MXPA98001978A - Composition and method for developing viscosity for extension in cleaning compositions - Google Patents

Abstract

The present invention relates to a viscoelastic and thickened cleaning formulation comprising, in aqueous solution: an active cleaning compound, and a viscoelastic thickening system comprising tetradecyldialkylamine oxide and a hydrophobic organic counter-ion, further characterized in that the formulation has a viscosity of at least 500 cP at 20 ° C, the present invention is characterized as a means of reducing the characteristic "bleach odor" found in the hypochlorite-containing cleaning compositions of the prior art, particularly those that volatilize after being supplied, the compositions of the present invention can also be formulated to have utility as a hard surface cleaner or as a drain opener.

Description

COMPOSITION AND METHOD FOR DEVELOPING VISCOSITY FOR EXTENSION IN CLEANING COMPOSITIONS BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to cleaning compositions having viscoelastic rheology and, in particular, to hypochlorite compositions having a viscoelastic rheology, which are formulated to have an increased spreading viscosity.

Description of the pertinent technique Much of the prior art has referred to the problem of developing thickening systems for use in certain compositions, which may optionally contain bleaching agents such as hard surface cleaning compositions or cleaners. Cleaners having increased viscosities are particularly beneficial for use in cleaning vertical or sloping surfaces, or in formulations designed for delivery through standing water such as drain openers. The effectiveness of such cleaning compositions and formulations is greatly improved by means of viscous compositions due, in part, to the increased residence time of the cleaner. Other problems associated with non-viscous compositions, such as the fogging of the product and its entrainment to unprotected surfaces, as well as the undesirable sizzle during application and use can also be minimized. The latter are considered objectionable phenomena in response to which the consumer's preference for a thickened product is well documented. In an approach to provide improved cleaning products, Hyna et al., In the U.S. patent. No. 3,684,722, teach the thickening of hypochlorite solutions through the use of an amine oxide and a fatty acid soap. The patent of E.U.A. No. 4,229,313, to Joy, describes cleaning compositions containing mixtures of straight and branched chain amine oxides. None of these references teach or suggest viscoelastic thickening systems. According to a slightly different approach, Schlip, in the U.S. patent. No. 4,337,163, discloses thickened chlorine bleach compositions containing an amine oxide or a quaternary ammonium compound and a saturated fatty acid soap. The Schlip compositions achieve kinematic viscosities of from 10 to 150 centistokes (cS), but the presence of a pH regulating salt is required. The patent of E.U.A. No. 4,576,728 to Stoddart, discloses a thickened shear thinning hypochlorite composition including 3- or 4-chlorobenzoic acid, 4-bromobenzoic acid, 4-toluic acid and 3-nitrobenzoic acid. in combination with an amine oxide. Bentham and others, in E.U.A. No. 4,399,050, describe hypochlorite compositions thickened with carboxylated surfactants, amine oxides and quaternary ammonium compounds. Citrone et al., E.U.A. No. 4,282,109, claim hypochlorite bleach thickened with a combination of C?-18 amine oxide plus alkali metal Ce-12 alkyl sulfate, with an amine oxide to sulphate ratio of at least 3: 4. Rórig, and others, in the patent of E.U.A. No. 4,842,771, describe a tertiary amine oxide containing at least one Cie or higher alkyl group in combination with cumene-, xylene- or toluene sulfonate, but which also requires 1-5% of an acid so that the pH does not exceed approximately 6. Rórig and others therefore exclude the possibility of alkaline cleaners. Rose et al., In the U.S. patent. No. 4,800,036, disclose viscoelastic hypochlorite solutions, thickened with "onium surfactant ions" and aromatic sulfonate or carboxylate counterions, wherein the onium moiety is a quaternary ammonium group. Rader et al., E.U.A. No. 5,336,426, and Smith, E.U.A. No. 5,389,157, describe both alkyl arylsulfonate with alkyl chain lengths of Ci -i,. Stoddart, E.U.A. No. 4,783,283, discloses a hypochlorite composition of shear thinning containing 0.1% to 5% of an amine oxide of C12-1S combined with 0.05% to 0.5% of an alkylated naphthalene or benzene sulfonate in which the alkyl group contains one to four carbon atoms. The Stoddart description is limited to combining an amine oxide with the two specified arylsulfonates, and no viscoelastic behavior is exhibited. Boden et al., Patent of E.U.A. No. 4,390,448, discloses a detergent system comprising a Cι-12 alkylsulfonate of diphenyl oxide and a dimethylamine oxide of Cn-13. Steinhauer, patent of E.U.A. No. 4,071,463, discloses thickened hypochlorite bleach compositions comprising Al-20 alkali metal alkyl sulfates, preferably highly branched C 12 alkyl groups, and alkaline builders. Many thickening agents of the prior art are not * suitable for use in cleaning compositions when, particularly as contemplated herein, they are used to thicken hypochlorite compositions. Inorganic thickeners, for example, have proven to be particularly problematic when used in spray type suppliers, since thickeners frequently clog the openings of the spray suppliers and therefore interfere with the delivery performance. Another problem that has not been adequately solved by the thickened cleaning compositions of the prior art is a reduction of the characteristic and commonly objectionable "bleach odor" typically found in hypochlorite cleaning compositions. This whitening odor can result from the real chlorine-releasing compounds, from molecular chlorine or from related compounds. Even when fragrances are added, a smell of bleach persists with conventional thickened cleaning products, causing much of the dissatisfaction of the consumer or end user. One approach that has been taken to reduce this bleach odor is to employ certain suppliers of the prior art which, unfortunately, volatilize the chlorine-containing compositions and can cause unpleasant associated inhalation experiences. In addition, these suppliers are characterized by the need to apply the material in the form of foam directly from the supplier on the surface to be cleaned. Consequently, these suppliers are relatively inefficient due to their inability to quickly apply the material in the form of foam when large areas of surface are to be cleaned. It is therefore an object of the present invention to provide thickened and viscoelastic compositions adaptable for use with hypochlorite bleaches, which have a viscoelastic rheology and which are suitable for delivery by means of a trigger sprinkler. It is another object of the present invention to provide a hypochlorite composition with reduced bleach formation and odor after its delivery. It is a further object of the present invention provide a thickened hypochlorite cleaning composition that is stable in phase under typical storage temperature conditions, as well as at elevated or low temperatures. It is a further object of the present invention to provide a thickened and stable hypochlorite composition with a viscoelastic rheology for greater effectiveness in drainage unclogging. A further object of the present invention is to provide a stable viscoelastic thickening system in bleaching that is effective at both a high and low ionic strength.

BRIEF DESCRIPTION OF THE INVENTION AND OBJECTS Surprisingly, it has now been discovered that increased viscosities can be obtained by employing thickening formulations comprising nonionic surfactants, in particular certain quaternary amine oxides, in combination with organic counterions. These formulations can provide exceptional viscoelastic rheological properties by simultaneously creating a technique for reducing "bleach odor" in cleaning or bleaching compositions containing hypochlorite. Therefore, the present invention provides adaptable thickened and viscoelastic compositions for the delivery of hypochlorite oxidants to bleaching or cleaning applications, and a method to produce them. The compositions of the invention have viscoelastic rheology and are formulated to have an increased extension viscosity. The viscous cleaning compositions of the present invention provide a number of different advantages over the thickened cleaning products of the prior art, among which are: that the hypochlorite composition is thickened with a viscoelastic rheology; the viscoelastic thickener is chemically stable as well as thermodynamically stable phase in the presence of a variety of active cleaning ingredients, including hypochlorite, and retains its stability over a wide range of temperatures (from about 1.8 ° C to about 37.8 ° C); Viscoelastic thickeners are effective at both high and low ionic strength; the composition results in a shear thinning behavior to facilitate its supply and extension viscosity for odor reduction; and thickening is achieved with relatively low levels of surfactant or active cleaning compound, which helps to improve the chemical and physical stability of the novel cleaning formulations. These and other advantages of the present invention will become apparent to those skilled in the art upon reading the following detailed description of the invention, including the preferred embodiments, as well as the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph of the shear viscosity against the concentration of diphenyl oxide disulfonate of Cie for different concentrations of amine oxide of C? «To determine regions of maximum viscosity for various embodiments of the present invention; Figure 2 is an enlarged scale execution of the graph of Figure 1 for the Cie concentration region of between 0.0% and 0.5% by weight; and Figure 3 is a graph of viscosity as a function of the total thickener system (e.g.

C14 / diphenyl oxide disulfonate of Cie) for various product formulations according to various embodiments of the invention.

DEFINITIONS In this document the following terms of the technique will be used, which have the meanings indicated below. As used herein, the terms "supplier" and "delivery device" refer to mechanical objects that can provide a stream or spray of a bleaching composition formulated with the thickening systems of the invention defined herein. Typically, a supplier is a device held by hand. For example, the delivery device may include a container for bleaching composition, a pump and a spray or current forming nozzle. The pump expels the bleaching composition from the container through the nozzle and into the atmosphere. Preferred delivery devices have parts that are resistant to chemical attack by the bleach or hypochlorite. Said suppliers may also include a suitable aerosol device having a propellant, an atomizer or both. The term "extension viscosity" describes the uniaxial resistance of a sample to flow along the stress vector of an extension flow field. An example of extension flow is a stretch deformation induced along an axis, which can be approximated by extracting fluid in opposite jets. In the extension flow, the velocity gradient goes in the same direction as the flow. In contrast, in the shear flow, the velocity gradient is perpendicular to the direction of flow. An extension flow field is much stronger than a shear flow field, causing a significant extension of the flexible particles (e.g., rod-shaped micelles) that might otherwise be deformed to a minimal extent in the shear force flow. The extension of flexible particles has a significant impact on the measured viscosity, since the friction of the particle is approximately proportional to its largest dimension. The extension properties of a sample may be more important than the shear properties in certain situations of practical importance, such as those of squeezing a sample through a hole, or controlling the jet breaking during the formation of the spray. "Micelles" as used herein, are structures that spontaneously form by self-association of individual portions such as surfactant molecules in a liquid medium. These molecular aggregates are in equilibrium with monomeric or dissolved-but not associated-surfactant molecules over a certain concentration for a given surfactant (also known as the critical micelization concentration or CMC) at certain temperature ranges. "Normal" micelles are characterized by relatively hydrophobic core regions comprising lipophilic (hydrophobic) parts of surfactants that avoid contact with water as much as possible, and outer hydrophilic regions formed by the lipophobic (hydrophilic) ends of the molecules. Depending on the number of surfactant molecules in the aggregate, the micellar forms may vary from spheres to elongated or elongated ellipsoids at the poles, the latter including elongated or bar-like micelles as well as disks. The micelles in bar form are also favored, inter alia, by stretching the alkyl chains. (See, e.g., Smith, U.S. Patent No. 5,011,538, which is incorporated herein by reference). The term "fog" as used in conjunction with the aqueous liquids herein, means fine drops of liquid suspended or falling through a mobile or stationary gas atmosphere. Specifically, a mist provides an undesirable drag of water droplets through a gas atmosphere. In contrast to a spray, a mist is generally defined as a particle of liquid suspended in gas, which has a diameter of less than about 10 μm, while a spray is a particle of liquid suspended in gas, which has a diameter of more than of approximately 10 μm. As used herein, "shear thinning" refers to the characteristic property possessed by a liquid, in which the application of a shear force to the liquid will result in an increased tendency toward flow in the liquid, and that subsequently it will cause an evident thinning of the liquid in the direction of the applied force. The term "viscoelastic" refers to liquids that exhibit a combination of behavior characterized as both viscous, ie, liquid type because the energy is dissipated through the liquid and as elastic, i.e. of the solid type because the energy is stored in the fluid. He Viscoelastic term is used herein in general association with the cleaning formulations of the present invention.

DETAILED DESCRIPTION OF THE INVENTION It has now surprisingly been discovered that stable thickening systems having viscoelastic rheologies can be prepared in aqueous solutions, from a tertiary amine oxide nonionic surfactant, in particular a tetradecyldialkylamine oxide and a hydrophobic counterion. The hydrophobic counterion is preferably an anionic species, such as alkyldiphenyl sulfonate ether, although compounds such as taurates, sarcosinates, salicylates, carboxylates, benzoic acid and derivatives thereof, as well as alkali metal salts of any of the previous When formulated with an active cleaning composition, the viscous compositions of the present invention exhibit a remarkable sensitivity to shear or shear thinning, and can be conveniently delivered without being undesirably carried over unprotected surfaces such as clothing, furniture , skin, eyes, etc. It is particularly surprising that the compositions are of a sufficiently fluid type for their ejection from spray suppliers, but they immediately recover their expected character after being emitted. sprayed, thus making possible an adequate adherence to the surface or surfaces that will be cleaned. This apparent dichotomy is possible due to the viscoelastic behavior and the shear thinning properties of the weighing elements of the present invention. This latter viscoelastic characteristic is generally called rapid viscosity recovery. The viscoelastic cleaning compositions of the present invention are fairly thermodynamically stable and exhibit good phase stability on a temperature scale of from about 1.8 ° C to about 37.80 ° C. Surprisingly, the viscoelastic product formulations of the invention also demonstrate a reduction in bleach odor when delivered through a nozzle or other constrictor orifice. It is noted that this odor reduction is mainly due to reduced mist formation, which is evidenced by the fact that the product formulations of the invention tend to develop larger droplets in the delivery opening. The formation of larger droplets after aeration, at the same time, is consistent with the increased exposure viscidity obeyed for the composition of the present invention. When the thickening systems of the invention are combined with at least one active cleaning compound, the inventive cleaning formulations may provide for viccosities varying, for example, from about 20% by weight. up to approximately 5,000 centipoises (cP) and even máe. Eetae cleaning formulations at the same time exhibit a greatly improved thickening, as well as the stabilization of the composition with a concomitant reduction of the bleach odor. These highly desirable characteristics can be obtained when the composition is employed in a wide variety of its injector to direct the composition as a spray, stream or otherwise over the hard surfaces which will be cleaned. More specifically, as mentioned above, the invention particularly contemplates the use of the composition in tapping type euminisers as the trigger-type supplies manually operated and sold, for example, by Specialty Packaging Producte. Inc., or Continental Sprayers, Inc. Suppliers of such types are also described, for example, in Dunning et al., U.S.A. No. 4,538,745, and Focaracci, patent of E.U.A. No. 4,646,973, both of which are incorporated in the foregoing by way of reference. In the described compositions, the composition is divided into relatively fine particles which are then directed as a spray on the surface to be cleaned. The aeration aerator is particularly desirable because of its ability to uniformly apply the composition to a relatively large surface area in a convenient manner. A first embodiment of the present invention therefore comprises an eetable cleaning composition that it has a viecoelastic rheology comprising, in aqueous solution: (a) an active cleaning compound; and (b) a viscoelastic skewing system further comprising (i) a tetradecyldialkylamine oxide and (ii) a hydrophobic organic counter ion. In addition, a number of additional components can be added to the above stable cleaning composition. The additional components work as will be described hereinafter, and serve to improve or increase the stability, rheology, efficiency and / or eetheicity or acceptance of the commercial product. The viecoelatericity is imparted to the cleaning formulations of the present invention by means of a specimen system including a tetradecyldialkylamine oxide and a hydrophobic organic counter ion. The viscosity of the surfactant reagent formulations of the present invention may vary from slightly greater than that of water to varioe milee de centipoieee (cP) at room temperature (about 20 ° C). Deede the consumer's point of view, a preferred viscosity scale is from about 20 cP to 3000 cP, preferably from about 40 cP to 2500 cP, and most preferably from about 50 cP to 2000 cP, although the optimum viscosity scale will depend on the particular rheological properties and what so sensitive is the thickener to the shear stress. For eu inietrar productoe Cleaning by means of a trigger-type sprinkler or nozzle, for example, is desirable viscoeidadee on the scale of about 20 cP to about 1,000 cP. For a destapacañoe, ee especially preferred viscosities in the scale of 100 cP to approximately 2,000 cP. According to one embodiment of the invention that provides an asperion cleaner, the viscosity is from 20 to 500 cP. The elements needed to be used in the cleaning formulations specified in the present invention are therefore an active cleaning composition on the surface such as a surfactant, and a viecoelastic appearance composition comprising also an amine oxide and a hydrophobic counterion, each of which are mentioned in more detail below.

Active Cleaning Compound A number of known cleaning compounds are compatible with the viecoelastic appearance systems of the present invention. These cleansing compounds interact with desired target substances either through chemical or enzymatic reaction or through physical interactions, all of which will be collectively referred to as reaction. The compounds reactive and useful include acids, bae, reducers, oxidants, solvents, enzymes, thioorganic compounds, tenenteactive agents or detergents, as well as mixtures of any of the previous Examples of enzymes include proteases, amylasae, lipaeae and celulaeae. Useful solvents include saturated hydrocarbons, ketone, carboxylic acid esters, terpenes, glycolic ethers, and eilamylates. The oxidizing, eg, bleaching agents are preferred as an active cleaning composition, and can be selected from halogen or peroxygenated bleaching agents. Particularly preferred oxidants are the halogen bleach sources which can be selected from various hypochlorite producing species, for example, bleached ree selected from the group consisting of alkali metal ealee and alkaline earth of halogenite, halogenoaminae, halogenoimine, halogenoimidae and halogenoamidae. It is believed that all of the above species produce hypohalogenosae whitening species in eitu. Hypochlorite and the compounds that produce hypochlorite in aqueous solution are the preferred halogen bleach source, although hypobromite is also suitable. Representative hypochlorite producing compounds include eodium hypochlorite, potaeium, lithium and calcium, chlorinated triethodium phosphate dodecahydrate, potassium and edeium dichloroieocyanurate, and hydroquinuric acid. Suitable organic bleaching sources for use include N-bromo- and heterocyclic N-chloro-imides such as trichlorocyanuric and tribromocyanuric acid; dibromo and dichlorocyanuric acid, as well as ehea of eodium and potassium miemoe; euccinimide, alonimide, phthalimide and naphthalimide N-bromuradae and N-chlordae; hydantoinae talee as dibromo- and dichlorodimethyl hydantoin and chlorobromodimethyl hydantoin; N-halogenoeulfamidae; halogenoamidae in which the halogenide is preferably chlorine or bromine; as a co-location of any of the above. Particularly preferred to be used as the active cleaning compound in the cleaning formulations of the present invention is sodium hypochlorite, which has the chemical formula NaOCl. The active cleaning compound is present in the product formulations of the invention in an amount ranging from about 0.1% to about 15% by weight, preferably from about 0.1% to 10% by weight and most preferably from about 0.2% to about 6% by weight. % by weight of the complete cleaning formulation.

Thickening System The novel screening compositions of the present invention comprise a nonionic surfactant further comprising an amine oxide and a hydrophobic counter ion.

These materials will be described in more detail below. to. Amine Oxide The nonionic surfactant suitable for use in this invention is an amine oxide. According to one In the embodiment of the invention, the amine oxide is preferably stable in bleaching. In general, it is preferred to use tertiary amine oxides, especially trialkylamine oxides, according to the following repre sentative structure: Ri 2 -N > 0 wherein R2 represents alkyl of Cm and R1 and R3 are each C? -3, most preferably methyl. When R1 and R2 both have methyl and R2 is alkyl that averages Ci *, the structure for the dimethyltetradecylamine oxide, a particularly preferred amine oxide, is obtained. Repreeentative examples of this particular nonionic surfactant include those sold under the name AMM0NYXR MO (available from Stepan Chemical Company) and BARL0XR 14 (available from Lonza, Inc.). The group R2 in the above repreeentative structure is preferably a straight chain portion, although some degree of branching at about the gamma carbon or further away from the nitrogen atom is acceptable. Generally, the more distant the carbon in relation to the amine group, the longer the branched chain. It is then considered that amine oxides having a branched R2 group are within the scope of the present invention, as long as the longer chain of the branched R2 group does not contain more than about 14 carbon atoms. The oxide of amine is present in an effective amount of composition, which comprises from about 0.1 to 5.0%, preferably from about 0.1 to 3.0% and most preferably from about 0.2 to 1.5% by weight of the total cleaning formulation of the present invention. A key consideration in the present invention relates to the chain length of the R2 group of the amine oxide. It is important that the amine oxide contains a relatively high percentage of R2 as tetradecylalkyl groups of C?, Which can be contrasted with the amine oxides described and claimed in the co-pending patent application of E.U.A. Serial No. 08 / 324,316, filed on October 17, 1994 to Choy et al. (Of common cession with the preend and inco or rada by way of reference thereto), which describes and claims seven years of alkyl groups that average 16 carbon atoms. Apart from that which occurs in the virtual and, in particular, the CIA alkyl chain group, it can also be mixed with alkyl groups containing longer chain lengths (eg, C10-12) and longer chain lengths (v. .gr., C15-? ß), as long as the average length of the alkyl group eea of C14 - However, the mixed chain lengths may result in the formation of mixed micelles, eliminating or detributing from this form the viecoeidadee of extension of the seventh aspect of the invention. For example, the amine oxides containing chain lengths alkyl shorter than about CIA tend to be hydrophilic and more soluble in aqueous solutions. These shorter chain alkyl groups in combination with the counterion then result in mixtures which do not exhibit high extension properties, and which subsequently exhibit viscoelastic deficient thickener characteristics. On the other hand, it is also worrisome that the alkyl groups of R2 with chain length much greater than about Ciß-iß (or those with more carbon atoms) tend to be excessively hydrophobic with chain length and are therefore not easily soluble in the sevenmae acuoeoe. The mixture of amine oxides containing group R2 with alkyl chain of CIS, therefore, in combination with a suitable counter-ion as described below, does not tend to impart spectral characteristics in the formation of viscoelastic mixture. In terms of a desirable CIA chain length content of the product formulations of the present invention, the above descriptions can be conceptually summarized by referring to the following equations: ACF = [Am.O.] x FC-IA Equation (1 ) where: ACF is the actual amount of CIA present in the final product formulation (expressed as a percentage by weight); [Am.O.] is the concentration of the amine oxide in the final product formulation in percentage in peeo; Y FC-IA, the fraction of R2 group of the amine oxide which is CIA alkyl, is further defined according to: FC-IA Equation (2) wherein: (R2 as CIA) repre- sents the amount of amine oxide for which R2 is CIA alkyl; and (R2totai) represents the total amount of amine oxide in the composition. Acceptable values for the term ACF according to the present invention are from about 0.1 to 5.0% by weight, preferably from about 0.1 to 3.0% and most preferably from about 0.2 to 1.5%. These values are consistent with those previously projected for the effective thickening amount of amine oxide. Equation (I) above can be more easily understood through the use of an example. Consider a situation in which the only alkyl groups R ^ of the amine oxide present are C12 and C, and furthermore that these groups are present in a ratio of 1: 2 for CI2: CIA. The quantity (R2 as CIA) would have a value of 2, (R2totai) would be 3 and FC-IA would have a value of 2/3. If enough amine oxide were used so that the concentration of amine oxide in the final product formulation was about 3.0% by weight, the ACF would have a final value of 2.0% by weight, characteristic of a viscoelastic liquid moderately thick according to with table I below.

TABLE I Typical values for ACF and corresponding characteristics of the viscoelastic thickened products according to the present invention In addition to the criterion beforehand, it should be noted, although not essentially essential, that the fraction of the shortest chain length (ie Cio-12 or less carbons) in a mixture containing CIA of R2-amine oxides should be Menoe of 40%, preferably less than 25% and most preferably less of 10% of the total number of R2 groups of amine oxide preeentee. It is also preferable that the group fraction R2 of longer chain length (i.e., Ciß-Ciß or máe carbonoe) in a 20% amine amine oxide mixture, preferably less than 15% and most preferably less than approximately 10% of the total number of R2 groups presentee. At the same time, it is preferable that the R2 group of the amine oxide comprises at least 60%, preferably at least 70%, and most preferably at least 80% of the total number of the R2 groups preempt as CIA- In one embodiment of the present invention, AMM0NYXR M0 is the preferred amine oxide. b. Organic counterion It has been surprisingly known that viscoelastic thickening systems as defined herein are obtained very successfully when the counterion is a sufficiently hydrophobic species. It has been found that said hydrophobic species are effective in promoting the formation of micelles, whose structure characterizes much of the preferred viecoelastic systems of the present invention. Accordingly, the organic contraεe suitable for use with the present invention can be selected from the group consisting of alkyl aryl ether sulfonate agents including alkylated diphenyl oxide sulfonates of the general structure: (S03-5? M (S03 * X *) n wherein R * and R5 can be H, alkyl that averages from 5 to 20 carbon atoms in length, or one of each; X ee H or an alkali metal selected from the connecting group of Na, K or Li, or a combination of loe mieme; and m and n can independently have value of 0 or 1. When X ee H, an acid diphenyl oxide sulfonate counter ion is obtained and a nonionic counter ion is obtained when X is an alkali metal. According to a preferred embodiment of the present invention, when R is alkyl, Rs ee H. When m and n each = 1, the structure is obtained for a particularly preferred disulfonate, a sulfonate. According to another embodiment of the invention, X ee preferably H. The diphenyl oxide disulfonatee according to the present invention tend to impart adequate clarity and are therefore preferred to be found in the composition of the invention. On the other hand, monosulfonates in which the total value for m and n = 1 (ie, + n = 1), tend to exhibit poor clarity characteristics and are therefore not preferred.

The chain length of the alkyl group of the counterion appears to be a key factor in the screening systems of the present invention. Although the chain length of alkyl group can be mixed with R * by creating a counterion of phenyl oxide dietitituid, the mixed chain lengths can result in the formation of mixed micelles and thus adversely affect the viscoeities of the system. eepeation of the invention. For this reason, monoalkyl-substituted phenyl oxide sulphates are generally preferred over dialkyl-substituted phenyl oxide sulfonates. Surprisingly, it has now been discovered that thickening systems with desirable rheological properties can be conveniently obtained by combining the amine oxides of the invention described above with diphenyl oxide sulfonate surfactants, particularly when the chain length of the alkyl group is found. in the order of 16 carbon atoms (Cie). The alkyldieulfonate of Cyan of diphenyl oxide provides a unique combination to generate an increased viecoelastic performance, as well as to provide an additional surfactant agent for improved cleaning performance. The diphenyl oxide sulfonates with alkyl chain lengths in the order of Cie or mae exhibit a significantly decreased aqueous solubility, marginally making the contribution of said species to the property of thickening of the viscoelastic eietemae of the invention. When the lengths of the alkyl chain of the counterion were shorter, for example in the order of Ce to C12, no larger exteneiones were observed in combination with the amine oxides of the invention described above, probably because of increased aqueous solubility. of this species of shorter chain length. For the above reasons, it is preferred that the combined fraction for longer chain lengths (ie C6-CIA or menoe carbone) and for longer chain lengths (ie, more carbon) in a mixture of counterions be less than 20%, preferably less than 15% and most preferably less than about 10% by weight, of the total weight of the alkyl groups present in the counterion. It is also preferred that the alkyl group of the counterion comprises at least 85%, preferably at least 95%, and most preferably at least 99% by weight, of the total amount of the groups R * or R5 preend. In one embodiment of the present invention, the counter-ion ee can be selected from the DOWFAX ™ agent of tenectant agent (available from Dow Chemical), especially monoalkyl diphenyl oxide sulfonates (or "MADS"), as well as POLY-TERGENT® 4C3 (Olin Chemical). DOWFAX ™ 8390, designated as a MADS-Ciß type surfactant, is a suitable counter-ion to be used in the present invention. Another suitable alkylsulfonic acid is DOWFAX ™ 2A0 corresponding to the structure immediately preceding when R¿ is H and R5 averages 16 carbon atoms. Other MDAS-Ciß DOWFAX ™ type counterions may also be suitable for use herein. The hydrophobic counterion is present in an effective amount of composition generally comprising from about 0.1% to 4.0%, preferably from about 0.1% to 3.0%, and most preferably from about 0.2% to 1.5% by weight of the total cleaning product formulation. of the present invention. The preferred ratio of amine oxide to counterion that can be used in viscoelastic thickening compositions according to the present invention is between 10: 1 and 1:10, preferably 4: 1 to 1: 2 and most preferably 2: 1 to 1: 1. According to one embodiment of the invention, the ratio is approximately 4: 3. The relationship dependence indicates that the structure of the mixed micelle is the determining factor for obtaining extension properties. Without being limited by a particular theoryThe applicants believe that the counterion promotes the formation of elongated bar-type micellar with the amine oxide. These micelles can form a network that results in efficient mapping. In this way, it has surprisingly been found that viscoelastic thickening as defined in the foregoing is more successfully obtained when the counterion is a sufficiently hydrophobic species. Said species are probably more effective in facilitating the formation of micelles.

Surfactant Coagents In certain cases, it may be especially desirable to use a viscoelatic cleaning preparation exhibiting a reduced tendency to accumulate or freeze at lower application or storage temperatures. In this context, temperatures on the scale from about 0 ° C to about 20 ° C are contemplated. Applicants have now determined that the thickening may be increased, and have surprisingly learned that the stability of fae at lower temperatures can be improved by mediating the addition of a surfactant coagent selected from the group consisting of quaternary ammonium compounds, betaines, sarcosinates , taurids and mixtures thereof. Amine oxides having R groups other than CIA can also be used, as long as the bar micelle formation is not adversely affected. Additionally, surfactant coagents may be added not for other purposes as desired, such as, but not necessarily limited to, detergency, solubilization, wettability, etc. The above surfactant coagents can be added in an effective amount to achieve the desired function of improved viscoelasticity at low temperatures, and can generally be added in a percentage range in pey from 0.0% to about 5.0%, and most preferably of about 0.1. % to about 2.0% of the total weight of the viscoelastic formulations of the present invention. From In accordance with a preferred embodiment of the invention, a suitable surfactant coagent can be chosen from the Cyan amine oxide / xylene sulfonate counter ion mixtures described and claimed in the co-pending application of E.U.A. Issue No. 08 / 324,316 previously described.

PH adjusting agent / pH regulator When desirable, pH adjusting agents can be added to the viscoelastic cleaning formulations of the present invention to achieve a certain pH. The pH regulator, on the other hand, can help maintain the pH once a desired pH level has been established. In the present invention, alkaline pH scales (ie, pH values of more than about 7.0) are generally favored for both rheology and maintenance of hypochlorite stability purposes. Examples of pH regulators that are suitable for use with the present invention include the alkali metal phosphates, polyphosphate, pyrophosphates, triphosphate, tetrafoephate, eilicatoe, metasilicates, polysilicates, carbonate, and hydroxide, and mix thereof. When the active cleaning composition is an oxidant, particularly a source of halogen bleaching, control of the pH level may be necessary to retain the ethability of the halogen source. To avoid protonation of the amine oxide, the pH must be above the pK of the oxide. amine. When the amine oxide is tetradecyldimethylamine oxide, for example, the pH should be above about 7.0. When the active halogen source is sodium hypochlorite, the pH is maintained above about 10.5, preferably above about 12. According to a preferred embodiment, the pH ee is about 13.5. Most preferred for adjusting the pH of the viechoelastic formulation formulations of the present invention are the alkali metal hydroxides, especially sodium hydroxide. The total amount of a pH adjusting agent or pH regulator including any amount inherently present with a bleach and any amount included separately, may vary from about 0% to 5%, preferably from about 0.1 to 1.0% by weight .

Electrolyte An electrolyte can be added to the viscoelastic screening systems of the present invention to promote the devel- opment of viecoeidad. The purpose of adding electrolyte, on the one hand, is to provide a source of ion, e.g., cation, wherein anionic surfactants are present in the aqueous solution. Without wishing to be bound by theory, the applicants believe that in an aqueous ionic solution it provides a charged medium in which the oleorese of the surface-active agent can interact, promoting the formation of micelle aggregates of molecular surfactant that give rise to the proprietary rheological properties of the invention. Ciertoe compueetos can function in the present invention both as a pH regulator and as an electrolyte. These regulators or electrolyte particles generally contain alkali metal salts of various inorganic acids such as: alkali metal saltse of phosphates, polyphosphates, pyrophosphates, triphosphates, tetrafoephates, silicate, metaeilicatoe, polyethylac, carbonate, hydroxides and mixtures thereof. Divalent equivalents, eg, alkaline earth salts of phosphates, carbonates, hydroxides, etc., can also function simply as pH regulators. If such compounds are used, they will be combined at least one of the aforementioned electrolyte or pH regulators to provide the proper pH adjustment. Inorganic salts such as alkali metal chlorides and sulfates, such as organic alkali metal salts, relatively soluble in gluconate, succinate and maleate bleach, can also be used as electrolytes to maintain the ionic strength for the desired rheology. It may be noted that when sodium hypochlorite is the active cleaning compound, sodium chloride will typically be present as a byproduct of hypochlorite formation and that an additional electrolyte is no longer necessary.

An especially preferred electrolyte / pH regulator for use with the viecoelatic cleaning formulations of the present invention is the alkali metal silicate. The preferred silicate is eioxide of eodium, which has the empirical formula Na2 ?: Si? 2. The ratio of sodium oxide to silicon dioxide is from about 1: 4 to 2: 1, preferably about 1: 2. The dietary silicate is available from numerous sources, such as PQ Corporation. The amount of deliberately added electrolyte can vary from about 0% to 10.0% and preferably from about 0.1% to 5% by weight of the total formulation.

Auxiliaries The viscoelastic thickening systems of the present invention can be formulated to include components such as fragrances, color agents, bleaches, solvents, chelating agents and improved detergency to increase the performance, the ettability or the eethenetic appearance of the composition. From about 0.01% to about 0.5% of a fragrance, such as that commercially available from International Flavore and Fragance, Inc., may be included in any of the modalities of the invention. They can also include colorant and pigments in small amounts. Two examples of widely used pigments which may be incorporated in the compositions of the present invention include the blue of overseas (UMB) and copper phthalocyanines. Suitable detergency builders which may optionally be included comprise carbonates, phosphate and pyrophosphate. As is known in the art, said builders function to reduce the concentration of free calcium or magnesium ions in the aqueous solution. Certain of the aforementioned pH buffering materials, eg, carbonates, phosphates, phosphonate, polyacrylate and pyrophosphates can also function as builders.

Active ingredients for unclogging drains An active ingredient in unclogging drains according to the present invention is an acid, base, solvent, oxidant, reductant, enzyme, surfactant, thioorganic compound or mixtures thereof, which is suitable for be used in uncovering drains. It is understood herein that the concept of "unclogging a drain" incorporates the cleaning or removal of congestion, discharge, or other form of accumulation that can commonly be found and that obey the drains of the lavaboe. In general, the materials of removal of obeccioncionee can act by means of any of the following methods: reacting chemically with the material of obstruction to fragment it or make it more soluble or dispereable in water; interact physically with the material of obetrucción by, eg, adeorción, abeorción, eolvatación or heating (ie, to melt the graea); or enzymatically catalyzing a reaction to fragment or render the clogging material more soluble or dispereable in water, etc. The material is activated for unclogging drains particularly suitable for alkali metal hydrochlorides and hypochlorites. The combination of loe ante rio re are also suitable. The drain cleaner can also contain various auxiliaries known in the art, including corrosion inhibitors, colorants and fragrances. Therefore, a second embodiment of the present invention is a drainage unclogging formulation that includes: (a) a viscoelastic thickener comprising tetradecyldialkylamine oxide and a hydrophobic organic counter ion; (b) an alkali metal hydroxide; (c) optionally an alkali metal silicate; (d) optionally an alkali metal carbonate; and (e) an asset for drainage uncovering. The component (a) comprises the seven viscoelastic thickening of the invention as previously described. The alkali metal hydroxide is preferably potassium or sodium hydroxide, and is present in an amount of between about 0.5% and 20%. The preferred alkali metal eilicate is one having the formula M20 (SiO) P wherein M is an alkali metal and p has a value between 0.5 and 4. When M is sodium, p is preferably 2.3. The alkali metal silicate can be present in a amount from about 0% to 5.0%. The preferred alkali metal carbonate is the carbonate of eodium, which is preferably present in a quantity of between about 0% and 5.0%. Approximately 1% to 10% in weight of an active cleaning ingredient is present, preferring to be on the scale of about 4% to 8%. Sodium chloride or other salts eimilaree can be added as a densifying agent, that is, an eububluence that imparts greater deneity than that of water to a particular composition, aiding the penetration or flow of the composition through the water of repoeo. The formation of bar-type micelles is allowed provided that the geometrical packing configurations allow it. That is, if the repulsive forces between the major groups of the surfactant can be reduced, such as those due to steric constrictions or elect roetáticoe factors such as ionic charge, then larger bar micelles can be formed. This can occur even at the same concentrations that typically would only form normal spherical micelle. The bar-type micelles give rise to a degree of extenesion based on the extension flow. The flow of extension, as in the nozzle of a sprinkler, is uniaxial and essentially stretches the molecules that pass through it. If the molecules are large but naturally coiled as in lae micelle bar, the flow of exteneion It will literally straighten the molecules without causing them to occupy much more volume than they occupy in a normal three-dimensional flow field. Due to the constricted movement and the loss of volume that is comparable to the moveree, the viscosity (of extension) is increased by factors of 10 to 1,000 times. The excess of viscoeity forms larger droplets in the nozzle, so that the flow field remains cohesive, thus minimizing the formation of fog. The larger droplets will also be raised faster by gravity, again minimizing contact with the bleaching solution. The layered formulations of the invention may also have utility as hard surface cleaners. Thickness solutions are clear and transparent and may have higher viscosity than hypochlorite solutions of the prior art. Because the viscosity thickening is more efficient, less surfactant is needed to achieve a higher viscosity, and the chemical and physical properties of the compositions generally improve. Menoe teneoactive agent also gives as a result a more effective composition as regards coetoe. As a cleaner of hard surfaces, the viscolatic rheology prevents the composition from being eeparated on a horizontal source and thus helps to protect the surface area from nearby bleaching. The viecoelaeticidad also produces the benefit of a thick system, eg, residence time increased on non-horizontal surfaces. On surface not horizontalee, the composition flows at a much slower speed, leaving a film that can promote an effective baetante cleaning. In a preferred embodiment, the composition of the present invention is not damaged by the additional increase in ionic strength for the preparation, nor does it require the addition of an electrolyte for the preparation. The viscoelastic compositions of the present composition are stable in phase and retain their rheology in solutions, corresponding to more than about 0.5% by weight of ionizable salt, eg, sodium chloride and sodium hypochlorite, at an ionic strength of approximately 0.09. g-ions / Kg of solution. It is expected that the viscoelatric rheology remains intact with an ionic force of at least about 6 g-ionee / Kg. The surfactant system also does not significantly degrade the hypochlorite, even after prolonged storage (more than two years). Compounds that vary from 0.5% in pee to 1.45% in peo of total surface active agent do not result in an appreciable loss of hypochlorite.

Experiments As defined above, a viscoelastic liquid is one that possesses both elastic and solid type properties and a viscous behavior. The solutions prepared from C12 or CIA amine oxidee they generally exhibit a very small viecoelastic behavior, demoted by a frequency sweep in the linear viecoelatric region with a Bohlin VOR rheometer. However, and surprisingly, the inventive combination of amine oxides of CIA with alkylarylene sulfonates of diphenyl oxide described herein, originates unique systems with large reepueetae viscoelastic and time of relaxation much greater than those established in the prior art. For example, the viscosities of more than 500 cP at a cutting speed of 5 rpm in a Brookfield RVTDV-II viscometer were measured at approximately 20 ° C when CIA amine oxide (0.65% by weight) and diphenyl oxide dieulfonate were used. Cie (0.51% in peeo) were added to LIQUID PLUMRR (The Clorox Company), a drainage drain product currently in use. An epoxide of diphenyl oxide eulfonate was evaluated to elucidate which chain length of the alkyl group would lead to optimal visco-elastic thickening properties. Again, 0.65% amine oxide was added in combination with different concentration of diphenyl oxide eulphonate. The results of this study are summarized in the data shown in Table II below. For each example shown in the table, the amine oxide contained at least 85% or improved alkyl group of C A, and the diphenyl oxide sulfonate contained at least 85% group C & amp; (See lesson # 1 in Table II below). When the The concentration of the active alkyl group was increased, the mixture was also increased, reaching viscosities above 1,000 cP at values approaching 2,500 cP at a 95% concentration of alkyl diphenyl ether (samples Nos. 2 and 3 in Table II below).

TABLE II Thickening as a function of the chain length of diphenyl oxide sulfonate for drain defatting formulations ^ *) containing 0.65% CIA amine oxide at 20 * C Annotations to table II < Typical formulations for the drainage mat used included the following: sodium hypochlorite, 5.8%; sodium hydroxide, 1.75%; sodium chloride, 4.5%; sodium silicate, 0.11%; balance, water. < b > Alkyl groups were linear unless indicated otherwise. (c) Balance comprised of other chain lengths of alkyl groups. < p The types of diphenyl oxide used corresponded to the following: MADS = onoalkyl diphenyl oxide diethonate MAMS = monoalkyl diphenyl oxide monoeulphonate DADS = dialkyl diphenyl oxide diethylene (•) This sample may contain a 5% contamination of MAMS. Another phenomenon that has been observed with the viscoelactic thickening systems of the present invention is the dependence of the amine oxide ratio of CIA to Ci6 diphenyl oxide sulfonate to achieve maximum viscosity. That is to say, that by increasing the amount of amine oxide of CIA, the amount of Ciß diphenyl oxide dieulfonate would need to achieve maximum viecoeity increases disproportionately.

This phenomenon is demonstrated in Table III below, as in Figures 1 and 2. Figure 3 shows a plot of viecidity as a function of the total concentration of the surface-active agent for the compositions in accordance with Table III below.

TABLE III Change in concentration of CIA amine oxide against diphenyl oxide disulfonate from Cie to achieve maximum viscosity of formulations for uncovering drains * »> at 20 ° C Annotations to table III < • > Typical formulations for uncovering used drains contained the following: sodium hypochlorite, 5.8%; sodium hydroxide, 1.75%; sodium chloride, 4.5%; sodium silicate, 0.11%; balance, water. Cb) The values calculated for the ratio of amine oxide of CIA to disulfonate of diphenyl oxide of Cie at maximum thickening may not coincide coincide with the values reported due to the rounding of loe numbere. The above definition and examples reveal that the stable and stable vaporization systems can be prepared for use by combining amine oxides from CÍ with Diphenyl oxide disulfonate from Cie. Still, the inventive methods of the invention can be formulated with various cleaning compositions to provide novel cleaning formulations. Although specific components and supplies have been used in the above description of the preferred embodiments of the novel viscoelastic formatting materials, other suitable materials and variations may be used in the sevenmes shown herein. In addition, other materials may be added to those used herein, and variations may be made in the thickened systems and in the viscoelastic formulations to improve, increase or otherwise modify the properties or increase the uses of the invention. It will be understood that various other details of the details, materials, steps, dispositions of components and systems that have been defined herein and which have been illustrated to explain the nature of the invention will be understood and can be made by those experts in the field. technique after reading this description, and that said changes are designed to be included within the principle and scope of this invention. The invention is further defined without limitation of scope or equivalents by the following claims.

Claims (24)

NOVELTY OF THE INVENTION CLAIMS

1. - A liquid, viscoelastic and eepeated cleaning composition that comprises: (a) a cleaning asset; and (b) a viscoelastic thickening system that essentially connects a tetradecyldialkylamine oxide and a hydrophobic organic counter ion; and further characterized in that the composition has a viscosity of at least 500 cP at 20 ° C.

2. The cleaning composition according to claim 1, further characterized in that the cleaning active is a hypochlorite-releasing compound.

3. The cleaning composition according to claim 2, further characterized in that the counterion is a Cyan-alkylsulfonate of diphenyl oxide.

4. A composition of liquid bleaching, extruded and viscoelastic to be used in an aeration supply to introduce the composition on a hard surface will be cleaned, the eminentizer tends to divide the composition into particles that give rise to the release of the odor bleach, the composition comprises: (a) an aqueous solution of an alkali metal hypochlorite; and (b) a viecoeláetico component that connects essentially an amine oxide and a hydrophobic organic material in a effective amount as to thicken the composition and effectively reduce the bleach odor when the composition is supplied on a surface that will be cleaned, and also to maintain the ability of the composition; The composition has a viscosity of at least about 20 cP at 20 ° C.

5. The bleaching composition according to claim 4, further characterized in that the amine oxide is an alkylamine oxide of CIA.

6. The bleaching composition prepared in accordance with claim 4, further characterized in that the counter ion is a C 1 or 16 alkyldie sulfonate of diphenyl oxide.

7. The bleaching composition according to claim 4, further characterized in that the counterion is an alkali metal arylsulfonate.

8. The liquid bleaching composition according to claim 4, further comprising a fragrance disclosed in hypochlorite bleach, and the reduction of the bleach odor increases the odor of the fragrance.

9. The liquid bleaching composition according to claim 4, further comprising a pH adjusting agent.

10. The thickened liquid bleaching composition according to claim 4, further characterized in that the pH is more than 7.0.

11. - The thickened liquid bleaching composition according to claim 4, which has a viscosity in the range of about 20-3,000 cP to achieve optimum atomization in a sprinkler type supplier.

12. A method for employing a thickened, viscoelastic liquid bleaching composition on a hard surface that will be cleaned, in which they comprise: (a) forming a liquid bleaching composition comprising (i) an aqueous solution of a hypochlorite of alkali metal, and (ii) a thickening component consisting essentially of a tetradecyldialkylamine oxide and a hydrophobic organic counterion in an amount effective to thicken the composition and to effectively reduce the bleach odor when the composition is delivered on a surface that it will be cleaned, and also to maintain the stability of the composition; and (iii) a pH adjusting agent in an amount effective to adjust the pH to more than about 10.5, the composition has a viscosity of at least about 20 cP at 20 ° C; and (b) directing with an aeration supply the composition of liquid bleaching thickened on the surface to be cleaned.

13. The method according to claim 12, further characterized in that the composition has a viscosity of at least 500 cP and a pH of at least 7.0 to 20 [deg.] C.

14. - The method of compliance with the claim 12, which further comprises a fragrance eetable in hypochlorite, and the reduction of the bleach odor achieved in the composition results in an increased fragrance aroma.

15. The method according to claim 12, further characterized in that the organic counterion is an alkylarylsulfonic acid of the general structure: wherein: R * and R5 are selected from the group comprising H, alkyl with an average length of C5-20, or one of each; X is H or an alkali metal selected from the group consisting of Na, K or Li, or a combination thereof; ymyn may independently have value 0 or 1.

16. A method for controlling the odor of bleach in a composition designed to be supplied by means of an aepereor which tends to divide the composition into particles and which results in odor release a bleach; the method comprises the steps of: (a) forming an aqueous solution of about 0.1% to about 10% by weight of an alkali metal hypochlorite; and (b) adding to the membrane a viecoelatric component that essentially connects a tetradecyldialkylamine oxide and an electron counter ion selected from the acid connecting group. alkylarylsulphonic diphenyl oxide in an amount effective to thicken the composition and to effectively reduce the bleach odor when the composition is supplied over a surface to be cleaned, and further to maintain the stability of the composition; the composition has a viscosity in the range of about 20 cP at 20 ° C.

17. The method according to claim 16, characterized in that the composition has a viscosity of more than about 500 cP.

18. The method according to claim 16, further characterized in that the composition has a viscosity of more than about 1,000 cP.

19. The method according to claim 16, further comprising the step of: (c) adding a stable fragrance in hypochlorite bleach, and reducing the bleach odor achieved in the composition also results in an increased odor of the fragrance.

20. The method according to claim 16, further comprising the step of: (d) adding to the composition a pH adjusting agent in an amount effective to adjust the pH to at least about 10.5. 21.- A composition to deepen viecoláetica drainage and prepared that includes, in aqueous solution: (a) an asset of drain drainage; and (b) a viecoeláetico eeteeamiento system consisting essentially of a tetradecyldialkylamine oxide and a hydrophobic organic counterion in an amount effective to remove the composition; and characterized furthermore because the composition has a viscosity of more than about 20 to 20 ° C and a deneity greater than that of water. 22. The composition for the drain drainage according to claim 21, further characterized in that the drain drainage asset is selected from the group that you connected of acids, base, oxidants, reducers, solvents, enzymes, detergents, thioorganic compounds and mixtures thereof. 23. The composition for unclogging drains according to claim 21, further characterized in that the organic counterion is alkylarylsulfonic acid of diphenyl oxide. 24. The composition according to claim 21, further characterized in that the uncapping asset of drains is sodium hypochlorite, which is present in an amount of about 1-10% in peeo; and further characterized in that the composition comprises in addition: (a) 0.5 to 20% by weight of an alkali metal hydroxide; (b) 0 to 5% by weight of an alkali metal silicate; and (c) 0 to 5% by weight of an alkali metal carbonate.