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
  • C11D17/0013—Liquid compositions with insoluble particles in suspension
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads

Definitions

• This invention relates to a stabilised gel system for supporting finely divided particulate matter in suspension, to detergent compositions and abrasive preparations based on such a stabilised gel system, and to the production thereof.
• each type of preparation contains the same basic ingredients and in both cases it has been necessary to incorporate materials which can only be regarded as inert diluents of the active compounds in the formulation.
• the diluent has been alkali metal sulphates whilst in the case of the liquid it has simply been water.
• Such surface active ingredients normally include an anionic surfactant or tenside and may further include one or more non-ionic surfactants.
• anionic surfactants include the sodium salts of alkyl benzene sulphonic acids and of alkyl sulphonic acids.
• non-ionic surfactants there can be mentioned polyalkylene oxide ethers of alkyl alcohols or alkylphenols, as well as the monoethanolamides of fatty acids, such as coconut fatty acid monoethanolamide.
• US-A-3708428 and US-A-3899447 teach detergent compositions containing silica colloids.
• the colloidal silica is formed in situ as a sol by the reaction of a preheated solution of a water-soluble or dispersible alkali silicate with a preheated anionic, detergent-forming organic acid.
• builders such as complex phosphates (e.g. sodium tripolyphosphate) should be restricted to levels of concentration of the order of 4.0% by weight or lower.
• EP-A-0191372 relates to two-component alkaline cleaners having a pH of 11 or greater.
• the cleaners are said to be suitable for cleaning rigid materials such as metal and glass.
• One of the components of the system is an aqueous silicic acid dispersion which contains detergent builder.
• the component containing the silicic acid dispersion also requires the presence of from 0.3 to 3% by weight of a stabiliser, which is usually based on xanthan.
• the present invention accordingly seeks to provide an improved liquid built detergent composition and a process for making same in which the problems encountered in the prior art are substantially obviated. It also seeks to provide an improved system for supporting finely divided particulate matter in suspension.
• a stabilised gel system for supporting finely divided particulate matter in suspension, the stabilised gel system comprising a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside.
• the tenside is one containing one or more sulphonate groups.
• Such a stabilised gel system can conveniently be produced by at least partially neutralising a sodium silicate solution with a tenside-forming acid containing one or more sulphonic acid groups.
• Such a stabilised gel system is normally acidic or near neutral in character.
• the pH of a liquid support system in accordance with the invention lies in the range of from 1.0 to 9.0. Normally it will have a pH of not more than 8.0, e.g. in the range of from 4.0 to 7.5.
• a liquid built detergent composition comprising a stabilised gel system comprising a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside and particles of a builder substantially uniformly distributed therein.
• an abrasive preparation comprising a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside in which are dispersed finely divided particles of an abrasive material.
• the tenside in such an abrasive preparation is one containing one or more sulphonate groups.
• Such an abrasive composition can be formulated as an oven cleaner, for example, or as a cleaner for hard surfaces.
• a process for the production of a stabilised gel system for supporting finely divided particulate matter in suspension which comprises neutralising a solution of an alkali metal silicate to a pH in the range of from 1.0 to 7.0 in the presence of a tenside thereby to produce a hydrosol of silicic acid stabilised by entanglement with tenside micelles.
• Neutralisation may be effected by addition of an acid to a solution of an alkali metal silicate that contains also at least one surfactant.
• the acid may be selected from hydrochloric acid, sulphuric acid, sulphamic acid, phosphoric acid, formic acid, acetic acid, citric acid, and mixtures of two or more thereof.
• neutralisation may be effected by titration of the solution of alkali metal silicate with a tenside-forming acid containing one or more sulphonic acid groups.
• a solution having a pH of not more than 7.0 is produced by dissolving in an aqueous medium a tenside-forming acid containing one or more sulphonic acid groups and an alkali metal tripolyphosphate and a solution of an alkali metal silicate is added thereto.
• the invention further relates to a process for the production of a liquid built detergent which comprises neutralising a solution of an alkali metal silicate such as sodium silicate, to a pH in the range of from 1.0 to 7.0 in the presence of a tenside thereby to produce a hydrosol of silicic acid stabilised by entanglement with tenside micelles and, either before or after completion of the neutralisation step, incorporating a builder in the composition.
• neutralisation can be effected by addition of an acid to a solution of an alkali metal silicate that also contains at least one surfactant and in which the builder is thereafter added.
• neutralisation can be effected by titration of the solution of alkali metal silicate with a tenside-forming acid containing one or more sulphonic acid groups.
• a solution having a pH of not more than 7.0 is produced by dissolving in an aqueous medium a tenside-forming acid containing one or more sulphonic acid groups and an alkali metal tripolyphosphate and a solution of an alkali metal silicate is added thereto.
• a stabilised gel system according to the invention comprises a hydrosol of silicic acid stabilised by entanglement with micelles of a tenside. Further evidence for such a structure is provided by electron microscopy studies on a liquid built detergent composition prepared from a stabilised gel system according to the invention.
• anionic surfactants which can be utilised in the present invention include alkyl benzene sulphonic acids, in which the alkyl group contains from 6 to 20 carbon atoms, for example from 10 to 14 carbon atoms, alkyl sulphonic acids containing from 10 to 26 carbon atoms, for example from 10 to 14 carbon atoms, and alpha-olefin sulphonic acids obtained by sulphonation of an alpha-olefin containing, for example from 10 to 22 carbon atoms, such as a C 16 to C 18 olefin or a mixture containing same.
• a surfactant containing a sulphonate group there may also be present a sulphated fatty alcohol or a sodium salt thereof;
• typical sulphated fatty alcohols include those containing from 10 to 26 carbon atoms, for example a sulphated fatty alcohol mixture containing C 10 , C 12 , C 14 , C 16 and C 18 fatty alcohols.
• Typical of such a fatty alcohol mixture is one containing alcohols in the following proportions: C 10 3.0%, C 12 57.0%, C 14 20.0%, C 16 9.0% and C 18 11.0%.
• a liquid built detergent composition according to the invention contains from 2% w/w up to 30% w/w of anionic surfactant (calculated as sulphonic acid) based upon the total weight of the composition.
• composition of the invention may further include one or more non-ionic surfactants.
• Typical non-ionic surfactants include fatty acid monoethanolamides such as coconut fatty acid monoethanolamide, a typical formulation for which is a mixture of monoethanolamides of fatty acids as follows: C 6 0.5%, C 8 6.5%, C 10 6.0%, C 12 49.5%, C 14 19.5%, C 16 8.5%, C 18 (stearic) 2.0%, C 18 (oleic) 6.0%, and C 18 (linoleic) 1.5%.
• non-ionic surfactants include polyoxyalkylene ethers of alkanols, typically polyoxyethylene ethers of alkanols containing from about 6 to about 20 ethylene oxide groups and based upon alkanols containing from about 6 to about 26 carbon atoms.
• alkanols and alkanol mixtures can be produced by hydrogenation of methyl esters produced by transesterification of naturally occurring vegetable oils such as coconut oil, sunflower oil, palm oil, rape seed oil, and the like, or of animal fats, such as tallow or lard.
• a typical polyoxyethylene ether of an alkanol is based upon lauryl alcohol condensed with approximately 8 moles of ethylene oxide.
• the concentration of non-ionic surfactant, if present, in the liquid built detergent composition ranges from 0.5% w/w up to 30% w/w based upon the total weight of the composition.
• liquid built detergent composition of the invention examples include preservatives, optical brighteners, bleaches, fragrances, zeolites, foam depressants, foam boosters and/or stabilisers, soaps, dyes, buffers, corrosion inhibition agents, bleach activators, enzymes, humectants, enzyme stabilisers, and the like.
• Such minor ingredients do not usually comprise more than 5% w/w each of the total composition, mostly less than 1% w/w each of the total composition, and more usually do not together amount to more than 5% w/w in total based upon the weight of the composition.
• a builder there can be mentioned in particular sodium tripolyphosphate. Potassium tripolyphosphate can alternatively be used.
• the pyrophosphates, metaphosphates, orthophosphates, tetraphosphate, phosphonates such as acetonodiphosphonates, aminotrismethylenephosphonates, ethylenediamine tetramethylene phosphonates, and carbonates of sodium and potassium have also been suggested as builders, as have also zeolites and organic sequestering agents, such as nitrilotriacetic acid, ethylene diamine tetraacetic acid, and polymeric carboxylic acids and their salts, such as polyacrylic acid and polymethacrylic acid.
• a typical liquid built detergent composition according to the invention comprises from 5% w/w up to 40% w/w based upon the total weight of the composition of a builder or builders.
• the pH is typically in the range of from 1.0 to 8.0, preferably about pH 4.0.
• a pH increase is often observed. In some cases the pH may rise above 7.0, when starting from a stabilised gel system at a pH of about 4.0; hence the final pH may be as high as 9.0 or even a little higher.
• the liquid built detergents of GB-B-2123846 are characterised by the fact that, upon centrifuging at 800 times normal Earth gravity for 17 hours at 25°C, these compositions separate into a first, predominantly aqueous, liquid phase, containing dissolved electrolyte, and at least one other phase. It is an advantage of our invention that, if a stabilised gel system is prepared of sufficient strength, then this may be used to prepare a liquid built detergent composition which does not separate into two or more phases upon centrifuging at 800 times normal Earth gravity for 17 hours at 25°C.
• the liquid built detergent composition if starting from sodium silicate as the precursor for the silicic acid hydrosol, from a mixture of ingredients that includes at least 3.0% by weight of sodium silicate (or an equivalent amount of another soluble silicate) up to 8% by weight based upon the total weight of the liquid built detergent composition.
• sodium silicate or equivalent
• alkylbenzene sulphonic acid or mixture of alkylbenzene sulphonic acids, is dissolved in about twice its own weight of water and added to the sodium silicate which was previously diluted with three times its weight of water. To the resulting transparent syrup, with slow stirring, are added all the other ingredients to produce a shining white, or glossy, pourable syrup which is further diluted with water to give the full batch of product at 100% by weight basis.
• a suitable alkyl benzene sulphonic acid is dodecyl benzene sulphonic acid.
• the sodium alkylbenzene sulphonate (e.g. sodium dodecyl benzene sulphonate) is twice diluted with water and placed in a pan and to it is added the sodium silicate syrup which can, if desired, be diluted with three volumes of water before addition to the pan.
• the mixture is slowly stirred and the pH value of the solution reduced to 8.0 by the use of the correct aliquot of the 25% hydrochloric acid. Once the reaction is over, which is about two minutes after the last addition of hydrochloric acid, the remainder of the water is added followed by the addition of the other ingredients in any order. Final adjustment to the required weight is by the last addition of water.
• a product similar to that of Example 1 is obtained.
• a liquid built detergent composition is prepared from the following ingredients: Dodecylbenzenesulphonic acid 10.0% Sodium silicate (47%) syrup about 6.5% Coconut Fatty Acid Monoethanolamide 1.4% Sodium carboxymethylcellulose 0.1% Sodium tripolyphosphate 24.2% Preservative 0.2% Alcohol ethoxylate 1.3% Hydrotrope H66 0.5% Antifoam 0.2% Fragrance 0.2% Enzyme - Esperase 0.4% Termamyl 0.4% Optical brightener 0.1% Water To 100%
• the alcohol ethoxylate used in this Example was a polyoxyethylene ether obtained by condensing 7 moles of ethylene oxide with a C 13/15 alcohol.
• the sodium carboxymethyl cellulose is dissolved in water.
• the coconut fatty acid monoethanolamide is also dissolved in hot water.
• the dodecylbenzene sulphonic acid is diluted with about twice its own weight of water.
• the sodium silicate syrup which has previously been diluted with about three times its own weight of water.
• Sufficient of this diluted sodium silicate syrup is added to give a pH of about 4.0.
• the sodium carboxymethyl cellulose solution is added, followed by the coconut fatty acid monoethanolamide solution, while continuing to stir.
• the sodium tripolyphosphate is added with stirring, followed by the other minor ingredients.
• the composition is diluted to the desired strength with water.
• the resulting composition is stable and does not separate out into separate layers even after several months storage. Moreover, upon centrifugation at 800g for 17 hours, no separation of phases can be detected. There is no sign of any formation of vesicles or spherulites, nor is there any evidence of any of the surfactant being present as a lamellar liquid crystal or solid hydrate. Hence, upon electron microscopic evaluation of the detergent composition of this Example, the observations recorded were consistent with a largely featureless granular structure with crystals of sodium tripolyphosphate distributed at random.
• a liquid built detergent composition is produced from the same ingredients as are used in Example 3 except that the addition of the sodium silicate syrup is delayed until after addition of the sodium tripolyphosphate.
• the sodium carboxymethyl cellulose and the coconut fatty acid monoethanolamide are each dissolved separately in hot water.
• the dodecylbenzene sulphonic acid is diluted with about twice its own weight of water.
• the sodium carboxymethyl cellulose solution and the coconut fatty acid ethanolamide solution are added in turn to the dodecylbenzene sulphonic acid solution with vigorous stirring to yield a solution having a pH of about 7.0 or lower, followed by the other minor ingredients.
• the sodium silicate syrup which has previously been diluted with twice its own weight of water, is added whilst continuing to stir vigorously. Finally the composition is diluted with water to the desired strength.
• the resulting liquid built detergent composition is similar to that of Example 3 except that it exhibits initially a somewhat lower viscosity. It does not separate into layers upon centrifugation at 800 g for 17 hours. It does not show any indication that any spherulites or vesicles are present, nor is there any evidence of any of the surfactant being present in the form of a lamellar liquid crystal or solid hydrate. Moreover, the results of electron microscopy evaluation indicate that the liquid built detergent composition of this Example has a largely featureless granular structure with randomly distributed crystals of sodium tripolyphosphate.
• a soft anionic gel or syrup can be loaded with fine abrasive and used as an oven, or hard surface, cleaner.
• the invention is not restricted, in its application, to pourable gel systems in heavy duty laundry detergents.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Detergent Compositions (AREA)
• Colloid Chemistry (AREA)
• Silicon Compounds (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

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• 1991
  • 1991-01-14 IE IE010891A patent/IE910108A1/en not_active IP Right Cessation
  • 1991-01-15 NZ NZ236770A patent/NZ236770A/en unknown
  • 1991-01-15 PT PT96485A patent/PT96485B/pt not_active IP Right Cessation
  • 1991-01-15 ES ES91902313T patent/ES2102392T3/es not_active Expired - Lifetime
  • 1991-01-15 DE DE69126660T patent/DE69126660T2/de not_active Expired - Fee Related
  • 1991-01-15 EP EP91902313A patent/EP0511261B1/en not_active Expired - Lifetime
  • 1991-01-15 CA CA002073759A patent/CA2073759C/en not_active Expired - Fee Related
  • 1991-01-15 WO PCT/GB1991/000052 patent/WO1991010720A1/en active IP Right Grant
  • 1991-01-15 AU AU71789/91A patent/AU7178991A/en not_active Abandoned
  • 1991-01-15 AT AT91902313T patent/ATE154827T1/de not_active IP Right Cessation

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