WO2023025739A1 - Detergent composition - Google Patents

Detergent composition Download PDF

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Publication number
WO2023025739A1
WO2023025739A1 PCT/EP2022/073365 EP2022073365W WO2023025739A1 WO 2023025739 A1 WO2023025739 A1 WO 2023025739A1 EP 2022073365 W EP2022073365 W EP 2022073365W WO 2023025739 A1 WO2023025739 A1 WO 2023025739A1
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WIPO (PCT)
Prior art keywords
radical
alkyl
surfactant
amino
foam
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PCT/EP2022/073365
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French (fr)
Inventor
Panchanan BHUNIA
Narayanan Subrahmaniam
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Unilever Ip Holdings B.V.
Unilever Global Ip Limited
Conopco, Inc., D/B/A Unilever
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Publication of WO2023025739A1 publication Critical patent/WO2023025739A1/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742Nitrogen containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention relates to a laundry cleaning composition; in particular, a solid laundry detergent composition having a desirable foam profile during the laundering process.
  • Synthetic detergents are widely used for laundering fabrics, due to their efficiency in cleaning and stain removal.
  • formulated laundry detergent composition includes various additives to provide improved cleaning and sensorial benefits. Proper foam level is a sensorial benefit which most consumers desire during the laundering process.
  • Foaming or sudsing is an important factor to consider when formulating a detergent composition. Foam is a significant consumer cue and acts as the primary reason by which a consumer perceives that a composition is having a cleaning effect.
  • GB1169496 A (Unilever, 1969) discloses a detergent composition having controlled sudsing properties.
  • the composition includes an anionic synthetic detergent, a nonionic synthetic detergent and/or a soap and an alkyl ether carboxylic acid.
  • US5877140 (Hardy et al., 1999) discloses a detergent composition which includes LAS, soap and an anionic compound to provide the dual performance benefits of excellent cleaning performance and suds suppression.
  • GB1305540 A (Kao, 1973) discloses a foam controlled detergent composition having one or more anionic surface-active agents and specific fatty acid salt.
  • WO 95/02665 A1 discloses a granular detergent composition having a surfactant and an antifoaming component.
  • WO 95/00117 A1 discloses a liquid detergent composition having a branched anionic surfactant.
  • WO 2018/095695 A1 (Unilever) liquid detergent composition having an ethoxylated alkyl ether sulphate, a surfactant selected from alkylbenzene sulfonate, alkyl sulphate or combinations thereof and a fatty acid ester.
  • rinse triggered antifoams which act on the foam and suppresses it at the rinse stage.
  • rinse triggered antifoam adds to the amount of chemicals incorporated in the composition and such compositions must be formulated carefully to avoid the antifoam being released during cleaning stage.
  • rinse triggered antifoams are generally expensive and provide no other performance benefit to the composition other than foam suppression. Therefore, it is desirable that their presence is minimised.
  • This benefit was preferably found across different consumer washing habits and fabric types present in the wash load. It was further preferably found that the detergent composition according to the first aspect of the present invention provides for removing the foam in a single rinse cycle.
  • composition shows good foaming during the main wash and quick foam removal during the rinse stage; thus, the composition provides good sensorial and the advantage of lower water consumption. This benefit is seen even when the wash liquor includes cold water or water at room temperature.
  • the present inventors have surprisingly found that the combination of the specific primary anionic surfactant and the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 provides the solid detergent composition with quick foaming in the wash liquor even in presence of the specific foam suppressing agent and the quick removal of the foam in the rinse liquor.
  • a solid laundry detergent composition comprising: i) a primary anionic detersive surfactant selected from the group consisting of sulphate surfactant, sulphonate surfactant, linear alkyl ether sulphate surfactant or mixtures thereof; ii) a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10; and, iii) a foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof;
  • a second aspect of the present invention disclosed is method of treating a textile surface with the detergent composition according to the first aspect comprising the steps of: i) preparing a wash liquor with an effective amount of foam by contacting the detergent composition according to the first aspect with a liquid; ii) soaking said textile surface in the wash liquor for a predetermined period of time; and, iii) rinsing the textile surface, wherein the number of rinses required for the removal of foam present in the rinse liquor is less than 3 rinses.
  • a primary anionic detersive surfactant selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof and a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 in a detergent composition to provide fast lather generation in the wash liquor during the main wash stage and rapid collapse of lather during rinse stage.
  • fabric As used herein, the terms “fabric”, “textile”, and “cloth” are used non-specifically and may refer to any type of flexible material consisting of a network of natural or artificial fibers, including natural, artificial, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, including blends of various fabrics or fibers.
  • foaming profile refers to the properties of foam character in washing and rinsing solutions formed with a detergent composition.
  • the foaming profile of a detergent composition includes but is not limited to the speed of foam generation upon dissolving the detergent composition, the volume and retention of foam in the washing cycle and the ease of rinsing the foam away in the rinsing cycle.
  • the solid detergent composition according to the first aspect of the present invention includes a primary anionic detersive surfactant, a foam suppressing agent and a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10.
  • the solid detergent composition according to the first aspect of the present invention includes a primary anionic detersive surfactant selected from the group consisting of sulphonate surfactant, sulphate surfactant, linear alkyl ether sulphate surfactant or mixtures thereof.
  • Suitable sulphonate surfactant includes methyl ester sulphonates, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates.
  • the alkyl chain in the alkyl benzene sulphonate is straight or branched, more preferably linear.
  • the alkyl benzene sulphonate is preferably in the salt form with the cation selected from alkali metal, alkaline earth metal or alkanolamine.
  • alkali metal selected from sodium or potassium, most preferably sodium.
  • Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, other suitable LAB includes high 2- phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
  • the sulphonate surfactant may also be selected from the modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefin sulfonate (AOS).
  • MLAS modified alkylbenzene sulfonate
  • MES methyl ester sulfonate
  • AOS alpha-olefin sulfonate
  • Suitable sulphate surfactant includes alkyl sulphate surfactant, preferably Cs to C22 preferably Cs to Cis alkyl sulphate, or predominantly C12 alkyl sulphate.
  • Conventional primary alkyl sulphate surfactants have the general formula: R"OSOs'M + wherein R" is typically a Cs to C20 alkyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation.
  • R" is a C10 to C18 alkyl group, preferably C10 to C15 alkyl group, and M is alkali metal, more specifically R" is C12 to C14 alkyl and M is sodium.
  • anionic alkyl sulphate surfactant useful herein include: C10 to C20 primary, branched-chain and random alkyl sulfates (AS), C10 to C18 secondary (2, 3)-alkyl sulfates having following formulae: wherein M is hydrogen or a cation which provides charge neutrality, and all M units, can either be a hydrogen atom or a cation depending upon the form or the relative pH of the system where the surfactant is used, with non-limiting examples of preferred cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9.
  • Primary anionic detersive surfactant may be an alkyl ether sulphate surfactant.
  • the alkyl ether sulphate surfactant may be branched or linear. Preferably it is linear.
  • the alkyl ether sulphate is a Cs to Cis alkyl ether sulphate.
  • the alkyl ether sulphate surfactant has an average degree of ethoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl ether sulphate is a Cs to Cis alkyl ether sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3 and most preferably from 0.5 to 1 .5.
  • the alkyl ether sulphate surfactant is a linear Cs to Cis alkyl ether sulphate having an average degree of ethoxylation of from 0.5 to 7, more preferably 1 to 3.
  • the alkyl ether sulphate surfactant will inevitably also contain some non- alkoxylated alkyl sulfate materials, which may constitute as much as 20 wt.% of the alkyl ether sulphate surfactant.
  • the alkyl ether surfactant may also include the midchain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303.
  • Primary anionic detersive surfactant according to the present invention are preferably a non-soap anionic surfactant.
  • the term “soap” is used herein in its popular sense, i.e. , the alkali metal of aliphatic, alkanes, or alkene monocarboxylic acids.
  • the anionic surfactant includes 0 wt.% to 10 wt.% alkyl sulfate surfactant, preferably 0.2 wt.% to 5 wt.% alkyl sulfate surfactant, preferably the alkyl sulfate surfactant is a primary alkyl sulphate surfactant (PAS).
  • PAS primary alkyl sulphate surfactant
  • the anionic surfactant may also preferably include from 0 wt.% to 10 wt.% MES, more preferably 0 wt.% to 5 wt.% MES.
  • the anionic surfactant may include a linear alkyl ether sulphate surfactant, preferably a linear alkyl ether sulphate surfactant with 1 to 7EO group, still preferably a sodium lauryl ether sulphate with 1 to 7 EO, still preferably SLES 1 to 3 EO, preferably included in the composition in an amount from 0 wt.% to 10 wt.%, preferably 0 wt.% to 5 wt.% SLES with 1 to 7 EO.
  • the detergent composition of the present invention includes from 3 wt.% to 50 wt.% of primary anionic detersive surfactant selected from sulphate surfactant, sulphonate surfactant, alkyl ether sulphate surfactant or mixtures thereof.
  • the detergent composition comprises at least 4 wt.%, still preferably at least 5 wt.%, still preferably at least 10 wt.%, most preferably at least 15 wt.% of the anionic surfactant, but typically not more than 45 wt.%, still preferably not more than 40 wt.%, still further preferably not more than 35 wt.%, still more preferably not more than 30 wt.% and most preferably not more than 25 wt.%, still more preferably not more than 20 wt.% of a primary anionic detersive surfactant based on the weight of the detergent composition.
  • the detergent composition according to the first aspect of the present invention preferably includes low levels of the primary anionic detersive surfactant.
  • the primary anionic detersive surfactant is present in an amount ranging from 2 wt.% to 20 wt.%, still preferably from 2 wt.% to 15 wt.%.
  • the present inventors have found that even when the primary anionic detersive surfactant is present at these low levels the detergent composition having a combination of the primary anionic detersive surfactant along with the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 and the foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof provides good foam profile in the initial main wash stage and quick reduction in the foam in the rinse stage while maintain good cleaning performance.
  • the primary anionic detersive surfactant is an alkali metal salt of C to Cis alkyl benzene sulfonic acid.
  • the ratio of the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 to the primary anionic detersive surfactant is in a ratio from 1 :1 to 1 :200, preferably 1:1 to 1 :160, still preferably from 1 :1 to 1:100, still preferably the ratio from 1:5 to 1 :200, further preferably the ratio is from 1 :5 to 1:160, still more preferably from 1 :5 to 1:100, still preferably 1:5 to 1 :80, more preferably 1:5 to 1 :50.
  • the total amount of primary anionic surfactant is greater than the branched Cs to C14 alkyl alkoxylated sulphated co- surfactant present in the composition.
  • solid laundry detergent composition includes a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant.
  • the solid detergent composition according to the present invention comprises from 0.05 wt.% to 5 wt.% branched Cs to C14 alkyl alkoxylated sulphated cosurfactant.
  • the solid detergent composition comprises at least 0.8 wt.%, preferably at least 0.1 wt.%, still preferably at least 0.15 wt.% still more preferably 0.25 wt.% and most preferably at least 0.5 wt.%, but typically not more than 4 w.t%, still preferably not more than 3 wt.%, still further preferably not more than 2 wt.% and most preferably not more than 1 wt.%.
  • the cosurfactant is a branched alkyl alkoxylated sulphate surfactant.
  • the alkyl group is preferably a Cs to C14, preferably Cs to Cw still preferably Cw branched alkyl alkoxylated sulphate surfactant.
  • the branched alkyl alkoxylated sulphate surfactant is preferably ethoxylated.
  • the number average degree of ethoxylation is from 2.5 to 10, still preferably 2.5 to 8, further preferably from 2.5 to 6, more preferably 3 to 6, still preferably from 3.5 to 4.5.
  • the branched alkyl alkoxylated sulphate surfactant is selected from the group consisting of C branched ethoxylated sulphate surfactant with a number average degree of ethoxylation of 3, 4 or 5. Also preferred is that the branched alkyl alkoxylated sulphate surfactant is a mixture of different Cw branched ethoxylated sulphate surfactant selected from the group consisting of an average degree of ethoxylation of 3, 4 and 5. More preferably the average degree of ethoxylation is 4 or 5, most preferably 4.
  • degree of ethoxylation refers to the number of moles of ethylene oxide reacted with one mole of the Cw branched alcohol to produce the non-ionic ethoxylated Cw branched alcohol surfactant. It should be recognized that a distribution of ethoxylated reaction products is normally obtained during ethoxylation of, for example, alcohols.
  • the branched alkyl alkoxylated sulphate surfactant may include some amount of the non-sulphated branched alkyl alkoxylated surfactant, however the amount of such nonsulphated surfactant is not more than 20 wt.%, still preferably not more than 15 wt.%, further preferably not more than 10 wt.% or may preferably be lower than 10 wt.%.
  • branched alkyl alkoxylated sulphate surfactant of the present invention are typically used in their neutralized form, for example as alkali metal salts.
  • the ratio of the branched alkyl alkoxylated sulphate cosurfactant to the primary anionic detersive surfactant in the composition is in a ratio from 1 :1 to 1 :200, still preferably the ratio is from 1 :1 to 1:160, still preferably from 1 :1 to 1 :100, more preferably 1:5 to 1 :80.
  • the solid laundry detergent composition according to the present invention comprises from 0.05 wt.% to 5 wt.% branched alkyl alkoxylated sulphate surfactant cosurfactant.
  • the solid detergent composition comprises at least 0.25 wt.%, preferably at least 0.3 wt.%, still preferably at least 0.4 wt.% and most preferably at least 0.5 wt.%, but typically not more than 4 w.t%, still preferably not more than 3 wt.%, still further preferably not more than 2 wt.% and most preferably not more than 1 wt.%.
  • the solid laundry detergent composition according to the first aspect of the present invention may include one or more additional cosurfactant.
  • the additional cosurfactant is selected from the group consisting of alkyl ether carboxylic acid surfactant, amino acid-based surfactant, amide surfactant, or mixtures thereof.
  • the additional cosurfactant is preferably an alkyl ether carboxylic acid cosurfactant or salts thereof.
  • the alkyl ether carboxylic acid surfactant has a general formula (I)
  • Ri is selected from saturated or mono-unsaturated, linear or branched, Cs to C14 alkyl or alkenyl chain; n has a value in the range from 1 to 20; and,
  • X represent H or a suitable cation selected from the group consisting of alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or mixtures thereof.
  • alkali metal is sodium.
  • Ri is either saturated or mono-unsaturated.
  • the mono-unsaturated alkyl group may contain a cis or trans double bond.
  • Ri may be linear or branched, more preferably linear.
  • Ri is selected from Cs to C14 alkyl or alkenyl group.
  • Preferably Ri is a Cs to C14 alkyl chain. Still preferably a Cs to C14 linear alkyl chain.
  • the n has a value in the range from 2 to 20, more preferably the average degree of ethoxylation is from 2 to 10.
  • Alkyl ether carboxylates are well known products in the art. They are usually obtained from the alkoxylation and subsequent carboxymethylation of fatty alcohols as described by Meijer and Smid in Polyether Carboxylates; Anionic Surfactants; Surfactant Science Series, Vol. 56 (p. 313-361), published by Helmut W. Stache, ISBN: 0-8247-9394-3.
  • the alkyl ether carboxylic acid/carboxylate (AEC) is usually derived from a fatty alcohol which is alkoxylated, usually with ethylene glycol and/or propylene glycol, a carboxylic acid is then introduced to the material to form the alkyl ether carboxylic acid.
  • Suitable examples of commercially available alkyl ether carboxylic acid surfactant include those marketed under the trade name AKYPO® by Kao Chemicals GmbH, Empicol® by Huntsman and Emulsogen® by Clariant.
  • the sodium salt of the alkyl ether carboxylic acid surfactant is most preferred.
  • a preferred salt is sodium.
  • suitable materials are oleyl alkyl ether (8EO) carboxylic acid, oleyl alkyl ether (10EO) carboxylic acid or laureth-5 carboxylic acid (5EO), and the sodium salts thereof.
  • the ratio of the alkyl ether carboxylic acid cosurfactant to the main anionic detersive surfactant in the composition is in a ratio from 1 :1 to 1 :200, still preferably the ratio is from 1 :1 to 1 :160, still preferably from 1 :1 to 1 :100, more preferably 1 :5 to 1 :80.
  • the amount of the alkyl ether carboxylic acid cosurfactant in the composition is preferably from 0.05 wt.% to 5 wt.%, still preferably from 0.25 wt.% to 5 wt.% most preferably 0.5 wt.% to 1 wt.%.
  • the additional cosurfactant is preferably an amino acid-based surfactant.
  • the aminoacid based surfactant is an anionic N-acyl amino acid surfactant.
  • the amino acidbased surfactant has a general formula (II) Formula II wherein,
  • R is selected from saturated or unsaturated C10 to C14 alkyl group
  • R1 is selected from H, Ci to C4 alkyl,
  • R2 is selected from H or all groups on a carbon of natural amino acids
  • R3 is selected from COOX, CH2 SO3X, where X is a suitable cation selected from the group consisting of alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or mixtures thereof more preferably selected from NH 4 + , Li + , Na + or K + .
  • the amino acid-based surfactant is a sarcosinate surfactant.
  • the amino acid based anionic surfactant can be a sarcosinate, for instance an acyl sarcosinate.
  • Nonlimiting examples of sarcosinates can be selected from the group consisting of sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, TEA- cocoyl sarcosinate, ammonium cocoyl sarcosinate, ammonium lauroyl sarcosinate, lauroylsarcosinate, disodium lauroamphodiacetate lauroyl sarcosinate, isopropyl lauroyl sarcosinate, potassium cocoyl sarcosinate, potassium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl
  • the amino acid-based surfactant is a taurate surfactant, for instance an acyl taurate.
  • the amino acid-based surfactant is a glycinate surfactant, for instance an acyl glycinate.
  • the taurate surfactant is a sodium methyl cocoyl taurate, sodium cocoyl taurate.
  • the glycinate surfactant is a sodium methyl cocoyl glycinate, sodium cocoyl glycinate.
  • the amino acid based anionic surfactant may be based on glutamate, for instance an acyl glutamate.
  • acyl glutamates can be selected from the group consisting of sodium cocoyl glutamate, disodium cocoyl glutamate, ammonium cocoyl glutamate, diammonium cocoyl glutamate, sodium lauroyl glutamate, disodium lauroyl glutamate, sodium cocoyl hydrolyzed wheat protein glutamate, disodium cocoyl hydrolyzed wheat protein glutamate, potassium cocoyl glutamate, dipotassium cocoyl glutamate, potassium lauroyl glutamate, dipotassium lauroyl glutamate, potassium cocoyl hydrolyzed wheat protein glutamate, dipotassium cocoyl hydrolyzed wheat protein glutamate, sodium capryloyl glutamate, disodium capryloyl glutamate, potassium capryloyl glutamate, dipotassium capryloyl glutamate, dipotassi
  • the amino acid based anionic surfactant can be an alaninate, for instance an acyl alaninate.
  • acyl alaninates can include sodium cocoyl alaninate, sodium lauroyl alaninate, and combination thereof. More preferably the acyl alaninates include sodium cocoyl alaninate, sodium lauroyl alaninate and combination thereof.
  • the amount of the amino acid-based surfactant in the composition is preferably from 0.2 wt.% to 5 wt.% most preferably 0.5 wt.% to 1 wt.%.
  • the ratio of the alkyl ether carboxylic acid surfactant to the main anionic detersive surfactant in the composition is in a ratio from 1 :1 to 1:200, still preferably the ratio is from 1 :1 to 1:160, still preferably from 1 :1 to 1 :100, more preferably 1:5 to 1 :80.
  • the amount of the alkyl ether carboxylic acid surfactant in the composition is preferably from 0.05 wt.% to 5 wt.%, still preferably from 0.25 wt.% to 5 wt.% most preferably 0.5 wt.% to 1 wt.%.
  • modified sarcosinates described in U.S Patent No. 5520820 (Castillo, et al.)
  • the modified sarcosinate have the formula (III):
  • R 1 is from C4 to C27 saturated or unsaturated hydrocarbon
  • M is H or a suitable cation selected from the group consisting of alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or mixtures thereof.
  • the alkali metal is sodium
  • n is an integer selected from 1 to 3.
  • Modified sarcosinates include those sold under the Hamposyl® tradename, such as lauroyl sacrosine (Hamposyl L).
  • the detergent composition according to the first aspect of the present invention has a primary anionic detersive surfactant and a cosurfactant and preferably the dynamic surface tension of an aqueous solution of the primary anionic detersive surfactant is lowered by at least 2 mN/m upon addition of the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant to the aqueous solution.
  • the dynamic surface tension is preferably lowered by at least 5 mN/m, still preferably at least 10 mN/m.
  • the dynamic surface tension is measured using maximum bubble pressure tensiometer BP 100.
  • the dynamic surface tension is measured at 100 milliseconds.
  • the water used for preparing the aqueous solution has a water hardness of 24°FH (Ca 2+ :Mg 2+ of 2:1).
  • the dynamic surface tension is preferably measured at a temperature of 21 °C to 22°C.
  • the ratio of the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant and the primary anionic detersive surfactant in the aqueous solution is preferably from 1 :1 to 1 :200.
  • the total concentration of the primary anionic detersive surfactant and the branched Cs to C14 alkyl alkoxylated sulphated co-surfactant in the aqueous solution when measuring the dynamic surface tension preferably ranges from 0.02 wt.% to 1.5 wt.%.
  • Dynamic surface tension (DST) is generally used to measure the capability of one solution to lower surface tension and wet substrate under high-speed process conditions. The present inventors have found that the addition of the cosurfactant into the solution of primary anionic surfactant lowers the dynamic surface tension, the combination of the primary anionic surfactant and the cosurfactant together exhibit a dynamic surface tension which is lower than the dynamic surface tension of an aqueous solution having only primary anionic surfactant.
  • composition includes a foam supressing agent.
  • the foam suppressing agent is selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof.
  • foam suppressing agent used herein should be understood to include both the terms antifoaming agent and defoaming agent.
  • the term “suppressing foam” should be understood as including both antifoaming and defoaming.
  • Antifoaming is the prevention of foam in whole or in part. Defoaming is the diminishing or eliminating an already existing foam.
  • foam suppressing agent also means agent which regulates the foam to a desired extent.
  • Additional foam suppressing agent may also include those selected from the group consisting of glycerol derivative, diester compound, fatty acid, soap, polyols or combinations thereof. More preferably the additional foam suppressing agent is selected from glycerol derivative, diester compound or mixtures thereof.
  • the foam suppressing agent is a delayed-release foam suppressing agent.
  • delayed release it is meant that the foam suppressing agent begins to suppress foam over time. The time delay may be adjusted depending on the time when the foam is required to be suppressed.
  • the foam suppressing agent may be a silicone compound.
  • the silicone compound includes a reactive siloxane structural unit comprising Si-0 moieties where the reactive siloxane is a polymer which may include one or more functional moieties selected from the group amino, amido, alkoxy, hydroxy, polyether, carboxy, hydride, mercapto, sulfate phosphate and/or quaternary ammonium moieties. These moieties may be attached directly to the siloxane backbone through a bivalent alkylene radical, (i.e., "pendant") or may be part of the backbone.
  • a bivalent alkylene radical i.e., "pendant”
  • Suitable functionalized siloxane polymers include materials selected from the group consisting of aminosilicones, amidosilicones, silicone polyethers, silicone-urethane polymers, quaternary ABn silicones, amino ABn silicones, and combinations thereof.
  • the silicone compound is an organopolysiloxane preferably having an amino-functional or a carboxyl-functional organic group.
  • Suitable organosilicone may be linear, branched, or cross linked.
  • the silicone compound may belong to the organosiloxane class of amino amino-functional organopolysiloxane, carboxy-functional organopolysiloxane, polydimethyl siloxane, silicone polyether or mixtures thereof.
  • the silicone compound may also be selected from a reactive siloxane which is a silicone aminoalcohol.
  • Yet another preferred silicone compound includes a reactive siloxane which is an aminosilicone.
  • the foam suppressing agent is an amino-functional organopolysiloxane (IV) which has at least one siloxane unit of the general formula . (iv a) and at least one siloxane unit of the general formula wherein:
  • R 1 is the same or different and is a hydrogen atom, a monovalent, optionally fluorine-, chlorine- or bromine- substituted Ci to Cis hydrocarbyl radical or a Ci to C12 alkoxy radical or a hydroxyl radical, preferably a Ci to C18 hydrocarbyl radical or a Ci to C3 alkoxy radical or a hydroxyl radical, where Q is an amino group of the general formula
  • R 2 is a divalent Ci to Cis hydrocarbyl radical, preferably a divalent C 2 to C4 hydrocarbyl radical hydrocarbyl radical
  • R 3 is a hydrogen atom or a Ci to C10 alkyl radical
  • R 4 is a hydrogen atom or a Ci to C10 alkyl radical
  • R 5 is a hydrogen atom or a Ci to C10 alkyl radical
  • a is 0, 1 or 2, preferably 0 or 1
  • b is 1 , 2 or 3, preferably 1
  • c is 0, 1 , 2 or 3, preferably 2 or 3
  • m is 2, 3 or 4, preferably 2 or 3
  • x is 0, 1 or 2, preferably 0 or 1 , and the sum of a+b is less than or equal to 3.
  • the hydrocarbyl radical mentioned may be saturated or unsaturated, linear, branched or a cyclic radical.
  • the ratio of siloxane units with the general formula (la) to (lb) is from 1 :1 to 1 :10,000 and preferably from 1 :2 to 1 :300.
  • the amino-functional organopolysiloxanes preferably have an average viscosity of 25 to 10,000 mPas, more preferably 50 to 5,000 mPas, at 25°C.
  • the foam suppressing agent is in solid form which includes an aminofunctional organopolysilioxane of formula IV and a carrier material selected from the group of sodium carbonate, sodium sulphate, aluminium silicate, potassium carbonate, potassium sulphate, sodium hydrogencarbonate, potassium hydrogencarbonate and zeolites, and mixtures thereof.
  • a carrier material selected from the group of sodium carbonate, sodium sulphate, aluminium silicate, potassium carbonate, potassium sulphate, sodium hydrogencarbonate, potassium hydrogencarbonate and zeolites, and mixtures thereof.
  • Another preferred foam suppressing agent is a modified amino-functional organopolysilioxane have the general formula (V) where R 2 is the same or different and is a monovalent Ci to C18 hydrocarbyl radical, R 1 is as defined above for (IVa) Q is as defined above for (IVa), k is 0 or 1 , m is 0 or an integer from 1 to 1000, n is 0 or an integer from 1 to 50, with the proviso that the organopolysiloxanes contain at least one Q radical per molecule.
  • amino-functional organopolysiloxanes of the formula (V) are aminofunctional polydimethylsiloxanes terminated by trimethylsiloxane units and aminofunctional polydimethylsiloxanes terminated by hydroxydimethylsiloxane units and Ci to C3 alkoxydimethylsiloxane units.
  • modified amino silicone organopolysiloxane useful in the present invention is the one having the formula (VI)
  • A is an amino radical of the formula or a protonated amino form and/or acylated amino form of the amino radical A, preferably A is -(CH2)3NH2 and -(CH2)3NH(CH2)2NH2;
  • X is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms or a polyoxyalkylene group G of the formula preferably G is -(CH2)3-(OC2H4) y -O-R 6
  • R 1 is a Ci to C10 alkylene radical, preferably a radical of the formula -CH2CH2CH2-,
  • R 2 is hydrogen or a Ci to C4 alkyl radical, preferably hydrogen
  • R 3 is a Ci to C10 alkylene radical, preferably a radical of the formula -CH2CH2-,
  • R 4 is a Ci to C10 alkylene radical, preferably a radical of the formula -CH2CH2CH2-
  • R 5 is a Ci to C4 alkylene radical, preferably a radical of the formula -CH2CH2-, or -CH 2 CH2(CH 3 )- or mixtures thereof;
  • R 6 is hydrogen or a Ci to C4 alkylene radical, preferably hydrogen or a methyl radical, more preferably hydrogen, n is an integer from 1 to 6, preferably from 1 to 3, m is an integer from 1 to 200, preferably from 1 to 80, x is 0 or 1 and y is an integer from 5 to 20, preferably from 5 to 12, with the proviso that on an average from 30 mol% to 60 mol%, preferably 30 mol% to 50 mol%, of the radicals X are polyoxyalkylene group G.
  • the modified amino silicone organopolysiloxane are generally a fluid and therefore need a carrier filler selected from the group comprising sodium carbonate, sodium sulphate, aluminum silicate, potassium carbonate, potassium sulphate, sodium bicarbonate, potassium bicarbonate and zeolites to form a free-flowing powder form.
  • a carrier filler selected from the group comprising sodium carbonate, sodium sulphate, aluminum silicate, potassium carbonate, potassium sulphate, sodium bicarbonate, potassium bicarbonate and zeolites to form a free-flowing powder form.
  • Still another preferred type of modified amino silicone organopolysiloxane useful in the present invention is the one having the formula (VII)
  • Y is an amino group of the general formula
  • R 1 is the same or different and is a monovalent Ci to Ge alkyl radical or a Ci to Ce alkoxy radical or a hydroxyl radical
  • R is a monovalent Ci to Ce alkyl radical
  • R 2 is a monovalent C2 to Ce alkyl radical
  • R 3 is a Ci to C10 alkylene radical
  • R 4 is a hydrogen or a Ci to C4 alkyl radical
  • R 5 and R 6 independently represent hydrogen or a Ci to C4 alkyl radical
  • j is an integer from 0 to 3
  • k is an integer from 0 to 3
  • z is an integer from 1 to 500
  • n is an integer from 1 to 70
  • m is an integer from 1 to 10
  • v is an integer from 0 to 15
  • x is an integer from 0 to 1.
  • the amino radical Y is preferably -(CH2)3NH2 and - (CH2)3NH(CH2)2NH2 and its protonated acylated form or its mixtures thereof.
  • These modified amino silicone organopolysiloxane are generally a fluid and therefore need a carrier filler.
  • the carrier filler is water-soluble with a water solubility of 50 to 500 g/L at 25°C. More preferably the carrier filler is selected from the group comprising sodium carbonate, sodium sulphate, aluminum silicate, potassium carbonate, potassium sulphate, sodium bicarbonate, potassium bicarbonate and zeolites, water soluble starch or mixtures thereof to form a free-flowing powder form.
  • silicone polyethers comprise a polydimethylsiloxane backbone with one or more polyoxyalkylene chains.
  • the polyoxyalkylene moieties may be incorporated in the polymer as pendent chains or as terminal blocks.
  • the foam suppressing agent may be polysiloxane having the structure: where R and R' are the same or different alkyl or aryl groups having from 1 to 6 carbon atoms; and x is an integer of at least 20.
  • the preferred polysiloxanes are polydimethylsiloxanes, where both R and R' are methyl groups.
  • the polysiloxanes usually have a molecular weight of from 500 to 200,000 and a kinematic viscosity of from 50 to 2x10 6 mm 2 sec’ 1 .
  • the polysiloxanes have a kinematic viscosity of from 5x10 2 to 5X10 4 mm 2 sec 1 , most preferably from 3X10 3 to 3X10 4 mm 2 se 1 at 25°C.
  • the polysiloxane is generally end blocked with trimethylsilyl groups, but other end-blocking groups are also suitable.
  • silicone oils examples include silicone oils 47v 100, 47v 5000 and 47v 12500 available from Rhone Poulenc; Silcolapse 430 and Silicone EP 6508 available from ICI; Rhodosil 454 available from Rhone Poulenc; and Silkonol AK 100 available from Wacker.
  • the silicone compound is an organosilicones selected from polydimethylsiloxane, dimethicone, dimethiconol, dimethicone crosspolymer, phenyl trimethicone, alkyl dimethicone, lauryl dimethicone, stearyl dimethicone and phenyl dimethicone, octyl amidomethicone, cetyl amidomethicone. Still preferably the silicone compound is selected from polydimethylsiloxane, octyl amidomethicone, cetyl amidomethicone and mixtures thereof.
  • foam suppressing agent examples include those available under the names DC 200 Fluid, DC 1664, DC 349, DC 346G available from Dow Corning Corporation, Midland, Ml, and those available under the trade names SF1202, SF1204, SF96, and Viscasil available from Momentive Silicones, Waterford, NY.
  • foam suppressing agent a further foam suppressing agent such as finely divided particulate silica may also be used in the composition of the present invention.
  • Any type of silica can be employed in the preparation of hydrophobic silica. Preferred examples are precipitated silica and pyrogenic silica which can be converted to a hydrophobic form. More preferably the foam suppressing agent includes a mixture of polydimethylsiloxane and silica.
  • Additional foam suppressing agent may also include those selected from the group consisting of glycerol derivative, diester compound, fatty acid, soap, polyols or combinations thereof. More preferably the additional foam suppressing agent is selected from glycerol derivative, diester compound or mixtures thereof.
  • the foam suppressing agent as disclosed in the present invention is preferably a cyclohexane polycarboxylic acid derivative of the formula (VIII) in which
  • R 1 may be identical or different. It is selected from straight chain or branched Ci to C - alkyl or C3 to Cs -cycloalkyl; m is 0, 1 , 2 or 3; n is 2, 3 or 4, and R is H or a straight chain or branched Ci to C30 alkyl, where at least one radical R is Ci to C30 alkyl.
  • R 1 is an alkyl group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl.
  • the R is an alkyl radical which includes those already mentioned under R 1 and n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, stearyl, n-eicosyl, where at least one radical R is n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, stearyl, n- eicosyl.
  • the R is isononyl.
  • the cyclohexane polycarboxylic acid derivatives may be selected from mono-, di-, tri-, tetra esters and anhydrides of cyclohexane polycarboxylic acids. Preferably, all the carboxylic acid groups are esterified.
  • the cyclohexane polycarboxylic acid derivative is chosen from the group consisting of ring-hydrogenated mono- and dialkyl esters of phthalic acid, isophthalic acid and terephthalic acid, ring-hydrogenated mono-, di- and trialkyl esters of trimellitic acid, of trimesic acid and of hemimellitic acid, or mono-, di-, tri- and tetra alkyl esters of pyrromellitic acid, where the alkyl groups may be linear or branched and in each case have 1 to 30, preferably 2 to 10, particularly preferably 3 to 18, carbon atoms, and mixtures of two or more thereof.
  • the cyclohexane polycarboxylic acid derivative is an alkyl ester of cyclohexane-1 ,4-dicarboxylic acid, alkyl ester of cyclohexane-1 ,2-dicarboxylic acid, mixed esters of cyclohexane-1 ,2-dicarboxylic acid with Ci to C13 alcohols, mixed esters of cyclohexane-1 ,3-dicarboxylic acid with Ci to C13 alcohols, mixed esters of cyclohexane-1 ,4-dicarboxylic acid with Ci to C13 alcohols, alkyl esters of cyclohexane- 1 , 3-dicarboxylic acid.
  • the cyclohexane polycarboxylic acid derivative is an alkyl ester of cyclohexane-1 ,2-dicarboxylic acid as given in the formula below where R 3 and R 4 are mutually independently selected from branched and unbranched C7 to C12 alkyl residues.
  • C7 to C12 alkyl is selected from n-heptyl, 1 -methylhexyl, 2- methylhexyl, 1 -ethyl pentyl, 2-ethyl pentyl, 1 -propylbutyl, 1-ethyl-2-methylpropyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, 2-propylhexyl, n-decyl, isodecyl, 2- propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl and the like.
  • C7 to C12 alkyl stands for n-octyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2- propylheptyl, n-undecyl or isoundecyl.
  • residues R 3 and R 4 both stand for 2-ethylhexyl, isononyl or 2- propylheptyl.
  • the alkyl ester of cyclohexane-1,2-dicarboxylic acid is preferably selected from the group consisting of di(isobutyl) ester of cyclohexane-1 , 2-dicarboxylic acid, di(2- ethylhexyl) ester of cyclohexane-1 , 2-dicarboxylic acid, di(isononyl) ester of cyclohexane-1 , 2-dicarboxylic acid.
  • Preferred ester groups are straight-chain or branched alkyl groups having 6 to 13 carbon atoms. Most preferably it is a di(isononyl) ester of cyclohexane-1 , 2-dicarboxylic acid.
  • Diisononylcyclohexane-1 , 2-dicarboxylate is commercially available under the name Hexamoll® DINCH (BASF AG).
  • the cyclohexane polycarboxylic acid derivatives are preferably prepared according to the process disclosed in WO 99/32427.
  • the foam suppressing agent is preferably a glycerol derivative.
  • the glycerol derivative has the general formula (IX) as mentioned herein below.
  • R 1 OCH 2 CH(OH)CH 2 OR 2 , iy . wherein the R 1 is H or Ci 2 to Cis saturated or unsaturated alkyl ester and R 2 is Ci 2 to Cis saturated or unsaturated alkyl ester.
  • the glycerol derivative is preferably glycerol monooleate, glycerol dioleate, glycerol monostearate, glycerol distearate and mixtures thereof, preferably the glycerol derivative is a glycerol monostearate, glycerol monooleate or mixtures thereof. Most preferably the glycerol derivative is a glycerol monooleate.
  • the foam suppressing agent is a glycerol derivative used in combination with methyl cellulose.
  • glycerol monooleate is used in combination with methyl cellulose.
  • the ratio of glycerol derivative to methyl cellulose is at least 0.6, preferably at least 0.75, more preferably 1.
  • the ratio of glycerol derivative to methyl cellulose is at most 1, preferably at most 2, more preferably at most 5, even more preferably at most 7.
  • the foam suppressing agent when it is a glycerol derivative is present in the detergent composition in an amount ranging from 0.5 wt.% to 5 wt.%.
  • the levels of the glycerol derivative in the detergent composition is at least 0.75 wt.%, still preferably at least 1 wt.%, still preferably at least 1.25 wt.%, most preferably at least 1.5 wt.%, but typically not more than 4.75 wt%, still preferably not more than 4.5 wt%, most preferably not more than 4 wt%.
  • foam suppressing agents include the monocarboxylic fatty acids and soluble salts thereof, which are described in US 2,954,347.
  • foam suppressing agents are described in EP-A-0210731 and EP-A-0210721.
  • the solid detergent composition according to the present invention comprises from 0.05 wt.% to 2.0 wt.% foam suppressing agent.
  • the solid detergent composition comprises at least 0.08 wt.%, preferably at least 0.1 wt.%, still preferably at least 0.2 wt.% and most preferably at least 0.4 wt.%, but typically not more than 1.5 w.t%, still preferably not more than 1.3 wt.%, still further preferably not more than 1.2 wt.% and most preferably not more than 1 wt.% where the foam suppressing agent is selected from silicone compound, amino silicone compound or mixtures thereof.
  • the detergent composition of the present invention includes a sodium carbonate builder.
  • the carbonate builder includes alkaline earth metal and alkali metal carbonates as disclosed in the German patent application No. 2,321,001.
  • the carbonate builder preferably includes further alkali metal carbonate, alkaline earth metal carbonate or mixtures thereof. Preferred further alkali carbonates potassium carbonate. It is further preferred that sodium carbonate makes up at least 75 wt.%, more preferably at least 85 wt.% and even more preferably at least 90 wt.% of the total weight of the alkali metal carbonate builder.
  • the detergent composition of the present invention includes from 0.1 wt.% to 40 wt.% sodium carbonate builder. More preferably the sodium carbonate builder is present in an amount ranging from 0 wt.% to 20 wt.% in the composition.
  • the detergent composition comprises at least 0.8 wt.%, still preferably at least 1 wt.%, still preferably at least 2 wt.%, most preferably at least 5 wt.% of the carbonate builder, but typically not more than 38 wt.%, still preferably not more than 35 wt.%, most preferably not more than 30 wt.% of sodium carbonate builder based on the weight of the cleaning composition.
  • the detergent composition of the present invention may preferably include further inorganic non-carbonate builder.
  • the other preferred builders may be selected from the group consisting of silicates, silica, zeolites phosphates or mixtures thereof.
  • Yet other non-carbonate builder may be organic builders which includes but are not limited to as succinates, carboxylates, malonates, polycarboxylates, citric acid or a salt thereof.
  • Suitable silicates include the water-soluble sodium silicates with an SiCh: Na2O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred.
  • the silicates may be in the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an SiCh: Na2O ratio of 2.0 is the most preferred silicate.
  • Silicates are preferably present in the detergent compositions in accordance with the invention at a level of from 5 wt.% to 50 wt.% of the composition, more preferably from 10 wt.% to 40 wt.% of the solid laundry detergent composition. Still more preferably the silicates are present in an amount ranging from 5 wt.% to 18 wt.% of the solid laundry detergent composition.
  • the composition is preferably phosphate builder free, that is the composition has no deliberately added phosphate builder such as STPP.
  • the detergent composition includes 0 wt.% to 8 wt.% phosphate builder, still preferably the composition has no deliberately added phosphate builder.
  • the solid laundry detergent composition includes 0 wt.% phosphate builder.
  • the detergent composition includes 0 wt.% to 8 wt.% zeolite, still preferably the composition has no deliberately added zeolite.
  • the solid laundry detergent composition includes 0 wt.% zeolite builder.
  • composition of the present invention is in the solid form.
  • the composition according to the present invention may be made via a variety of conventional methods known in the art and those which includes but is not limited to the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tabletting, or spraydrying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying.
  • the detergent composition may be made by any of the conventional processes, especially preferred is the technique of slurry making and spray drying.
  • compositions herein can take a variety of physical solid forms including forms such as powder, granule, particulate ribbon, noodle, paste, tablet, flake, pastille and bar, and preferably the composition is in the form of powder, granules or a tablet, still preferably the composition is in the form of a powder.
  • the composition may be in the form of a unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein.
  • the composition according to the present invention may preferably be in a form selected from powder, unit dose or pouch form, tablet, gel, paste, bar, or flake.
  • the composition is for manualwashing.
  • the composition of the present invention is a solid laundry detergent composition.
  • the composition is prepared using a mixing route or a spray drying process, preferably the composition in the form of a spray -dried powder.
  • compositions preferably have a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.
  • the composition according to the present invention has a pH of from 8 to 13, preferably from 8.5 to 12, more preferably 8.5 to 11 when measured at 1 wt.% dilution in deionised water at 25°C.
  • the sodium carbonate builder provides the desired pH to the composition.
  • the composition of the present invention preferably also includes further alkaline source which is selected from bicarbonates and semi-bicarbonates.
  • the composition may preferably include a buffer.
  • the solid detergent composition includes from 1 wt.% to 3.5 wt.%, still preferably 1 wt.% to 3 wt.% water.
  • the solid detergent composition is either agglomerated or spray-dried.
  • the detergent composition of the present invention may preferably include one or more of the optional ingredients selected from the group consisting of cleaning and care ingredients.
  • the optional ingredients include one or more adjunct cleaning additives selected from polymers, enzymes, enzyme stabilizer, brightening agents, hueing agent, bleach, chelating agent, humectant, perfume, filler or carrier, an alkalinity system, a buffer or combinations thereof.
  • composition of the present invention may preferably include polymers which provide cleaning or care benefits.
  • the cleaning polymer includes but is not limited to soil release polymer, carboxylate polymers, antiredeposition polymers, cellulosic polymers, care polymers, dye-transfer inhibiting polymer, amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil suspending polymers or mixtures thereof.
  • Suitable carboxylate polymer includes polymers such as a maleate/acrylate random copolymer or polyacrylate homopolymer.
  • Suitable carboxylate polymers homopolymeric or copolymeric carboxylic acids, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of acrylic acid or methacrylic acid with maleic acid. Preferred representatives of this group are sodium polyacrylate and sodium salts of acrylic acid-maleic acid copolymers.
  • Soil release polymers are designed to modify the surface of the fabric to facilitate the ease of removal of soil.
  • Suitable soil release polymers are sold by Clariant under the TexCare® series of polymers, e.g. TexCare® SRN240.
  • Other suitable soil release polymers are sold by Rhodia under the Repel-o-Tex® series of polymers, e.g. Repel-o- Tex® SF2.
  • a preferred polymer is selected from the group consisting of polyester soil release polymer, both end-capped and non-end-capped sulphonated or unsulphonated PET/POET polymers.
  • the levels of these soil release polymer in the adjunct particle is from 3 wt.% to 15wt.%.
  • Anti-redeposition polymers are designed to suspend or disperse soil.
  • antiredeposition polymers are polyethylene glycol polymers, polycarboxylate polymers, polyethyleneimine polymers or mixtures thereof.
  • Such polymers are available from BASF under the trade name Sokalan®CP5 (neutralised form) and Sokalan®CP45 (acidic form).
  • Suitable antiredeposition polymers are ethoxylated and or propoxylated polyethylene imine or polycarboxylate materials, for example, acrylic acid-based homo or copolymers available under the trademark ACLISOL from Dow Chemical, Alcosperse from Akzonobel or Sokolan from BASF.
  • Suitable care polymers include cellulosic polymers that are cationically modified or hydrophobically modified. Such modified cellulosic polymers can provide anti- abrasion benefits and dye lock benefits to fabric during the laundering cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose.
  • the cleaning composition is preferably substantially free of phosphate based sequestering polymers.
  • substantially free it is meant herein that no phosphate based sequestering polymers is deliberately added.
  • composition of the present invention preferably includes one or more enzymes.
  • Preferred examples of the enzymes include those which provide cleaning performance and/or fabric care benefits.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, xyloglucanase, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, G-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
  • a typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with one or more of amylase, mannanase and cellulase.
  • the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or from 0.001% to about 0.5% enzyme protein by weight of the detergent composition.
  • Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Maxatase®, Maxaca®l, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, 10 Excellase® and Purafect OXP® by Genencor International, those sold under the tradename Opticlean® and Optimase by Solvay Enzymes.
  • Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd, Denmark), 15 KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, California) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan).
  • suitable amylases include NATALASE®, STAINZYME and STAINZYME PLUS® and mixtures thereof.
  • Preferred lipases would include those sold under the tradenames Lipex® and Lipolex®.
  • Suitable endoglucanases are sold under the tradenames Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).
  • Other preferred enzymes include pectate lyases sold under the tradenames Pectawash®, Pectaway®, Xpect® and mannanases sold under the tradenames Mannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite® (Genencor International Inc., Palo Alto, California).
  • the enzyme-containing compositions described herein may optionally comprise from 0.001% to 10%, by weight of the composition, of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, chlorine bleach scavengers and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the cleaning composition.
  • a reversible protease inhibitor such as a boron compound, including borate, 4-formyl phenylboronic acid, phenylboronic acid and derivatives thereof, or compounds such as calcium formate, sodium formate and 1,2-propane diol may be added to further improve stability.
  • Optical brighteners or other brightening or whitening agents may be incorporated at levels from 0.01% to 1.2%, by weight of the composition.
  • Commercial brighteners suitable for the present invention can be classified into subgroups, including but not limited to: derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylic acid, methinecyanines, dibenzothiophene-5, 5- dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents.
  • Preferred commercially available Brighteners includes Tinopal AMS-GX by Ciba Geigy Corporation, Tinopal UNPA-GX by Ciba-Geigy Corporation, Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • the brighteners may be added in particulate form or as a premix with a suitable solvent, for example nonionic surfactant, monoethanolamine, propane diol.
  • the composition may comprise a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents).
  • hueing agent provides a blue or violet shade to fabric.
  • Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade.
  • Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including 30 premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof.
  • Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Additional surfactants:
  • the detergent composition according to the present invention may include additional surfactants selected from but not limited to non-ionic surfactant, amphoteric surfactant cationic surfactant, zwitterionic surfactant, or mixtures thereof.
  • Non-limiting examples of nonionic surfactants include: C12 to C18 alkyl ethoxylates, Ce to C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; C12 to C18 alcohol and Ce to C12 alkyl phenol condensates with ethylene oxide/propylene oxide block alkyl polyamine ethoxylates alkylpolysaccharides and ether capped poly(oxyalkylated) alcohol surfactants.
  • Non-limiting examples of cationic surfactants include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylate quaternary ammonium (AQA) surfactants, dimethyl hydroxyethyl quaternary ammonium, dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants and cationic ester surfactants.
  • AQA alkoxylate quaternary ammonium
  • Non-limiting examples of zwitterionic or ampholytic surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
  • zwitterionic surfactants includes betaines, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, Cs to C18 (for example from C12 to Cis) amine oxides and sulfo and hydroxy betaines, such as N- alkyl-N, N-dimethylammino-1-propane sulfonate where the alkyl group can be Cs to Cis and in certain embodiments from C10 to C14.
  • the solid laundry detergent composition includes fillers such as sodium sulphate, sodium chloride, calcite, dolomite or mixtures thereof.
  • Fillers such as sodium sulphate, sodium chloride, calcite, dolomite or mixtures thereof.
  • a method for laundering a textile surface with the detergent composition according to the first aspect of the present invention comprising the steps of: i) preparing an aqueous wash liquor with an effective amount of foam by contacting the detergent composition according to the first aspect with a liquid; ii) soaking said textile surface in the wash liquor for a predetermined period of time; and, iii) optionally rinsing the textile surface.
  • the rinsing of the textile surface is carried in less than 3 rinsing steps, preferably less than 2 rinsing steps more preferably in a single rinsing step.
  • the method includes the step of preparing an aqueous wash liquor of the detergent composition in a liquid.
  • the wash liquor is preferably prepared by dissolving the detergent composition in water.
  • washing includes, but is not limited to, scrubbing, wiping and mechanical agitation.
  • compositions are preferably employed at concentrations of from about 200 ppm to about 10,000 ppm in solution.
  • the water temperatures preferably range from about 5°C to about 100°C.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of the detergent composition in accordance with the invention.
  • an effective amount of the detergent composition it is meant from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 65 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • Hand-washing methods, and combined handwashing with semiautomatic washing machines are also included.
  • a primary anionic detersive surfactant selected from the group consisting of sulfate surfactant, sulphonate surfactant, alkyl ether sulphate surfactant or mixture thereof
  • a foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof and a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 in a detergent composition to provide good lather generation in the wash liquor during the main wash stage and collapse of lather during rinse stage and wherein the rinse stage requires less than 3 rinses.
  • Aqueous solution Ex A 2 grams of a solid laundry detergent composition having 20 wt.% primary anionic detersive surfactant (sodium linear alkyl benzene sulphonate, NaLAS) was added to 1000 mL of water having a hardness of 24°FH (Ca:Mg 2:1) and stirred for complete dissolution. The concentration of NaLAS in the aqueous solution was 0.04 wt.%.
  • primary anionic detersive surfactant sodium linear alkyl benzene sulphonate, NaLAS
  • Aqueous solution Ex 1 2 grams of a solid laundry detergent composition having 20 wt.% primary anionic detersive surfactant (sodium linear alkyl benzene sulphonate, NaLAS) and 0.5 wt.% sodium salt of C alkyl ether carboxylic acid (cosurfactant) was added to 1000 mL of water having a hardness of 24°FH (Ca:Mg 2:1) and stirred for complete dissolution.
  • the concentration of NaLAS in the aqueous solution was 0.04 wt.% and the concentration of cosurfactant was 0.001 wt.%.
  • the ratio of the cosurfactant to primary detersive surfactant was 1:40.
  • Dynamic surface tension measurement 50 mL of the above prepared solution was taken, and the dynamic surface tension was measured using a maximum bubble pressure tensiometer BP 100 (from Kruss), at 100 milliseconds. The dynamic surface tension was recorded for each solution and provided in table 1 below.
  • LAS Linear alkyl benzene sulphonate (primary anionic detersive surfactant)
  • AEC C alkyl ether carboxylic acid surfactant (cosurfactant)
  • Silicone oil foam suppressing agent
  • Foam measurement method The foam volume generated by the various detergent compositions as provided in table 2 was measured using the automated cylinder shake protocol.
  • the cylinder was clamped in an automated cylinder shake (rotating device), which clamps the cylinder with respect to an axis of rotation that traverses the center of the graduated cylinder.
  • the cylinder was rotated at a speed of 30 revolutions per minute. The cylinder was allowed to complete 5 full revolution and stopped at a vertical position. The height of the foam from the bottom was recorded in mL and provided in Table 2 below.
  • the cylinder was again rotated and was allowed to complete 5 more revolutions and thereafter stopped at a vertical position. The height of the foam after the 10 revolutions was measured from the bottom and recorded in mL, the measured foam height provided in Table 2 below.
  • the detergent composition according to the present invention shows good foam as compared to the comp Ex B (LAS without foam suppressing agent) and Comp Ex C (LAS with foam suppressing agent).
  • the composition according to the present invention achieves quick foam reduction as compared to the Comp Ex B and is comparable to Comp Ex C.
  • the detergent composition according to the present invention exhibits good foam volume in the initial wash cycle and thereafter it also provides desirable low sudsing properties in the rinse stage which minimizes the wastage of clean water required for rinsing.
  • the detergent composition according to the present invention (Ex 3) having LAS (primary anionic surfactant), C10 branched alkyl sulphated surfactant with 4EO group shows good foam as compared to the comp Ex D (LAS without foam suppressing agent) and Comp Ex E (LAS with silicone foam suppressing agent).
  • the composition according to the present invention achieves quick foam reduction as compared to the Comp Ex D and is comparable to Comp Ex E.
  • a comparative composition (Ex F) having LAS, and a nonionic surfactant as the foam suppressing agent gives lesser foam in the wash stage and foam reduction is also not easy in the rinse stage.
  • the foam reduction in the comparative composition Ex G having LAS, C10 branched alkyl sulphated cosurfactant with 4EO group and nonionic surfactant foam suppressing agent is not easy.
  • the composition according to the present invention Ex 3 having LAS, C10 branched alkyl sulphated surfactant with 4EO group and silicone foam suppressing agent gives good foam in the wash stage which is easily rinsed off in the rinse stage of the washing process even under cold water and room temperature conditions.

Abstract

The present invention relates to a laundry detergent composition having a desirable foam profile during the laundering process. It is thus an object of the present invention to provide a detergent composition which provides good foam profile. It is yet another objection of the present invention to provide a detergent composition which reduces the amount of water required for rinsing. The present inventors have found that a detergent composition having specifically selected primary anionic detersive surfactant when present in combination with cosurfactant and a foam suppressing agent surprisingly provides good foam formation in the wash stage while eliminating the foam quickly during the rinsing stage.

Description

DETERGENT COMPOSITION
Field of the Invention
The present invention relates to a laundry cleaning composition; in particular, a solid laundry detergent composition having a desirable foam profile during the laundering process.
Background of the Invention
Synthetic detergents are widely used for laundering fabrics, due to their efficiency in cleaning and stain removal. In addition to the synthetic detergents, formulated laundry detergent composition includes various additives to provide improved cleaning and sensorial benefits. Proper foam level is a sensorial benefit which most consumers desire during the laundering process.
Foaming or sudsing is an important factor to consider when formulating a detergent composition. Foam is a significant consumer cue and acts as the primary reason by which a consumer perceives that a composition is having a cleaning effect.
Unfortunately, while foam is easy to generate, it also needs to be removed from the substrate after cleaning. High volume of foam in the washing cycle typically results in foam being carried over to the rinse liquor and requiring additional time, energy, and water to thoroughly rinse the laundered articles. It is therefore advantageous to have high foam volume generation at early stages in the wash cycle for consumer acceptance. Followed by quick collapse of the foam to a lower volume toward the end of the wash cycle, these aspects of the foaming profile of a detergent composition allows for complete cleaning and minimum wastage of clean water.
Several attempts at saving water after laundering fabric with high foaming compositions have been made in the past. Laundry formulations such as rinse aids have been used to help reduce the foam carried by the laundered fabric into the rinse water. Rinse aids reduce the amount of water used during rinsing. However, the use of rinse aids adds an extra step and the consume needs to use an additional product in the washing process. In today’s fast paced world, consumers look for a single composition which provides multiple benefits. Accordingly, there is a need for a detergent composition which provides good foam profile, good cleaning benefits and reduces water consumption. This need is particularly felt by consumers who dwell in regions where there is acute shortage of water.
In addition to the above, synthetic detergents are associated with environmental concerns. Synthetic detergents are derived from non-renewable resources and pollute water bodies when they are ultimately discharged into rivers and lakes. Thus, there is a need for a detergent composition which has lower levels of these ingredients. However, reducing the levels of the synthetic detergent in the formulation significantly deteriorates the foaming profile of the detergent composition. Compositions with low detergent levels have lower foam generation or provide foam which may not be well retained during the washing cycle. This poor foaming profile makes the detergent composition less acceptable to consumers who highly value the foaming profile of the detergent composition.
Accordingly, there remains a need for a laundry cleaning composition containing an environmentally friendly composition with lower levels of synthetic detergents while providing desired foaming profile, that is a high volume of well retained foam generated quickly upon dissolving the detergent composition in a washing solution and where the foam quickly collapses towards the end of the washing cycle to aid in easier removal of foam at the rinse stage.
Thus, there is a need for a cleaning composition that reduces and preferably eliminates foam in the rinse without adversely affecting the formation of foam in the initial washing step.
GB1169496 A (Unilever, 1969) discloses a detergent composition having controlled sudsing properties. The composition includes an anionic synthetic detergent, a nonionic synthetic detergent and/or a soap and an alkyl ether carboxylic acid.
US5877140 (Hardy et al., 1999) discloses a detergent composition which includes LAS, soap and an anionic compound to provide the dual performance benefits of excellent cleaning performance and suds suppression. GB1305540 A (Kao, 1973) discloses a foam controlled detergent composition having one or more anionic surface-active agents and specific fatty acid salt.
WO 95/02665 A1 (The Procter & Gamble Company, 1995) discloses a granular detergent composition having a surfactant and an antifoaming component.
WO 95/00117 A1 (The Procter & Gamble Company, 1995) discloses a liquid detergent composition having a branched anionic surfactant.
WO 2018/095695 A1 (Unilever) liquid detergent composition having an ethoxylated alkyl ether sulphate, a surfactant selected from alkylbenzene sulfonate, alkyl sulphate or combinations thereof and a fatty acid ester.
Some solutions towards addressing this problem of foaming at the rinse stage, were provided by incorporating rinse triggered antifoams which act on the foam and suppresses it at the rinse stage. However, such rinse triggered antifoam adds to the amount of chemicals incorporated in the composition and such compositions must be formulated carefully to avoid the antifoam being released during cleaning stage. Further such rinse triggered antifoams are generally expensive and provide no other performance benefit to the composition other than foam suppression. Therefore, it is desirable that their presence is minimised.
There remains a need for providing detergent composition for laundering fabrics which provides desired foam profile at different laundering steps there continues to be a need for a solid cleaning composition which provides good foam profile while maintaining good cleaning performance.
It is thus an object of the present invention to provide a solid laundry detergent composition which provides good foam profile.
It is another object of the present invention to provide a solid laundry detergent composition which provides good cleaning performance.
It is yet another object of the present invention to provide a solid laundry detergent composition which is environmentally friendly. It is yet another object of the present invention to provide a solid laundry detergent composition which reduces the amount of water required for rinsing.
It is yet another object of the present invention to provide a solid laundry detergent composition which gives good foaming in the wash stage and quick foam reduction in rinse stage even in cold water or wash liquor at room temperature conditions.
Summary of the Invention
The present inventors have found that a detergent composition having specifically selected primary anionic detersive surfactant when present in combination with branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 and a foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound or mixtures thereof surprisingly provides good foam formation in the wash stage while eliminating the foam quickly during the rinsing stage. This benefit was preferably found across different consumer washing habits and fabric types present in the wash load. It was further preferably found that the detergent composition according to the first aspect of the present invention provides for removing the foam in a single rinse cycle.
The composition shows good foaming during the main wash and quick foam removal during the rinse stage; thus, the composition provides good sensorial and the advantage of lower water consumption. This benefit is seen even when the wash liquor includes cold water or water at room temperature.
The present inventors have surprisingly found that the combination of the specific primary anionic surfactant and the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 provides the solid detergent composition with quick foaming in the wash liquor even in presence of the specific foam suppressing agent and the quick removal of the foam in the rinse liquor.
According to a first aspect of the present invention disclosed is a solid laundry detergent composition comprising: i) a primary anionic detersive surfactant selected from the group consisting of sulphate surfactant, sulphonate surfactant, linear alkyl ether sulphate surfactant or mixtures thereof; ii) a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10; and, iii) a foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof;
According to a second aspect of the present invention disclosed is method of treating a textile surface with the detergent composition according to the first aspect comprising the steps of: i) preparing a wash liquor with an effective amount of foam by contacting the detergent composition according to the first aspect with a liquid; ii) soaking said textile surface in the wash liquor for a predetermined period of time; and, iii) rinsing the textile surface, wherein the number of rinses required for the removal of foam present in the rinse liquor is less than 3 rinses.
According to a third aspect of the present invention disclosed is the use of a primary anionic detersive surfactant, a foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof and a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 in a detergent composition to provide fast lather generation in the wash liquor during the main wash stage and rapid collapse of lather during rinse stage.
As used herein, the terms "fabric", "textile", and "cloth" are used non-specifically and may refer to any type of flexible material consisting of a network of natural or artificial fibers, including natural, artificial, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, including blends of various fabrics or fibers.
As used herein, "foaming profile" refers to the properties of foam character in washing and rinsing solutions formed with a detergent composition. The foaming profile of a detergent composition includes but is not limited to the speed of foam generation upon dissolving the detergent composition, the volume and retention of foam in the washing cycle and the ease of rinsing the foam away in the rinsing cycle.
Detailed description of the Invention
The solid detergent composition according to the first aspect of the present invention includes a primary anionic detersive surfactant, a foam suppressing agent and a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10.
Primary anionic detersive surfactant
The solid detergent composition according to the first aspect of the present invention includes a primary anionic detersive surfactant selected from the group consisting of sulphonate surfactant, sulphate surfactant, linear alkyl ether sulphate surfactant or mixtures thereof.
Suitable sulphonate surfactant includes methyl ester sulphonates, alpha olefin sulphonates, alkyl benzene sulphonates, especially alkyl benzene sulphonates. Preferably C9 to C15 alkyl benzene sulphonates (LAS), still preferably C10 to C13 alkyl benzene sulphonates (LAS), still preferably the benzene sulphonates (LAS) has at least 50 wt.% of C12 alkyl benzene sulphonates, still preferably 80 wt.% C12 alkyl benzene sulphonates. Preferably the alkyl chain in the alkyl benzene sulphonate is straight or branched, more preferably linear. The alkyl benzene sulphonate is preferably in the salt form with the cation selected from alkali metal, alkaline earth metal or alkanolamine. Preferably alkali metal selected from sodium or potassium, most preferably sodium. Suitable alkyl benzene sulphonate (LAS) is obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, other suitable LAB includes high 2- phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®. The sulphonate surfactant may also be selected from the modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefin sulfonate (AOS).
Suitable sulphate surfactant includes alkyl sulphate surfactant, preferably Cs to C22 preferably Cs to Cis alkyl sulphate, or predominantly C12 alkyl sulphate. Conventional primary alkyl sulphate surfactants have the general formula: R"OSOs'M+ wherein R" is typically a Cs to C20 alkyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. In specific embodiments, R" is a C10 to C18 alkyl group, preferably C10 to C15 alkyl group, and M is alkali metal, more specifically R" is C12 to C14 alkyl and M is sodium. Specific, non-limiting examples of anionic alkyl sulphate surfactant useful herein include: C10 to C20 primary, branched-chain and random alkyl sulfates (AS), C10 to C18 secondary (2, 3)-alkyl sulfates having following formulae:
Figure imgf000008_0001
wherein M is hydrogen or a cation which provides charge neutrality, and all M units, can either be a hydrogen atom or a cation depending upon the form or the relative pH of the system where the surfactant is used, with non-limiting examples of preferred cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9.
Primary anionic detersive surfactant may be an alkyl ether sulphate surfactant. The alkyl ether sulphate surfactant may be branched or linear. Preferably it is linear.
Preferably the alkyl ether sulphate is a Cs to Cis alkyl ether sulphate. Preferably the alkyl ether sulphate surfactant has an average degree of ethoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl ether sulphate is a Cs to Cis alkyl ether sulphate having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3 and most preferably from 0.5 to 1 .5. Most preferably the alkyl ether sulphate surfactant is a linear Cs to Cis alkyl ether sulphate having an average degree of ethoxylation of from 0.5 to 7, more preferably 1 to 3. Frequently the alkyl ether sulphate surfactant will inevitably also contain some non- alkoxylated alkyl sulfate materials, which may constitute as much as 20 wt.% of the alkyl ether sulphate surfactant. The alkyl ether surfactant may also include the midchain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303.
Primary anionic detersive surfactant according to the present invention are preferably a non-soap anionic surfactant. The term “soap” is used herein in its popular sense, i.e. , the alkali metal of aliphatic, alkanes, or alkene monocarboxylic acids. Preferably the anionic surfactant includes 0 wt.% to 10 wt.% alkyl sulfate surfactant, preferably 0.2 wt.% to 5 wt.% alkyl sulfate surfactant, preferably the alkyl sulfate surfactant is a primary alkyl sulphate surfactant (PAS). The anionic surfactant may also preferably include from 0 wt.% to 10 wt.% MES, more preferably 0 wt.% to 5 wt.% MES. The anionic surfactant may include a linear alkyl ether sulphate surfactant, preferably a linear alkyl ether sulphate surfactant with 1 to 7EO group, still preferably a sodium lauryl ether sulphate with 1 to 7 EO, still preferably SLES 1 to 3 EO, preferably included in the composition in an amount from 0 wt.% to 10 wt.%, preferably 0 wt.% to 5 wt.% SLES with 1 to 7 EO.
The detergent composition of the present invention includes from 3 wt.% to 50 wt.% of primary anionic detersive surfactant selected from sulphate surfactant, sulphonate surfactant, alkyl ether sulphate surfactant or mixtures thereof. Preferably the detergent composition comprises at least 4 wt.%, still preferably at least 5 wt.%, still preferably at least 10 wt.%, most preferably at least 15 wt.% of the anionic surfactant, but typically not more than 45 wt.%, still preferably not more than 40 wt.%, still further preferably not more than 35 wt.%, still more preferably not more than 30 wt.% and most preferably not more than 25 wt.%, still more preferably not more than 20 wt.% of a primary anionic detersive surfactant based on the weight of the detergent composition.
The detergent composition according to the first aspect of the present invention preferably includes low levels of the primary anionic detersive surfactant. Preferably the primary anionic detersive surfactant is present in an amount ranging from 2 wt.% to 20 wt.%, still preferably from 2 wt.% to 15 wt.%. The present inventors have found that even when the primary anionic detersive surfactant is present at these low levels the detergent composition having a combination of the primary anionic detersive surfactant along with the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 and the foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof provides good foam profile in the initial main wash stage and quick reduction in the foam in the rinse stage while maintain good cleaning performance. Preferably the primary anionic detersive surfactant is an alkali metal salt of C to Cis alkyl benzene sulfonic acid.
In the solid laundry detergent composition according to the present invention the ratio of the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 to the primary anionic detersive surfactant is in a ratio from 1 :1 to 1 :200, preferably 1:1 to 1 :160, still preferably from 1 :1 to 1:100, still preferably the ratio from 1:5 to 1 :200, further preferably the ratio is from 1 :5 to 1:160, still more preferably from 1 :5 to 1:100, still preferably 1:5 to 1 :80, more preferably 1:5 to 1 :50. In the detergent composition of the present invention the total amount of primary anionic surfactant is greater than the branched Cs to C14 alkyl alkoxylated sulphated co- surfactant present in the composition.
Branched Cs to C14 alkyl alkoxylated sulphated Cosurfactant
According to the first aspect of the present invention disclosed solid laundry detergent composition includes a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant. Preferably the solid detergent composition according to the present invention comprises from 0.05 wt.% to 5 wt.% branched Cs to C14 alkyl alkoxylated sulphated cosurfactant. Preferably the solid detergent composition comprises at least 0.8 wt.%, preferably at least 0.1 wt.%, still preferably at least 0.15 wt.% still more preferably 0.25 wt.% and most preferably at least 0.5 wt.%, but typically not more than 4 w.t%, still preferably not more than 3 wt.%, still further preferably not more than 2 wt.% and most preferably not more than 1 wt.%.
Branched alkyl alkoxylated sulphate cosurfactant:
The cosurfactant is a branched alkyl alkoxylated sulphate surfactant. The alkyl group is preferably a Cs to C14, preferably Cs to Cw still preferably Cw branched alkyl alkoxylated sulphate surfactant. The branched alkyl alkoxylated sulphate surfactant is preferably ethoxylated. The number average degree of ethoxylation is from 2.5 to 10, still preferably 2.5 to 8, further preferably from 2.5 to 6, more preferably 3 to 6, still preferably from 3.5 to 4.5. Preferably the branched alkyl alkoxylated sulphate surfactant is selected from the group consisting of C branched ethoxylated sulphate surfactant with a number average degree of ethoxylation of 3, 4 or 5. Also preferred is that the branched alkyl alkoxylated sulphate surfactant is a mixture of different Cw branched ethoxylated sulphate surfactant selected from the group consisting of an average degree of ethoxylation of 3, 4 and 5. More preferably the average degree of ethoxylation is 4 or 5, most preferably 4. As used herein, the term “degree of ethoxylation” refers to the number of moles of ethylene oxide reacted with one mole of the Cw branched alcohol to produce the non-ionic ethoxylated Cw branched alcohol surfactant. It should be recognized that a distribution of ethoxylated reaction products is normally obtained during ethoxylation of, for example, alcohols.
The branched alkyl alkoxylated sulphate surfactant may include some amount of the non-sulphated branched alkyl alkoxylated surfactant, however the amount of such nonsulphated surfactant is not more than 20 wt.%, still preferably not more than 15 wt.%, further preferably not more than 10 wt.% or may preferably be lower than 10 wt.%.
The branched alkyl alkoxylated sulphate surfactant of the present invention are typically used in their neutralized form, for example as alkali metal salts.
The ratio of the branched alkyl alkoxylated sulphate cosurfactant to the primary anionic detersive surfactant in the composition is in a ratio from 1 :1 to 1 :200, still preferably the ratio is from 1 :1 to 1:160, still preferably from 1 :1 to 1 :100, more preferably 1:5 to 1 :80.
Preferably the solid laundry detergent composition according to the present invention comprises from 0.05 wt.% to 5 wt.% branched alkyl alkoxylated sulphate surfactant cosurfactant. Preferably the solid detergent composition comprises at least 0.25 wt.%, preferably at least 0.3 wt.%, still preferably at least 0.4 wt.% and most preferably at least 0.5 wt.%, but typically not more than 4 w.t%, still preferably not more than 3 wt.%, still further preferably not more than 2 wt.% and most preferably not more than 1 wt.%.
Additional cosurfactant
Along with the primary anionic detersive surfactant and the branched Cs to C14 alkyl alkoxylated sulphated co-surfactant the solid laundry detergent composition according to the first aspect of the present invention may include one or more additional cosurfactant. The additional cosurfactant is selected from the group consisting of alkyl ether carboxylic acid surfactant, amino acid-based surfactant, amide surfactant, or mixtures thereof.
Alkyl ether carboxylic acid cosurfactant:
The additional cosurfactant is preferably an alkyl ether carboxylic acid cosurfactant or salts thereof. The alkyl ether carboxylic acid surfactant has a general formula (I)
Ri-(OCH2CH2)n-OCH2-COOX . (I) wherein:
Ri is selected from saturated or mono-unsaturated, linear or branched, Cs to C14 alkyl or alkenyl chain; n has a value in the range from 1 to 20; and,
X represent H or a suitable cation selected from the group consisting of alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or mixtures thereof. Preferably the alkali metal is sodium.
Ri is either saturated or mono-unsaturated. The mono-unsaturated alkyl group may contain a cis or trans double bond. Ri may be linear or branched, more preferably linear. Ri is selected from Cs to C14 alkyl or alkenyl group. Preferably Ri is a Cs to C14 alkyl chain. Still preferably a Cs to C14 linear alkyl chain. The n has a value in the range from 2 to 20, more preferably the average degree of ethoxylation is from 2 to 10.
Alkyl ether carboxylates are well known products in the art. They are usually obtained from the alkoxylation and subsequent carboxymethylation of fatty alcohols as described by Meijer and Smid in Polyether Carboxylates; Anionic Surfactants; Surfactant Science Series, Vol. 56 (p. 313-361), published by Helmut W. Stache, ISBN: 0-8247-9394-3.
The alkyl ether carboxylic acid/carboxylate (AEC) is usually derived from a fatty alcohol which is alkoxylated, usually with ethylene glycol and/or propylene glycol, a carboxylic acid is then introduced to the material to form the alkyl ether carboxylic acid. Suitable examples of commercially available alkyl ether carboxylic acid surfactant include those marketed under the trade name AKYPO® by Kao Chemicals GmbH, Empicol® by Huntsman and Emulsogen® by Clariant. The sodium salt of the alkyl ether carboxylic acid surfactant is most preferred.
When in the form of an alkyl ether carboxylate salt, a preferred salt is sodium. Nonlimiting examples of suitable materials are oleyl alkyl ether (8EO) carboxylic acid, oleyl alkyl ether (10EO) carboxylic acid or laureth-5 carboxylic acid (5EO), and the sodium salts thereof.
The ratio of the alkyl ether carboxylic acid cosurfactant to the main anionic detersive surfactant in the composition is in a ratio from 1 :1 to 1 :200, still preferably the ratio is from 1 :1 to 1 :160, still preferably from 1 :1 to 1 :100, more preferably 1 :5 to 1 :80. The amount of the alkyl ether carboxylic acid cosurfactant in the composition is preferably from 0.05 wt.% to 5 wt.%, still preferably from 0.25 wt.% to 5 wt.% most preferably 0.5 wt.% to 1 wt.%.
Amino acid-based additional cosurfactant
The additional cosurfactant is preferably an amino acid-based surfactant. The aminoacid based surfactant is an anionic N-acyl amino acid surfactant. The amino acidbased surfactant has a general formula (II)
Figure imgf000013_0001
Formula II wherein,
R is selected from saturated or unsaturated C10 to C14 alkyl group,
R1 is selected from H, Ci to C4 alkyl,
R2 is selected from H or all groups on a carbon of natural amino acids,
R3 is selected from COOX, CH2 SO3X, where X is a suitable cation selected from the group consisting of alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or mixtures thereof more preferably selected from NH4 +, Li+, Na+ or K+.
Preferably the amino acid-based surfactant is a sarcosinate surfactant. The amino acid based anionic surfactant can be a sarcosinate, for instance an acyl sarcosinate. Nonlimiting examples of sarcosinates can be selected from the group consisting of sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium myristoyl sarcosinate, TEA- cocoyl sarcosinate, ammonium cocoyl sarcosinate, ammonium lauroyl sarcosinate, lauroylsarcosinate, disodium lauroamphodiacetate lauroyl sarcosinate, isopropyl lauroyl sarcosinate, potassium cocoyl sarcosinate, potassium lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, TEA- cocoyl sarcosinate, TEA-lauroyl sarcosinate, and combinations thereof. Preferably the sarcosinate surfactant is a sodium C to C^alkyl sarcosinate.
Preferably the amino acid-based surfactant is a taurate surfactant, for instance an acyl taurate. Also preferred is that the amino acid-based surfactant is a glycinate surfactant, for instance an acyl glycinate. Preferably the taurate surfactant is a sodium methyl cocoyl taurate, sodium cocoyl taurate. Preferably the glycinate surfactant is a sodium methyl cocoyl glycinate, sodium cocoyl glycinate.
Preferably the amino acid based anionic surfactant may be based on glutamate, for instance an acyl glutamate. Non-limiting examples of acyl glutamates can be selected from the group consisting of sodium cocoyl glutamate, disodium cocoyl glutamate, ammonium cocoyl glutamate, diammonium cocoyl glutamate, sodium lauroyl glutamate, disodium lauroyl glutamate, sodium cocoyl hydrolyzed wheat protein glutamate, disodium cocoyl hydrolyzed wheat protein glutamate, potassium cocoyl glutamate, dipotassium cocoyl glutamate, potassium lauroyl glutamate, dipotassium lauroyl glutamate, potassium cocoyl hydrolyzed wheat protein glutamate, dipotassium cocoyl hydrolyzed wheat protein glutamate, sodium capryloyl glutamate, disodium capryloyl glutamate, potassium capryloyl glutamate, dipotassium capryloyl glutamate, disodium hydrogenated tallow glutamate, sodium myristoyl glutamate, disodium myristoyl glutamate, potassium myristoyl glutamate, dipotassium myristoyl glutamate, sodium cocoyl/hydrogenated tallow glutamate, sodium cocoyl/ glutamate, sodium hydrogenated tallowoyl Glutamate, TEA-cocoyl glutamate, TEA-hydrogenated tallowoyl glutamate, TEA-lauroyl glutamate, and mixtures thereof. More preferably the acyl glycinates include sodium cocoyl glycinate, sodium lauroyl glycinate and combination thereof.
The amino acid based anionic surfactant can be an alaninate, for instance an acyl alaninate. Non-limiting example of acyl alaninates can include sodium cocoyl alaninate, sodium lauroyl alaninate, and combination thereof. More preferably the acyl alaninates include sodium cocoyl alaninate, sodium lauroyl alaninate and combination thereof.
The amount of the amino acid-based surfactant in the composition is preferably from 0.2 wt.% to 5 wt.% most preferably 0.5 wt.% to 1 wt.%.
The ratio of the alkyl ether carboxylic acid surfactant to the main anionic detersive surfactant in the composition is in a ratio from 1 :1 to 1:200, still preferably the ratio is from 1 :1 to 1:160, still preferably from 1 :1 to 1 :100, more preferably 1:5 to 1 :80. The amount of the alkyl ether carboxylic acid surfactant in the composition is preferably from 0.05 wt.% to 5 wt.%, still preferably from 0.25 wt.% to 5 wt.% most preferably 0.5 wt.% to 1 wt.%.
Also preferred are the modified sarcosinates described in U.S Patent No. 5520820 (Castillo, et al.) The modified sarcosinate have the formula (III):
Figure imgf000015_0001
Where, R1 is from C4 to C27 saturated or unsaturated hydrocarbon, M is H or a suitable cation selected from the group consisting of alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or mixtures thereof. Preferably the alkali metal is sodium, n is an integer selected from 1 to 3. Modified sarcosinates include those sold under the Hamposyl® tradename, such as lauroyl sacrosine (Hamposyl L).
Dynamic surface tension
The detergent composition according to the first aspect of the present invention has a primary anionic detersive surfactant and a cosurfactant and preferably the dynamic surface tension of an aqueous solution of the primary anionic detersive surfactant is lowered by at least 2 mN/m upon addition of the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant to the aqueous solution. The dynamic surface tension is preferably lowered by at least 5 mN/m, still preferably at least 10 mN/m. The dynamic surface tension is measured using maximum bubble pressure tensiometer BP 100. The dynamic surface tension is measured at 100 milliseconds. Preferably the water used for preparing the aqueous solution has a water hardness of 24°FH (Ca2+:Mg2+ of 2:1). The dynamic surface tension is preferably measured at a temperature of 21 °C to 22°C. The ratio of the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant and the primary anionic detersive surfactant in the aqueous solution is preferably from 1 :1 to 1 :200. The total concentration of the primary anionic detersive surfactant and the branched Cs to C14 alkyl alkoxylated sulphated co-surfactant in the aqueous solution when measuring the dynamic surface tension preferably ranges from 0.02 wt.% to 1.5 wt.%. Dynamic surface tension (DST) is generally used to measure the capability of one solution to lower surface tension and wet substrate under high-speed process conditions. The present inventors have found that the addition of the cosurfactant into the solution of primary anionic surfactant lowers the dynamic surface tension, the combination of the primary anionic surfactant and the cosurfactant together exhibit a dynamic surface tension which is lower than the dynamic surface tension of an aqueous solution having only primary anionic surfactant.
Foam supressinq agent
According to a first aspect of the present invention disclosed composition includes a foam supressing agent. The foam suppressing agent is selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof.
The term “foam suppressing agent” used herein should be understood to include both the terms antifoaming agent and defoaming agent. Similarly, the term "suppressing foam" should be understood as including both antifoaming and defoaming. Antifoaming is the prevention of foam in whole or in part. Defoaming is the diminishing or eliminating an already existing foam. The term foam suppressing agent also means agent which regulates the foam to a desired extent.
Additional foam suppressing agent may also include those selected from the group consisting of glycerol derivative, diester compound, fatty acid, soap, polyols or combinations thereof. More preferably the additional foam suppressing agent is selected from glycerol derivative, diester compound or mixtures thereof.
Preferably the foam suppressing agent is a delayed-release foam suppressing agent. By “delayed release” it is meant that the foam suppressing agent begins to suppress foam over time. The time delay may be adjusted depending on the time when the foam is required to be suppressed.
Silicone compound:
The foam suppressing agent may be a silicone compound. Preferably the silicone compound includes a reactive siloxane structural unit comprising Si-0 moieties where the reactive siloxane is a polymer which may include one or more functional moieties selected from the group amino, amido, alkoxy, hydroxy, polyether, carboxy, hydride, mercapto, sulfate phosphate and/or quaternary ammonium moieties. These moieties may be attached directly to the siloxane backbone through a bivalent alkylene radical, (i.e., "pendant") or may be part of the backbone. Suitable functionalized siloxane polymers include materials selected from the group consisting of aminosilicones, amidosilicones, silicone polyethers, silicone-urethane polymers, quaternary ABn silicones, amino ABn silicones, and combinations thereof. Preferably the silicone compound is an organopolysiloxane preferably having an amino-functional or a carboxyl-functional organic group. Suitable organosilicone may be linear, branched, or cross linked. The silicone compound may belong to the organosiloxane class of amino amino-functional organopolysiloxane, carboxy-functional organopolysiloxane, polydimethyl siloxane, silicone polyether or mixtures thereof.
Amino-functional organopolysiloxane:
The silicone compound may also be selected from a reactive siloxane which is a silicone aminoalcohol. Yet another preferred silicone compound includes a reactive siloxane which is an aminosilicone.
Preferably the foam suppressing agent is an amino-functional organopolysiloxane (IV) which has at least one siloxane unit of the general formula
Figure imgf000017_0001
. (iv a) and at least one siloxane unit of the general formula
Figure imgf000017_0002
wherein:
R1 is the same or different and is a hydrogen atom, a monovalent, optionally fluorine-, chlorine- or bromine- substituted Ci to Cis hydrocarbyl radical or a Ci to C12 alkoxy radical or a hydroxyl radical, preferably a Ci to C18 hydrocarbyl radical or a Ci to C3 alkoxy radical or a hydroxyl radical, where Q is an amino group of the general formula
-R2-[NR3-(CH2)m-]xNR4R5 or forms thereof with partial or full protonation on the nitrogen atoms - NH2 CH2CH2NH(CH2)3 is a preferred example.
R2 is a divalent Ci to Cis hydrocarbyl radical, preferably a divalent C2 to C4 hydrocarbyl radical hydrocarbyl radical, R3 is a hydrogen atom or a Ci to C10 alkyl radical, R4 is a hydrogen atom or a Ci to C10 alkyl radical, R5 is a hydrogen atom or a Ci to C10 alkyl radical, a is 0, 1 or 2, preferably 0 or 1 , b is 1 , 2 or 3, preferably 1 , c is 0, 1 , 2 or 3, preferably 2 or 3, m is 2, 3 or 4, preferably 2 or 3, and x is 0, 1 or 2, preferably 0 or 1 , and the sum of a+b is less than or equal to 3. The hydrocarbyl radical mentioned may be saturated or unsaturated, linear, branched or a cyclic radical.
Preferably the ratio of siloxane units with the general formula (la) to (lb) is from 1 :1 to 1 :10,000 and preferably from 1 :2 to 1 :300. The amino-functional organopolysiloxanes preferably have an average viscosity of 25 to 10,000 mPas, more preferably 50 to 5,000 mPas, at 25°C.
Preferably the foam suppressing agent is in solid form which includes an aminofunctional organopolysilioxane of formula IV and a carrier material selected from the group of sodium carbonate, sodium sulphate, aluminium silicate, potassium carbonate, potassium sulphate, sodium hydrogencarbonate, potassium hydrogencarbonate and zeolites, and mixtures thereof.
Another preferred foam suppressing agent is a modified amino-functional organopolysilioxane have the general formula (V)
Figure imgf000018_0001
where R2 is the same or different and is a monovalent Ci to C18 hydrocarbyl radical, R1 is as defined above for (IVa) Q is as defined above for (IVa), k is 0 or 1 , m is 0 or an integer from 1 to 1000, n is 0 or an integer from 1 to 50, with the proviso that the organopolysiloxanes contain at least one Q radical per molecule.
Examples of amino-functional organopolysiloxanes of the formula (V) are aminofunctional polydimethylsiloxanes terminated by trimethylsiloxane units and aminofunctional polydimethylsiloxanes terminated by hydroxydimethylsiloxane units and Ci to C3 alkoxydimethylsiloxane units.
Yet another type of modified amino silicone organopolysiloxane useful in the present invention is the one having the formula (VI)
XR-?Si(OSiAR)rt(OSiR 'LiOSiR,X
"" . (VI) where:
A is an amino radical of the formula
Figure imgf000019_0001
or a protonated amino form and/or acylated amino form of the amino radical A, preferably A is -(CH2)3NH2 and -(CH2)3NH(CH2)2NH2; X is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms or a polyoxyalkylene group G of the formula
Figure imgf000019_0002
preferably G is -(CH2)3-(OC2H4)y-O-R6
R1 is a Ci to C10 alkylene radical, preferably a radical of the formula -CH2CH2CH2-,
R2 is hydrogen or a Ci to C4 alkyl radical, preferably hydrogen,
R3 is a Ci to C10 alkylene radical, preferably a radical of the formula -CH2CH2-,
R4 is a Ci to C10 alkylene radical, preferably a radical of the formula -CH2CH2CH2-, R5 is a Ci to C4 alkylene radical, preferably a radical of the formula -CH2CH2-, or -CH2CH2(CH3)- or mixtures thereof;
R6 is hydrogen or a Ci to C4 alkylene radical, preferably hydrogen or a methyl radical, more preferably hydrogen, n is an integer from 1 to 6, preferably from 1 to 3, m is an integer from 1 to 200, preferably from 1 to 80, x is 0 or 1 and y is an integer from 5 to 20, preferably from 5 to 12, with the proviso that on an average from 30 mol% to 60 mol%, preferably 30 mol% to 50 mol%, of the radicals X are polyoxyalkylene group G.
The modified amino silicone organopolysiloxane are generally a fluid and therefore need a carrier filler selected from the group comprising sodium carbonate, sodium sulphate, aluminum silicate, potassium carbonate, potassium sulphate, sodium bicarbonate, potassium bicarbonate and zeolites to form a free-flowing powder form. Still another preferred type of modified amino silicone organopolysiloxane useful in the present invention is the one having the formula (VII)
Y/R1 3 iO(RR2SiO (YR1SiO)„(Me2SiO)vSiRI 3A ,vl h where:
Y is an amino group of the general formula
-R3— [NR4— (CH2)„— ],NR5R6 or the protonated or acylated amino forms of the amino group Y,
R1 is the same or different and is a monovalent Ci to Ge alkyl radical or a Ci to Ce alkoxy radical or a hydroxyl radical, R is a monovalent Ci to Ce alkyl radical, R2 is a monovalent C2 to Ce alkyl radical, R3 is a Ci to C10 alkylene radical, R4 is a hydrogen or a Ci to C4 alkyl radical, R5 and R6 independently represent hydrogen or a Ci to C4 alkyl radical, j is an integer from 0 to 3, k is an integer from 0 to 3, z is an integer from 1 to 500, n is an integer from 1 to 70, m is an integer from 1 to 10, v is an integer from 0 to 15, x is an integer from 0 to 1. The amino radical Y is preferably -(CH2)3NH2 and - (CH2)3NH(CH2)2NH2 and its protonated acylated form or its mixtures thereof.
These modified amino silicone organopolysiloxane are generally a fluid and therefore need a carrier filler. Preferably the carrier filler is water-soluble with a water solubility of 50 to 500 g/L at 25°C. More preferably the carrier filler is selected from the group comprising sodium carbonate, sodium sulphate, aluminum silicate, potassium carbonate, potassium sulphate, sodium bicarbonate, potassium bicarbonate and zeolites, water soluble starch or mixtures thereof to form a free-flowing powder form.
Yet another preferred silicone compound is where the reactive siloxane may preferably be a silicone polyether. In general, silicone polyethers comprise a polydimethylsiloxane backbone with one or more polyoxyalkylene chains. The polyoxyalkylene moieties may be incorporated in the polymer as pendent chains or as terminal blocks. Such silicones are described in US Publication No. 2005/0098759, and US Patent Nos. 4,818,421 and 3,299,112. The foam suppressing agent may be polysiloxane having the structure:
Figure imgf000021_0001
where R and R' are the same or different alkyl or aryl groups having from 1 to 6 carbon atoms; and x is an integer of at least 20. The preferred polysiloxanes are polydimethylsiloxanes, where both R and R' are methyl groups. The polysiloxanes usually have a molecular weight of from 500 to 200,000 and a kinematic viscosity of from 50 to 2x106 mm2sec’1. Preferably, the polysiloxanes have a kinematic viscosity of from 5x102 to 5X104 mm2 sec1, most preferably from 3X103 to 3X104 mm2 se 1 at 25°C. The polysiloxane is generally end blocked with trimethylsilyl groups, but other end-blocking groups are also suitable. Examples of suitable commercially available polysiloxanes are the polydimethyl siloxanes, "Silicone 200 Fluids", available from Dow Corning, having viscosities of from 50 to 5x104 mm2 sec1. Other examples of silicone oils include silicone oils 47v 100, 47v 5000 and 47v 12500 available from Rhone Poulenc; Silcolapse 430 and Silicone EP 6508 available from ICI; Rhodosil 454 available from Rhone Poulenc; and Silkonol AK 100 available from Wacker.
Preferably the silicone compound is an organosilicones selected from polydimethylsiloxane, dimethicone, dimethiconol, dimethicone crosspolymer, phenyl trimethicone, alkyl dimethicone, lauryl dimethicone, stearyl dimethicone and phenyl dimethicone, octyl amidomethicone, cetyl amidomethicone. Still preferably the silicone compound is selected from polydimethylsiloxane, octyl amidomethicone, cetyl amidomethicone and mixtures thereof. Examples include those available under the names DC 200 Fluid, DC 1664, DC 349, DC 346G available from Dow Corning Corporation, Midland, Ml, and those available under the trade names SF1202, SF1204, SF96, and Viscasil available from Momentive Silicones, Waterford, NY. In addition to the abovementioned foam suppressing agent a further foam suppressing agent such as finely divided particulate silica may also be used in the composition of the present invention. Any type of silica can be employed in the preparation of hydrophobic silica. Preferred examples are precipitated silica and pyrogenic silica which can be converted to a hydrophobic form. More preferably the foam suppressing agent includes a mixture of polydimethylsiloxane and silica.
Additional foam suppressing agent
Additional foam suppressing agent may also include those selected from the group consisting of glycerol derivative, diester compound, fatty acid, soap, polyols or combinations thereof. More preferably the additional foam suppressing agent is selected from glycerol derivative, diester compound or mixtures thereof.
Diester compound:
The foam suppressing agent as disclosed in the present invention is preferably a cyclohexane polycarboxylic acid derivative of the formula (VIII)
Figure imgf000022_0001
in which
R1 may be identical or different. It is selected from straight chain or branched Ci to C - alkyl or C3 to Cs -cycloalkyl; m is 0, 1 , 2 or 3; n is 2, 3 or 4, and R is H or a straight chain or branched Ci to C30 alkyl, where at least one radical R is Ci to C30 alkyl.
Preferably R1 is an alkyl group selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl. Preferably the R is an alkyl radical which includes those already mentioned under R1 and n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, stearyl, n-eicosyl, where at least one radical R is n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, stearyl, n- eicosyl. Preferably the R is isononyl.
The cyclohexane polycarboxylic acid derivatives may be selected from mono-, di-, tri-, tetra esters and anhydrides of cyclohexane polycarboxylic acids. Preferably, all the carboxylic acid groups are esterified. Preferably the cyclohexane polycarboxylic acid derivative is chosen from the group consisting of ring-hydrogenated mono- and dialkyl esters of phthalic acid, isophthalic acid and terephthalic acid, ring-hydrogenated mono-, di- and trialkyl esters of trimellitic acid, of trimesic acid and of hemimellitic acid, or mono-, di-, tri- and tetra alkyl esters of pyrromellitic acid, where the alkyl groups may be linear or branched and in each case have 1 to 30, preferably 2 to 10, particularly preferably 3 to 18, carbon atoms, and mixtures of two or more thereof.
Preferably the cyclohexane polycarboxylic acid derivative is an alkyl ester of cyclohexane-1 ,4-dicarboxylic acid, alkyl ester of cyclohexane-1 ,2-dicarboxylic acid, mixed esters of cyclohexane-1 ,2-dicarboxylic acid with Ci to C13 alcohols, mixed esters of cyclohexane-1 ,3-dicarboxylic acid with Ci to C13 alcohols, mixed esters of cyclohexane-1 ,4-dicarboxylic acid with Ci to C13 alcohols, alkyl esters of cyclohexane- 1 , 3-dicarboxylic acid.
More preferably the cyclohexane polycarboxylic acid derivative is an alkyl ester of cyclohexane-1 ,2-dicarboxylic acid as given in the formula below where R3 and R4 are mutually independently selected from branched and unbranched C7 to C12 alkyl residues. Preferably, C7 to C12 alkyl is selected from n-heptyl, 1 -methylhexyl, 2- methylhexyl, 1 -ethyl pentyl, 2-ethyl pentyl, 1 -propylbutyl, 1-ethyl-2-methylpropyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, 2-propylhexyl, n-decyl, isodecyl, 2- propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl and the like. Particularly preferably C7 to C12 alkyl stands for n-octyl, n-nonyl, isononyl, 2-ethylhexyl, isodecyl, 2- propylheptyl, n-undecyl or isoundecyl. Preferably the residues R3 and R4 both stand for 2-ethylhexyl, isononyl or 2- propylheptyl.
Figure imgf000024_0001
The alkyl ester of cyclohexane-1,2-dicarboxylic acid is preferably selected from the group consisting of di(isobutyl) ester of cyclohexane-1 , 2-dicarboxylic acid, di(2- ethylhexyl) ester of cyclohexane-1 , 2-dicarboxylic acid, di(isononyl) ester of cyclohexane-1 , 2-dicarboxylic acid. Preferred ester groups are straight-chain or branched alkyl groups having 6 to 13 carbon atoms. Most preferably it is a di(isononyl) ester of cyclohexane-1 , 2-dicarboxylic acid. Diisononylcyclohexane-1 , 2-dicarboxylate is commercially available under the name Hexamoll® DINCH (BASF AG). The cyclohexane polycarboxylic acid derivatives are preferably prepared according to the process disclosed in WO 99/32427.
Glycerol derivative:
The foam suppressing agent is preferably a glycerol derivative. The glycerol derivative has the general formula (IX) as mentioned herein below.
R1OCH2CH(OH)CH2OR2 ,iy. wherein the R1 is H or Ci2 to Cis saturated or unsaturated alkyl ester and R2 is Ci2 to Cis saturated or unsaturated alkyl ester.
The glycerol derivative is preferably glycerol monooleate, glycerol dioleate, glycerol monostearate, glycerol distearate and mixtures thereof, preferably the glycerol derivative is a glycerol monostearate, glycerol monooleate or mixtures thereof. Most preferably the glycerol derivative is a glycerol monooleate.
In a preferred embodiment the foam suppressing agent is a glycerol derivative used in combination with methyl cellulose. Preferably glycerol monooleate is used in combination with methyl cellulose. The ratio of glycerol derivative to methyl cellulose is at least 0.6, preferably at least 0.75, more preferably 1. The ratio of glycerol derivative to methyl cellulose is at most 1, preferably at most 2, more preferably at most 5, even more preferably at most 7.
Preferably the foam suppressing agent when it is a glycerol derivative is present in the detergent composition in an amount ranging from 0.5 wt.% to 5 wt.%. Preferably the levels of the glycerol derivative in the detergent composition is at least 0.75 wt.%, still preferably at least 1 wt.%, still preferably at least 1.25 wt.%, most preferably at least 1.5 wt.%, but typically not more than 4.75 wt%, still preferably not more than 4.5 wt%, most preferably not more than 4 wt%.
Other suitable foam suppressing agents include the monocarboxylic fatty acids and soluble salts thereof, which are described in US 2,954,347. Other foam suppressing agents are described in EP-A-0210731 and EP-A-0210721.
Preferably the solid detergent composition according to the present invention comprises from 0.05 wt.% to 2.0 wt.% foam suppressing agent. Preferably the solid detergent composition comprises at least 0.08 wt.%, preferably at least 0.1 wt.%, still preferably at least 0.2 wt.% and most preferably at least 0.4 wt.%, but typically not more than 1.5 w.t%, still preferably not more than 1.3 wt.%, still further preferably not more than 1.2 wt.% and most preferably not more than 1 wt.% where the foam suppressing agent is selected from silicone compound, amino silicone compound or mixtures thereof.
Carbonate builder
The detergent composition of the present invention includes a sodium carbonate builder. Examples of the carbonate builder includes alkaline earth metal and alkali metal carbonates as disclosed in the German patent application No. 2,321,001.
The carbonate builder preferably includes further alkali metal carbonate, alkaline earth metal carbonate or mixtures thereof. Preferred further alkali carbonates potassium carbonate. It is further preferred that sodium carbonate makes up at least 75 wt.%, more preferably at least 85 wt.% and even more preferably at least 90 wt.% of the total weight of the alkali metal carbonate builder. The detergent composition of the present invention includes from 0.1 wt.% to 40 wt.% sodium carbonate builder. More preferably the sodium carbonate builder is present in an amount ranging from 0 wt.% to 20 wt.% in the composition. Preferably the detergent composition comprises at least 0.8 wt.%, still preferably at least 1 wt.%, still preferably at least 2 wt.%, most preferably at least 5 wt.% of the carbonate builder, but typically not more than 38 wt.%, still preferably not more than 35 wt.%, most preferably not more than 30 wt.% of sodium carbonate builder based on the weight of the cleaning composition.
Non-carbonate builder
In addition to the sodium carbonate builder the detergent composition of the present invention may preferably include further inorganic non-carbonate builder. The other preferred builders may be selected from the group consisting of silicates, silica, zeolites phosphates or mixtures thereof. Yet other non-carbonate builder may be organic builders which includes but are not limited to as succinates, carboxylates, malonates, polycarboxylates, citric acid or a salt thereof.
Suitable silicates include the water-soluble sodium silicates with an SiCh: Na2O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiCh: Na2O ratio of 2.0 is the most preferred silicate.
Silicates are preferably present in the detergent compositions in accordance with the invention at a level of from 5 wt.% to 50 wt.% of the composition, more preferably from 10 wt.% to 40 wt.% of the solid laundry detergent composition. Still more preferably the silicates are present in an amount ranging from 5 wt.% to 18 wt.% of the solid laundry detergent composition.
The composition is preferably phosphate builder free, that is the composition has no deliberately added phosphate builder such as STPP. Preferably the detergent composition includes 0 wt.% to 8 wt.% phosphate builder, still preferably the composition has no deliberately added phosphate builder. Most preferably the solid laundry detergent composition includes 0 wt.% phosphate builder. Preferably the detergent composition includes 0 wt.% to 8 wt.% zeolite, still preferably the composition has no deliberately added zeolite. Most preferably the solid laundry detergent composition includes 0 wt.% zeolite builder.
Form of the composition
The composition of the present invention is in the solid form. The composition according to the present invention may be made via a variety of conventional methods known in the art and those which includes but is not limited to the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tabletting, or spraydrying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying. The detergent composition may be made by any of the conventional processes, especially preferred is the technique of slurry making and spray drying.
The compositions herein can take a variety of physical solid forms including forms such as powder, granule, particulate ribbon, noodle, paste, tablet, flake, pastille and bar, and preferably the composition is in the form of powder, granules or a tablet, still preferably the composition is in the form of a powder. The composition may be in the form of a unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein. The composition according to the present invention may preferably be in a form selected from powder, unit dose or pouch form, tablet, gel, paste, bar, or flake. Preferably the composition is for manualwashing. Preferably, the composition of the present invention is a solid laundry detergent composition. Preferably the composition is prepared using a mixing route or a spray drying process, preferably the composition in the form of a spray -dried powder.
The compositions preferably have a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.
The composition according to the present invention has a pH of from 8 to 13, preferably from 8.5 to 12, more preferably 8.5 to 11 when measured at 1 wt.% dilution in deionised water at 25°C. The sodium carbonate builder provides the desired pH to the composition. In addition to the sodium carbonate builder which is essential, the composition of the present invention preferably also includes further alkaline source which is selected from bicarbonates and semi-bicarbonates. The composition may preferably include a buffer.
Moisture content:
The solid detergent composition includes from 1 wt.% to 3.5 wt.%, still preferably 1 wt.% to 3 wt.% water. Preferably the solid detergent composition is either agglomerated or spray-dried.
Optional ingredients
The detergent composition of the present invention may preferably include one or more of the optional ingredients selected from the group consisting of cleaning and care ingredients. The optional ingredients include one or more adjunct cleaning additives selected from polymers, enzymes, enzyme stabilizer, brightening agents, hueing agent, bleach, chelating agent, humectant, perfume, filler or carrier, an alkalinity system, a buffer or combinations thereof.
Polymers:
The composition of the present invention may preferably include polymers which provide cleaning or care benefits. The cleaning polymer includes but is not limited to soil release polymer, carboxylate polymers, antiredeposition polymers, cellulosic polymers, care polymers, dye-transfer inhibiting polymer, amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil suspending polymers or mixtures thereof.
Suitable carboxylate polymer includes polymers such as a maleate/acrylate random copolymer or polyacrylate homopolymer. Suitable carboxylate polymers homopolymeric or copolymeric carboxylic acids, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of acrylic acid or methacrylic acid with maleic acid. Preferred representatives of this group are sodium polyacrylate and sodium salts of acrylic acid-maleic acid copolymers.
Soil release polymers are designed to modify the surface of the fabric to facilitate the ease of removal of soil. Suitable soil release polymers are sold by Clariant under the TexCare® series of polymers, e.g. TexCare® SRN240. Other suitable soil release polymers are sold by Rhodia under the Repel-o-Tex® series of polymers, e.g. Repel-o- Tex® SF2. A preferred polymer is selected from the group consisting of polyester soil release polymer, both end-capped and non-end-capped sulphonated or unsulphonated PET/POET polymers. Preferably the levels of these soil release polymer in the adjunct particle is from 3 wt.% to 15wt.%.
Anti-redeposition polymers are designed to suspend or disperse soil. Typically, antiredeposition polymers are polyethylene glycol polymers, polycarboxylate polymers, polyethyleneimine polymers or mixtures thereof. Such polymers are available from BASF under the trade name Sokalan®CP5 (neutralised form) and Sokalan®CP45 (acidic form). Suitable antiredeposition polymers are ethoxylated and or propoxylated polyethylene imine or polycarboxylate materials, for example, acrylic acid-based homo or copolymers available under the trademark ACLISOL from Dow Chemical, Alcosperse from Akzonobel or Sokolan from BASF.
Suitable care polymers include cellulosic polymers that are cationically modified or hydrophobically modified. Such modified cellulosic polymers can provide anti- abrasion benefits and dye lock benefits to fabric during the laundering cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose.
Examples of suitable sequestering polymers are DEQUEST™, organic phosphonate type sequestering polymers sold by Monsanto and alkanehydroxy phosphonates. The cleaning composition is preferably substantially free of phosphate based sequestering polymers. By substantially free, it is meant herein that no phosphate based sequestering polymers is deliberately added.
Enzymes:
The composition of the present invention preferably includes one or more enzymes. Preferred examples of the enzymes include those which provide cleaning performance and/or fabric care benefits.
Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, xyloglucanase, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, G-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with one or more of amylase, mannanase and cellulase. When present in a detergent composition, the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or from 0.001% to about 0.5% enzyme protein by weight of the detergent composition. Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Maxatase®, Maxaca®l, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, 10 Excellase® and Purafect OXP® by Genencor International, those sold under the tradename Opticlean® and Optimase by Solvay Enzymes. Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd, Denmark), 15 KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, California) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include NATALASE®, STAINZYME and STAINZYME PLUS® and mixtures thereof. Preferred lipases would include those sold under the tradenames Lipex® and Lipolex®. Suitable endoglucanases are sold under the tradenames Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark). Other preferred enzymes include pectate lyases sold under the tradenames Pectawash®, Pectaway®, Xpect® and mannanases sold under the tradenames Mannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite® (Genencor International Inc., Palo Alto, California).
Enzyme stabilizing system:
The enzyme-containing compositions described herein may optionally comprise from 0.001% to 10%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, chlorine bleach scavengers and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the cleaning composition. In the case of detergent compositions comprising protease, a reversible protease inhibitor, such as a boron compound, including borate, 4-formyl phenylboronic acid, phenylboronic acid and derivatives thereof, or compounds such as calcium formate, sodium formate and 1,2-propane diol may be added to further improve stability.
Brightening agents:
Optical brighteners or other brightening or whitening agents may be incorporated at levels from 0.01% to 1.2%, by weight of the composition. Commercial brighteners suitable for the present invention can be classified into subgroups, including but not limited to: derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylic acid, methinecyanines, dibenzothiophene-5, 5- dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Preferred commercially available Brighteners includes Tinopal AMS-GX by Ciba Geigy Corporation, Tinopal UNPA-GX by Ciba-Geigy Corporation, Tinopal 5BM-GX by Ciba-Geigy Corporation. The brighteners may be added in particulate form or as a premix with a suitable solvent, for example nonionic surfactant, monoethanolamine, propane diol.
Fabric hueing agents:
The composition may comprise a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents). Typically the hueing agent provides a blue or violet shade to fabric. Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade. Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including 30 premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof. Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Additional surfactants:
In addition to the primary anionic detersive surfactant and the cosurfactant the detergent composition according to the present invention may include additional surfactants selected from but not limited to non-ionic surfactant, amphoteric surfactant cationic surfactant, zwitterionic surfactant, or mixtures thereof.
Non-ionic surfactant
Non-limiting examples of nonionic surfactants include: C12 to C18 alkyl ethoxylates, Ce to C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; C12 to C18 alcohol and Ce to C12 alkyl phenol condensates with ethylene oxide/propylene oxide block alkyl polyamine ethoxylates alkylpolysaccharides and ether capped poly(oxyalkylated) alcohol surfactants.
Cationic surfactant
Non-limiting examples of cationic surfactants include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylate quaternary ammonium (AQA) surfactants, dimethyl hydroxyethyl quaternary ammonium, dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants and cationic ester surfactants.
Zwitterionic surfactant
Non-limiting examples of zwitterionic or ampholytic surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants includes betaines, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, Cs to C18 (for example from C12 to Cis) amine oxides and sulfo and hydroxy betaines, such as N- alkyl-N, N-dimethylammino-1-propane sulfonate where the alkyl group can be Cs to Cis and in certain embodiments from C10 to C14.
Fillers
Optionally the solid laundry detergent composition includes fillers such as sodium sulphate, sodium chloride, calcite, dolomite or mixtures thereof. Methods of laundering:
According to a second aspect of the present invention, disclosed is a method for laundering a textile surface with the detergent composition according to the first aspect of the present invention comprising the steps of: i) preparing an aqueous wash liquor with an effective amount of foam by contacting the detergent composition according to the first aspect with a liquid; ii) soaking said textile surface in the wash liquor for a predetermined period of time; and, iii) optionally rinsing the textile surface.
Preferably the rinsing of the textile surface is carried in less than 3 rinsing steps, preferably less than 2 rinsing steps more preferably in a single rinsing step.
According to a second aspect the method includes the step of preparing an aqueous wash liquor of the detergent composition in a liquid. The wash liquor is preferably prepared by dissolving the detergent composition in water.
In the next step, preferably the textile surface is subjected to a washing step prior to the aforementioned optional rinsing step. For purposes of the present invention, washing includes, but is not limited to, scrubbing, wiping and mechanical agitation.
The compositions are preferably employed at concentrations of from about 200 ppm to about 10,000 ppm in solution. The water temperatures preferably range from about 5°C to about 100°C.
Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of the detergent composition in accordance with the invention. By an effective amount of the detergent composition it is meant from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 65 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Hand-washing methods, and combined handwashing with semiautomatic washing machines are also included. According to a third aspect of the present invention disclosed is the use of a primary anionic detersive surfactant selected from the group consisting of sulfate surfactant, sulphonate surfactant, alkyl ether sulphate surfactant or mixture thereof, a foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof and a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 in a detergent composition to provide good lather generation in the wash liquor during the main wash stage and collapse of lather during rinse stage and wherein the rinse stage requires less than 3 rinses.
The invention will now be illustrated more fully with the aid of the following non-limiting examples. It will be appreciated that other modifications of the present invention within the skill of those in the art can be undertaken without departing from the spirit and scope of this invention. All of the formulations exemplified hereinafter are prepared via conventional formulation and mixing methods unless specific methods are given. All parts, percentages, and ratios herein are by weight unless otherwise specified.
Examples
Example 1: Measurement of the dynamic surface tension
Aqueous solution Ex A: 2 grams of a solid laundry detergent composition having 20 wt.% primary anionic detersive surfactant (sodium linear alkyl benzene sulphonate, NaLAS) was added to 1000 mL of water having a hardness of 24°FH (Ca:Mg 2:1) and stirred for complete dissolution. The concentration of NaLAS in the aqueous solution was 0.04 wt.%.
Aqueous solution Ex 1: 2 grams of a solid laundry detergent composition having 20 wt.% primary anionic detersive surfactant (sodium linear alkyl benzene sulphonate, NaLAS) and 0.5 wt.% sodium salt of C alkyl ether carboxylic acid (cosurfactant) was added to 1000 mL of water having a hardness of 24°FH (Ca:Mg 2:1) and stirred for complete dissolution. The concentration of NaLAS in the aqueous solution was 0.04 wt.% and the concentration of cosurfactant was 0.001 wt.%. Here the ratio of the cosurfactant to primary detersive surfactant was 1:40. Dynamic surface tension measurement: 50 mL of the above prepared solution was taken, and the dynamic surface tension was measured using a maximum bubble pressure tensiometer BP 100 (from Kruss), at 100 milliseconds. The dynamic surface tension was recorded for each solution and provided in table 1 below.
Table 1
Figure imgf000035_0001
It was seen that when the cosurfactant and the primary anionic detersive surfactant are present in the specified ratio ranges, then the addition of the cosurfactant lowered the dynamic surface tension.
Example 2
Different comparative detergent compositions and detergent compositions according to the present invention were prepared having the ingredients as provided in Table 2. The detergent compositions used the following ingredients:
LAS: Linear alkyl benzene sulphonate (primary anionic detersive surfactant) AEC: C alkyl ether carboxylic acid surfactant (cosurfactant)
Silicone oil: foam suppressing agent
Builder: sodium carbonate
Filler: sodium sulphate
Foam measurement method: The foam volume generated by the various detergent compositions as provided in table 2 was measured using the automated cylinder shake protocol.
In the automated cylinder shake protocol firstly a known amount of the detergent powder was added in a beaker containing water to form a 3gpl wash liquor The water had a hardness of 24° FH (Ca:Mg, 2:1). The beaker was placed on a magnetic stirrer for 20 minutes at a speed of 150 rpm for complete dissolution of the detergent composition in water to form an aqueous liquor (AL). A. In a first set of foam measurement, 40 mL of the aqueous liquor (AL) formed above was taken in a 250 mL stoppered graduated glass cylinder. The glass cylinder is marked at 2 mL intervals and has a height of 14 inches from the inside of the bottom to the 250 mL mark. Next the cylinder was clamped in an automated cylinder shake (rotating device), which clamps the cylinder with respect to an axis of rotation that traverses the center of the graduated cylinder. a) The cylinder was rotated at a speed of 30 revolutions per minute. The cylinder was allowed to complete 5 full revolution and stopped at a vertical position. The height of the foam from the bottom was recorded in mL and provided in Table 2 below. b) After noting the foam height, the cylinder was again rotated and was allowed to complete 5 more revolutions and thereafter stopped at a vertical position. The height of the foam after the 10 revolutions was measured from the bottom and recorded in mL, the measured foam height provided in Table 2 below.
B. In a second set of foam measurement, 4 mL of the prepared aqueous liquor (AL) was taken in the 250 mL stoppered graduated glass cylinder. To this 36 mL of water was added. The water had a hardness of 24° FH (Ca:Mg, 2:1). Next the cylinder was clamped in an automated cylinder shake (rotating device) and rotated for 5 revolutions and 10 revolutions respectively as described above and the measured foam height after 10 revolutions were recorded and provided in Table 2 below.
In the rest time between the first and the second sequence of 5 rotations in this set of experiment is maintained the same way as in the first set of experiment.
Table 2
Figure imgf000037_0001
As shown in the data, in the first set of experiment which is demonstrative of the main wash stage in a laundering process in which the consumers desired foam, the detergent composition according to the present invention (Ex 2) shows good foam as compared to the comp Ex B (LAS without foam suppressing agent) and Comp Ex C (LAS with foam suppressing agent). In the 2nd set of experiments which is demonstrative of the rinse stage in a laundering process where the foam needs to be removed quickly, it is clearly seen that the composition according to the present invention achieves quick foam reduction as compared to the Comp Ex B and is comparable to Comp Ex C.
Thus, the above set of examples clearly show that the detergent composition according to the present invention exhibits good foam volume in the initial wash cycle and thereafter it also provides desirable low sudsing properties in the rinse stage which minimizes the wastage of clean water required for rinsing.
Example 3
Different comparative detergent compositions and detergent compositions according to the present invention were prepared having the ingredients as provided in Table 3 having different foam suppressing agents. Table 3
Figure imgf000038_0001
As shown in the data, in the first set of experiment which is demonstrative of the main wash stage in a laundering process in which the consumers desired foam, the detergent composition according to the present invention (Ex 3) having LAS (primary anionic surfactant), C10 branched alkyl sulphated surfactant with 4EO group shows good foam as compared to the comp Ex D (LAS without foam suppressing agent) and Comp Ex E (LAS with silicone foam suppressing agent). In the 2nd set of experiments which is demonstrative of the rinse stage in a laundering process where the foam needs to be removed quickly, it is clearly seen that the composition according to the present invention achieves quick foam reduction as compared to the Comp Ex D and is comparable to Comp Ex E.
Also, seen in the table above is that a comparative composition (Ex F) having LAS, and a nonionic surfactant as the foam suppressing agent gives lesser foam in the wash stage and foam reduction is also not easy in the rinse stage. Similarly, the foam reduction in the comparative composition Ex G having LAS, C10 branched alkyl sulphated cosurfactant with 4EO group and nonionic surfactant foam suppressing agent is not easy. On the other hand, the composition according to the present invention Ex 3 having LAS, C10 branched alkyl sulphated surfactant with 4EO group and silicone foam suppressing agent gives good foam in the wash stage which is easily rinsed off in the rinse stage of the washing process even under cold water and room temperature conditions.

Claims

1 A solid laundry detergent composition comprising: i) a primary anionic detersive surfactant selected from the group consisting of sulphate surfactant, sulphonate surfactant, alkyl ether sulphate surfactant or mixture thereof; ii) a branched Cs to C14 alkyl alkoxylated sulphated co-surfactant with a number average degree of ethoxylation in the range from 2.5 to 10; and, iii) a foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound or mixtures thereof.
2 A composition according to claim 1 wherein the dynamic surface tension of an aqueous solution of the primary anionic detersive surfactant is reduced by at least 2 mN/m upon addition of the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant to the aqueous solution, where the surface tension is measured using maximum bubble pressure tensiometer BP 100, at 100 milliseconds and where the ratio of the cosurfactant to the primary anionic detersive surfactant in the aqueous solution is from 1 :1 to 1 :200 and wherein the total amount of the primary anionic surfactant and the cosurfactant in the aqueous solution ranges from 0.02 wt.% to 0.15 wt.%.
3 A composition according to claim 1 wherein the composition comprises a sodium carbonate builder.
4 A composition according to claim 1 or 2 wherein the composition comprises an additional cosurfactant selected from the group consisting of: i) alkyl ether carboxylic acid surfactant having the general formula (I):
Ri-(OCH2CH2)n-OCH2-COOX . (I) wherein:
Ri is selected from saturated or mono-unsaturated, linear or branched, average chain length is from Cs to C14 alkyl or alkenyl chain; n has a value in the range from 1 to 20; and, X represent H or a suitable cation selected from the group consisting of alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or mixtures thereof; or, ii) amino acid-based surfactant having the general formula (II):
Figure imgf000041_0001
wherein,
R is selected from saturated or unsaturated Cs to C14 alkyl group,
Ri is selected from H, Ci to C4 alkyl,
R2 is selected from H or all groups on a carbon of natural amino acids,
R3 is selected from COOX, CH2 SO3X, where X is selected from the group consisting of alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or mixtures thereof, preferably selected from NH4 +, Li+, Na+ or K+; or, combinations thereof. A composition according to claim 1 wherein the foam suppressing silicone compound or amino silicone compound is selected from the group consisting of: i) amino-functional organopolysiloxane (IV) having at least one siloxane unit of the general formula
Figure imgf000041_0002
> (IVa) and at least one siloxane unit of the general formula
Figure imgf000041_0003
> (IVb) wherein:
R1 is the same or different and is a hydrogen atom, a monovalent, optionally fluorine-, chlorine- or bromine- substituted Ci to Cis hydrocarbyl radical or a Ci to C12 alkoxy radical or a hydroxyl radical, preferably a Ci to Cis hydrocarbyl radical or a Ci to C3 alkoxy radical or a hydroxyl radical, where Q is an amino group of the general formula
-R2-[NR3-(CH2)m-]xNR',R5 or forms thereof with partial or full protonation on the nitrogen atoms, R2 is a divalent Ci to C18 hydrocarbyl radical, preferably a divalent C2 to C4 hydrocarbyl radical hydrocarbyl radical,
R3 is a hydrogen atom or a Ci to C10 alkyl radical, R4 is a hydrogen atom or a Ci to C10 alkyl radical, R5 is a hydrogen atom or a Ci to C10 alkyl radical, a is 0, 1 or 2, preferably 0 or 1 , b is 1 , 2 or 3, preferably 1 , c is 0, 1 , 2 or 3, preferably 2 or 3, m is 2, 3 or 4, preferably 2 or 3, and x is 0, 1 or 2, preferably 0 or 1 , and the sum of a+b is less than or equal to 3; or, ii) amino-functional organopolysiloxane having the general formula V
Figure imgf000042_0001
where R2 is the same or different and is a monovalent Ci to C18 hydrocarbyl radical, R1 is the same or different and is a hydrogen atom, a monovalent, optionally fluorine-, chlorine- or bromine- substituted Ci to C18 hydrocarbyl radical or a Ci to C12 alkoxy radical or a hydroxyl radical, preferably a Ci to C18 hydrocarbyl radical or a Ci to C3 alkoxy radical or a hydroxyl radical, where Q is an amino group of the general formula
-R2-[NR3-(CH2)m-]xNR4R5 or forms thereof with partial or full protonation on the nitrogen atoms, k is 0 or 1 , m is 0 or an integer from 1 to 1000, n is 0 or an integer from 1 to 50, with the proviso that the organopolysiloxanes contain at least one Q radical per molecule; or, iii) amino-functional organopolysiloxane having the general formula VI
XR^SiCOSiARj^OSiR^OSiR^
Figure imgf000043_0001
where:
A is an amino radical of the formula
Figure imgf000043_0002
or a protonated amino form and/or acylated amino form of the amino radical A, X is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms or a polyoxyalkylene group G of the formula
Figure imgf000043_0003
R1 is a Ci to C alkylene radical, preferably a radical of the formula -CH2CH2CH2-,
R2 is hydrogen or a Ci to C4 alkyl radical, preferably hydrogen,
R3 is a Ci to C10 alkylene radical, preferably a radical of the formula -CH2CH2-,
R4 is a Ci to C10 alkylene radical, preferably a radical of the formula -CH2CH2CH2-,
R5 is a Ci to C4 alkylene radical, preferably a radical of the formula -CH2CH2-, or -CH2CH2(CH3)- or mixtures thereof;
R6 is hydrogen or a Ci to C4 alkylene radical, preferably hydrogen or a methyl radical, more preferably hydrogen, n is an integer from 1 to 6, m is an integer from 1 to 200, x is 0 or 1 and y is an integer from 5 to 20, with the proviso that on an average from 30 to 60 mol% of the radicals X are polyoxyalkylene group G; or, iv) amino-functional organopolysiloxane having the general formula VII
Figure imgf000044_0001
where:
Y is an amino group of the general formula
Figure imgf000044_0002
or the protonated or acylated amino forms of the amino group Y
R1 is the same or different and is a monovalent Ci to Ce alkyl radical or a Ci to Ce alkoxy radical or a hydroxyl radical,
R is a monovalent Ci to Ce alkyl radical,
R2 is a monovalent C2 to Ce alkyl radical,
R3 is a Ci to C10 alkylene radical,
R4 is a hydrogen or a Ci to C4 alkyl radical,
R5 and R6 independently represent hydrogen or a Ci to C4 alkyl radical. j is an integer from 0 to 3, k is an integer from 0 to 3, z is an integer from 1 to 500, n is an integer from 1 to 70, m is an integer from 1 to 10, v is an integer from 0 to 15, x is an integer from 0 to 1. A composition according to claim 1 wherein the co-surfactant is a C10 branched alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 6. A composition according to claim 6 wherein the co-surfactant is a C10 branched alkyl alkoxylated sulphated cosurfactant with a degree of ethoxylation in the range of 3, 4 or 5, preferably 4. A composition according to any one of the preceding claims wherein the primary anionic detersive surfactant is an alkali metal salt of C10 to C18 alkyl benzene sulfonic acid. A composition according to any one of the preceding claims wherein the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant and the primary anionic detersive surfactant is present in a ratio of 1 :1 to 1:200. A composition according to any one of the preceding claims wherein the branched Cs to C14 alkyl alkoxylated sulphated cosurfactant is present in an amount ranging from 0.05 wt.% to 5 wt.% in the composition. A composition according to any one of the preceding claims wherein the primary anionic detersive surfactant is present in an amount ranging from 2 wt.% to
20 wt.% in the composition. A composition according to any one of the preceding claims wherein the sodium carbonate builder is present in an amount ranging from 0 wt.% to 20 wt.% in the composition. A composition according to any one of the preceding claims wherein the foam suppressing agent is present in an amount ranging from 0.05 wt.% to 2 wt.% in the composition. A method of laundering a textile surface with the detergent composition according to any one of the preceding claims comprising the steps of: i) preparing a wash liquor having an effective amount of foam by contacting the detergent composition according to any one of the preceding claims 1 to 13 with a liquid; ii) soaking said textile surface in the wash liquor for a predetermined period of time; and, iii) rinsing the textile surface where the number of rinses required to remove the foam formed in step (i) is less than 3 rinses. Use of a primary anionic detersive surfactant selected from the group consisting of sulfate surfactant, sulphonate surfactant, alkyl ether sulphate surfactant or mixture thereof, a foam suppressing agent selected from the group consisting of silicone compound, amino silicone compound, or mixtures thereof; and a branched Cs to C14 alkyl alkoxylated sulphated cosurfactant with a number average degree of ethoxylation in the range from 2.5 to 10 to provide good lather generation in the wash liquor during the main wash stage and collapse of lather during rinse stage and wherein the rinse stage requires less than 3 rinses.
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