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
  • 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
  • C11D1/143—Sulfonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
• • 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

Definitions

• This invention relates to liquid detergent compositions and especially to so-called light duty liquids intended primarily for dishwashing. More particularly the invention concerns dishwashing liquid detergent compositions that have been formulated to secure improved particulate soil removal ability without any loss in other performance areas such as grease and oily soil removal and sudsing capability.
• Dishwasing liquid detergent formulations of this type include magnesium salts and magnesium surfactants such as alkyl sulphates, alkyl ether sulphates and alkyl benzene sulphonates and GB-A-1,524,441, 1,551,074, 2,010,893A and EP-A-0039110 are representative disclosures of the state of the art. The art teaches that these formulations have enhanced performance, particularly when used in water of low mineral hardness. Dishwashing liquid detergent compositions containing alkane and alkene sulphonates are also known, examples of such disclosures including those in GB-A-1,050,848,1,339,069, 1,382,295, 1,451,228, 1,551,074 and 1,567,421.
• Formulations of this type employing total surfactant levels in excess of 25% by weight cannot tolerate significant levels of inorganic detergent builder salts whilst retaining a clear single phase solution form and additionally, the presence of inorganic salts gives rise to aesthetically undesirable residues on the washed crockery or cutlery. Consequently, these formulations are normally substantially completely free of detergent builder salts, while metal chelating agents, if incorporated, are only employed in trace amounts.
• particulate materials are also a significant component of food residues and the low levels, or total absence, of detergent builder materials in conventional dishwashing liquid detergents make these formulations less than optimum in terms both of suds stability in the presence of particulate soil and of particulate soil suspension during the washing process. It has now been found that, certain combinations of ingredients, more particularly an alkali earth metal alkyl sulphate and an ethoxylated alcohol, can provide an unexpected improvement in particulate soil handling capability without any sacrifice of the grease and oily soil removal performance of a dishwashing liquid formulation.
• a clear homogeneous magnesium containing liquid detergent composition having a chill point of not more than 5°C comprising a surfactant mixture in a hydrotrope-water system, characterised in that the surfactant mixture is formed by the combination of
• the present invention comprises a surfactant system containing paraffin or olefine sulphonate, alkyl ether sulphate, alkyl sulphate and ethoxylated nonionic surfactant components in a liquid vehicle composed of hydrotrope and water.
• the alkyl sulphate surfactant component is a primary alkyl sulphate in which the alkyl group contains 10-16 carbon atoms, more preferably an average of 12-15 carbon atoms preferably in a linear chain.
• C 10 ⁇ C 16 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 C 13 ⁇ C 15 alcohols in the ratio 67% C, 3 , 33% C, 5 sold under the trade name Lutensol by BASF GmbH and Synperonic (RTM) by ICI Ltd, and Lial 125 (a highly branched C 12 ⁇ C 15 primary alcohol) 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 alkyl sulphate component is present at a level of from 6% to 18% by weight of the composition, more generally from 8% to 16% 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 0.40-0.60X preferably 0.45-0.55X where X is the number of moles of C 10 ⁇ C 16 alkyl sulphate present.
• the magnesium ion content is adjusted to provide the stoichiometric equivalent of the alkyl sulphate present.
• the magnesium ion will be present at a level of from 0.15% to 0.70% by weight, preferably from 0.35% to 0.60% by weight of the composition.
• paraffin sulphonate (s-alkane sulphonate), or a-olefine sulphonate (alkene sulphonate) component comprises from 3% to 15%, more preferably from 4% to 12% by weight of the formulation.
• Secondary alkane sulphonates useful in the present invention preferably have from 13 to 18 carbon atoms per molecule, and most desirably from 14 to 17, and are characterised by a high solubility in water compared to alkyl aryl sulphonates and other sulphuric acid reaction products used for dishwashing detergent compositions.
• 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 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. by the sulpho- chlorination method in which chlorine and sulphur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulphonyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulphonates.
• the proportions of disulphonate or higher sulphonated material will be minimized but some may be present.
• 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 usually produced when an excess of sulphonating agent is present, may have the sulphonate groups distributed over different carbon atoms of the paraffin base, and mixtures of the monosulphonates and disulphonates may be present.
• 'a-olefine sulphonates' or 'alkene sulphonates' is used herein to mean compounds which can be produced by the sulphonation of alpha-olefines by means of uncomplexed sulphur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have been formed in the reaction are hydrolysed to give the corresponding hydroxy-alkane sulphonates.
• the sulphur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example by liquid S0 2 , chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 2 , etc., when used in the gaseous form.
• inert diluents for example by liquid S0 2 , chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gaseous S0 2 , etc., when used in the gaseous form.
• the alpha-olefines from which the olefine sulphonates are derived are mono-olefines having 12 to 16 carbon atoms, preferably 12 to 14 carbon atoms. Preferably, they are straight chain olefines. Olefine sulphonates having more than 16 carbon atoms do not give the desired high lathering performance in the mixtures according to the invention; those with fewer than 12 carbon atoms have reduced detergent properties. In addition to the true alkene sulphonates and a proportion of hydroxy-alkane sulphonates, the olefine sulphonates may contain minor amounts of other materials, arising from impurities in the original olefine stock and from side reactions during the sulphonation and neutralisation processes.
• the alkyl ether sulphate component comprises a primary alkyl ethoxy sulphate derived from the condensation product of a C lo -Cl, alcohol with an average of from 0.5 to 6 ethylene oxide groups.
• the C'O-C'6 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 sulphate and alkyl ether sulphate in which the carbon chain length distributions are the same.
• C 12 ⁇ C 15 alkyl ether sulphates are preferred and the level of alkyl ethoxy sulphate in the compositions lies between 0.5% and 20% by weight of the compositions, generally in the range from 4% to 14% by weight.
• the conventional average degree of ethoxylation is from 0.5 to 3 groups per mole of alcohol, but as conventional ethoxylation processes result in a distribution of individual ethoxylates ranging from 1 to 10 ethoxy groups per mole of alcohol, the average can be obtained in a variety of ways. 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.
• the cations, other than magnesium, that may be used in the neutralisation of the anionic surfactants may be sodium, potassium, ammonium or alkanolammonium, but ammonium is a preferred cation because of its depressive effect on the chill point temperature of the compositions.
• Preferred compositions have chill points of less than 0°C.
• the surfactant system also comprises an ethoxylated C 8 ⁇ C 12 primary alcohol having an HLB (hydrophilic-lipophilic balance) in the range from 7.5 to 12.0, preferably from 8.0 to 9.5.
• the primary alcohol may be linear or branched in structure and can be derived from sources such as those described in connection with the alkyl sulphate component.
• Preferred materials are those in which the alcohol is derived from a C 9 ⁇ C 11 hydrocarbon fraction in which the hydrocarbon material contains up to 25% methyl branching, and the level of ethoxylation provides an average of 2-3, more preferably 2.5 ethoxy groups per mole of alcohol.
• a desirable optional component of the invention is a suds boosting agent at a level of up to 5%, preferably from 3% to 4% by weight.
• the suds-promoting agent may be selected from C 12 ⁇ C 14 mono- and di-C2--C3 alkanolamide, C 12 ⁇ C 14 alkyl amides condensed with up to 15 moles of ethylene oxide per mole of amide and tertiary amine oxides containing a C 8 -C, 8 alkyl group.
• alkanolamides examples include coconut alkyl monoethanolamide, coconut alkyl diethanolamide and coconut alkyl mono and di isopropanolamides.
• Examples of the ethoxylated amides include coconut alkyl amide condensed with an average of six moles of ethylene oxide, lauryl amide condensed with an average of eight moles of ethylene oxide, myristyl amide condensed with an average of ten moles of ethylene oxide and coconut amide condensed with an average of eight moles of ethylene oxide.
• Amine oxides useful in the present invention have one alkyl or hydroxyalkyl moiety of from 8 to 18 carbon atoms, preferably from 8 to 16 carbon atoms and two moieties selected from alkyl groups and hydroxyalkyl groups containing 1 to 3 carbon atoms.
• amine oxides examples include dimethyl octylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, methylethyl hexadecylamine oxide, and dimethyl - 2-hydroxyoctadecylamine oxide.
• tertiary amine oxide is a C 12 -C 14 alkyl dimethyl amine oxide in which the C 12 ⁇ C 14 alkyl group is derived from coconut oil.
• the balance of the formula comprises a hydrotrope-water system in which the hydrotrope may be urea, a C l -C 3 alkanol, or a lower alkyl benzene sulphonate salt such as toluene, cumene or xylene sulphonate.
• the preferred hydrotrope is ethanol which is employed at from 3% to 10% by weight of the composition, preferably at from 4% to 8%.
• Optional ingredients of the liquid detergent compositions of the invention include thickeners such as guar gum, antibacterial agents such as glutaraldehyde and Bronopol (RTM), antitarnish agents such as
• the individual anionic surfactants can be made as aqueous solutions of alkali metal or ammonium salts which are then mixed together with the hydrotrope, and the suds booster, if this is included, following which the magnesium ion can be introduced as a water soluble salt such as the chloride or acetate. Optional minor ingredients are then added after which the pH and viscosity is adjusted.
• This method has the advantage of utilising conventional techniques and equipment but results in the introduction of additional chloride or acetate ions which can increase the chill point temperature (the temperature at which inorganic salts precipitate as crystals in the liquid).
• An alternative method of carrying out the invention is to mix the alcohol and alcohol ethoxylate together and carry out a single sulphation and neutralisation.
• the alcohol and alcohol ethoxylate should be mixed in a weight ratio lying in the range 45:1 to 1:5.5.
• Sulphation can take place by means of any of the conventional sulphating agents such as e.g., sulphur trioxide or chlorosulphonic acid.
• Neutralisation of the alkyl ether sulphuric acid and the alkyl sulphuric acid is carried out with a magnesium oxide or hydroxide slurry which avoids the addition of chloride or sulphate ions.
• the magnesium salt of the alkyl ether sulphuric acid has relatively greater aqueous solubility than the alkyl sulphuric acid component.
• the separately neutralised paraffin sulphonate salt, and the neutralised alkyl and alkyl ether sulphate salts and the hydrotrope are then added to the final mixing tank and the C B -C, 2 alcohol ethoxylate and any optional ingredients added before the pH is adjusted as above.
• a further and preferred modification of the above technique involves the preparation of a single alcohol ethoxylate feedstock whose composition is the same as, or closely approximates that of, the alcohol and alcohol ethoxylate blend.
• alcohol ethoxylates having an average degree of ethoxylation in the range 0.5 to 1.0, more usually 0.75 to 0.95 are preferred.
• the paraffin sulphonate was performed by S0 2 sulphonation of C 14 ⁇ C 17 n-alkanes and caustic soda neutralisation of the resultant sulphonic acid to give an approximately 60% active paste starting material. This was diluted with water and a little ethanol to form a 30% active solution in which the monoethanolamide was dispersed with agitation to assist its solution. A blend of the alcohol and alcohol ether condensate was sulphated using chlorosulphonic acid as the sulphating agent and the mixed sulphuric acids were then neutralised with magnesium hydroxide and ammonia respectively.
• the actual neutralisation was carried out using a 'heel' formed by the diluted paraffin sulphonate paste, in which the ammonia and magnesium hydroxide were dispersed before addition of the mixed sulphuric acids.
• the pH was then trimmed to pH 6.6 with ammonia before the ethoxylated nonionic and other minor ingredients (dye, perfume) were added to form the final composition.
• the finished product had a viscosity of 0.23 Pa ⁇ s at 20°C and a chill point of -3°C.
• the n-paraffin is sulphonated and neutralised to produce the sodium paraffin sulphonate as in Example I.
• the blend of C 12 ⁇ C 13 alcohol and C 12 ⁇ C 13 alcohol ethoxylate are sulphonated using gaseous S0 3 and are then neutralised by addition to an ethanol water mixture in which the ammonia and magnesium hydroxide have been dispersed. Further ethanol, the amide and C 9 ⁇ C 11 alcohol ethoxylate are added to this mixture together with paraffin sulphonate salt. Perfume, colour and pH trimming acid forming the minor components are then added to complete formation of the product which has a chill point of -3°C.
• Formulations A, B and C are commercially available liquid detergent products while formulation D is in accordance with the invention.
• This 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 ml of product solution at a concentration of 0.12% and a temperature of 45°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.
• the grease soil comprises a mixture * of fatty acids in a cooking oil base and 1 ml of this mixture (MFFA) is added to each cylinder. Where particulate soil is included it is all added at this stage.
• MFFA this mixture
• the cylinders are restarted and allowed to rotate for 1 minute.
• the suds height is noted and 1 ml of the 2% MFFA 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 0.5 cms.
• formulation B was compared to formulation D and also to a formulation D' from which the ethoxylated primary alcohol component was omitted.
• the beakers plus the residue were weighed, and the beakers were washed out and then re-weighed to give the weight of residue. The test was then repeated reversing the equipment for each product.
• test is predictive of the ranking of products in terms of their particulate soil suspension capability under normal usage conditions.

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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)

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• 1983
  • 1983-10-14 DE DE8383306237T patent/DE3370164D1/de not_active Expired
  • 1983-10-14 AT AT83306237T patent/ATE25856T1/de not_active IP Right Cessation
  • 1983-10-14 EP EP83306237A patent/EP0107946B1/en not_active Expired
  • 1983-10-26 CA CA000439792A patent/CA1217112A/en not_active Expired
  • 1983-10-28 JP JP58202496A patent/JPS59135292A/ja active Granted

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