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
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/65—Mixtures of anionic with cationic compounds
  • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
• • 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
  • C11D1/662—Carbohydrates or derivatives
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/32—Amides; Substituted amides
• • 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
  • C11D1/18—Sulfonic acids or sulfuric acid esters; Salts thereof derived from amino alcohols
  • C11D1/20—Fatty acid condensates
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
• • 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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/90—Betaines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/92—Sulfobetaines ; Sulfitobetaines

Definitions

• This invention relates generally to aqueous liquid detergent compositions and more particularly to liquid detergent compositions intended to remove soils of a largely greasy nature from hard surfaces such as dishes and other articles used in food preparation and consumption.
• Liquid detergent compositions intended for use as dishwashing products conventionally take the form of aqueous solutions containing a mixture of one or more sulphate and sulphonate anionic detergents as 'core' surfactant materials together with a suds promoting or stabilising agent.
• the suds stabilisation agent can take a number of forms but is normally an amide derivative, an amine oxide, an ethoxylated aliphatic alcohol, a zwitterionic surfactant such as a betaine, or a mixture of several of these. Usage levels of these types of materials are conventionally in the range of 2-8% normally 3-5% by weight of the composition.
• N-alkanoyl N-alkyl glucamines One group of amide derivatives that have been suggested for suds promoting and stabilising purposes are the N-alkanoyl N-alkyl glucamines. These materials are derived from glucose and can be prepared by reacting a lower alkylamine with glucose to form a glucamine and then treating this with a methyl ester of a fatty acid of the required chain length to give the N-alkanoyl-N-alkyl glucamine.
• EP-A-285,768 discloses the use of N-polyhydroxyalkyl fatty acid amides as thickening agents for liquid aqueous surfactant systems.
• GB-A-809060 discloses detergent compositions comprising at least one water soluble salt of an organic sulphuric reaction product having in its molecular structure a sulphuric acid or a sulphonic acid radical and an amide derivative of the above type in an amount of from 5% to 60% by weight of the water soluble organic sulphuric reaction product.
• the amide derivatives are stated to provide an improvement in the sudsing characteristics of the compositions at temperatures below 100°F particularly in Latin American countries where washing is carried out at temperatures as low as 60°F.
• the surfactant combination can be used alone
• the preferred and exemplified embodiments are granular products incorporating phosphate builder and sodium sulphate filler.
• an unbuilt liquid or gel-form detergent composition in the form of a physically stable aqueous solution comprising from 20 to 50% by weight of the composition of a core surfactant mixture, comprising by weight of the mixture,
• the cation(s) of the water soluble anionic sulfate or sulfonate surfactant shall be such as to correspond to the cation(s) in the detergent composition, and where a mixture of cations is present, in the weight proportions in which each cation is present in the mixture.
• compositions in accordance with the invention employ component b) compounds in which the polyhydroxyhydrocarbyl moieties are derived from glucose or mixtures thereof with maltose in which maltose comprises ⁇ 25% by weight of the mixture.
• Commercially available technical grade glucose contains maltose as an impurity at a level of up to 5% by weight.
• references hereinafter to glucamines are to be construed as material including up to 5% by weight of the corresponding material derived from maltose.
• Suitable anionic sulphate or sulphonate surfactants include C10-C16 alkyl ethoxy sulphates containing an average of up to 6 moles of ethylene oxide per mole of alkyl ethoxysulphate, C10-C18 paraffin sulphonates, and N-C9-C17 acyl-N-C1-C4 alkyl glucamine sulphates.
• compositions in accordance with the invention incorporate an anionic surfactant system comprising from 9% to 18% by weight of the composition of a primary C12-C14 alkyl ethoxy sulphate stock containing an average of from 0.4 to 4.0 ethylene oxide groups per mole of C12-C14 alkyl ethoxy sulphate, preferably from 0.3 to 3.0, together with from 9% to 15% by weight of the composition of N-coconut acyl-N-methyl glucamine.
• an anionic surfactant system comprising from 9% to 18% by weight of the composition of a primary C12-C14 alkyl ethoxy sulphate stock containing an average of from 0.4 to 4.0 ethylene oxide groups per mole of C12-C14 alkyl ethoxy sulphate, preferably from 0.3 to 3.0, together with from 9% to 15% by weight of the composition of N-coconut acyl-N-methyl glucamine.
• compositions employ an anionic surfactant to glucamine weight ratio of between 2:1 and 1:1.
• Particularly preferred compositions contain from 10% to 18% by weight of C12-C14 alkyl ethoxy sulphate and from 7% to 15% by weight of the glucamine surfactant.
• the alkyl ethoxy sulphates themselves comprise a mixture of material containing an average of approximately 0.8 moles of ethylene oxide/mole and material containing an average of approximately 3.0 moles of ethylene oxide/mole in a weight ratio of between 2:1 and 5:1 preferably approximately 4:1.
• compositions in accordance with the invention also contain 1%-8%, most preferably 2%-7% by weight of a suds booster selected from C10-C16 alkyl mono or di-C2-C3 alkanolamides, C12-C14 alkyl or alkyl amido betaines, C12-C14 alkyl sulphobetaines, C10-C16 alkyl di C1-C4 alkyl or di C2-C4 hydroxyalkyl amine oxides, C9-C12 primary alcohol ethoxylates containing an average of from 7 to 12 ethylene oxide groups per mole of alcohol and mixtures thereof.
• a suds booster selected from C10-C16 alkyl mono or di-C2-C3 alkanolamides, C12-C14 alkyl or alkyl amido betaines, C12-C14 alkyl sulphobetaines, C10-C16 alkyl di C1-C4 alkyl or di C2-C4 hydroxyalkyl amine
• Preferred suds boosters comprised mixtures of C12-C14 alkyl betaine, in an amount of from 1% to 5% preferably from 1.5% to 3% by weight of the composition, together with C9-C12 primary alcohol ethoxylate (preferably C10 alkyl EO8) in an amount of from 6% to 8% by weight of the composition.
• compositions Another preferred component of such compositions is Mg++, at a level of up to 1.5% more preferably from 0.5% to 1.0% by weight of the compositions.
• Especially preferred compositions also contain calcium in addition to the magnesium ion at a level of from 0.3% to 0.5% by weight.
• Detergent compositions in accordance with the present invention comprise a mixture of core surfactants in an amount of from 20% to 50% by weight of the composition, preferably from 22% to 40% by weight.
• the mixture comprises from 5% to 95% by weight of the mixture of at least one water-soluble anionic sulphate or sulphonate surfactant salt together with from 95% to 5% by weight of the mixture of a N-C8-C16 acyl-N-C1-C4 alkyl glucamine nonionic surfactant.
• the mixture comprises from 20% to 80% of the anionic surfactant and from 80% to 20% of the alkyl glucamine, and most preferably from 40% to 70% anionic surfactant and from 60% to 30% alkyl glucamine.
• the anionic surfactant can essentially be any organic sulphate or sulphonate surfactant salt but is usually selected from C11-C15 alkyl benzene sulphonates, C10-C16 alkyl sulphates and their ethoxy analogues containing up to six moles of ethylene oxide per mole of alkyl ethoxy sulphate, C13-C18 paraffin sulphonates C10-C16 olefin sulphonates, C10-C20 alkyl glyceryl ether sulphonates, C9-C17 acyl-N-C1-C4 alkyl or C2-C4 hydroxyalkyl glucamine sulphates and mixtures of any of the foregoing.
• the anionic surfactant is selected from alkyl ethoxy sulphates, alkyl glyceryl ether sulphonates and paraffin sulphonates.
• Alkyl benzene sulphonates useful in compositions of the present invention are those in which the alkyl group, which is substantially linear, contains 10-16 carbon atoms, preferably 11-13 carbon atoms, a material with an average carbon chain length of 11.8 being most preferred.
• the phenyl isomer distribution, i.e. the point of attachment of the alkyl chain to the benzene nucleus, is not critical, but alkyl benzenes having a high 2-phenyl isomer content are preferred.
• Suitable alkyl sulphates are primary alkyl sulphates in which the alkyl group contains 10-16 carbon atoms, more preferably an average of 12-14 carbon atoms preferably in a linear chain.
• C10-C16 alcohols derived from natural fats, or Ziegler olefin build-up, or OXO synthesis, form suitable sources for the alkyl group.
• Examples of synthetically derived materials include Dobanol 23 (RTM) sold by Shell Chemicals (UK) Ltd., Ethyl 24 sold by the Ethyl Corporation, a blend of C13-C15 alcohols in the ratio 67% C13, 33% C15 sold under the trade name Lutensol by BASF GmbH and Synperonic (RTM) by ICI Ltd., and Lial 125 sold by Liquichimica Italiana.
• Examples of naturally occurring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
• Alkyl ethoxy sulphate surfactants comprise a primary alkyl ethoxy sulphate derived from the condensation product of a C10-C16 alcohol with an average of up to 6 ethylene oxide groups.
• the C10-C16 alcohol itself can be obtained from any of the sources previously described for the alkyl sulphate component.
• C12-C13 alkyl ether sulphates are preferred.
• Blends can be made of material having different degrees of ethoxylation and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent processing steps such as distillation.
• Secondary alkane sulphonates useful in the present invention have from 13 to 18 carbon atoms per molecule, more desirably 13 to 15 atoms per molecule. These sulphonates are preferably prepared by subjecting a cut of paraffin, corresponding to the chain lengths specified above, to the action of sulphur dioxide and oxygen in accordance with the well-known sulphoxidation process. The product of this reaction is a secondary sulphonic acid which is then neutralized with a suitable base to provide a water-soluble secondary alkyl sulphonate. Similar secondary alkyl sulphonates may be obtained by other methods, e.g.
• the sulphochlorination method in which chlorine and sulphur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulphonyl chlorides being hydrolysed and neutralized to form the secondary alkyl sulphonates.
• the monosulphonate may be terminally sulphonated or the sulphonate group may be joined on the 2-carbon or other carbon of the linear chain.
• any accompanying disulphonate may have the sulphonate groups distributed over different carbon atoms of the paraffin base, and mixtures of the monosulphonates and disulphonates may be present.
• Olefin sulphonates useful in the present invention are mixtures of alkene-1-sulphonates, alkene hydroxysulphonates, alkene disulphonates and hydroxydisulphonates and are described in the commonly assigned US-A-3332880 issued to P.F. Pflaumer & A. Kessler on July 25 1967.
• Suitable alkyl glyceryl ether sulphonates are those derived from ethers of coconut oil and tallow.
• sulphate surfactants include the N-C9-C17 acyl-N-C1-C4 alkyl glucamine sulphates, preferably those in which the C9-C17 acyl group is derived from coconut or palm kernel oil. These materials can be prepared by the method disclosed in US-A-2717894.
• the counter ion for the anionic surfactant component can be any one of sodium, potassium, magnesium, ammonium or alkanol-ammonium or a mixture thereof.
• sodium is the preferred counter ion but potassium is preferred over sodium where it is of importance that the compositions of the invention are completely clear and have a high resistance to precipitate formation.
• liquid detergent compositions in accordance with the invention have a chill point less than 8°C preferably less than 5°C, and are at least partially neutralised by ammonium ions.
• calcium and/or magnesium ions can either be introduced as the oxide or hydroxide to neutralise the surfactant acid or can be added to the composition as a water soluble salt.
• the addition of appreciable levels of such salts to dishwashing compositions in accordance with the invention raises the temperature at which inorganic salt crystals form in the compositions on cooling and the amount added in this way should therefore be minimised.
• mixtures of calcium and magnesium ions may be added in order to provide up to 1% Ca++ by weight of the composition, more preferably from 0.3% to 0.5% Ca++ and up to 1.50% Mg++, more preferable from 0.5% to 1.0% by weight.
• the preferred mixtures are rich in magnesium and more preferably provide a Ca++:Mg++ weight ratio of from 1:1 to 1:4.
• Compositions incorporating Mg++ and/or Ca++ are especially valuable for conditions of very low water hardness ( ⁇ 2° Clark) and also for product concentrations greater than 0.5% by weight.
• the second core surfactant component of the unbuilt liquid compositions of the invention is a compound of the general formula wherein Z is a polyhydroxy hydrocarbyl moiety having a linear hydrocarbyl chain with at last three hydroxy groups groups connected directly to the chain, said moiety being derived from glucose and mixtures thereof with maltose, the maltose comprising not more than 33% by weight of the mixture, R is a saturated or unsaturated aliphatic group of from 8 to 16 carbon atoms, or a mixture of such groups, and R1 is a C1-C4 alkyl or C2-C4 hydroxyl alkyl group.
• R may be derived from any of the sources of hydrocarbyl groups discussed hereinbefore with reference to the anionic surfactant but is preferably natural in origin.
• R has an average chain length of from 12 to 14 carbon atoms and is derived from coconut oil or palm kernel oil.
• R1 is preferably a methyl group.
• Preferred levels of the N-alkanoyl -N-alkyl glucamine in liquid and gel-form compositions of the present invention lie between 8% and 25% by weight, more preferably between 9% and 18% and most preferably between 10% and 15% by weight.
• compositions in accordance with the invention can be formulated with calcium ions in the absence of magnesium ions, but require the use of N-alkanoyl -N-alkyl glucamines of high purity in which the levels of unreacted starting materials, impurities and by-products, particularly fatty acids, are minimised.
• the balance of the liquid detergent composition can be made up by water or, in the case of a gel-form composition by a gelling agent and water.
• other functional components are also included and the combined weights of the anionic surfactant(s) and glucamine components lie in the range from 20% to 40%, more preferably from 22% to 30% by weight.
• a highly desirable optional component is one or more suds modifiers or promoters, normally present at an individual level of from 1% to 8% by weight of the composition.
• One such suds promoting agent is a C10-C16 alkyl mono- or di-C2-C3 alkanolamide, examples including coconut alkyl monoethanolamide, coconut alkyl diethanolamide and palm kernel and coconut alkyl mono-and di-isopropanol amides.
• the palm kernel or coconut alkyl residue may either be 'whole cut', including the C10 and C16 fractions or may be the so-called 'narrow-cut' C12-C14 fraction, Synthetic sources of the C10-C16 alkyl group can also be used.
• Another useful suds promoting agent is a zwitterionic surfactant of general formula wherein R1 is C10-C16 alkyl, R2 is C1-C3 alkyl, R3 is a -(CH2)3 group or a group, Y is n & m are O or 1, and X ⁇ is CH2COO ⁇ or SO3; provided that where X ⁇ is CH2COO ⁇ , m is O, and where X ⁇ is SO3, n is O and m is 1.
• R1 has an average carbon chain length of from 12 to 16 carbon atoms and may be derived from synthetic sources, in which case the chain may incorporate some branching, or from natural fats and oils, in which case the chains are linear and may include minor amounts of C8-C10 and C14-C18 moieties.
• Synthetic sources for the R1 group may be the same as those mentioned previously for the alkyl group in the anionic surfactant component.
• a further class of suds promoting agents useful in the invention are the amine oxides of general formula R1R2R3N ⁇ O wherein R1 is an alkyl group containing from 10 to 16 carbon atoms and R2 and R3 are each independently selected from C1-C3 alkyl and C2-C3 hydroxy alkyl groups.
• Preferred members of this class include dimethyldodecyl amine oxide, dimethyl tetradecyl amine oxide, bis-(2 hydroxyethyl) dodecylamine oxide and analogues thereof in which the dodecyl or tetradecyl moiety is derived from natural sources such as coconut or palm kernel oil.
• a preferred suds modifying agent is an ethoxylated alcohol or a mixture of ethoxylated alcohols of defined constitution.
• the ethoxylated alcohol comprises a C6-C13 aliphatic alcohol ethoxylate containing an average of from 1.5 to 25, more preferably from 2 to 15 and most preferably from 6 to 10 moles of ethylene oxide per mole of alcohol.
• the aliphatic alcohol ethoxylate contains not more than 1% by weight of unethoxylated alcohol where the ethoxylated alcohol contains an average of less than 8 moles of ethylene oxide and not more than 2% by weight of unethoxylated alcohol where the ethoxylated alcohol contains an average of from 8 to 25 moles of ethylene oxide per mole of alcohol.
• the starting alcohol may be a primary or secondary alcohol but is preferably a primary alcohol which may be derived from natural or synthetic sources.
• natural fats or oils, or products of Ziegler olefin build up reactions or OXO synthesis may all be used as the source of the hydrocarbon chain, the structure of which may be linear or branched in type.
• the preferred alcohol chain length range is from C9 to C11 as it has been found that the sudsing volume and mileage performance of compositions in accordance with the invention is optimum when incorporating ethoxylates made from such alcohols. It is also desirable for performance reasons that the hydrophilic-lipophilic balance (HLB) of the ethoxylated alcohol is in the range from 8.0 to 17.0, more preferably from 11.0 to 17.0 and most preferably from 11.0 to 15.0.
• a preferred alcohol ethoxylate is a primary alcohol ethoxylate containing an average of 10 carbon atoms in the alkyl chain, condensed with an average of 8 ethylene oxide groups per mole of alcohol.
• E av As discussed with respect to alkyl ethoxy sulphate as the anionic surfactant component, the normal (base catalysed) ethoxylation process to produce an average degree of ethoxylation E av of 6 results in a distribution of ethoxylate species which ranges from 1 to 15 moles of ethylene oxide per mole of alcohol. An increase in E av causes some change in this distribution, principally a reduction in the level of unethoxylated material, but an increase in E av from 3 to 5 will still leave approximately 5-10% of such material in the ethoxylated product.
• this level of unethoxylated material will give rise to phase stability/chill point problems and/or will result in a product having a fatty alcohol odour which is unacceptable to consumers and cannot be masked by conventional detergent perfumes.
• the maximum level of unethoxylated alcohol that can be tolerated in the ethoxylated alcohol component is 1% by weight. More preferably the unethoxylated alcohol level is not more than 0.7% and most preferably is less than 0.5% by weight of the ethoxylated alcohol component.
• Distillation under vacuum is employed to remove the undesired material and this also removes a portion of the monoethoxylate fraction, thereby increasing the E av of the remaining material.
• the level of monoethoxylate is not more than 5% by weight of the ethoxylated alcohol.
• compositions in accordance with the invention are used, each being present at a level of from 1% to 10% more preferably from 2% to 8% by weight.
• One such preferred combination is a C12-C14 alkyl dimethyl betaine and a C9-C11 alcohol condensed with an average of from 7 to 9 moles of ethylene oxide per mole of alcohol, each material being present in an amount of from 2% to 8% by weight of the composition.
• the balance of the formula comprises a hydrotrope-water system in which the hydrotrope may be urea, a C1-C3 aliphatic alcohol, a lower alkyl or dialkyl benzene sulphonate salt such as toluene sulphonate, xylene sulphonate, or cumene sulphonate, or mixtures of any of these.
• the hydrotrope may be urea, a C1-C3 aliphatic alcohol, a lower alkyl or dialkyl benzene sulphonate salt such as toluene sulphonate, xylene sulphonate, or cumene sulphonate, or mixtures of any of these.
• compositions in accordance with the present invention preferably employ a mixture such as urea-alcohol-water, alcohol-lower alkyl benzene sulphonate-water or urea-lower alkyl benzene sulphonate-water in order to achieve the desired viscosity, and to remain stable and easily pourable.
• a mixture such as urea-alcohol-water, alcohol-lower alkyl benzene sulphonate-water or urea-lower alkyl benzene sulphonate-water in order to achieve the desired viscosity, and to remain stable and easily pourable.
• the preferred alcoholic hydrotrope is ethanol which is employed at from 3% to 10% by weight of the composition, preferably at from 4% to 8%, usually in admixture with urea.
• compositions having an organic active concentration greater than about 40% by weight mixtures of ethanol with urea and/or lower alkyl benzene sulphonates are preferred. Mixtures of hydrotropes can, of course, be employed for cost effectiveness reasons irrespective of any stability/viscosity considerations.
• Optional ingredients of the liquid detergent compositions of the invention include opacifiers such as ethylene glycol distearate, thickeners such as guar gum, antibacterial agents such as glutaraldehyde and Bronopol (RTM), antitarnish agents such as benzoxytriazole, heavy metal chelating agents such as ETDA or ETDMP, perfumes and dyes.
• opacifiers such as ethylene glycol distearate
• thickeners such as guar gum
• antibacterial agents such as glutaraldehyde and Bronopol (RTM)
• antitarnish agents such as benzoxytriazole
• heavy metal chelating agents such as ETDA or ETDMP
• perfumes and dyes include opacifiers such as ethylene glycol distearate, thickeners such as guar gum, antibacterial agents such as glutaraldehyde and Bronopol (RTM), antitarnish agents such as benzoxytriazole, heavy metal chelating agents such as
• compositions of the invention can be made in a number of ways but it is preferred that any zwitterionic surfactant included therein is incorporated towards the end of the making process if not actually forming the last ingredient to be added. This minimises the risk of any degradation of the zwitterionic surfactant under the acid conditions existing at the beginning of the making process and also facilitates the control of the viscosity of the finished product.
• the glucamine surfactant should not be exposed to a pH lower than 4 or higher than 10 to prevent hydrolysis of the surfactant.
• the anionic surfactant(s) can be made as aqueous solutions of alkali metal or ammonium salts with pH adjusted between 4 and 10 which are then mixed together with the N-alkanoyl -N-alkyl glucamine, followed by any ethoxylated nonionic surfactant and other suds booster(s) and the hydrotrope, after which any calcium or magnesium ion can be introduced as a water soluble salt such as the chloride or sulphate. Any zwitterionic surfactant and minor ingredients are then added at the same time as the pH and viscosity are adjusted.
• This method has the advantage of utilising conventional techniques and equipment but does result in the introduction of additional chloride or sulphate ions which can increase the chill point temperature (the temperature at which inorganic salts precipitate as crystals in the liquid).
• the desired alcohol and alcohol ethoxylate can be mixed together and a single sulphation and neturalisation can then be carried out on these two materials.
• the alcohol and alcohol ethoxylate should be mixed in a weight ratio lying in the range from 4:3 to 1:6.
• a single alcohol ethoxylate stock is produced in which the levels of alcohol and ethoxylated alcohol species are controlled to provide the desired ratio of these starting materials.
• Sulph(on)ation of the alcohol and alcohol ethoxylate can employ any of the conventional sulph(on)ating agents such as sulphur trioxide or chlorosulphonic acid.
• Neutralisation of the alkyl ether sulphuric acid and the alkyl sulphuric acid is then carried out with the appropriate alkali or with a magnesium, calcium or magnesium/calcium oxide or hydroxide slurry. If the amount of anionic surfactant is not sufficient to permit all of the desired Ca++ and Mg++ ions to be added in this way, the remainder can then be added in the form of a water soluble salt.
• Gel compositions of the present invention can be prepared using the general method described in US Patent No. 4615819.
• Compositions in accordance with the invention are characterised by a low interfacial tension, (IFT) which is an indication of the ability to emulsify grease and oily soils, a high polypropylene cup (PPC) weight loss, which demonstrates the ability to remove greasy soils from surfaces and suspend the soils in solution, together with a superior skin mildness. This combination is not normally found in liquid detergent compositions.
• IFT interfacial tension
• PPC polypropylene cup
• compositions in accordance with the invention display superior suds mileage performance in both hard and soft water, by comparison with prior art compositions.
• IFT IFT Measurement of IFT gives an indication of the ability of a surfactant sample to emulsify a soil under a defined set of conditions. IFT was determined by means of a Spinning Drop Tensiometer and a University of Texas Model 500 manufactured by the University of Texas, Austin, Texas, USA. Two instruments were employed, viz. a Model SITE 04, manufactured by Krüss GmbH Horscaftliche Labortechnik, Borsteler Cvice 85-99a, D2000 Hamburg 61 FRG under conditions representative of those encountered in Europen manual dishwashing practice.
• the Polypropylene Cup Test method measures the overall grease handling capability of a product under conditions simulating those found in manual dishwashing practice.
• the test involves the measurement of the amount of solid fat removal from the base of a polypropylene cup at a temperature below that at which the fat melts.
• a fat soil is prepared by making a mixture of the following fats: 70% solid 100% vegetable oil (Spry CRISP'N'DRY manufactured by Van den Berghs, Burgess Hill, W. Hampshire, England) 30% liquid 100% corn oil (MAZZOLA manufactured by CPC(UK) Ltd., Claygate House, Esher, Surrey, England) The mixture is heated until it becomes miscible,after which it is cooled and stored at a temperature ⁇ 0°C. For use, approximately 150 ml of fat is melted in a glass beaker and held at 70-75°C.
• a 0.12% solution of the test product is prepared at 50-55°C and 100 ⁇ 0.1g added to each of five glass jars which are then sealed with a lid.
• the sealed jars are placed in a water bath located in the constant temperature room and set at 45-46°C such that the solution in each jar is at a temperature of 43.8 ⁇ 0.1°C.
• a similar procedure is followed for each product under test as well as for the standard product against which the test products are being compared.
• the standard product should have a grease handling performance in the same general area as that of the experimental product at the same concentration. This can be achieved by adjusting the weight ratio of the liquid and solid fat serving as the soil composition so that the standard (reference) product provides 20-35% fat removal under the conditions of the test while the test product can have a fat removal of from 20 to 80%. The same batch of fat must be used for the test and reference products.
• Total suds is the total volume of suds generated during a standard dishwashing test and is a measure of the perceived foaming ability of the formulation. Suds mileage is a measurement of the soil loading required to reduce the suds of a test solution to a defined minimum under standard conditions of product concentration, temperature and water hardness. It reflects the perceived useful life of a manual dishwashing solution. Suds mileage of the compositions under identical test conditions was made using a prepared mixed food soil and a prepared greasy soil in the mechanical sudsing test method described.
• Rice/Mince/Egg "Real Meal” 1 x 392g Tin Tyne Brand Minced Beef & Onion1 1 x 439g Tin Ambrosia Creamed Rice Pudding2 1 Egg 25 mls 2% Mixed Free Fatty Acid (MFFA) in Corn Oil* 25 mls Corn Oil 1 Marketed by Master Foods, Kings Lynn, Norfolk, England. 2 Marketed by Ambrosia Creamery, Lifton, Devon, England. * 4g Oleic Acid, 4g Linoleic Acid, 2g Stearic Acid, 5g Palmitic Acid, 735g Pure Corn Oil.
• MFFA Mixed Free Fatty Acid
• the method uses 4 cylinders of length 30 cm and diameter 10 cm fixed side by side, and rotatable at a speed of 24 rpm about a central axis. Each cylinder is charged with 500 mls of product solution at a concentration of 0.12% and a temperature of 48°C. The outer two cylinders are used for one of the products being compared and the inner two for the other product.
• the cylinders are rotated for 2 minutes, stopped, the initial suds are measured and a soil load is then added typically in 2ml aliquots. After 1 minute the cylinders are restarted and allowed to rotate for 1 minute. The suds height is noted and 2 mls of the soil is added to each cylinder. After 1 minute the cylinders are restarted. This process continues until the suds height in the cylinder is lower than 0.6 cms.
• the total of all of the suds height measurements in each test (i.e. until the suds height becomes lower than 0.6 cms) forms the Total Suds measurement.
• a range of core surfactant systems was prepared containing a mixture of alkyl ethoxysulphate surfactant and N-lauroyl-N-methyl glucamine.
• the alkyl ethoxysulphate was derived from a C12-C14 primary alcohol condensed with an average of 0.8 moles of ethylene oxide per mole of alcohol and neutralised with a mixture of ammonium and magnesium ions so as to contain 0.22 moles of magnesium per mole of alkyl ethoxysulphate.
• a simulated product of 30% core surfactant concentration was first made in distilled water.
• IFT (Pa.cm) AES GA weight ratio Water Hardness 100:0 75:25 65:35 50:50 25:75 0:100 2° 0.35 0.12 0.12 0.14 0.16 0.10 18° 0.21 0.09 0.07 0.12 0.06 0.07 PPC 2° 1.0 - 1.6 1.5 - 1.3
• compositions A - E were prepared:
• Composition A represents a comparative commercially available liquid detergent dishwashing product while Compositions B, C, D & E are in accordance with the invention.
• IFT, PPC and suds mileage values were obtained for all five products and the results are expressed below. 1.
• IFT (Pa.cm) A B C D E 2°Clark 0.15 0.08 0.08 0.09 0.08 18°Clark 0.11 0.06 0.06 0.07 0.06 2.

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