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
  • C11D1/825—Mixtures of compounds all of which are non-ionic
• • 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
• • 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
  • 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
  • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • 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
  • C11D1/667—Neutral esters, e.g. sorbitan 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the present invention relates to aqueous liquid detergent compositions that comprise a structure of surfactant material and to a process of preparing aqueous liquid detergent compositions that comprise lamellar droplets of surfactant material.
• Liquid detergent compositions are well-known in the art and offer several advantages over solid compositions. For example, liquid compositions are easier to measure, to dispense and to dissolve into a laundering liquor. Further, liquid compositions give more confidence to the consumer of being safer and less harsh to the washed or laundered textile than solid compositions. This may be the reasons why heavy duty and light duty built laundry liquid detergent products have been gaining in popularity since their market introduction at the expense of powdered detergent products.
• Isotropic liquids are liquids in which all ingredients are dissolved and, contrary to structured liquids, there is no structure present in isotropic liquid.
• Structuring may be brought about to endow properties such as consumer preferred flow properties and/or turbid appearance.
• Many structured liquids are also capable of suspending particulate solids, such as particles of clay that may be used to provide a fabric-softening effect to fabrics. Examples of structured liquids without suspended solids are given in US-A-4,244,840, whilst examples where solid particles are suspended are disclosed in EP-A-160 342; EP-A-38 101; EP-A-140 452 and also in the aforementioned US-A-4,244,840.
• Structured liquids can either be internally structured, in which case the structure is formed by primary ingredients, preferably by surfactant material, or they can be externally structured in which case the structure is provided by a three dimensional matrix structure using secondary additives like preferably polymers and silicate material. Externally structured liquids may however provide a high viscosity, especially upon storage. This generally makes internally structured liquids preferred over externally structured.
• surfactant material may form.
• An example thereof are lyotropic liquid crystalline phases. These phases may e.g. be present in the form of lamellar structures or in the form of hexagonal structure.
• lamellar structures are defined as one or more bi-layers of surfactant material.
• lamellar structures according to the invention contain at least two bi-layers of surfactant material. These two bi-layers will form a stack.
• the lamellar structure may exist in various forms, e.g. lamellar planar structures and lamellar droplets of surfactant bi-layers (the bi-layers are concentrically stacked) .
• Liquids with lamellar droplets provide a desirable combination of physical stability and solid-suspending properties with useful flow properties, i.e. low viscosity with stability.
• Such liquids have for example been described in A. Jurgens, Microstructure and Viscosity of Liquid Detergent, Tenside Surfactants Detergent 26 (1989) 222 and J.C. van de Pas, Liquid Detergents, Tenside
• the dispersed structuring phase in liquids with lamellar droplets of surfactant material consists of an onion-like configuration comprising concentric bilayers surfactant molecules between which water is trapped.
• Presence and identity of bi-layers of surfactant material in a liquid may be determined by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, X-ray or neutron diffraction and by electron microscopy.
• Concentric bi-layers of surfactant material can be easily detected when viewed under a transmission microscope, such as a thin film techniques. Additionally, they may be detected using a microscope under polarised light. When maltese or extinction crosses appear, they contain concentric bi-layers. Concentric bi-layers can further be detected by way of Freeze Fraction Electron Microscopy, a method well-known to the skilled man.
• WO 91/00331 discloses aqueous structured liquid detergent compositions comprising lamellar droplets of surfactant material.
• the compositions comprise relatively high nonionic levels, e.g. 50-100% by weight of the total surfactant.
• These liquids have also been described in "Physical stability and microstrucure of concentrated dispersions of lamellar liquid-crystalline droplets containing nonionic surfactants in aqueous electrolyte solution", Schepers, Toet and Van de Pas, American Chemical Society, Vol. 9, No. , 1993.
• Some of the exemplified liquids comprise lamellar droplets consisting of an isotropic core surrounded by concentrically stacked bi ⁇ layers, see in particular figure 4.
• WO 91/09107 describes the use of high shear in the preparation of aqueous liquid detergent compositions comprising a deflocculating polymer.
• WO 91/16409 discloses aqueous liquids with lamellar surfactant droplets and comprising primary alkyl sulphate material, fatty acid and nonionic surfactants.
• EP-A-346,995 discloses aqueous liquid detergent compositions comprising lamellar droplets of surfactant material and a deflocculating polymer having hydrohylic backbone and a hydrophobic sidechain.
• the Examples disclose structured liquids which contain lamellar droplets of surfactant material.
• EP-A-328,176 discloses structured liquid detergent compositions which comprises non-encapsulated liquid surfactant droplets (phase biii) .
• Examples XI-XIV disclose liquids with lamellar droplets of surfactant material (phase ci or a so-called G-phase) and a phase called the "isotropic detergent" which is identified as phase biii.
• the nonionic surfactant level in Example XIV is 50% by weight of the total surfactant.
• EP-A-328,177 discloses liquids with lamellar droplets and comprising Salting-Out Resistant surfactant material which is used as a stabiliser in the liquid.
• Salting-Out Resistant surfactant material which is used as a stabiliser in the liquid.
• Alkylpolyglucoside is an example of such a SOR surfactant material.
• liquid compositions comprising particular stabilisers.
• the described liquids may comprise high nonionic levels and comprise isotropic droplets of surfactant material dispersed in a continuous isotropic or anisotropic phase.
• the structure of droplets flocculates and requires the particular stabiliser in order to be pourable.
• Holland discloses nonionic-water liquids with a lamellar and an L2 phase, see pages 17-19.
• GB-A-1,068,554 discloses aqueous emulsions comprising surfactant, potassium salts and stabiliser material.
• EP-A-354,010 discloses aqueous liquids comprising a sperulitic phase and nonionic surfactants.
• EP-A-430,330 discloses aqueous liquids with an anisotropic (or neat) phase which do not comprise a solid phase.
• EP-A-572,723 discloses lamellar structured compositions comprising a polyhydroxy fatty acid amide and EP-A-328,177 discloses lamellar structured liquids comprising stabilising surfactants.
• EP-A-86,614 discloses aqueous liquid detergent compositions comprising lamellar droplets of surfactant material that may contain nonionic surfactant material and solid particles. The exemplified liquids that contain nonionic surfactants however are diluted.
• liquid detergent compositions that not only allows preparation of physically stable liquids, but it also has high formulation flexibility and various ingredients may included without adversely effecting stability.
• a further advantage of the liquid form is the high enzyme stability.
• liquid detergent composition comprising lamellar droplets of surfactant material, wherein the surfactant material comprises high levels of nonionic surfactant, may show stability problems, high viscosities and/or a drift in the viscosity upon storage, in particular at higher temperatures.
• nonionic liquids can be prepared physically stable, low viscous and/or having low viscosity drift upon storage, by including a stabilising agent.
• aqueous liquid detergent compositions with lamellar droplets comprising high levels of nonionic surfactant material can be stably formulated by including a stabilising agent in the liquid.
• These nonionic surfactant containing liquid compositions may either have an internal radial symmetry or may lack such a structure.
• the surfactant in these liquids may comprise up to 100% of nonionic surfactant, i.e. without any anionic surfactant (ratio 1:0), but may also comprise nonionic and anionic surfactants in the ratio as specified hereunder.
• liquid detergent composition comprising lamellar droplets of surfactant material, wherein the surfactant material comprises high levels of nonionic surfactant
• the stability and/or deflocculation of liquid detergent composition may be improved by carefully adjusting the sodium to potassium ratio of the liquid.
• These nonionic surfactant containing liquid compositions may either have an internal radial symmetry or they may lack such a structure.
• the surfactant in these liquids may comprise up to 100% of nonionic surfactant, i.e. without any anionic surfactant (ratio 1:0) but may also comprise nonionic and anionic surfactants in the ratio as specified hereunder.
• liquid detergent composition comprising lamellar droplets of surfactant material, wherein the surfactant material comprises high levels of nonionic surfactant, may be improved by also including high levels of solid particles in the liquid.
• liquid detergent composition comprising lamellar droplets of surfactant material, wherein the surfactant material comprises high levels of nonionic surfactant, may be improved by carefully choosing the conditions of the preparation process.
• the invention provides an aqueous structured liquid detergent composition comprising lamellar droplets of surfactant material, said composition comprising a weight ratio of nonionic surfactant to anionic surfactants that is smaller than 95:5 and that is higher than 50:50, said composition comprising:
• a nonionic sugar stabilising agent containing a sugar unit selected from apiose, arabinose, galactose, lyxose, mannose, gallose, altrose, idose, arabinose, ribose, talose, xylose, maltose, lactose, sucrose and sorbitan; ii) at least 10%, preferably at least 15% by weight of solid particles; iii) anionic surfactants selected from C12-C18 alkyl sulphate, sulphonate, mono unsaturated fatty acids and mixtures thereof, wherein the anionic sulphate or sulphonate comprises at least 3 c- atoms on both sides of the C-atom to which the sulphate or sulphonate group is attached; iv) enzymes; or v) mixtures thereof.
• a sugar unit selected from apiose, arabinose, galactose, lyxose, mannose, gallose
• the invention further provides an aqueous structured liquid detergent composition
• aqueous structured liquid detergent composition comprising lamellar droplets of surfactant, wherein said surfactant comprises material present in concentric bi-layer form consisting of one or more bi-layers of surfactant material that have a joined thickness which is smaller than the radius of the droplet, wherein the composition comprises
• a nonionic sugar stabilising agent containing a sugar unit selected from apiose, arabinose, galactose, lyxose, mannose, gallose, altrose, idose, arabinose, ribose, talose, xylose, maltose, lactose, sucrose and sorbitan; ii) at least 10%, preferably at least 15% by weight of solid particles; iii) anionic surfactants selected from C12-C18 alkyl sulphate, sulphonate, mono unsaturated fatty acids and mixtures thereof, wherein the anionic sulphate or sulphonate comprises at least 3 c- atoms on both sides of the C-atom to which the sulphate or sulphonate group is attached; iv) enzymes; or v) mixtures thereof.
• a sugar unit selected from apiose, arabinose, galactose, lyxose, mannose, gallose
• the invention further provides a process of preparing aqueous liquid detergent compositions with lamellar droplets that comprise surfactant material, said liquid comprising nonionic surfactants at a level of more than 50% by weight of the total surfactant material, said process comprising the mixing of water, electrolyte material and surfactant material to create a lamellar structure, characterised in that thereafter lamellar structure is subjected to a post-shear operation.
• the invention further provides a process of preparing aqueous liquid detergent compositions with lamellar droplets that comprise surfactant material comprising nonionic surfactants at a level of more than 50% by weight of the total surfactant material, wherein a mixture of water, electrolyte material and surfactant material is prepared from which a lamellar structure is created, characterised in that the viscosity of the mixture is increased by:
• liquid form of the present invention enables formulation of liquid detergent compositions comprising relatively high nonionic surfactant levels and relatively low anionic surfactant without giving in on physical stability, having a high formulation flexibility (i.e. various ingredients may included without adversely effecting stability) and further having a high enzyme stability.
• the concentric bi-layer form of the surfactant in the droplets of the liquids according to the invention consists of one or more bi-layers of surfactant material that have a joined thickness that is smaller than the radius of the droplet.
• the joined thickness is smaller than 99% of the radius, more preferably 50% of the radius, most preferably smaller than 25% of the radius, in particular smaller than 10% of the radius.
• the compositions according to the invention have one or more concentric bi-layers of surfactant material that form a shell which is present on the outside of the droplet.
• the droplet further comprises surfactant material, preferably present in a non-concentric form inside this shell of concentric bi-layers of surfactant material.
• This surfactant material may e.g. be present in the form of planar structures, micelles, solution or liquid surfactant phase.
• Other materials, such as salt, water and enzymes may also be present inside the droplets.
• the lamellar droplets of surfactant do not contain solid particles with a size larger than l ⁇ m, more preferably with a size larger than O.l ⁇ m, most preferably with a size larger than O.Ol ⁇ m.
• compositions according to this aspect of the invention may contain nonionic surfactants at a level of 100% by weight of the total surfactants.
• the ratio of nonionic to anionic surfactants is smaller than 95:5 and e.g. higher than 50:50. More preferably, the ratio is smaller than 90:10, most preferably smaller than 85:15. More preferably, the ratio is higher than 55:45, most preferably higher than 60:40. Ratios that are in particular preferred are higher than 65:35, e.g. ratios that are higher than 70:30.
• the nonionic to anionic surfactant weight ratios are based on the ionic form of the anionic surfactant.
• compositions according to this aspect of the invention contain a ratio of nonionic surfactant, having an SOR (salting-out resistance) of less than 6.4, to anionic surfactants that meet the nonionic to anionic ratios.
• SOR salting-out resistance
• compositions according to this aspect of the invention further comprise from 1.5 to 5% by weight of a decoupling polymer as defined hereunder.
• a decoupling polymer as defined hereunder.
• Liquids containing lamellar droplets which lack an internal radial symmetry may be detected by way of light or electron microscopy and preferably by way of transmission (e.g. film) or freeze fractioning.
• polarised light is used for light microscopy and in that case no bi ⁇ refringence can be seen in the core of the droplets and, depending on the thickness of the bilayers, bi-refringence can be seen on the outside of the droplets.
• the Na+:K+ molar ratio in the liquid is at most 10:1, more preferably at most 8:1, most preferably at most 5:1, in particular preferred is at most 3:1, e.g. at most 2:1.
• the Na+:K+ molar ratio is at least 1:10, more preferably at least 1;8, most preferably at least 1:5. In particular preferred is the molar ratio of at least 1:3.
• a suitable molar ratio is at least 1:2.
• the stabilising agent is a nonionic polyhydroxy stabilising agent which contains 1 or 2 sugar units, preferably 1 sugar unit and, preferably, the sugar unit is a pentose or hexose ring structure.
• the stabilising agent preferably contains free hydroxy groups.
• the sugar unit is selected from aldoses such as apiose, arabinose, galactose, lyxose, mannose, gallose, altrose, idose, arabinose, ribose, talose, xylose, maltose, lactose, sucrose and sorbitan.
• aldoses such as apiose, arabinose, galactose, lyxose, mannose, gallose, altrose, idose, arabinose, ribose, talose, xylose, maltose, lactose, sucrose and sorbitan.
• the sugar stabiliser comprises an alk(en)yl side-chain that is C6 or higher, preferably C8 or higher, more preferably CIO or higher; from 0 to 30 alkylene oxide groups, preferably ethylene oxide groups, may be present between the sugar ring and the alk(en)yl side chain; and the alk(en)yl side chain may be connected to the sugar ring or the EO groups by way of ether or ester bonds.
• Preferred stabilising agents are ethers, esters and amides of an acid (or alcohol) with an alk(en)yl chain and a sugar unit.
• An example of such a compound has the formula R2-C0- NR1-Z, wherein Rl is H a Cl-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy propyl, or a mixture thereof, R2 is C5-C31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain, or an alkoxylated derivative thereof.
• a preferred stabilising agent is a sorbitan derivative, more preferably an ester of sorbitan and one or more fatty acids and/or an ether of sorbitan and one or more ethoxy groups and/or a mixture thereof.
• the sorbitan derivative have the following structure:
• Rl-4 is - (CH2CH20)n-R'l-4 and wherein:
• - n is 0 to 30, preferably to 20;
• R'l-4 is H or C10-C20 fatty acid.
• the composition comprises at least 0.1%, more preferably at least 0.5%, most preferably at least 1.0% by weight of stabilising agent and preferably at most 20%, more preferably at most 15%, most preferably at most 10%, in particular at most 7.5% by weight of the composition, e.g. at most 5% by weight of the composition.
• compositions according to this aspect of the invention contain a ratio of nonionic surfactant (having an SOR of less than 6.4) to anionic surfactants that meet the nonionic to anionic ratios.
• SOR is as defined hereunder.
• Solid Particles A further embodiment of the invention relates to aqueous liquid detergent compositions with lamellar droplets that comprise high levels of nonionic surfactant material as well as at least 5% by weight of solid particles.
• the level of solid particles is at least 10% by weight, more preferably at least 15% by weight and most preferably at least 20% by weight.
• the level of solid particles is at most 25% by weight, more preferably at most 35% by weight, most preferably at most 30% by weight of the composition.
• the solid particles are selected from zeolite, STP, silicate material and mixtures thereof, and more preferably zeolite material and/or silicate material, most preferably zeolite material.
• solid particles not only add to the structuring of the liquids, but also positively influence the molar ratio of the ions in the liquid. Both effects result in liquids with lamellar droplets of surfactant material that are more stable. Moreover, we believe that the solid particles provide a further structuring in the liquid which enhances the physical stability.
• aqueous liquid detergent compositions contain relatively high levels of nonionic surfactant material can be made stable by incorporating solid particles and using highly concentrated liquids.
• the liquids comprise water at a level of at most 50%, more preferably at most 40% by weight of the composition.
• compositions according to the invention comprise anionic surfactants selected from C12-C18 alkyl sulphate, C12-C18 alkyl sulphonate, mono unsaturated fatty acids and mixtures thereof.
• anionic surfactants are selected from secondary C12-C18 alkyl sulphate, sulphonate and mixtures thereof, more preferably these anionic surfactants molecules comprise at least 3 C-atoms on both sides of the C-atom to which the sulphate or sulphonate group is attached. Without wishing to be bound, it is believed that the V-shape of these surfactants assist in creating the structure.
• the ratio between nonionics and these anionic surfactants is from 50:50 to 95:5. More preferably, the ratio is smaller than 90:10, most preferably smaller than 85:15. Most preferably, the ratio is higher than 55:45, in particular higher than 60:40. Ratios that are more in particular preferred are higher than 65:35, e.g. ratios that are higher than 70:30.
• the level of these anionics surfactants is at least 5%, more preferably at least 10%, most preferably at least 15% by weight of the composition.
• the level of these anionics surfactants is at most 50%, more preferably at most 45%, most preferably at most 35%, e.g. at most 30% by weight of the composition.
• Other anionic surfactants may also be present.
• post shear is defined also to include “extension”, terminology well known to the skilled man.
• Post shear may be applied by way of a extrusion plastometer, a shear valve, a colloid mill or combinations thereof.
• Shear rates are preferably at least 3,000/s, more preferably at least 5,000/s and preferably at most 30,000/s for an extrusion plastometer, the back pressure is preferably from 0.1 to 10 bar for a shear valve and the shear rate is preferably from 1,000/s to 100,000/s for a colloid mill.
• the viscosity of the continuous phase i.e. water and electrolyte material without surfactant material, and consequently the stability of the resulting liquid with lamellar droplets of surfactant material can be increased by a method selected from: a) adjusting the Na:K molar ratio to a ratio of from 10:1 to 1:10; b) by adding polymer material; c) by adding at least 5% by weight of solid particles; and d) combinations thereof.
• the Na+:K+ molar ratio in the mixture of water, electrolyte and surfactant is adjusted to a ratio of at most 8:1, more preferably at most 5:1, most preferably at most 3:1, e.g. at most 2:1.
• the Na+:K+ ratio is at least 1:8, more preferably at least 1:5 and most preferably at least 1:3.
• a suitable molar ratio is at least 1:2.
• polymer material is added to the mixture of water, electrolyte and surfactant at a level of from 0.1 to 5% by weight of the mixture.
• solid particles are added to the mixture of water, electrolyte material and surfactant material at a level of at least 10% by weight of solid material, more preferably at least 15% by weight, most preferably at least 20% by weight, in particular at least 25% by weight, e.g. at least 30% by weight. Preferably at most 50% by weight of the composition.
• the solid material is selected from zeolite, STP, silicate and mixtures thereof.
• compositions of the invention also comprise surfactant materials, preferably at a level of at least 10% by weight of the composition, more preferred at least 15% by weight, most preferred at least 20% by weight of the composition; and preferably at a level of at most 70% by weight, more preferably at most 60%, most preferably at most 50% by weight.
• the surfactant material may comprise one or more surfactants selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and mixtures thereof.
• surfactants selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and mixtures thereof.
• they may be chosen from any of the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol.I, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.II by Schwartz, Perry & Berch (Interscience 1958) , in the current edition of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners Company or in 'Tensid-Taschenbuch' , H.Stache, 2nd Edn. , Carl Hanser Verlag, M ⁇ nchen & Wien, 1981.
• Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkyl oxides, especially ethylene oxide, either alone or with propylene oxide.
• Specific nonionic detergent compounds are alkyl (C 6 - C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-di-amine.
• Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.
• compositions according to the invention comprise high levels of nonionic surfactant with a low electrolyte tolerance. It has been found that it is advantageous to use these kind of nonionic surfactants to create the structure of the liquids of the present invention.
• Composition of the invention preferably comprise nonionic surfactants having an SOR of less than 6.4, preferably less than 6.0.
• SOR salting-out resistance
• 200 ml is prepared of a 5% by weight aqueous solution of the surfactant in question.
• Trisodium nitrolotriacetate (NTA) is added at room termperature (ca 25°C) until phase separation occurs, as observed the onset of cloudiness.
• the abbreviation SOR will be used for salting- out resistance.
• the weight ratio of nonionic surfactant with a SOR of less than 6.4 to anionic surfactants is smaller than 95:5 and higher than 50:50.
• the ratio is smaller than 90:10, more preferably smaller than 85:15.
• the ratio is higher than 55:45, more preferably higher than 60:40, most preferably higher than 65:35, e.g. higher than 70:30.
• compositions of the present invention may preferably further comprise surfactant material (including nonionic surfactant material) with an SOR of 6.4 or higher.
• surfactant material including nonionic surfactant material
• SOR an SOR of 6.4 or higher.
• compositions of the present invention may contain synthetic anionic surfactant ingredients, which are preferably present in combination with the above mentioned nonionic materials.
• Suitable anionic surfactants are usually water- soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
• Suitable synthetic anionic surfactant compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C I8 ) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C, 0 -C ⁇ 5 ) benzene sulphonates; sodium alkyl glycerol ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 -C l8 ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts
• an alkali metal soap of a mono- or di-carboxylic acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, alk(en)yl succinate for example dodecyl succinate, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
• the sodium or potassium soaps of these acids can be used.
• Surfactant Material Also possible is the use of salting out resistant active materials such as for example described in EP-A-0,328,177, especially the use of alkylpolyglycoside surfactants such as for example disclosed in EP-A-70,074. Also alkyl mono glucosides may be used. Further, alkyl glucose ether may be used and/or polyhydroxy fatty acid amides as described in WO 92/06157, more particular the amides used in the Examples thereof.
• Salting-Out Electrolyte Compositions according to the invention may optionally also contain electrolyte in an amount sufficient to bring about structuring of the detergent active material.
• the compositions contain from 0% (preferably 1%) to 60%, especially from 5% (preferably 10%) to 45% of a salting-out electrolyte.
• Salting-out electrolyte has the meaning ascribed in specification EP-A-79,646, that is all electrolytes having a lyotropic number of less than 9.5, preferably less than 9.0.
• Preferred salting-out electrolytes are selected from alkali metal and ammonium salts of phosphates (including pyro, ortho and poly phosphates) , silicates, borates, carbonates, sulphates, citrates nitriloacetate and succinates.
• compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
• Examples of phosphorous containing inorganic detergency builders include the water-soluble salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and phosphonates.
• Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant builders may also be used. Sometimes it is however preferred to minimise the amount of phosphate builders.
• non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds) , potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
• organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine- tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylie acids, CMOS, tartrate mono succinate, tartrate di succinate and citric acid. Citric acids or salts thereof are preferred builder materials for use in compositions of the invention.
• the level of non-soap builder material is from 5-40 % by weight of the composition, more preferred from 5 to 25 % by weight of the composition.
• composition according to the present invention further comprises from 1.5 to 5% by weight of a decoupling polymer selected from deflocculating polymer having a hydrophilic backbone and one or more hydrophobic side- chains, or being a block copolymer having alternating hydrophobic and hydrophilic groups, or having nonionic monomers and ionic monomers.
• a decoupling polymer selected from deflocculating polymer having a hydrophilic backbone and one or more hydrophobic side- chains, or being a block copolymer having alternating hydrophobic and hydrophilic groups, or having nonionic monomers and ionic monomers.
• EP-A-346,995 describes deflocculating polymers having a hydrophilic backbone and one or more hydrophobic side-chains
• WO 91/06622 describes deflocculating polymers being a block copolymer consisting of alternating hydrophobic and hydrophilic groups
• WO 91/06622 describes deflocculating polymers being a block copolymer consisting of alternating hydrophobic and hydrophilic groups
• 91/06623 describes deflocculating polymers consisting of nonionic monomers and ionic monomers and GB 2 237 813 describes deflocculating polymers consisting of a hydrophobic backbone and one or more hydrophilic side- chains.
• the deflocculating polymer is present at a level of from 1.5 to 5 % by weight of the composition.
• compositions of the present invention are concentrated. Therefore, the water level in the liquid detergent compositions according to the present invention is preferably at least 10%, more preferably at least 20%, most preferably at least 30% by weight of the composition and preferably at most 60% by weight, more preferably at most 50%, most preferably at most 40% by weight of the composition.
• lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes (at a level of 0.5-5% by weight) such as proteases, amylases and lipases (including Lipolase (Trade Mark) ex Novo) , enzyme stabilizers, anti-redeposition agents, germicides and colorants.
• biodegradable materials are preferred for environmental reasons.
• compositions of the invention preferably have a viscosity of less than 2,500 mPas at 21 s-1, more preferred less than 1,500 Pas, most preferred less than 1,000 mPas nad higher than lOOmPas, especially preferred between 100 and 750 mPas at 21 s-1.
• Liquid compositions according to the invention are physically stable and have a relatively low viscosity, In the context of the present invention, physical stability is defined in terms of the maximum separation compatible with most manufacturing and retail requirements. Stable compositions will yield no more than 10%, preferably no more than 5%, most preferred no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
• liquid compositions of the invention have a pH of between 6 and 14, more preferred from 6.5 to 13, especially preferred from 7 to 12.
• the pH is at least 6, more preferably at least 7.5, most preferably at least 8.
• the pH is at most 12, more preferably at most 10, most preferably at most 9.
• a preferred method for the preparation of liquid detergent compositions involves the dispersing of the electrolyte ingredient (if present) together with the minor ingredients except for the temperature sensitive ingredients -if any- in water of elevated temperature, followed by the addition of the builder material- if any-, the detergent active material (possibly as a premix) under stirring and thereafter cooling the mixture and adding any temperature sensitive minor ingredients such as enzymes perfumes etc.
• the deflocculating polymer may for example be added after the electrolyte ingredient or as the final ingredient. Preferably, the deflocculating polymers are added prior to the formation of the lamellar structure.
• the detergent compositions of the invention will be diluted with wash water to form a wash liquor for instance for use in a washing machine.
• concentration of liquid detergent composition in the wash liquor is preferably from 0.1 to 10 %, more preferred from 0.1 to 3% by weight.
• compositions were prepared by mixing the ingredients in the order listed.
• Example 4 The following formulations were prepared by adding the ingredients in the order listed to water.
• the formulations with the stabiliser has lower separation and lower viscosity drift upon storage.
• This Example illustrates the benefit of post shear and the use of various stabilisers in stabilisation of high nonionic formulations.
• the compositions were prepared by adding the ingredients in the order listed at a temperature of 50-55°C.
• Citric acid 9.14 9.14 9.14 9.14 Glycerol 4.17 4.17 4.17 4.17
• Tween 21 is sorbitan monolaurate with 4 EO groups. Unsheared
• Example 6 This provides an example of high nonionic formulations and illustrates the benefits of the presence of solid particles and the use of post shear.
• the compositions were prepared by adding the ingredients in the order listed at a temperature of 50-55°C. Apart from the zeolite levels, formulations 15 and 16 are equivalent, the ingredients of composition 16 are present in the same ratio as in composition 15.
• Formulation 15 16 17 Water to 100 to 100 to 100
• compositions were prepared by adding the ingredients in the order listed at a temperature of 50-55°C.
• composition was sheared with an extrusion plastometer at a shear rate of 10,000 sec "1 .
• Example 8 The following example demonstrates that post-shear can also be effective using a device which would be practical to use in factories - namely a shear valve. This was a diaphragm valve - the diaphragm is screwed down until a suitably narrow constriction to flow is achieved.
• the compositions were prepared by adding the ingredients in the order listed at a temperature of 50-55°C.
• the following liquid was prepared by adding the ingredients in the order listed while keeping the temperature as close to 50°C as possible.
• the actives were added as premix.
• the formulation was cooled to 30°C before addition of perfume.
• Formulation 24 of Example 9 was prepared. Samples of the liquid were passed through an diaphragm shear valve. The results were:-
• Formulation 25 contains lamellar droplets that lack internal symmetry and contain non-concentric surfactant material.
• Example 12 The following formulation was prepared:
• Formulation 26 contains lamellar droplets that lack internal symmetry and contain non-concentric surfactant material.
• the following formulation was prepared by premixing the sulfate and nonionic and adding this premix to a solution of citrate, borate, glycerol and the polymer. Thereafter, the mixture stirred with an overhead stirrer for 30 minutes at room temperature.
• the formulation was studied under polarized light microscopy and no Maltese crosses were identified.
• the liquid contains droplets with a size in the range of 2-20 ⁇ m; these lack radial symmetry; the joined thickness of the bi-layers in the droplets is smaller than the radius of the droplet (less than 25%, i.e. less than about 10%, of the radius) ; the droplets consist only of a few lamellar bi- layers, as found using a transmission electron microscope.
• the composition shows high flexibility in incorporation of ingredients.
• Nonionic 1 13 Nonionic 2 2) 13 Glycerol 4
• Nonionic 1 is Synperonic A7, ex ICI 2
• Nonionic 2 is Synperonic A3, ex ICI
• the liquid did not show phase separation during 5 weeks at 37°C.
• the droplets in the liquid showed no radial symmetry. At increasing polymer concentrations, the droplets become smaller.
• the enzyme half live is high (protease larger than 10 weeks and lipase 5 weeks at 37°C) . Stability is further increased if post shear is applied, if higher polymre levels are used and if zeolite level is increased.
• Nonionic 1 is Synperonic A7, ex ICI
• Nonionic 2 is Synperonic A3, ex ICI 3) Polymer All of EP 346995
• Composition 1 Ingredients % by weight
• Composition 2 was made by adding on top of composition 1 20% by weight of zeolite 4A material, ex Wissalith P (added during preparation before the active premix) .
• Composition 3 was made by adding 2% of polymer to the composition 1 instead of 1% by weight.
• Composition 4 was made by adding 2% of polymer to the composition 2 instead of 1% by weight.
• Composition 5 was made by adding 0% of polymer to the composition l instead of 1% by weight.
• Liquid compositions 1-4 contain droplets that have a structure lacking internal symmetry.
• composition 4 does not show no phase separation after 1 week.
• the composition was centrifuged and the zeolite was removed, whereafter the resulting liquid was remixed.
• the remixed composition (which is equal to composition 3) showed phase separation after a week storage similar to composition 3. It can be concluded that presence of solid particles increases stability.
• Enzyme stability was measured in the liquid of Example 19 and found to be very good: 92% for lipase and 74% for protease after 4 weeks at 37°C.
• Zeolite level (% by weight) 13 15.5 18 20 Separation (4 weeks ambient) 4 2 0 0
• Example 22 The liquids of Examples 1 and 21 and 2K of EP-A-623670 were prepared.
• Example 1 resulted in a liquid which, when studied under the electron microscope, was found to contain surfactant droplets in an isotropic continuous phase.
• the surfactant droplets did not show birefringent under the electron microscope.
• Study of the droplets with freeze-fraction electron microscopy revealed that the surfactant droplets had a lamellar coating on the outside and stacks of surfactant in the core.
• the level of solid particles was estimated to be about 5% by weight of the composition.

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• 1995
  • 1995-03-30 TW TW084103057A patent/TW294720B/zh active
  • 1995-09-28 BR BR9509052A patent/BR9509052A/pt not_active Application Discontinuation
  • 1995-09-28 JP JP8511395A patent/JPH09511779A/ja active Pending
  • 1995-09-28 KR KR1019970702086A patent/KR970706384A/ko not_active Application Discontinuation
  • 1995-09-28 AU AU36531/95A patent/AU3653195A/en not_active Abandoned
  • 1995-09-28 WO PCT/EP1995/003859 patent/WO1996010625A1/en not_active Application Discontinuation
  • 1995-09-28 CA CA002199019A patent/CA2199019A1/en not_active Abandoned
  • 1995-09-28 CN CN95195369A patent/CN1159825A/zh active Pending
  • 1995-09-28 EP EP95934119A patent/EP0783564A1/en not_active Withdrawn
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