EP0813588A1

EP0813588A1 - Cleaning compositions with reduced skin malodor

Info

Publication number: EP0813588A1
Application number: EP96905471A
Authority: EP
Inventors: Henry Cheng Na; Pedro Antonio Rodriguez; Marco Petri
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1995-03-03
Filing date: 1996-02-14
Publication date: 1997-12-29
Also published as: AR001141A1; WO1996027651A1; CO4700543A1; AU4921896A

Abstract

Compositions comprising halogen bleach and bleach boosters as well as cleaning compositions comprising halogen bleach, bleach boosters, surfactants, and controlling halogen induced skin malodor by including -NH2 compounds that reduce the formation of malodor on human skin.

Description

CLEANING COMPOSITIONS WITH REDUCED SKIN MALODOR

This is a continuation-in-part application of pending application U.S. Serial Number 08/398,477, filed March 3, 1995.

FIELD OF THE INVENTION

The present invention relates to cleaning compositions comprising halogen bleach, bleach boosters, surfactants, the means for controlling halogen induced skin malodor and optionally builders, perfumes, abrasives and/or carrier and adjunct materials that are suitable for the controlling of skin malodor when said composition contacts human skin. The present invention also relates to a method for cleaning surfaces with a composition comprising bleach, bleach boosters and -NH2 compounds that reduce the formation of malodor on human skin.

BACKGROUND OF THE INVENTION

Hard surface cleaners can be in liquid, solid or viscous semi-solid form. Known liquid, solid and viscous semi-solid hard surface cleaners can comprise detergent surfactants, water and optionally certain organic solvents, builders, buffers, and/or perfumes as well as other adjunct materials. Solid and viscous semi-solid forms of hard surface cleaners may optionally comprise as adjunct ingredients one or several abrasive materials. Solid and viscous semi-solid, hard surface cleaners containing abrasive materials are used primarily as "scouring" agents. It has long been known that abrasive materials can be used in conjunction with hard surface cleaners to remove commonly encountered soils or soap scums.

The inclusion of hypohalitθ into hard surface cleaners has steadily grown. In fact, hypochlorite-containing hard surface cleaners are among the most effective materials available for cleaning since hypochlonte serves both as a strong oxidizer to assist in the chemical degradation, breakup and removal of stains and soils, and also an inexpensive and effective disinfectant. This dual role of hypochlorite (as a bleach and disinfectant) together with its shelf stability and compatibility with other optional ingredients has contributed to the increased use of sodium hypochlorite or other positive halogen precursors, in the formulation of hard surface cleaners. Kitchen and bathroom sink, tub, shower, toilet bowl and counter top surfaces, including vinyl, acrylic, and marble, are areas which have been the focus for developments in increased hard surface cleaning capacity. These surfaces are subject not only to exogenous bacteria, fungi and mildews endemic to most households, but to pathogens which are derived from urine and feces. Therefore, the inclusion of hypochlorite into these formulations as a strong and versatile disinfectant is an added benefit to consumers.

To insure proper hygiene and sanitary conditions, a formidable cleaning task must be undertaken to remove the undissolved sediments, grease, soap films, scums, hard water scale and rust stains that form on ceramic surfaces, counter tops and bathroom floors during normal usage. Cleaning is especially difficult in the case of hardened and dried soap films, scums, caked-on residues and scaling due to hard water/undissolved dirt where it is necessary to use more than simple wiping to remove the unwanted sediments.

During the use of hypohalite-containing hard surface cleaners, contacting the cleaning solution, which contains available halogen, with the human skin results in the production of malodor on the skin known as "Bleached Hand" odor. This "Bleached Hand" odor is believed to result from the contact between, for example, in the case of hypochlorite, the positive chlorine ions present and the protein in the skin and differs from the "chlorine odor" of the hypochlorite bleach per se. Because the active ingredients of hard surface cleaners, especially hypochlorite bleach, cannot distinguish between dirt, cleaning utensils and exposed human skin during scouring process, the only protection once afforded the skin was the use of gloves.

Japanese Kokai 63-108099 discloses a liquid laundry bleach comprising sodium hypochlorite and a skin malodor control compound. However, the problem which is addressed in JP 63-108099, namely the occasional and unfortuitous exposure or accidental splashing of a laundry bleach onto human skin during the fabric laundering process is far less of a problem than the skin malodor that occurs through the deliberate act of scouring a soap scum soiled bath tub or kitchen dirt with a hypohalite containing cleanser. This difference is due to several factors. First, during scrubbing and scouring there is a prolonged exposure time to a large quantity of hypohalite containing solution. Second, during the act of scrubbing and scouring, the skin is weakened by exposure to the active cleaning ingredients and abrasives and the skin becomes worn and abused which results in the underlying layers of less-protected skin coming into contact with strong solutions of hypochlorite. Therefore the levels of hypohalite must be substantially lower in these intimate contact formulations while allowing for the full cleaning potential of the compositions.

Surprisingly, liquid additive bleaches, such as those described in JP 63-108099 comprising a skin malodor control compound and levels of hypohalite higher than those normally found in scouring compositions, are also further improved by the addition of bleach boosters. The bleach boosters described in the present invention provide for enhanced hypohalite activity at all practical levels of hypohalite concentration, for example in "concentrates" and at "industrial levels", which are not readily available to consumers. The same increased benefits afforded to scrubbing and scouring compositions comprising hypohalite and bleach boosters are obtainable by the formulator of higher concentrated pourable hypohalite bleaches.

It has now been discovered that the inclusion of certain specific compounds containing the -NH2 moieties into cleaners containing hypohalite or positive halogen generating materials in combination with the aforementioned bleach boosters, reduces the formation of active halogen- induced malodors on the skin while maintaining optimal bleaching and disinfecting levels. The present invention by its effectiveness in controlling hypohalite derived malodor on the skin, precludes the necessity of gloves or other protection of the exposed skin during cleaning. This also protects against the inadvertent splashing of the solution onto skin such as the face, neck, leg, forearm etc. Also because of the action of these -NH2 compounds, a means is now available to prepare surface cleaning compositions that reduce skin malodor formation which comprise hypohalite bleaches, bleach boosters and surfactants.

It is thus an object of the present invention to prevent the formation of malodors on the skin due from exposure to hypohalite or active halogen forming solutions. It is another object herein to provide a hypohalite- containing cleaner that will prevent the formation of malodor on exposed skin. Yet another object herein is to provide a means of preventing malodor formation on the exposed human skin when hypohalite cleaning compositions containing bleach boosters are used. BACKGROUND ART

Various references relate to hypochlorite and other bleach compositions comprising additional ingredients. See for example U.S. Pat. No. 3,583,922 issued June 8, 1971; U.S. Pat. No. 3,749,672 issued July 31, 1973; U.S. Pat. No. 4,148,742 issued April 10, 1979; U.S. Pat. No. 4,257,906 issued March 24,1981; U.S. Pat. No. 4,088,611 issued May 9, 1978; U.S. Pat. No. 4,201,687 issued May 6, 1980; U.S. Pat. No. 4,233,173 issued November 11 , 1980; and Japanese Kokai 63/108099 (Derwent Abs. No. 88-171056/25).

SUMMARY OF THE INVENTION

The present invention relates to compositions comprising a halogen bleach, a bleach booster and a means for controlling the halogen induced skin malodor arising from exposure of bleach to human skin. The present invention also comprises other adjunct ingredients and carriers suitable for use in the cleaning compositions of the present invention.

The level of bleach is from 0.01% to 10.0%, preferably 0.5% to 2.0%. The amount of bleach booster present is measured relative to the amount of bleach. The molar ratio of bleach to bleach booster is from 1 : 0.05 to 1 : 4. The amount of malodor control compound present is enough to reduce malodor formation on human skin. Molar ratios of bleach to malodor control compound of from 1 : 0.1 to about 1 : 5 are typically sufficient but the formulator may adjust the amount of malodor control compound to meet any unusual demands.

The present invention also relates to a composition comprising a) from 0.01% to 10% by weight, of a halogen bleach; b) a bleach booster such that the mole ratio of said bleach in (a) to bleach booster is from 1 : 0.1 to 1 : 2; c) a malodor control compound such that the mole ratio of said bleach in (a) to malodor control compound is from 1 : 0.1 to 1 : 5; and d) the balance comprising carrier and adjunct ingredients with the pH of said liquid solution being greater that 11.

The present invention further relates to a liquid cleaning composition comprising a) from 0.01 % to 10% by weight, of a halogen bleach; b) a bleach booster such that the mole ratio of said bleach in (a) to bleach booster is from 1 : 0.1 to 1 : 2; c) a malodor control compound such that the mole ratio of said bleach in (a) to malodor control compound is from 1 : 0.1 to 1 : 5; d) from about 0.1% to about 95% by weight, a detersive surfactant; e) the balance comprising carrier and adjunct ingredients with the pH of said liquid solution being greater that 11.

It is also an object of the present invention to provide an abrasive scouring cleanser comprising: a) a halogen bleach; b) a bleach booster; c) a malodor control compound d) a detersive surfactant e) an abrasive; f) the balance comprising carrier and adjunct ingredients such that the pH of a liquid abrasive scouring cleanser embodiment is higher than 11 and has a viscosity of from 0.5 to 3000 centipoise measured at 22° C. For solid embodiments an aqueous solution of the abrasive scouring cleanser will have a resulting pH greater than 11.

Also, the present compositions include cleaning compositions comprising: a) a halogen bleach selected from the group consisting of hypobromites, hypoiodites, and mixtures thereof; b) a detersive surfactant; c) an organic or inorganic derived -NH2 compound effective for controlling halogen induced skin malodor; and d) the balance comprising carrier and adjunct ingredients, and wherein further said composition has a pH greater than about 11.

The present invention also relates to a method for cleaning hard surfaces, said method comprising contacting by scrubbing or scouring a surface in need of cleaning with a cleaning composition according to the present invention.

The malodor control compositions of the present invention control, direct, mediate and or suppress the "free available halogen". What is meant by the "free available halogen" is the amount of positive halogen that is present in solution in a form that will potentially react with human skin tissue to produce malodor. The activity of available halogen is mediated by the -NH2 compounds that comprise the malodor control agents of the present invention.

The present invention in relating to a method of cleaning surfaces that results in the control of halogen induced skin malodor achieves this effect by the inclusion of positive halogen scavengers into the cleaning composition. Additionally the method provides for sustained bleach activity by the inclusion of bleach boosters that do not subsequently compromise the positive halogen scavenger effectiveness of the halogen mediators of the present invention. These positive halogen mediators or scavengers are organic compounds which contain the -NH2 functionality and these compounds serve to mediate or control the equilibria and hence control the activity of positive halogen that are formed by bleach solutions.

The present invention provides for cleaning compositions that can be solid, liquid, semi-solid or more preferably gels, pastes and liquids having a viscosity greater than water. For liquid embodiments of the present invention, the preferred viscosity will be in the range of from 0.5 to 2000 centipoise as measured, for example, by techniques and methods described in "Physico-Chemical Methods", Reilly, J. and Rae, W. N.; Vol. 1 (5th ed.), pages 667-692; D. Van Nostran pub.

Suitable carriers for the present invention include water and volatile solvents that are compatible with hypohalites. Aqueous solutions of the present invention will be alkaline, suitably buffered and preferably have a pH greater than 11.

Solid and viscous semi-solid embodiments may optionally comprise abrasives such as carbonates, silicates and other suitable abrasive materials such as those disclosed in U.S. Pat. No. 4,051 ,056, Hartman, issued September 27, 1977.

Finally, the present invention includes processes for manufacturing the present invention hypochlorite-containing cleaning compositions. Said processes comprise the steps of: (a) predissolving the -NH2 compound effective for controlling malodor with the bleach booster; (b) mixing the mixture of (a) with the remaining components of the composition not including a hypochlorite halogen bleach; and (c) combining a hypochlorite halogen bleach and the mixture from (b), preferably by adding the hypochlorite to the mixture of (b). All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (°C) unless otherwise specified. All documents cited are, in relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides compositions and methods having reduced malodor formation on human skin comprising the following ingredients.

Bleach - The present invention comprises bleaching agents that are oxidative bleaches and subsequently lead to the formation of positive halide ion. Common among these types of bleaches are the alkaline metal and alkaline earth metal hypochlorites, hypobromites and hypoiodites although other bleaches that are organic based sources of halide, such as chloroisocyanurate, are also applicable. Preferred bleach has the formula M(OX)_y where: M is a member selected from the group consisting of sodium, potassium, magnesium, calcium, and mixtures thereof; 0 is an oxygen atom; X is a member selected from the group consisting of chlorine, bromine, iodine, and mixtures thereof; and y is 1 or 2 depending on the charge of M. The preferred embodiment of the invention will effectively contain hypochlorite or hypochlorite and hypobromite.

What is meant by "effectively contain" is that when a bleach booster such as NaBr, for example, is formulated into a composition comprising a hypochlorite based bleach, there is necessarily a formation of hypobromite, which in itself is a bleach and a necessary chemical artifact of the boosting process. Without wishing to be limited by theory, it is believed that the following chemical reaction sequence accounts for the formation of hypobromite when hypochlorite and sodium bromide are formulated into the present invention.

OCl- + Br *- OBr + Cl"

Hypobromite, thus formed, being a bleaching agent in of itself, is therefore a source of positive halogen and is susceptible to sequestration by the means provided in the present invention.

The preferred hypohalite bleaches that comprise the present invention are sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, sodium hypobromite, potassium hypobromite, calcium hypobromite, magnesium hypobromite, sodium hypoiodite and potassium hypoiodite, more preferably sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, most preferably sodium hypochlorite. A preferred organic-based bleach is chloroisocyanurate, however any organic halide that produces active halide ion is suitable for use in the present invention.

The malodor control composition of the present invention comprises bleach which is present at a level from about 0.01% to about 10%, preferably about 0.01% to about 2%, more preferably from about 0.1% to about 2%, most preferably from about 0.5% to about 2%, by weight.

Boosters -The present invention comprises bleach boosters. Bleach boosters are those compounds that in an alkaline pH environment are capable of releasing a halide ion, undergoing an oxidation, a reduction or other disproportionation that otherwise yields an activated halide ion. Typically boosters containing bromine atoms and iodine atoms are used in the presence of chlorine atom based bleaches and iodine is used when bromine based bleaches are employed as the primary bleaching agent. Preferred bleach booster has the formula M(X)_y where: a) M is a member selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, copper, zinc, and mixtures thereof; and b) X is the radical bromide, hypobromite, bromate, iodide, hypoiodite, iodate, and mixtures thereof; wherein y is 1 or 2.

While not wishing to be limited by theory, it is believed that the boosters have the effect, as in the case of hypochlorite based bleach, of converting the hypochlorite bleach into a more reactive and or a more stable species, for example, hypobromite, thus providing for the full utility of the bleach formulated. Bleach boosters of the present invention may be added as a precursor which itself can be a bleach booster, for example, iodide ion is a suitable bleach booster according to the present invention but, the ratio of hypohalite and iodide can be adjusted by the formulation to provide for the in situ formation of iodate, a preferable bleach booster. The boosters thus formed by oxidation/reduction or other disproportionations, for example, iodate, may be instead added directly.

The bleach boosters of the present invention are of the formula MX where M is a member selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, copper, and zinc while the X is halogen. The preferred bleach boosters are the sodium and potassium salts of bromine and iodine, more preferably sodium and potassium bromide and iodide. The present invention comprises bleach boosters that are present such that the mole ratio of bleach to bleach booster is from about 1 : 0.1 to about 1 : 2, preferably from about 1 : 0.2 to about 1 : 1.

Malodor Control - The present invention comprises a means for controlling malodor or "bleached hand smell" on the skin. While not intending to be limited by theory, the principle component of "Bleached Hand" malodor on the skin is 1-pyrroline. This material is formed from the amino acid L-proline when the keratin protein found in the stratum corneum layers of the skin is exposed to free positive halogen, especially positive chlorine. The rate of formation and the amount of 1-pyrroline that is formed varies from individual to individual but the general mechanism of formation is believed to be universal. The degradation of skin protein is believed to begin with the rapid halogenation of a protein amide bond nitrogen when the skin is exposed to solutions containing hypohalite. If this N- halogenation occurs adjacent to the amino acid L-proline, the ensuing protein fragmentation results in the formation of 1-pyrroline. The rate of protein degradation, once the N-halogenation has occurred is variable from individual to individual and, in some cases, formation of malodor on the skin continues for several days after exposure to "free available halogen".

The halogen mediating, malodor control agents of the present invention are organic and inorganically derived -NH2 compounds. (Examples of preferred positive halogen mediators and malodor control agents are suiphamic acid, sulphamide, p-toluenesulphonamide, imidodisulphonamide, benzenesulphonamide, melamine, cyanamide, alkyl sulfonamides, and mixtures thereof. At pH levels of the present invention, which are greater than 11, the above mentioned malodor control agents may be de-protonated, that is they may be in the form of a salt and therefore due to expediency, ease of synthesis or preparation, or due to formulation practices the salt form of any or all of the above mentioned malodor control agents will suffice. Although any suitable cation will suffice for the purposes of the present invention, sodium, potassium, lithium, magnesium, calcium, and mixtures thereof are preferred.

In addition, the present invention includes compositions comprising the aforementioned -NH2 compounds for control of malodor when a source of positive halogen is present and comes into contact with the human skin. The halogen may be chlorine, bromine, iodine, or mixtures thereof and the source of positive halogen may be, but is not limited to hypochlorite, hypobromite, hypoiodite, and mixtures thereof. The present invention is effective whether the source of positive halogen is present at the time of formulation or if the source is generated in situ, for example during storage or especially, during usage as is the case when bleach boosters are present.

The present invention comprises malodor control agents that are prsent such that the mole ration of hypohalite bleach to malodor control agent is from about 10 : 1 to about 1 : 10, preferably from about 5 : 1 to about 1 : 2, more preferably from about 3 : 1 to about 1 : 2.

Surfactant - The instant cleaning compositions contain from about 0.1 % to about 95% by weight of a surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterinonic surface active agents. For liquid systems, surfactant is preferably present to the extent of from about 0.1 % to 20% by weight of the composition. For solid (i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems, surfactant is preferably present to the extent of from about 1.5% to 30 % by weight of the composition.

Anionic surfactants can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. ( Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are the sodium or potassium alkyl sutfates, especially those obtained by sulfating the higher alcohols (C8-18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid ester of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut alcohols) and about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals. contain from 8 to 12 carbon atoms; the reaction products of fatty acids are derived from coconut oil sodium or potassium salts of tatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil and sodium or potassium beta-acetoxy- or beta-acetamido- alkanesulfonates where the alkane has from 8 to 22 carbon atoms.

Additionally, secondary alkyl sulfates may be used by the formulator exclusively or in conjunction with other surfactant materials and the following identifies and illustrates the differences between sulfated surfactants and otherwise conventional alkyl sulfate surfactants. Non- limiting examples of such ingredients are as follows.

Conventional primary alkyl sulfates, such as those illustrated above, have the general formula ROS03-M+ wherein R is typically a linear C₈-C22 hydrocarbyl group and M is a water solubiizing cation. Branched chain primary alkyl sulfate surfactants (i.e., branched-chain "PAS") having 8-20 carbon atoms are also know; see, for example, Eur. Pat. Appl. 439,316, Smith et al., filed January 21 , 1991.

Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure

CH₃(CH2)n(CHOS03-M⁺)(CH₂)mCH3 wherein m and n are integers of 2 of greater and the sum of m + n is typically about 9 to 17, and M is a water-solublizing cation.

In addition, the selected secondary (2,3) alkyl sulfate surfactants used herein may comprise structures of formulas I and II

CH3(CH₂)χ(CHOSθ3-M⁺)CH₃

I

CH₃(CH2)y(CHOSθ3-M⁺)CH2CH₃

II for the 2-sulfate and 3-sulfate, respectively. Mixtures of the 2- and 3-sulfate can be used herein. In formulas I and II, x and (y+1 ) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16. M is a cation, such as an alkali metal, ammonium, alkanolammonium, triethanol-ammonium, potassium, ammonium, and the like, can also be used.

The aforementioned secondary alkyl sulfates are those prepared by the addition of H2SO4 to olefins. A typical synthesis using alpha olefins and sulfuric acid is disclosed in U.S. Pat. No. 3,234,258, Morris, issued February 8, 1966 or in U.S. Pat. No. 5,075,041, Lutz, issued December 24,1991. The synthesis conducted in solvents which afford the secondary (2,3) alkyl sulfates on cooling, yields products whcih, when purified to remove the unreacted materials, randomly sulfated materials, unsulfated by¬ products such as C10 and higher alcohols, secondary olefin sulfonates, and the like, are typically 90 + % pure mixtures of 2- and 3- sulfated materials (some sodium sulfate may be present) and are white, non tacky, apparently crystalline, solids. Some 2,3-disulfates may also be present, but generally comprise no more than 5 % of the mixture of secondary (2,3) alkyl mono- sulfates. Such materials are available as under the name "DAN", e.g., "DAN 200" from Shell Oil Company.

Carriers. Suitable carriers for the present invention are water and volatile solvents that are compatible with hypohalite.

Abrasives. An essential component of many solid or viscous semi- solid hard surface cleaning compositions is the abrasive material added to facilitate the action of scouring. Abrasive scouring cleansers provide a convenient and useful means for carrying out the sanitizing of porcelain and tile surfaces, especially tubs, showers and toilet bowls. The particulate abrasive material within such compositions serves to abrade and loosen soil adhering to hard surfaces and further serves to create more intimate contact between hard surface stain and the surfactant and or bleaching agents also present in the cleansing compositions.

Abrasive cleaners have traditionally contained water-insoluble, relatively hard, particulate mineral material as the abrasive agent. The most common such abrasive agent is finely divided silica sand having particle size varying between about 1 and 300 microns and specific gravity of about 2.1 or higher. While such material is generally very effective in scouring soil and stains from the surfaces being treated, abrasive material of this type tends to be difficult to rinse away from the toilet bowl, shower or bathtub surface.

It has been discovered that abrasive compositions of this desired type can be realized by utilizing a particular type of expanded perlite abrasive in combination with the surfactants, filler material, and other optional scouring material ingredients listed herein. The abrasive materials suitable to the present invention are those contained in U.S. Pat. No. 4,051,056, Hartman, issued September 27, 1977 and included herein by reference.

ADJUNCT MATERIALS

The compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the surface to be cleaned, or to modify the aesthetics of the composition (e.g., perfumes, colorants, dyes, etc.). The following are illustrative examples of such adjunct materials but are not meant to be exclusive or limiting in scope.

Buffers - Buffers can be included in the formulations herein for a variety of purposes. One such purpose is to adjust the cleaning surface pH to optimize the hard surface cleaner composition effectiveness relative to a particular type of soil or stain. Buffers may be included to stabilize the adjunct ingredients with respect to extended shelf life or for the purpose of maintaining compatibility between various aesthetic ingredients. The hard surface cleaner of the present invention optionally contains buffers to adjust the pH in a range above 11. Non-limiting examples of such suitable buffers are potassium carbonate, sodium carbonate, and trisodium phosphate, however, the formulator is not restricted to these examples or combinations thereof.

Chelatino Agents - The cleaning compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Examples of such compatible chelating agents are ethane-1-hydroxy-1,1- diphosphonic acid (EHDP) and dipicolinic acid.

Perfumes. Perfumes are an important ingredient especially for the liquid composition embodiment. Perfume is usually used at levels of from 0% to 5%. In U.S. Pat. No. 4,246,129, Kacher, issued January 20, 1981 (incorporated herein by reference), certain perfume materials are disclosed which perform the added function reducing the solubility of anionic sulfonate and sulfate surfactants.

Other Adjunct Ingredients. As a preferred embodiment, the conventional adjunct ingredients employed herein can be selected from bleach stabilizers, pigments, color speckles, suds boosters, suds supressors, anti-tarnish and/or anti-corrosion agents, soil-suspending agents, germicides, alkalinity sources, hydrotropes, anti-oxidants, clay soil removal/anti-redeposition agents, polymeric dispersing agents, etc. Procedure for Determining Available Chlorine (from NaOCI . A 100 mL Erlenmeyer flask equipped with a magnetic stirring bar is tared to the last significant decimal place. The sample to be analyzed is charged to the flask and weighed. 50 mL's of distilled and de-ionized water is added to the sample. Slowly and with sufficient stirring, 10 mL's of glacial acetic acid is added to the flask containing the sample. 1 mL of a 50% aqueous solution of potassium iodide is then added. The sample is then titrated with a stock solution of 0.1 N sodium thiosulfate until the solution goes from deep amber color to clear. % available chlorine = (# mL's of 0.1 N Na2S θ x 0355. mass of sample, gms MALODOR EVALUATION PROCEDURES SAMPLE IMMERSION METHOD

1. The hands and forearms of each subject is thoroughly washed with a hand soap, (e.g., IVORY SOAP, available from the Procter & Gamble Co.) Hands are patted dry.

2. Each hand is then submerged into the test solutions up to the wrist and held immersed for a total of 30 seconds.

3 Each hand is then separately rinsed under warm running tap water for 5 seconds.

4. Each hand is then patted dry with separate towels.

5. Each hand is then evaluated by panelists at periods of 0, 15, 30, 45, 60, and 120 minutes.

SAMPLE APPLICATION METHOD

2. To the back or palm of each hand is applied 3 mL of the solution to be tested. The solution is allowed to spread over the surface of the skin for 30 seconds.

3. Each hand is then rinsed with running 80° F tap water for 5 seconds.

4. Each hand is then patted dry with separate towels.

EXAMPLES OF BOOSTED BLEACH MALODOR CONTROL COMPOSITIONS The following table lists examples of the direct application of the present invention for the control of malodor or human skin exposed to compositions comprising hypochlorite or hypochlorite forming ingredients.

Quantities on a weight % basis

ComDonent Example No.

1 2 3 4 5 6 surfactant 0.25 3.5 5.5 6.5 6.1 9.5 sulphamic acid 1.30 1.9 2.2 — — — sodium sulfamate — — — 0.5 — 2.3 melamine — — — — 0.23 — sodium hypochlorite 0.9 1.4 1.4 — — — calcium hypochlorite — — — 0.5 — — sodium — — — — 1.2 2.0 dichlorocyanurate tetrapotassium 6.0 — — — 13.0 — pyrophos. tripotassium phosphate 2.0 — — — 12.0 — sodium tripolyphosphate — — — 1.6 — — sodium silicate — 0 0..0044 0 0..0055 — 0.5 — sodium periodate — 0 0..0011 — — — — — sodium acetate ------ ------ —-— 0.3 — — sodium bromide — 1.8 1.5 sodium iodide — —— 00..0033 — — 1.1 potassium bromide 1.1 —— 11..11 1.5 1.0 perfume — 0.28 0.1 calcium carbonate — — — — 39.0 1.1 calcium oxide — — — — 2.8 — perlite abrasive 6.5 — — — 22.5 0.5 sodium hydroxide 0.8 1.6 1.8 0.8 1.1 1.0 potassium hydroxide — — — 0.85 — — dyes and perfume 0.75 0.28 0.28 0.28 — — miscellaneous — — 0.02 — — 22.5 lanolin — — — — — 2.1 carboxymβthylcellulose — — — — — 2.6 moisture/distilled water bal. bal. bal. bal. bal. bal. Use of these hard surface cleaning compositions comprising -NH2 compounds substantially reduces the formation of malodor associated with the exposure of human skin to hypochlorite when the skin is contacted with said solution.

ExamDle No. 7

ComDonent Weight % amine oxide surfactant 2.25 coconut fatty acid 0.9 sodium octyl sulfate 1.1 caustic soda 2.35 sodium silicate 0.4 perfume 0.275 dye 0.0046 periodic acid 0.0106 sodium hypochlorite 1.4 sulfamic acid 2.2 sodium bromide 0.5 carrier fillers balance

ExamDle No. 8

ComDonent Weight % amine oxide surfactant 2.40 coconut fatty acid 0.9 sodium octyl sulfate 1.1 caustic soda 1.38 sodium silicate 0.4 perfume 0.275 dye 0.0046 periodic acid 0.0106 sodium hypochlorite 1.4 sulfamic acid 0.93 potassium iodide 0.5 carrier/fillers balance

WHAT IS CLAIMED IS:

Claims

1. A cleaning composition comprising: a) a halogen bleach, preferably from 0.01 % to 10% by weight; b) a bleach booster, preferably such that the molar ratio of said bleach in

(a) to bleach booster is from 1 :0.05 to 1 :4; c) an organic or inorganic derived -NH compound effective for controlling halogen reduced skin malodor, preferably such that the molar ratio of said bleach in (a) to malodor control compound is from 10:1 to 1:10; and d) the balance comprising carrier and adjunct ingredients such that said composition has a pH greater than 11 , preferably comprising from 0.1% to 95% by weight, of a detersive surfactant and/or an abrasive.

2. A composition according to Claim 1 wherein said composition comprises a bleach of the formula M(OX)y where: a) M is a member selected from the group consisting of sodium, potassium, magnesium, calcium, and mixtures thereof; b) O is an oxygen atom; and c) X is a member selected from the group consisting of chlorine, bromine, iodine, and mixtures thereof; wherein y is 1 or 2.

3. A composition according to either of Claims 1 or 2 wherein said bleach booster has the formula (MX)_y where: a) M is a member selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, copper, zinc, and mixtures thereof: and b) X is a member selected from the group consisting of bromide, hypobromite, bromate, iodide, hypoiodite, iodate, and mixtures thereof; where y is 1 or 2.

4. A composition according to any of Claims 1 - 3 wherein said malodor control compound is a member selected from the group consisting of sulphamic acid, sodium sulphamate, potassium sulphamate, sufamide, p-toluenesulphonamide, imidodisulphonamide, benzenesulphonamide, melamine, cyanamide, alkyl sulfonamide, and mixtures thereof.

5. A composition according to any of Claims 1 - 4 wherein said adjunct ingredient is a member selected from the group consisting of detersive surfactants, buffers, builders, chelants, filler salts, abrasives, perfumes, colorants, thickeners, and mixtures thereof.

6. A composition according to any of Claims 1-5 wherein the viscosity is from 0.5 to 3000 centipoise at 22° C.

7. A composition according to any of Claims 1-6 wherein the molar ratio of bleach to malodor control agent is from 10:1 to 1:10, preferably from 5:1 to 1:2, more preferably from 3 : 1 to 1 : 2.

8. A composition according to any of Claims 1 -7 wherein the molar ratio of bleach to bleach booster is from 1:0.1 to 1:2.

9. A method for cleaning hard surfaces, said method comprising contacting by scrubbing or scouring a surface in need of cleaning with a composition according to any of Claims 1-8.

10. A process for manufacturing hypochlorite-containing compositions according to any of Claims 1-9, said process comprising the steps of: a) pre-dissolving the -NH compound effective for controlling malodor with the bleach booster; b) mixing the mixture of (a) with the remaining components of the composition not including the hypochlorite bleach; and c) combining a hypochlorite halogen bleach and the mixture from (b).