INTERNALLY-CARBONATING CLEANING COMPOSITION AND METHOD OF USE

Abstract: Carpeting, upholstery, drapery and other textile fibers are cleaned by applying to the fibers, at ambient pressures, an aqueous, chemically carbonated detergent cleaning composition prepared by admixing a carbonate salt solution, and an acid solution, such that the acid reacts with the carbonate salt to produce carbon dioxide coincident with application to a textile to be cleaned. Citric acid and sodium carbonate are the preferred acid and carbonate salt. The compositions are preferably prepared and applied at an elevated temperature in the range of between about 140 and 200 DEG F.

Description: t INTERNALLY-CARBONATING CLEANING COMPOSITION AND METHOD OF USE FIELD OF THE INVENTION This invention relates to internally-carbonating compositions for cleaning textile fibers. More particularly this invention relates to compositions containing detergents which are internally carbonated by mixing the components of the composition coincident with their application to a textile to be cleaned so as to develop a carbonating or carbon dioxide producing reaction on the textile resulting in the removal of soils and other materials from the textile. This carbonating composition has an improved ability to penetrate textile fibers and dissolve aLnd/or lift both inorganic and organic materials from the fibers, and the ability to use carbon dioxide effervescence even when the components are applied at relatively high temperatures. BACKGROUND OF THE INVENTION There are myriad types of cleaning compositions for cleaning textile fibers such as carpets, upholstery, drapery, clothing, bedding, linens, and the like. Most of these are based on soaps or other detergents which are generically referred to as "surfactants." By "surfactant" is meant a synthetic amphipathic molecule having a large non-polar hydrocarbon end that is oil- soluble and a polar end that is water soluble. Soap is also an amphipathic molecule made up of an alkali salt, or mixture of salts, of long-chain fatty acids wherein the acid end is polar or hydrophilic and the fatty acid chain is non-polar or hydrophobic. Surfactants are further classified as non-ionic, anionic or cationic. Anionic or nonionic detergents are the most common. Surfactants and soaps are formulated to loosen and disperse soil from textile fibers either physically or by chemical reaction. The soil can then be solubilized or suspended in such a manner that it can be removed from the fibers being cleaned. These function because the hydrophobic ends of the molecules coat or adhere to the surface of soils and oils and the water soluble hydrophilic (polar) ends are soluble in water and help to solubilize or disperse the soils and oils in an aqueous environment. A major problem associated with the use of surfactants in cleaning fibers has been that large amounts of water were generally required to remove the surfactants and suspended or dissolved particles. Also, surfactants generally leave an oily hydrophobic coating of the fiber surface. The inherent oily nature of the hydrophobic end of the surfactants causes premature resoiling of the fiber surface even when the surfaces have a surfactant coating which is only a molecule thick. The greater the concentration of surfactants used, the greater the potential for resoiling after cleaning. The residues left by surfactants also sometimes cause irritation or allergic reactions to people who are sensitive to these chemicals. There are also environmental problems associated with the use of soaps and other surfactants. In addition to requiring relatively large amounts of water, some are non-biodegradable and some contain excessive amounts of phosphates which are also environmentally undesirable. It would therefore be desirable to utilize a composition in which the concentration of surfactants are kept at a minimum, while retaining the cleaning ability of the composition. This concern over health and the environment has prompted an emphasis on the use of less toxic, more natural cleaning components. The quest for carpet cleaning compositions that have a balance of cleanability and resoiling resistance, however, has sometimes resulted in compositions containing unnatural components that have a greater potential to cause allergenic reactions and other health and environmental problems. Normal soaps prepared from the base hydrolysis of naturally occurring fats and oils are not suitable for carpet cleaning because of the propensity of their residues to attract soils. In order to make these residues less soil attracting, detergents are synthetically modified. Another long existing problem in carpet cleaning is oxidative yellowing or "brown out" as it is commonly called. The usual conditions that increase the potential for brown out are a higher pH cleaner and/or prolonged drying times. Ordinarily the higher the concentration of solids in the cleaning composition the greater the potential for this oxidative yellowing to produce a noticeable discoloration on the carpet. Thus, by having a high pH and requiring large quantities of water to flush out residue, soaps and other surfactants tend to increase the risk of brown out. The combination of a silicate fabric softening agent, a neutralizing or "souring" agent such as citric acid, a disintegrating agent comprising citric acid, hydrogen, carbonate and a filler material which may be ammonium sulfate, zeolite A or urea has been described in connection with the laundering of fabrics. In United States Patent, No. 4,814,095, "After Wash Treatment Preparation Based On Layer Silicate" the use of these compounds is demonstrated for use as a fabric softener. However, as noted on col. 3, lines 21-25 of that patent, the crucial performance feature of the composition, i.e. the fabric-softening property, is distinguished by the presence of a suitable layer silicate. As the patent discusses, the silicate layer is deposited on the textile fibers. While this may be advantageous for softening fabrics, it is undesirable for cleaning carpets, upholstery and other fabrics which are not thoroughly rinsed due to the fact that the excessive silicate residue can be abrasive. In addition, the residue leaves the carpet, upholstery or other material more prone to resoiling than carpet or upholstery without the residue. Furthermore, the large amounts of water required to flush silicate particulates from the carpet or upholstery increases the textile's drying time and increases the risk of brown out. A significant improvement in the art of cleaning textile fibers, and carpets and upholstery in particular, is taught in U.S. Patent 4,219,333. This patent shows that, when detergent solutions are carbonated under a positive gauge pressure and applied to the fibers at ambient temperature, the solution rapidly penetrates the fibers and, through the effervescent action of the carbonation, quickly breaks up and lifts the suspended soil and oil particles to the surface of the fiber from which they can be removed by vacuuming or transfer to an adsorptive surface such as to a rotating pad. Moreover, because less soap or other surfactant needs to be applied to the fibers, less water is needed to affect the cleaning, the fibers dry more rapidly than do fibers treated with conventional steam cleaning or washing applications, and little residue is left on the fibers. This results in less resoiling due to the reduced residue and in a decreased likelihood of brown out because of the more rapid drying of the fibers. The invention claimed in U.S. Patent 5,244,468 provides some resolution to the surfactant problem in that it claims the use of carbonated urea containing non- detergent compositions formed from the reaction between a carbonate salt and a naturally occurring acid or acid forming material. However, the invention still requires the presence of a positive gauge pressure to retain the proper degree of carbonation. In the past, in order to prepare a carbonated solution it was necessary to pressurize the cleaning solution in a container with carbon dioxide from an outside source, e.g. a C0 2 cylinder, and shake the container, preferably during C0 2 introduction, to insure that the solution was carbonated. Carbon dioxide tanks necessary to accomplish this pressurization are heavy and inconvenient to have on site for attachment to sprayers when cleaning solution is being applied to carpets. The benefits of carbon dioxide as a volatile builder salt have outweighed the inconvenience of having a carbon dioxide tank on location during cleaning. In addition, a disadvantage of externally carbonating a solution under positive pressure is that excess carbon dioxide may be expelled into the air or surrounding atmosphere, and there is always the danger that carbon dioxide can be expelled accidentally from the pressurized cylinder in which it is contained. It has also been known for a significant amount of time that hot cleaning solutions will clean textiles and other materials better than cool solutions. Many currently available carpets require an elevated temperature for proper cleaning. However, until the present invention, it has been unclear how to achieve the cleaning advantages of a carbonated solution combined with those of a heated solution. When a carbonated solution is heated, the cleaning efficiency gained by heating the solution is offset by the diminished solubility of the carbon dioxide in the solution. Thus, the more the solution is heated, the less carbonation it will carry for cleaning. Additionally, it has also been known that the pH of a cleaning solution may significantly affect its cleaning efficiency. As was discussed above, new generation carpets are sensitive to elevated pH solutions, and will be damaged if an alkaline solution stays on the carpet for any significant length of time. Until the present invention, it has been difficult to obtain the benefits of elevated pH solutions without affecting the stain resistance of new generation carpets, or causing brown out. Thus, there is a need for a cleaning solution which combines the benefits of a carbonated solution and those of a heated solution, without the traditional problems associated with surfactants, and other fillers. OBJECTS AND SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a surfactant containing cleaning composition which rapidly penetrates textile fibers removing the soils and oils therefrom with a lifting action. It is also an object of this invention to provide a carbonating surfactant containing cleaning composition at an elevated temperature wherein the carbonating reaction rapidly penetrates textile fibers, suspending soils and oils for removal without leaving significant amounts of soil attracting residues on the fibers. It is an additional object of this invention to provide a process for the cleaning of textile fibers with a carbonating solution at an elevated temperature wherein soils and oils are effectively removed from the fibers, with small amounts surfactant, and suspended in an aqueous environment for a sufficient time to allow the suspended materials and aqueous environment to be extracted or removed from the fibers. It is a further object of this invention to provide a surfactant containing cleaning solution wherein the carbonating reaction is utilized at an ambient pressure but at an elevated temperature. It is another object of this invention to provide a surfactant containing cleaning composition which comprises two solutions, preferably at elevated temperature, which may be mixed coincident with their application to a textile to be cleaned to create an internally-carbonating solution with the carbonating reaction occurring immediately prior to application or directly on the textile being cleaned. A further object of this invention is to provide a cleaning composition at elevated temperatures which is internally-carbonated by chemical reaction and does not require the presence of pressure from an externally applied gas to create or maintain carbonation. These and other objects are accomplished by means of a cleaning solution which is not maintained under a positive gauge pressure by means of an externally applied gas and which is prepared by combining an effective amount of an acid or acid forming material which is natural and non-polluting to the environment and a carbonate salt that produces carbon dioxide when reacted with the acid in an aqueous medium, i.e. water, with a small amount of detergent. Applying the ingredients to a textile simultaneously or in close succession with the carbonation gives a unique cleaning ability that is unexpected due to the small amounts of detergent which will typically be in the solution. The present composition removes soils and oils from fibers by suspending the soil in the freshly carbonated solution until it can be removed. This composition is concurrently internally carbonating and applied at ambient pressure, thereby avoiding the extra step of precarbonating the solution by external means such as highly pressurized carbon dioxide tanks or maintaining the pressure by means of externally applied carbon dioxide or other gases. Additionally, the present composition leaves little, if any, soil attracting residue on the fibers and therefore does not attract or retain soils or oils which come into contact with the fibers following cleaning. Furthermore, because the carbonating reaction occurs infinitesimally before or at the time of application on the textile, the ingredients may be heated to achieve a heated composition while retaining the effervescent action of freshly prepared carbon dioxide bubbles. The reaction of the ingredients causes the newly prepared carbon dioxide to penetrate the fibers, thereby making the carbon dioxide solubility or temperature of the composition of little importance. The composition can also be used with other protectors such as fluorochemical and other polymers such as are marketed under tradenames such as "Teflon" or "Scotchgard" . When other cleaning agents are used with protectors, they tend to diminish the effectiveness of the protector. When the cleaning composition of the instant invention is used, however, the soil protection is actually enhanced rather than diminished. The compositions of the present invention can be applied to fibers as internally carbonated solution, the degree of carbonation which will depend upon whether the solutions are mixed immediately before being applied (i.e. mixed as they are sprayed on the textile) or whether one of the solutions is applied to the textile, and then followed by the other solution. DETAILED DESCRIPTION OF THE INVENTION As used herein the term "acid" or "acid forming material" shall mean a member selected from the group consisting of citric acid, succinic acid, tartaric acid, adipic acid, oxalic acid, glutaric acid, malic acid, maleic acid and mixtures thereof. Citric acid or a citrate salt are preferred. The term "carbonate salt" shall mean a member selected from the group consisting of sodium carbonate, sodium percarbonate, sodium bicarbonate, lithium carbonate, lithium percarbonate, sodium bicarbonate, potassium carbonate, potassium percarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate and mixtures thereof. Sodium carbonate, sodium bicarbonate or mixtures of sodium carbonate and sodium bicarbonate are preferred. Prior to the issuance of U.S. Patent 5,244,468, the ability of a solution of an acid or acid forming materials, and a carbonate salt that produces carbon dioxide when reacted with the acid to surround and suspend soil and or hydrophobic particles such as greases, oils and the like is not believed to have been previously known or used in the cleaning arts. Such combinations, along with other ingredients, have been used in association with surfactants to control or maintain the pH of the cleaning solution. Moreover, the carbonating of such combinations coincident with their use as cleaning agents per se is novel and unexpected particularly when the carbonating is effected at elevated temperatures at the time of utilization. The addition of additives such as detergent further increased the cleaning ability of the carbonated solution. The mixture of carbonate salts and acids produces carbon dioxide either hydrogen bonds to the fibers or produces an interactive substance or complex that breaks up and lifts the soil from the fabric. Other additives commonly found in commercial cleaning compositions may be added without departing from the scope of this invention provided they do not interfere with the carbonating reaction. These may include compatible bleaches, optical brighteners, fillers, fragrances, antiseptics, germicides, dyes, stain blockers and similar materials. The coincident carbonating and application of the composition results in a rapid lifting action due to the presence of a multitude of effervescent carbon dioxide bubbles. The soils or oil on the fibers being cleaned are either surrounded by the complex of carbon dioxide and detergent, or prevented from adhering to the fibers by the bonding of the carbon dioxide and detergent to the fibers. In either event, the soils are freed and can be lifted from the fibers into the surrounding carbonated aqueous environment. By "aqueous" is meant the presence of water, but that does not suggest that copious amounts of water need to be present. A slight dampening of the fiber may be sufficient to promote the lifting action of the effervescent carbonating solution and to loosen or dislodge the soil particle or oil from the fiber. The detergent and carbon dioxide interactive substance or complex holds the soil particles in suspension for a time sufficient for them to be removed from the fiber by means of vacuuming or adsorption onto a textile pad, toweling or similar adsorbent material. An important advantage of this invention is that only minimal amounts of solution are required to effect a thorough cleaning of textile fibers without leaving any residue. Normally, excess amounts of water are used to remove unwanted detergent residues. The terms "coincident", "concurrent", "simultaneous", "infinitesimally before", "immediately after" and the like, when referring to the carbonating reaction and application of the carbonated solution to a fiber substrate means that the acid and carbonate components along with detergent are brought together in an aqueous admixture just prior to application to the fiber substrate, at the time of application on the fiber substrate or by sequential application of the acid and carbonate components on the fiber substrate. Obviously, when mixed just prior to application, the carbonating reaction begins infinitesimally before the carbonated solution contacts the substrate. On the other hand, if a solution of acid or carbonate is placed on the fiber substrate prior to the other solution being applied, i.e. sequentially, the carbonating occurs "on" the substrate fibers "upon" or "immediately following" the application of the second solution. Another option is to apply an acid containing solution and a carbonate containing solution simultaneously or in such a manner that the carbonation reaction occurs at the time the solutions reach the fiber substrate. In any event, the time lapse between bringing the acid solution and carbonate solution together and the concurrent release of carbon dioxide is minimal and all embodiments are encompassed by the above terminology. What is important is that the release of carbon dioxide into the aqueous detergent solution at an appropriate pH occurs in such a manner as to promote carbon dioxide expansion, contact between the fibers to be cleaned with carbon dioxide and detergent from the solution resulting in the maximum cleaning ability of the non-detergent solution. As noted above the components of the cleaning composition may be applied to the textile simultaneously, e.g. mixed immediately before application, or during application. In the alternative, the components of the cleaning composition may be applied, and thus mixed, in any desired order. For example, a solution containing detergent and a carbonate salt can be sprayed directly on the textile, followed by the acid solution. Alternatively, the acid solution could be sprayed first and then the solution containing the carbonate salt and detergent. Either procedure works well because solutions with a pH which is not neutral tend to clean much better than those that are neutral. By applying one of solutions first and then the other, the solution on the carpet is temporarily moved from a neutral pH and cleans the carpet more efficiently. While the solutions could also be mixed before application to the carpet or other textile, the components should not be mixed a significant amount of time before application (i.e. precarbonated) , as the carbon dioxide will escape over time unless maintained under a positive gauge pressure. Those skilled in the art will recognize that numerous combinations and spraying sequences could be applied, and that some or all of the ingredients could be heated prior to being applied to the carpet. Typically, the detergent is added to the carbonate solution due to increased solubility. However, to which solution the detergent will be added will depend on the solubility of the particular detergent in acidic and basic solutions. Additionally, the detergent could also be added independently (i.e. three solutions being mixed). Since many detergents, anionic detergents in particular, tend to be alkaline, it may be preferable to add the detergent to the carbonate salt solution. 12 In a preferred embodiment, the acid solution and carbonate salt solution will be brought together just prior to or at the time of contact with the textile fibers being cleaned. One means for such application is disclosed in copending application Serial No. , titled "Dual Solution Application System" and filed of even date herewith as Attorney Docket No. T2433. In the system disclosed, the acid and carbonate salt solutions are heated in separate reservoirs or containers to about 140-200° F. and pumped from their respective reservoirs to a valve means for each solution. When the valves are simultaneously opened, the hot solutions enter a small mixing chamber through a restricted orifice for each solution. There is a pressure differential across the orifice which causes the hot solutions to enter and combine in the mixing chamber at essentially ambient pressure. The lowering of the pressure across the orifices prompts the hot solutions to enter the chamber with turbulence or mixing to begin the carbonating reaction. The mixture then exits the chamber through a larger exit orifice which does not restrict the pressure but merely directs the flow of the mixed carbonating solution through a line to a manifold directly above the textile fibers for deposit on the fibers in sheet or large droplet form. The time lapse between the valves being opened, the two solutions entering the mixing chamber, passing to the manifold and onto the textile fibers is momentary, i.e. from fractions of a second up to a few seconds. The carbonating reaction begins immediately and lasts for up to 10 to 15 seconds. The temperature drop between the hot solutions at the valves and the carbonating solution exiting the manifold is only a few degrees, i.e. about 2 to 15 degrees depending on the length of the lines feeding the hot solutions from the reservoirs to the valves and the distance from the mixing chamber to the manifold. An alternate method of practicing the invention is to apply a buffered solution containing the carbonate and detergent to the textile first. The buffered carbonate solution enables the greatest degree cleaning due to the relatively high pH of the solution in that stains, greases, and other materials may be more readily removed at an elevated or more alkaline pH. However, high pH solutions may damage some new generation carpets if prolonged contact is permitted. Thus by adding a sufficient amount of citric or some other acid to the carbonate solution as a buffer, the pH can kept between 8 and 10. This range prevents the carpet from being damaged in the event that the acid solution is not applied immediately after the carbonate solution, as may be the case if the operator runs out of acid solution. While buffering the carbonate solution may somewhat lessen the total amount of carbon dioxide that is generated by reacting the acid and carbonate solutions, keeping the carbonate solution at a pH level between 8 and 11 enables the mixture to produce enough carbon dioxide to thoroughly clean the carpet or other textile. Likewise, the acid solution, usually citric acid may be buffered by a small amount of carbonate salt to a pH of between about 3 to 6. This pre-buffering of the two solutions provides a means that, should either solution be applied to a fiber substrate without the other, the substrate will not be harmed. Moreover, when the two solutions do combine they will have a relatively neutral pH. By the terms "relatively" or "generally" neutral pH is meant a pH that will not harm the fabric due to either an acidic or basic nature if left on the fabric for an extended period of time. Such pH will usually be in the range of 6 to 8 and will preferably be about 7. Thus, the textile being cleaned undergoes a momentary increase in pH, to improve cleaning, followed by significantly more effervescent activity than has been achieved with prior methods utilizing physically generated carbon dioxide (e.g. from a pressurized container) . Each of these results in a cleaner textile, without the use of copious amounts of water. The application of the acid helps reduce the risk of brown out or other damage to the carpet. It may also be desirable to buffer the acid and carbonate salt solutions in their respective reservoirs even if they are to be applied simultaneously just as a precaution against any adverse consequences resulting from either too high or low pH. The carbonating solution, whether applied as a carbonate solution and an acid solution or brought together as a single solution for contact with the fiber substrate, will preferably be applied as a "sheet". By "sheet" is meant a thin sheet, film, large droplet or tear of solution as contrasted to an atomized spray or mist of small droplets. It is difficult to contact a fiber substrate with an atomized mist or spray of small droplets at an elevated temperature because the solution cools rapidly between the time the droplet leaves a spray head or atomizer and contacts a fiber substrate. However, when utilized as a sheet, the temperature of the solution may be more precisely controlled. Because of the rapid generation of carbon dioxide resulting from the combining of heated solutions, the carbon dioxide expands rapidly to produce greater volume and surface and thus cover a fiber substrate as effectively as an atomized solution. Furthermore, application of a sheet, as contrasted to an atomized mist, is safer from a health standpoint since the chances of inhaling the composition are greatly reduced. In accordance with the preferred method, both of the carbonate and acid solutions may be applied to the carpet or other textile in sheets of solution at a temperature ranging from ambient up to about 200° F. Many "Extra Life" carpets require that the carpet fiber be momentarily increased to a temperature in excess of about 140° F. in order to restore its "memory" i.e. to reset the yarn fibers to their original orientation. Therefore, it may be desirable to apply solutions at temperature ranges of between about 140 to 200° F. Thus, in an alternate preferred embodiment, a hot acid solution and a hot base solution are mixed momentarily before application to the carpet. Because the carbonating reaction occurs just before or on the carpet or other textile, the lack of carbon dioxide solubility in a heated solution is of minimal importance, as the carbon dioxide bubbles still form and fully penetrate the carpet. As noted above, the carbonating action lasts for up to about 15 seconds even in hot solutions. Furthermore, the previously unavailable cleaning advantages of a heated composition are gained. Normally, the acid-base reactions have very fast reaction rates which are controlled by diffusion. However, the reaction rate may be slowed by a number of equilibria involved. For example, in the reaction of citric acid with sodium carbonate, the release of carbon dioxide is controlled by the following equilibria: Λ3CgH5θ 7 ♦£ H + H 2 CgH5θ 7 H 2 C 6 H 5 0 7 - Ϊ± H + + HC 6 H 5 0 7 2' HC 6 H 5 0 7 2 " Ϊ± H * + C 6 H S 0 7 3' Once these protons are released from the weak acid, they must then react with the carbonate ion before carbon dioxide can be released . These equilibria are as follows : H' + C0 3 2_ ≠ HC0 3 - H* + HCO 3 " st H 2 C0 3 H 2 C0 3 i- H 2 0 + C0 2 These complex equilibria slow the production of C0 2 enough to allow considerable chemical release of C0 2 to occur after the cleaning solution has been applied to the carpet or other fiber substrate to be cleaned. Thus, chemically produced and released carbon dioxide is more effective than physically released carbon dioxide (i.e. from a pressurized container) in that the cleaning solution can be hot, and more carbon dioxide can be released once the solution has been absorbed into the soil that is to be removed from the carpet. Similar results may be obtained using any of the polybasic acids and carbonate salts listed above. In some instances it is not visually apparent that the carbonating reaction is occurring when the heated solutions are combined. However, when a textile fiber is immersed in a hot admixed acid/carbonate salt solution there is an immediate presence of effervescence on the surface of the fibers, indicating that the carbonating reaction is present. A distinct advantage of the present invention is that the solution is self-neutralizing. In the embodiment wherein the carbonate solution is applied first followed by the acid containing solution, the temporary higher pH attributable to the carbonate solution allows the solution to clean more efficiently due to the pH elevation. Because the pH drops to a safe, neutral pH within a short period of time, the safety for pH sensitive stain resistant carpets is maintained. The chemical reaction which produced the carbon dioxide also lowers the pH. Therefore, the carbonate solution is effectively neutralized by the weak acid solution. Also, these two reactants produce a third material, sodium citrate, which acts as a buffer to maintain the pH at a near neutral level. The overall reaction may be depicted as follows: 2H 3 C 6 H 5 0 7 + 3Na 2 C0 3 J± 3H 2 0 + 3C0 2 + 2Na 3 C 6 H 5 0 7 It is critical that the amounts of acid and carbonate salt along with detergent which mix together are carefully controlled and are consistent to produce a neutral solution containing the proper amount of detergent. Therefore, concentrations of solutions and flow rates must be monitored and controlled and adjusted as necessary to provide a neutral environment having the proper degree of carbonation and neutralization. The ratio of acid to carbonate salt to detergent may vary somewhat depending on the specific carbonate salt and acid utilized. Typically, the acid and carbonate salts will each be present in their respective solutions in amounts ranging between about 0.1 and 16% by weight in each. Preferably these will be present in amounts ranging between about 0.5 and 10.0% by weight in each solution. Therefore, assuming that each solution is combined on an equal volume basis, the combined solution would contain each ingredient in amounts ranging from between about 0.05 and 8.0% each with amounts of between about 0.25 and 5% being preferred. However, these are guidelines only and the only limitation relative to concentration is what is functional as any amount may be used which will not require copious amounts of water to be removed from the carpet or other textile. The actual amounts of each ingredient in said combined solution is not readily determined due to the reaction between the acid and carbonate sale and the accompanying release of carbon dioxide. Ratios of dibasic acids to carbonate salts will be different from ratios of tribasic acids to carbonate salts as will the ratios of acids to carbonates, bicarbonates and percarbonates, etc. What is important is that the ratio of acid to carbonate salt be such that the overall reaction results in an essentially neutral pH following the release of carbon dioxide from the reaction mixture. Suitable surfactants or detergents for use with the present invention comprise all classes of detergents, i.e. anionic, cationic, non-ionic and amphoteric. All of these detergents function by lowering surface tension, thus hastening the cleaning of textile fibers. Of these classes, the nonionic and anionic detergents seem to work best and anionic detergents are particularly preferred. Suitable classes of nonionic detergents are alkyl phenol-ethylene oxide condensates, polyoxyalkylene alkanols and condensation products of a fatty alcohol with ethylene oxide. Anionic detergents which can be used include straight and branched chain alkylaryl sulfonates wherein the alkyl group contains from about 8 to 15 carbon atoms; the lower aryl or hydrotropic sulfonates such as sodium dodecyl benzene sulfonate and sodium xylene sulfonate; the olefin sulfonates, such as those produced by sulfonating a C 10 to C 20 straight chained olefin; hydroxy C 10 to C 24 alkyl sulfonates; water soluble alkyl disulfonates containing from about 10 to 24 carbon atoms, the normal and secondary higher alkyl sulfates, particularly those having about 8 to 20 carbon atoms in the alkyl residue; sulfuric acid esters of polyhydric alcohols partially esterified with higher fatty acids; the various soaps or salts of fatty acids containing from 8 to 22 carbon atoms, such as the sodium, potassium, ammonium and lower alkanol-amine salts of fatty acids and sarcosinates of fatty acids. Preferred anionic detergents are those having the formula: R'AM' wherein R' is C 8 to C 20 alkyl, aralkyl, or alkaryl; A is a sulfate (S0 4 ) , sulfonate (S0 3 ) , or sarcosinate (CON(CH 3 )CH 2 COO) radical; M' is a positive ion selected from the group consisting of sodium, potassium or R" 4 N wherein R" is H, methyl, ethyl or hydroxyethyl . Typical alkyl groups include decyl, lauryl (dodecyl) , myristyl (tetradecyl) , palmityl (hexadecyl) and stearyl (octadecyl) . Typical aralkyl groups include 2- phenylethyl, 4-phenylbutyl and up to 8-phenyloctyl and the various isomers thereof. Alkaryl groups include all ortho-, meta- and para- alkyl substituted phenyl groups such as p-hexylphenyl, 2, 4, 6-trimethylphenyl and up through p-dodecylphenyl . Specifically included are alkylbenzene sulfonates, alkyl sarcosinates and alkyl sulfates. Particularly preferred are sodium, potassium, ammonium and lower alkyl or aryl amine salts of C 8 to C 20 alkyl sulfates. While typical detergents or surfactants are enumerated herein, it is to be emphasized that there are literally thousands of surfactant or detergent mixtures and the recital of a representative number or class is not meant to be a limitation as to the scope of the surfactants or detergents which can be used in the present invention. The invention is directed to the combination of a surfactant or detergent in a carbonating solution at an elevated temperature coincident with application to a textile fiber and not to any new or novel class of detergents or surfactants. Therefore, the only limitation as to the detergent or surfactant to be utilized is functionality. The concentration of detergent or surfactant in the carbonating solution will be as low as possible and still retain the advantages attributable to the presence of that ingredient. Typically, concentrations of 0.05 to 5% by weight of the carbonating solution will be sufficient. In accordance with the principles of the invention, ingredients such as bleaches, optical brighteners, carpet protectors, stain blockers and the like, may be added to the solutions provided that these ingredients do not significantly interfere with the ability of the mixture to clean the textile and impart anti-resoiling properties to the textile fibers. Therefore, ingredients such as silicates for fabric softening and filling agents such as zeolites and other components which leave excessive residue on a textile fiber unless removed by copious amounts of water are not permissible additives. The solution can also applied to the textiles, particularly carpeting or upholstery, in any other suitable manner, i.e. by pouring the composition onto the textiles or submerging the textile in the composition. When so applied the carbonated cleaning composition breaks into a myriad of tiny effervescent bubbles which rapidly penetrate into the textile fibers. Preferably, following application of the carbonating solution, it may be mechanically worked into the fibers by a carpet rake, agitation or similar means. The effervescent action breaks up and lifts the soil or oil particles to the surface of the fibers where they can be readily removed by vacuuming or adsorption onto a different, but more adsorbent textile, such as a rotating pad or piece of toweling. Because the carbon dioxide bubbles promote rapid drying, little or no solution is left on the fibers being cleaned. This contributes to the anti-resoiling properties of the invention. As stated above, the acid solution, carbonate solution and the detergent can be mixed and applied to make a composition in any desired order. It is the resulting internally-carbonating composition to which the present invention is drawn. In addition to the above, it has been found that using "hard" water to form the carbonate salt solution causes calcium carbonate to precipitate from the solution. Over time, the precipitate interferes with the valves and filters of cleaning machines. It has been found that adding a small but effective amount of a chelating agent, such as EDTA (ethylene diamine tetraacetic acid) prevents the calcium carbonate precipitate from interfering with the practice of the other aspects of the invention. EXAMPLES A light blue, level loop, nylon carpet was selected for purposes of testing. One section of the carpet was removed as the control. The remainder of the carpet was soiled extensively with crankcase oil and dirt, and the soiled carpet was trampled repeatedly with foot traffic over a 24 hour period. The carpet was irreparably soiled but was considered a useful material for purposes of showing cleaning effectiveness of various test solutions within the scope of the invention. This carpet was divided into four 2 x 2 foot sections. The reflectometer used was a Photovolt 577 Reflectance and Gloss Meter with a "D" search unit. The reflectometer was set at 99.9% by using the control sample. All four sections had an average reflectance within 1%. All sections were cleaned using solutions prepared with the same set of ingredients . Example 1 A solution containing 2.6 % citric acid was heated to 180 °F. Another solution containing 2.6 % sodium carbonate and 0.2 % sodium lauryl sulfate was also heated to 180 °F. A 90 ml sample of each heated solution was mixed and metered immediately onto the carpet as a sheet of liquid at ambient pressure as described above. There was noticeable effervescence as the solution reached the carpet fibers. Example 2 The second section was treated with identical equipment and solutions as described in the first section except that the solutions were mixed and applied at room temperature. There was still noticeable effervescence resulting from the carbonating reaction on the surface of the carpet fibers but not as pronounced as in Example 1. Example 3 The third section was cleaned using 90 ml of the same two solutions, but the solutions were mixed in a single container 30 minutes before application. The resulting solution was heated to 180 °F before application. There was no noticeable bubbling indicating that carbonation was present in the solution. Example 4 The fourth section was cleaned using the same solution and conditions as described in section three except that the solution was applied at room temperature. Results: Each carpet sample was then rubbed fifty times with a terry cloth within five minutes of application and let stand for abut 30 minutes until dry to the touch. Three reflectometer readings were then taken of each sample. The results reported were the average of the readings which did not vary more than ±2%. The average reflectance for each section after cleaning was the following: Example 1 65.6 % Example 2 51.2 % Example 3 54.8 % Example 4 49.6 % In considering the above results it is to be remembered that the treated sections were soiled beyond recovery. However, the results indicated that the hot carbonated solutions of Example 1, applied at ambient pressure, clearly removed the most soil. The solutions of Example 3, precarbonated but not immediately used, were still somewhat more effective when applied at ambient pressure as a hot solution. There was probably some residual carbonation remaining in the Example 3 solutions when used. The solutions carbonated and applied at ambient pressure and temperature as shown in Example 2 were almost equivalent to those of Example 3 showing that carbonation at the time of application (Example 2) and application of a heated precarbonated solution (Example 3) each contributed to the cleaning properties as they were somewhat better than the precarbonated solutions allowed to set for a time and then applied at ambient temperature and pressure as shown in Example 4. Had the solutions of Examples 1-4 been applied to a less soiled carpet, as would be found in actual use, the reflectometer readings would have been considerably higher. However, the ranking of the order of cleaning effectiveness would have been the same. Example 5 To avoid solutions with high and low pH, buffered solutions were prepared and tested as described in Example 1. The first solution in this test contained 1 % citric acid, and 0.3 % sodium carbonate as a buffer. The second solution contained 1 % sodium carbonate and 0.3 % citric acid as a buffer, and .2 % lauryl sulfate. The pH of the first solution was about 5. The pH of the second solution was about 9.5. The same procedure used in Example 1 was followed except that a normally soiled light blue colored carpet removed from a hallway was used to evaluate these solutions when admixed and applied as a carbonating solution. The reflectance after cleaning was found to be 92.8 %. Example 6 An acid solution and a carbonate salt solution at a temperature of about 140-180° F. were mixed in equal volume in such a way as to produce an internally carbonating reaction when applied as a sheet at the surface of the fiber in the manner as described for Examples 1-4. ACIDS Solution A contained 2.6 % citric acid. Solution B contained 2.6 % citric acid and 1 % of a fluorochemical polymer containing 0.2 % of a condensed phenolic stain blocking resin. Solution C contained 2.7 % malic acid. Solution D contained 3.0 % tartaric acid, and Solution E contained 2.4 % succinic acid. CARBONATE SALTS Solution F contained 2.6 % sodium carbonate. Solution G contained 2.6 % sodium carbonate and 0.2 % lauryl sulfate. Solution H contained 2.6 % sodium carbonate, Solution I contained 2.6 % sodium carbonate and 1 % of the ammonium salt of a polymer of 2, 5-furandione and ethenylbenzene. Solution J contained 2.6 % sodium carbonate and 0.2 % EDTA. Solution K contained 2.6 % sodium carbonate and 0.2 % Neodol 25-7™ (a nonionic detergent which is a condensation product of a mixed C 12 to C 15 fatty alcohol with 6 to 14 moles of ethylene oxide) . Solution L contained 2.6 % sodium carbonate and 0.2% sodium dodecyl benzene sulfate. Solution M contained 2.6 % sodium carbonate and 0.2 % Benzyl alkyl C 12 -C 16 dimethyl ammonium chloride, and Solution N contained 2..6 % sodium carbonate and 0.2 % sodium dedecyl benzene sulfate and 1 % sodium tripolyphosphate. Selectively combining an acid solution with a carbonate solution yielded the following results: Selectively combining an acid solution with a carbonate solution yielded the following results: Acid Base Results A F 54.3 % A G 65.6 % A H 66.4 % A I 59.2 % A J 65.3 % A K 65.1 % A L 66.3 % A M 57.6 % A N 68.5 % B F 66.6 % C H 66.2 % D G 64.2 % E H 63.7 % C N 66.9 % Although this invention has been described and illustrated by reference to certain specific formulation, these are exemplary only and the invention is limited only in scope by the following claims and functional equivalents thereof.

Claims: CLAIMS What is claimed is: 1. An internally-carbonating cleaning composition at ambient pressure for cleaning textiles prepared by combining solutions consisting essentially of: (a) an aqueous carbonate salt solution having a pH of between about 8 and 11; and (b) an aqueous acidic solution having a pH of between about 3 and 6; and (c) a detergent; wherein the relative proportions of carbonate salt, and acid are such that the carbonate reacts with the acid when said solutions are combined so as to create an aqueous composition having a generally neutral pH and from which carbon dioxide is released into the surrounding atmosphere. 2. The cleaning composition of Claim 1 wherein the carbonate solution contains a carbonate salt selected from the group consisting of sodium carbonate, sodium percarbonate, sodium bicarbonate, lithium carbonate, lithium percarbonate, lithium bicarbonate, potassium carbonate, potassium percarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate and mixtures thereof . 3. The cleaning composition of Claim 2 wherein the acid solution contains an acid selected from the group consisting of citric acid, succinic acid, tartaric acid, adipic acid, glutaric acid, malic acid and oxalic acid. 4. The cleaning composition of Claim 3 wherein the concentration of said acid in said acid solution and said carbonate salt in said carbonate salt solution is between about 0.1 and 16% by weight each prior to forming said composition. 5. The cleaning composition of Claim 4 wherein said solutions are at a temperature of between about 140 and 200° F. when combined. 6. The cleaning composition of Claim 5 wherein the carbonate salt is sodium carbonate. 7. The cleaning composition of Claim 6 wherein the acid is citric acid. 8. The cleaning composition of Claim 1, wherein the detergent is selected from the group consisting of anionic detergents, cationic detergents, non-ionic detergents and amphoteric detergents, and wherein the detergent comprises between about 0.5 and 5 percent of the composition by weight. 9. The cleaning composition of Claim 8, wherein the composition contains an anionic detergent. 10. The cleaning composition of Claim 8, wherein the composition contains an nonionic detergent. 11. The cleaning composition of Claim 10 wherein the detergent is contained in the carbonate salt solution prior to combining solutions. 12. The cleaning composition of Claim 4 wherein said acid solution is buffered by a carbonate salt to a pH of between about 3 and 6 and said carbonate salt solution is buffered by an acid at a pH of between about 8 and 11 prior to combining said solutions. 13. The cleaning composition of claim 1 further comprising a chelating agent. 14. The cleaning composition of claim 13, wherein the chelating agent comprises EDTA. 15. The cleaning composition of claim 14, wherein the EDTA is added to the carbonate salt solution. 16. A method of cleaning textile fibers which comprises applying to said fibers, an internally- carbonating cleaning composition at ambient pressure said composition being prepared coincident with said application by combining solutions consisting essentially of (a) an aqueous carbonate salt solution having a pH of between about 8 and 11; (b) an aqueous acidic solution comprising an acid having a pH of between about 3 and 6; and (c) detergent wherein the relative proportions of carbonate salt, and acid are such that the carbonate reacts with the acid when said solutions are combined so as to create an aqueous composition having a generally neutral pH and from which carbon dioxide is released into the surrounding atmosphere causing carbon dioxide to come into contact with said textile fibers. 17. The method according to Claim 16 wherein the carbonate salt is a member selected from the group consisting of sodium carbonate, sodium percarbonate, sodium bicarbonate, lithium carbonate, lithium percarbonate, lithium bicarbonate, potassium carbonate, potassium percarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate. 18. The method according to Claim 17 wherein the acid solution contains an acid selected from the group consisting of citric acid, succinic acid, tartaric acid, adipic acid, glutaric acid, malic acid and oxalic acid. > 19. The method according to Claim 18 wherein the concentration of said acid in said acid solution and said carbonate salt in said carbonate salt solution is between about 0.1 and 16% by weight each prior to the coincident preparation and application of said composition. 20. The method according to Claim 19 wherein said solutions are at a temperature of between about 140 and 200° F. at the time of said coincident preparation and application of said composition to textile fibers. 21. The method according to Claim 19 wherein the carbonate salt is sodium carbonate. 22. The method according to Claim 21 wherein the acid is citric acid. 23. The method according to Claim 16 wherein the method further includes selecting a detergent from the group consisting of anionic detergents, cationic detergents, non-ionic detergents and amphoteric detergents, and wherein the detergent comprises between about 0.5 and 5 percent of the composition by weight. 24. The method according to Claim 23 wherein the method further consists of disposing at least some of the detergent in the carbonate salt solution prior to combining solutions. 25. The method according to claim 16, wherein the method further includes placing an effective amount of a chelating agent in the carbonate salt solution, in order to minimize the precipitation of carbonates from said solution. 26. The method according to Claim 20 wherein said acid solution is buffered by a carbonate salt to a pH of between about 3 and 6 and said carbonate salt solution is buffered by an acid at a pH of between about 8 and 11 prior to said coincident preparation and application of said composition to textile fibers. 27. A method of cleaning textile fibers which comprises (a) providing an aqueous carbonate salt solution at an elevated temperature said solution having a pH of between about 8 and 11; (b) providing an aqueous acid solution at an elevated temperature said acid solution having a pH of between about 3 and 6; (c) providing a detergent; (d) causing said carbonate salt solution, said detergent and said acid solution to be combined at essentially ambient pressure to form a carbonating detergent solution at an elevated temperature; and (e) directing said carbonating detergent solution at an elevated temperature directly onto said textile fibers at ambient pressure as a spray or sheet of solution such that the carbonating solution and the carbon dioxide produced by said carbonating solution comes into contact with and cleans said textile fibers. 28. The method according to Claim 27 wherein said carbonating detergent solution coming into contact with said textile fibers is at an essentially neutral pH. 29. The method according to Claim 28 wherein the carbonate salt solution contains a member selected from the group consisting of sodium carbonate, sodium percarbonate, sodium bicarbonate, lithium carbonate, lithium percarbonate, lithium bicarbonate, potassium carbonate, potassium percarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate and mixtures thereof. 30. The method according to Claim 29 wherein the acid solution contains an acid selected from the group consisting of citric acid, succinic acid, tartaric acid, adipic acid, glutaric acid, malic acid, oxalic acid and mixtures thereof. 31. The method according to Claim 30 wherein the concentration of said acid in said acid solution and said carbonate salt in said carbonate salt solution is between about 0.1 and 16% by weight. 32. The method according to Claim 31 wherein detergent is contained in said carbonate salt solution. 33. The method according to Claim 32 wherein the detergent is present in an amount sufficient to be present in said carbonating solution in an amount of between about 0.1 to 5% by weight. 34. The method according to Claim 33 wherein said elevated temperature is a temperature of between about 140 and 200° F. 35. The method according to Claim 34 wherein the carbonate salt is sodium carbonate. 36. The method according to Claim 35 wherein the acid is citric acid. 37. The method according to Claim 35 wherein the acid solution is buffered at a pH of between 3 and 6 by a carbonate sale and the carbonate salt solution is buffered at a pH of between 8 and 11 by an acid. 38. The method according to Claim 33 wherein the amount of carbonating solution applied is sufficient to contact the textile fibers with carbon dioxide and detergent without saturating said fibers . 39. The method according to Claim 38 wherein, following application of said carbonating solution, said fibers are contacted with absorbent means to remove remaining carbonating solution and soil and residue released from said fibers by said solution. 40. The method according to Claim 39 wherein said absorbent means is in the form of a rotating absorbent pad. 41. A method of cleaning textile fibers which comprises (a) providing an aqueous carbonate salt/detergent solution at an elevated temperature said solution having a pH of between about 8 and 11; (b) providing an aqueous acid solution at an elevated temperature said acid solution having a pH of between about 3 and 6; (c) directing said carbonate salt solution at an elevated temperature directly onto said textile fibers at ambient pressure as a spray or sheet of solution; and, (d) immediately directing said acid solution onto the same textile fibers at an elevated temperature at ambient pressure as a spray or sheet of solution whereby said carbonate salt/detergent solution and said acid solution are combined on said fibers to form a carbonating solution at an elevated temperature such that the carbonating solution and the carbon dioxide produced by said carbonating solution comes into contact with and clean said textile fibers. 42. The method according to Claim 41 wherein said carbonating solution is formed on and comes into contact with said textile fibers at an essentially neutral pH. 43. The method according to Claim 42 wherein the carbonate salt solution contains a member selected from the group consisting of sodium carbonate, sodium percarbonate, sodium bicarbonate, lithium carbonate, lithium percarbonate, lithium bicarbonate, potassium carbonate, potassium percarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate and mixtures thereof. 44. The method according to Claim 43 wherein the acid solution contains an acid selected from the group consisting of citric acid, succinic acid, tartaric acid, adipic acid, glutaric acid, malic acid, oxalic acid and mixtures thereof. 45. The method according to Claim 44 wherein the concentration of said acid in said acid solution and said carbonate salt in said carbonate salt solution is between about 0.1 and 16% by weight. 46. The method according to Claim 45 wherein the detergent is present in an amount sufficient to be present in said carbonating solution in an amount of between about 0.1 to 5% by weight. 47. The method according to Claim 46 wherein said elevated temperature is a temperature of between about 140 and 200° F. 48. The method according to Claim 47 wherein the carbonate salt is sodium carbonate. 49. The method according to Claim 48 wherein the acid is citric acid. 50. The method according to Claim 49 wherein the acid solution is buffered at a pH of between 3 and 6 by a carbonate salt and the carbonate salt solution is buffered at a pH of between 8 and 11 by an acid. 51. The method according to Claim 46 wherein the amount of carbonate salt solution and acid solution applied to form said carbonating solution is sufficient to contact the textile fibers with carbon dioxide and detergent without saturating said fibers. 52. The method according to Claim 51 wherein, following formation of said carbonating solution, said fibers are contacted with absorbent means to remove remaining carbonating solution and soil and residue released from said fibers by said solution. 53. The method according to Claim 52 wherein said absorbent means is in the form of a rotating absorbent pad.

Inventors: HARRIS ROBERT D, HARRIS, ROBERT, D.
Applicants: HARRIS RES INC, HARRIS RESEARCH, INC.
Application year: 1995
Main classification: C11D3
IPC codes: C11D3