# Patent

## Title
Liquid cleaning compositions with improved enzyme compatibility and/or stability

## Abstract

In one embodiment, a cleaning composition includes a surfactant system having an invert structure; and at least one enzyme.

## Background
RELATED APPLICATIONS
This non-provisional application is related and claims priority to U.S. Patent Application No. 61/510,448, filed Aug. 31, 2011, which is incorporated herein by reference.


BACKGROUND
The present invention relates to liquid cleaning compositions.
Liquid cleaning compositions are used more widely than non-liquid cleaning compositions, such as granules, pastes, gels, and mulls. Consumers favor liquid cleaning compositions for convenience and appearance. Liquid cleaning compositions are easily measurable, readily dissolvable in water, and are capable of being applied to heavily stained areas in concentrated solution for pre-treatment. Furthermore, a clear or opaque liquid with a particular color is aesthetically appealing to consumers. In addition, liquid cleaning compositions can incorporate many performance enhancing ingredients that cannot withstand dry operation while eliminating certain environmentally hazardous ingredients, such as phosphate builder.
Although enzymes are one key to improved detergent efficiency, the amount of enzyme in a detergent is limited by a variety of factors. Particularly, it is seen that with higher concentrations comes an increased rate of enzyme self-annihilation. The enzymes' basic nature to break down proteins causes it to split other enzymes at higher detergent concentrations.
The foregoing, and the fact that these enzymes are rather expensive, has forced conventional liquid cleaning compositions to have enzyme concentrations down around 10% to minimize the self-annihilation and cost. However, this not only lowers detergent effectiveness, but also decreases the shelf life of the product due to the gradual loss of enzyme concentration as the enzyme concentration deteriorates.
In an effort to overcome the foregoing problems, expensive chemicals have been added to solutions in an effort to stabilize the enzymes by reducing deterioration seen after production. However, adding such chemicals increases the product price. This technique also further dilutes the solution, thus requiring a larger dosage of the detergent for a given cleaning job. Moreover, the dilution directly increases the cost of packaging and shipping due to more energy use and handling efforts.
Thus, there is a strong need for a liquid cleaning composition that is effective even though packaged in a concentrated form. There is also a strong and unmet need for such a liquid composition that has improved enzyme stability. Moreover, there is also a need for a liquid composition that is more environmentally friendly.
BRIEF SUMMARY
A cleaning composition according to one embodiment includes a surfactant system having an invert structure; and at least one enzyme. A method of making a cleaning composition according to one embodiment includes combining a surfactant system and at least one enzyme to create such a cleaning composition.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph showing the non-linear relationship between the dosing concentration of the present cleaning composition and the cleaning performance.
FIG. 2 is a chart showing the stain removal performance of a cleaning composition according to one embodiment across a variety of dosage amounts for a variety of soils.
FIG. 3 is a chart showing trend lines applied to some of the data from FIG. 1.
FIG. 4 is a chart showing a comparative example of cleaning efficacy of a cleaning composition according to one embodiment and TIDE 2X for a variety of soils.
FIG. 5 is a chart showing a comparative example in which 12.5 grams of an experimental cleaning composition according to one embodiment was used, but 60 grams of the TIDE 2X was used.
FIG. 6 is a chart of results of pretreatment using the experimental cleaning composition according to one embodiment and pretreatment using TIDE 2X.
FIG. 7 is a chart showing the relatively nonlinear relationship between dosage and cleaning efficacy for the experimental cleaning composition according to one embodiment.
FIG. 8 is a chart showing the relationship between dosage and cleaning efficacy for TIDE 2X under identical conditions as used to generate the data in FIG. 7.
FIG. 9 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for blood, milk and carbon on cotton, with pretreatment.
FIG. 10 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for carbon black in olive oil on both cotton (denoted by −C in legend) and cotton-polyester textiles (denoted by −CP in legend), with pretreatment.
FIG. 11 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for dust sebum on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 12 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for grass on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 13 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for clay on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 14 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for make up on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 15 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for tomato on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 16 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for blood, milk and carbon on cotton, using a “standard dose” of 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 17 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for carbon black in olive oil on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 18 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for dust sebum on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 19 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for grass on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 20 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for ground in clay on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 21 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for make up on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 22 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition according to one embodiment and TIDE 2X for tomato on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 23 is a chart depicting the results of an experiment conducted to exemplify the surprising and unexpected freezing point behavior of embodiments described herein.



DETAILED DESCRIPTION
The following description is made for the purpose of illustrating the general principles of the present invention and is not meant to limit the inventive concepts claimed herein. Further, particular features described herein can be used in combination with other described features in each of the various possible combinations and permutations.
Unless otherwise specifically defined herein, all terms are to be given their broadest possible interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defined in dictionaries, treatises, etc.
It must also be noted that, as used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless otherwise specified. The term “or” or “and/or” is used as a function word to indicate that two words or expressions are to be taken together or individually. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to”). The endpoints of all ranges directed to the same component or property are inclusive and independently combinable.
As will soon become apparent, several embodiments of the present cleaning composition surprisingly provide excellent cleaning efficacy with lower active doses of cleaning ingredients, e.g., less than about 22 grams of cleaning composition per 69 liters of wash water (referred to herein as “external water”). Also surprisingly, the cleaning efficacy of some embodiments is relatively flat across a variety of concentrations. These results were not expected. Rather, one would not expect effective cleaning at the dosages disclosed herein. Moreover, one would expect the cleaning efficacy to change significantly with increasing concentration of cleaning ingredients, as is observed in compositions currently on the market.
In addition, the inventors have surprisingly and unexpectedly discovered that some embodiments of the present invention have a low viscosity, where a higher viscosity at the disclosed concentrations was expected.
In addition, the inventors have surprisingly and unexpectedly discovered that some embodiments of the present invention exhibit a lower freezing point while maintaining stability.
The inventors have also surprisingly and unexpectedly discovered that some embodiments of the present invention exhibit a significant reduction in freeze/thaw cycle damage, which is contrary to what one skilled in the art would expect to observe. This surprising benefit is also believed to make some embodiments of the present invention more immune to dust and other contaminants.
Thus, embodiments of the cleaning compositions exhibiting the unexpected results provide several advantages over known compositions, including but not limited to the ability to create an efficacious cleaning composition in a highly concentrated form (e.g., 4×, preferably 5×, more preferably 6× and higher concentrates) relative to conventional unconcentrated detergents, thereby minimizing packaging requirements and energy consumption for packaging and shipping; lower quantities of actives are required per washload, reducing the cost of the products, as well as minimizing the amount of cleaning actives added to sewer and septic systems and the environment; less packaging to recycle or add to landfills; etc. Moreover, the low viscosity of some embodiments coupled with low dosage requirements enable pump dispensing of said embodiments of the present cleaning composition.
FIG. 1 shows the cleaning efficacy of an illustrative cleaning composition according to one embodiment in terms of percent of stain removed as a function of grams of cleaning composition added to 69 liters of water, which is the amount of water used by a typical standard washing machine for a standard load. The percent stain removal is determined according to ASTM D4265 “Standard Guide for Evaluating Stain Removal Performance in Home Laundering” using a colorimeter that measures in the L, a, b, spaces and calculates Y in National Bureau of Standards X, Y, Z space. Y value is used for the calculation is as follows:

AVERAGE PERCENT STAIN/SOIL REMOVAL=(Average Final Y Reading−Average Y Initial Reading)×100/(99.9−Average Initial Reading)

FIG. 1 is representative of what has been observed in some embodiments of the cleaning compositions described herein. As indicated by FIG. 1, there is no linear relationship between the concentration and/or dosage amount of some embodiments of the present cleaning composition and the stain removal performance. Rather, as shown in FIG. 1, the cleaning efficacy of the illustrative cleaning compositions is substantially flat (e.g., stain removal does not vary by more than 10% cleaning efficiency, indicated in the y-axis of FIG. 1, preferably no more than 5% cleaning efficiency variation in the y-axis) across a range of dosages, and for a variety of soils and stains.
In addition, the outstanding cleaning performance of embodiments of the present composition can be maintained with minimal agitation or heat. As noted above, one would have expected the cleaning efficacy to change significantly with increasing concentration of cleaning ingredients, as is observed in compositions currently on the market. Without wishing to be bound by any theory, it is believed that the surprisingly flat response as represented in FIG. 1 is likely indicative of: 1) strong surface adsorption to the clothing and soil or stain soon after introduction of the cleaning composition to the wash water, 2) followed by direct interaction with the soil or stain, and 3) finally culminating in dilution with water. This is a very different mechanism than is typically observed of detergent compositions currently in use. Such existing detergent compositions: 1) deploy to water first, 2) contact the surface of the clothing and soil or stain by agitation/impact, 3) the micelles break to deploy, 4) the micelles directly interact with the soil or stain, and 5) finally culminating in dilution with water.
Accordingly, as compared to conventional cleaning compositions, the present composition has enhanced cleaning performance with lesser amounts of detergent and with moderate or no agitation and/or heat during use. Since the present cleaning composition does not contain excessive amount of water as the conventional compositions do, it is more efficient, in terms of time and energy consumptions, to package, ship, and use the present cleaning composition. Moreover, lesser agitation and heat during cleaning reduces energy consumption as well as attendant substrate damage, e.g., damage to the clothing being cleaned. Further, because the cleaning efficacy is flat across a range of concentrations, a lesser amount of active ingredients is required per load, i.e., less of the cleaning composition need be added per load of laundry.
In addition, note that any range of values disclosed herein is intended to include any integer value within the disclosed range and any non-integer value within the disclosed range, as well as any value between any two of the integers or non-integers within the disclosed range. For example, a range disclosed as “less than 10%” is intended to include any percentage value between 0% and 10%, such as 0.01%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.9%. 9.99%, etc., as well as any value in between any two of the disclosed percentages, for example 0.015%, 0.15%, 1.1%, 2.2%, 3.3%, 4.4%, 5.5%, 6.6%, 7.7%, 8.8%, 9.89%, etc. Similarly, a range disclosed as “greater than 10%” is intended to include any percentage value higher than 10%, such as 10.01%, 10.1%, 11%, 12%, 13%, 14%, 15%, 20%, 25%, 50%, 75%, 80%, 90%, 99%, 100%, 150%, 250%, 1000%, etc.
Of course, as would be understood by a skilled artisan reading the present descriptions, where referring to a percentage composition such as weight percent (wt %), volumetric percent (vol %), atomic percent (at %) etc. that are definitively bounded to a 100% upper limit, no disclosed range is intended to include any value greater than 100% or any composition resulting in a compound having greater than one hundred volumetric, weight atomic, etc. percent of any single constituent or any combination of constituents.
The skilled artisan will further comprehend that the same principles laid out above with reference to percentage ranges also applies to ratios described herein.
Henceforth, and unless otherwise noted or defined (such as by indication of cleaning efficiency percentage above), as understood herein all percentage values are made with reference to percentage by weight, i.e. weight percent (wt %). Furthermore, note that wt % as used herein refers to the percentage by weight of the component relative to the total weight of the composition of which the component forms a part.
Embodiments generally showing the foregoing unexpected results include a surfactant system comprising a nonionic surfactant in combination with an anionic surfactant; water present in an amount from 0 to about 40 wt % (where “about X wt %” means “X±3 wt %”) based on a total weight of the cleaning composition; a solvent system comprising a polyalcohol, the solvent system being present in an amount effective to solubilize the surfactant system in the water; and an enzyme present in an amount of less than about 15 wt %.
In accordance with the present disclosures, “surfactants” may include any type as described herein, and may also include any type of surfactant suitable for use in an aqueous solution to envelop a reagent such as an enzyme solubilized in the aqueous solvent. In addition, “enzymes” as understood and described herein may include any type of enzyme as disclosed in the present descriptions, as well as any type of enzyme understood by a skilled artisan as being suitable for use in a liquid cleaning composition.
The cleaning composition is preferably in the form of an invert emulsion. Moreover, the cleaning composition is characterized as exhibiting about a constant cleaning efficacy (i.e., not varying by more than about 10% between highest and lowest values across the range when cleaning efficacy is measured in terms of % stain removal (e.g., high and low values are 40% and 50%, respectively), more preferably not varying by more than about 5%) as measured using test procedure ASTM D4265 when the cleaning composition is added to 69 liters of exterior water in amounts ranging from about 9 to about 22 grams of cleaning composition, and about 9 to about 18 grams (where “about X grams” means “X±1 gram”) of cleaning composition. It should also be noted that the dosages of cleaning composition disclosed herein work with lesser amounts of water than the 69 liters disclosed herein for purposes of demonstrating a cleaning composition concentration, i.e., similar cleaning efficacy results at higher concentrations of cleaning composition. Moreover, one will appreciate that the amount of cleaning composition added to external water may be increased or decreased based on the amount of external water, e.g., if the volume of external water is higher, more cleaning composition may be added.
In one embodiment, the present composition has the same or similar cleaning performance with the dosage amount that is half of that of a conventional cleaning composition such as TIDE 2X liquid laundry detergent, sold by Procter & Gamble. In one embodiment, the present composition has the same or similar cleaning performance with the dosage amount that is one third of that of a conventional cleaning composition. In one embodiment, the present composition has the same or similar cleaning performance with the dosage amount that is one fourth of that of a conventional cleaning composition. In one embodiment, the present composition has the same or similar cleaning performance with the dosage amount that is one fifth of that of a conventional cleaning composition. In one embodiment, the present composition has the same or similar cleaning performance with the dosage amount that is one sixth of that of a conventional cleaning composition.
In one embodiment, the present invention includes a cleaning composition comprising a surfactant system; a solvent system; and optionally water; wherein the water is present in an amount from 0 to about 55 wt % (e.g., 55±2 wt %) based on the total weight of the cleaning composition. The surfactant system comprises a nonionic surfactant in combination with an anionic surfactant.
The solvent system is present in an amount effective to solubilize the water (if present) in the surfactant system, i.e., the solvent system is present in an amount effective to push the surfactant system through its gel phase and to solubilize in the water. The term “liquid” includes solution, suspension, dispersion, emulsion, and the like. Preferably, the cleaning composition includes a water-in-oil emulsion, i.e., an “invert emulsion”. In one preferred embodiment, the water is present in an amount from about 5 to about 50 wt %. One particularly preferred solvent system comprises a polyalcohol.
In one embodiment, the present invention includes a cleaning composition comprising a surfactant system; a solvent system; and optionally water; wherein the water is present in an amount from 0 to about 55 wt % (e.g., 55±2 wt %) based on the total weight of the cleaning composition. In one preferred embodiment, water is present in an amount from about 5 to about 50 wt %. The surfactant system is selected from the group consisting of an nonionic surfactant; an amphoteric surfactant; a nonionic surfactant in combination with an anionic surfactant; an anionic surfactant in combination with an anionic polymer with dispersing property; an amphoteric surfactant in combination with an anionic surfactant; an amphoteric surfactant in combination with an anionic polymer with dispersing property; and combinations thereof. The solvent system comprises a polyalcohol. Preferably, the continuous phase is a water-in-oil emulsion, i.e., an “invert emulsion”.
It is preferred that when the surfactant system contains a nonionic surfactant in combination with an anionic surfactant, the weight ratio of the nonionic surfactant to the anionic surfactant is from about 1:1 to about 4:1, and water is present in an amount from >0 to about 55 wt % based on the total weight of the cleaning composition.
Particularly good enzyme stability has been noted when the weight ratio of the nonionic surfactant to the anionic surfactant is between 2 and 3, and even better enzyme stability is found between 2.3 and 2.7. In one approach, the surfactant system is present in an amount of between about 35 wt % and about 50 wt % based on the total weight of the cleaning composition.
It is also preferred that when the surfactant system contains an amphoteric surfactant and does not contain any anionic surfactant or anionic polymer with dispersing property, the exterior pH for the cleaning composition is from about 7 to about 12. It is also preferred that when the surfactant system contains an amphoteric surfactant in combination with an anionic surfactant or an anionic polymer with dispersing property, the exterior pH for the cleaning composition is from about 7 to about 12. The “exterior pH” refers to the pH of the water to which the cleaning composition is added, e.g., in a consumer's washing machine.
The cleaning performance of some embodiments of the present cleaning compositions can be adjusted for the intended use by modulating the water content and the solvent system. In certain instances, the surfactant molecules of the present composition either form “invert micelles” or do not aggregate to form any micelles at all. By “invert micelles,” it is meant water-in-oil type of micelles wherein the lipophilic region of the surfactant molecule points outward, while the hydrophilic region of the surfactant molecule points toward the center of the micelle and are in contact with water. During the cleaning process, the active ingredients in the present composition gets to the surface to be cleaned very quickly with minimal dilution, or without the dilution step.
In one embodiment of the present invention, the cleaning composition comprises a nonionic surfactant; an anionic surfactant; a solvent system comprising a polyalcohol; and water; wherein the weight ratio of the nonionic surfactant to the anionic surfactant is from about 1 to about 4, and water is present in an amount from about 10 to about 55 wt % based on the total weight of the cleaning composition. In another embodiment, water is present in an amount from about 10 to about 45 wt %. In another embodiment, water is present in an amount from about 15 to about 40 wt %. In another embodiment, water is present in an amount from about 20 to about 35 wt %.
As used herein, “water” refers to “total water”, which is meant to include both the water molecules that can freely move around in the cleaning composition, i.e., “free water,” and the water molecules the movement or activity of which is substantially weakened or reduced by their interaction with other ingredients. In other words, free water refers to the portion of the total water available to behave as water in solubilizations (solvent actions) or in hydrolyses. The present cleaning composition has very low free water concentration, i.e., very low water activity, because much or all of the total water is tied up or “locked” by the surfactant system and the solvent system. Thus, in some embodiments having substantially no free water, when a water-soluble capsule is used to encapsulate the cleaning composition, such a capsule would not be dissolved by the present composition due to its low water activity. Low water activity also favors the deployment of surfactants to surfaces for the removal of stains when the present cleaning composition is diluted by a large amount of water during use. Moreover, cannibalistic enzyme activity is believed to increase relative to an amount of free water. Keeping the total amount of free water limited may afford the opportunity to increase enzyme life. While the water activity is very low in the present cleaning composition, the total water content is preferably maintained to an appropriate level to avoid potential problems. For example, when the total water content is extremely low, moisture from the environment may diffuse into the cleaning composition through a water soluble film, thereby undermining the integrity of the product. Furthermore, the total water content may need to be at a certain level to dissolve or stabilize some water soluble builders and surfactants, such as anionic surfactants.
In another embodiment, the weight ratio of the nonionic surfactant to the anionic surfactant is from about 1.25:1 to about 3.50:1. In another embodiment, the weight ratio of the nonionic surfactant to the anionic surfactant is from about 1.40:1 to about 3.25:1. In another embodiment, the weight ratio of the nonionic surfactant to the anionic surfactant is from about 1.50:1 to about 2.75:1. In another embodiment, the weight ratio of the nonionic surfactant to the anionic surfactant is about 2:1.
In another embodiment, the anionic surfactant can be replaced partially or entirely with an anionic polymer with dispersing property. That is, in one embodiment, the cleaning composition comprises a nonionic surfactant; a mixture of an anionic surfactant and an anionic polymer with dispersing property; a solvent system comprising a polyalcohol; and water. Preferably, the weight ratio of the nonionic surfactant to the mixture of the anionic surfactant and the anionic polymer with dispersing property is from about 1 to about 4, and water is present in an amount from about 5 to about 55 wt % based on the total weight of the cleaning composition. In another embodiment, the cleaning composition comprises a nonionic surfactant; an anionic polymer with dispersing property; a solvent system comprising a polyalcohol; and water. Preferably, the weight ratio of the nonionic surfactant to the anionic polymer with dispersing property is from about 1 to about 4, and water is present in an amount from about 5 to about 55 wt % based on the total weight of the cleaning composition. When used together as a mixture, the anionic surfactant and the anionic polymer with dispersing property can be in any weight or molar ratio.
In yet another embodiment, the cleaning composition does not contain an anionic surfactant nor an anionic polymer with dispersing property. That is, the cleaning composition comprises a nonionic surfactant; a solvent system comprising a polyalcohol; and water. Preferably, water is present in an amount from about 5 to about 55 wt % based on the total weight of the cleaning composition.
In yet another embodiment, the nonionic surfactant can be replaced partially or entirely with an amphoteric surfactant. That is, in one embodiment, the cleaning composition comprises an amphoteric surfactant; an anionic surfactant, an anionic polymer with dispersing property, or a mixture thereof; a solvent system comprising a polyalcohol; and water. Preferably, water is present in an amount from about 5 to about 55 wt % based on the total weight of the cleaning composition. In another embodiment, the cleaning composition comprises a mixture of a nonionic surfactant and an amphoteric surfactant; an anionic surfactant, an anionic polymer with dispersing property, or a mixture thereof; a solvent system comprising a polyalcohol; and water. Preferably, water is present in an amount from about 5 to about 55 wt % based on the total weight of the cleaning composition. When used together as a mixture, the nonionic surfactant and the amphoteric surfactant can be in any weight or molar ratio. When used together as a mixture, the anionic surfactant and the anionic polymer with dispersing property can be in any weight or molar ratio. It is also preferred that the weight ratio of the nonionic surfactant, the amphoteric surfactant, or a mixture thereof to the anionic surfactant, the anionic polymer with dispersing property, or a mixture thereof is from about 1 to about 4.
By “nonionic surfactants,” it is meant surfactants that do not contain any ionic groups. Examples of suitable nonionic surfactants include ethoxylated alcohols including alkyl poly(ethylene oxide) and alkylphenol poly(ethylene oxide); copolymers of poly(ethylene oxide) and poly(propylene oxide), a.k.a. Poloxamers or Poloxamines; alkyl polyglucosides, e.g., dodecyl glucoside, octyl glucoside), and decyl maltoside; fatty alcohols, e.g.) cetyl alcohol and oleyl alcohol; cocamide MEA; cocamide DEA; polysorbates, e.g. Tween 20, Tween 80, and dodecyl dimethylamine oxide.
In one embodiment, the nonionic surfactants include an ethoxylated alcohol including fatty alcohol ethoxylate. In another embodiment, the ethoxylated alcohol has the formula: R1(OC2H4)nOH, wherein R1 is a hydrocarbon group, and n is an integer from 2 to 12. Preferably, n is an integer from 3 to 9. The term “hydrocarbon” denotes an organic compound containing only carbon and hydrogen. In one embodiment, the hydrocarbon group is an aliphatic group. By “aliphatic,” it is meant hydrocarbon having carbon atoms linked in open chains. Examples of aliphatic groups include, but are not limited to alkyl, alkenyl, and alkynyl groups. In one embodiment, R1 is an aliphatic group having 6 to 22 carbon atoms. In another embodiment, R1 is an alkyl group having 8 to 20 carbon atoms.
In another embodiment, the nonionic surfactants include an ethoxylated fatty acid ester. The fatty acid preferably has 8 to 18 carbon atoms with 10 to 14 carbon atoms more preferred. Examples of the ethoxylated fatty acid ester include ethoxylated fatty acid methyl ester, such as coco methyl ester ethoxylate and palm methyl ester ethoxylate.
In one embodiment, the nonionic surfactant is present in an amount from about 10 to about 60 wt % based on the total weight of the cleaning composition. In another embodiment, the nonionic surfactant is present in an amount from about 12.5 to about 55 wt %. In another embodiment, the nonionic surfactant is present in an amount from about 15 to about 50 wt %. In another embodiment, the nonionic surfactant is present in an amount from about 17.5 to about 45 wt %. In another embodiment, the nonionic surfactant is present in an amount from about 20 to about 40 wt %. In another embodiment, the nonionic surfactant is present in an amount from about 25 to about 35 wt %.
By “anionic surfactants,” it is meant surfactants containing one or more anionic groups and having net negative charges. Illustrative anionic surfactants may be based on sulfate, sulfonate or carboxylate anions, examples of which include, but are not limited to perfluorooctanoate (PFOA or PFO); perlluorooctanesulfonate (PFOS); sodium dodecyl sulfate (SDS), ammonium lauryl sulfate, and other alkyl sulfate salts; sodium laureth sulfate, also known as sodium tauryl ether sulfate (SLES); alkyl benzene sulfonate; and fatty acid salts.
In one embodiment, the anionic surfactant is a sulfonate salt and/or a sulfate salt, each of which independently contains an organic radical having 6 to 22 carbon atoms. In one embodiment, the organic radical is selected from the group consisting of a fatty acid group or a salt thereof, an ester of a fatty acid group, an alkyl group, an alkenyl group, an alkyl ether group, an alkenyl ether group, and a mixture thereof. In one embodiment, the sulfonate salt and/or sulfate salt is independently an alkali metal salt, such as sodium salt, or an ammonium or amine salt.
Useful anionic surfactants may also include water-soluble salts of the higher fatty acids, i.e., “soaps”, are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Additional non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term “alkyl” is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383. Also useful are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-C13 LAS.
In one embodiment, the anionic surfactant is present in an amount from about 5 to about 55 wt % based on the total weight of the cleaning composition. In another embodiment, the anionic surfactant is present in an amount from about 6 to about 50 wt %. In another embodiment, the anionic surfactant is present in an amount from about 7 to about 45 wt %. In another embodiment, the anionic surfactant is present in an amount from about 8 to about 40 wt %. In another embodiment, the anionic surfactant is present in an amount from about 10 to about 35 wt %. In another embodiment, the anionic surfactant is present in an amount from about 12 to about 30 wt %. In another embodiment, the anionic surfactant is present in an amount from about 13 to about 20 wt %.
The term “an anionic polymer with dispersing property” denotes a polymer which contains an anionic group and has the property of preventing the redeposition of detached soil or dirt on the surface being cleaned, and also preventing the flocculation of soil or dirt particles into larger, precipitating aggregates, and thereby keeping the particles suspended in a working solution. Examples of the anionic polymer with dispersing property include sodium carboxymethyl cellulose (CMC), salts of polyaspartic acid, salts of polyacrylic acid and/or maleic acid, salts of polyitaconic acid, carboxymethylinulin, etc.
As used herein, the terms “amphoteric surfactant” and “zwitterionic surfactant” are used interchangeably and denote a surfactant containing both positive charge (e.g., cationic group) and negative charge (e.g., anionic group) and carrying a total net charge of zero. Examples of amphoteric surfactant include, but are not limited to dodecyl betaine, cocamidopropyl betaine, coco ampho glycinate, and combinations thereof. When the amphoteric surfactant is used in the cleaning composition, it is preferred that the exterior pH for the cleaning composition is from about 7 to about 12, with the pH from about 8 to about 11 more preferred and the pH from about 9 to about 10 most preferred.
The term “humectant,” as used herein, refers to a hygroscopic substance. For example, the humectant can be a compound containing multiple hydrophilic groups, such as hydroxyl, amine, carboxyl, esterified carboxyl, and combinations thereof. Examples of humectants include glycerine, propylene glycol, and glyceryl triacetate. Others can be polyols, such as sorbitol, xylitol and maltitol, or polymeric polyols, such as polydextrose or natural extracts like quillaia, or lactic acid or urea. Preferably, the humectant is a polyalcohol. By “polyalcohol,” it is meant an organic compound containing multiple hydroxyl groups, particularly the organic compounds having an alkyl backbone. Examples of polyalcohol include ethylene glycol, glycerin, polyethylene glycol (PEG), and the like. In one embodiment, the solvent system further comprises a methyl ether of a polyalcohol. That is, the solvent system comprises a polyalcohol and a methyl ether of a polyalcohol. In another embodiment, in addition to the polyalcohol and the methyl ether of a polyalcohol, the solvent system further comprises an ingredient selected from the group consisting of a methyl ester of a fatty acid, an alcohol, water, and a mixture thereof. In one specific embodiment, the solvent system comprises a polyalcohol, a methyl ether of a polyalcohol, a methyl ester of a fatty acid, and an alcohol. In one example, the methyl ether of a polyalcohol is 1,3 propanediol. In another example, the methyl ester of a fatty acid is coco methyl ester. In yet another example, the alcohol is ethanol or methanol.
In one embodiment, the solvent system is present in an amount from about 1.5 to about 55 wt % based on the total weight of the cleaning composition. In another embodiment, the solvent system is present in an amount from about 5 to about 30 wt %. In another embodiment, the solvent system is present in an amount from about 9 to about 22 wt %. In one embodiment, the weight ratio of the polyalcohol and the methyl ether of a polyalcohol is from about 1.0 to about 2.7. In another embodiment, the weight ratio of the polyalcohol and the methyl ether of a polyalcohol is from about 1.4 to about 2.5.
The present cleaning composition may further comprise an additive such as a digestive enzyme, an enzyme stabilizer, a fragrant agent, a non-phosphate builder, an antiredeposition agent, a booster, and/or other additives. To achieve the desired cleaning performance and/or stability, the amount and ratio of various ingredients of the surfactant system and a solvent system as well as the amount of water can be adjusted in view of the a digestive enzyme, an enzyme stabilizer, a fragrant agent, a non-phosphate builder, an antiredeposition agent, a booster, and/or other additives. Thus, though ranges are presented by way of example herein, the actual amount of additive may be higher or lower than the range.
In one embodiment, the present cleaning composition further comprises a digestive enzyme. The digestive enzymes can be any enzyme found in the alimentary tract of a human or animal that breaks down food or other organic materials so that the host organism can absorb it. Examples of the digestive enzyme include, but are not limited to one or more protease enzymes, one or more amylase enzymes, one or more cellulase enzymes, one or more lipase enzymes, one or more manninase enzymes, and combinations thereof. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, other cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. In one embodiment, the digestive enzyme product is present in an amount from about 0 to about 12 wt % based on the total weight of the cleaning composition. In another embodiment, the digestive enzyme product is present in an amount from about 2 to about 10 wt %. In another embodiment, the digestive enzyme product is present in an amount from about 3 to about 8 wt %. The active enzyme content in the enzyme product is typically between about 3 and about 10 wt %, though could be higher or lower. For example, in one illustrative embodiment, an enzyme product includes about 50 to 55%, water, about 40% propylene glycol or other poly alcohol, about 3 to about 8% active enzyme substance. A stabilizer may also be present, especially in the case of proteases.
In one embodiment, the present cleaning composition further comprises an enzyme stabilizer, i.e., a substance to stabilize the digestive enzyme. Enzymes for use in detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes. In case of aqueous compositions comprising protease, a reversible protease inhibitor, such as a boron compound, can be added to further improve stability. In one embodiment, the enzyme stabilizer is present in an amount from about 0 to about 2 wt % based on the total weight of the cleaning composition. In another embodiment, the enzyme stabilizer is present in an amount from about 0.001 to about 1 wt %. In another embodiment, the enzyme stabilizer is present in an amount from about 0.01 to about 0.1 wt %.
In another embodiment, the cleaning composition may contain one or more additional components that may tint articles being cleaned, such as a fluorescent whitening agent. Any fluorescent whitening agent suitable for use in a laundry detergent composition may be used in the composition of the present invention. The most commonly used fluorescent whitening agents are those belonging to the classes of diaminostilbene-sulphonic acid derivatives, diarylpyrazoline derivatives and bisphenyl-distyryl derivatives. In one embodiment, the additional component is present in an amount from about 0 to about 2 wt % based on the total weight of the cleaning composition. In another embodiment, the additional component is present in an amount from about 0.001 to about 1 wt %. In another embodiment, the additional component is present in an amount from about 0.005 to about 0.1 wt %.
In one embodiment, the cleaning composition further comprises a fragrant agent, e.g., a compound or ingredient which imparts a pleasant smell to the cleaning composition. Any fragrant agent known in the art can be used. In one embodiment, the fragrant agent is present in an amount from about 0 to about 5 wt % based on the total weight of the cleaning composition. In another embodiment, the fragrant agent is present in an amount from about 0.01 to about 2 wt %. In another embodiment, the fragrant agent is present in an amount from about 1 to about 2 wt %.
In one embodiment, the present cleaning composition further comprises a builder, preferably a non-phosphate builder. The non-phosphate builder may be an organic or inorganic substance. Examples of non-phosphate builder include, but are not limited to sodium carbonate, calcium carbonate, calcium chloride, magnesium carbonate, ethylenediaminetetraacetic acid (EDTA), nitriloacetic acid (NTA), borates, zeolites, alkyl or hydroxyalkyl cellulose derivatives, and combinations thereof. Preferably, the non-phosphate builder is an alkyl cellulose derivative, hydroxyalkyl cellulose derivative, carboxyalkyl cellulose derivative, or a combination thereof. Alkyl, hydroxyalkyl, carboxyalkyl cellulose derivatives are cellulose chemically modified by alkyl, hydroxyalkyl, or carboxyalkyl groups. Examples of an alkyl, hydroxyalkyl, and carboxyalkyl cellulose derivatives include, but are not limited to methyl cellulose, hydroxypropyl ether cellulose, carboxy methyl ether cellulose, carboxymethyl inulin, poly itaconates, or an alkali salt of any of the foregoing, or a mixture thereof, and a combination thereof. In one embodiment, the builder is present in an amount from about 0 to about 15 wt % based on the total weight of the cleaning composition.
In one embodiment, the present cleaning composition further comprises an antiredeposition agent. By “antiredeposition agent,” it is meant additive used in the cleaning composition to help prevent soil from resettling on a surface after it has been removed during cleaning. Anti-redeposition agents are typically water-soluble and are sometimes negatively charged. In one embodiment, the antiredeposition agent is a cellulose acetate based polymeric material, for example, carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), and the like. Other examples of antiredeposition agent includes, but are not limited to polyvinylpyrrolidone, poly-4-vinylpyridine-N-oxide (PVnO), polyvinyl acetate, polyvinyl alcohol, and the like. Dependent on the intended use and the desired performance, the fragrant agent, the non-phosphate builder, and the antiredeposition agent may be in various percentages and ratios in the cleaning composition.
In yet another embodiment, the present cleaning composition further comprises a booster. A “booster” is an additive used in the cleaning composition to improve or “boost” the cleaning efficacy of the active cleaning ingredients in the cleaning composition. Some boosters condition water to make detergents work more effectively. In one approach, the booster is or includes an alkalinity agent that causes the water to which it is added to become more alkaline. Illustrative boosters include borates such as sodium borate decahydrate (also known as “borax”), which has many chemical properties that contribute to its cleaning power. Sodium borate decahydrate and other borates clean and bleach by converting some water molecules to hydrogen peroxide (H2O2). This reaction is more favorable in hotter water. The pH of sodium borate decahydrate is about 9.5, so it produces a basic solution in water, thereby increasing the effectiveness of bleach and other cleaning ingredients. In other embodiments, the booster is a metal carbonate such as sodium carbonate.
Although not critical to its intended use and performance, it is preferred that the cleaning composition is compatible with external additives, i.e., additives that are added to a laundry or surface to be cleaned by a consumer separately from the cleaning composition. Illustrative external additives include boosters, water softening compositions, alkalinity agents, vinegar, baking soda, etc.
Although not critical to its intended use and performance, it is preferred that the cleaning composition is environmentally friendly. In particularly preferred embodiments, the cleaning composition does not comprise any ingredient that is not environmentally friendly. As used herein, the cleaning composition or ingredient thereof is considered to be environmentally friendly if it meets one or more of the following conditions. For example, it is preferred, although not critical, that the cleaning composition contains material derived from natural, and/or sustainable (e.g., renewable) sources, and not petroleum. It is also preferred, although not critical, that all the ingredients of the cleaning composition can be degraded through biological or natural processes. In one approach, all ingredients and the finished formula is considered readily biodegradable according to the OECD 301F biodegradability standard. It is also preferred, although not critical, that none of the ingredients of the cleaning composition are known to appreciably accumulate in the environment and/or in animals.
In one embodiment of the present invention, the cleaning composition comprises one or more nonionic surfactants in an amount ranging from about 13 to about 58 wt %, with from about 22 to about 44 wt % preferred, and from about 24 to about 39 wt % more preferred; one or more anionic surfactants in an amount ranging from about 10 to about 50 wt %, with from about 12 to about 35 wt % preferred, and from about 13 to about 22 wt % more preferred; one or more polyalcohol in an amount ranging from about 3 to about 26 wt %, with from about 8 to about 20 wt % preferred, and from about 12 to about 18 wt % more preferred; an alcohol in an amount ranging from about 0 to about 8 wt %, with from about 0 to about 4 wt % preferred, and from about 0 to about 2 wt % more preferred; a methyl ether of a polyalcohol in an amount ranging from about 0 to about 10 wt %, with from about 2 to about 7 wt % preferred, and from about 3 to about 5 wt % more preferred; a methyl ester of a fatty acid in an amount ranging from about 0 to 25 about 6 wt %, with from about 0 to about 4 wt % preferred, and from about 0 to about 3 wt % more preferred; added water in an amount ranging from about 0 to about 10 wt %, with from about 0 to about 5 wt % preferred, and from about 0 to about 2 wt % more preferred; one or more fragrance agents in an amount ranging from about 0 to about 4 wt %, with from about 0 to about 2.5 wt % preferred, and from about 0 to about 2 wt % more preferred; one or more digestive enzymes in an amount ranging from about 0 to about 11 wt %, with from about 2.5 to about 9.5 wt % preferred, and from about 5 to about 8 wt % more preferred; one or more enzyme stabilizers in an amount ranging from about 0 to about 5 wt %, with from about 0 to about 3 wt % preferred, and from about 0 to about 2 wt % more preferred; and antiredeposition agents in an amount ranging from about 0 to about 2 wt %, with from about 0 to about 1 wt % preferred, and from about 0 to about 0.5 wt % more preferred. In one illustrative embodiment, the one or more nonionic surfactants are a combination of sodium sulfonate mixture of a fatty acid or an ester of a fatty acid and sulfonate of secondary alkane, wherein the sodium sulfonate mixture of a fatty acid or an ester of a fatty acid is in an amount from about 10 wt % to about 30 wt % and sulfonate of secondary alkane is in an amount from about 0 wt % to about 20 wt %; the one or more anionic surfactants are a combination of one or more fatty alcohol ethoxylates and one or more ethoxylated fatty acid methyl esters, wherein the fatty alcohol ethoxylates is in an amount from about 13 wt % to about 38 wt % and the ethoxylated fatty acid methyl ester is in an amount from about 0 wt % to about 20 wt %; and the one or more polyalcohol is a combination of 1,3-propanediol and glycerin, wherein 1,3-propanediol is in an amount from about 0 wt % to about 5 wt % and glycerin is in an amount from about 3 wt % to about 11 wt %. In another example of the embodiment, the alcohol is ethanol; the methyl ester of a polyalcohol is dipropylene glycol methyl ester; and the methyl ester of a fatty acid is coco methyl ester. In another example of the embodiment, the one or more digestive enzymes are a combination of various subtilisin proteases; and the enzyme stabilizer is CaCl (30% aqueous solution). In another example of the embodiment, the non-phosphate builder is sodium polyaspartate; and the antiredeposition agent is a biodegradable polyester, such as Clariant Texcare SRN 240. Additional nonionic surfactants are those of the formula R1(OC2H4)nOH, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of C12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
Unlike conventional liquid cleaning compositions, which contain preservatives to inhibit microbial growth therein, various embodiments of the present cleaning composition do not require the presence of any preservative. In some embodiments, the present cleaning composition does not contain any preservative. As used herein, “preservative” is a compound that is added to the cleaning composition to inhibit microbial growth.
In other embodiments, the present cleaning composition contains a preservative to inhibit microbial growth. For example, preservatives may optionally be included in various embodiments as a way to further boost microbial protection for gross bacteria, virus and/or fungi contamination introduced e.g., by a consumer, through a contaminated ingredient, contaminated storage container, equipment, processing step or other source. Any conventional preservative known in the art may be used. Some illustrative preservatives include: potassium sorbate, sodium benzoate, benzoic acid, phenoxyethanol, benzyl alcohol, dehydroxyacetic acid, sodium borate, boric acid, usinic acid, phenols, quaternary ammonia compounds, glycols, isothiazolinones (methyl, benzyl, chloro), DMDM hydantoin, hexidine, ethanol, polyaminopropyl biguanide, phenylphenol, imidazolidinyl urea, iodopropynyl butyl carbamate, parabens, formaldehyde, salicylic acid or salts, caprylyl glycol, D-glucono-1,5 lactone, sodium erythorbate, sodium hydroxymethylglycinate, peroxides, sodium sulfite, bisulfate, glucose oxidase, lacto peroxidase, and other preservatives compatible with the cleaning ingredients. Some other natural materials might also be considered like cinnamon, fruit acids, essential oils like thyme and rosemary, willow bark, aspen bark, tocopherol, curry, citrus extracts, honeysuckle, and amino acid based preservatives. Especially preferred are preservatives that do not compete with the cleaning ingredients (cationic materials) and do not have reported health or environmental issues (parabens, formaldehyde etc.). Some of the more preferred preservatives are: phenoxyethanol, benzoic acid/potassium sorbate, enzymes, borates and the natural solutions above. In one embodiment, the preservative is present in an amount less than about 5 wt % based on the total weight of the cleaning composition. In another embodiment, the preservative is present in an amount from about 0.01 to about 2 wt %. In another embodiment, the fragrant agent is present in an amount from about 0.01 to about 1 wt %.
In one embodiment, the present cleaning composition has a viscosity of about 200 centipoise (e.g., 200±20 cp) or less at 23° C. In another embodiment, the present cleaning composition has a viscosity of less than about 100 centipoise. In yet another embodiment, the present cleaning composition has a viscosity of less than about 50 centipoise. As noted above, the inventors have surprisingly and unexpectedly discovered that some embodiments of the present invention have such a low viscosity. This result was contrary to what was expected, i.e., what was expected was a higher viscosity at the disclosed concentrations of components.
Table 1 sets forth illustrative formulation parameters that provide cleaning compositions characterized as exhibiting about a constant cleaning efficacy as measured using the aforementioned test procedure when the cleaning composition is added to 69 liters of exterior water in amounts ranging from about 9 to about 22 grams of cleaning composition. One practicing the present invention using formulations derived from Table 1 should obtain results similar to those shown in the FIGS. appended hereto.







TABLE 1







Cleaning Composition A











Wt. Percentage



Ingredients
Range







Water
 4-10



LAE 24-7
25-30



Dipropylene glycol methyl ether
2-5



Ethanol
0-2



Stilbene brightener
.01-.05



LAE 24-3
1-2



polyalcohols
6-8



Methyl ester
0.5-1  



Methyl ester ethoxylates
4-7



Methyl ester sulfonate 40% aqueous
35-40



Fragrance
1-2



Protease Liquid
3-6



Amylase Liquid
1-4



Antiredeposition agent
0.5-1  



CaCl2
  0-0.5



Enzyme preservative
qs










One practicing the present invention using formulations derived from Table 1 should obtain results similar to those shown in the FIGS. appended hereto. FIG. 1 has already been discussed.
In one embodiment, the present invention provides a water-soluble or water-rupturable capsule encapsulating the present cleaning composition. “Water-soluble” or “water-rupturable,” as used interchangeably herein describes a capsule which can be dissolved or broken apart upon contacting with sufficient amount of free water to thereby discharge the present cleaning composition or expose the present cleaning composition to water in the surrounding environment. The water-soluble capsule can be made from any water-soluble material in a method known to one skilled in the art. By “water-soluble material” it is meant any substance that readily dissolves or ruptures in free water. The water-soluble material can be a polymeric material or non-polymeric material. Examples of suitable water-soluble material include, but are not limited to, polyvinyl alcohol, polyethylene oxide, methyl cellulose, partially hydrolyzed polyvinyl acetate, alginates, gelatin, carageenan, cellulosics, and combinations thereof. The water-soluble material may be used in plasticized form. That is, the water-soluble material may be mixed or treated with plasticizers, such as, for example, glycerin, sorbitol, and the like. Films of polyvinyl alcohol are most preferred. The invention encompasses the use of materials having water solubilities ranging from partial solubility in hot water to complete solubility in cold water. Moreover, to enhance the performance or stability of the water-soluble capsule, it may contain ingredients besides the above-described water-soluble material. Examples of additional ingredients include, but are not limited to, brighteners, builders, activators, enzymes, and the like.
Depending on the intended use and desired performance, the water-soluble capsule can be in any shape or thickness. For example, the capsule can be in a shape of round, oval, rectangular, square, triangle, diamond, or a combination thereof. By “thickness,” it is meant to be the length from the inner surface of the capsule to the outer surface of the capsule. In one specific embodiment, the thickness of the capsule is from about 0.5 to about 10 mils. Preferably, the capsule is in the form of a rounded film. The capsule can be transparent, semi-transparent, or opaque. The capsule may also be of any color.
In one embodiment, the present invention includes a container containing one or more capsules as described above.
In another embodiment, the present invention provides a container, such as, e.g., a metered dose container, comprising the present cleaning composition directly. The container may be in any shape or size depending on the intended use and other functional consideration. For example, the container may be in a shape that is space-saving for storage or transportation purpose, or in a shape that can be easily held/grabbed by a consumer for convenience of use, or both.
In one embodiment, the container has an opening and is in such a shape that consumer's hand can easily reach in and take any of the capsules inside the container. In another embodiment, the container is in a shape to serve as a dispenser, and thereby the consumer's hand can easily reach in and take any of the capsules inside the container. In another embodiment, the container is in a shape to serve as a dispenser, and thereby the consumer's hand does not need to reach inside the container for distributing the capsules. In another embodiment of the present invention, the container is in a shape which allows stacking. In one embodiment of the present invention, the container comprises a chamber for each capsule.
In another embodiment, the container comprises a hand pump dispenser for dispensing the aforementioned metered doses. While larger metered doses are provided in some embodiments, preferred metered dose sizes are less than about 5 ml (where “about X ml” means X±0.25 ml), more preferably between about 2 and about 4 ml. In one approach, the cleaning composition is added to a volume of external water by pumping a hand pump dispenser no more than 8 times, where the hand pump dispenser dispenses about 4 ml (maximum) or less per pump. In particularly preferred approaches, the hand pump dispenser is pumped no more than 6 times, where the hand pump dispenser dispenses about 3 ml or less per pump. The volume of external water in these approaches is 69 liters, which is the standard water volume used in a washload in a standard washing machine. Those skilled in the art will appreciate that the numbers of pumps can be adjusted based on the volume of cleaning composition dispensed per pump and/or for washloads having higher or lower external water volumes. As a general guideline, in particularly preferred approaches, less than about 0.32 grams of the cleaning composition is dissolved per liter of external water, and more preferably less than about 0.26 grams of the cleaning composition is dissolved per liter of external water.
Such low dosing is permitted by the surprising low in-use concentration requirements enabled by the present cleaning composition, as well as the surprisingly low viscosity. This is a great improvement over previous attempts to provide pump-dispensable detergents, which required pumping of significantly larger quantities of detergent. Such prior art attempts generally used a “condiment type” dispenser on a very large reservoir, making the container overly-tall, heavy (when full), and generally difficult to handle. Thus, embodiments of the present invention fill a heretofore unmet need in the marketplace for a cleaning composition that is effective at low dosages and has a low viscosity, thereby permitting cost-effective manufacture and use of the present cleaning composition in a hand pump dispenser that is small enough to be easily handled and used by a consumer.
In one illustrative embodiment, the volume of the container is less than about 1 liter, preferably less than about 0.75 liters. In one approach, the hand pump dispenser has an average circumference of a sidewall extending along its longitudinal axis of less than about 12 inches, more preferably less than about 10 inches, even more preferably less than about 8 inches. This smaller circumference allows the container to be gripped by one hand and the pump operated with the same hand.
A further benefit enabled by the pumpability of the present cleaning composition is the ability to easily target stains during pretreatment. For example, the cleaning composition may be applied directly and accurately to the immediate vicinity of the stain in a more controlled manner than was previously available, i.e., via pouring out of a bottle or cap. Moreover, there is less chance for creating a mess due to spills, overpours, etc.
In another embodiment, the container may comprise multiple chambers wherein at least one of the chambers contain the present cleaning composition, and at least one of the chambers are empty. For example, the container may be a bottle having dual chambers where a consumer may put water in the empty chamber and then mix the water with some or all of the cleaning composition in another chamber for the purpose of diluting the cleaning composition in situ.
The container may be made of any material depending on the intended use and other functional consideration. Examples of suitable material include, but are not limited to glass, plastic, wood, metal, alloy, fabric, porcelain, clay, polymer, and combinations thereof. Preferably, the container is made of a recyclable material. The container may also be in any form suitable for consumer products. Examples of the suitable form include, but are not limited to bottle, canister, pouch, box, etc. The container may comprise an opening with a lid, zip, or other means to open and close the opening as needed. The lid may optionally be a hinged lid, such as a flip-top. The container may optionally comprise a handle.
In one embodiment, the container includes a label, printing, etc. with directions to follow one or more of the methods set forth herein.
In one embodiment, the present invention provides a method for cleaning a non-textile surface. The method comprises dissolving the present cleaning composition in a volume of water to form a diluted aqueous cleaning composition; and applying the diluted aqueous cleaning composition to a non-textile surface to clean the surface. The cleaning composition may be dissolved by adding the present cleaning composition directly into a volume of water, by adding a water-soluble capsule containing the present cleaning composition into a volume of water, etc. The amount of the cleaning composition may be predetermined. Depending on the condition of a non-textile surface, the non-textile surface may be pre-treated by directly applying the cleaning composition to the non-textile surface.
In one embodiment, the present invention provides a method comprising directly applying a first amount of the cleaning composition to a non-textile surface; dissolving a second amount of the present cleaning composition in a volume of water to form a diluted aqueous cleaning composition; and applying the diluted aqueous cleaning composition in a volume of water to form a diluted aqueous cleaning composition; and applying the diluted aqueous cleaning composition to the non-textile surface to clean the surface.
In another embodiment of a method for cleaning a non-textile surface, the method comprises applying an amount of the cleaning composition to a non-textile surface; and washing the non-textile surface with water. This method allows a consumer to clean the non-textile surface manually. For example, a consumer may spray or otherwise apply the present cleaning composition directly to the surface of a plate or other non-textile surface, rub the surface with hands or scrub it with a brush or a wiping piece, and then wash the surface with water. In another approach, the cleaning composition may be applied to the non-textile surface as a pretreatment, with or without wiping or scrubbing. The non-textile surface is then later rinsed with water.
In one embodiment, the present invention provides a method for cleaning laundry. The method comprises dissolving the present cleaning composition in a volume of water to form a diluted aqueous cleaning composition; and contacting the diluted aqueous cleaning composition with the laundry to clean the same. The cleaning composition may be dissolved by adding the present cleaning composition directly into a volume of water, by adding a water-soluble capsule containing the present cleaning composition into a volume of water, by adding the present cleaning composition into a detergent receptacle of a washing machine, etc. Moreover, the laundry may or may not be in the water prior to addition of the cleaning composition to the water. The amount of the cleaning composition may be predetermined. Depending on the condition of laundry, the laundry may be pre-treated by directly applying the cleaning composition to the laundry. In one embodiment, the present invention provides a method comprising directly applying a first amount of the cleaning composition to the laundry; dissolving a second amount of the present cleaning composition in a volume of water to form a diluted aqueous cleaning composition; and applying the diluted aqueous cleaning composition to the laundry to clean the same.
Examples
This section sets forth several illustrative embodiments, along with representative test results. Unless otherwise specified, data was derived using the testing procedures set forth in ASTM D4265.
Tables 2 and 3 below list the ingredients of two exemplary cleaning compositions of the present invention.







TABLE 2







Cleaning Composition B*










Ingredients
Wt. Percentage














LAE 91-6
31.00



LAE 25-3
4.00



water
25.70



propylene glycol
5.00



ethanol 190 proof
5.00



dipropylene glycol methyl ether
3.30



Fragrance compound
0.50



sodium dodecylbenzene sulfonate
18.00



protease liquid
2.40



amylase liquid
1.60



2000 mw sodium polyacrylate 40%
1.50



sodium borate
2.00

















TABLE 3







Cleaning Composition C*










Ingredients
Wt. Percentage














LAE25-7
31.18



coco methyl ester 6 EO
8.00



LAE 25-3
4.00



water
0.00



tripropylene glycol
5.00



ethanol 190 proof
5.00



1,3 propanediol
3.30



Fragrance compound
1.50



secondary alkane sulfonate 60%
34.00



protease liquid
5.00



amylase liquid
2.00



3000 mw polyaspartate
0.50



stilbene type optical brightener
0.02



4-formyl phenyl boronic acid
0.50







*Depending on the water content in various ingredients, the total water concentration in the cleaning composition may be from about 10% to about 40% although most of the water content is not free water.






FIG. 2 shows the stain removal performance of Composition D listed in Table 4, below, across a variety of dosage amounts for a variety of soils. Note that FIG. 2 includes the data used in FIG. 1 and some additional data. To generate the data, test method ASTM D4265 was followed for each dosing amount of Composition D having a data point on the graph of FIG. 2.
FIG. 3 shows trend lines applied to some of the data from FIG. 1.







TABLE 4







Cleaning Composition D











Wt.



Ingredients
Percentage







Water
 8-20



Alcohol Ethoxylate
25-35



Alcohol
0.2-5.5



Dipropylene Glycol Methyl Ether
0-5



1,(2 or 3) Propanediol
0-2



Glycerin
 6



Fragrance compound
0-2



Ester and Alkane sulfonates
 5-15



Alkyl Ester Ethoxylates
 0-10



Anti-redeposition Agent
0-2



Enzymes
0-7



TOTAL
100.0










FIG. 4 illustrates a comparative example of the cleaning efficacy of a formulation of an experimental cleaning composition (ECC, hereinafter referred to as the “experimental cleaning composition”) based on Composition A vs. TIDE 2X (t2x) concentrated liquid detergent. The “blank” data was obtained from a run without any detergent. Each composition was used at a dose of 12.5 grams per 69 liters of water and the aforementioned test method was used. The key for the X-axis referrents is shown in Table 5.







TABLE 5





Key for abbreviations in FIGS. 4-8



















carbon black
cotton - poly
cbo - cp



in olive oil



dust sebum
cotton - poly
ds - cp



grass
cotton - poly
grs - cp



ground-in
cotton - poly
cly - cp



clay



makeup
cotton - poly
mkp - cp



tomato
cotton - poly
tmto - cp



blood/milk/carbon
cotton
b/m/cb - c



black



carbon black
cotton
cbo - c



in olive oil



cocoa
cotton
cco - c



coffee
cotton
cfe - c



dust sebum
cotton
ds - c



grass
cotton
grs - c



ground-in
cotton
cly - c



clay



makeup
cotton
mkp - c



tomato
cotton
tmto - c










As shown in FIG. 4, the cleaning composition (LH) outperformed TIDE 2X in nearly every test.
Referring to FIG. 5, there is shown a comparative example in which 12.5 grams of the experimental cleaning composition was used, but 60 grams of the TIDE 2X was used. These is the “standard dose” for each composition to clean an average size load of laundry in a standard washing machine. As shown in FIG. 5, the cleaning efficacy of the cleaning composition is similar to that of TIDE 2X, and even superior in many cases, even though a much smaller amount of the detergent was added to the washing machine.
FIG. 6 shows a chart of results of pretreatment using the experimental cleaning composition and pretreatment using TIDE 2X. In this experiment, 3 drops of each of the detergents were each added to a respective stain and allowed to soak into the fabric. Then the foregoing cleaning procedure was used to wash the fabrics, using the standard dose. This modified ASTM D4265 test emulates typical household pretreatment behavior. As shown in FIG. 6, the cleaning efficacy of the cleaning composition was similar, and in many cases superior, to that of TIDE 2X.
FIG. 7 shows the relatively nonlinear relationship between dosage and cleaning efficacy for the experimental cleaning composition when used according to the aforementioned test procedure at 100° F. As a comparative example, FIG. 8 shows the relationship between dosage and cleaning efficacy for TIDE 2X under identical conditions. Note that, in the significantly smaller dosage range shown in the x-axis of FIG. 7 (0 to about 15 grams), the cleaning efficacy of TIDE 2X exhibits a relatively linear relationship between dosage and cleaning efficacy.
FIGS. 9-15 are graphs illustrating the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for various soils on cotton and/or a 60/40 cotton/polyester blend, using the pretreatment scheme detailed for FIG. 6, across various external water temperatures. As shown, the experimental cleaning composition provides comparable cleaning efficacy as the TIDE 2X, and in most cases, a better cleaning efficacy at lower temperatures.
FIG. 9 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for blood, milk and carbon on cotton, with pretreatment.
FIG. 10 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for carbon black in olive oil on both cotton (denoted by −C in legend) and cotton-polyester textiles (denoted by −CP in legend), with pretreatment.
FIG. 11 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for dust sebum on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 12 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for grass on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 13 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for clay on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 14 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for make up on both cotton and cotton-polyester textiles, with pretreatment.
FIG. 15 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for tomato on both cotton and cotton-polyester textiles, with pretreatment.
FIGS. 16-22 are graphs illustrating the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for various soils on cotton and/or a cotton/polyester blend using a standard dose of each detergent, i.e., 12.5 grams of the experimental cleaning composition per 69 liters of water and 60 grams of TIDE 2X per 69 liters of water, across various external water temperatures. As shown, the experimental cleaning composition provides comparable cleaning efficacy as the TIDE 2X, and in most cases, a better cleaning efficacy at lower temperatures.
FIG. 16 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for blood, milk and carbon on cotton, using a “standard dose” of 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 17 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for carbon black in olive oil on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 18 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for dust sebum on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 19 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for grass on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 20 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for ground in clay on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 21 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for make up on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
FIG. 22 is a graph depicting the comparative cleaning efficacy vs. temperature under identical conditions for the experimental cleaning composition and TIDE 2X for tomato on both cotton and cotton-polyester textiles, using 12.5 grams of the experimental cleaning composition and 60 grams of TIDE 2X, respectively, per load.
As yet another comparative example, Table 6 shows the relative cleaning efficacy of a cleaning composition as set forth in Table 1 compared to another leading brand cleaning composition. It was surprisingly found that the super concentrate formulation according to one embodiment of the present invention was able to beat the performance of the leading brand with 12 mls, vs. 44.3 mls of the leading brand.
The data in Table 6 was derived according to the following parameters. The standards used were ASTM D 4265-98—Standard Guide for Evaluating Stain Removal Performance in Home Laundering (modified); and ASTM E 97—Standard Method for Directional Reflectance Factor, 45-deg 0-deg, of Opaque Specimens by Broad band Filter Reflectometry.
The products tested were GreenWorks h-e natural Laundry Detergent LC#09-T0428 and a cleaning composition as set forth in Table 1. The procedure was as follows.
Artificially soiled fabrics were acquired from Test Fabrics Inc. The fabrics were selected to evaluate a good cross section of polar and non-polar soils. Unsoiled bleached cotton swatches were included in the full wash cycle to monitor anti-redeposition properties. A 50/50 used motor/olive oil mixture was prepared and applied to cotton and poly-cotton swatches for inclusion in all of the wash cycles.
The “L, a, b and y” value for each stained fabric type was determined with a Hunter colorimeter 45/0 using a UV filter, prior to cleaning.
The swatches were then laundered as follows. Three swatches for every soil were used for each detergent. The washing machine model was a top loader—Performa (model# PAVT920AWW). The washing machine settings were: regular setting, 12 minute, medium water, warm wash, (33° C.) and cold rinse. Used 8 ballast (4 cotton/4 poly-cotton) sheets from Test Fabrics Inc. Water hardness of 125 ppm.
“L, a, b and Y” values of cleaned fabric swatches were measured using a colorimeter with a UV filter. Each of the three swatches for each stain were measured twice and then stacked on top of each other during measurement, (as per recommendations from Hunter lab outlined in bulletin, “Measuring Fabric Using the Lab Scan”). The first measurement was taken and then the swatch was turned 90° and the second measurement was taken. The 6 measurements were averaged and recorded. The L, a, b values were then used to calculate the delta E, which is a change in color of the stained fabric, according to the following equation.

√{square root over ((L1−L2)2+(a1−a2)2+(b1−b2)2)}

L1—initial L value
L2—final L value
a1—initial a value
a2—final a value
b1—initial b value
b2—final b value









TABLE 6






GreenWorks h-e
LH 12.0 IT 1.16



LC#09-T0428
LC#09-T0445


Stain
Dosage: 44.3 mL/load
Dosage: 12 mL/load

















Grass Stain (PCS-8) (poly-
6.39
7.03


cotton)


Grass Stain (CS-8)
4.18
4.33


(cotton)


Coffee (poly-cotton)
0.44
0.49


Coffee (cotton)
1.27
1.67


Cocoa EMPA 112 (cotton)
10.45
13.88


Blood/Milk/Carbon
14.43
16.55


EMPA 116 (cotton)


Blood (cotton)
15.45
18.17


Red Wine EMPA 114
10.02
9.08


(cotton)


Tomato Beef Sauce
10.00
10.45


(cotton)


Dust sebum (cotton)
6.14
6.35


Oil Stain (cotton)
36.85
37.52


Oil Stain (poly-cotton)
13.26
14.50


Delta E total:
128.9
140.0









In further embodiments, which may include all, none or some of the features disclosed herein in any combination, liquid cleaning compositions include one or more amine neutralized organic acids (ANOAs). It has surprisingly been found that adding an ANOA to a liquid cleaning composition having a surfactant or surfactant blend with an invert structure (surfactant has invert micelles, as described above) reduces the freezing point of the liquid cleaning composition. Freezing point may refer to the temperature at which the composition begins to freeze, as well as a slush point where certain components begin to freeze thereby forming a slush. The lowered freezing point is very useful for increasing storage stability of the liquid cleaning composition.
Additionally, the addition of the ANOA stabilizes liquid cleaning compositions having a surfactant or surfactant blend with an invert structure. One would have expected the addition of an ANOA to thicken and even destabilize concentrated aqueous solutions. However, the inventors have surprisingly discovered that the ANOA actually stabilizes the cleaning compositions, as well as lowers the freezing point thereof. Such benefits could not have been predicted.
Any ANOA may be used. Illustrative ANOAs include, but are not limited to, those created from alcohol amines such as ethanolamines and/or propanolamines; and organic acids such as lactic acid, citric acid, acetic acid, and tartaric acid. Examples include monoisopropylamine (MIPA) citrate, MIPA lactate, triethanolamine (TEA) citrate, TEA lactate, etc.
The ANOA is preferably present in a concentration of greater than 0 wt % to about 5 wt % based on a total weight of the cleaning composition. Illustrative ranges of concentrations of the ANOA in the composition include 0.001-5 wt %, 0.01-3 wt %, 1-5 wt %, 0.001-2 wt %, etc.
In one experiment, two otherwise identical compositions were formed, except to one was added 0.2 wt % lactic acid. In the composition without the lactic acid, the freezing point was about 38° F. In the composition with the lactic acid, the freezing point was about 28° F.
In some embodiments, the concentration of ANOA in the cleaning composition is below a level that would provide chlorine control for 1 parts per million chlorine, and preferably 3 part per million chlorine, in 69 liters of external water when a normal dose of the concentrated cleaning composition (e.g., per use instructions on the product packaging) is added to 69 liters of external water.
When ANOA is used in conjunction with any of the illustrative cleaning compositions set forth herein, similar cleaning efficacy should be observed.
In one illustrative embodiment, a liquid cleaning composition is set forth in Table 7. The various ingredients may be any known in the art as well as those set forth elsewhere herein. In an experiment conducted using a formulation as set forth in Table 7 and a substantially identical comparative formulation not having the ANOA, the freezing point was observed to be about 26° F. for the comparative example, and about 11° F. when MIPA lactate was added to a concentration of 1.2% w/w. The approximate drop in freezing point was proven repeatable using MIPA citrate. This significant drop in freezing point was not expected.










TABLE 7







INGREDIENT
% w/w









Nonionic actives
about 25-35



Anionic actives
about 10-15



Enzymes
about 0-10



Fragrance
about 0-2



Brightener
about 0-0.05



Solvent
about 15-20



Water and additives
Remainder



Amine neutralized organic acids
about >0-5










A method according to one embodiment includes adding an ANOA to a liquid cleaning composition for lowering a freezing point thereof. The ANOA is preferably added during the fabrication of the liquid cleaning composition, and may be added any time in the fabrication process.
In further embodiments, one or more ANOAs can be added to concentrated cleaners such as floor cleaners, dish cleaners, laundry boosters, soap, etc. in an effective amount to lower the freezing point of the composition, e.g., 5 wt % or less. Moreover, one or more ANOAs may be added to other concentrates such as hand/body wash or lotion (e.g., for mixing/dilution where consumer adds water; APC; bath; specialty products; dilutable stain or carpet treatments that may come in super concentrate format that may be simply dropped into a container or appliance and water added thereto; etc. Concentrates to which ANOA may be added may be known in the art, have formulations that are presently being sold; have formulations that are yet to be invented or marketed, etc.
The inventors have also surprisingly and unexpectedly discovered that some embodiments of the present invention exhibit a significant reduction in freeze/thaw cycle damage, which is contrary to what one skilled in the art would expect to observe. Moreover, some embodiments provide the benefit of both a lower freeze point as well as reduced freeze/thaw cycle damage. These benefits are very beneficial, as compositions may encounter cold temperatures and multiple freeze/thaw cycles during the distribution process, and in some cases, storage.
While not wishing to be bound by any theory, during a freeze/thaw cycle, it is believed that seed crystals want to form in a composition upon freezing. These crystals remain after the thaw, and can act as nucleation sites for further degradation of the composition during subsequent freeze/thaw cycles. It is theorized that once the crystals are present in a composition, the energy required to catalyze growth of the crystals is reduced, resulting in accelerated degradation of the composition overall. The adverse effect on a composition is apparent.
Again, the inventors have surprisingly and unexpectedly discovered that the concentrated cleaning compositions described herein resist freeze/thaw cycle damage. This surprising discovery was made after filing of the above-referenced provisional patent application, and the findings were confirmed by the inventors in experiments conducted by the inventors. The precise mechanism enabling the foregoing benefit is not known at this time. However, without wishing to be bound by any theory, it is presently theorized that the discovery is a synergistic effect of the unique formulae of the compositions described herein, in which amine neutralized organic acids in the compositions are co-cyclable, meaning that they may coexist in the water phase and in the solvent phase. The amine neutralized organic acid may ease the transition of other components from a frozen to a liquid state, acting as a co-solvent with adaptive properties, e.g., ionic and non-ionic properties, acting as a Louis acid and Louis base. The organic acid is believed to adapt to the system and go to the lowest energy, and it acts as a “lubricant” that assists in the transition from the frozen elements to the liquid elements.
This surprising benefit is also believed to make the some embodiments of the present invention more immune to dust and other contaminants, which could act as nucleation sites for creation of the aforementioned crystals. Because the cleaning compositions have a lower freezing point and/or are more resistant to freeze/thaw damage, the cleaning compositions have a higher tolerance to dust and other contaminants.
Experimentation has confirmed the foregoing freeze/thaw damage resistance benefit is repeatable in compositions having an organic acid without an amine, but with some alkaline component. The alkaline component may be one or more chemicals known in the art that provide alkalinity as well as some known material having an alkaline component already mixed therewith and added to the composition.
Illustrative alkaline components include but are not limited to at least partially neutralized builders such as neutralized polyacrylic acid, STTP, carbonates, bicarbonates, etc.
In some embodiments, the concentration of organic acid in a concentrated cleaning composition is below a level that would provide chlorine control for 1 parts per million chlorine, and preferably 3 part per million chlorine, in 69 liters of external water when a normal dose of the concentrated cleaning composition (e.g., per use instructions on the product packaging) is added to 69 liters of external water.
FIG. 23 is a chart depicting the results of an experiment conducted to exemplify the surprising and unexpected freezing point behavior discussed in detail above. In the experiment, METHOD brand Laundry Detergent (Lavender Cedar scent), referred to in this section as the “detergent”, was used as the base cleaning composition. The detergent was, at the time of the filing of the provisional patent application to which this application claims priority, for sale at retailers across the United States and directly from Method Products Inc., 637 Commercial Street, Suite 300 San Francisco, Calif. 94111 and methodhome.com. A mixture (“mixture”) of MIPA and lactic acid (88 wt % active) was separately created to form an ANOA. The mixture consisted of 2 parts by weight MIPA to 3 parts by weight lactic acid. The mixture was then added to the detergent as shown in Table 8, below. Each composition was frozen in a freezer having an internal temperature of about 2° F., then allowed to thaw, then refrozen, then thawed again, then refrozen for a third time, then allowed to thaw. During the third thaw, the temperature of the slurry of liquid in equilibrium with frozen composition was measured and recorded as the freeze point, as listed in Table 8. Note that the phase change is both isotropic and isothermal.









TABLE 8






Mixture of



Detergent
MIPA:LA
Freeze Point


(wt %)
(wt %)
(° F.)

















100
0
39.2


99
1
39.7


98
2
37.2


97.5
2.5
36.0


97
3
35.2









As shown in Table 8, and in FIG. 23 which is a smoothed graph of the data in Table 8, the freeze point rose when the concentration of the mixture increased from 0 to 1 wt %. This increase in freeze point is typical of what would be expected to happen upon addition of a salt to a high surfactant system. However, when the concentration of the mixture in the composition was increased, the freeze point surprisingly and unexpectedly decreased. Moreover, the higher the concentration of the mixture, the lower the freezing point. For example, the trend indicates that the use of 3% or more of the mixture in the composition would push the freeze point below refrigerator temperatures, e.g., 34-35° F.
The results of Table 8 and FIG. 23 are exemplary of what one would now expect to achieve when using an ANOA with a concentrated cleaning composition as disclosed herein, as confirmed by observations by the inventors of behavior of similar compositions.
An added benefit of the addition of ANOA to a cleaning composition is that the ANOA may function as a builder. Moreover, its addition reduces an amount of alcohol that might otherwise be added. The lower alcohol content not only increases viscosity, but also reduces the VOC content of the resulting composition.
In addition, the inventors have surprisingly and unexpectedly discovered that some embodiments of the present invention have a low viscosity, where a higher viscosity at the disclosed concentrations was expected.
In addition, the inventors have surprisingly and unexpectedly discovered that some embodiments of the present invention exhibit a lower freezing point while maintaining stability.
In another aspect of the present invention, a cleaning composition according to various embodiments includes improved enzyme compatibility and/or stability. This in turn enables the use of higher concentrations of enzymes in a cleaning composition.
In some embodiments, the concentration of water in the composition is low enough that invert micelles are observed, and the concentration of enzymes therein is high, e.g., greater than 1% active enzyme by weight, preferably greater than 2%, 3%, 4%, 5%, 6%, or 7% active enzymes by weight and any range between these values, based on a total weight of the cleaning composition. The enhanced stability may permit use of enzymes in an active enzyme concentration of greater than 10% (e.g., 11%, 12%, 13%, 14%, 15%, and any range between these values) by weight, based on a total weight of the cleaning composition. In other approaches, the cleaning composition may have 1 wt % or less of active enzymes. Enzymes are typically sold in an “enzyme product” having components including the active enzymes, stabilizers, and perhaps other adjuncts and additives such as a solvent and/or water. The active enzyme content in the enzyme product is typically between 5 and 10 wt %, though could be higher or lower. Accordingly, in some embodiments, a total amount of enzyme product components present in the cleaning composition is 10 wt % or less based on a total weight of the cleaning composition. In other embodiments, total amount of enzyme product components present in the cleaning composition is greater than 10 wt % based on a total weight of the cleaning composition. In yet other embodiments, a total amount of enzyme product components present in the cleaning composition is 7 wt % or less based on a total weight of the cleaning composition. In other embodiments, total amount of enzyme product components present in the cleaning composition is greater than 7 wt % based on a total weight of the cleaning composition. In still further embodiments, a total amount of enzyme product components present in the cleaning composition is 14 wt % or less based on a total weight of the cleaning composition. In other embodiments, total amount of enzyme product components present in the cleaning composition is greater than 14 wt % based on a total weight of the cleaning composition.
Consequently, the small concentration of water in the composition in the highly-enzyme-concentrated solution is primarily or completely contained within the inverted micelles. Due to the insolubility of the enzymes in the solvent, it is presently believed, though unknown, that the enzymes are also primarily contained within these inverted micelles. This, however, causes a drastic reduction of volume that the enzymes are restricted to, thus causing the enzyme concentration in each invert micelle to increase dramatically.
As explained above, one skilled in the art would expect that this high concentration of enzymes would bring about instability and an increase in enzyme decay rate due to the enzymes' basic nature to break down proteins and other enzymes. As a result, the inventors were expecting to have to add large amounts of preservatives and/or stabilizers such as propylene glycol, and glycerin, or borates and take precautions to try and reverse the negative effects expected in solutions with higher concentrations of enzymes.
However when this embodiment was tested, the inventors surprisingly and unexpectedly discovered that the enzyme stability remained at 95% over the time period of 8 weeks, a result that was unheard of for any conventional detergent. The mechanism for this surprising finding is presently unknown. Without wishing to be bound by any theory, it is hypothesized that enzymes may require water to react. Because virtually all of the water found in this solution has been associated to micellar surfactant and other ingredients, there is not enough to allow the enzymes to react, thus giving them a longer shelf life and effectiveness.
This finding greatly reduces cost, due to the fact that enzymes are an expensive ingredient. Because the surprising enzyme stability effectively lengthens the shelf life of the cleaning composition in terms of enzyme concentration, lower enzyme concentrations may be used in some embodiments for a given shelf life, e.g., 6 months, 1 year, 2 years, etc. Because enzymes are a very large portion of the cost of manufacturing cleaning compositions, the improvement in their effective lifetime is an enormous achievement.
Moreover, because the rate of enzyme self-annihilation is dramatically slowed, the initial amount of enzyme concentration may be increased to levels previously considered impractical, such as greater than about 12%, 13%, 14% or 15% by weight. Higher enzyme concentrations in turn greatly enhance cleaning efficacy.
The surprisingly and unexpectedly long enzyme stability period increases the effectiveness of the detergent when it interacts with water, e.g., the wash water, due to the greater number of enzymes remaining in the cleaning composition after a period of time compared to a conventional detergent which has a much faster enzyme decay rate, as well as an overall lower initial concentration of enzymes.
By way of comparison, conventional detergents are high water systems, thus providing a robust environment for the hydrolytic reactions to occur, in turn allowing the enzymes to start decaying as soon as the enzyme is introduced to the aqueous solution. Such decay is believed to begin in conventional detergents even as early as while the conventional detergents are still in production.
In various embodiments, the cleaning composition may have a material composition as set forth elsewhere herein, in any combination, with the proviso that the surfactant system concentration is high enough, and/or the water concentration is low enough, that the surfactant system has an invert structure with invert micelles. In further embodiments, any such cleaning compositions may have a materials composition substantially as described herein, except having a relatively higher total concentration of enzymes than set forth.
Accordingly, a cleaning composition in some embodiments may include any of the materials set forth herein, in any combination and/or concentration, with the proviso that the surfactant system has an invert structure. Moreover, various embodiments of the cleaning composition may be useful as a laundry detergent, hard surface cleaner, etc. Moreover, the cleaning composition may be a concentrate. For example, the cleaning composition may be concentrated such that a recommended dosage of the cleaning composition is at least 2.5 times smaller than one or more conventional 2X branded detergents currently on the market, for the same amount of water. The recommended dosage is typically found on the product packaging.
The cleaning composition may be packaged in any manner, including, but not limited to bottling, encapsulation in a packet, etc.
There has thus been described several embodiments of a cleaning composition and potential packaging, which surprisingly provide unexpected and unobvious results, such as, in some approaches, a generally flat cleaning efficacy profile across a range of dosages; in some approaches, a low viscosity that enables single-handed pumping of the cleaning composition; and/or in some approaches a surprisingly lower freezing point with improved stability; and/or in further approaches excellent enzyme stability. Moreover, the ability to package the composition in a handheld pump that provides a large number of laundry loads per package meets a long felt and unresolved market need for such a product.
In one illustrative example, a cleaning composition according to the present disclosures may include a surfactant system having an invert structure and at least one enzyme; regarding the surfactant system, the composition may include a surfactant in a range from about 25 wt % to about 65 wt %, or alternatively in a range from about 35 wt % to about 50 wt %; the surfactant system may include a nonionic surfactant and/or an anionic surfactant individually or in combination, and may include a combination of a nonionic surfactant and an anionic surfactant in any ratio disclosed or suggested herein; furthermore, regarding the enzyme, the composition may include a total enzyme product component in any amount as disclosed herein, e.g. about 7 wt % or less, about 7 wt % or more, greater than about 10 wt %, greater than about 10 wt %, about 14 wt % or less, greater than about 14 wt %, etc., each amount being based on the total cleaning composition weight; the composition may also include a total amount of active enzyme(s) in any amount as disclosed herein, e.g. about 1 wt % or less, greater than about 1 wt %, etc., again based on the total cleaning composition weight; the cleaning composition may also include water in an amount less than about 50 wt %; now regarding solvents, the cleaning composition may include a solvent system, the solvent system may be present in an amount effective to solubilize the water in the surfactant system, and the solvent system may include a polyalcohol; and the composition may include a brightener; moreover the cleaning composition may exclude ingredients that are not environmentally friendly; the composition may be concentrated, and the concentration may be such that a recommended dosage of cleaning composition is at least 2.5 times smaller than a conventional 2X branded detergent.
While various embodiments have been described above, it should be understood that they have been presented by way of example only, and not limitation. Thus, the breadth and scope of a preferred embodiment should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

## Claims

1. A cleaning composition, comprising:
a surfactant system having an invert structure, wherein the surfactant system is present in an amount ranging from about 25 wt % to about 65 wt % based on a total weight of the cleaning composition;
at least one enzyme product present in the cleaning composition in an amount ranging from 3 wt % to about 15 wt % based on the total weight of the cleaning composition; and
water present in the cleaning composition in an amount from 40 wt % or less based on the total weight of the cleaning composition,
wherein the cleaning composition is characterized by an initial enzyme activity level, and
wherein the cleaning composition is characterized by a retained enzyme activity level of at 95% of the initial enzyme activity level after being stored for about 8 weeks,
wherein the cleaning composition comprises no enzyme stabilizers,
wherein the cleaning composition comprises no borates.

2. The cleaning composition of claim 1, wherein the at least one enzyme product comprises one or more active enzymes, and
wherein a total amount of the one or more active enzymes present in the cleaning composition is in a range from 5 wt % to 15 wt % based on the total weight of the cleaning composition.

3. The cleaning composition of claim 1, wherein a total amount of the one or more active enzymes present in the cleaning composition is in a range from 11 wt % to 15 wt % based on the total weight of the cleaning composition.

4. The cleaning composition of claim 1, wherein the at least one enzyme product comprises a plurality of active enzymes, and wherein a total amount of the plurality of active enzymes present in the cleaning composition is in a range from 12 wt % to 15 wt % based on the total weight of the cleaning composition.

5. The cleaning composition of claim 1, wherein the surfactant system comprises a nonionic surfactant in combination with an anionic surfactant.

6. The cleaning composition of claim 5, wherein a weight ratio of the nonionic surfactant to the anionic surfactant is from 2 to 3.

7. The cleaning composition of claim 5, wherein a weight ratio of the nonionic surfactant to the anionic surfactant is from 2.3 to 2.7.

8. The cleaning composition of claim 5, wherein the surfactant system is present in an amount ranging from about 35 wt % to about 50 wt %.

9. The cleaning composition of claim 1, wherein the surfactant system is present in an amount ranging from about 35 wt % to about 50 wt %.

10. The cleaning composition of claim 9, further comprising a solvent system comprising a polyalcohol, the solvent system being present in an amount effective to solubilize the water in the surfactant system.

11. The cleaning composition of claim 1, further comprising a brightener.

12. The cleaning composition of claim 5, wherein a weight ratio of the nonionic surfactant to the anionic surfactant is from about 1 to about 4.

13. The cleaning composition of claim 1, wherein the water is present in an amount from greater than 0 wt % to less than or equal to about 35 wt %.

14. The cleaning composition of claim 1, wherein the cleaning composition comprises at least a 5X concentrate.

15. The cleaning composition of claim 1, wherein the cleaning composition is readily biodegradable.

16. The cleaning composition of claim 1, wherein the cleaning composition is in a form of a single water-in-oil emulsion, wherein micelles of the surfactant system are inverted in the composition.

17. A method of making a cleaning composition, the method comprising:
combining a surfactant system and at least one enzyme to create a cleaning composition as in claim 1.

18. The cleaning composition of claim 5, further comprising an amine neutralized organic acid (ANOA),
wherein the cleaning composition is characterized by a freezing point lower than a freezing point of an otherwise identical cleaning composition lacking the ANOA.

19. The cleaning composition of claim 18, wherein the cleaning composition is characterized by a freezing point at least 10° F. lower than a freezing point of an otherwise identical cleaning composition lacking the at least one ANOA.

20. The cleaning composition of claim 18, wherein the ANOA is present in the cleaning composition in an amount greater than 0 wt % and less than or equal to about 5 wt % based on the total weight of the cleaning composition.

21. The cleaning composition of claim 18, wherein the ANOA is MIPA lactate present in an amount greater than 0 wt % and less than or equal to 3 wt %.

22. The cleaning composition of claim 18, wherein the ANOA is a compound selected from a group consisting of:
monoisopropylamine (MIPA) citrate, MIPA lactate, triethanolamine (TEA) citrate, and TEA lactate.

23. The cleaning composition of claim 18, wherein the ANOA is MIPA citrate present in an amount greater than 0 wt % and less than or equal to about 1.2 wt %.

24. The cleaning composition of claim 16, wherein a plurality of enzymes of the enzyme product are contained within the inverted micelles.

25. The cleaning composition of claim 1, wherein the cleaning composition has substantially no free water.

26. A cleaning composition, comprising:
a surfactant system comprising:
a nonionic surfactant present in an amount ranging from about 15 to about 60 wt % based on a total weight of the cleaning composition, and
an anionic surfactant present in an amount ranging from about 15 to about 55 wt % based on the total weight of the cleaning composition,
wherein the surfactant system comprises invert micelles;

one or more active enzymes present in an amount ranging from 4 wt % to 15 wt % based on the total weight of the cleaning composition; and
water present in the cleaning composition in an amount ranging from greater than 0 wt % to less than or equal to 40 wt % based on the total weight of the cleaning composition,
wherein the cleaning composition is in a form of a single water-in-oil emulsion,
wherein the cleaning composition is characterized by an initial enzyme activity level,
wherein the cleaning composition is characterized by a retained enzyme activity level of at 95% of the initial enzyme activity level after being stored for about 8 weeks,
wherein the cleaning composition comprises no enzyme stabilizers or borates.

27. The cleaning composition of claim 26, wherein the one or more active enzymes are contained within the invert micelles of the surfactant system.

28. The cleaning composition of claim 26, wherein the one or more active enzymes are present in an amount ranging from 12 wt % to 15 wt % based on the total weight of the cleaning composition.