Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/34—Derivatives of acids of phosphorus
  • C11D1/345—Phosphates or phosphites
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• This invention relates to liquid detergent compositions and preferably compositions having a stable spherulitic structure and comprising a substantial proportion of non-ionic surfactant.
• the invention is especially applicable to the formulation of liquid detergent compositions having a controlled foaming character e.g. suitable for use in a front loading washing machine. It is also of value in preparing compositions suitable for use in low temperature wash regimes.
• a good balance of mobility and high pay load of useful ingredients is most readily obtained if the surfactants can be constrained to adopt a spherulitic structure by the presence of an appropriate concentration of an electrolyte which salts surfactants out of aqueous micellar solution and forms them into spherulites, which are believed to consist of a number of concentric shells, each comprising a curved surfactant bilayer, alternating with shells of aqueous electrolyte solution.
• spherulites are sufficiently closely packed, a stable structured liquid is formed, capable of suspending solid particles of builder. Compositions of this type are discussed in detail in our GB-A-2 153 380, the disclosure of which is incorporated herein by reference.
• mixtures of linear alkyl benzene sulphonates with alkyl ether sulphates, amine­oxides, or alkanolamides are all capable of forming stable spherulitic compositions and exhibit relatively cost-effective detergency, at least for natural fibres.
• compositions however have two disadvantages, which apply, respectively to those markets where front loading washing machines are commonly used, and to markets in which washing is carried out at low or ambient temperatures and/or the washload includes a high proportion of synthetic fibre.
• a further problem which may arise when liquid detergents are exported or sold at a point remote from the source of surfactant is the cost of transporting the water and builder content of the liquid detergent. It is convenient to be able to transport the active material as a concentrate in a form suitable for blending and dilution at a site closer to the point of sale. Such compositions need to be pourable and non-separating, but also to be relatively the cost of transporting the water and builder content of the liquid detergent. It is convenient to be able to transport the active material as a concentrate in a form suitable for blending and dilution at a site closer to the point of sale. Such compositions need to be pourable and non-separating, but also to be relatively concentrated. Many bulk surfactants, however, are difficult to concentrate above about 30% due to the formation of immobile M phases.
• Our invention provides a surfactant system for use in a liquid detergent consisting essentially of: an active mixture of (a) at least 50% by weight, based on the total weight of the surfactants present, of anionic surfactants comprising at least 20%, based on the total weight of the surfactants present, of an alkyl benzene sulphonate, and (b) at least 2% by weight, based on the total weight of the surfactants present, of an alkoxylated non-ionic surfactant having an HLB below 12; and sufficient water to provide a non-separating pourable spherulitic or G phase composition.
• the surfactant concentration of the surfactant system is greater than 28%, e.g. greater than 30% and preferably between 30 and 80%.
• the surfactant concentration is greater than 35% e.g. 40 to 75% especially 50 to 70% by weight.
• the surfactant system preferably consists essentially of surfactant and water together with such traces of sodium sulphate as are unavoidably present as an impurity in the anionic surfactant. It is, however, possible to include minor proportions of non-surfactant electrolytes in order to modify the viscosity and/or phase structure of the composition. We generally prefer that such electrolytes be present in proportions of less than 10%, preferably less than 5%, usually less than 2%, e.g. less than 1% of the total weight of the surfactant system. The presence of organic solvents is not preferred.
• our invention provides a liquid detergent composition
• a liquid detergent composition comprising water, sufficient of an active mixture as aforesaid to provide a total surfactant concentration of from 5 to 25%, by weight of the composition; and a dissolved surfactant desolubilising electrolyte in a concentration adapted to provide a non-sedimenting spherulitic composition.
• the liquid detergent composition of our invention additionally comprises suspended solid particles of a builder.
• the alkyl benzene sulphonate preferably has an average of from 10 to 14 aliphatic carbon atoms, e.g. 12, and is preferably a linear alkyl benzene sulphonate. Particularly preferred are alkyl benzene sulphonates containing a broad range of different homologues and isomers.
• the anionic surfactant comprises at least one C14-22 mono-and/or di-alkyl phosphate ester in a proportion of up to 50% e.g. 2 to 40%, preferably 5 to 30% especially 10 to 20% of the total weight of the anionic surfactant present.
• the anionic surfactant may additionally or alternatively comprise other sulphonated and/or sulphated surfactants and/or carboxylates.
• the anionic surfactant may comprise a mixture of alkyl benzene sulphonate with from 5 to 100%, preferably 10 to 50% e.g. 15 to 30% of a C8 ⁇ 20 (preferably C10 ⁇ 14) alkyl sulphate, based on the weight of alkyl benzene sulphonate.
• the composition preferably comprises from 5 to 150%, preferably 20 to 120% e.g.
• C8 ⁇ 20 (preferably C16 ⁇ 18) alkyl polyalkyleneoxy sulphate based on the weight of alkylbezene sulphonate.
• the alkyl polyalkyleneoxy sulphate preferably comprises an average of from 1 to 10 e.g. 1.5 to 5 molar parts of ethylene oxide.
• Other anionic surfactants which may be present include olefin sulphonates, parafin sulphonates, fatty acid sulphonates, sulphosuccinates, sulphosuccinamates and soaps.
• the counter ion of the anionic surfactant may be sodium, lithium, potassium, ammonium, or a lower alkyl ammonium or mono-di- or tri-alkanolammonium or a mixture of such ions.
• the non-ionic surfactant is preferably an ethoxylated alcohol but may alternatively be an ethoxylated carboxylic acid, alkyl amine, alkanolamide, alkylphenol, or ester such as an ethoxylated glyceryl, sorbitan, phosphate or phosphonate ester.
• the alkyl groups of the non-ionic surfactant may be straight chain and primary, but comprise preferably at least some branched chain alkyl groups. It is often found that the greater the proportion of branched chain alkyl groups and the amount of branching, the more effective the detergency of the product.
• the alkyl groups of the non-ionic surfactant have an average of from 8 to 20, preferably 10 to 18 carbon atoms.
• ethoxylated C9 ⁇ 15 e.g. C9 ⁇ 11 or C12 ⁇ 13 branched chain alcohols are especially preferred from the point of view of detergency, but ethoxylated C16 ⁇ 18 linear alcohols give suerior foam inhibition.
• C8 ⁇ 15 alkyl groups are preferred.
• the number of ethylene oxide groups is selected, according to the alkyl chain length, to provide the desired HLB. Typically there are from 1 to 12, e.g. 2 to 8, ethylene oxide groups. It is possible to replace one or more of the ethylene oxide groups with propylene oxide.
• the HLB of the non-ionic surfactant is preferably from 2 to 12 e.g. 3 to 10 especially 3.5 to 8.
• ethoxylates of feedstocks containing at least 20%, more preferably at least 30%, especially at least 50%, e.g. at least 60%, branched chain alcohols.
• the non-ionic surfactant may comprise a proportion of free C8 ⁇ 22 alcohol. This is especially preferred for low foam compositions.
• the latter typically contain C14 to 22 fatty alcohols, e.g. in proportions up to 100% by weight of the total anionic surfactant.
• High foam, low temperature compositions may contain minor proportions of unethoxylated fatty alcohols, corresponding to the feed stock of the fatty alcohol ethoxylate.
• the latter are usually C9 to 5, e.g. C9 ⁇ 11 alcohols. We do not exclude the presence of polyethylene glycol in the nonionic surfactant.
• any fatty alcohol or polyethylene glycol are deemed to be included in the total ethoxylated non-ionic surfactant when estimating the HLB of the latter or in defining relative proportions of non-ionic surfactant.
• the HLB may be taken for the purpose of this specification as being one fifth of the weight percentage of ethylene oxide based on the weight of non-ionic surfactant.
• the total proportion of surfactant is from 5 to 25% of the liquid of the total weight detergent composition.
• the total proportion of surfactant is preferably less than 20%, e.g. less than 14%, most preferably 6 to 12% based on the weight of the liquid detergent composition.
• higher concentrations of total surfactant are preferred e.g. greater than 18%, especially 20 to 25% based on the total weight of the liquid detergent composition.
• the detergent composition of our invention comprises an electrolyte in a quantity sufficient to provide a non-sedimenting spherulitic composition.
• electrolyte is used herein to refer to any water-soluble compound which is dissolved in the composition, which ionises in solution and which is capable of salting the surfactants out of micellar solution to form a spherulitic composition, but which is not itself a surfactant.
• the electrolyte may, preferably, comprise any of the water-soluble builders, or a dissolved portion of a sparingly soluble builder.
• Suitable electrolytes therefore include citrates, orthophosphates, nitrilotriacetates, condensed phosphates such as pyrophosphates, tripolyphosphates or tetraphosphates, soluble phosphate glasses such as hexametaphosphates, carbonates, silicates, phosphonates, such as acetodiphosphonates, aminotris(methylene phosphonates), ethylene diamine tetrakis(methylene phosphonates), diethylene triamine pentakis(methylene phosphonates) and higher homologues of the same series, and ethylenediamine tetracetates.
• electrolyte or part thereof, a buffer such as a borate, or less preferably a non-functional salt such as a chloride, bromide, iodide, nitrate or the like.
• Organic electrolytes such as formate or acetate may also be present.
• Sulphate is normally present in minor amounts as an impurity of the anionic surfactant, but may give rise to undesirable crystallisation in amounts greater than about 3%. We therefore prefer to avoid the use of higher concentrations of sulphate.
• the cationic portion of the electrolyte is preferably an alkali metal, e.g. lithium, potassium or, more preferably, sodium.
• the total concentration of dissolved electrolyte is preferably greater than 1%, typically 2 to 12%, depending upon the concentration of surfactant and the total proportion of non-ionic to anionic. Higher concentrations of surfactant and/or higher proportions of non-ionic surfactant require lower concentrations of electrolyte to form non-separating, spherulitic compositions. If the concentration of surfactant and/or the proportion of non-ionic surfactant is sufficiently high, any adventitious sodium sulphate may be sufficient to ensure a stable spherulitic composition without the adition of extra electrolyte.
• the builder is preferably sodium tripolyphosphate and is preferably present in excess of its solubility, as suspended solid particles.
• the composition may contain zeolites and/or solid particles of any of the builders referred to above under the discussion of electrolytes.
• the low-foaming compositions of our invention containing phosphate esters have been found to prevent excessive foaming but not to suppress foaming entirely at the wash stage, giving visible confirmation that the detergent is present and acting. There is however little or no foaming in the rinse water.
• foam suppressing agents such as C16 ⁇ 18 fatty alkanolamides and/or hydrocarbons in addition to or instead of the phosphate ester.
• foam suppressing agents such as C16 ⁇ 18 fatty alkanolamides and/or hydrocarbons
• silicones we prefer, however, not to use silicones as the antifoams, although it is possible, according to our invention, to achieve effective foam suppression with reduced proportions of silicone antifoam compared with those conventionally used. Minor amounts of silicone may be added as protective agent if it is desired to include enzymes in the formulation, for example as described in European Patent Application 87301489.2.
• Detergent compositions of our invention may contain the usual minor ingredients.
• these include an anti-redeposition agent such as sodium carboxymethyl cellulose, in conventional amounts, an optical brightener and perfumes and/or colouring.
• the compositions may contain suspended particles of fabric softeners such as bentonite or synthetic clays, or may generally contain any of the other minor ingredients, builders and electrolytes listed in our aforesaid GB-A-2153380 and in substantially the same proportions.
• a specially preferred liquid detergent composition for low foam use comprises..
• the above preferred compositon will normally contain conventional proportions of soil suspending agent, such as carboxymethyl cellulose, optical brightening agents and perfumes. It preferably contains minor amounts e.g. 0.1 to 2% each of sodium silicate, an alkanolamine such as triethanolamine and/or of phosphonate. It may optionally contain antifoams such as silcones and/or phosphate esters, fabric softeners, such as bentonite, enzymes such as proteases and/or lipases, preferably dispersed in a protective medium such as silicone and preservatives such as formaldehyde.
• soil suspending agent such as carboxymethyl cellulose, optical brightening agents and perfumes. It preferably contains minor amounts e.g. 0.1 to 2% each of sodium silicate, an alkanolamine such as triethanolamine and/or of phosphonate. It may optionally contain antifoams such as silcones and/or phosphate esters, fabric softeners, such
• a further type of preferred composition where low foam is not a requirement, but where washing efficiency at low temperatures is an important consideration, comprises: water; from 6 to 12 e.g. 7 to 10% sodium linear C10 ⁇ 14 alkyl benzene sulphonate; optionally but preferably from 6 to 12 e.g. 7 to 10% sodium C14 ⁇ 20 (preferably C16 ⁇ 18) alkyl polyethyleneoxy sulphate having an average of from 1 to 5 e.g. 2 to 4 ethyleneoxy groups per molecule; from 1 to 8% preferably 2 to 7% of C8 ⁇ 15 (preferably C9 ⁇ 11) alcohol ethoxylate having an average of from 1 to 5.5. e.g. 2 to 5 ethylene oxide groups per molecule; and from 15 to 30%, preferably 19 to 26% of sodium tripolyphosphate.
• the composition preferably contains the usual minor ingredients, such as soil suspending agent, optical brightner and perfume, in conventional amounts.
• the invention will be illustrated by the following examples, each of which was made by mixing the ingredients in the percentages by weight based on the total composition in the following tables, with the balance in each case water.
• the surface active ingredients i.e. those components listed in the tables down to and including the C16 ⁇ 18 alcohol in the case of examples 1 to 18, were mixed together with sufficient water to form pourable, turbid mixtures having active concentrations between 30 and 50% by weight.
• samples were centrifuged at 20,000g for 90 minutes to determine the optimum concentrations, at which no separation could be observed.
• the resulting pourable non-separating aqueous spherulitic or lamellar compositions were storable.
• the aqueous active mixtures could also be perfumed and/or combined with the appropriate proportion of carboxymethyl cellulose and/or optical brightening agent and/or phosphonate, with adjustment of concentration when required.
• the active concentrate was mixed with the builder (sodium tripolyphosphate, and/or zeolite) and sufficient water to provide the desired final composition.
• the builder sodium tripolyphosphate, and/or zeolite
• Each of examples 1 to 18 provided a stable non-sedimenting spherulitic composition having foaming characteristics suitable for use in front loading washing machines and giving good washing performance with both natural and synthetic fibres.
• compositions gave moderate, controlled foaming during the wash cycle and little or no foaming during the rinse cycles.

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• Crystallography & Structural Chemistry (AREA)
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• 1987
  • 1987-06-10 GB GB878713574A patent/GB8713574D0/en active Pending
• 1988
  • 1988-05-31 IL IL86564A patent/IL86564A0/xx unknown
  • 1988-05-31 IS IS3353A patent/IS3353A7/is unknown
  • 1988-06-01 NZ NZ224863A patent/NZ224863A/en unknown
  • 1988-06-01 ZA ZA883892A patent/ZA883892B/xx unknown
  • 1988-06-03 ZW ZW70/88A patent/ZW7088A1/xx unknown
  • 1988-06-03 GB GB08813132A patent/GB2205852A/en not_active Withdrawn
  • 1988-06-03 EP EP19880305114 patent/EP0295021A3/de not_active Withdrawn
  • 1988-06-08 MA MA21538A patent/MA21296A1/fr unknown
  • 1988-06-08 TN TNTNSN88056A patent/TNSN88056A1/fr unknown
  • 1988-06-09 ZM ZM33/88A patent/ZM3388A1/xx unknown
  • 1988-06-09 NO NO882540A patent/NO882540L/no unknown
  • 1988-06-09 BR BR8802818A patent/BR8802818A/pt not_active Application Discontinuation
  • 1988-06-09 CS CS884008A patent/CS8804008A3/cs unknown
  • 1988-06-09 AU AU17543/88A patent/AU1754388A/en not_active Abandoned
  • 1988-06-09 HU HU882995A patent/HUT48920A/hu unknown
  • 1988-06-09 DK DK314488A patent/DK314488A/da not_active Application Discontinuation
  • 1988-06-09 PT PT87711A patent/PT87711B/pt not_active IP Right Cessation
  • 1988-06-10 DD DD88316653A patent/DD270721A5/de not_active IP Right Cessation
  • 1988-06-10 PL PL27300688A patent/PL273006A1/xx unknown
  • 1988-06-10 JP JP63141888A patent/JPS644700A/ja active Pending
  • 1988-06-10 CN CN198888103546A patent/CN88103546A/zh active Pending
  • 1988-06-10 KR KR1019880007003A patent/KR890000650A/ko not_active Application Discontinuation
  • 1988-06-10 BG BG084441A patent/BG47649A3/xx unknown
  • 1988-06-10 OA OA59412A patent/OA08905A/xx unknown
  • 1988-06-10 FI FI882792A patent/FI882792L/fi not_active IP Right Cessation
  • 1988-06-30 IN IN469DE1988 patent/IN172745B/en unknown

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