Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/044—Hydroxides or bases
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
  • C11D3/3956—Liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/04—Carboxylic acids or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/143—Sulfonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides

Definitions

• 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.
• 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.
• component a a carbomer or an alkali metal carboxylate
• component b at least one compound selected from alkali metal hydroxides, alkaline earth metal hydroxides, sodium tripolyphosphates, pyrophosphates, bicarbonates
• 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.
• 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.
• the second anionic surfactant is a secondary alkane sulphonate.
• the secondary alkane sulphonate is a compound of the formula
• 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 C 522 alkyl ether sulphates.
• 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 CaCO 3 and MgCO 3 .
• composition may include one or more components selected from colourants and fragrances and combinations thereof.
• 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.
• 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%.
• 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%.
• 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.”
• 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%.
• 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.
• 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.
• optional substances such as fragrances and colourants, may be present in an amount from 0% to 2% by weight.
• 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.
• 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;
• 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%.
• 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.
• 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%.
• 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.
• component c) - the first surfactant - may be an amine oxide and, in particular, a C 10 to C 18 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.
• 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.
• R j R.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 C 12 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.
• 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 j O is in the range 3.35 to 3.25.
• Excess sodium hydroxide may be provided according to the component b, chosen.
• compositions may include other materials of a non-essential nature. 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 (MgCO 3 ), calcite (CaCO 3 ), 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 cm 3 and preferably from 2.4 to 6 g
• 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.
• compositions may be by means that are conventional in the art. Agitation may be used advantageously.
• 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.
• the composition 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.
• a second aspect according to the invention relates to improved thickened aqueous bleach containing compositions which contain abrasives.
• 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.
• 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
• 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).
• 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.
• 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.
• 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.
• 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.
• 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.
• alkali metal carboxylates are provides a technical grade mixtures which include various proportions of different alkyl chains within the such a mixture.
• 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.
• alkali metal carboxylates which have a significant preponderance of C20, C22 and higher fatty acids lead to excessive thickening of the compositions.
• alkali metal carboxylates which have a significant preponderance of more C14, C12 and lower fatty acids leads to excessive viscosity loss of the compositions.
• many prior art fatty acid carboxylates known to the art are not necessarily suitable in the present inventive compositions.
• 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.
• 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.
• 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.
• 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.
• an appropriate material such as a caustic, i.e., an alkali metal hydroxide such as sodium hydroxide
• 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.
• 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.
• 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:
• 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;
• 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;
• 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.
• 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
• each Rl independently is a straight chained C1-C4 alkyl group, preferably both Rl are methyl groups;
• 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.
• 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.
• 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.
• 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:
• 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:
• 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.
• HOSTAPUR SAS from H ⁇ chst 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:
• 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.
• 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.
• 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:
• 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 are unsubstituted C6-C12 straight chained alpha olefins, or is tetrapropylene.
• 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.
• 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.
• 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
• 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.
• the alkali metal salt is preferably present in amount of 1 0 - 3 0%wt , more preferably from 1.5 - 2 5%wt, and bones preferably about 2 0%wt based on the total weight of the composition
• an alkali metal hydroxide is the preferably used as the pH adjusting agent for maintaining the alkalinity of compositions according to the second aspect of the invention. 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
• a detergency builder constituent examples include known detergency builders of which are compatible in the bleach containing composition according to the invention
• 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 t ⁇ polyphosphate, 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
• organic builder salts 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.
• 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.
• these organic builder salts are omitted as they frequently undesirably react with the bleach in the inventive compositions.
• 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
• hypochlorites such as alkali metal hypochlorites
• 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.
• 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.
• further materials particularly alkali metal salts (alkali metal chlorides) which further materials are among the required constituents according to the invention.
• alkali metal salts alkali metal chlorides
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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
• 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.
• compositions according to the invention are desirably produced utilizing a stirrer which ensures that a homogenous composition is produced.
• 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.
• 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
• 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.
• 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
• Example 2 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 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.
• 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.
• 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.
• compositions 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.
• 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
• compositions according to the examples of Table l were produced generally in accordance with the following protocol:
• 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.
• 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 sodium hypochlorite, sodium hydroxide and sodium metasilicate are mixed to homogeneity.
• the mixture of the sodium hypochlorite, sodium hydroxide and sodium metasilicate were added thereto while stirring continued. 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.
• compositions of Table l were evaluated for chlorine stability under accelerated aging conditions over a period of weeks.
• 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.
• Table 3 lists the average available chlorine readin s over the duration of the test.
• compositions exhibited excellent retention of available chlorine over the duration of the accelerated aging test.
• Example 1 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.

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