Drycleaning Deodorizing And Disinfecting Compositions And Processes

Abstract

Disinfection of, and production of bacteria growth inhibiting fabrics or textiles is accomplished by simultaneous dry cleaning and disinfection procedures involving contact of the textile with an antimicrobial agent containing drycleaning solution in the form of an emulsion of the "water-in-oil" type and which contains a fat solvent in the continuous phase and an aqueous solution of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride in the dispersed phase. The emulsion is also effective to deodorize textiles and other objects.

Parent Case Text

This application is a continuation-in-part of my copending application Ser. No. 52,764, filed July 6, 1970 now U.S. Pat. No. 3,697,220, which application was a continuation-in-part of application Ser. No. 852,491, filed Aug. 22, 1969 and now abandoned.

Description

This invention relates to the drycleaning of fabrics or textiles and more particularly to certain chemically disinfected textiles that contain a bacteria growth inhibitor and to certain drycleaning and disinfecting compositions and methods.

There is a false popular belief that the drycleaning of textiles or woven fabrics involves a germicidal process which is destructive of the vegetative forms of pathogenic or disease causing microorganisms. It is well established however, that such procedures have only limited antibacterial effects, (see "Microbiology of Dry Cleaning" by Robert R. Banville and Ethel McNeil, "Appl. Microbiol." 14:1-7. 1966) and that many bacteria carry through the drycleaning process on the fabrics or textiles and/or are redeposited on the fabrics and textiles during the cleaning procedures. Such carry through and redepositions are, of course, undesirable because there is the resultant spread of disease producing bacteria which, if destroyed during the drycleaning procedure, would be incapable of causing subsequent human infection.

The inventor is unaware of any commercialized drycleaning procedure that simultaneously cleans and disinfects textiles or fabrics. On the other hand, it is known to fumigate textiles with formaldehyde vapors as a step separate and apart from the cleaning step and as a means for disinfecting the textiles by the destruction of the pathogenic bacteria therein.

Procedures for simultaneously cleaning and disinfecting textiles have been proposed in the past but suffer from one or more disadvantages which have prevented their commercialization insofar as the inventor is aware. For example, it is known to incorporate formaldehyde or formalin, as a disinfectant or germicide, in organic fat solvents that may be used in drycleaning procedures. The compositions, however, suffer the disadvantage that during the cleaning process, the formaldehyde imparts a pungent odor to the textile and which requires removal by a subsequent neutralization step. This added step of course, substantially increases the time and cost of cleaning and disinfecting the fabrics. The incorporation of other antimicrobial agents in the fat solvents suitable for use in commerical drycleaning processes has also been proposed. Among the problems which have confronted investigators in this field, however, is that of finding an antimicrobial agent which is compatible with the solvents and detergents used in commerical drycleaning procedures and which is also germicidally effective and economical to use in treating the textiles under the normal conditions which are encountered in modern commerical drycleaning establishments.

The inventor has discovered that 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is not only compatible with the commerically employed organic fat solvents, such as perchloroethylene and stoddard solvent, and with the usual nonionic and anionic detergents that are employed in the commerical drycleaning procedures, but that the compound serves as an effective antimicrobial agent in system involving such fat solvents and detergents and is capable of accomplishing the disinfection of the textiles under the operating conditions which are normally encountered in commerical drycleaning plants.

The antimicrobial agent advocated for use herein is insoluble in such organic fat solvents as perchloroethylene and stoddard solvent, but has a high degree of solubility in water that amounts to better than 2.2 grams of the 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride per gram of water. This has led to the discovery that the antimicrobial agent can be introduced as an additive to the current day drycleaning compositions and will therein become soluble in the small amounts of water which normally enter the system with the textiles during the cleaning procedures. This introduced water becomes emulsified and colloidally dispersed by the synthetic detergents and consequently, the compositions of the invention are emulsions of the "water-in-oil" type and wherein the antimicrobial agent is present in an aqueous solution that constitutes the dispersed phase of the emulsion while the organic fat solvent provides the continuous phase of the emulsion. Textiles which are contacted by the compositions of the invention, as by being immersed and agitated with the compositions in accord with conventional drycleaning procedures, and which are thereafter dried are not only cleaned and disinfected but have been found to thereafter inhibit bacterial growth as will be subsequently apparent.

A general object of the invention is to provide improvements in the field of drycleaning.

Yet another object of the invention is to provide drycleaning and disinfecting compositions which can be used for the drycleaning of textiles and woven fabrics in accord with conventional drycleaning techniques and without the need for modifying or changing the equipment used in the current commerical drycleaning procedures.

Yet another object of the invention is to provide a process for drycleaning and disinfecting fabrics or textiles and which can be carried out in commerical drycleaning equipment without the modification of such equipment or changes in the drycleaning techniques that are usually employed.

Yet a further object of the invention is to provide drycleaning solutions which contain an antimicrobial agent which without imparting odors to the textiles is capable of effectively disinfecting textiles that are cleaned in such solutions.

Yet a further object of the invention is to provide drycleaning solutions which contains an antimicrobial agent which is capable of effectively disinfecting, sanitizing, and deodorizing textiles that are cleaned in such solutions.

Yet another object of the invention is to provide compositions for use in drycleaning and disinfecting textiles and which can be easily prepared and maintained by people which are basically unskilled in the formulation of chemical compositions and which can also be economically used for such purposes.

A further object of the invention is to provide a drycleaning and disinfecting process which not only disinfects fabrics and other textiles subjected to the process but which imparts bacteria growth inhibiting properties to the textiles thus subjected to the process.

Another object of the invention is to provide textiles which have bacteria growth inhibiting properties.

In accord with the invention, the textile drycleaning and disinfecting compositions are emulsions of the so-called "water-in-oil" type and comprise a liquid organic fat solvent that forms the medium or continuous phase of the emulsion, an aqueous solution of 1-(3-chloroallyl)-3,5,7-triaza-1-azondiaadamantane chloride which is colloidally dispersed in the fat solvent, and an emulsifier in amounts sufficient to provide a stable emulsion so that the antimicrobial agent containing dispersed phase will be brought into effective contact with textiles subjected to cleaning procedures involving the use of the compositions.

The fat solvent may be one or more of the liquid organic solvents that are suitable for drycleaning purposes, such as chlorinated lower aliphatic hydrocarbons, exemplified by perchloroethylene, carbontetrachloride, trichloroethylene, etc. and the aromatic and saturated aliphatic hydrocarbons such as stoddard solvent, benzene, benzol and the gasolines. In modern drycleaning plant practices stoddard solvent or perchloroethylene are by far the most widely used and preferred.

Information currently available indicates that emulsions which are suitable for the cleaning and disinfecting of textiles under commerical drycleaning plant practices should have at least 0.1 ounce (weight) of the additive present per one hundred gallons of the emulsion in order to effectively disinfect textiles which are cleaned in the compositions. Available information also indicates that the antimicrobial agent adheres to and impregnates the textiles during the cleaning procedures and is accordingly progressively removed from the emulsions with each batch of garments that are treated by the solutions. Accordingly, in plant practice the 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride content of the emulsions is replenished periodically on the basis of the weight of the textiles treated in the emulsions and in this respect, it has been found that one hundred gallons of an emulsion which initially contains one ounce of the 1-(3-chloroallyl)-3,5,7-triaza-1-azondiaadamantane chloride will effectively clean and disinfect nine hundred pounds of garments before the concentration of the additive diminishes to an unacceptable level for satisfactory disinfection of the further treated textiles.

Insofar as the water content of the emulsions is concerned, the amount of water need be no more than enough to dissolve effective amounts of the antimicrobial agent. In this respect, the weight of water in the emulsion should preferably exceed 45 percent of the weight of the 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride content of the emulsion in order to insure complete solution of the antimicrobial agent and its dispersement throughout the emusion. In commerical drycleaning plant practices the drycleaning compositions usually contain from one pint to as much as a quart of water per hundred gallons of the cleaning solution because of the water content of the garments that are charged to the solutions. The amount, of course, varies in accord with existing humidity conditions but it has been found that the amount of water which exists in such compositions is more than adequate to dissolve the amounts of the antimicrobial agent and which would normally be added during the drycleaning procedures.

Insofar as the emulsifier in the composition is concerned, the emulsifier can be any one or more of the soaps or synthetic detergents that are useful as cleaning aids or boosters in commerical drycleaning solutions and which, among other things, serve to dispose the water content of such solutions and provide stable emulsions. Examples of suitable emulsion forming surfactants of the nonionic type are the products formed by condensing the alkalene oxides, for example, with the high molecular weight fatty alcohols, amines, carboxylic acids, amides and alkylphenols to mention a few. Examples of the emulsion forming surfactants of the anionic type are the soaps, fatty alcohol sulfates, alkane sulfonates, alkylaryl sulfonates, succinic acid ester sulfonates, and fatty acid ester sulfonates to mention a few. The surfactants which serve as the emulsifier are used in amounts which are sufficient to provide a stable emulsion and are preferably employed in small amounts between about 0.5 and 2.0 percent by weight of the emulsion.

In carrying out the process aspects of the invention, the textiles are immersed and agitated in the drycleaning compositions advocated herein so as to thoroughly contact the textile with the drycleaning and disinfecting composition and the contact between the composition and the textiles is maintained for a period of time which is sufficient to destroy the vegetative forms of the pathogenic microorganism introduced with the textiles. The contact time or period will, of course, vary in accord with the type and strain of bacteria adhering to or otherwise incorporated with the textile, but even with the more resistant strains of bacteria, a contact time of fifteen minutes under the usual drycleaning conditions which exist in commerical drycleaning plant practices has been found to provide satisfactory garment disinfection. As will be subsequently seen, compositions contemplated herein have shown one hundred percent germicidal activity against Salmonella Choleraesuis where contact has been maintained for fifteen minutes and similar activity against strains of Staphylococcus Aureus where contact has been maintained for five minutes. Following the contact with the compositions, the textiles need only be dried in the usual manner.

Textiles treated in accord with the process are impregnated with bacteria growth inhibiting amounts of the antimicrobial agent and current information indicated that the growth of vegetative forms of such bacteria as staphylococcus aureus may be inhibited in fabrics or garments containing residual amounts in excess of about 0.5 grams of the antimicrobial agent per pound of fabric.

Textiles treated in accordance with the present invention are not only cleaned and disinfected, they are also deodorized. Conventional drycleaning is effective to deodorize textiles to a certain degree, but the degree of deodorization is not as great as is desired. Certain odors, such as those of domestic aminals, particularly cats, are only poorly removed by conventional drycleaning. The technique of the present invention is effective to deodorize textiles and is particularly effective in removing difficult to remove odors, such as the odor of cats. The compositions of the present invention are also effective to destroy urine, perspiration, vomit and personal illness odors from garments without contributing an odor of its own.

It has also been discovered that 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride is effective to remove smoke odors. Smoke odors may be removed from textiles only with great difficulty, particularly when the textiles have been subjected to heavy smoke such as that resulting from a fire. Normal drycleaning is not effective to remove such odors. When it is desired to remove heavy smoke odors from textiles, the concentration of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride in the drycleaning solvent should be increased over the amount needed merely to disinfect. Smoke odors are effectively removed by drycleaning if the chloride is present in an amount exceeding 12 ounces per 100 gallons of the drycleaning solvent.

The preferred method of removing smoke odors from textiles may be accomplished with a conventional drycleaning machine. Such machines generally employ about 60 to 100 gallons of solvent, which solvent is maintained in a storage tank and circulated through a filtration system into the cleaning apparatus. To remove smoke odors, the fabrics are placed in the drycleaning machine and the machine is run in a conventional manner for about 15 minutes to remove general soil and stains. The filter is then turned off so that solvent is no longer circulated through the system. About 2 to 3 ounces of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, dissolved in a small amount of water (about 2 to 6 ounces), is added directly to the solvent retained in the cleaning apparatus (typically about 10 to 20 gallons). The machine is then operated for about 5 to 10 minutes, without circulation of solvent through the system, after which time the solvent retained in the cleaning apparatus is dumped, the solvent retained by the textiles is extracted, and the textiles are tumble dried. The solvent used to remove the smoke odors may be subsequently distilled and returned to the system. Of course, the smoke removal procedure is effective to disinfect the textile materials.

Dispersions of at least 12 ounces of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride in 100 gallons of drycleaning solvent are also effective to remove smoke odors from materials other than textiles. Smoke odors, such as those resulting from a fire in a building, can be removed from walls, furniture, etc. by washing the item with the dispersion. No special equipment is required; the smoke damaged item may be merely swabbed down with the dispersion and allowed to dry.

EXAMPLE 1

100 gallons of a basic commerical drycleaning solvent essentially consisting of perchloroethylene, a 1 1/2 percent (wt) charge of detergent material, and a small amount (about 1 quart) of water emulsified therein, was modified by the addition of 1 ounce of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride to provide a drycleaning and disinfecting composition for use in comparative testing of the germicidal activity of the base solvent and the additive containing emulsified composition in a 100 gallon commerical drycleaning plant.

The testing method used was that of Banville & McNeil (Applied Microbiology, Vol. 14, No. 1, 1966) and the test culture was Staphylococcus Aureus (FDA No. 209) grown in a nutrient broth as specified in Official Methods of Analysis, A. O. A. C.

1 cc. of nutrient broth containing 100 .times. 10.sup.6 organisms per cc. was absorbed in each of two 1 square inch cotton toweling swatches which were then air dried for 12 hours. One of the dried swatches was agitated for 5 minutes in 50 cc. of the base solvent while the other swatch was agitated for an identical period in 50 cc. of the disinfecting composition after the composition had been previously used on a commerical scale to clean and disinfect 200 lbs. of garments. After a 1 hour drying time, the swatches were separately pulverized in a blender and diluted to 1 liter with sterile water. 0.01 cc. samples of each diluted solution were then streaked onto nutrient agar plates in triplicate, and the plates were then incubated at 37.degree.c and examined after 24 hours, 48 hours and 72 hours. The colonies were counted at each examination with the results shown below:

COLONIES Incubation Period 24 hr. 48 hr. 72 hr. Base Solvent Control Plate 1 16.0* 17.0* 17.2* Control plate 2 20.0* 20.8* 21.0* Control Plate 3 18.0* 18.8* 19.0* Disinfectant Composition Test Plate 1 0 0 0 Test Plate 2 0 0 0 Test Plate 3 0 0 0 *times 10.sup.6

EXAMPLE II

1 ounce of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride was added to 100 gallons of a basic commerical drycleaning solvent which was in use in a 100 gallon commerical size drycleaning plant and which essentially consisted of perchloroethylene, a 1 1/2% (wt) charge of detergent material, and a small amount (about 1 quart) of water emulsified therein to provide a drycleaning and disinfecting composition with respect to test cultures of staphylococcus aureus and salmonella choleraesuis grown in nutrient broth.

The official A. O. A. C. use-dilution method, modified to utilize 1 square inch cotton toweling swatch as carriers was used, with 30 swatches being used for each test and 10 swatches for each control. Procedurally 1 cc. of broth, containing 100 .times. 10.sup.6 organisms per cc. was placed on each swatch and the swatches air dried for 24 hours. The swatches used in the tests were agitated for 5 minutes, 10 minutes and 15 minutes in respective 200 cc. samples of the drycleaning and disinfecting composition after the composition had been previously used on a commerical scale to clean and disinfect 460 pounds of garments, whereas, the swatches used in the control runs were agitated for like periods in 200 cc. samples of the basic solvent.

All swatches were aseptically transferred to a vacuum-desiccator and after 1 hour of desiccation transferred to nutrient broth tubes and incubated at 37.degree.c for 48 hours. Each tube was then examined for growth with the results shown below.

Test Control Runs (30 Tubes*) (10 Tubes*) Staphylococcus Aureus Contaminated Swatches 5 min. Agitation 30 neg. 10 plus Salmonella Choleraesuis Contaminated Swatches 5 min. agitation 21 neg.-9 plus 10 plus 10 min. agitation 28 neg.-2 plus 10 plus 15 min. agitation 30 neg. 10 plus * neg.=no growth plus=growth

EXAMPLE III

To determine the bacterial growth inhibiting properties of textiles cleaned and disinfected in drycleaning and disinfecting compositions containing 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride and to determine the replenishment cycle for compositions initially containing 1 ounce of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride per 100 gallons of composition, two runs were made in a 100 gallon commerical size drycleaning plant where the equipment was successively charged with weighed and usually approximately 20 lbs. of garments, that were agitated in the equipment for 20 minutes with the solvent composition before being removed and dried. The composition at the beginning of each run consisted essentially of perchloroethylene, a small amount (about 1 quart) of water, 1 1/2 percent (wt) of detergent material, and 1 ounce of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride.

The method used is in Federal Specification No. UU-P-510, Paragraphs 4.4.2.1-4.4.2.4 and the test culture was staphylococcus aureus (F. D. A. No. 209), grown in nutrient broth as specified in Official Methods of Analysis, A. O. A. C.

Procedurally, and at selected intervals during each run, 1 square inch test swatches of cotton toweling were laundered in the emulsified drycleaning and disinfecting composition along with other garments. After air drying, each test swatch was placed on the surface of a pour plate that had been freshly prepared and inoculated with 0.1 cc. of the test culture. The specimens were then allowed to incubate at 37.degree.c for 24 hours before the zone of inhibition, as measured in millimeters from the edge of the swatch to the edge of the bacterial growth, was recorded, the results being shown below and wherein it is evident that the compositions have a satisfactorily long life before the need for replenishment of the 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride arises and that the swatches have bacteria growth inhibiting properties.

Total Garment Poundage Preceding Test Switch Test Swatch Zone of Inhibition First Run 100 2 mm. 200 2 mm. 340 2 mm. 870 1 mm. 1370 No Zone Second Run 600 2 mm. 700 1 mm. 800 1 mm. 900 1/2 mm. 1000 No Zone

EXAMPLE IV

Similar results may be secured by substituting stoddard solvent for perchloroethylene in the prior examples.

While the above examples have been set forth as illustrative of the invention, it should be understood that it is intended herein to cover all such modifications as fall within the true spirit and scope of this invention.

Claims

What is claimed as new and what it is desired to secure by Letters Patent of the United States is:

1. An emulsion of the "water-in-oil" type for use in drycleaning, deodorizing, and disinfecting consisting essentially of:

A. an organic drycleaning solvent;

B. an emulsifying agent in an amount sufficient to stabilize the emulsion; and

C. an aqueous solution of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride colloidally dispersed in said drycleaning solvent, said aqueous solution being present in an amount of at least one pint per 100 gallons of the emulsion and said chloride being present in an amount exceeding 12 ounces per 100 gallons of the emulsion.

2. The emulsion of claim 1 where the solvent is stoddard solvent.

3. The emulsion of claim 1 where the solvent is perchloroethylene.

4. An emulsion for use in drycleaning and disinfecting, deodorizing in accord with claim 1 where said emulsifying agent consists essentially of an anionic surfactant.

5. An emulsion for use in drycleaning and disinfecting, deodorizing in accord with claim 1 where said emulsifying agent consists essentially of a nonionic surfactant.

6. A method for simultaneously drycleaning, deodorizing, and disinfecting a textile comprising:

A. contacting an odoriferous textile for a period of time in excess of five minutes with a stable emulsion consisting essentially of:

1. an organic drycleaning solvent;

2. an emulsifying agent in an amount sufficient to stabilize the emulsion; and

3. an aqueous solution of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride colloidally dispersed in the solvent, said emulsion containing about one pint to one quart of water and said chloride being present in the emulsion in an amount exceeding 0.1 ounce per 100 gallons of the emulsion;

B. thereafter removing the textile from the emulsion; and

C. drying the textile.

7. A method in accord with claim 6 where the solvent is stoddard solvent.

8. A method in accord with claim 6 where the solvent is perchloroethylene.

9. A method for simultaneously drycleaning, deodorizing and disinfecting textiles in accord with claim 6 where said emulsifying agent consists essentially of an anionic surfactant.

10. A method for simultaneously drycleaning, deodorizing and disinfecting textiles in accord with claim 6 where said emulsifying agent consists essentially of a nonionic surfactant.

11. A process effective to simultaneously dryclean, disinfect, and remove smoke odors from a textile comprising:

A. contacting the textile for at least 5 minutes with a stable emulsion of the "water-in-oil" type consisting essentially of:

1. an organic drycleaning solvent;

2. an emulsifying agent in an amount sufficient to stabilize the emulsion; and

3. an aqueous solution of 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride colloidally dispersed in said solvent, said aqueous solution being present in an amount of at least one pint per 100 gallons of said emulsion, and said chloride being present in the emulsion in an amount exceeding 12 ounces per 100 gallons of said solvent;

B. thereafter removing the textile from the emulsion; and

C. drying the textile.

12. A method in accord with claim 11 where the solvent is stoddard solvent.

13. A method in accord with claim 11 where the solvent is perchloroethylene.

14. The emulsion of claim 1, in which said aqueous solution contains an amount of water exceeding 45 percent by weight of said chloride.

15. The emulsion of claim 1, in which said aqueous solution is present in an amount of no more than one quart per 100 gallons of emulsion.

16. The method of claim 6, in which said emulsifying agent consists essentially of a mixture of anionic and nonionic surfactants.

17. The method of claim 6, in which said odoriferous textile has the odor of cats.

18. The method of claim 6, in which said chloride is present in said solution in an amount exceeding 12 ounces per 100 gallons of said emulsion.

19. The method of claim 6, in which said aqueous solution contains an amount of water exceeding 45 percent by weight of said chloride.

20. The method of claim 6, in which said emulsifying agent consists essentially of a mixture of anionic and nonionic surfactants.

21. The process of claim 11, in which said aqueous solution contains an amount of water exceeding 45% by weight of chloride.

22. The process of claim 11, in which said aqueous solution is present in an amount of no more than one quart per 100 gallons of said emulsion.

23. The process of claim 11, in which said emulsifying agent consists essentially of a mixture of anionic and nonionic surfactants.