EP0110731A2 - Non-evaporative solidification of detergent pastes - Google Patents
Non-evaporative solidification of detergent pastes Download PDFInfo
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- EP0110731A2 EP0110731A2 EP83307439A EP83307439A EP0110731A2 EP 0110731 A2 EP0110731 A2 EP 0110731A2 EP 83307439 A EP83307439 A EP 83307439A EP 83307439 A EP83307439 A EP 83307439A EP 0110731 A2 EP0110731 A2 EP 0110731A2
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- Prior art keywords
- foregoing
- surfactant
- phase
- alkyl sulphate
- solid
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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
- C11D13/00—Making of soap or soap solutions in general; Apparatus therefor
- C11D13/14—Shaping
- C11D13/20—Shaping in the form of small particles, e.g. powder or flakes
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
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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
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0069—Laundry bars
Definitions
- the present invention relates to the preparation of non-soap detergent solids, especially in bar, tablet or powder form, by non-evaporative solidification of aqueous detergent pastes.
- NSD non-soap laundry detergents
- the term includes the sulphated and sulphonated anionic surfactants, non-ionic, Zwitterionic, amphoteric and semi-polar surfactants and mixtures thereof, including mixtures with minor proportions of soap.
- the term excludes soap and active mixtures containing major proportions of soap.
- the term includes those cationic surfactants, which are effective as laundry cleaning agents or fabric softeners generally used in admixture with non- ionic or amphoteric surfactants.
- soap was the only laundry surfactant of industrial significance. It was used mainly in the form of moulded bars, or sometimes as a powder. It suffers, however, from the major disadvantage that it forms an insoluble curd with alkaline earth metals, which commonly occur in water especially in "hard” water areas.
- NSD which, apart from a small proportion sold as liquid detergents, is invariably supplied as a powder formed by the evaporation of a slurry of NSD, with builders and other auxiliary detergent ingredients, in water. Evaporation is normally effected in a spray drier.
- the conventional dried NSD powder has certain disadvantages.
- the energy cost of evaporating substantial quantities of water is high, and the capital cost and relative sophistication of spray driers is prohibitive for many developing countries seeking to establish an indigenous detergent industry.
- a market persists, even in industrialised countries, for laundry surfactants in the form of bars for repeated use, or of rapidly soluble tablets which can be used as a convenient means of adding measured amounts of surfactant to the wash liquor.
- Spray drying technology is not well adapted to satisfy this demand.
- a method for the manufacture of solid NSD formulations which comprises mixing an aqueous NSD surfactant comprising a water soluble alkyl sulphate, sulphocarboxylate or sulphoester, at a concentration and temperature such that it is present as "G" phase, with builder and, optionally, other ingredients of solid laundry detergent compositions, and forming the mixture into a solid composition by non-evaporative solidification.
- an aqueous NSD surfactant comprising a water soluble alkyl sulphate, sulphocarboxylate or sulphoester
- non-evaporative solidification embraces those processes which rely primarily upon one or more of the following three phenomena to effect solidification, that is to say:
- the first of the foregoing phenomena (A) requires a "G" phase which exists only at a substantially elevated temperature and which is converted to the hydrated solid phase on cooling to ambient temperature.
- Suitable higher temperature "G” phase surfactants include sodium, potassium and tris (hydroxyethyl) ammonium alkyl sulphates, olefin sulphonates and alkyl benzene sulphonates.
- the second phenomenon (B) depends on the effects of electrolyte in raising the temperature of the "G" phase/solid phase transition boundary, and hence, effectively increasing the temperature at which the "G” phase solidifies, enabling a normally liquid crystalline surfactant composition to be obtained as the hydrated solid at ambient temperature.
- Suitable electrolytes to be used in raising the transition temperature include, for example, sodium silicate, sodium sulphate, sodium chloride, or sodium carbonate.
- the surfactant is anionic a common cation is employed to maximise the effect, thus where, as will normally be the case,the surfactant is a sodium salt, the preferred electrolyte will be a water soluble, strongly dissociable sodium salt.
- the amount of electrolyte required will depend upon the particular NSD and the extent to which the other non-evaporative solidification effects such as cooling or hydration of hydratable salts is relied upon.
- the third of the aforesaid phenomena (C) involves the abstraction of water from the "G” phase by a hydratable compound, in an amount sufficient to convert the "G" phase into a hydrated solid.
- anhydrous hydratable salt capable of exerting a dessicant action on a "G" phase surfactant
- the most convenient is anhydrous tetrasodium pyrophosphate or sodium tripolyphosphate, which are commonly included in NSD formulations as builders.
- the hydratable compound may be a partially hydrated compound.
- non-evaporative solidification does not exclude the possibility that some evaporation of moisture occurs during the process. Incidental evaporation of moisture is inevitable when aqueous materials are handled, especially at elevated temperatures. The term merely indicates that techniques are employed which do not rely on evaporation to effect solidification. It is possible within the scope of our invention to use evaporation in conjunction with the non-evaporative techniques. However, if the evaporation requires expensive drying equipment or removes a sufficiently large proportion of the moisture to increase, substantially, the energy costs, then a part of the economic benefit of the invention will have been forfeited.
- the NSD feed in the process of our invention is essentially present as a "G" phase, although it may be possible in certain circumstances to add minor proportions of the NSD in other forms, e.g. as a dilute aqueous solution, or as an anhydrous or partially hydrated solid product. In the latter case the addition of the anhydrous surfactant may contribute to the non-evaporative solidification by raising the active concentration, and may in fact constitute some or all of the hydratable compound.
- the “G” phase is a pumpable fluid which is formed over a narrow range of concentrations which range usually lies somewhere between 45% and 80% by weight of active ingredient and is characterised by a lamellar structure in which the surfactant molecules are associated to form plates of indefinite size separated by planes of water molecules.
- concentration of a surfactant in the "M 1 " phase is progressively increased a phase change occurs to give either a hydrated solid phase, or, if the temperature is sufficiently elevated, to convert the M l phase progressively to a fluid "G" phase until a viscosity minimum is reached. Further increase in the concentration of the "G” phase causes the viscosity to rise until a further phase change occurs, leading to the formation of a hydrated solid phase.
- hydrated solid phase has been used broadly to include those systems which comprise suspensions of solid or immobile gel phases in one or more viscous or gel phase to provide a more or less rigid material.
- C l ... C n are the concentrations of the individual active components and g 1 ... g n are the concentrations at which each component forms a "G" phase of minimum viscosity.
- This formula enables the concentration of the mixture corresponding to the minimum viscosity "G" phase to be estimated in a majority of cases.
- any "G" phase can be located very rapidly and easily, using standard laboratory equipment by making a test composition having an active concentration of say 75% (or, where appropriate, whatever concentration has been estimated on the basis of the foregoing formula) and placing a sample on a slide on the block of a heated stage microscope.
- the mixture is in an M 1 phase, water may be allowed to evaporate from the edges of the sample under the cover disc and any phase changes observed. If any M 2 phase or hydrated solid is present, water may be added around the edge of the cover disc and allowed to diffuse into the composition. If no "G" phase is located in this way samples may be heated progressively on the block and the operations repeated.
- the composition is pumpable at concentrations within a range of ⁇ 10%, preferably - 5%, e.g. ⁇ 2.5% of the minimum viscosity concentration. This range tends to be broader at more elevated temperatures. Compositions may be obtained, at the limits of the range in which one or more solid or gel phase is suspended in a continuous "G" phase. Such compositions may be useful according to the invention.
- the "G” phase may generally be prepared by converting a suitable precursor to the NSD in the presence of the appropriate quantity of water (e.g. an alkyl sulphuric or fatty ester sulphonic acid may be neutralised with aqueous alkali of the appropriate strength).
- Mixed NSD may be prepared either by mixing the separately prepared components, each preferably in the "G" phase, or where this is impractical, by preparing one component from its precursor in the presence of the other component as described in our British Patent 2,022,125.
- alkyl sulphates available for NSD solid formulations have been either substantially anhydrous solids and therefore difficult to mix with other ingredients, or more usually dilute solutions containing more than 60% water, which cannot be solidified at ambient temperatures except by evaporation of a major proportion of the water content.
- Non-evaporative solidification has not therefore been contemplated.
- Our invention takes advantage of a property of the more concentrated fluid "G" phase alkyl sulphates, namely their sensitivity to small changes in active or electrolyte concentration or of temperature, which enables them to be much more easily converted into hydrated solids than the more conventional detergent solutions.
- the alkyl sulphate for use according to our invention may be potassium, ammonium or lower alkyl ammonium or alkylolammonium alkyl sulphate. Particularly preferred are sodium alkyl sulphates. Sodium alkyl sulphates do not form "G" phases at ambient temperatures and are normally only available as dilute solutions less than 30% active concentration. Solid anhydrous or hydrated sodium alkyl sulphate cannot normally be melted, but tends to decompose on heating. The instability of alkyl sulphuric acids has prevented the adoption of dry neutralisation for making sodium alkyl sulphate based solid NSD formulations.
- alkyl sulphates would be attractive alternatives to alkyl benzene sulphonate for many developing countries who could prepare the former by sulphation of locally produced vegetable based feedstocks rather than imported petrochemical feedstocks required for the latter.
- sodium alkyl sulphates are prepared at temperatures of, e.g. 70°C, or even lower where mixed alkyl feedstocks were used, and the water used in the neutralisation is controlled within narrow limits to form the "G" phase, a pumpable and stable hot fluid can be obtained which is mixable with other detergent ingredients and which can be solidified by cooling to form a solid composition.
- the solid composition will normally be formed by extrusion.
- the hot alkyl sulphate mixture may be injected into a mould and cooled to form cast bars. Also, depending upon the consistency and physical form of the mixture, it may be milled to a powder and sold as such, or compacted into rapidly soluble tablets.
- the alkyl sulphate for use according to preferred embodiments of our invention is typically sodium C 8-20 linear alkyl sulphates, preferably a mixed C 10-18 alkyl sulphate. Particularly preferred is lauryl alkyl sulphate.
- Other alkyl sulphates which may be used include potassium, lithium, ammonium, monoethanolemine, diethanolamine triethanolamine and mono-, di- tri-and tetra alkylammonium salts having up to 6 carbon atoms, preferably 1 to 4 carbon atoms per cation. Salts of mixtures of the aforesaid cations and branched chain alkyl sulphates are also useful.
- alkyl sulphate may be used in admixture with any other "G" phase forming anionic NSD, or nonionic, Zwitterionic, amphoteric or semi-polar NSD or mixtures thereof.
- Cationic surfactants preferably in conjunction with non-ionic or amphoteric surfactants, may also be used.
- the alkyl sulphate constitutes at least 30% more preferably at least 50% e.g. at least 75% of the total surfactant.
- the alkyl sulphate constitute at least 80% and preferably substantially all of the anionic surfactant.
- the non-ionic surfactant is preferably present in a proportion of from 1 to 49% especially 2 to 20% e.g. 3 to 10% of the total weight of surfactant.
- the alkyl sulphate may be used in conjunction with, or be replaced by, a sulphonated fatty acid or ester such as the methyl ester of coconut fatty acid.
- the surfactant may contain an at least sparingly water-soluble, alkali metal, ammonium, alkylolamine or amine, alkylbenzene sulphonate, alkyl ether sulphate, olefin sulphonate, alkane sulphonate, alkyl phenol sulphate, alkyl phenol ether sulphate, alkylethanolamide sulphate, or alkylethanolamide ether sulphate, each having at least one alkyl or alkenyl groups with from 10 to 20 aliphatic carbon atoms.
- Said alkyl or alkenyl groups are preferably straight chain primary groups but may optionally be secondary, or branched chain groups.
- ether refers to polyoxethylene, poloxypropylene, glyceryl and mixed polyoxyethylene-oxy propylene or mixed glyceryl-oxyethylene or glyceryl-oxy propylene groups, typically containing from 1 to 20 oxyalkylene groups.
- the sulphonated or sulphated surfactant may be sodium dodecyl benzene sulphonate, potassium hexadecyl benzene sulphonate, sodium dodecyl dimethyl benzene sulphonate, ammonium lauryl monethoxy sulphate, or monoethanolamine cetyl 10 mole ethoxylate sulphate.
- anionic surfactants useful according to the present invention include fatty alkyl sulphosuccinates, fatty alkyl ether sulphosuccinates, fatty alkyl sulphosuccinamates, fatty alkyl ether sulphosuccinamates, acyl sarcosinates, acyl taurides, isethionates, and alkyl ether carboxylates.
- Anionic phosphate fatty esters may also be used.
- Preferred anionic surfactants are sodium salts.
- Other salts of commercial interest include those of potassium, lithium, ammonium, monoethanolamine, diethanolamine triethanolamine, and alkyl amines containing up to six aliphatic carbon atoms.
- the surfactants may optionally but preferably contain nonionic surfactants.
- the nonionic surfactant may preferably be, e.g. a C 10-22 ethanolamide such as coconut monoethanolamide.
- Other nonionic surfactants which may optionally be present include ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkylolamides, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters, and the propoxylated, or ethoxylated and propoxyTated, analogues of all the aforesaid ethoxylated nonionics, all having a C 8-22 alkyl or alkenyl group, or any other nonionic surfactant which has hitherto been incorporated in powder compositions, e.g. amine oxide
- the preferred nonionics for our invention are the less water soluble compounds, for example those ethoxylates having an HLB range of 7-18, e.g. 12-15. However, more water soluble ones may sometimes be present, usually in minor amounts. In particular, fatty alkanolamides may be useful, in minor proportions, as internal lubricants to assist in the mixing and plodding of the alkyl sulphates.
- compositions of our invention may also contain amphoteric surfactant, usually as a minor component of the active material.
- Amphoteric surfactants include betaines and sulphobetaines formed by substituting a suitable tertiary nitrogen compound having a long chain alkyl or alkenyl group with a B-acid-forming substituting agent such as chloroacetic acid.
- suitable tertiary nitrogen containing compounds include: tertiary amines having one or two long chain alkyl or alkenyl groups, optionally a benzyl group and any other substituent a short chain alkyl group; imidazoline having one or two long chain alkyl or alkenyl groups and amidoamines having one or two long chain alkyl or alkenyl groups.
- the surfactant is mixed with builders and other auxiliary detergent ingredients.
- builder is sometimes used loosely in the detergent art to include any non-surfactant whose presence in a detergent formulation enhances the cleaning effect of the surfactant. More usually, however, the term is restricted to those typical "builders”, which are primarily useful as means of preventing or ameliorating the adverse effects on washing of calcium ions, e.g. by chelation, sequestering, precipitation or absorption of the ions, and secondarily as a source of alkalinity and buffering.
- builder refers to additives which produce the foregoing effects to a substantial extent.
- phosphate and condensed phosphate salts such as sodium or potassium orthophophates, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates and amino tris methylene phosphonates. It also includes alkali metal carbonates, zeolites and other "molecular sieves" and such organic sequestrants as salts nitrilotriacetic acid, citric acid and ethylene diamine tetracetic acid.
- compositions of our invention may contain fillers which help to provide a suitable physical form of bar.
- auxiliary detergent ingredients may comprise anti redeposition agents such as sodium carboxy methyl cellulose, perfumes, dyes, optical brightening agents, hydrotopes, buffers, bleach activators, alkalis and the like.
- auxiliaries are present in proportions of. less than 10% and more usually less than 5% wt. each and less than 25%, e.g. less than 15% total.
- an NSD bar according to our invention will have the following composition:
- the filler may comprise any inert solid having suitable physical properties, e.g. sodium sulphate or talc.
- the other auxiliaries may include any or all of:- sodium carboxymethyl cellulose or other soil suspending agent; enzymes; dyestuffs; perfumes; optical brighteners; oxidising bleaches such as peroxides, perborates, percarbonates or hypochlorites; gums; starches; water soluble synthetic polymers; organic polyelectrolytes such as polyacrylic acid; and hydrotropes. Tablets for addition to washing machines may contain minor proportions of soap as foam depressants, and/or silicone anti foams.
- the properties of the "G" phase surfactant may further be modified by the inclusion of mono- di- or tri-glycerides, fatty alcohols, glycerol, glycols, polyethylene glycol or polypropylene glycol, which may help to lubricate the mixture in cases where difficulties are encountered with mixing or extrusion.
- composition of the fatty alcohol was:-
- the resulting phase was then allowed to age for a minimum period of 1/2 hour to allow it to harden off.
- the mixture were then passed 3 - 4 time through a 30 rpm. 200 lbs/ft "sunlab” plodding machine to make them plastic enough to be extruded through the same machine in the form of bars.
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Abstract
Description
- The present invention relates to the preparation of non-soap detergent solids, especially in bar, tablet or powder form, by non-evaporative solidification of aqueous detergent pastes.
- The acronym "NSD" will be used herein to refer to the surfactant components of non-soap laundry detergents, which term comprises all those surfactants, other than salts of alkyl and alkenyl carboxylic acids, which are useful as laundry cleaning agents. The term includes the sulphated and sulphonated anionic surfactants, non-ionic, Zwitterionic, amphoteric and semi-polar surfactants and mixtures thereof, including mixtures with minor proportions of soap. The term excludes soap and active mixtures containing major proportions of soap. The term, however, includes those cationic surfactants, which are effective as laundry cleaning agents or fabric softeners generally used in admixture with non- ionic or amphoteric surfactants.
- Where the context permits, references herein to "solid" surfactants or detergents are to those which are solid at ambient temperatures.
- Until the middle of the present century, soap was the only laundry surfactant of industrial significance. It was used mainly in the form of moulded bars, or sometimes as a powder. It suffers, however, from the major disadvantage that it forms an insoluble curd with alkaline earth metals, which commonly occur in water especially in "hard" water areas.
- During the last four decades soap has been largely replaced for laundry use, at least in the industrialised countries, by NSD, which, apart from a small proportion sold as liquid detergents, is invariably supplied as a powder formed by the evaporation of a slurry of NSD, with builders and other auxiliary detergent ingredients, in water. Evaporation is normally effected in a spray drier.
- The conventional dried NSD powder, however, has certain disadvantages. The energy cost of evaporating substantial quantities of water is high, and the capital cost and relative sophistication of spray driers is prohibitive for many developing countries seeking to establish an indigenous detergent industry. Moreover, a market persists, even in industrialised countries, for laundry surfactants in the form of bars for repeated use, or of rapidly soluble tablets which can be used as a convenient means of adding measured amounts of surfactant to the wash liquor. Spray drying technology is not well adapted to satisfy this demand.
- These difficulties have led to the evolution, especially in some developing countries, of NSD bars for laundry use. Such bars are described in B.P.1,013,992 and in "Detergent Manufacture" by Marshall Sittig, published by Noyes Data Corp. 1976, Pp 325. et seq.
- Several techniques have been described for the manufacture of such bars, e.g.: dry mixing of surfactant, builder, and other ingredients, with minimal water added as plasticiser; mixing builder with aqueous NSD solution and evaporating surplus water, and "dry neutralisation", i.e. neutralisation of the substantially anhydrous sulphonic acid percursor of a sulphonated NSD with solid sodium carbonate.
- In practice the cost of evaporating substantial amounts of water, the physical difficulty of dry mixing the ingredients, and the lack of commercially available or econornically viable solidifiable anhydrous surfactants have combined to limit manufacturers to the technique of dry neutralisation. This in turn has effectively limited the choice of NSD for such use to the only commercially available sulphonic acid precursor which is sufficiently stable to be transported from a sulphonation plant to the manufacturing sites in developing countries where NSD bars have hitherto been mainly produced.
- The normal technique of manufacture of NSD bars, for nearly 20 years has been to mix the alkyl benzene sulphonic acid precursor with excess sodium carbonate and any other desired ingredients of the finished detergent bar, such as sodium tripolyphosphate or tetrasodium pyrophosphate builder, sodium sulphate filler, non-ionic foam booster, carboxymethyl cellulose soil suspender, sodium silicate, optical brightening agent, perfumes and colourings, at sufficiently elevated temperature to form a plastic mass which may be extruded and cut into solid bars, which in turn may optionally be milled or ground to a powder.
- The practical limitation of the dry neutralisation technique to alkyl benzene sulphonate based NSD is a disadvantage, since other surfactant systems are often preferable for reasons of economics and/or effectiveness. In particular, alkyl benzene sulphonates require petrochemical feedstocks on which many developing countries wish to reduce their dependence. Unneutralised sulphonic acids are generally less safe than the corresponding neutralised surfactants to transport and handle.
- We have now discovered a method for the manufacture of solid NSD laundry formulations which does not require evaporation of substantial quantities of water, or investment in expensive drying plant, but which permits the use of alkyl sulphates, fatty acid sulphonates and fatty ester sulphonates which can be readily obtained from vegetable oil feedstocks commonly available in developing countries. Our invention does not require the transport or handling of unneutralised sulphonic acids. Our invention provides a method of manufacture which is cheap, simple and particularly adapted to the technological requirements of developing countries, but wich provides products of superior performance capable of satisfying consumer demands in both developing and industrialised countries.
- According to our invention, there is provided a method for the manufacture of solid NSD formulations, which comprises mixing an aqueous NSD surfactant comprising a water soluble alkyl sulphate, sulphocarboxylate or sulphoester, at a concentration and temperature such that it is present as "G" phase, with builder and, optionally, other ingredients of solid laundry detergent compositions, and forming the mixture into a solid composition by non-evaporative solidification.
- Generally, the term "non-evaporative solidification" embraces those processes which rely primarily upon one or more of the following three phenomena to effect solidification, that is to say:
- (A) Cooling of a "G" phase composition which exists as a "G" phase only at elevated temperatures and which is solid at ambient temperatures;
- (B) Addition to a fluid "G" phase of sufficient electrolyte to elevate the "G" phase/hydrated solid transition temperature to such an extent that the composition is solid at ambient temperatures; and
- (C) Removal of sufficient water from a "G" phase by addition thereto of at least one hydrateable compound, to convert the NSD into a` solid.
- The first of the foregoing phenomena (A) requires a "G" phase which exists only at a substantially elevated temperature and which is converted to the hydrated solid phase on cooling to ambient temperature. Suitable higher temperature "G" phase surfactants include sodium, potassium and tris (hydroxyethyl) ammonium alkyl sulphates, olefin sulphonates and alkyl benzene sulphonates.
- The second phenomenon (B) depends on the effects of electrolyte in raising the temperature of the "G" phase/solid phase transition boundary, and hence, effectively increasing the temperature at which the "G" phase solidifies, enabling a normally liquid crystalline surfactant composition to be obtained as the hydrated solid at ambient temperature. Suitable electrolytes to be used in raising the transition temperature include, for example, sodium silicate, sodium sulphate, sodium chloride, or sodium carbonate. Typically, where the surfactant is anionic a common cation is employed to maximise the effect, thus where, as will normally be the case,the surfactant is a sodium salt, the preferred electrolyte will be a water soluble, strongly dissociable sodium salt. The amount of electrolyte required will depend upon the particular NSD and the extent to which the other non-evaporative solidification effects such as cooling or hydration of hydratable salts is relied upon.
- The third of the aforesaid phenomena (C) involves the abstraction of water from the "G" phase by a hydratable compound, in an amount sufficient to convert the "G" phase into a hydrated solid.
- Although any anhydrous hydratable salt capable of exerting a dessicant action on a "G" phase surfactant may be used, the most convenient is anhydrous tetrasodium pyrophosphate or sodium tripolyphosphate, which are commonly included in NSD formulations as builders. The hydratable compound may be a partially hydrated compound.
- The method of non-evaporative solidification will often rely upon two or all three of the above phenomena. E.g. addition of sodium silicate and anhydrous sodium tripolyphosphate to a "G" phase surfactant will simultaneously increase the electrolyte concentration, increase the active concentration as the anhydrous tripolyphosphate is converted to hexahydrate, and raise the temperature of the mixture. The latter may, for example, be extruded and cooled to form a solid extrudate.
- The term "non-evaporative solidification" does not exclude the possibility that some evaporation of moisture occurs during the process. Incidental evaporation of moisture is inevitable when aqueous materials are handled, especially at elevated temperatures. The term merely indicates that techniques are employed which do not rely on evaporation to effect solidification. It is possible within the scope of our invention to use evaporation in conjunction with the non-evaporative techniques. However, if the evaporation requires expensive drying equipment or removes a sufficiently large proportion of the moisture to increase, substantially, the energy costs, then a part of the economic benefit of the invention will have been forfeited.
- The NSD feed in the process of our invention is essentially present as a "G" phase, although it may be possible in certain circumstances to add minor proportions of the NSD in other forms, e.g. as a dilute aqueous solution, or as an anhydrous or partially hydrated solid product. In the latter case the addition of the anhydrous surfactant may contribute to the non-evaporative solidification by raising the active concentration, and may in fact constitute some or all of the hydratable compound.
- The "G" phase is a pumpable fluid which is formed over a narrow range of concentrations which range usually lies somewhere between 45% and 80% by weight of active ingredient and is characterised by a lamellar structure in which the surfactant molecules are associated to form plates of indefinite size separated by planes of water molecules.
- Typically when alkyl sulphates and ester sulphonates are prepared in aqueous solutions of increasing concentration, the molecules are first found to associate inspherical clusters (micelles), which micelles with increasing concentration become rod-like. At higher concentrations the micelles become more crowded causing a rise in the viscosity of the solution and, in the great majority of cases, eventually rearrange to form a regular hexagonal array of rod-like surfactant micelles in an aqueous medium (the rigid "M1" liquid crystal phase). If the concentration of a surfactant in the "M1" phase is progressively increased a phase change occurs to give either a hydrated solid phase, or, if the temperature is sufficiently elevated, to convert the Ml phase progressively to a fluid "G" phase until a viscosity minimum is reached. Further increase in the concentration of the "G" phase causes the viscosity to rise until a further phase change occurs, leading to the formation of a hydrated solid phase.
- The foregoing description is somewhat simiplified. The term "hydrated solid phase" has been used broadly to include those systems which comprise suspensions of solid or immobile gel phases in one or more viscous or gel phase to provide a more or less rigid material.
-
- Cl ... Cn are the concentrations of the individual active components and g1 ... gn are the concentrations at which each component forms a "G" phase of minimum viscosity. This formula enables the concentration of the mixture corresponding to the minimum viscosity "G" phase to be estimated in a majority of cases. Where g is not known, or a component does not fonn a "G" phase, or the above formula is not applicable, then any "G" phase can be located very rapidly and easily, using standard laboratory equipment by making a test composition having an active concentration of say 75% (or, where appropriate, whatever concentration has been estimated on the basis of the foregoing formula) and placing a sample on a slide on the block of a heated stage microscope. Examination between crossed polarisers will reveal in which phase the sample is present. The various phases each have a characteristic appearance which is easily identified by comparison for example with the photographs of typical liquid crystal phases in the classic paper by Rosevear, JAOCS Vol.31 P.628 (1954) or in J. Colloid and Interfacial Science, Vol.30 No.4. P.500. They may also be identified by X-ray or neutron diffraction.
- If the mixture is in an M1 phase, water may be allowed to evaporate from the edges of the sample under the cover disc and any phase changes observed. If any M2 phase or hydrated solid is present, water may be added around the edge of the cover disc and allowed to diffuse into the composition. If no "G" phase is located in this way samples may be heated progressively on the block and the operations repeated.
- Usually, the composition is pumpable at concentrations within a range of ± 10%, preferably - 5%, e.g. ± 2.5% of the minimum viscosity concentration. This range tends to be broader at more elevated temperatures. Compositions may be obtained, at the limits of the range in which one or more solid or gel phase is suspended in a continuous "G" phase. Such compositions may be useful according to the invention.
- The "G" phase may generally be prepared by converting a suitable precursor to the NSD in the presence of the appropriate quantity of water (e.g. an alkyl sulphuric or fatty ester sulphonic acid may be neutralised with aqueous alkali of the appropriate strength). Mixed NSD may be prepared either by mixing the separately prepared components, each preferably in the "G" phase, or where this is impractical, by preparing one component from its precursor in the presence of the other component as described in our British Patent 2,022,125.
- Typically alkyl sulphates available for NSD solid formulations have been either substantially anhydrous solids and therefore difficult to mix with other ingredients, or more usually dilute solutions containing more than 60% water, which cannot be solidified at ambient temperatures except by evaporation of a major proportion of the water content. Non-evaporative solidification has not therefore been contemplated. Our invention takes advantage of a property of the more concentrated fluid "G" phase alkyl sulphates, namely their sensitivity to small changes in active or electrolyte concentration or of temperature, which enables them to be much more easily converted into hydrated solids than the more conventional detergent solutions.
- The alkyl sulphate for use according to our invention may be potassium, ammonium or lower alkyl ammonium or alkylolammonium alkyl sulphate. Particularly preferred are sodium alkyl sulphates. Sodium alkyl sulphates do not form "G" phases at ambient temperatures and are normally only available as dilute solutions less than 30% active concentration. Solid anhydrous or hydrated sodium alkyl sulphate cannot normally be melted, but tends to decompose on heating. The instability of alkyl sulphuric acids has prevented the adoption of dry neutralisation for making sodium alkyl sulphate based solid NSD formulations. Yet, alkyl sulphates would be attractive alternatives to alkyl benzene sulphonate for many developing countries who could prepare the former by sulphation of locally produced vegetable based feedstocks rather than imported petrochemical feedstocks required for the latter.
- However, if sodium alkyl sulphates are prepared at temperatures of, e.g. 70°C, or even lower where mixed alkyl feedstocks were used, and the water used in the neutralisation is controlled within narrow limits to form the "G" phase, a pumpable and stable hot fluid can be obtained which is mixable with other detergent ingredients and which can be solidified by cooling to form a solid composition.
- The solid composition will normally be formed by extrusion. Alternatively, where the hot alkyl sulphate mixture is sufficiently fluid it may be injected into a mould and cooled to form cast bars. Also, depending upon the consistency and physical form of the mixture, it may be milled to a powder and sold as such, or compacted into rapidly soluble tablets.
- The alkyl sulphate for use according to preferred embodiments of our invention is typically sodium C8-20 linear alkyl sulphates, preferably a mixed C10-18 alkyl sulphate. Particularly preferred is lauryl alkyl sulphate. Other alkyl sulphates which may be used include potassium, lithium, ammonium, monoethanolemine, diethanolamine triethanolamine and mono-, di- tri-and tetra alkylammonium salts having up to 6 carbon atoms, preferably 1 to 4 carbon atoms per cation. Salts of mixtures of the aforesaid cations and branched chain alkyl sulphates are also useful.
- The alkyl sulphate may be used in admixture with any other "G" phase forming anionic NSD, or nonionic, Zwitterionic, amphoteric or semi-polar NSD or mixtures thereof. Cationic surfactants, preferably in conjunction with non-ionic or amphoteric surfactants, may also be used.
- Preferably the alkyl sulphate constitutes at least 30% more preferably at least 50% e.g. at least 75% of the total surfactant. In particular, we prefer the the alkyl sulphate constitute at least 80% and preferably substantially all of the anionic surfactant. Mixtures of alkyl sulphates with minor proportions of non-ionic surfactants, especially alkylolamides, are particularly preferred. The non-ionic surfactant is preferably present in a proportion of from 1 to 49% especially 2 to 20% e.g. 3 to 10% of the total weight of surfactant.
- The alkyl sulphate may be used in conjunction with, or be replaced by, a sulphonated fatty acid or ester such as the methyl ester of coconut fatty acid.
- The surfactant may contain an at least sparingly water-soluble, alkali metal, ammonium, alkylolamine or amine, alkylbenzene sulphonate, alkyl ether sulphate, olefin sulphonate, alkane sulphonate, alkyl phenol sulphate, alkyl phenol ether sulphate, alkylethanolamide sulphate, or alkylethanolamide ether sulphate, each having at least one alkyl or alkenyl groups with from 10 to 20 aliphatic carbon atoms. Said alkyl or alkenyl groups are preferably straight chain primary groups but may optionally be secondary, or branched chain groups. The expression "ether" hereinbefore refers to polyoxethylene, poloxypropylene, glyceryl and mixed polyoxyethylene-oxy propylene or mixed glyceryl-oxyethylene or glyceryl-oxy propylene groups, typically containing from 1 to 20 oxyalkylene groups. For example, the sulphonated or sulphated surfactant may be sodium dodecyl benzene sulphonate, potassium hexadecyl benzene sulphonate, sodium dodecyl dimethyl benzene sulphonate, ammonium lauryl monethoxy sulphate, or monoethanolamine cetyl 10 mole ethoxylate sulphate.
- Other anionic surfactants useful according to the present invention include fatty alkyl sulphosuccinates, fatty alkyl ether sulphosuccinates, fatty alkyl sulphosuccinamates, fatty alkyl ether sulphosuccinamates, acyl sarcosinates, acyl taurides, isethionates, and alkyl ether carboxylates. Anionic phosphate fatty esters may also be used.
- Preferred anionic surfactants are sodium salts. Other salts of commercial interest include those of potassium, lithium, ammonium, monoethanolamine, diethanolamine triethanolamine, and alkyl amines containing up to six aliphatic carbon atoms.
- The surfactants may optionally but preferably contain nonionic surfactants. The nonionic surfactant may preferably be, e.g. a C10-22 ethanolamide such as coconut monoethanolamide. Other nonionic surfactants which may optionally be present, include ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkylolamides, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters, and the propoxylated, or ethoxylated and propoxyTated, analogues of all the aforesaid ethoxylated nonionics, all having a C8-22 alkyl or alkenyl group, or any other nonionic surfactant which has hitherto been incorporated in powder compositions, e.g. amine oxides.
- The preferred nonionics for our invention are the less water soluble compounds, for example those ethoxylates having an HLB range of 7-18, e.g. 12-15. However, more water soluble ones may sometimes be present, usually in minor amounts. In particular, fatty alkanolamides may be useful, in minor proportions, as internal lubricants to assist in the mixing and plodding of the alkyl sulphates.
- Compositions of our invention may also contain amphoteric surfactant, usually as a minor component of the active material.
- Amphoteric surfactants include betaines and sulphobetaines formed by substituting a suitable tertiary nitrogen compound having a long chain alkyl or alkenyl group with a B-acid-forming substituting agent such as chloroacetic acid. Examples of suitable tertiary nitrogen containing compounds include: tertiary amines having one or two long chain alkyl or alkenyl groups, optionally a benzyl group and any other substituent a short chain alkyl group; imidazoline having one or two long chain alkyl or alkenyl groups and amidoamines having one or two long chain alkyl or alkenyl groups.
- The surfactant is mixed with builders and other auxiliary detergent ingredients.
- The term "builder" is sometimes used loosely in the detergent art to include any non-surfactant whose presence in a detergent formulation enhances the cleaning effect of the surfactant. More usually, however, the term is restricted to those typical "builders", which are primarily useful as means of preventing or ameliorating the adverse effects on washing of calcium ions, e.g. by chelation, sequestering, precipitation or absorption of the ions, and secondarily as a source of alkalinity and buffering. The term "builder" as used herein refers to additives which produce the foregoing effects to a substantial extent. It includes sodium tripolyphosphate and other inorganic phosphate and condensed phosphate salts such as sodium or potassium orthophophates, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates and amino tris methylene phosphonates. It also includes alkali metal carbonates, zeolites and other "molecular sieves" and such organic sequestrants as salts nitrilotriacetic acid, citric acid and ethylene diamine tetracetic acid.
- Compositions of our invention may contain fillers which help to provide a suitable physical form of bar.
- Other auxiliary detergent ingredients may comprise anti redeposition agents such as sodium carboxy methyl cellulose, perfumes, dyes, optical brightening agents, hydrotopes, buffers, bleach activators, alkalis and the like. Typically such auxiliaries are present in proportions of. less than 10% and more usually less than 5% wt. each and less than 25%, e.g. less than 15% total.
-
- All percentages are by weight and all ingredients (except water) are quoted as the anhydrous compounds.
- The filler may comprise any inert solid having suitable physical properties, e.g. sodium sulphate or talc. The other auxiliaries may include any or all of:- sodium carboxymethyl cellulose or other soil suspending agent; enzymes; dyestuffs; perfumes; optical brighteners; oxidising bleaches such as peroxides, perborates, percarbonates or hypochlorites; gums; starches; water soluble synthetic polymers; organic polyelectrolytes such as polyacrylic acid; and hydrotropes. Tablets for addition to washing machines may contain minor proportions of soap as foam depressants, and/or silicone anti foams.
- The properties of the "G" phase surfactant may further be modified by the inclusion of mono- di- or tri-glycerides, fatty alcohols, glycerol, glycols, polyethylene glycol or polypropylene glycol, which may help to lubricate the mixture in cases where difficulties are encountered with mixing or extrusion.
-
-
- The above examples were prepared in the following way.
- 1) The powdered ingredients were mixed together in a 1 gallon capacity "Hobart" dough mixture machine.
- 2) Fatty alcohol, where used, was then added in the liquid state and stirred into the powder mix.
- 3) The sodium lauryl sulphate paste, pre-heated to a temperature of about 60°C, to convert it into the mobile "G" phase, was then added and stirred into the powder mix.
- 4) Finally, either the sodium silicate liquor or water was incorporated.
- The resulting phase was then allowed to age for a minimum period of 1/2 hour to allow it to harden off.
- The mixture were then passed 3 - 4 time through a 30 rpm. 200 lbs/ft "sunlab" plodding machine to make them plastic enough to be extruded through the same machine in the form of bars.
Claims (28)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83307439T ATE33994T1 (en) | 1982-12-07 | 1983-12-07 | SOLIDIFICATION OF DETERGENT PASTES WITHOUT SOLVENT EVOLUTION. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8234861 | 1982-12-07 | ||
GB8234861 | 1982-12-07 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0110731A2 true EP0110731A2 (en) | 1984-06-13 |
EP0110731A3 EP0110731A3 (en) | 1986-07-09 |
EP0110731B1 EP0110731B1 (en) | 1988-05-04 |
Family
ID=10534799
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83307439A Expired EP0110731B1 (en) | 1982-12-07 | 1983-12-07 | Non-evaporative solidification of detergent pastes |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0110731B1 (en) |
JP (1) | JPS59115400A (en) |
KR (1) | KR900004559B1 (en) |
AT (1) | ATE33994T1 (en) |
AU (1) | AU560525B2 (en) |
BR (1) | BR8306706A (en) |
DE (1) | DE3376487D1 (en) |
GB (1) | GB2131447B (en) |
IN (1) | IN160448B (en) |
MY (1) | MY8700135A (en) |
PH (1) | PH20175A (en) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0178893A2 (en) * | 1984-10-18 | 1986-04-23 | Ecolab Inc. | Solid detergent compositions |
GB2189255A (en) * | 1986-04-15 | 1987-10-21 | Degussa | Detergent bar |
EP0349200A2 (en) * | 1988-06-29 | 1990-01-03 | The Procter & Gamble Company | Process for making concentrated surfactant granules |
EP0349201A2 (en) * | 1988-06-29 | 1990-01-03 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
EP0403148A2 (en) * | 1989-06-09 | 1990-12-19 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
US5096608A (en) * | 1985-05-13 | 1992-03-17 | The Procter & Gamble Company | Ultra mild skin cleansing composition |
WO1992009676A1 (en) * | 1990-12-03 | 1992-06-11 | Henkel Kommanditgesellschaft Auf Aktien | Solid washing agents |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
US5665692A (en) * | 1995-02-13 | 1997-09-09 | The Procter & Gamble Company | Process for producing detergent agglomerates in which particle size is controlled |
WO1999024550A1 (en) * | 1997-11-10 | 1999-05-20 | The Procter & Gamble Company | Process for preparing a detergent tablet |
WO2000004114A2 (en) * | 1998-07-15 | 2000-01-27 | Henkel Kommanditgesellschaft Auf Aktien | Method for producing fatty alcohol sulfate containing washing and cleaning agent bodies |
EP1191091A1 (en) * | 2000-09-20 | 2002-03-27 | Cognis Deutschland GmbH | Free-flowing aqueous fatty alcohol sulphate pastes |
US6391845B1 (en) | 1997-11-26 | 2002-05-21 | The Procter & Gamble Company | Detergent tablet |
US6462007B1 (en) | 1998-01-26 | 2002-10-08 | The Procter & Gamble Company | Multi-layer detergent tablet |
US6486117B1 (en) | 1997-11-10 | 2002-11-26 | The Procter & Gamble Company | Detergent tablet |
US6548473B1 (en) | 1997-11-26 | 2003-04-15 | The Procter & Gamble Company | Multi-layer detergent tablet having both compressed and non-compressed portions |
WO2009125336A3 (en) * | 2008-04-07 | 2010-02-18 | Ecolab Inc. | Ultra-concentrated solid degreaser composition |
US11905493B2 (en) | 2019-09-27 | 2024-02-20 | Ecolab Usa Inc. | Concentrated 2 in 1 dishmachine detergent and rinse aid |
US11932830B2 (en) | 2017-11-14 | 2024-03-19 | Ecolab Usa Inc. | Solid controlled release caustic detergent compositions |
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US5000652A (en) * | 1986-09-22 | 1991-03-19 | International Business Machines Corporation | Wafer transfer apparatus |
GB8800763D0 (en) * | 1988-01-14 | 1988-02-17 | Unilever Plc | Detergent compositions |
JP2526831B2 (en) * | 1988-06-13 | 1996-08-21 | 井関農機株式会社 | Walk-behind farm work machine |
JP2820257B2 (en) * | 1988-12-02 | 1998-11-05 | 井関農機株式会社 | Rice transplanter planting depth control device |
JP6955030B2 (en) * | 2017-04-27 | 2021-10-27 | エコラボ ユーエスエー インコーポレイティド | Solid Control Release Carbonate Detergent Composition |
BR112020015170A2 (en) | 2018-01-26 | 2021-01-26 | Ecolab Usa Inc. | solidified liquid surfactant and solid cleaning compositions, and method for cleaning a surface |
JP7485606B2 (en) | 2018-01-26 | 2024-05-16 | エコラボ ユーエスエー インコーポレイティド | Solidification of liquid anionic surfactants |
WO2019148090A1 (en) | 2018-01-26 | 2019-08-01 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
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CH281137A (en) * | 1945-07-10 | 1952-02-29 | Brunel Henri | A method of manufacturing a detergent product. |
US3639286A (en) * | 1968-05-28 | 1972-02-01 | Mario Ballestra | Synthetic detergent in bar or cake form and the method to manufacture same |
AU461648B2 (en) * | 1971-01-14 | 1975-06-05 | Bell Chemicals Pty. Ltd | Improvements inthe manufacture of detergent-powders |
EP0014979A1 (en) * | 1979-02-23 | 1980-09-03 | Henkel Kommanditgesellschaft auf Aktien | Process for producing rinsing blocks for the hygiene of water-closets |
-
1983
- 1983-11-28 IN IN791/DEL/83A patent/IN160448B/en unknown
- 1983-12-05 PH PH29924A patent/PH20175A/en unknown
- 1983-12-06 AU AU22103/83A patent/AU560525B2/en not_active Ceased
- 1983-12-06 BR BR8306706A patent/BR8306706A/en unknown
- 1983-12-07 DE DE8383307439T patent/DE3376487D1/en not_active Expired
- 1983-12-07 AT AT83307439T patent/ATE33994T1/en not_active IP Right Cessation
- 1983-12-07 EP EP83307439A patent/EP0110731B1/en not_active Expired
- 1983-12-07 KR KR1019830005793A patent/KR900004559B1/en not_active IP Right Cessation
- 1983-12-07 GB GB08332607A patent/GB2131447B/en not_active Expired
- 1983-12-07 JP JP58229974A patent/JPS59115400A/en active Pending
-
1987
- 1987-12-30 MY MY135/87A patent/MY8700135A/en unknown
Patent Citations (4)
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CH281137A (en) * | 1945-07-10 | 1952-02-29 | Brunel Henri | A method of manufacturing a detergent product. |
US3639286A (en) * | 1968-05-28 | 1972-02-01 | Mario Ballestra | Synthetic detergent in bar or cake form and the method to manufacture same |
AU461648B2 (en) * | 1971-01-14 | 1975-06-05 | Bell Chemicals Pty. Ltd | Improvements inthe manufacture of detergent-powders |
EP0014979A1 (en) * | 1979-02-23 | 1980-09-03 | Henkel Kommanditgesellschaft auf Aktien | Process for producing rinsing blocks for the hygiene of water-closets |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0178893A3 (en) * | 1984-10-18 | 1989-09-20 | Ecolab Inc. | Method of forming solid detergent compositions |
EP0178893A2 (en) * | 1984-10-18 | 1986-04-23 | Ecolab Inc. | Solid detergent compositions |
US5096608A (en) * | 1985-05-13 | 1992-03-17 | The Procter & Gamble Company | Ultra mild skin cleansing composition |
GB2189255A (en) * | 1986-04-15 | 1987-10-21 | Degussa | Detergent bar |
GB2189255B (en) * | 1986-04-15 | 1990-08-29 | Degussa | A detergent in bar form |
EP0349200A2 (en) * | 1988-06-29 | 1990-01-03 | The Procter & Gamble Company | Process for making concentrated surfactant granules |
EP0349201A2 (en) * | 1988-06-29 | 1990-01-03 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
EP0349201A3 (en) * | 1988-06-29 | 1990-06-20 | The Procter & Gamble Company | Detergent granules from cold dough using fine dispersion granulation |
EP0349200A3 (en) * | 1988-06-29 | 1990-06-20 | The Procter & Gamble Company | Process for making concentrated surfactant granules |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
TR24394A (en) * | 1989-06-09 | 1991-09-01 | Procter & Gamble | HIGH DETERGENT PARTS THAT CAN BE SPREADED IN COLD WATER |
US5045238A (en) * | 1989-06-09 | 1991-09-03 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
EP0403148A3 (en) * | 1989-06-09 | 1991-02-20 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
EP0403148A2 (en) * | 1989-06-09 | 1990-12-19 | The Procter & Gamble Company | High active detergent particles which are dispersible in cold water |
WO1992009676A1 (en) * | 1990-12-03 | 1992-06-11 | Henkel Kommanditgesellschaft Auf Aktien | Solid washing agents |
US5399297A (en) * | 1990-12-03 | 1995-03-21 | Henkel Kommanditgesellschaft Auf Aktien | Solid detergents |
US5665692A (en) * | 1995-02-13 | 1997-09-09 | The Procter & Gamble Company | Process for producing detergent agglomerates in which particle size is controlled |
US5574005A (en) * | 1995-03-07 | 1996-11-12 | The Procter & Gamble Company | Process for producing detergent agglomerates from high active surfactant pastes having non-linear viscoelastic properties |
US6486117B1 (en) | 1997-11-10 | 2002-11-26 | The Procter & Gamble Company | Detergent tablet |
US6413928B1 (en) | 1997-11-10 | 2002-07-02 | The Procter & Gamble Company | Process for preparing a detergent tablet |
WO1999024550A1 (en) * | 1997-11-10 | 1999-05-20 | The Procter & Gamble Company | Process for preparing a detergent tablet |
US6391845B1 (en) | 1997-11-26 | 2002-05-21 | The Procter & Gamble Company | Detergent tablet |
US6548473B1 (en) | 1997-11-26 | 2003-04-15 | The Procter & Gamble Company | Multi-layer detergent tablet having both compressed and non-compressed portions |
US6462007B1 (en) | 1998-01-26 | 2002-10-08 | The Procter & Gamble Company | Multi-layer detergent tablet |
WO2000004114A2 (en) * | 1998-07-15 | 2000-01-27 | Henkel Kommanditgesellschaft Auf Aktien | Method for producing fatty alcohol sulfate containing washing and cleaning agent bodies |
WO2000004114A3 (en) * | 1998-07-15 | 2001-08-23 | Henkel Kgaa | Method for producing fatty alcohol sulfate containing washing and cleaning agent bodies |
EP1191091A1 (en) * | 2000-09-20 | 2002-03-27 | Cognis Deutschland GmbH | Free-flowing aqueous fatty alcohol sulphate pastes |
WO2009125336A3 (en) * | 2008-04-07 | 2010-02-18 | Ecolab Inc. | Ultra-concentrated solid degreaser composition |
US11932830B2 (en) | 2017-11-14 | 2024-03-19 | Ecolab Usa Inc. | Solid controlled release caustic detergent compositions |
US11905493B2 (en) | 2019-09-27 | 2024-02-20 | Ecolab Usa Inc. | Concentrated 2 in 1 dishmachine detergent and rinse aid |
Also Published As
Publication number | Publication date |
---|---|
EP0110731B1 (en) | 1988-05-04 |
AU560525B2 (en) | 1987-04-09 |
DE3376487D1 (en) | 1988-06-09 |
PH20175A (en) | 1986-10-14 |
KR900004559B1 (en) | 1990-06-29 |
EP0110731A3 (en) | 1986-07-09 |
GB2131447B (en) | 1986-04-30 |
ATE33994T1 (en) | 1988-05-15 |
GB2131447A (en) | 1984-06-20 |
AU2210383A (en) | 1984-06-14 |
JPS59115400A (en) | 1984-07-03 |
BR8306706A (en) | 1984-07-17 |
GB8332607D0 (en) | 1984-01-11 |
IN160448B (en) | 1987-07-11 |
KR840007102A (en) | 1984-12-05 |
MY8700135A (en) | 1987-12-31 |
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