EP0829530B1 - Improvements to hard surface cleaners - Google Patents

Improvements to hard surface cleaners Download PDF

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Publication number
EP0829530B1
EP0829530B1 EP97116919A EP97116919A EP0829530B1 EP 0829530 B1 EP0829530 B1 EP 0829530B1 EP 97116919 A EP97116919 A EP 97116919A EP 97116919 A EP97116919 A EP 97116919A EP 0829530 B1 EP0829530 B1 EP 0829530B1
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Prior art keywords
surfactant
electrolyte
composition according
phase
product
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EP97116919A
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German (de)
English (en)
French (fr)
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EP0829530A1 (en
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Alexander Unilever Research Lab. Allan
Alan John Unilever Research Lab. Fry
David Hayes
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GB929219042A external-priority patent/GB9219042D0/en
Priority claimed from GB939302991A external-priority patent/GB9302991D0/en
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to improvements to hard surface cleaners, and in particular to hard surface cleaners containing suspended particles.
  • Hard surface cleaners containing abrasive particles are well known.
  • Typical compositions comprise one or more surfactants in solution and a plurality of abrasive particles dispersed therein.
  • surfactants in solution
  • a plurality of abrasive particles dispersed therein.
  • one or more surfactant components act as a suspending agent, usually in combination with a dissolved electrolyte.
  • the presence of the electrolyte causes the surfactant component(s) to thicken by the establishment of a lamellar phase.
  • an additional non-surfactant suspending agent such as a clay or polymer is present.
  • compositions which comprise non-abrasive particles such as hygiene agents, i.e. water-insoluble or sparingly soluble bleaching agents and the present invention includes such compositions within its scope.
  • the viscosity of the product generally varies with the shear applied. This property is usually referred to as 'shear thinning'.
  • the viscosity achieved under various rates of shear is important in determining the product properties.
  • Surfactants employed as suspending agents in liquid abrasive cleaners have included, alkyl benzene sulphonates, alcohol ethoxylates, alkyl amido ethoxylates, fatty acid soaps and secondary alkyl sulphonates. Combinations of these surfactants, together with electrolytes are used to form the suspending systems in a number of commercial products.
  • suspending surfactant system must be both pourable and have a high yield stress, i.e. it must be dosable and must be capable of suspending macroscopic particles.
  • the fine structure of such systems generally consists of generally spherical structures ranging from about 0.05 to about 10 microns in diameter. These structures are believed to comprise alternating bilayers of surfactant molecules spaced apart by thin layers of aqueous electrolyte solution, i.e. lamellar phase.
  • the suspending system is not the only structure which surfactants can form in the presence of water.
  • the above-mentioned surfactants can also form structured aqueous liquids which are viscous but are not capable of suspending particles.
  • compositions of surfactant and water may separate into two or more mixed phases with different physical properties.
  • suspending system is stable over the range of temperatures encountered in use and sufficiently suspending to maintain the abrasive particles in suspension for the shelf life of the product. It is also desirable that the interactions of other components in the composition with the suspending surfactants, do not modify the rheology of the overall composition to an extent that the desired shear-thinning property is lost.
  • Some surfactant combinations form suspending systems more readily than others.
  • Mixtures of alkyl benzene sulphonates with alcohol ethoxylates and, optionally, small amounts of fatty soaps comprise the suspending surfactant system used in a number of successful commercial products.
  • a variety of electrolytes can be used with such systems, including alkali metal carbonates, citrates, halides (particularly chlorides) phosphates, sulphates, ammonium salts and acetates.
  • the multivalent anions are preferred for reasons of cost and due to the additional benefits which these components bring: such as alkalinity from carbonate and builder activity from citrate.
  • Surfactant/electrolyte suspending systems can have a relatively narrow formulation window within which consumer-preferred viscosities must be achieved, depending on the type of surfactant present.
  • a problem with surfactant-containing suspending systems is that some of the surfactants which most readily form suspending systems, and are therefore commonly in use, are not as desirable for environmental reasons as other surfactant systems.
  • PAS primary alcohol sulphate
  • PAS primary alcohol sulphate
  • Non-suspending systems comprising 1-1.2% PAS, 0.1-1.5% of a mixed nonionic system and low molecular weight non-thickening polymer are disclosed in GB-A-2160887 (Bristol-Myers: 1984).
  • Non-suspending surfactant systems comprising relatively high levels of PAS in combination with ether-sulphates and semi-polar non-ionic detergents (such as amine oxides, phosphine oxides and sulphoxides) are disclosed in GB-A-1524441 (P&G: 1976).
  • EP-A-0107946 (P&G, 1983, see Example II) discloses an unstructured dishwashing composition in which PAS is the most predominant single surfactant species present but never exceeds 50% of the total surfactant system.
  • EP-A-0125711 (Unilever, 1983) discloses almost electrolyte-free, structured liquid compositions comprising polymer, ethoxylated alcohol surfactants and PAS in a ratio such that the PAS is never in excess of one third of the total surfactant present.
  • the other product is believed to have comprised 50% of a calcite abrasive in a PAS/nonionic/sodium acetate surfactant system.
  • a calcite abrasive in a PAS/nonionic/sodium acetate surfactant system.
  • the high level of abrasive led to difficulties in rinsing.
  • lower levels of abrasive are desirable in that compositions with low levels of abrasive are more easily rinsed.
  • polymers as a part of the suspending system.
  • Known polymers include poly-saccharides, e.g. sodium carboxymethyl cellulose and other chemically modified cellulose materials, xanthan gum and other non-flocculating structuring agents such as Biopolymer PS87 referred to in US Patent No. 4 329 448.
  • Polymers of acrylic acid cross-linked with a poly-functional agent for example members of the CARBOPOL (RTM: Goodrich) family, are also be used as structuring agents in suspending systems.
  • the amount of such structuring agents can be as little as 0.001% but is more typically at least 0.01% by weight of the composition.
  • Commercial products typically contain around 0.1-0.4%wt of the cross-linked acrylic acid polymer.
  • At least partially esterified resins such as an at least partially esterified adduct of rosin and an unsaturated dicarboxylic acid or anhydride, or an at least partially esterified derivatives of copolymerisation products of mono-unsaturated aliphatic, cycloaliphatic or aromatic monomers having no carboxy groups and unsaturated dicarboxylic acids or anhydrides thereof as deposition agents.
  • Suitable copolymers of the latter type are copolymers of ethylene, styrene and vinylmethylether with maleic acid, fumaric acid, itaconic acid, citraconic acid and the like and the anhydrides thereof including the styrene/maleic anhydride copolymers.
  • polymers are of use where the surfactant system structures poorly at low shear, i.e. where storage stability is poor.
  • polymers have the disadvantage of also increasing the viscosity at high shear and therefore increasing the effort required in cleaning operations using the product.
  • products should derive their structural and rheological properties both from a polymeric structuring agent and from surfactant-electrolyte interactions.
  • Known products have therefore comprised a surfactant such as alkyl benzene sulphonate, a co-surfactant such as an alcohol ethoxylate, an electrolyte and a polymer.
  • the present invention provides a stable, structured, liquid, hard surface cleaning composition
  • a stable, structured, liquid, hard surface cleaning composition comprising a continuous aqueous phase, a dispersed lamellar phase and 1-80%wt on product of a dispersed, suspended particulate phase, said product comprising at least 2 and not more than 25%wt on aqueous phase of surfactant, said surfactant comprising primary alcohol sulphate (i) and ethoxylated alcohol nonionic surfactant (ii) wherein the weight ratio of (i):(ii) falls in the range 5:1 to 0.45:1, said composition further comprising 1 to 20%wt dissolved electrolyte on product CHARACTERISED IN THAT, said electrolyte has a monovalent anion, said electrolyte is present in weight excess over the total surfactant present, said particulate phase comprises calcium carbonate, dolomite, sodium hydrogen carbonate, potassium sulphate, alumina, hydrated alumina, feldspar,
  • the formulations described herein provide products which are stable under the range of commonly encountered storage temperatures, exhibit acceptable cleaning properties and rheology and comprise relatively higher proportions of the more preferable surfactants having regard to biodegradation properties than previously known compositions.
  • m the average degree of ethoxylation
  • monovalent anion electrolyte needs to be present in weight excess over the total surfactant present in the composition: whereas either monovalent or divalent anions can be used as the electrolyte with the shorter chain ethoxylates (i.e where m is less than or equal to 5).
  • the electrolyte solution comprises significant levels of multivalent anions.
  • High molecular weight hydrophilic polymer is an optional ingredient of compositions according to the present invention.
  • compositions will comprise 0.01-2% of a hydrophilic polymer having a average molecular weight in excess of 500,000 Dalton.
  • the polymer is of sufficiently high molecular weight to remain in the continuous phase when hydrated and that the affinity of the polymer for water, causes a partial repartitioning of water from the lamellar phase of the product into the continuous phase of the product, increasing the effective concentration of surfactant and electrolyte in the lamellar phase and improving the structuring properties of that phase.
  • Preferred types of polymer include poly-carboxylates, poly-saccharides and mixtures thereof, including co-polymers within or between these classes or co-polymers with styrenes and so forth.
  • poly-carboxylates Preferred amongst the poly-carboxylates are the crosslinked poly-acrylates, crosslinked poly-methacrylates, and mixtures thereof.
  • Crosslinked, poly-acrylates are the most preferred polymers. These materials are available from a variety of commercial sources as illustrated hereafter by way of example.
  • poly-saccharides are xanthan and guar gums, cellulose ethers, and mixtures thereof.
  • Preferred levels of polymer are 0.05-1% on product, more preferably 0.1-0.5wt% with levels of around 0.1-0.3 being particularly preferred for the cross-linked poly-acrylate, so as to achieve the desired viscosity.
  • the levels of polymer present should be such that the viscosity, as measured at 25°Celsius, at a shear rate of 21 sec -1 falls in the range 300-2500 mPas. It is particularly preferred that the viscosity at this shear rate should fall into the range 600-1800 mPas. Such viscosities facilitate easy dosing.
  • the viscosity at lower rates of shear, i.e below 10 -3 sec -1 should be sufficiently high to provide for storage stability of the product in that significant particle sedimentation should be avoided.
  • the viscosity at higher rates of shear i.e above 100 sec -1 should be sufficiently low to provide for ergonomic use of the product and avoid excessive effort being required in use.
  • compositions according to the present invention in which the particles are chemically reactive, suspended, hygiene agents rather than chemically inert abrasives, polymer is not an essential component but where present a polymer should be selected which is chemically stable in the presence of the hygiene agent.
  • Primary alcohol sulphates and ethoxylated alcohol nonionic surfactants having more than 5 and less than or equal to 10 moles of ethoxylation per mole of surfactant are essential ingredients of the compositions according to the present invention.
  • the ratio of primary alcohol sulphate (i) to the one or more of said ethoxylated alcohol nonionic surfactants (ii), expressed as (i)/(ii) in weight% falls in the range 5-0.45. More preferably the ratio falls into the range 2-0.6. Even more preferably the ratio falls into the range 1.5-0.75 and is most preferably around 1.
  • PAS primary alcohol sulphate
  • the preferred primary alcohol sulphate comprises a mixture of materials of the general formulation: ROSO 3 X wherein R is a C 8 to C 18 (mean chain length) primary alkyl group and X is a solubilising cation.
  • Suitable cations include sodium, magnesium, potassium, ammonium and mixtures thereof.
  • C8-18 (mean chain length) PAS is preferred due to its detergent and structuring properties. Above mean alkyl chain lengths of C18, the material tends to become too insoluble for use, whereas below mean chain lengths of C8 the material tends to become too soluble for use. C10-C16 (mean chain length) PAS is particularly preferred as materials with this chain length average have optimal detergent properties and are readily available.
  • the ethoxylated alcohols are preferably of the general formula: R 1 -(OCH 2 CH 2 ) m -A-OH wherein R 1 is the residue of a branched, or unbranched, C 8 to C 18 preferably primary, alcohol, A is preferably absent or is the residue of a polyol of at least two carbons and two hydroxyl groups, and the average degree of ethoxylation (i.e. the ethylene oxide chain length) m is greater than 5 and less than or equal to 10.
  • R1 can be a 2-hydroxy alkyl residue of the same chain length.
  • A can be the residue of an alkylene glygol or a sugar. Generally, A will be absent.
  • the alcohol ethoxylates are excellent detergents, available at low cost in commercial quantities and exhibit concentration-sensitive interactions with electrolyte and PAS enabling the formation of a suspending system.
  • the overall surfactant system consists of: 2-10% primary alcohol sulphate (i) and 2-10% ethoxylated alcohol (ii) in a weight ratio of (i)/(ii) which falls in the range 2.0-0.6 , and, 0.1-2% of a fatty acid soap having a mean of C10-C18 carbon atoms.
  • Electrolyte is an essential component of compositions according to the present invention.
  • the monovalent anions are selected from the group comprising chlorides, bromides, iodides, acetates, bicarbonates, and mixtures thereof having regard to the chemical nature of the particulate phase such that where the particulate phase is chemically reactive, the electrolyte is selected to be inert towards the particulate phase.
  • the preferred ratio's of the surfactants are as described above.
  • a dispersed, suspended particulate phase comprising calcium carbonate, dolomite, sodium hydrogen carbonate, potassium sulphate, alumina, hydrated alumina, feldopar, talc or silica is an essential ingredient of compositions according to the present invention.
  • the dispersed suspended particulate phase comprises a particulate abrasive which is either insoluble in the aqueous phase or present in such excess that the solubility of the abrasive in the aqueous phase is exceeded and consequently solid abrasive exists in the composition.
  • Preferred abrasives for use in general purpose compositions have a Moh hardness below 6 although higher hardness abrasives can be employed for specialist applications.
  • Suitable abrasives can be selected from, particulate zeolites, calcites, silicas, silicates, carbonates, aluminas, bicarbonates, borates, sulphates and polymeric materials such as polyethylene.
  • Preferred average (weight average) particle sizes for the abrasive fall in the range 0.5-200 microns, with values of around 10-100 microns being preferred. In this range an acceptable compromise between good cleaning behaviour and low substrate damage is achieved.
  • Preferred levels of abrasive range from 5-70wt% on product, preferably in the range 20-40wt%, most preferably around 35wt%. Such levels of abrasive give effective cleaning and good rinsing.
  • the most preferred abrasives are calcium carbonate (as calcite), mixtures of calcium and magnesium carbonates (as dolomite), sodium hydrogen carbonate, potassium sulphate, zeolite, alumina, hydrated alumina, feldspar, talc and silica. Calcite and dolomite are particularly preferred due to their low cost, hardness and colour.
  • the electrolyte is other than acetate.
  • the particles used in embodiments of the present invention preferably have a density lower than 2.7 gm/cm 3 : this excludes unmodified calcite.
  • calcite it should be used at levels below 50% on product in order to improve rinsing performance.
  • the suspending systems of the present invention are capable of suspending calcite at relatively low levels, i.e. 20-40%wt, at which levels particle-particle interactions are reduced as compared with higher levels of calcite.
  • the particulate phase can also comprise a hygiene agent, preferably a solid organic peracid.
  • a hygiene agent preferably a solid organic peracid.
  • hygiene agents include diperoxy-dodecanedioic acid (DPDA) and ⁇ -N,N-phthaloyl-amino-peroxy-caproic acid (PAP).
  • insoluble hygiene agents include triclosan (2,4,4'-trichloro-2'-hydroxy diphenyl ether) and insoluble derivatives thereof. These may be present in combination with the abrasive particles.
  • compositions according to the present invention can comprise a solvent.
  • Solvents are an optional component and are not essential to the practice of the present invention.
  • Preferred solvents are selected from: propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, dipropylene glycol mono t-butyl ether, diethylene glycol hexyl ether, ethyl acetate, methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, n-methyl pyrrolidine and mixtures thereof.
  • the preferred solvents are propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, ethanol, isopropyl alcohol, diethylene glycol monobutyl ether and mixtures thereof.
  • compositions of the invention can further comprise other non-essential components selected from the group comprising: perfumes, colours, whitening agents (such as titanium dioxide) and dyes, hygiene agents, foam-control agents, preservatives and mixtures of one or more thereof.
  • foam control agents comprise calcium sensitive soaps.
  • Particularly preferred soaps are the C10-C18 saturated or unsaturated fatty acids and salts thereof.
  • Preferred levels of soap range from 0.1-2% of a fatty acid soap having C10-C18 carbon atoms. It is particularly preferred that the ratio of soap to total active should fall into the range: 1:5-1:20.
  • PAS Primary alcohol sulphate
  • LAS linear alkyl benzene sulphonate
  • PAS forms a gel phase at concentrations above 30%wt in aqueous solution, depending on the chain lengths of the PAS and degree of branching and remains in this phase until higher concentrations, of around 70% are reached, where a pumpable phase is again formed.
  • Compositions which comprise both polymers and PAS are difficult to prepare as the production process must not at any stage form a composition in which the PAS or the polymer form a significant quantity of gel. Gels can be formed, when PAS and polymer are mixed, due to the reduction of the water activity in the PAS caused by the presence of the polymer and subsequent competition for the available water.
  • hydrophilic, high molecular weight polymers such as the crosslinked polyacylates should not be exposed to other than mildly alkaline conditions as such conditions will cause gelling of the polymer.
  • these polymers cannot be dissolved at high concentrations in neutral aqueous solution.
  • initial suspension of abrasives in the absence of a suspending system requires high shear which can incorporate air into any viscous mixture which is formed during mixture of components. This air is difficult to remove.
  • the cleaning compositions of the present invention may be prepared by a process which comprises the steps of:
  • One particularly preferred process route comprises:
  • An alternative preferred process route comprises:
  • Figure 1 shows the lamellar regions for formulations containing either PAS or alkyl benzene sulphonate with a 6.5 EO nonionic surfactant at varying levels of electrolyte levels
  • Figure 2 shows the lamellar regions for formulations containing either PAS and a nonionic surfactant at varying electrolyte levels and for varying environmental conditions
  • Figure 5 shows the lamellar regions for formulations containing PAS with a 6.5 EO nonionic surfactant at varying mono-valent electrolyte levels.
  • Surfactants Empicol-LX [RTM ex Albright & Wilson], a sodium salt of naturally derived, linear, primary alcohol sulphate having an average alkyl chain length in the range C 12 -C 14 ; Dobanol 23-6.5 [RTM ex. Shell], an alcohol ethoxylate surfactant having an average ethylene oxide chain length (EO) of 6.5 units.
  • Prifac 7901 [RTM ex. Unichema]
  • a mixed chain-length fatty acid having a similar chain length distribution to the fatty acids obtainable from coconut oil.
  • Abrasive MM5F Calcite [ex. Minerva].
  • Examples 19-20 and 23 illustrate the results of a plurality of experiments relating to lamellar phase of a range of compositions based on PAS, nonionics and electrolytes, in the absence of minors.
  • the results of examples 19-20 are shown in the accompanying figures 1-2 and 5.
  • the process routes used to obtain the compositions of examples 19, 20 and 23 were selected from processes 1-4 as mentioned above or were minor modifications thereupon.
  • liquid samples of the compositions were examined after at least three days storage at the specified temperatures. A small sample was placed between glass slides and examined using polarised light, transmission microscopy. The presence of a lamellar phase was indicated by a characteristic 'Maltese cross' pattern generally believed to be caused by the presence of a lamellar phase dispersion.
  • Figure 1 shows the stable lamellar regions for formulations containing either PAS (Empicol LX) or alkyl benzene sulphonate together with a 6.5 EO nonionic surfactant (Dobanol 23 6.5 EO) at a constant total surfactant level of 10%wt and at varying electrolyte levels.
  • PAS Epicol LX
  • Dobanol 23 6.5 EO 6.5 EO nonionic surfactant
  • the electrolyte was sodium chloride and stability was assessed at 25° Celsius. From figure 1, it can be seen that, the existence of a lamellar phase depends on both the selection of the correct electrolyte level and the correct ratio of surfactants.
  • lamellar-phase formulations can be made over a relatively wide formulation range.
  • the range of electrolyte levels and surfactant ratios which enable the formation of a lamellar phase (Region B) is markedly smaller.
  • the electrolyte was changed from NaCl to sodium carbonate, supplying a divalent cation (Example 19b), no lamellar phase region could be found (see also examples 16 and 18).
  • FIG. 2 shows the stable lamellar regions for formulations containing both sodium PAS (Empicol LX) and a 6.5 EO nonionic surfactant (Dobanol 23 6.5 EO) at varying ratios to a constant total surfactant level of 10%, at varying levels of electrolyte (sodium chloride) and under varying environmental conditions.
  • These conditions are 1,2 and 4 as discussed above and the limits of the boxes marked 1, 2 and 4 indicate the limits of stability under the specified conditions. It can be seen that for general stability under a practical range of storage conditions over a temperature range of 4-37° Celsius, the preferred range of electrolyte levels and surfactant ratios is particularly narrow (Region C). Outside of this region not all of the formulations produce the lamellar phase and the formulations would consequently not be capable of suspending particles under certain conditions of storage.
  • FIG. 5 shows the stable lamellar regions at 25°Celsius for formulations containing various ratios of PAS (Empicol LX) with a 6.5 EO nonionic surfactant (Dobanol 23-6.5) at a total surfactant level of 10% and at varying mono-valent cation electrolyte levels.
  • the cation is ammonium as opposed to sodium. It is to be noted that relatively high levels of electrolyte are required to form a lamellar phase. High levels of electrolyte are discouraged for reasons of residue deposition and corrosiveness.
  • compositions were prepared by mixing the components as listed, under shear, at room temperature.
  • electrolyte which can be used is dependent on the nature of the nonionic surfactant.
  • the electrolyte must contain a monovalent anionic species such as a halide, preferably chloride. Examples 24 and 24C illustrate this point: the formulation was unstable when the divalent carbonate was employed instead of the monovalent chloride.

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EP97116919A 1992-09-09 1993-09-07 Improvements to hard surface cleaners Expired - Lifetime EP0829530B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9219042 1992-09-09
GB929219042A GB9219042D0 (en) 1992-09-09 1992-09-09 Improvements to hard surface cleaners
GB939302991A GB9302991D0 (en) 1993-02-15 1993-02-15 Improvements to hard surface cleaners
GB9302991 1993-02-15
EP94908829A EP0659205B1 (en) 1992-09-09 1993-09-07 Improvements to hard surface cleaners

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EP94908829A Division EP0659205B1 (en) 1992-09-09 1993-09-07 Improvements to hard surface cleaners
EP94908829.8 Division 1994-03-17

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EP97116919A Expired - Lifetime EP0829530B1 (en) 1992-09-09 1993-09-07 Improvements to hard surface cleaners
EP94908829A Expired - Lifetime EP0659205B1 (en) 1992-09-09 1993-09-07 Improvements to hard surface cleaners

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JP (1) JP3516449B2 (pt)
AU (1) AU679454B2 (pt)
BR (1) BR9307025A (pt)
CA (1) CA2144065C (pt)
DE (2) DE69320355T2 (pt)
ES (2) ES2154867T3 (pt)
WO (1) WO1994005757A1 (pt)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8029772B2 (en) 2001-12-21 2011-10-04 Rhodia Inc. Stable surfactant compositions for suspending components
US8828364B2 (en) 2007-03-23 2014-09-09 Rhodia Operations Structured surfactant compositions

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5741770A (en) * 1989-09-22 1998-04-21 Colgate-Palmolive Co. Liquid crystal composition
US5723431A (en) * 1989-09-22 1998-03-03 Colgate-Palmolive Co. Liquid crystal compositions
EP0732394A3 (en) * 1995-03-13 1999-02-03 Unilever N.V. Detergent compositions
CO4770890A1 (es) * 1996-03-06 1999-04-30 Colgate Palmolive Co Composiciones cristalinas liquidas que contienen particulas de madera o abrasivo
CA2247902A1 (en) * 1996-03-06 1997-09-12 Myriam Mondin Liquid crystal detergent compositions
EP0798372A3 (en) * 1996-03-29 1999-12-08 Unilever N.V. Detergent composition
NZ333153A (en) * 1996-06-14 2000-07-28 Colgate Palmolive Co Liquid crystal compositions
US6194364B1 (en) 1996-09-23 2001-02-27 The Procter & Gamble Company Liquid personal cleansing compositions which contain soluble oils and soluble synthetic surfactants
GB9708500D0 (en) * 1997-04-25 1997-06-18 Unilever Plc Abrasive cleaning composition
WO1999064553A1 (en) * 1998-06-09 1999-12-16 Unilever N.V. Hard surface cleaners
CN1354784A (zh) * 1998-09-25 2002-06-19 荷兰联合利华有限公司 洗涤剂组合物
WO2001077273A1 (en) * 2000-04-05 2001-10-18 Unilever N.V. Solid dispersible abrasive compositions
EP1321514A1 (fr) * 2001-12-21 2003-06-25 Maclean S.A. Détergent liquide à action récurante contenant du polyéthylène particulaire
GB2392166A (en) * 2002-08-22 2004-02-25 Reckitt Benckiser Inc Composition separable into two phases
US20050119152A1 (en) * 2003-11-14 2005-06-02 Hecht Stacie E. Liquid detergent composition comprising a solubilizing anionic surfactant
WO2006012465A1 (en) 2004-07-21 2006-02-02 Colgate-Palmolive Company Structured body wash
NZ562671A (en) 2005-04-21 2011-01-28 Colgate Palmolive Co Liquid detergent composition comprising surfactants, suspending agents, beads and water.
GB2434586A (en) * 2006-01-24 2007-08-01 Henkel Uk Structured liquid abrasive composition
PL2308957T3 (pl) 2006-12-15 2013-08-30 Colgate Palmolive Co Ciekła kompozycja detergentowa
AR072859A1 (es) * 2008-05-23 2010-09-29 Colgate Palmolive Co Metodos y composiciones liquidas de limpieza
GB201108912D0 (en) * 2011-05-27 2011-07-13 Reckitt Benckiser Nv Composition
ES2794400T5 (es) 2015-11-13 2023-07-04 Procter & Gamble Composiciones de limpieza que contienen un tensioactivo de tipo alquilsulfonato ramificado y un tensioactivo no iónico de cadena corta
WO2017079961A1 (en) 2015-11-13 2017-05-18 The Procter & Gamble Company Cleaning compositions containing branched alkyl sulfate surfactant with little or no alkoxylated alkyl sulfate
EP3374481A1 (en) 2015-11-13 2018-09-19 The Procter and Gamble Company Detergent compositions
WO2018223368A1 (en) * 2017-06-08 2018-12-13 The Procter & Gamble Company Non-homogeneous compositions
JP7443515B2 (ja) 2019-12-16 2024-03-05 ザ プロクター アンド ギャンブル カンパニー 一体型吐出ノズルを備える液体吐出システム

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4329448A (en) * 1979-07-10 1982-05-11 Lever Brothers Company Microbial heteropolysaccharide
EP0086614A1 (en) * 1982-02-05 1983-08-24 Albright & Wilson Limited Liquid detergent compositions
EP0125711A1 (en) * 1983-04-19 1984-11-21 Unilever N.V. General-purpose cleaning composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080221B1 (en) * 1981-11-13 1985-07-24 Unilever N.V. Stable liquid detergent suspensions
AU575399B2 (en) * 1984-06-21 1988-07-28 S.C. Johnson & Son, Inc. Hard surface cleaning composition
GB8823655D0 (en) * 1988-10-07 1988-11-16 Unilever Plc Liquid detergent compositions
CA2083331C (en) * 1991-11-26 1998-08-11 Johannes H. M. Akkermans Detergent compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4329448A (en) * 1979-07-10 1982-05-11 Lever Brothers Company Microbial heteropolysaccharide
EP0086614A1 (en) * 1982-02-05 1983-08-24 Albright & Wilson Limited Liquid detergent compositions
EP0125711A1 (en) * 1983-04-19 1984-11-21 Unilever N.V. General-purpose cleaning composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Oral Presentation C10 by Mr. Brock at the 3rd CESIO International Surfactant Congress & Exhibition, at the Barbican Centre, City of London on 1-5 June 1992 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8029772B2 (en) 2001-12-21 2011-10-04 Rhodia Inc. Stable surfactant compositions for suspending components
US8394361B1 (en) 2001-12-21 2013-03-12 Rhodia Operations Stable surfactant compositions for suspending components
US8828364B2 (en) 2007-03-23 2014-09-09 Rhodia Operations Structured surfactant compositions

Also Published As

Publication number Publication date
JPH08501120A (ja) 1996-02-06
DE69320355T2 (de) 1999-02-11
CA2144065C (en) 2003-11-11
AU4976193A (en) 1994-03-29
ES2154867T3 (es) 2001-04-16
DE69320355D1 (de) 1998-09-17
BR9307025A (pt) 1999-06-29
EP0829530A1 (en) 1998-03-18
CA2144065A1 (en) 1994-03-17
AU679454B2 (en) 1997-07-03
WO1994005757A1 (en) 1994-03-17
EP0659205B1 (en) 1998-08-12
DE69329782D1 (de) 2001-01-25
DE69329782T2 (de) 2001-05-03
ES2122243T3 (es) 1998-12-16
EP0659205A1 (en) 1995-06-28
JP3516449B2 (ja) 2004-04-05

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