EP0968272A1

EP0968272A1 - Improvements in or relating to organic compositions

Info

Publication number: EP0968272A1
Application number: EP98900311A
Authority: EP
Inventors: Thomas Weibel; Ann Marie Lynch; Pranil Pooran Hagroo; Leonard February
Original assignee: Reckitt and Colman Inc; Reckitt and Colman South Africa Pty Ltd; Reckitt Benckiser South Africa Pty Ltd
Current assignee: Reckitt Benckiser LLC; Reckitt Benckiser South Africa Pty Ltd
Priority date: 1997-01-10
Filing date: 1998-01-08
Publication date: 2000-01-05
Also published as: AU5491998A; WO1998030672A1

Abstract

One aspect of the invention relates to a pourable cleaning composition having a bleaching action and suitable for cleaning hard surfaces includes: a) a carbomer; b) a compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, sodium tripolyphosphates, pyrophosphates, bicarbonates, sesquicarbonates and mixtures thereof; c) a first nonionic or zwitterionic surfactant; d) a second anionic surfactant and e) an alkali or alkaline earth metal hypochlorite. A second aspect of the invention relates to an aqueous thickened bleach composition comprising (in parts by weight based on the total weight of the composition): a) 0.5 - 5.0 % of an alkali metal carboxylate; b) 0.5 - 4.0 % of an alkali metal salt, preferably an alkali metal chloride; c) 0.25 - 6.0 % of a water dispersible nonionic amine oxide; d) 0.5 - 8.0 % of a water dispersible anionic surfactant system including one or more sulfate or sulfonate surfactants; e) 0.01 - 10.0 % of a bleach releasing material, such as an alkali metal hypochlorite; f) 0.1 - 10.0 % of a pH adjusting agent for maintaining the alkalinity of the composition; g) 1.0 - 50 % of an abrasive material, preferably a particulate abrasive material; h) optionally, 0.05 - 3.0 % of a detergency builder, and the balance to 100 % being water. The compositions of the invention show good shelf life, exhibit a high level of bleach stability and show good stain and soil removal, particularly from hard surfaces.

Description

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOSITIONS

This invention relates to a pourable aqueous bleach composition, suitable for use in cleaning hard surfaces such as are found, for example, in lavatories and kitchens. Pourable scouring cleansing compositions often may contain such constituents as an alkali metal sulphate (as an anionic surfactant), an amine oxide (as a non-ionic surfactant), sodium hydroxide (as an electrolyte), a chlorine releasing bleaching agent and optionally a suspended particulate abrasive.

However, the viscosities of such compositions tend to increase with storage time and, consequently, they exhibit poor flow properties.

According to the invention there is provided an aqueous cleaning composition comprising, a) a carbomer or an alkali metal carboxylate (hereinafter component a); b) at least one compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, sodium tripolyphosphates, pyrophosphates, bicarbonates, sesquicarbonates, alkali metal salts and mixtures thereof (hereinafter component b); c) a first surfactant selected from nonionic and zwitterionic surfactants and mixtures thereof (hereinafter component c); d) a second surfactant selected from anionic surfactants (hereinafter component d); e) a compound which is selected from an alkali metal and alkaline earth metal hypochlorite.

In a first aspect of the present invention, the inventors have found, surprisingly, that the use of carbomer in combination with certain surfactants reduces these drawbacks and leads to a reduction in abrasiveness of the resultant composition. According to a first aspect of the invention, there is provided a pourable aqueous cleaning composition comprising: a) a carbomer; b) at least one compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, sodium tripolyphosphates, pyrophosphates, bicarbonates, sesquicarbonates and mixtures thereof; c) a first surfactant selected from nonionic and zwitterionic surfactants and mixtures thereof; d) a second surfactant which is an anionic surfactant; and e) a compound selected from alkali metal and alkaline earth metal hypochlorites. In a preferred composition of the first aspect of the invention, the carbomer is a polycarboxylate polymer. It is preferably hypochlorite stable. The ratio of the first surfactant to carbomer is desirably in the range 1 to 8, more preferably 3 to 6 and most preferably 4 to 5 by weight.

In a further preferred form of the first aspect of the invention, the second anionic surfactant is a secondary alkane sulphonate. Preferably, the secondary alkane sulphonate is a compound of the formula

R, R, CHSO₃- M⁺ in which R, is a C_8.22 alkyl or C_8.22 alkenyl, R^ is selected from C,_₆ alkyl groups and M⁺ is a monovalent cation.

In an alternative, a further preferred composition according to the first aspect of the invention, the second, anionic surfactant includes a component selected from alkali or alkaline earth metal C_5.22 alkyl sulphates and alkali or alkaline earth metal C₅₂₂ alkyl ether sulphates.

In a still further preferred form of the first aspect of the invention, the composition additionally includes an abrasive. The abrasive may be in particulate form. It is preferably selected from calcite and perlite abrasives. The calcite may be selected from CaCO₃ and MgCO₃.

Still further, the composition may include one or more components selected from colourants and fragrances and combinations thereof.

In a further preferred composition according to the first aspect of the invention, the first surfactant (component c) is preferably selected from C_8.22 alkyl oxides, C_8.22 alkenyl oxides and betaines.

The chlorine releasing bleaching agent is preferably a compound selected from alkali metal and alkaline earth metal hypochlorites.

In a preferred composition according to the first aspect of the invention, component a) - the carbomer - is present in an amount of 0.05 to 5% by weight, more preferably 0.1 to 2% and, most preferably, 0.4 to 1.2%.

In a preferred composition according to the first aspect of the invention, component b) is present in an amount of 0.5 to 12% by weight, more preferably 0.8 to 5% and, most preferably, 1.0 to 3%. In a preferred composition according to the first aspect of the invention, the first surfactant (component c) is present in an amount of 0.1 to 15% by weight, more preferably 0.5 to 5% and, still more preferably from 0.2 to 4.5%, especially 0.2 to 3.5%wt, particularly 0.2 to l%wt."

In a preferred composition according to the first aspect of the invention, the second anionic surfactant (component d) is present in an amount of 0.1 to 15%₀ by weight, more preferably 0.4 to 9.5% and, most preferably, 0.7 to 3%. In a preferred composition according to the first aspect of the invention, the hypochlorite (component e) is present in an amount sufficient to provide from 1 to 6% available chlorine, more preferably 1 to 3% and most preferably 1 to 2% by weight. In a preferred composition according to the first aspect of the invention, the abrasive is present in an amount of 0 to 50% by weight, more preferably 5 to 50%.

The viscosity of a composition according to the first aspect of the invention is preferably in the range of 600 to 3000cps, measured on a Brookfield RVT viscometer using a spindle number 3 at 50 rpm and a temperature of 20 deg.C.

Further, optional substances, such as fragrances and colourants, may be present in an amount from 0% to 2% by weight.

Further according to the first further aspect of the invention, there is provided a method of cleaning a hard surface requiring such cleaning includes the steps of applying a pourable aqueous cleaning composition comprising: a) a carbomer; b) at least one compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, sodium tripolyphosphates, pyrophosphates, bicarbonates, sesquicarbonates and mixtures thereof; c) a surfactant selected from nonionic and zwitterionic surfactants and mixtures thereof; d) an anionic surfactant; and e) a chlorine releasing bleaching agent compound selected from alkali metal and alkaline earth metal hypochlorites, in an amount effective for providing cleaning or bleaching treatment to such surface.

In a preferred embodiment, the method includes the further step of removing the applied composition from the surface having allowed time for effective treatment to take place.

Primary thickening of a composition of the final aspect of the invention is performed by the carbomer, component aO, which is water dispersible and, desirably, bleach stable. The carbomer, being a dry powder resin, performs a suspending function where particulate material is present in the composition. Preferred carbomers are polycarboxylate polymers. Suitable examples include, without limitation, Carbopol 676, Carbopol 695 and Carbopol 672 available from the BF Goodrich Company of Cleveland, Ohio. Other carbomers that may be used are carboxyvinyl polymers. In this instance, an inorganic abrasive would not be included in the composition. The carbomer should have a molecular weight in the range from 500 000 to 10 000 000 and preferably 2 000 000 to 6 000 000 and most preferably about 3 000 000. The thickening effect is desirably enhanced by cross- linking, for which suitable agents may be included. These must be selected not to render the chlorine ineffective or the composition unstable.

The carbomer concentration (component a) in the composition is desirably in the range from 0.05% to 5% by weight, preferably from 0.1% to 2% and most preferably 0.4% to 1.2%.

Component b) is generally present in the concentration range of 0.5 to 12% by weight, more preferably 0.8 to 5% and, most preferably, 1.0 to 3%. Preferably sodium hydroxide is selected to be in excess so as to provide - in combination with sodium silicate in solution - a stabilising effect in regard to the chlorine releasing bleaching agent. The hydroxide also acts as a pH modifier and a neutraliser in respect of the carbomer.

A secondary thickening effect is achieved in the composition by the inclusion of component c) - the nonionic and/or zwitterionic surfactant, or mixture thereof. This helps to form a system which aids the cleaning properties of the composition. Component c) should be resistant to chlorine-releasing agents and desirably is present in an amount of 0.1 to 5%> by weight of the composition, more preferably 0.5 to 5% and, most preferably, 1 to 3.5%.

Examples of suitable nonionic or zwitterionic surfactants may be selected from C_{8 22} alkyl oxides, C_8.22 alkenyl oxides and betaines. Exemplary betaines are N-carboxymethyl- N-dimethyl-N-(9-octadecenyl) ammonium hydroxide and N-carboxymethyl-N-cocoalkyl-N- dimethyl ammonium hydroxide.

Alternatively, component c) - the first surfactant - may be an amine oxide and, in particular, a C₁₀ to C₁₈ alkyl dimethyl amine oxide such as myristyl amine oxide. The former is available under the trade name EMPIGEN OH25 from Albright and Wilson of England, or as Ninox M, available from Stepan Europe of France. Where the nonionic surfactant component is an amine constituent, the carbomer is thought to react with it to form a thickened, stable, oily emulsion in aqueous medium.

The weight ratio of the first surfactant (component c) to carbomer (component a) should be in the range from 1 to 8. More preferably, the range is from 3 to 6 and most preferably from 4 to 5. The second surfactant (component d) is preferably a secondary alkane sulphonate.

Preferred such compounds have the formula

R_jR.CHSO,- M⁺, in which R, is a C_8.22 alkyl or a C_{8 22} alkenyl, _ is selected from C ₆ alkyl groups and M⁺ is a monovalent cation. Further preferred anionic surfactants are sodium C₁₂ to C,₈ alkyl sulphonates. A preferred example is sold under the registered trade mark Hostapur SAS 60 by Farbwerke Hoechst AG of Germany. Also desirable are straight chain alkali metal dodecyl diphenyloxide disulphonates, such as of sodium.

The second surfactant (component d) may alternatively be or in addition include an alkali or alkaline earth metal C_{5 22} alkyl sulphate or an alkali or alkaline earth metal C_{5 22} alkyl ether sulphate. Its concentration should preferably be in the range from 0 to 10% by weight, more preferably 0.2 to 5%o and, most preferably, 0.5 to 2%. A suitable example is sodium lauryl ether sulphate. This is sold under the trade name Empicol ESB3 or Empicol 0405, supplied by Albright & Wilson.

The chlorine releasing bleaching agent (component e) is preferably a compound selected from alkali metal and alkaline earth metal hypochlorites. It has a dual stabilising and cleaning function. The available chlorine concentration in the composition should be in the range from 1 to 6% by weight, more preferably 1 to 3% and, most preferably, 1 to 2%. Sodium hypochlorite is a preferred example. Other examples include the hypochlorites of potassium, calcium and lithium. The agent selected should be substantially free of impurities such as chloride salts which may reduce the stability of the composition.

The hypochlorite in the composition is desirably stabilised by means of stabiliser, typically a sodium silicate solution and an excess of sodium hydroxide. A commercially obtainable example is sold under the trade name SILCHEM^^tm) 3379 wherein the ratio SiO-^Na_jO is in the range 3.35 to 3.25. Excess sodium hydroxide may be provided according to the component b, chosen.

Other materials of a non-essential nature may be included. These may for example be colourants, fragrances, buffers, builders, etc. These materials are present in the composition in a concentration range generally of up to 2% by weight.

The composition may additionally include one or more abrasives - preferably in particulate form, with the particle nominal size and density combination selected to render it stably suspensible therein. Any suitable base stable abrasive may be used. The abrasive concentration should be 50% by weight or lower and preferably in the range from 5% to 50%.

The abrasive may be inorganic or organic and should have a hardness of 1 or greater on the Moh scale. Preferably the hardness will be in the range 2 to 8 and more preferably about 1.5 to 6. Suitable examples of inorganic abrasives may be any one or more of magnesite (MgCO₃), calcite (CaCO₃), dolomite, felspar, diatomaceous earth, pumice, talc, alumina, silica and nitrides and carbides of group IVB, VB and VIB metals of the periodic table such as those of titanium, tantalum, chromium and molybdenum. Preferred examples are sodium silicate and sodium metasilicate (pentahydrate). The average particle size should be in the range from 1 to 100 micrometres. The preferred range is, however, from 10 to 50 micrometres. Particle density should be in the range from 2 to lOg cm³ and preferably from 2.4 to 6 g cm³.

Organic abrasives may include materials based on comminuted polymers such as melamine granules and urea formaldehyde. The composition may optionally include further components such as silicates. The balance of the composition is made up of water, preferably de-ionised.

Preparation of the compositions may be by means that are conventional in the art. Agitation may be used advantageously.

In use, the composition will be applied to a surface to be cleaned in an amount effective for providing satisfactory cleaning and thereafter the applied composition is removed from the surface, having allowed time for effective cleaning treatment to have taken place. Tests conducted show that abrasiveness in the inventive compositions is less than in comparable compositions not containing a resin carbomer in effective concentration.

Compositions according to the first aspect of the invention are capable of remaining substantially homogeneously viscous, that is to say the components do not exhibit a noticeable degree of separation or settling. The composition thus formed appears opaque where it includes abrasive. It exhibits thixotropic behaviour. When poured on to a surface to be cleaned, the composition remains coherent in that it does not spread rapidly or break into discrete drops or patches. Its viscosity range may be from 600cp to 3000cp when measured on a Brookfield RVT viscometer using spindle number 3 at 50rpm and at a temperature of 20 deg.C. Preferably it should be in the range from lOOOcp to 1400cp, when being used with a specific gravity (SG) in the range from 1.01 to 1.05. If left to stand, the viscosity tends to increase.

A second aspect according to the invention relates to improved thickened aqueous bleach containing compositions which contain abrasives.

It is particularly difficult to produce aqueous bleach stable, thickened abrasive cleaning compositions which offer the simultaneous benefits of: good bleach stability which provides an acceptable shelf life for a product; acceptable viscosity characteristics; relatively low cost; and of course efficacy in removing stains and in effectively disinfecting surfaces, especially on inclined hard surfaces such is tiled, enameled and porcelain surfaces such as are typically associated with bathrooms. While the art provides a number of such compositions directed to satisfying these requirements, these compositions have not uniformly met with success. The present invention overcomes may of these shortcomings in the prior art. According to a second aspect of the invention there is provided an aqueous thickened bleach compositions comprising in parts by weight (based on the total weight of the composition): a) 0.5 - 5.0 of an alkali metal carboxylate, preferably a sodium salt thereof; b) 0.5 - 4.0 of an alkali metal salt, preferably an alkali metal chloride; c) 0.05 - 5.0 of a water dispersible nonionic amine oxide; d) 0.1 - 8.0 of a water dispersible anionic surfactant system including one or more sulfate or sulfonate surfactants, which system most preferably includes a minor amount of an alkyl diphenyl ether disulfonate surfactant; e) 0.01 - 10.0 of available chlorine in a bleach releasing material, such as an alkali metal hypochlorite; f) 0.1 - 10.0 of an pH adjusting agent for maintaining the alkalinity of the composition; g) 1.0 - 50 of an abrasive material, preferably a particulate abrasive material; h) 0.05 - 3.0 of an detergency builder; and, the balance being water to provide 100 %wt.

A composition according to the second aspect of the invention is a stable, single phase, thickened bleach containing composition capable of adhering to vertical or inclined surfaces longer than thinner compositions. Such a composition is effective as an agent for stain and soil removal as well as disinfection. The high level of bleach stability and single solution phase behaviour of the composition enables the composition to have an acceptable shelf life. The compositions exhibit little or no visibly discernible syneresis during its normal shelf life (6-9 months) and shelf life storage conditions (20°C). In particularly preferred embodiments the compositions exhibit little or no syneresis under accelerated aging test conditions (40°C for a ten week period) and at the same time exhibited good bleach stability. Such is particularly important for use and storage of the product in warm climate countries (South Africa, Brazil, etc.) Compositions of the second aspect according to the invention are alkaline in character, desirably having a pH of about 12 or more, exhibit very favorable viscosity characteristics, are good hard surface cleaners and feature good bleach stability over time. The compositions may also include minor amounts, generally not more than at total of 5%wt, desirably less than 3%wt. of one or more optional constituents including ones which may improve the aesthetic appeal of the compositions, viz., perfumes and colorants. Such optional constituents should not undesirably affect the shelf stability or rheology of the compositions.

Compositions according to the second aspect of the invention include alkali metal carboxylate, such as sodium, lithium, potassium or ammonium carboxylates, preferably linear C8 - C24 carboxylates. These are also frequently referred to as fatty acid soaps.

Desirably these carboxylates include linear or branched alkyl chains, preferably linear, are at least 90%), more preferably at least 98% saturated, and most preferably are essentially completely (> 99.5%) saturated. Typically, alkali metal carboxylates are provides a technical grade mixtures which include various proportions of different alkyl chains within the such a mixture. Thus, the actual content and distribution of different alkyl chains may vary between such mixtures, as well as between suppliers of technical grade mixtures. The inventors have surprisingly found that the selection of the alkali metal carboxylate constituent strongly influences the rheological characteristics of the compositions according to the second aspect of the invention being taught herein. The use of alkali metal carboxylates which have a significant preponderance of C20, C22 and higher fatty acids lead to excessive thickening of the compositions. The use of alkali metal carboxylates which have a significant preponderance of more C14, C12 and lower fatty acids leads to excessive viscosity loss of the compositions. Thus, many prior art fatty acid carboxylates known to the art are not necessarily suitable in the present inventive compositions.

Most preferably as the alkali metal carboxylates are technical grade mixtures which include at least 55% weight, preferably at least 75%wt. of C16 and C18 fatty acids, less than 15%wt. of one or more C20, C22 and higher fatty acids, and less than 30%wt. of one or more C14, C12 and lower fatty acids. Yet more preferably the alkali metal carboxylates are technical grade mixtures which include at least 25% weight of C16 fatty acids, 60%wt. of C18 fatty acids, less than 15%wt, preferably less 10%wt. of one or more C20, C22 and higher fatty acids, and less than 15%wt, preferably less than 10%wt. of one or more C14, C12 and lower fatty acids. These carboxylates are preferably provided as sodium salts of the acids recited as such salts are widely available at a relatively low cost.

It has been found by the inventors that the use of alkali metal carboxylates within the preferred and most preferred weight range indicated above avoid the formation of an undesired amount of a filamentious network in the compositions. Such provides an undesirably high amount of viscoelastic behavior to the compositions which severely detracts from the delivery characteristics of the formulations from a consumer package, i.e., bottle.

Certain commercially technical grade mixtures of alkali metal carboxylates which satisfy available materials which fulfill the preferred weight range distributions are known, and are commercially available. However, a preponderance of technical grade mixtures of alkali metal carboxylates do not comprise a distribution of fatty acids within the preferred weight ranges, but this has been overcome by the inventors as well. In accordance with a specific and particularly preferred embodiment, the alkali metal carboxylate is provided as the resultant reaction product of a technical grade mixture of fatty acids having a particularly desirable distribution of alkyl chain lengths of the said fatty acids as described above, with a stochiometric excess of an appropriate material such as a caustic, i.e., an alkali metal hydroxide such as sodium hydroxide, in an aqueous medium. It is also contemplated that the technical grade mixture of fatty acids may be added to the composition of the invention as it is being formulated, wherein the acid groups of the fatty acids may react with an available co-reactant, such as available alkali metal hydroxide, and thus form the alkali metal carboxylate in situ.

Technical grade mixtures of fatty acids are frequently to be preferred as they often provide a more specific fatty acid distribution than many commercially available alkali metal carboxylate in a raw material form. One preferred technical grade mixture of fatty acids is: HYSTRENE 7018 (Humko Chem., a division of Witco Corp.) which is a technical grade mixture of fatty acids with the following weight distribution of alkyl chains: 2%wt. myrisitic acid, 0.5%wt. pentadecanoic acid, 30% palmitic acid, 2.6% margaric acid, and 65% stearic acid.

Further examples of useful alkali metal carboxylates useful in the present compositions according to the second aspect of the invention are illustrated in the examples.

The alkali metal carboxylate constituent is preferably present in an amount of preferably from 0.8 - 1.2%w , and more preferably is present in an amount of about l%wt, based on the total weight of the composition.

The nonionic amine oxide of the compositions of the second aspect of the invention are preferably selected from:

A) Alkyl di (lower alkyl) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. The lower alkyl groups include between 1 and 7 carbon atoms. Examples include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide;

B) Alkyl di (hydroxy lower alkyl) amine oxides in which the alkyl group has about 10- 20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples are bis(2-hydroxyethyl) cocoamine oxide, bis(2-hydroxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide;

C) Alkylamidopropyl di(lower alkyl) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples are cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and D) Alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Preferably the amine oxide constituent is an alkyl di (lower alkyl) amine oxide as denoted above and which may be represented by the following structure: l

R₂ — N — *^»0

R₁ wherein each Rl independently is a straight chained C1-C4 alkyl group, preferably both Rl are methyl groups; and,

R2 is a straight chained C8-C18 alkyl group, preferably is C10-C14 alkyl group, most preferably is a C12 alkyl group.

Each of the alkyl groups may be linear or branched, but most preferably are linear. Most preferably the amine oxide constituent is lauryl dimethyl amine oxide. Technical grade mixtures of two or more amine oxides may be used, wherein amine oxides of varying chains of the R2 group are present. Preferably, the amine oxides used in the present invention include R2 groups which comprise at least 50%wt., preferably at least 60%wt. of C12 alkyl groups and at least 25%wt. of C14 alkyl groups, with not more than 15%wt. of C16, C18 or higher alkyl groups as the R2 group. The water dispersible amine oxide of the compositions of the second aspect of the invention is preferably present in an amount of from 0.25 - 0.75%wt., and more preferably is present in an amount of about 0.4 - 0.6 %wt, based on the total weight of the composition.

The anionic surfactant system of the compositions of the second aspect of the invention includes one or more anionic sulfates and/or sulfonates selected from primary or secondary alkyl sulfates, alkyl ether sulfonates, and preferably include a minor, but effective amount of one or more diphenyl disulfonates. Each of these materials are commercially available as surfactants and are frequently provided in a salt form in an aqueous carrier.

Exemplary useful alkyl sulfates include those according to the formula:

O

II© Q

RO — (CH₂CH₂0)χ S — O M^

wherein

R is an alkyl chain having from about 8 to about 18 carbon atoms, which may be saturated or unsaturated, and where the longest linear portion of the alkyl chain is 15 carbon atoms or less on the average of the alkyl chain; M is a counterion, such as an alkali metal, ammonium or substituted ammonium cation, and x is from 0 to 4.

A particularly preferred primary alkyl sulfate is sodium lauryl sulfate. A particularly useful secondary alkyl sulfate are those according to the general structure:

S0₃ ^"X⁺

CH₃-(CH₂)— CH-(CH₂)— CH₃ where: n, m are each separately number of from 1 - 18 inclusive, and more desirably n and m are each selected such that n + m is a number of from 10 - 14 inclusive; and,

X represents a counterion, desirably an alkali metal or ammonium counterion, yet more desirably is lithium, potassium or sodium, especially sodium.

There materials are commercially available under the trade name HOSTAPUR SAS from Hόchst AG (Germany) of which various technical grade aqeuous mixtures are presently commercially available.

Alkyl ether sulfates which are desirably included in the inventive compositions include those according to the general structure:

R — θ-C H₂C H₂ — O-S 0₃ ^"X' ^ 'n wherein: X represents a counterion, desirably an alkali metal or ammonium counterion, yet more desirably is lithium, potassium or sodium, especially sodium;

R represents a hydrophobic alkyl group, desirably a linear or branched C6-C16 alkyl group which may be straight chained or branched, may be optionally substituted but desirably is an unsubstituted linear straight chained CIO - C14 alpha olefins, and most desirably is a C 12 alpha olefin; n is a number of from 1 - 8 inclusive, but desirably is from 2 - 3 inclusive.

The inventors have surprisingly found that the inclusion of a minor, but effective amount of one or more alkyl diphenyl ether disulfonates as part of the anionic surfactant system very advantageously improves the rheological characteristics of the compositions subsequent to accelerated aging testing, which is a useful approximation of shelf life. At the same time the presence of these anionic compounds does not undesirably effect either the bleach stability of the compositions, and at least equally importantly do not undesirably solubilize the other constituents and thereby decrease the viscosity or thixotropic characteristics of the inventive compositions subsequent to such accelerated aging testing. In particularly preferred inventive compositions these alkyl diphenyl ether disulfonates are necessarily present.

Non-limiting examples of particularly useful alkyl diphenyl ether disulfonates are commercially available in anionic surfactant compositions from the Dow Chemical Co. under the trade designation DOWFAX, of which those which conform to the following general structure are particularly useful:

wherein: X represents a counterion, desirably an alkali metal or ammonium counterion, yet more desirably is lithium, potassium or sodium, especially sodium, and, R represents a hydrophobic alkyl group, desirably a linear or branched C6-C16 alkyl group which may be straight chained or branched, may be optionally substituted but desirably are unsubstituted C6-C12 straight chained alpha olefins, or is tetrapropylene. Of these, particularly useful are those available as DOWFAX 3B2 which is described as being a sodium salt according to the general structure depicted above and wherein R is a C6 olefin; and, DOWFAX 2A1 which is described as being a sodium salt according to the general structure depicted above and wherein R is tetrapropylene.

The water dispersible anionic surfactant system is preferably present in an amount of from 0.5 - 1.5%wt, more preferably present in an amount of about 0.8 - 1.2%wt, and most preferably at about l%wt. based on the total weight of the composition. These recited amounts include the alkyl diphenyl ether disulfonates which are preferably also present in the inventive compositions.

One or more alkali metal salts are included in the compositions of the second aspect of the invention as it has been observed that such materials favorably improve the thickening of the compositions. These may be added to the compositions separately, or they may form part of a different material which is used in the inventive compositions. For example, the alkali metal hypochlorites which are preferred for use in the invention are frequently supplied in commercial preparations which also include an amount of a salt, such as sodium chloride, which may satisfy the requirement for the presence of an alkali metal salt. The alkali metal salt may be selected from any number of water-soluble alkali metal salts and mixtures thereof, with the alkali metal preferably defined as lithium, potassium, or sodium, and the anion ion preferably defined as a halide (such as chloride, fluoride, bromide, iodide, and so on) More preferably, the alkali metal salt is selected from the group consisting of sodium chloride, lithium chloride, potassium chloride, and mixtures thereof For purposes of cost and availability, the alkali metal salt most favored is sodium chloride and may be used in varying amounts to reduce alkali metal hypochlorite degradation, limited only by the avoidance of a "salting out" of the solution (where the surfactants become insoluble in water) The "salting out" phenomenon is well-known to those skilled in the art, as described, for example, in an article by P Mukerjee in J. of Physical Chemistry, Vol 69, No 11, p 4038 (1965) (hereby incorporated by reference) and references cited therein The alkali metal salt is preferably present in amount of 1 0 - 3 0%wt , more preferably from 1.5 - 2 5%wt, and mots preferably about 2 0%wt based on the total weight of the composition

As the pH adjusting agent for maintaining the alkalinity of compositions according to the second aspect of the invention, an alkali metal hydroxide is the preferably used It is to be understood however, that other known art pH buffers may be employed as long as the stability and viscosity of the composition are not adversely affected, inter alia, carbonate buffers The alkali metal of the preferred hydroxide may be lithium, potassium, or sodium, and sodium hydroxide and potassium hydroxide are particularly useful pH stabilizers due to cost and availability, with sodium hydroxide most preferred The alkali metal hydroxide is included in the composition in an effective amount to adjust the composition to a pH level of at least about 11, more preferably from 12 to 13 5, and most preferably within the range from 12 5 to 13 2

The pH adjusting agent for maintaining the alkalinity of the composition is present in amounts of from 0 1- 10 0%wt , more desirably from 0 2 - 2 0%wt , and most desirably from 0 4 - 1 5%wt, and particularly desirably about 1 0%wt based on the total weight of the composition

The inventive compositions according to the second aspect of the invention include a minor but effective amount of a detergency builder constituent Examples of such materials include known detergency builders of which are compatible in the bleach containing composition according to the invention Desirably the detergency builder constituent is one or more inorganic compounds such as alkali metal carbonates (including bicarbonates, sesquicarbonates), phosphates, polyphosphates and silicates (including metasilicates, orthosilicates) Such materials may be hydrous or anhydrous More specific examples include sodium tπpolyphosphate, sodium carbonate, potassium carbonate, sodium polyphosphate, potassium pyrophosphate, potassium tripolyphosphate, and sodium hexametapho sphate The detergency builder constituent is preferably present in an amount of from 0.1 - 2.0%wt, more preferably from 0.5 - 2.0%wt, and most preferably in an about of 1 - 1.5%wt. based on the total weight of the composition according to the second aspect of the invention. In particularly preferred embodiments, the inventive compositions according to the second aspect of the invention are substantially free of phosphates and phosphate containing materials.

These materials may be used singly, or in mixtures, and may also be used in conjunction with sequestrants such as organic builder salts. By way of non-limiting example such include alkali metal polycarboxylates including water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartarate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates, as well as sodium and potassium tartrate mono- and di-succinates. As noted, these organic builder salts may be used individually, as a combination of two or more organic builder salts, as well as in conjunction with one or more detergency builders, including those indicated above. Desirably however, these organic builder salts are omitted as they frequently undesirably react with the bleach in the inventive compositions. Most desirably, a minor amount of an alkali metal metasilicate or alkali metal orthosilicate, especially sodium metasilicate is present as a detergent builder constituent in the inventive compositions, as it has been observed by the inventors that such are effective and do not deleteriously effect the bleach stability or viscous characteristics of the inventive compositions described herein.

The available chlorine in a bleach releasing material of compositions according to the second aspect of the invention is preferably 0.1 - 3.5%wt., and more preferably 0.5 - 2.5%t. of

As the bleach releasing material, hypochlorites (such as alkali metal hypochlorites) as well as hypochlorite precursors may be used in the compositions according to the second aspect of the invention. Exemplary hypochlorite producing species, include halogen bleaches selected from the group consisting of the alkali metal and alkaline earth salts of hypohalite, haloimines, haloimides and haloamides. Representative hypochlorite producing compounds include sodium, potassium, lithium and calcium hypochlorite. A preferred material is sodium hypochlorite which is effective, and widely commercially available.

It is to be noted that frequently, commercially available hypochlorite containing materials from commercial sources include an appreciable amount of one or more further materials, particularly alkali metal salts (alkali metal chlorides) which further materials are among the required constituents according to the invention. The presence of such further materials it to be accounted for when producing the inventive compositions. The compositions according to the second aspect of the invention include abrasive material, preferably a particulate abrasive material such as any of a variety of dispersible particulate solids including but not limited to inorganic materials such as: carbonate salts including poorly water soluble alkali metal carbonates particularly calcium carbonate; calcite, dolomite, feldspar, diatomaceous earth, talc, bentonite, pumice, alumina, silica which and, oxides such as aluminum and titanium oxides. Other abrasive materials based on organic polymers may also find use in the inventive compositions, especially those in finely comminuted or particulate form. Such materials may be used singly or in combination. Desirably these abrasive materials are bleach stable, comminuted materials, with an average particle diameter falling within the range of from about 0.1 - 500 micrometers, more desirably fall within the range of from about 1 - 50 micrometers, and most desirably fall within the range of from about 5 to about 15 micrometers.

The abrasive material is preferably present in an amount of from 5.0 - 40%w , more preferably from 8.0 - 35%wt, and most preferably is present in an about of 8.0 - 16%wt. based on the total weight of the composition.

The individual constituents described above are available from a variety of commercial suppliers, often as technical grade mixtures of the recited compounds, which are frequently provided in a salt form, and are typically supplied in a liquid carrier such as water and/or an organic solvent.

The compositions of the second aspect of the invention are viscous in nature, and desirably exhibit a viscosity of between about 500 and 4000 cps, and more desirably from 700 to 2000 cps at a temperature of 25 °C as measured using a Brookfield RNT viscometer at a speed of 50 rpm. It is to be noted that the viscosity of a newly made composition is frequently less viscous than subsequent to aging, and that the compositions may exhibit thickening upon standing or storage over extended periods of time, such as 3 - 6 months. Such thickening however is not considered to be deleterious to the overall performance of the composition, as it has also been observed that the composition taken on thixotropic characteristics and may be easily rendered flowable by simply agitating the composition, such as by briefly shaking the container containing the composition.

The compositions according to the second aspect of the invention most desirably include no further additional thickener constituents, and such as colloidal thickeners, particularly colloidal aluminium oxides, gums or cellulose based thickeners.

The compositions according to the second aspect of the invention also exhibit excellent synerersis characteristics as exhibiting almost no separation of the constituents, even on long term standing, particularly under the accelerated aging test conditions outlined below. Compositions of the second aspect of the invention are not only viscous, but also exhibit excellent shelf-life both in terms of retardation of alkali metal hypochlorite degradation and single solution phase behavior. The alkali metal hypochlorite degradation has been slowed to render a composition having an alkali metal hypochlorite half-life of at least about 30 days, more preferably at least three months and most preferably at least six months. Hypochlorite degradation may be measured by alkali metal hypochlorite titration over time (which may be accomplished by numerous techniques known to those skilled in the art). Observation of the single solution phase behavior of the composition may be made visually. The high level of stability combined with the high level of viscosity provides for a commercially desirable composition useful as a multi-purpose cleaning composition.

A particularly preferred embodiment of the second aspect of the invention is an aqueous thickened bleach containing compositions having a pH of 12 or greater which comprises, (preferably consists essentially of), in parts by weight (based on the total weight of the composition): a) 0.5 - 5.0 of an alkali metal carboxylate which comprises alkali metal salts of at least

55%wt., preferably at least 75%wt. of C16 and C18 fatty acids, less than 15%wt. of one or more C20, C22 and higher fatty acids, and less than 30%>wt. of one or more C14, C12 and lower fatty acids; b) 0.5 - 4.0 of an alkali metal salt, preferably an alkali metal chloride; c) 0.05 - 5.0 of a water dispersible nonionic amine oxide; d) 0.1 - 8.0 of a water dispersible anionic surfactant system including one or more sulfate or sulfonate surfactants, which system also includes a minor amount of an alkyl diphenyl ether disulfonate surfactant; e) 0.01 - 10.0 of available chlorine in a bleach releasing material, such as an alkali metal hypochlorite; f) 0.1 - 10.0 of an pH adjusting agent for maintaining the alkalinity of the composition; g) 1.0 - 50 of an abrasive material, preferably a particulate abrasive material; h) 0.05 - 3.0 of an detergency builder; i) 0 - 5% of one or more optional constituents; and, the balance being water to provide 100 %wt. of the compositions.

Such compositions may be characterized by very favorable viscosity characteristics, good bleach stability over time, and most preferably are substantially free of phosphates, phosphate containing materials, and further substantially free of further thickener components such as colloidal aluminum oxides, gums and cellulose based thickeners. The high viscosity characteristic of the composition makes it particularly well-suited for use as a hard surface cleaner and disinfectant, such as, a bathroom cleaner, a toilet bowl cleaner, a mold and mildew cleaner, a laundry additive, and so on. Additional optional ingredients include suitable hypochlorite-stable colorants, perfumes, perfume blends, and so on, as known to those skilled in the art.

Any number of techniques may be employed to prepare the compositions of the second aspect of the invention, as within the knowledge of one skilled in the art. The compositions according to the invention are desirably produced utilizing a stirrer which ensures that a homogenous composition is produced. One such mixing device includes a conventional variable speed, electrically operated stirrer equipped with a standard mixing propeller. A preferred mixing device is a Cowles blade. Such a Cowles blade desirably includes a surface coating which does not undesirably react with any of the constituents used to form the inventive compositions.

While the order of the addition of the constituents may vary, but preferably the order of addition of the various constituents is as described below with reference to the examples.

An exemplary process for producing the inventive compositions according to the second aspect of the invention is as follows. A first preblend mixture is made by adding about 6-8% of the deionized water at 30-35°C to a clean glass beaker and with moderate stirring, adding in the sodium chloride or other salt (potassium salt) for a sufficient time in order to dissolve the same. A second preblend mixture is made by adding about 6-8%> of the deionized water at 30-35°C to a further clean glass beaker, adding in the sodium metasilicate and providing moderate stirring for a sufficient time in order to dissolve the same. Both the first and the second preblend mixture are allowed to cool to 30°C or less. A primary mixture is formed by adding about 65-85% of the deionized water to a clean glass beaker, which is heated to 75-80°C. Under moderate stirring, and with the maintenance of the temperature at 75-80°C about one-third of the total amount of sodium hydroxide is added until dissolved. Afterwards, the fatty acid carboxylic acid

(HYSTRENE 7018) is added, and mixing continued until full solubilization was attained. It is to be noted that where a fatty acid carboxylate salt is utilized, it is added instead of the sodium hydroxide and the fatty acid carboxylic acid recited immediately above, and stirred until dissolved in the deionized water. Next is added the amine oxide constituent, and again stirring continued until solubilization was reached. Subsequently the secondary alkyl sulfonate was added to the mixture again stirring continued until solubilization was reached. Next the ether sulfate constituent was added, while stirring continued until solubilization was reached. Subsequently the diphenyl disulfonate constituent was added and stirring continued until solubilization was reached. Stirring during the process steps above was at a moderate speed, sufficient to provide good mixing, but not excessive to avoid entrainment of excess air into the mixture. Next, the first preblend mixture was added under moderate stirring conditions to ensure that a uniform mixture was formed. The resulting primary mixture was allowed to cool to 25-30°C.

A third preblend mixture was formed by adding 6-8% of the deionized water at 20- 30°C to a third beaker, and under moderate stirring conditions, the calcium carbonate was uniformly dispersed. To another glass beaker under moderate stirring conditions was added any remaining deionized water, the hypochlorite constituent, the remaining sodium hydroxide (or other, i.e., potassium salt) and the second preblend mixture. The contents of these two glass beakers were then combined, under moderate stirring to ensure homogeneous mixing of the constituents. Thereafter, this third preblend mixture was added to the primary mixture under adequate stirring conditions to ensure the formation of a uniform composition. It is noted that when the third preblend mixture was added to the primary mixture, that a thickening of the stirring primary mixture was observed. This was compensated for by increasing the rotational speed of the mixing blade (either a conventional propeller, a conventional flat bladed blade or a Cowles blade) while this thickening was observed, afterwards slowly decreasing the rotational speed as the apparent viscosity of the primary mixture decreased. Subsequently any optional constituents, such as fragrances, etc. are added and mixing continued under moderate stirring conditions for 10-30 minutes to ensure the formation of a uniformly mixed product. It is to be understood that the various named constituents indicated above may be substituted by or used with other similar constituents identified in this specification.

The invention is further illustrated in the following Examples in which weight percentages are by total weight of the final composition unless otherwise indicated.

Example 1 A thickened abrasive bleach cleaner according to the first aspect of the invention can be made up by mixing sequentially the following components (quantities are expressed in weight percentages) into 50g of de-ionised water: i) 0.8g of carbomer Carbopol 676, which serves to create an opaque mixture of increased viscosity; ii) lg of NaOH, which acts as a pH modifier and as a neutralising agent for the carbomer; iii) 3.5g of myristyl amine oxide, which acts as a secondary thickener, causing the mixture to take on the appearance of an oily emulsion; iv) lg of sodium lauryl ether sulphate, an anionic surfactant that acts as a secondary thickener; v) 27g of 7.5%) sodium hypochlorite solution, which provides 2.025g available chlorine. vi) 0.5g of tetrapotassium pyrophosphate, which acts as a detergency builder and alkali; vii) 0.07g of perfume, which is bleach stable; and viii) 0.5g of sodium silicate.

The mixture is made up to lOOg through the addition of more de-ionised water and thoroughly mixed. It was applied to a visibly soiled enamelised surface and exhibited excellent cleaning performance, as evidenced by the appearance of the surface after the composition was wiped away. Example 2

A thickened bleach composition according to the first aspect of the invention as set out in the table below can be prepared by mixing the tabulated components together analogously as described in example 1.

The product thus obtained had an opaque, creamy appearance and was visibly viscous, although easily pourable. When applied to an enamel surface, it remained coherent. It also exhibited excellent cleaning performance.

Example 3

The following formulation according to the first aspect of the invention was made by mixing together the following constituents: 1. Carboxypolymethylene 0.45g

2. Caustic soda 1. lg

3. Myristyl amine oxide (Empigen OH 25) 3.5g

4. Sodium lauryl ether sulphate (Empicol 0405) 1.0g

5. 7.5%) Sodium hypochlorite solution giving 1.5g available chlorine 20g 6. Phthalocyanine green #7 0.25g

7. Fragrance 0.07g

8. Soft water 73.65g

The finished product had the appearance of a pale green clear liquid gel and a scent typical of the perfume it included but with a faint chlorine odour. The viscosity was determined at 1200cps and the specific gravity was 1.03. The pH was 13.5 and available chlorine 1.5%. The composition exhibited excellent cleaning performance when applied to a ceramic tiled surface. Example 4

An exemplary formulation according to the first aspect of the invention was made by mixing together the following constituents:

1. Soft water 72.98g 2. Carbopol 672 0.8g

3. Sodium hydroxide 1 0g

4. Potassium carbonate 0.5g

5. Amine lauryl oxide (Empigen OB) 3.5g

6. 7.5%) Sodium hypochlorite solution 20g (available chlorine 1.5 g)

7. Sodium Silicate (Silchem 3379) 0.2g

8. Sodium Secondary Alkane sulphonate (Hostapur SAS60) 1.4g

9. Perfume and pigment 0.02g The product obtained was a clear liquid gel and displayed good cleaning performance.

Example 5

The following formulation according to the first aspect of the invention was made by mixing together the following constituents (quantities are expressed in weight % active): 1. Water 79.58g

2. Carboxypolymethylene 0.8g

3. Caustic soda lg

4. Myristyl amine oxide (Empigen OH 25) 1.05g

5. Calcium carbonate 15g 6. Sodium lauryl ether sulphate (Empicol 0405) 0.28g

7. Available chlorine from Active sodium hypochlorite 1.5g

8. Phthalocyanine green 0.25g

9. Fragrance 0.07g

10. Sodium silicate 0.5g The finished product had a light green colour and appeared as an opaque viscous fluid. Its perfumed scent was tinged with a faint chlorine odour.

The viscosity was determined at 1300cps. The pH was 13.06. When applied to a ceramic tiled surface, its grease cleaning efficacy at full strength exceeded that of similar products on the market. Example 6

Certain formulations according to the second aspect of the invention are listed in Table 1, and the order of producing the compositions are described below. The constituents indicated on Table 1, are the respective weights 'as supplied' of the named constituent. The commercial source, and weight percentage of actives in the "as supplied" constituent is indicated on Table 2, following. Where no weight percentage of actives indicated in Table 2, it is presumed that the constituent is comprised of "100%wt." actives.

(1) fatty acid carboxylatel was the sodium salt of a mixture of fatty acids having a distribution of 2.9%wt. C14, 28.6%wt. C16, 63.7%wt. C18, 1.6%wt. C20 fatty acids, 3.2%wt. other fatty acids

(2) fatty acid carboxylate2 was the reaction product of a technical grade mixture of fatty acids having a distribution of 2%wt. C14, 30%wt. C16, 65%wt. C18, and 3%wt. other fatty acids, with a stoichiometric excess of sodium hydroxide in an aqueous medium which formed the sodium salts of the fatty acids

(3) a decyl dimethyl amine oxide was used, BARLOX 10 (Lonza Corp., Fairlawn, NJ) (30%wt. actives)

(4) a sodium lauryl ether sulfate, STANDAPOL ES-1 (28%wt. actives), having an average of 1 ethoxy group per lauryl chain (Henkel Corp., Gulph Mills, PA)

The source of the constituents denoted on Table 1, above is described and detailed in Table

Each of the compositions according to the examples of Table lwere produced generally in accordance with the following protocol:

First, approximately 60% of the total water used to make the formulation was heated to within a few degrees above 80°C and poured into a clean 2 litre beaker. Next, a variable speed, electrically operated stirrer equipped with a coated Cowles blade was placed in the water and stirring was initiated. The speed of blade rotation was set at a slow speed (approx. 150 - 200 rpm). Next the sodium stearate was slowly added in a dropwise or slow stream manner such that undue aeration /foam formation and partial solubilization was minimized. The temperature was maintained at about 75 - 80 °C during and after the addition of the stearate, and stirring continued until the sodium stearate completely dissolved.

Thereafter, the lauryl dimethyl amine oxide was added by slowly pouring it into the beaker. Stirring continued at the same speed as before, and continued until the solution was homogeneous. Next, each of the anionic surfactant constituents were added individually, pausing between each addition for sufficient time such that the mixture became homogenous. Generally subsequent to the addition of the anionic surfactants the mixture appeared to be translucent or opaque.

The remaining volume of water was dispensed into a separate small beaker. To the beaker, the sodium chloride was added and mixed using a further electrically operated stirrer until the sodium chloride was fully dissolved. Thereafter this solution was slowly poured into the two litre beaker and the mixing continued until a homogenous mixture was once again formed. It was observed that due to this addition, thickening of the mixture occurs and an increase in the rotational speed of the Cowles blade may be made in order to maintain the initial agitational requirement. While stirring continued, the contents of the beaker were allowed to cool to within a few degrees below 30°C. During this cooling process care should was taken to monitor and if necessary adjustments were made to the rotational speed of the Cowles blade such that the breakup of the filamentous network formed during the cooling process was avoided.

In a further clean beaker, the sodium hypochlorite, sodium hydroxide and sodium metasilicate are mixed to homogeneity. After the contents of the 2 liter beaker were sufficiently cooled as above the mixture of the sodium hypochlorite, sodium hydroxide and sodium metasilicate were added thereto while stirring continuted. At this point, a further thickening of the mixture was observed and again, if necessary the rotational speed of the Cowles blade was adjusted to avoid the breakup of the filamentious network formed. At the same time, care was taken to maintain the temperature of the composition to avoid crystallization of the anionic soap, and its precipitation from the mixture. Stirring of the mixture was maintained to ensure homogeneity thereof, typically for a period of approximately 20 mintutes. Thereafter, the abrasive material was slowly added to the mixture and the speed of the Cowles blade was increased by approximately 75 - 100%, and thereafter was returned to the prior rotational speed which had been set just prior to the addition of the abrasive material. The mixture was stirred to homogeneity, after which the stirrer was deactivated and removed. The resulting compositions were thickened mixtures which were homogenous in appearance, and smooth in texture. Evaluation of Chlorine Stability:

Certain of the exemplary compositions of Table lwere evaluated for chlorine stability under accelerated aging conditions over a period of weeks. In the test, the initial available chlorine content was determined by %C12 by the sodium thiosulfate method, and again determined at periodic intervals over the duration of the test. The samples of the compositions were maintained at elevated temperatures of 40C for a ten week period, and testing was performed at weekly intervals. The following Table 3 lists the average available chlorine readin s over the duration of the test.

As may be seen from the results of Table 3, the compositions exhibited excellent retention of available chlorine over the duration of the accelerated aging test.

It was observed that during the harsh conditions of the accelerated aging test, the composition according to Example 1 exhibited no synerersis until the fifth week of the test. At the tenth week of the test, the observed syneresis was minor, being only 8/200 mm.

The accelerated aging test was also performed for Examples 1, 2 and 3 of Table 1 and these samples also exhibited no syneresis until the fifth week of the test.

Claims

1. An aqueous cleaning composition comprising, a) a carbomer or an alkali metal carboxylate (hereinafter component a); b) at least one compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, sodium tripolyphosphates, pyrophosphates, bicarbonates, sesquicarbonates, alkali metal salts and mixtures thereof (hereinafter component b); c) a first surfactant selected from nonionic and zwitterionic surfactants and mixtures thereof (hereinafter component c); d) a second surfactant selected from anionic surfactants (hereinafter component d); e) a compound which is selected from an alkali metal and alkaline earth metal hypochlorite.

2. An aqueous thickened bleach composition comprising (in parts by weight based on the total weight of the composition): a) 0.5 - 5.0%) of an alkali metal carboxylate; b) 0.5 - 4.0%) of an alkali metal salt, preferably an alkali metal chloride; c) 0.25 - 6.0 %> of a water dispersible nonionic amine oxide; d) 0.5 - 8.0% of a water dispersible anionic surfactant system including one or more sulfate or sulfonate surfactants; e) 0.01 - 10.0%) of a bleach releasing material, such as an alkali metal hypochlorite; f) 0. 1 - 10.0%) of an pH adjusting agent for maintaining the alkalinity of the composition; g) 1.0 - 50%) of an abrasive material, preferably a particulate abrasive material; h) optionally, 0.05 - 3.0% of an detergency builder, and the balance to 100%> being water.

3. A composition according to Claim 1 or Claim 2 comprising in parts by weight (based on the total weight of the composition): a) 0.5 - 5.0%) of an alkali metal carboxylate; b) 0.5 - 4.0 of an alkali metal salt, preferably an alkali metal chloride c) 0.4 - 6.0% of a water dispersible nonionic amine oxide; d) 0.5 - 8.0 of a water dispersible anionic surfactant system including one or more sulfate or sulfonate surfactants; e) 0.01 - 10.0 of a bleach releasing material, such as an alkali metal hypochlorite; f) 0.1 - 10.0 of an pH adjusting agent for maintaining the alkalinity of the composition; g) 1.0 - 50 of an abrasive material, preferably a particulate abrasive material; h) optionally, 0.05 - 3.0 of an detergency builder, and, the balance being water.

4. The compositions according to Claim 2 or Claim 3 in which a) the alkali metal carboxylate is an alkali metal carboxylate which comprises alkali metal salts of at least 55%>wt, preferably at least 75%wt. of C16 and C18 fatty acids, less than 15%>wt. of one or more C20, C22 and higher fatty acids, and less than 30%wt. of one or more C14, C12 and lower fatty acids and d) the water dispersible anionic surfactant system further includes a diphenyl disulfonate surfactant;

5. A thickened aqueous bleach containing composition according to any one of Claims 2 to 4, having a pH of 12 or greater which comprises (in parts by weight based on the total weight of the composition): a) 0.5 - 5.0 of one or more essentially completely saturated alkali metal carboxylates which comprise alkali metal salts of at least 55%wt, preferably at least 75%>wt. of C16 and C18 fatty acids, less than 15%wt. of one or more C20, C22 and higher fatty acids, and less than 30%wt. of one or more C14, C12 and lower fatty acids; b) 0.5 - 4.0 of an alkali metal salt, preferably an alkali metal chloride; c) 0.05 - 5.0 of a water dispersible nonionic amine oxide; d) 0.1 - 8.0 of a water dispersible anionic surfactant system including one or more sulfate or sulfonate surfactants, which system also includes a minor amount of an alkyl diphenyl ether disulfonate surfactant; e) 0.01 - 10.0 of available chlorine in a bleach releasing material, such as an alkali metal hypochlorite; f) 0.1 - 10.0 of an pH adjusting agent for maintaining the alkalinity of the composition; g) 1.0 - 50 of an abrasive material, preferably a particulate abrasive material; h) 0.05 - 3.0 of an detergency builder; i) 0 - 5% of one or more optional constituents; and, the balance being water to provide 100 %>wt. ; the compositions preferably being substantially free of phosphates, phosphate containing materials, and preferably further substantially free of further thickener components such as colloidal aluminum oxides, gums and cellulose based thickeners.

6. A thickened aqueous bleach composition according to any one of Claims 1 or 6 having a pH of 12 or greater which consists essentially of, in parts by weight (based on the total weight of the composition): a) 0.5 - 5.0 of one or more essentially completely saturated alkali metal carboxylates which comprise alkali metal salts of at least 55%>wt, preferably at least 75%_>wt. of C16 and C18 fatty acids, less than 15%wt. of one or more C20, C22 and higher fatty acids, and less than 30%wt. of one or more C14, C12 and lower fatty acids; b) 0.5 - 4.0 of an alkali metal salt, preferably an alkali metal chloride; c) 0.05 - 5.0 of a water dispersible nonionic amine oxide; d) 0.1 - 8.0 of a water dispersible anionic surfactant system including one or more sulfate or sulfonate surfactants, which system also includes a minor amount of an alkyl diphenyl ether disulfonate surfactant; e) 0.01 - 10.0 of available chlorine in a bleach releasing material, such as an alkali metal hypochlorite; f) 0.1 - 10.0 of an pH adjusting agent for maintaining the alkalinity of the composition; g) 1.0 - 50 of an abrasive material, preferably a particulate abrasive material; h) 0.05 - 3.0 of an detergency builder; i) 0 - 5%> of one or more optional constituents; and, the balance being water to provide 100 %wt. of the compositions; the compositions preferably being substantially free of phosphates, phosphate containing materials, and preferably further substantially free of further thickener components such as colloidal aluminum oxides, gums and cellulose based thickeners.

7. A process for the production of forming a thickened aqueous bleach containing composition according to any one of Claims 2 to 6, characterized by the process step of: forming the one or more essentially completely saturated alkali metal carboxylates in situ by adding a stochiometric excess of an alkali metal hydroxide with a mixture of fatty acids which comprises at least 55%wt., preferably at least 75%. wt. of C16 and C18 fatty acids, less than 15%>wt. of one or more C20, C22 and higher fatty acids, and less than 30%>wt. of one or more C14, C12 and lower fatty acids.

8. A pourable aqueous cleaning composition comprising : a) a carbomer; b) at least one compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, sodium tripolyphosphates, pyrophosphates, bicarbonates, sesquicarbonates and mixtures thereof; c) a first surfactant selected from nonionic and zwitterionic surfactants and mixtures thereof; d) a second, anionic surfactant; and e) a compound selected from alkali metal and alkaline earth metal hypochlorites.

9. A composition according to Claim 8, wherein the carbomer is a polycarboxylate polymer.

10. A composition according to Claim 9, wherein the carbomer is a carboxyvinyl polymer.

1 1. A composition according to any one of the Claims 8 to 10, in which the ratio of the first surfactant to carbomer is desirably in the range 1 to 8 by weight.

12. A composition according to any one of the preceding claims, wherein the anionic surfactant is selected from a secondary alkane sulphonate (preferably the secondary alkane sulphonate is a compound of the formula

R_j PL, CHSO₃- M⁺ in which

R_j is a C_{8 22} alkyl or C_8.22 alkenyl, R--, is selected from C_{1 6} alkyl groups and M⁺ is a monovalent cation; or a surfactant selected from alkali or alkaline earth metal C_{5 22} alkyl sulphates and alkali or alkaline earth metal C_{5 22} alkyl ether sulphates and whereby the composition optionally includes a particulate abrasive.

13. A composition according to any one of the Claims 8 to 12, wherein the carbomer is present in an amount of 0.5 to 5%> by weight of the composition.

14. A method of cleaning a hard surface requiring such cleaning includes the step of applying a pourable aqueous cleaning composition comprising: a) a carbomer; b) at least one compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, sodium tripolyphosphates, pyrophosphates, bicarbonates, sesquicarbonates and mixtures thereof; c) a first surfactant selected from nonionic and zwitterionic surfactants and mixtures thereof; d) a second, anionic surfactant; and e) a chlorine releasing bleaching agent in an amount effective for providing cleaning treatment to such surface.

15. A method according to claim 14 including the further step of removing the applied composition from the surface, having allowed time for effective treatment to take place.