EP0181212A1 - Flüssige Detergenszusammensetzungen - Google Patents
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- Publication number
- EP0181212A1 EP0181212A1 EP85308098A EP85308098A EP0181212A1 EP 0181212 A1 EP0181212 A1 EP 0181212A1 EP 85308098 A EP85308098 A EP 85308098A EP 85308098 A EP85308098 A EP 85308098A EP 0181212 A1 EP0181212 A1 EP 0181212A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- weight
- alcohol
- sulphate
- average
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
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- 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
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- 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
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- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- This invention relates to aqueous liquid detergent compositions and particularly to dishwashing compositions incorporating a mixture of anionic, ethoxylated nonionic and zwitterionic surfactants.
- Liquid detergent compositions intended for use as dishwashing products conventionally take the form of clear aqueous solutions containing a mixture of one or more sulphate and sulphonate anionic surfactants together with a suds stabilising agent.
- a suds stabilising agent typified by the disclosures of British Patent Specifications Nos. 1,524,441 and 1,551,074, British published Patent Application No. 2,010,893 A and European Patent Application Publication No. 0039110.
- the art teaches that these formulations have enhanced performance, particularly when used in water of low mineral hardness.
- Ethoxylated nonionic surfactants constitute a class of . materials capable of solubilising other components in aqueous media but this capability is strongly dependent on their average degree of ethoxylation (E av ).
- Highly ethoxylated nonionic surfactants, (i.e. E av >20) are'very hydrophilic in nature and thus tend to reduce the oily soil removal capability of liquid dishwashing detergent formulations, which is undesirable where oil and grease removal is an important criterion of consumer acceptance.
- nonionic surfactants having low levels of ethoxylation i.e. E av ⁇ 2 are relatively hydrophobic and have a limited ability to form homogeneous solutions with other components in the absence of other surfactant species.
- a feature shared by all ethoxylated nonionic surfactants is the presence of a level of unethoxylated material, the magnitude of which depends on the degree of ethoxylation, but which can constitute up to 20% by weight of the nonionic surfactant.
- Unethoxylated C 6 -C 13 aliphatic primary alcohols are odorous materials having a low water solubility, and these characteristics are discernible in the ethoxylated alcohols to an extent which depends on the level of ethoxylation, the effect diminishing as E av increases.
- Liquid dishwashing detergent compositions containing alkyl sulphates and/or alkyl benzene sulphonates have been found to be particularly subject to odour and storage stability problems when formulated with ethoxylated nonionic surfactants containing the normal spread of ethoxylated species, and this effect is tore pronounced when the composition also contains magnesium ions.
- Zwitterionic surfactants are also known components of detergent compositions particularly in combination with other surfactant species. Disclosures of compositions of this type are provided by European Patent Application Publication No. 0036625 and UK Patent Application No. 2103236A, both of which relate to liquid detergent compositions containing mixtures of alkyl ethoxy sulphates in combination with other anionic surfactants and a surface active betaine. Another disclosure is provided by Thiele et al USP 3,634,266 which describes an amylase-containing liquid detergent composition in which the surfactant system comprises a mixture of alkyl ethoxy sulphate, ethoxylated nonionic and sulphobetaine species.
- zwitterionic detergent in providing enhanced grease and particulate soil removal performance is a function not only of the structure of the zwitterionic surfactant itself, but also of the detergent composition into which it is blended.
- zwitterionic surfactants that give a suds mileage benefit and/or acceptable greasy soil redeposition performance in one detergent matrix do not give a similar benefit over the same range of usage conditions in other matrices.
- a physically stable enzyme-free liquid detergent composition comprising from 22% to 65% by weight of a surfactant system composed of a mixture of anionic, nonionic & zwitterionic surfactants in an organic solubiliser/hydrotrope-water medium wherein
- R 1 is C 10 -C 16 alkyl
- R 2 is methyl and n is 0 and more preferably the zwitterionic surfactant is a C 12 -C 14 alkyl betaine, present in an amount of from 0.5% to 5%, most preferably in an amount of from 1.0% to 2.5% by weight of the composition
- the ethoxylated aliphatic alcohol has an HLB 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.
- Preferred compositions in accordance with the invention contain from 3 to 5% of a C 9 -C 11 primary alcohol condensed with an average of from 6 to 10 moles of ethylene 5 oxide per mole of alcohol.
- the ethoxylated aliphatic alcohol contains less than 0.7%, most preferably less than 0.5% of unethoxylated material, and in highly preferred compositions the level of mono-ethoxylated C 9 -C 11 alcohol is no more than 5% by weight of the nonionic surfactant.
- compositions incorporates a three component anionic surfactant system, comprising 6-12% by weight of the composition of C 10 -C 16 primary alkyl sulphate, 6-14% of a C 10 -C 16 primary alkyl ethoxysulphate containing an average of from 1.5 to 3 ethoxy groups per alkyl group, and 5-15% of a C 10 -C 16 alkyl benzene sulphonate.
- the cations in this system are a mixture of ammonium and magnesium ions, the level of magnesium corresponding to approximately one half of the molar amount of alkyl sulphate present.
- compositions in accordance with the invention incorporate an anionic surfactant system containing from 15 to 20% by weight of the composition of a primary C 12 -C 14 alkyl ethox y sulphate stock containing an average of from 0.8 to 2.0 ethylene oxide groups per mole of C 12 -C 14 alkyl ethoxy sulphate, this alkyl ethoxy sulphate stock also including from 6 to 10%, by weight of the composition, of C 12 -C 14 alkyl sulphate, together with from 5 to 10% by weight of the composition of a C 11 . 8 linear alkyl benzene sulphonate component.
- compositions in accordance with the invention also contain 2%-8%, most preferably 3%-4% by weight of a suds booster selected from C10-C16 alkyl mono or di-C 2 -C 3 alkanolamide.
- Detergent compositions in accordance with the present invention comprise a mixture of anionic surfactants of defined constitution, in an amount of from 22% to 65% by weight of the composition, together with from 1% to 10% by weight of an ethoxylated nonionic surfactant having a low content of unethoxylated material and from 0.25% to 10% by weight of a zwitterionic surfactant of defined structure.
- compositions in accordance with the invention incorporate an alkyl sulphate and an alkyl benzene sulphonate component in combination with an alkyl ethoxy sulphate.
- the alkyl sulphate component is a primary alkyl sulphate in which the alkyl group contains 10-16 carbon atoms, more preferably an average of 12-14 carbon atoms preferably in a linear chain.
- C 10 -C 16 alcohols derived from natural fats or Z iegler olefin build-up or OXO synthesis, form suitable sources for the alkyl group.
- Examples of synthetically derived materials include D obanol 23 (RT M ) sold by Shell Chemicals (UK) Ltd, Ethyl 24 sold by the Ethyl Corporation, a blend of C 13 -C 15 alcohols in the ratio 67% C 13' 33% C 15 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.
- the level of the alkyl sulphate component lies in the range of from 4% to 20% by weight of the composition, more generally from 4% to 16% by weight.
- the usage level lies in the range from 6% to 12% by weight, most preferably in the range from 6% to 10% by weight.
- the alkyl sulphate is associated with a source of magnesium ions which, as will be described hereinafter, can either be introduced as the oxide or hydroxide to neutralise the acid or can be added to the composition as a water soluble salt.
- a source of magnesium ions which, as will be described hereinafter, can either be introduced as the oxide or hydroxide to neutralise the acid or can be added to the composition as a water soluble salt.
- the addition of appreciable levels of magnesium salts to the dishwashing compositions of the invention raises the temperature at which inorganic salt crystals form in the compositions on cooling and is therefore less preferable.
- the molar amount of magnesium ion in the compositions is controlled to correspond to 0.35-0.65X, preferably 0.45-0.55X where X is the number of moles of C 10 -C 16 alkyl sulphate present. Most preferably the magnesium ion content is adjusted to provide the stoichiometric equivalent i.e. half the molar amount of the alkyl sulphate present. In practice the magnesium ion will be present at a level of fran about 0.15% to about 0.70% by weight, preferably from 0.25% to 0.45% by weight of the composition.
- 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.
- an alkylbenzene sulphonate content of from 5% to 20% by weight of the composition is required generally from 5% to 15% by weight.
- an alkylbenzene sulphonate content of from 5% to 10% by weight is used and highly preferred compositions in accordance with this aspect of the invention have from 6% to 8% of C11.8 alkyl benzene sulphonate.
- the alkyl ethoxy sulphate surfactant component comprises a primary alkyl ethoxy sulphate derived from the condensation product of a C 10 -C 16 alcohol with an average of up to 6 ethylene oxide groups.
- the C 10 -C 16 alcohol itself can be obtained from any of the sources previously described for the alkyl sulphate component. It has, however, been found preferable to use alkyl sulphates and alkyl ether sulphates in which the carbon chain length distributions are the same.
- C12-C13 alkyl ether sulphates are preferred and the level of alkyl ethoxy sulphate in the composition lies between 5% and 24% by weight of the compositions, generally in the range from 6% to 14% by weight. In the preferred compositions, the level lies in the range from 6% to 12% by weight, most preferably in the range from 8% to 12% by weight.
- Blends can be made of material having different degrees of ethoxylatior. and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent processifg steps such as distillation.
- the level of its usage in the composition is from 10% to 25% by weight, more preferably from 15% to 20% by weight.
- the counter ion for the alkyl ethoxy sulphate component can be any one of sodium, potassium, ammonium or alkanol-ammonium or a mixture thereof.
- a significant proportion (e.g. 30%) of the counter ions for the alkyl ethoxy sulphate component should be ammonium and in order to achieve the lowest possible chill point temperatures the alkyl ethoxy sulphate should be completely neutralized by ammonium ions.
- compositions in accordance with the invention are independently selected in the same manner as those for the alkyl ethoxy sulphate.
- at least 70% of the neutralising cations for the anionic surfactants should be ammonium ions.
- the ethoxylated nonionic surfactant component of the invention is 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 9 moles of ethylene oxide and not more than 2% by weight of unethoxylated alcohol where the ethoxylated alcohol contains an average of from 9 to 25 moles of ethylene oxide per mole of alcohol.
- the starting alcohol may be a primary alcohol or secondary 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 C 9 to c 11 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 (H LB ) 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.
- H LB hydrophilic-lipophilic balance
- the normal (base catalysed) ethoxylation process to produce an average degree of ethoxylation 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 deterqent 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. In preferred embodiments of the invention the level of monoethoxylate is not more than 5% by weight of the ethoxylated alcohol.
- the level of usage of the ethoxylated alcohol conponent in compositions of the invention is from 1% to 10% by weight more preferably from 2 to 6% by weight and most preferably from 3% to 5% by weight.
- the third component of the compositions of the invention is a zwitterionic surfactant, present in an amount of from 0.25% to 10%, more preferably from 0.5% to 5% and most preferably from 1% to 2.5% by weight of the compositions.
- the zwitterionic surfactant has the general formula: wherein R 1 is C 10 -C 16 alkyl
- R 1 has an average carbon chain length of from 12 to 14 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 C 8 -C 10 and C 14 -C 18 moieties.
- Synthetic sources for the R 1 group may be the same as those mentioned previously for the alkyl group in the alkyl sulphate component.
- compositions incorporating the C 12 -C 14 amido betaine and C 12 -C 14 sulpho betaine display the benefits of the invention
- the most preferred compositions utilise a C 12 -C 14 alkyl betaine as the zwitterionic surfactant component, the C 12 -C 14 alkyl group being derived from a coconut or palm kernel oil feedstock.
- a highly preferred optional ingredient of the composition according to the invention is a suds-promoting agent present at a level of from 2% to 8% by weight of the composition, preferably from 3% to 6% and most preferably 3%-4%.
- the suds-promoting agent is normally a C 10 -C 16 alkyl mono- or di-C 2 -C 3 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 C IO and C 16 fractions or may be the so-called 'narrow-cut' C 12 -C 14 fraction. Synthetic sources of the C 10 -C 16 alkyl group can also be used.
- the balance of the formula comprises a hydrotrope-water system in which the hydrotrope may be urea, a C I -C 3 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 C I -C 3 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 sulphonate 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 B ronopol ( R T M ), 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 B ronopol ( R T M )
- 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 B ronopol ( R T M ), antitarnish agents such as benzoxy
- compositions of the invention can be made in a number of ways but it is preferred that the zwitterionic surfactant 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.
- individual anionic surfactants can be made as aqueous solutions of alkali metal or ammonium salts which are then mixed together with the ethoxylated nonionic surfactant, followed by the suds booster and the hydrotrope, after which any magnesium ion can be introduced as a water soluble salt such as the chloride or sulphate.
- the zwitterionic surfactant and any optional 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 alcohol and alcohol ethoxylate can be mixed together and a single sulphation and neutralisation 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 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.
- Sulf(on)ation of the alcohol, alcohol ethoxylate and alkyl benzene q pn 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 oxide or hydroxide slurry which avoids the addition of chloride or sulphate ions.
- the alkyl benzene sulphonic acid is added to a neutralising medium, comprising ammonium hydroxide in an ethanol-water solution, to which the ethoxylated nonionic surfactant has also been added.
- a neutralising medium comprising ammonium hydroxide in an ethanol-water solution, to which the ethoxylated nonionic surfactant has also been added.
- This paste then forms a 'heel' to which the suds booster and a magnesium hydroxide slurry are added followed by the mixed alkyl sulphuric and alkyl ether sulphuric acids.
- the neutralisation of the alkyl sulphate and alkyl ether sulphate actives is carried out to a pH ⁇ 4 in order to ensure dissolution of the magnesium hydroxide, after which the pH is adjusted to the finished product pH of 6.6-7.3 and the minor ingredients (colour, perfume, bactericides etc.) are added before the zwitterionic component is blended and final adjustment of the viscosity is carried out.
- a further and preferred variation involves the neutralisation of the mixed alkyl sulphuric and alkyl ether sulphuric acids in the alcoholic ammonia solution and the use of this paste, at a surfactant concentration of from 40 to 60% by weight and a pH of from 7 to 8, as the 'heel' to which the monoethanolamide suds booster, magnesium hydroxide slurry and alkyl benzene sulphonic acid are added.
- the pH of the system after the sulphonic acid is added must be in the range of from 2 to 4 to ensure complete dissolution of the magnesium hydroxide.
- the minor ingredient addition, pH trimming, zwitterionic surfactant incorporation and viscosity adjustment are as before.
- compositions in accordance with the invention are dear single phase liquids, but the invention also embraces opaque products containing dispersed phases provided that such products are physically stable (i.e., do not separate) on storage.
- compositions A-D In the preparation of Compositions A-D, a mixture of alcohol and alcohol ethoxylate was sulphated using so 3 -air sulphation, and was then neutralised to a solution pH of 4 in an alcoholic ammonium hydroxide solution to which magnesium hydroxide had been added in an amount corresponding to half the molar quantity of alkyl sulphate present. After dissolution of the magnesium hydroxide, ammonia was added to form a neutralising solution for the alkyl benzene sulphonic acid. A separate sulphonation of the alkyl benzene was employed to produce the alkyl benzene sulphonic acid which was added to the alkaline solution of the other actives and neutralised with the excess ammonia to pH 7.
- composition A The monoethanolamide and, where present, the betaine were then added before final pH trimming to pH 6.8.
- the chill point of Composition A was -5°C.
- Compositions incorporating ethoxylated nonionic surfactant i.e. E-H were prepared in a similar manner except that the ethoxylated nonionic surfactant was added during the final pH trimming operation.
- the Cake Mix is McDougall's Sponge Mix
- the free fatty acids comprise 2 parts oleic acid 2 parts linoleic acid 1 part stearic acid 2.5 parts palmitic acid 367 parts corn oil to give 2% MFFA mixture.
- 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 47°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.
- all of the Cake Mix soil (5g) is added together at this stage with 1 ml of the 2% MFFA.
- 1 ml of the 6% FA soil alone is added.
- the cylinders are restarted and allowed to rotate for 1 minute.
- the suds height is noted and 1 ml of the 2% MFFA or 6% FA (depending on the test) 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 0.3 cms.
- compositions A-D show that little, if any, benefit is obtained from increasing zwitterionic level above 1.5% by weight of the composition.
- Products J, K and L in accordance with the invention although providing the suds mileage benefits of the invention do not all perform equally well in other areas.
- Product J which comprises the addition of 1.5% alkyl betaine to Product I, improves suds mileage and grease cutting but shows technical deficiencies in initial suds level and grease redeposition.
- Product K in which the anionic surfactant level has been slightly increased, eliminates the initial suds performance deficiency of Product J.
- a highly preferred embodiment of the invention is constituted by Product L in which the ratio of alkyl benzene sulphonate to alkyl sulphate/alkyl ether sulphate has been significantly reduced.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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GB8428149 | 1984-11-07 | ||
GB848428149A GB8428149D0 (en) | 1984-11-07 | 1984-11-07 | Liquid detergent compositions |
GB858526302A GB8526302D0 (en) | 1984-11-07 | 1985-10-24 | Liquid detergent compositions |
GB8526302 | 1985-10-24 |
Publications (2)
Publication Number | Publication Date |
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EP0181212A1 true EP0181212A1 (de) | 1986-05-14 |
EP0181212B1 EP0181212B1 (de) | 1988-11-09 |
Family
ID=26288427
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19850308098 Expired EP0181212B1 (de) | 1984-11-07 | 1985-11-07 | Flüssige Detergenszusammensetzungen |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0181212B1 (de) |
DE (1) | DE3566126D1 (de) |
ES (1) | ES8708009A1 (de) |
IE (1) | IE58219B1 (de) |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0232153A2 (de) * | 1986-02-03 | 1987-08-12 | Unilever Plc | Reinigungsmittel |
EP0387063A2 (de) * | 1989-03-10 | 1990-09-12 | Unilever Plc | Reinigungsmittel |
US5102574A (en) * | 1989-02-27 | 1992-04-07 | Lever Brothers Company, Division Of Conopco, Inc. | Liquid non-aqueous detergents comprising narrow-range ethoxylates |
WO1992006161A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | Detergent compositions containing polyhydroxy fatty acid amides and suds enhancing agent |
WO1992006156A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium |
WO1992006171A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | Liquid detergent compositions |
GB2251101A (en) * | 1990-12-22 | 1992-06-24 | Samsung Electronics Co Ltd | Redundant means and method for a semiconductor memory device |
WO1993005132A1 (en) * | 1991-09-06 | 1993-03-18 | The Procter & Gamble Company | Detergent compositions containing calcium and polyhydroxy fatty acid amide |
US5209874A (en) * | 1989-04-26 | 1993-05-11 | Shell Oil Company | Liquid surface active compositions |
WO1994004640A1 (en) * | 1992-08-21 | 1994-03-03 | The Procter & Gamble Company | Concentrated liquid detergent composition comprising an alkyl ether sulphate and a process for making the composition |
US5336445A (en) * | 1990-03-27 | 1994-08-09 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing beta-aminoalkanols |
US5342549A (en) * | 1990-01-29 | 1994-08-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine |
EP0633308A1 (de) * | 1993-07-09 | 1995-01-11 | Colgate-Palmolive Company | Flüssiges Reinigungsmittel auf der Basis von starkschäumenden nichtionischen oberflächenaktiven Mitteln |
TR26609A (tr) * | 1991-11-21 | 1995-03-15 | Procter & Gamble | ANYONIK SüRFAKTANLARI, POLIHIDROKSI YAGLI ASIT AMIDLERI VE ÖNEM TASIYAN BIR SEKILDE SECILEN KÖPüK ARTTIRICI MADDEYI IHTIVA EDEN DETERJAN BILESIMLER. |
US5454983A (en) * | 1992-01-23 | 1995-10-03 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol |
US5531933A (en) * | 1993-12-30 | 1996-07-02 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders |
US5534198A (en) * | 1994-08-02 | 1996-07-09 | The Procter & Gamble Company | Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity |
US5536451A (en) * | 1992-10-26 | 1996-07-16 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant |
US5536450A (en) * | 1993-11-12 | 1996-07-16 | The Procter & Gamble Comany | Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume |
US5540864A (en) * | 1990-12-21 | 1996-07-30 | The Procter & Gamble Company | Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol |
US5540865A (en) * | 1990-01-29 | 1996-07-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine |
WO1996024655A1 (en) * | 1995-02-09 | 1996-08-15 | Unilever Plc | Light duty cleaning compositions |
WO1997015650A1 (en) * | 1995-10-23 | 1997-05-01 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
WO1998005745A2 (en) * | 1996-08-08 | 1998-02-12 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
GB2321253A (en) * | 1997-01-16 | 1998-07-22 | Mcbride Robert Ltd | Liquid detergent formulation |
WO2008074667A1 (en) * | 2006-12-20 | 2008-06-26 | Unilever N.V. | Dishwashing composition |
EP1939274A1 (de) * | 2006-12-20 | 2008-07-02 | Unilever N.V. | Geschirrspülzusammensetzung |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2010893A (en) * | 1977-12-22 | 1979-07-04 | Unilever Ltd | Liquid Detergent Composition |
EP0036625A1 (de) * | 1980-03-26 | 1981-09-30 | Henkel Kommanditgesellschaft auf Aktien | Flüssige Reinigungsmittel |
EP0039110A1 (de) * | 1980-04-24 | 1981-11-04 | THE PROCTER & GAMBLE COMPANY | Flüssige Reinigungsmittelzusammensetzungen |
EP0062371A1 (de) * | 1981-04-03 | 1982-10-13 | THE PROCTER & GAMBLE COMPANY | Flüssige Detergenszusammensetzungen |
EP0125854A2 (de) * | 1983-05-14 | 1984-11-21 | The Procter & Gamble Company | Flüssige Reinigungsmittelzusammensetzungen |
-
1985
- 1985-11-06 ES ES548571A patent/ES8708009A1/es not_active Expired
- 1985-11-06 IE IE276785A patent/IE58219B1/en not_active IP Right Cessation
- 1985-11-07 DE DE8585308098T patent/DE3566126D1/de not_active Expired
- 1985-11-07 EP EP19850308098 patent/EP0181212B1/de not_active Expired
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2010893A (en) * | 1977-12-22 | 1979-07-04 | Unilever Ltd | Liquid Detergent Composition |
EP0036625A1 (de) * | 1980-03-26 | 1981-09-30 | Henkel Kommanditgesellschaft auf Aktien | Flüssige Reinigungsmittel |
EP0039110A1 (de) * | 1980-04-24 | 1981-11-04 | THE PROCTER & GAMBLE COMPANY | Flüssige Reinigungsmittelzusammensetzungen |
EP0062371A1 (de) * | 1981-04-03 | 1982-10-13 | THE PROCTER & GAMBLE COMPANY | Flüssige Detergenszusammensetzungen |
EP0125854A2 (de) * | 1983-05-14 | 1984-11-21 | The Procter & Gamble Company | Flüssige Reinigungsmittelzusammensetzungen |
Cited By (39)
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EP0232153A3 (en) * | 1986-02-03 | 1989-09-27 | Unilever Plc | Detergent compositions |
AU588967B2 (en) * | 1986-02-03 | 1989-09-28 | Unilever Plc | Detergent compositions |
EP0232153A2 (de) * | 1986-02-03 | 1987-08-12 | Unilever Plc | Reinigungsmittel |
US5102574A (en) * | 1989-02-27 | 1992-04-07 | Lever Brothers Company, Division Of Conopco, Inc. | Liquid non-aqueous detergents comprising narrow-range ethoxylates |
EP0387063A2 (de) * | 1989-03-10 | 1990-09-12 | Unilever Plc | Reinigungsmittel |
EP0387063A3 (de) * | 1989-03-10 | 1991-09-04 | Unilever Plc | Reinigungsmittel |
US5209874A (en) * | 1989-04-26 | 1993-05-11 | Shell Oil Company | Liquid surface active compositions |
US5540865A (en) * | 1990-01-29 | 1996-07-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine |
US5342549A (en) * | 1990-01-29 | 1994-08-30 | The Procter & Gamble Company | Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine |
US5336445A (en) * | 1990-03-27 | 1994-08-09 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing beta-aminoalkanols |
WO1992006171A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | Liquid detergent compositions |
WO1992006156A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides and magnesium |
TR26013A (tr) * | 1990-09-28 | 1993-11-01 | Procter & Gamble | N-alkanoil-n-alkil glukaminleri ihtiva eden sulu sivi deterjan bilesimleri |
TR26011A (tr) * | 1990-09-28 | 1993-11-01 | Procter & Gamble | Aniyonik kapiller aktif cisimleri, polihidroksi yag asit amidlerini ve magnezyumu iceren deterjan bilesimleri |
WO1992006161A1 (en) * | 1990-09-28 | 1992-04-16 | The Procter & Gamble Company | Detergent compositions containing polyhydroxy fatty acid amides and suds enhancing agent |
US5540864A (en) * | 1990-12-21 | 1996-07-30 | The Procter & Gamble Company | Liquid hard surfce detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol |
GB2251101A (en) * | 1990-12-22 | 1992-06-24 | Samsung Electronics Co Ltd | Redundant means and method for a semiconductor memory device |
GB2251101B (en) * | 1990-12-22 | 1995-03-22 | Samsung Electronics Co Ltd | Redundant means and method for a semiconductor memory device |
TR26664A (tr) * | 1991-09-06 | 1995-03-15 | Procter & Gamble | Kalsiyum ve polihidroksi yagli asit amidi ihtiva eden deterjan bilesimleri |
WO1993005132A1 (en) * | 1991-09-06 | 1993-03-18 | The Procter & Gamble Company | Detergent compositions containing calcium and polyhydroxy fatty acid amide |
TR26609A (tr) * | 1991-11-21 | 1995-03-15 | Procter & Gamble | ANYONIK SüRFAKTANLARI, POLIHIDROKSI YAGLI ASIT AMIDLERI VE ÖNEM TASIYAN BIR SEKILDE SECILEN KÖPüK ARTTIRICI MADDEYI IHTIVA EDEN DETERJAN BILESIMLER. |
US5454983A (en) * | 1992-01-23 | 1995-10-03 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol |
WO1994004640A1 (en) * | 1992-08-21 | 1994-03-03 | The Procter & Gamble Company | Concentrated liquid detergent composition comprising an alkyl ether sulphate and a process for making the composition |
US5536451A (en) * | 1992-10-26 | 1996-07-16 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant |
EP0633308A1 (de) * | 1993-07-09 | 1995-01-11 | Colgate-Palmolive Company | Flüssiges Reinigungsmittel auf der Basis von starkschäumenden nichtionischen oberflächenaktiven Mitteln |
US5536450A (en) * | 1993-11-12 | 1996-07-16 | The Procter & Gamble Comany | Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume |
US5531933A (en) * | 1993-12-30 | 1996-07-02 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders |
US5534198A (en) * | 1994-08-02 | 1996-07-09 | The Procter & Gamble Company | Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity |
WO1996024655A1 (en) * | 1995-02-09 | 1996-08-15 | Unilever Plc | Light duty cleaning compositions |
AU714639B2 (en) * | 1995-02-09 | 2000-01-06 | Unilever Plc | Light duty cleaning compositions |
WO1997015650A1 (en) * | 1995-10-23 | 1997-05-01 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
WO1998005745A2 (en) * | 1996-08-08 | 1998-02-12 | Colgate-Palmolive Company | Light duty liquid cleaning compositions |
WO1998005745A3 (en) * | 1996-08-08 | 1998-07-09 | Colgate Palmolive Co | Light duty liquid cleaning compositions |
GB2321253A (en) * | 1997-01-16 | 1998-07-22 | Mcbride Robert Ltd | Liquid detergent formulation |
GB2321253B (en) * | 1997-01-16 | 2000-10-18 | Mcbride Robert Ltd | Liquid detergent formulation |
WO2008074667A1 (en) * | 2006-12-20 | 2008-06-26 | Unilever N.V. | Dishwashing composition |
EP1939274A1 (de) * | 2006-12-20 | 2008-07-02 | Unilever N.V. | Geschirrspülzusammensetzung |
AU2007336423B2 (en) * | 2006-12-20 | 2010-10-14 | Unilever Plc | Dishwashing composition |
RU2454456C2 (ru) * | 2006-12-20 | 2012-06-27 | Юнилевер Н.В. | Состав для мытья посуды |
Also Published As
Publication number | Publication date |
---|---|
IE58219B1 (en) | 1993-08-11 |
DE3566126D1 (en) | 1988-12-15 |
ES548571A0 (es) | 1987-09-01 |
EP0181212B1 (de) | 1988-11-09 |
IE852767L (en) | 1986-05-07 |
ES8708009A1 (es) | 1987-09-01 |
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