Patent Grant
7402554
The present invention relates to cleaning compositions and containers therefore. Specifically, the present invention relates to cleaning compositions containing high levels of surfactant and glycerol and containers therefore. The present invention also generally relates to foam-generating dispensers.
Compositions containing high levels of surfactant, such as concentrated dish washing compositions, hand soap compositions, shampoo compositions, laundry compositions, scrubbing compositions, etc. are well known and have typically provided in a liquid, a gel or a paste. While liquids and pastes may be useful in a variety of situations, such physical forms are no longer considered new and exciting. Also, while it is desirable to provide new and interesting physical forms, the use of the above compositions has typically been limited to application or pre-application of such liquids, gels and pastes into a substrate, and then the additional step of direct application to the desired surface.
While it is known to employ a foam-generating dispenser to make low-surfactant level compositions foam (i.e., body washes containing >12% surfactant), this approach has not to date succeeded for high surfactant microemulsion or protoemulsion compositions, as there is typically a direct correlation between increased surfactant levels and increased viscosity. Specifically, the rheology of high surfactant microemulsion or protoemulsion compositions makes it difficult to achieve acceptable foam without extremely turbulent and violent flow characteristics. As such turbulent flow characteristics often require excessive physical exertion or a highly-pressurized container, the practical result is that formulators are often required to lower the viscosity of their products so as to match the limitations of the foam-generating dispensers currently on the market. Therefore, this approach imparts an artificial, physical constraint upon formulators' freedom to achieve the best performing and/or lowest cost composition if foam-generation is desired.
Because of these physical constraints, solvent systems for such compositions may utilize solvents such as water, ethanol or propylene glycol to achieve the foam-generation desired. Glycerol is a polar compound known to have a relatively higher viscosity than water or ethanol or propylene glycol. It is derived from natural materials such as triglycerides and provides a non-petroleum derived materials useful in microemulsion and protoemulsions having high surfactant levels. Use of glycerol and/or propylene glycol in oil-in-water microemulsions is discussed in U.S. Pat. No. 6,008,180 and U.S. Pat. No. 6,121,228 as an optional solubilizing agent.
Accordingly, the need exists for a foam-generating dispenser which is able to produce foam from a high surfactant microemulsion or protoemulsion composition and to provide improved cleaning of surfaces such as dishes. The need further exists for a foam-generating dispenser which may produce such foam, without the need for excessive physical exertion, and/or the need to use an aerosol propellant with the use of a petroleum-derived solvent, such as glycerol.
The present invention relates to foam-generating kit containing a non-aerosol container with a foam-generating dispenser and a high surfactant microemulsion or protoemulsion composition with a solvent system comprising from about 0.5% by weight of the high surfactant microemulsion or protoemulsion composition of glycerol. The high surfactant microemulsion or protoemulsion composition contains, by weight of the high surfactant microemulsion or protoemulsion composition, at least about 20% of a surfactant system.
It has now been found that the combination of a foam-generating dispenser and a high surfactant microemulsion or protoemulsion composition with glycerol can simultaneously provide acceptable foaming without excessive physical exertion and without employing an aerosol propellant. Without intending to be limited by theory, it is believed that when an increasingly turbulent flow path is produced, even a high surfactant microemulsion or protoemulsion composition can be made to produce acceptable foam.
Furthermore, it is believed that a cleaning composition dispensed from a foam-generating dispenser according to the present invention may provide better and/or faster cleaning than the same composition dispensed in another manner. Without intending to be limited by theory it is believed that the physical foam generation forces the high surfactant microemulsion or protoemulsion composition to a state where it possesses an increased overall surface area. As most cleaning interactions such as speed and completeness of oil emulsification are directly related to the surface area covered, we believe that the form of the present invention can significantly improve overall cleaning. It has now been found that inclusion of glycerol to the cleaning composition provides an improvement in the composition's ability to solubilize food-type oils and/or greases such as canola oil while not significantly affecting adversely the viscosity of the composition. Without being bound by theory, the ability to solubilize a significant quantity of food-type oils and/or greases is an important additional cleaning benefit provided by a microemulsion or protomicroemulsion composition. Improving that cleaning benefit by increasing the percentage of a food-type oil and/or grease that is solubilized by the composition and/or decreasing the time required for a food-type oil and/or grease to be solubilized is an important advantage of glycerol incorporation into the composition.
Solubilization of food-type oils and/or greases is important to uses of cleaning compositions, especially in cleaning compositions for dishes, as e.g., residual oils and greases on surfaces are often harder to remove.
In addition, in the case of a microemulsion and/or a protomicroemulsion, it has surprisingly been found that by forcing the physical generation of foam, the present invention achieves the aesthetic benefit of physical foam, without chemically tying up the surfactant at the air-water interface. Instead, even though there is foam, a greater percentage of the surfactant is chemically available to bind to dirt, oils, etc., than if the foam was created by normal methods such as intermixing surfactant and water.
The aesthetic benefit of foam, without being bound to a theory, is believed to be related to the weight:volume ratio of the foam. The lower the viscosity of the composition, the resulting foam from the foam-generating dispenser tends to have a higher weight:volume ratio and a more aesthetically pleasing foam that is creamy and smooth.
These and other features, aspects, advantages, and variations of the present invention, and the embodiments described herein, will become evident to those skilled in the art from a reading of the present disclosure with the appended claims, and are covered within the scope of these claims.
While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the invention will be better understood from the following description of the accompanying figure in which like reference numerals identify like elements, and wherein:
The figure herein is not necessarily drawn to scale.
All percentages, ratios and proportions herein are by weight of the final high surfactant microemulsion or protoemulsion composition, unless otherwise specified. All temperatures are in degrees Celsius (° C.) unless otherwise specified.
As used herein, the term “comprising” means that other steps, ingredients, elements, etc. which do not affect the end result can be added. This term encompasses the terms “consisting of” and “consisting essentially of”.
As used herein, the term “dish” or “dishes” means any dishware, tableware, cookware, glassware, cutlery, cutting board, food preparation equipment, etc. which is washed prior to or after contacting food, being used in a food preparation process and/or in the serving of food.
As used herein, the terms “foam” and “suds” are used interchangeably and indicate discrete bubbles of gas bounded by and suspended in a liquid phase.
As used herein, the term “microemulsion” or “ME” means a oil-in-water emulsion which has the ability to emulsify oil into non-visible droplets. Such non-visible droplets typically have maximum diameter of less than about 100 angstroms (Å), preferably less than 50 Å as measured by methods known in the art, such as ISO 7027 which measures turbidity at a wavelength of 880 nm. Turbidity measuring equipment is easily available from, for example, Omega Engineering, Inc., Stamford, Conn., U.S.A.
As used herein, the term “protomicroemulsion” or “PME” means a composition which may be diluted with water to form a microemulsion.
Incorporated and included herein, as if expressly written herein, are all ranges of numbers when written in a “from X to Y” or “from about X to about Y” format. It should be understood that every limit given throughout this specification will include every lower or higher limit, as the case may be, as if such lower or higher limit was expressly written herein. Every range given throughout this specification will include every narrower range that falls within such broader range, as if such narrower ranges were all expressly written herein.
Container
The container useful herein is a non-aerosol container and typically has a hollow body for holding a high surfactant microemulsion or protoemulsion composition, preferably a dishwashing composition, and is most often a bottle or canister formed of plastic, glass, and/or metal, preferably a polymer or resin such as polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polystyrene, ethyl vinyl alcohol, polyvinyl alcohol, thermoplastic elastomer, and combinations thereof, although other materials known in the art may also be used. Such containers will typically hold from about 100 mL to about 2 L of liquid, preferably from about 150 mL to about 1.2 L of liquid, and more preferably from about 200 mL to about 1 L of liquid, and are well known for holding liquid consumer products. Such containers are widely available from many packaging suppliers.
Operatively attached to the container either directly or indirectly is a foam-generating dispenser for generating foam. When activated, the foam-generating dispenser generates foam and concurrently dispenses the foamed composition from the container. The foam-generating dispenser may be formed as either integral with, or separate from the container. If formed separately, the foam-generating dispenser may attach to the container via methods known in the art such as by employing a transition piece, corresponding threaded male and female members, pressurized and non-pressurized seals, locking and snap-on parts, and/or other methods known in the art. Preferably, the foam-generating dispenser is attached to the container via a transition piece and/or with corresponding threaded male and female members which allow easy refilling.
The foam-generating dispenser may interact with the high surfactant microemulsion or protoemulsion composition via any method so as to generate foam, such as a chemical reaction, an enzymatic reaction, and/or a mechanical action. However, a mechanical action is preferred herein, and typically involves a mechanism which imparts or mixes a gas, such as air, nitrogen, carbon dioxide, etc., directly into the dishwashing composition in a turbulent manner as it dispenses, so as to physically form the foam. Preferably, the foam-generating dispenser includes a gas imparting mechanism to form the foam from air via an air injection piston, foam-generating aperture, an impinging surface, a mesh or net, a pump, and/or a sprayer, more preferably, an air injection piston, a pump, an impinging surface, a plurality of meshes or nets, and/or a sprayer which injects or imparts air from the atmosphere into the dishwashing composition. In a highly preferred embodiment, the foam-generating dispenser employs at least two, preferably from three to five, meshes wherein the high surfactant microemulsion or protoemulsion composition flows through these meshes in series so as to generate the foam. Without intending to be limited by theory, it is believed that by flowing through the above meshes in series, the high surfactant microemulsion or protoemulsion composition is repeatedly turbulently mixed with air, thereby multiplying the foam-generating effect beyond that of any single mesh. As the percentage of surfactant system of the high surfactant microemulsion or protoemulsion composition increases, additional meshes may be added to provide the desired level of foaming and/or quality of foam.
The foam-generating dispenser also typically includes an activator, preferably a manual activator such as, for example, a trigger, a pressure-activated pumping mechanism, a button, and/or a slider, more preferably a button and/or a pressure-activated pumping mechanism which can be activated with a single finger. For certain applications, such as in industry or in public facilities, other activators may be useful, such as an electronic activator, a computer-controlled activator, an electric eye or an infrared detection activator, a manual lever-assist activator, etc. The foam-generating dispenser useful herein generates foam having a foam to weight ratio of greater than about 2 mL/g, more preferably from about 3 mL/g to about 10 mL/g, and even more preferably from about 4 mL/g to about 8 mL/g. Furthermore, the foam-generating dispenser useful herein generates at least about 2 mL foam, preferably from about 3 mL to about 10 mL, and more preferably from about 4 mL to about 8 mL, per mL of dishwashing composition. “Creamy” and “smooth” foams having fine bubbles dispersed relatively evenly throughout may be especially preferred for their aesthetic and/or performance characteristics. In certain cases, preferred foams are those which do not significantly degrade into liquid over a period of 3 minutes are especially preferred. Specifically, when the foam is dispensed onto a clean glass surface (e.g., a PYREX™ plate) and let sit for 3 minutes at 25° C., less than 1 mm of liquid should be apparent. Preferably, no liquid is visible at the edge of the foam after 3 minutes. However, in other cases, it has also been found that a certain amount of liquid (i.e., non-foam) is also preferable, as this liquid then permeates into the applicator (e.g., a sponge), and further extends the mileage of the high surfactant microemulsion or protoemulsion composition when it is used for, example, cleaning dishes.
In a preferred embodiment, the foam-generating dispenser contains a sponge therein or attached thereon, either in place of, or in addition to one or more meshes. A sponge also produces foam as the high surfactant microemulsion or protoemulsion composition is turbulently forced through its, open-celled structure. Such a sponge may be contained within the interior of the foam-generating dispenser and/or may also be located at the end of the nozzle, as desired. Without intending to be limited by theory, it has been found that additional meshes and/or a sponge located slightly within, and/or at the tip of the nozzle are especially useful herein, as they serve to generate the foam immediately prior to dispensing.
Preferred foam-generating dispensers useful herein include: T8900, OpAd FO, 8203, and 7512 series foamers from Afa-Polytek, Helmond, The Netherlands; T1, F2, and WR-F3 series foamers from Airspray International, Inc., Alkmaar, The Netherlands or North Pompano Beach, Fla., U.S.A.; TS-800 and Mixor series foamers from Saint-Gobain Calmar, Inc., City of Industry, Calif., U.S.A.; pump foamers and squeeze foamers from Daiwa Can Company, Tokyo, Japan; TS1 and TS2 series foamers from Guala Dispensing USA, Inc., Hillsborough, N.J., U.S.A.; and YT-87L-FP, YT-87L-FX, and YT-97 series foamers from Yoshino Kogyosho Co., Ltd., Tokyo, Japan. Also see the foam-generating dispensers discussed in the Japanese-language publications Food & Package, (2001) vol. 42, no. 10, pp 609-13; Food & Package, (2001) vol. 42, no. 11, pp 676-79; and Food & Package, (2001) vol. 42, no. 12, pp 732-35. Variations and modifications of existing foam-generating dispensers are especially useful herein, especially by modifying air piston:product piston volume ratio, mesh/net sizes, impinging angle, etc., as well as optimization of the sizes and dimensions of the cylinder, rod, dip tube, nozzle, etc.
High Surfactant Microemulsion or Protoemulsion composition
The high surfactant microemulsion or protoemulsion composition herein is typically a cleaning composition, preferably a dishwashing composition, and more preferably a hand dishwashing composition. Such a high surfactant microemulsion or protoemulsion composition therefore includes a surfactant system, and a solvent system comprising glycerol. The composition may further comprise other components in the solvent system and one or more optional ingredients known in the art of cleaning such as a dye, an enzyme, a perfume, a thickener, a pH controlling agent, a reducing or oxidizing bleach, an odor control agent, antioxidants and free radical inhibitors, and a mixture thereof.
The surfactant system herein typically includes an anionic surfactant, an amphoteric surfactant, a cationic surfactant, a nonionic surfactant, a zwitterionic surfactant, or a mixture thereof, preferably an alkyl sulfate, an alkoxy sulfate, an alkyl sulfonate, an alkoxy sulfonate, an alkyl aryl sulfonate, an amine oxide, a betaine or a derivative of aliphatic or heterocyclic secondary and ternary amine, a quaternary ammonium surfactant; an amine, a singly or multiply alkoxylated alcohol, an alkyl polyglycoside, a fatty acid amide surfactant, a C8-C20 ammonia amide, a monoethanolamide, a diethanolamide, an isopropanolamide, a polyhydroxy fatty acid amide and a mixture thereof. A mixture of anionic and nonionic surfactants is especially preferred. The surfactants useful herein may further be branched and/or linear, substituted or unsubstituted, as desired. See also “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).
The anionic surfactant useful herein includes water-soluble salts or acids of the formula ROSO3M, wherein R preferably is a C6-C20 linear or branched hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C10-C14 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation or ammonium or substituted ammonium, but preferably sodium and/or potassium.
Other suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstituted linear or branched C6-C20 alkyl or hydroxyalkyl group having a C10-C20 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C14 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 5, more preferably between about 0.5 and about 2, and M is H or a cation which can be, for example, a metal cation, ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates (abbreviated herein as CX-YEmS, where X-Y represents the alkyl group chain length, E represents an ethoxy moiety, S represents a sulfate moiety and where m is the same as described above) as well as alkyl propoxylated sulfates are thus preferred herein. Exemplary surfactants are C10-C14 alkyl polyethoxylate (1.0) sulfate, C10-C14 polyethoxylate (1.0) sulfate, C10-C14 alkyl polyethoxylate (2.25) sulfate, C10-C14 polyethoxylate (2.25) sulfate, C10-C14 alkyl polyethoxylate (3.0) sulfate, C10-C14 polyethoxylate (3.0) sulfate, and C10-C14 alkyl polyethoxylate (4.0) sulfate, C10-C18 polyethoxylate (4.0) sulfate. In a preferred embodiment the anionic surfactant is a mixture of alkoxylated, preferably ethoxylated and non-alkoxylated sulfate surfactants. In such a preferred embodiment the preferred average degree of alkoxylation is from about 0.4 to about 0.8.
Other particularly suitable anionic surfactants for use herein are alkyl sulphonates and alkyl aryl sulphonates, including water-soluble salts or acids of the formula RSO3M wherein r is a C6-C20 linear or branched, saturated or unsaturated alkyl or aryl group, preferably a C10-C20 alkyl or aryl group and more preferably a C10-C14 alkyl or aryl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternay ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Also highly preferred are the linear and branched alkyl benzene sulphonates and more preferably linear alkyl benzene sulphonate.
The ratio of anionic sulphonate surfactant to anionic sulfate surfactant is selected to achieve the desires cleaning, such as grease soil removal. In one embodiment, a ratio of from 1:1 to about 1:25 or the anionic sulphonate surfactant to anionic sulfate surfactant is preferred. More preferred is a ratio of 1:10 to 1:20 wherein the anionic sulphonate surfactant is an alkyl aryl sulphonates and the anionic sulfate surfactant is a mixture of alkoxylated, preferably ethoxylated and non-alkoxylated sulfate surfactants.
In a further preferred embodiment, the carbon chain of the anionic surfactant comprises one or more alkyl, preferably C1-4 alkyl, branching units. In such a case, the average percentage branching of the anionic surfactant is greater that about 30%, more preferably from about 35% to about 80% and more preferably from about 40% to about 60%, by weight of the anionic surfactant.
The amphoteric surfactant herein is a surfactant whose charge changes according to the pH of the PME, if applicable, or the ME, and is preferably selected from the various amine oxide surfactants. Amine oxides are semi-polar surfactants and include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. In one embodiment, the one alkyl moiety of from about 10 to about 18 carbon atoms may comprises one or more alkyl, preferably C1-4 alkyl, branching units such as those discussed in U.S. Pat. No. 6,376,713 B1 or longer branching units such as those disclosed in U.S. Ser. Nos. 11/274909, published as US20060105936 and 11/272559, published as US2006015931, both filed Nov. 11, 2005.
Preferred are amine oxides of the formula:
where R1 is a C10-C14 alkyl and R2 and R3 are methyl or ethyl, and those described in U.S. Pat. No. 4,316,824 to Pancheri, granted on Feb. 23, 1982; U.S. Pat. No. 5,075,501 to Borland and Smith, granted on Dec. 24, 1991; and U.S. Pat. No. 5,071,594 to Borland and Smith, granted on Dec. 10, 1991.
Preferred amine oxide surfactants have the formula:
where R3 is an alkyl, a hydroxyalkyl, an alkyl phenyl group or a mixture thereof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R5 is an alkyl or a hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure. Preferred amine oxide surfactants include the C10-C18 alkyl dimethyl amine oxides and the C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
Also suitable are amine oxides such as propyl amine oxides, represented by the formula:
where R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms and R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl.
A further suitable species of amine oxide semi-polar surface active agents comprise compounds and mixtures of compounds having the formula:
where R1 is an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R2 and R3 are each methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl and n is from 0 to about 10.
Other suitable, non-limiting examples of the amphoteric surfactant useful in the present invention includes amido propyl betaines and derivatives of aliphatic or heterocyclic secondary and ternary amines in which the aliphatic moiety can be straight chain, or branched and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and at least one aliphatic surfactant contains an anionic water-solubilizing group.
Further examples of suitable amphoteric surfactants are disclosed in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).
Amphoteric surfactants may be present from about 0.1 to about 10% by weight of the high surfactant microemulsion or protoemulsion composition, preferably from about 1% to about 8% by weight of the high surfactant microemulsion or protoemulsion composition. The ratio of amphoteric surfactant to anionic sulfate surfactant is selected to achieve the desires cleaning, such as grease soil removal. In one embodiment, a ratio of from 1:1 to about 1:10 of the amphoteric surfactant to anionic sulfate surfactant is preferred. More preferred is a ratio of 1:1 to 1:6 wherein the amphoteric surfactant is an amine oxide and the anionic sulfate surfactant is a mixture of alkoxylated, preferably ethoxylated and non-alkoxylated sulfate surfactants.
Cationic surfactants useful herein include quaternary ammonium salts having at least one C10-C14 alkyl chain, charge-balanced with an anion, such as chloride. Preferred cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula:
[R2(OR3)y][R4(OR3)y]2R5N+X31
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of —CH2CH2—, —CH2CH(CH3)—, —CH3CH(CH2OH)—, —CH2CH2CH2—, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, ring structures formed by joining the two R4 groups, —CH2CHOHCHOHCOR6CHOH—CH2OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not O; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Other cationic surfactants useful herein are also described in U.S. Pat. No. 4,228,044, Cambre, issued Oct. 14, 1980, Mono-alkoxylated and di-alkoxylated ammonium salts may also be used herein, and are commonly available from suppliers such as Clariant Corporation, Charlotte N.C., USA and Akzo Nobel nv, Arnhem, the Netherlands.
Zwitterionic surfactants may also be useful herein and can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678 Laughlin, et al., issued Dec. 30, 1975 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants. Zwitterionic surfactants particularly useful herein include commonly-available betaine surfactants, particularly lauryl amido propyl betaine, C12-C16 cocoamido propyl betaine, and a mixture thereof.
The PME or ME herein also contains less than about 10%, preferably from about 0% to about 10%, more preferably from about 0% to about 5%, and even more preferably from about 0% to about 3% nonionic surfactant. Nonionic surfactants useful herein are generally disclosed in U.S. Pat. No. 3,929,678 to Laughlin, et al., issued Dec. 30, 1975, at column 13, line 14 through column 16, line 6. Other nonionic surfactants useful herein include the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TERGITOL® 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles ethylene oxide), TERGITOL® 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NEODOL® 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NEODOL® (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), marketed by Shell Chemical Company, and KYRO® EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, Cincinnati, Ohio, U.S.A. Other commercially available nonionic surfactants include DOBANOL 91-8® marketed by Shell Chemical Co. and GENAPOL UD-080® marketed by Hoechst. This category of nonionic surfactant is referred to generally as “alkyl ethoxylates.”
Also useful herein is a nonionic surfactant selected from the group consisting of an alkyl polyglycoside surfactant, a fatty acid amide surfactant, a C8-C20 ammonia amide, a monoethanolamide, a diethanolamide, an isopropanolamide, and a mixture thereof. Such nonionic surfactants are known in the art, and are commercially-available. A particularly preferred nonionic surfactant useful herein is a C9-C12 alkyl polyglycoside from Cognis Corp. USA, Cincinnati, Ohio. Preferred alkylpolyglycosides have the formula:
R2O(CnH2nO)t(glycosyl)x,
wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
Fatty acid amide surfactants include those having the formula:
wherein R6 is an alkyl group containing from about 7 to about 21, preferably from about 9 to about 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and —(C2H4O)xH where x varies from about 1 to about 3.
Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
The composition herein may comprise up to about 20%, preferably from about 0.5% to about 10%, of a polyhydroxy fatty acid amide surfactant. If present, the polyhydroxy fatty acid amide surfactant component is typically of the formula:
where R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-4 alkyl, more preferably C1 or C2 alkyl, even more preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, even more preferably straight chain C11-C15 alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. R2—C(O)—N< is preferably selected from cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, and a mixture thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. Z preferably will be selected from the group consisting of —CH2—(CHOH)n—CH2OH, —CH(CH2OH)—(CHOH)n-1—CH2OH, —CH2—(CHOH)2)CHOR)(CHOH)—CH2OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R is H or a cyclic or aliphatic monosaccharide. Even more preferred are glycityls wherein n is 4, particularly —CH2—(CHOH)4—CH2OH.
The high surfactant microemulsion or protoemulsion composition contains, by weight of the high surfactant microemulsion or protoemulsion composition, at least about 20% of a surfactant system; preferably from about 20% to about 99% of a surfactant system; more preferably from about 20% to about 80%; more preferably from about 25% to about 75%; more preferably from about 25% to about 65% of, more preferably from about 30% to about 65%, more preferably from about 35% to about 50% of a surfactant system.
The solvent system useful herein comprises glycerol. Further solvents useful herein are typically selected from the group consisting of water, alcohols, glycols, polyols, ether alcohols, and a mixture thereof, more preferably the group consisting of water, glycols, ethanol, glycol ethers, water, and a mixture thereof, even more preferably the group consisting of propylene carbonate, propylene glycol phenyl ether, tripropyleneglycol n-propyl ether, diethylene glycol n-butyl ether, water, and a mixture thereof. The solvent herein preferably has a solubility in water of at least about 12%, more preferably of at least about 50%, by weight of the solution.
The high surfactant microemulsion or protomicroemulsion composition contains by weight at least about 0.5% glycerol, preferably from about 1% to about 25% glycerol, more-preferably from about 2% to about 16% glycerol, even more preferably about 4% to about 10% glycerol.
Glycerol is present in the solvent system at a ratio of from about 1:1 to about 1:35 with the surfactant system, preferably in a ratio of from about 1:2 to about 1:20, more preferably from about 1:3 to about 1:15, even more preferably from about 1:3 to about 1:10. The viscosity and cleaning of the high surfactant microemulsion or protoemulsion composition is likewise, surprisingly acceptable with the inclusion of glycerol in the solvent system.
In one embodiment, the inclusion of propylene glycol derivatives, such as ether derivatives, provide surprising levels of grease soil removal when the high surfactant microemulsion or protoemulsion composition is from about 20% to about 30% by weight of the high surfactant microemulsion or protoemulsion composition.
Solvents which are capable of decreasing the product viscosity and/or imparting a shear-thinning or non-Newtonian rheology profile to the compositions may be present, but are not preferred herein, as such solvents are typically expensive, and do not provide significant non-shear related benefits. Accordingly, in a preferred embodiment, the high surfactant microemulsion or protoemulsion composition herein acts as a Newtonian Fluid throughout the relevant shear-range during use in the foam-generating dispenser. Preferred solvents useful herein which impart a Newtonian behavior include mono, di and poly hydroxy alcohols, ethers, and mixtures thereof. Alkyl carbonates such as propylene carbonate are also preferred.
The enzyme useful herein includes a cellulase, a hemicellulase, a peroxidase, a protease, a gluco-amylase, an amylase, a lipase, a cutinase, a pectinase, a xylanase, a reductase, an oxidase, a phenoloxidase, a lipoxygenase, a ligninase, a pullulanase, a tannase, a pentosanase, a malanase, a β-glucanase, an arabinosidase and a mixture thereof.
A microemulsion or a protomicroemulsion composition, and especially a dishwashing composition typically also contains a low water-soluble oil having a solubility in water of less than about 10,000 ppm, preferably from about 0 parts per million (ppm) to about 1,500 ppm, by weight of the low water-soluble oil, and more preferably from about 1 part per trillion to about 100 ppm. Preferred low water-soluble oils useful herein include terpenes, isoparaffins, phenyl ethers, other oils having the above solubility, and a mixture thereof. A preferred phenyl ether oil is propyleneglycol phenyl ether.
The high-surfactant-concentration microemulsion or protomicroemulsion contains by weight preferably at least about 2% of the low water-soluble oil, more preferably from about 4% to about 16%, even more preferably about 6% to about 12%. In the absence of a foam-generating dispenser, the composition typically has an effective foaming dilution range of less than about 50%, preferably from about 0% to about 40%, and more preferably from about 0% to about 35% of the dilution range. However, in an embodiment of the invention herein, the composition, when used with the foam-generating dispenser, has an effective foaming dilution range of at least about 50%, preferably from about 50% to about 100%, more preferably from about 75% to about 100%, and even more preferably from about 85% to about 100% of the dilution range. The effective foaming dilution range is calculated as follows: The suds generation curves of Graph I are generated by testing various dilutions of a composition via the suds cylinder test herein. Such a curve can be generated either with or without dispensing from a foam-generating dispenser into the cylinders. “Effective foam” is defined herein as foam which is at least half (50%) the maximum volume of foam generated for a given composition according to the suds generation curve. Accordingly, in Graph I for when the foam-generating dispenser is not employed, effective foam is formed from about 28% to about 2% product concentration, which translates into an effective foaming dilution range of 26% (i.e., 28%−2%). However, when the same composition is employed with (i.e., dispensed from) the foam-generating dispenser, it can be seen that effective foam is generated from the point of dispensing (100% product concentration) until a product concentration of about 3% is reached. This is because the kit generates foam at a substantially different composition to water dilution than the dilution at which the maximum volume of foam is formed according to the suds cylinder test. Thus, the effective foaming dilution range when the composition in
The composition herein has an oil solubilization curve which is generated by the oil solubilization test defined herein. “Effective oil solubilization” is defined herein as oil solubilization which is at least 20% of the maximum amount of oil solubilized for a given composition according to the oil solubilization curve which is plotted as a function of product concentration (i.e., dilution). Accordingly, in Graph I, the maximum amount of oil solubilized is about 4.7 at a 70% product concentration, and thus the effective oil solubilization is an amount of at least about 0.94. The effective oil solubilization occurs from dilution ranges of about 96% to about 42%, which translates into an effective oil solubilization dilution range of about 54%.
As it can be seen in Graph I, there is virtually no overlap between the suds generation curve without a foam-generating dispenser and the effective oil solubilization dilution range. Similarly, it can be seen that absent a foam-generating dispenser, there is no overlap between the effective foaming dilution range (28% to 2%) and the effective oil solubilization dilution range (from 42% to 96%). In contrast, when a foam-generating dispenser is employed, the effective foaming dilution range (from 3% to 100%) completely (100%) overlaps the entire effective oil solubilization dilution range (from 42% to 96%). In a preferred embodiment, the effective foaming dilution range overlaps the effective oil solubilization dilution range, preferably the effective foaming dilution range overlaps the effective oil solubilization dilution range by at least about 10%, more preferably by from about 25% to about 100%, and even more preferably from about 50% to about 100%, especially in the case of a microemulsion or a protomicroemulsion. Furthermore, it is highly preferred that the effective foaming dilution range overlaps the point in the oil solubilization curve where the oil solubilization is at a maximum. Thus, the present invention encourages a user to use the product at a concentration/product dilution which more effectively solubilizes oil, and thereby optimizes cleaning.
The high surfactant microemulsion or protoemulsion composition herein typically has a viscosity of less than about 300 mPa*s, preferably less than about 100 mPa*s, more preferably less than about 65 mPa*s, even more preferably less than about 55 mPa*s, even more preferably less than about 50 mPa*s, and most preferably less than about 40 mPa*s at 20° C.
While the high surfactant microemulsion or protoemulsion composition is preferably sold within the container as a single item. this is not necessary, as refills, and separate components within the same kit are contemplated herein.
Shaped Applicator
It has further been discovered that a shaped applicator can surprisingly provide significantly improved results and ease of use as comparator to a normal applicator. The shaped applicator is designed and sized to be easily held in the hand and is used to apply the foamed dishwashing composition to the surface to be cleaned, i.e., the dish.
As the shaped applicator will often be used for scrubbing, it is preferred that at least one surface thereof contain an abrasive surface. The shaped applicator is typically selected from a porous material such as a natural or artificial sponge, a brush, a metal scouring device, a woven material, a nonwoven material, an abrasive material, a plastic material, a cloth material, a microfiber cleaning material, a polymeric material, a resin material, a rubber material, or a mixture thereof, preferably a natural or artificial sponge, a brush, a metal scouring device, an abrasive material, a foam rubber material, a functional absorbent material (FAM) described in U.S. Pat. No. 5,260,345 to DesMarais, et al., issued on Nov. 9, 1993 or U.S. Pat. No. 5,889,893 to Dyer, et al., issued on May 4, 1999, a polyurethane foam, and a mixture thereof, and more preferably a natural or artificial sponge, a brush, an abrasive material, a foam rubber material, and a mixture thereof, with all types of open-celled structures being highly preferred.
Test Methods
The viscosity herein is measured on a Brookfield viscometer model # LVDVII+ at 20° C. This viscometer can also be used to measure viscosity at other temperatures (e.g., 25° C). The spindle used for these measurements is a S18 spindle with the appropriate speed to measure products of different viscosities; e.g., 12 rpm to measure products of viscosity less than about 100 mPa*s.
To measure the solubilization capacity, 10.0 g of product (this amount includes water, if testing at a specific dilution) to be tested, pre-equilibrated at ambient temperature (i.e., at about 20° C.) is placed in a 25 mL scintillation vial. To this, food grade canola oil dyed with 0.045% of Pylakrome RED-LX1903 (a mixture of SOLVENT RED 24 CAS# 85-83-6 and SOLVENT RED 26 CAS# 4477-79-6, available from Pylam Products, Tempe, Ariz., U.S.A.) dye is added, and the vial capped. The weight of added oil is determined gravimetrically with an accuracy of 0.001 g. The vial is shaken vigorously by hand for 10 seconds, briefly sonicated if necessary (e.g., with a Branson Bath Sonicator, Model 5510R-DTH set to degass) to remove entrapped air introduced by shaking from the product, and allowed to stand until it becomes clear as determined by visual endpoint established when a line of text 1.59 mm to 3.18 mm ( 1/16th to ⅛th inch) in height is able to be read through the solution or until 15 minutes (900 seconds) has passed, whichever comes first. If the vial becomes clear, the endpoint time is recorded and the experiment is repeated with a fresh sample of product wherein an incrementally higher weight of canola oil is added. Typically, the weight of canola oil added corresponds to an integer multiple of 0.25% of canola oil in the product (e.g., 0.50%, 0.75%, 1.00%, 1.25%, 1.50%, 1.75%, 2.00%, etc). The solubilization capacity in percent is calculated as follows:
Solubilization Capacity (%)=100*[canola oil (g)/product (g)]
For Example, if a sample prepared with 0.100 g of canola oil (1.00%) clears within the prescribed 15 minutes (900 seconds), a subsequent sample prepared with 0.125 grams canola oil (1.25%) would be tested. The % oil solubilization is recorded as the maximum percentage of canola oil which was successfully solubilized (i.e., the vial is clear within 900 sec) by 10.0 g of product.
Typically, solubilization capacity is measured at product concentration of 100%, 85%, and 75%. A product concentration of e.g., 75% is prepared by mixing 7.5 g of a microemulsion or protomicroemulsion composition with 2.5 g of distilled water.
When tested at 100% product concentration, preferably the microemulsion or protomicroemulsion composition herein solubilizes at least about 1% of canola oil, preferably at least about 1.5%, more preferably at least about 2%.
When tested at 85% product concentration, preferably the microemulsion or protomicroemulsion composition herein solubilizes at least about 1% of canola oil, preferably at least about 1.5%, more preferably at least about 2%.
When tested at 75% product concentration, preferably the microemulsion or protomicroemulsion composition herein solubilizes at least about 0.5% of canola oil, preferably at least about 0.75%, more preferably at least about 1%, even more preferably at least about 2%.
The sudsing profile can be measured by employing a suds cylinder tester (SCT), and using the data to plot a suds generation curve. The SCT has a set of 4 cylinders. Each cylinder is typically 30 cm long, and 10 cm in diameter. The cylinder walls are 0.5 cm thick, and the cylinder bottom is 1 cm thick. The SCT rotates a test solution in a closed cylinder, typically a plurality of clear plastic cylinders, at a rate of about 21 revolutions per minute, for 2 minutes, after which the suds height is measured. Soil may then be added to the test solution, agitated again, and the resulting suds height measured, again. Such a test may be used to simulate the initial sudsing profile of a composition, as well as its sudsing profile during use, as more soils are introduced from the surface being washed.
The sudsing profile test is as follows:
The compositions according to the invention preferably have a sudsing profile maxima of at least about 2 cm, more preferably at least about 3 cm, and even more preferably about 4 cm.
Foam to weight ratio is a measurement of the mL of foam generated per gram of product. Foam to weight ratio is measured as follows: a volumetric measuring device, such as a graduated cylinder is weighed to get a tare weight. Then, the product is dispensed, using the foam-generating dispenser, if appropriate, into a graduated cylinder a set number of strokes for non-continuous dispensing devices or for a set time period for continuous dispensing devices. 10 strokes for non-continuous devices (pumps, sprayers) or 10 seconds for continuous devices is the suggested duration. The dispensing rate in the test should be consistent with the dispensing rate during normal usage scenarios. For example, 120 strokes per minute for trigger sprayers, or 45 strokes per minute for palm pumps.
The volume of foam generated is measured in mL using the volumetric measuring device. The volumetric measuring device containing the dispensed product is weighed in grams. The tare weight of the volumetric measuring device is subtracted from this weight. The result is the grams of the product dispensed. Finally, the foam to weight ratio in mL/g is calculated by dividing the volume of foam generated (in mL) by the weight product dispensed (in g). The foam to weight ratio of mL/g is easily converted to mL foam per mL of product by multiplying by the density of the high surfactant microemulsion or protoemulsion composition. The foam volume:weight ratio of the high surfactant microemulsion or protoemulsion composition is preferably at least about 2 mL/g, more preferably at least about 3 mL/g, more preferably at least about 4 mL/g.
Examples of the invention are set forth hereinafter by way of illustration and are not intended to be in any way limiting of the invention. The examples are not to be construed as limitations of the present invention since many variations thereof are possible without departing from its spirit and scope.
A foam-generating kit contains a 300 mL hollow plastic container filled with a composition of Tables—3 below, and an attached T1 series foamer from Airspray, similar to that shown in
Formulas 1B and 1D are comparative formulations without the required glycerol in the composition.
Formulas 1F, 1H and 1J are comparative formulations without the required glycerol in the composition.
Formulas 2C and 2D are comparative formulations without the required glycerol in the composition.
Tables 4-6 discuss the % solubilization of canola oil in the reported seconds for the Formulations of Tables 1-3 above when tested by the above disclosed testing methodology.
Formulas 1B and 1D are comparative formulations without the required glycerol in the composition.
Formulas 1F, 1H and 1J are comparative formulations without the required glycerol in the composition.
Formulas 2C and 2D are comparative formulations without the required glycerol in the composition.
The solubilization measurement results demonstrate that substitution of an equal weight glycerol for propylene glycol in the above microemulsion/protomicroemulsion compositions can result in an increase in its solubilization capacity for canola oil and/or a decrease in the time required for this solubilization to occur. This is surprising considering that glycerol is a more-polar solvent than propylene glycol.
The results also demonstrate that even partial substitution of glycerol for propylene glycol in a microemulsion/protomicroemulsion composition can result in an improvement in solubilization of canola oil.
The results further demonstrate that glycerol can be incorporated into microemulsion/protomicroemulsion compositions without substantially increasing the viscosity of the composition. This is surprising considering that glycerol is a much-more viscous solvent than propylene glycol.
A foam-generating kit according to Example 1 is prepared, except that the T1 foamer is modified with a sponge at the tip, instead of a third mesh. The sponge is an artificial sponge which is cut into shape and is securely affixed immediately inside of the nozzle. The foam generated is creamy and aesthetically pleasing. All documents cited in the Detailed Description of the Invention are, are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
This application is a continuation-in-part application that claims the benefit of the filing date of U.S. patent application No. 10/787,343 filed Feb. 26, 2004, which claims priority to U.S. patent application No. 60/502,673 and U.S. patent application No. 60/502,668, both filed Sep. 12, 2003, U.S. patent application No. 60/472,954 filed May 23, 2003, and U.S. patent application No. 60/451,063 filed Feb. 28, 2003.
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