limits. In practical operation the desirable content of the mixture is predetermined and the mixture dissolved in water in an amount predetermined to be necessary to effect the desired degree of detergency and other valuable functions. When the mixture is dissolved in water in a suitable container the calcium of the hypochlorite is precipitated as insoluble calcium carbonate. The clear solution may then be decanted and supplied to the cleaning operation. Since an amount of carbonate equivalent to the calcium ion present is removed from the solution, the amount of soda ash present in the original mixture should be in excess of an amount equivalent to the calcium hypochlorite present. In this way an excess of soda ash will remain in the solution imparting thereto valuable detergent qualities. In many cases it is desirable to have the solutions used in a lower pH range. The pH value which would be imparted to the solution by the excess sodium carbonate may be lowered by incorporating in the dry mixture at predetermined proportion of sodium bicarbonate. In addition to the variation permitted in the new salt mixtures of this invention between the proportion sodium carbonate, sodium bicarbonate when present, and calcium hypochlorite with respect to each other, there is considerable latitude permissible in the proportion of the organic detergent salt with respect to the total quantity of the above-mentioned inorganic salts present. The relative amount of organic detergent incorporated in the mixture is governed by the amount of detergent and wetting action desired in the specific operation for which the mixture is to be employed. In general I have found that dry mixtures containing between 2 and 3 parts by weight of the above-referred to inorganic salt mixture and one part by weight of the organic detergent salt mixture, are satisfactory. Such mixtures represent a proportion of organic detergent in the total dry mixture of from 25-33%. Tests which I have conducted indicate that solutions of salt mixtures when the components are within these concentration limits closely approach a maximum penetrating or wetting ability. It is to be understood, however, that a greater or less proportion of detergent salt than the amount just mentioned may sometimes be preferred.

I have found that the new salt mixtures of the present invention are particularly useful in the art of rug cleaning. The use of such mixtures makes possible an efficient and simple one step process for the cleaning of rugs, carpets and other fabrics. In the past rugs have customarily been subjected to a shampooing preceded by beat ing and vacuum treatments and followed by cumbersome rinsing and drying steps. One of the greatest difficulties encountered was the loosening and complete removal of the adhesive dirt held at the base of the pile by soot and other greasy materials which collects in such a fabric with constant use. Complete removal was seldom accomplished in actual rug cleaning practice. A further major difficulty was the complete elimination of soap solution from the rug, and particularly from the base of the pile after shampooing. In spite of copious rinsing, satisfactory removal was seldom accomplished. As a result of this failure to completely remove the soap it remained as a coating on the fibers thus increasing the tendency of dust particles to adhere to the fiber in such a way that ordinary cleaning methods, including the use of vacuum cleaners, failed to remove such dirt. In addition, the soap residue frequently became rancid thus preventing the pile from regaining its fresh springy appearance. Such difiiculties are overcome and many independent improvements attained by the use of the salt mixtures of this invention in such a cleaning process. The increased solubility of the mixture facilitates the removal of the reagents from the fabric thus eliminating extensive rinsing operations. The loss of substantial proportions of cleansing agent accompanied by the precipitation of insoluble soaps when hard waters are used is avoided. The increased wetting and penetrating action of solutions prepared from the mixtures of the present invention result in increased efliciency of soil removal and time of reaction as compared to the results obtained by the use of soaps. In the case of fabrics having a "sheen finish, the original sheen is restored. The colors of the fabric are freshened and the designs clarifled. Stains are removed and the fabric is efflciently deodorized and disinfected.

The following will serve as illustrative examples of the use of the mixture of my invention in two specific instances of rug cleaning. In these examples the dry salt mixture used had the following approximate composition: 16% calcium hypochlorite; 26% sodium carbonate; 26% sodium bicarbonate; and 30% of a mixture consisting es- Eentially of sod ium laur yl sulfate with small proportions of sodium'myristyfsulfate and sodium palmityl sulfate. 2 lbs. of the dry salt mixture were dissolved in 50 gallons of water at approximately 72 F. The solution was thoroughly stirred and the precipitated calcium carbonate allowed to settle. The clear solution was fed by gravity into the center of a mechanical rotary brush with which the rug which was spread on the door was scrubbed. The rug is usually cleaned on both sides in the same manner; in most cases the back of the rug being cleaned first. By this expedient the greasy and wax-like materials at the base of the pile are hydrolyzed thus freeing the dirt particles so that they are readilyemulsifled and brought to the surface when subjected to the subsequent cleaning on the right side. The cleaning of a 9 x 12 rug should take approximately 3 minutes on each side by such a procedure.

An alternative procedure to the just described "floor method of operation involves the .use of an automatic feeder machine. The rug to be cleaned was fed into a device having arranged therein flat brushes which vibrated alternately in a direction parallel to the direction of travel of the rug. An aqueous solution containing from 1 lbs. to 2 lbs. of the detergent salt mixture of the present invention per 50 gallons of water at a temperature up to 100 F. was applied to the rug or carpet just prior to its contact with the horizontally vibrating brushes. After treatment on one side the rug was turned and the reverse side treated in the same manner. The fabric was rinsed and wrung in a subsequent stage of its passage thru the machine.

It is to be understood that while the new and improved dry stable salt mixture of the present invention is particularly useful in the cleaning of rugs, its use is not restricted to this purpose, but may advantageously be applied to operations where simultaneous detergent and germicidal or bleaching action is desired.

I claim:

1. A substantially dry stable salt mixture comprising a stable calcium hypochlorite, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, and a synthetic organic water soluble detergent salt which does not produce an insoluble precipitate in the presence of calcium ions.

2. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, and a synthetic organic water soluble detergent salt which does not produce an insoluble precipitate in the presence of calcium ions.

3. A substantially dry stable salt mixture comprising a stable calcium hypochlorite, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate and a synthetic organic water soluble detergent salt whichdoes not produce an insoluble precipitate in the presence of calcium ions.

4. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate, and a synthetic organic water soluble detergent salt which does not produce an insoluble precipitate in the presence of calcium ions.

5. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate, and a water soluble detergent sulfate salt of a higher alcohol which does not produce an insoluble precipitate in the presence of calcium ions and which is selected from the class consisting of the alkali metal alcohol sulfates, the alkaline earth metal alcohol sulfates and ammonium alcohol sulfates.

6. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate, and a detergent sodium salt of a higher alcohol sulfate which does not produce an insoluble precipitate in the presence of calcium ions.

'7. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mix- ;uzg. sodium bicarbonate, and sodium lauryl sul- 8. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture. sodium bicarbonate, and a water soluble salt of a sulfonated organic compound of high molecular weight having detergent properties which does not produce an insoluble precipitate in the presence of calcium ions.

9. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate, and sodium ethylene palmitate sulfonate.

10. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate and sodium ethylene methyl lauramide sulfonate.

11. A substantially dry stable salt mixture comprising a stable calcium hypochlorite containing upwards of 50% available chlorine and substantially free of calcium chloride, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate and a water soluble quaternary ammonium salt having detergent properties and containing at least one high molecular weight organic group as a substituent.

12. An aqueous solution formed by dissolving in water a stable calcium hypochlorite, sodium carbonate in excess of that necessary to react with all of the calcium present and. a synthetic organic water soluble detergent salt which does not produce an insoluble precipitate in the presence of calcium ions.

13. An aqueous solution formed by dissolving in water a stable calcium hypochlorite, sodium carbonate in excess of that necessary to react with all of the calcium present, sodium bicarbonate, and a synthetic organic water soluble detergent salt which does not produce an insoluble precipitate in the presence of calcium ions.

14. A substantially dry stable salt mixture comprising a stable calcium hypochlorite, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, and a synthetic organic water soluble detergent salt which does not produce an insoluble precipitate in the presence of calcium ions, said salts being present inthe ratio of 1 part by weight of the organic detergent salt to about 2 to 3 parts by weight of the inorganic salts.

15. A substantially dry stable salt mixture comprising a stable calcium hypochlorlte, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate, and a synthetic organic water soluble detergent salt which does not produce an insoluble precipitate in the present of calcium ions, said salts being present in the ratio of 1 part by weight of the organic detergent salt to about 2 to 3 parts by weight of the inorganic salts.

16. A substantially dry stable salt mixture comprising a stable calcium hypochlorite, sodium carbonate in an amount in excess of that necessary to react with all of the calcium present in the mixture, sodium bicarbonate, and sodium lauryl sulfate, said salts being present in the ratio of 1 part by weight of sodium lauryl sulfate to about 2 to 3 parts by weight of the inorganic salts.

VARTON MARDIRAS KALUSDIAN.