EP0829530A1 - Verbesserung von Reinigern für harte Oberflächen - Google Patents

Verbesserung von Reinigern für harte Oberflächen Download PDF

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Publication number
EP0829530A1
EP0829530A1 EP97116919A EP97116919A EP0829530A1 EP 0829530 A1 EP0829530 A1 EP 0829530A1 EP 97116919 A EP97116919 A EP 97116919A EP 97116919 A EP97116919 A EP 97116919A EP 0829530 A1 EP0829530 A1 EP 0829530A1
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EP
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Prior art keywords
electrolyte
surfactant
composition according
product
phase
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EP97116919A
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English (en)
French (fr)
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EP0829530B1 (de
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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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Publication of EP0829530A1 publication Critical patent/EP0829530A1/de
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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 non-ionic system and low molecular weight non-thickening polymer are disclosed in GB 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 1524441 (P&G: 1976).
  • EP 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 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 polysaccharides, 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 co-polymerisation 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.
  • 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.
  • a stable, structured, liquid 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 2-25%wt on product of surfactant, said surfactant comprising primary alcohol sulphate (i) and alkoxylated nonionic surfactant (ii) wherein the ratio (i)/(ii) falls in the range 20 to 0.40 said composition further comprising 1-20% dissolved electrolyte on product.
  • High molecular weight hydrophillic polymer is an optional ingredient of compositions according to the present invention.
  • compositions will comprise 0.01-2% of a hydrophillic 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, polysaccharides 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 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 alkoxylated nonionic surfactants are essential ingredients of the compositions according to the present invention.
  • the ratio of primary alcohol sulphate (i) to the one or more 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 is 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 preferred alkoxylated non-ionic surfactants are selected from the group comprising alkoxylated: alkyl polyglucosides, alcohols, alkyl sulphoxides, alkyl polyglycerols, fatty acid esters, amides and amines and mixtures thereof.
  • the most preferred nonionic surfactant is selected from the group comprising ethoxylated alcohols 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 1-14.
  • R1 can be a 2-hydroxy alkyl residue of the same chain length.
  • A can be the residue of an alkylene glycol or a sugar. Generally, A will be absent. It should be noted that propoxy residues can replace the ethoxy residues in whole or in part.
  • 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.
  • Optimum detergent properties are obtained where m is (mean for the surfactant) in the range 1-14.
  • ethoxylated alcohols are those which have m less than or equal to 10. These shorter chain ethoxylated alcohols have better biodegradability than the longer chain ethoxylated alcohols, and it becomes progressively more difficult to form a suspending system with the longer ethoxylate chain ethoxylated alcohols.
  • 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.
  • 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).
  • preferred embodiments of the present invention comprise:
  • 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.
  • preferred embodiments of the present invention comprise:
  • said electrolyte comprises 25-100mole% multivalent anions on total anions.
  • the multivalent anions are selected from the group comprising, carbonates, citrates, sulphates and mixtures thereof. Carbonates alone, or mixtures comprising carbonates are particularly preferred.
  • Preferred levels of electrolyte fall in the range 1-10%, more preferably 2-8%. It is particularly preferred that the anions of the electrolyte comprise at least 50mole% carbonate.
  • a dispersed, suspended particulate phase 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 comprise a hygiene agent, preferably a solid organic peracid.
  • hygiene agents include diperoxy-dodecanedioic acid (DPDA) and e-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 or to the exclusion of 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 pyrollidone 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.
  • 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.
  • the 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.
  • a stable, liquid composition comprising a continuous aqueous phase and a dispersed, suspended particulate phase, wherein the particles comprise calcite, dolomite, bicarbonate and mixtures thereof, and the aqueous phase comprises:
  • 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.
  • hydrophillic, 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.
  • a further aspect of the present invention provides a process for the preparation of a cleaning composition which comprises the steps of:
  • One particularly preferred process route comprises:
  • An alternative preferred process route comprises:
  • Viscosity was measured at 21 sec -1 , at 25 Celsius using a Haake RV2 as supplied, with the MV cup provided with the MV2 bob. Results are given in mPas.
  • Comparative examples 4 and 6 showed unstable, many-phase behaviour and consequently the viscosity of these products was not measured.
  • Example 2 illustrates that while a stable product can be made without polymer the viscosity of the product under the shear conditions specified is undesirably low.
  • Examples 1,3, 5, and 7 are embodiments of the invention.
  • the products of examples 1-3, 5 and 7 were all stable under storage conditions 1 and 3-5 as described above.
  • TABLE 2 provides examples showing that other polymers can be employed at various levels.
  • EXAMPLE 8 9 10 11 12 13 14 15 PolyGel DB 0.12 - - - - - - N-467-45 - 0.30 0.20 - - - - N-467-100 - - - 0.30 - - - - Alcogum - - - - 0.20 0.10 - - Kelzan-T - - - - - - 0.10 0.30 Lial-123S 3.25 3.25 3.25 3.22 3.22 3.25 3.25 Synperonic A3 3.25 3.25 3.25 3.25 3.22 3.22 3.25 3.25 Prifac 7901 0.65 - - - - - 0.65 0.65 ratio PAS/NI 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Na 2 CO 3 2.60 3.25 3.25 3.25 3.25 3.25 3.25 3.25 NaHCO 3 0.65 - - - -
  • Viscosity was measured at 21 sec -1 , at 25 Celsius using a Haake RV2 as supplied, with the MV cup provided with the MV2 bob. Results are given in mPas.
  • Examples 8-15 illustrate that stable compositions according to the present invention can be prepared with acceptable viscosity using alternative polymers.
  • Table 3 shows the effect of modification of the surfactant system.
  • EXAMPLE 16 17 18 PolyGel DB 0.12 0.12 0.12 Lial-123S 3.25 3.25 3.25 Dobanol-6.5 3.25 - - Dobanol91-2.5 - 3.25 - Synperonic A7 - - 3.25 Prifac 7901 0.65 0.65 0.65 ratio PAS/NI 1.00 1.00 Na 2 CO 3 2.60 2.60 NaHCO 3 0.65 0.65 0.65 Calcite 35.0 35.0 35.0 35.0 Lindalia 0.21 0.21 0.21 Proxel 0.03 0.03 0.03 Water ----to 100%----- Process: 1 1 1 Viscosity: Unst 1400 Unst
  • Viscosity was measured at 21 sec -1 , at 25 Celsius using a Haake RV2 as supplied, with the MV cup provided with the MV2 bob. Results are given in mPas.
  • Comparative Examples 16 and 18 illustrate that in the presence of electrolyte based on divalent anions (carbonate), compositions wherein the ethoxylate has a ethoxy chain length of greater than 5 are unstable.
  • Example 17 illustrates that an embodiment of the present invention formulated with a non-ionic having a shorter ethoxy chain is stable in comparison with the Examples 16 and 18. This sample was stable when stored as described above.
  • Examples 19-23 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 19-21 are shown in the accompanying figures 1-5.
  • the process routes used to obtain the compositions of examples 19-23 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.
  • the alkyl benzene sulphonate/non-ionic surfactant systems of the prior art (Region A)
  • lamellar-phase formulations can be made over a relatively wide formulation range.
  • the primary alkyl sulphate/non-ionic surfactant system employed in the compositions of the present invention 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. 3 shows the stable lamellar regions at 25 Celsius for formulations containing PAS (Empicol LX) with a 3.0 EO nonionic surfactant (Synperonic A3) at a total surfactant level of 10% and at varying electrolyte (NaCl) levels. It can be seen that for these short-chain ethoxylates in combination with PAS the ranges over which a lamellar phase (Region D) can be formed in the presence of a monovalent cation electrolyte (sodium chloride) are much larger than with the corresponding higher EO compositions.
  • PAS Empicol LX
  • Synperonic A3 3.0 EO nonionic surfactant
  • NaCl electrolyte
  • Figure 4 shows the stable lamellar regions at 25 Celsius for formulations containing PAS (Empicol LX) with a 3.0 EO nonionic surfactant (Synperonic A3) at a constant surfactant level of 10%wt on product and at varying divalent cation electrolyte (sodium carbonate) levels.
  • PAS Empicol LX
  • Synperonic A3 3.0 EO nonionic surfactant
  • the region over which a lamellar phase can be formed (Region E) is indicated.
  • 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.
  • PAS Empicol LX
  • Dobanol 23-6.5 6.5 EO nonionic surfactant
  • the cation is ammonium as opposed to sodium.
  • 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.
  • examples whose number is not suffixed by a letter i.e. examples 24, 25 and 26
  • the formulations were stable in all four of the storage regimes described above.
  • examples whose number is suffixed by letter the compositions were unstable under one or more of the storage conditions. Ratios of PAS to nonionic for the formulations are given in the table. None of the compositions were stable if electrolyte was omitted.

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Colloid Chemistry (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
EP97116919A 1992-09-09 1993-09-07 Verbesserung von Reinigern für harte Oberflächen Expired - Lifetime EP0829530B1 (de)

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
GB9302991 1993-02-15
GB939302991A GB9302991D0 (en) 1993-02-15 1993-02-15 Improvements to hard surface cleaners
EP94908829A EP0659205B1 (de) 1992-09-09 1993-09-07 Verbesserung von reinigern für harte oberflächen

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EP94908829A Division EP0659205B1 (de) 1992-09-09 1993-09-07 Verbesserung von reinigern für harte oberflächen
EP94908829.8 Division 1994-03-17

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EP0829530A1 true EP0829530A1 (de) 1998-03-18
EP0829530B1 EP0829530B1 (de) 2000-12-20

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EP94908829A Expired - Lifetime EP0659205B1 (de) 1992-09-09 1993-09-07 Verbesserung von reinigern für harte oberflächen

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JP (1) JP3516449B2 (de)
AU (1) AU679454B2 (de)
BR (1) BR9307025A (de)
CA (1) CA2144065C (de)
DE (2) DE69320355T2 (de)
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Cited By (8)

* Cited by examiner, † Cited by third party
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WO1999064553A1 (en) * 1998-06-09 1999-12-16 Unilever N.V. Hard surface cleaners
WO2000018868A1 (en) * 1998-09-25 2000-04-06 Unilever N.V. Detergent composition
WO2005049776A1 (en) * 2003-11-14 2005-06-02 The Procter & Gamble Company Liquid detergent composition comprising a solubilizing anionic surfactant
WO2017079958A1 (en) * 2015-11-13 2017-05-18 The Procter & Gamble Company Cleaning compositions containing a branched alkyl sulfate surfactant and a short-chain nonionic surfactant
WO2018223368A1 (en) * 2017-06-08 2018-12-13 The Procter & Gamble Company Non-homogeneous compositions
US10266791B2 (en) 2015-11-13 2019-04-23 The Procter & Gamble Company Detergent compositions
US10647944B2 (en) 2015-11-13 2020-05-12 The Procter & Gamble Company Cleaning compositions containing branched alkyl sulfate surfactant with little or no alkoxylated alkyl sulfate
US11975348B2 (en) 2019-12-16 2024-05-07 The Procter & Gamble Company Liquid dispensing system comprising an unitary dispensing nozzle

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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 (de) * 1995-03-13 1999-02-03 Unilever N.V. Waschmittelzusammensetzungen
AR006129A1 (es) * 1996-03-06 1999-08-11 Colgate Palmolive Co Una composicion detergente cristal liquida acidica y un proceso para remover escoria de jabon, costra de cal y suciedad grasosa de superficies durascon dicha composicion.
CO4770890A1 (es) * 1996-03-06 1999-04-30 Colgate Palmolive Co Composiciones cristalinas liquidas que contienen particulas de madera o abrasivo
EP0798372A3 (de) * 1996-03-29 1999-12-08 Unilever N.V. Waschmittelzusammensetzung
ATE209249T1 (de) * 1996-06-14 2001-12-15 Colgate Palmolive Co Flüssigkristallzusammensetzungen
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
AU2001262090A1 (en) * 2000-04-05 2001-10-23 Unilever Plc Solid dispersible abrasive compositions
IL162227A0 (en) 2001-12-21 2005-11-20 Rhodia Stable surfactant compositions for suspending components
EP1321514A1 (de) * 2001-12-21 2003-06-25 Maclean S.A. Flüssiges Reinigungsmittel mit Polyethylen-Abrasiv-Teilchen
GB2392166A (en) * 2002-08-22 2004-02-25 Reckitt Benckiser Inc Composition separable into two phases
ES2372292T3 (es) 2004-07-21 2012-01-18 Colgate-Palmolive Company Producto de limpieza corporal estructurado.
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
ES2407861T3 (es) 2006-12-15 2013-06-14 Colgate-Palmolive Company Composición de detergente líquida.
WO2008118381A1 (en) 2007-03-23 2008-10-02 Rhodia Inc. Structured surfactant compositions
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

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GB2160887A (en) * 1984-06-21 1986-01-02 Bristol Myers Co Hard surface cleaning composition
EP0362916A2 (de) * 1988-10-07 1990-04-11 Unilever N.V. Flüssige Waschmittelzusammensetzungen
EP0544492A1 (de) * 1991-11-26 1993-06-02 Unilever Plc Teilchenförmige Waschmittelzusammensetzungen

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GB2160887A (en) * 1984-06-21 1986-01-02 Bristol Myers Co Hard surface cleaning composition
EP0362916A2 (de) * 1988-10-07 1990-04-11 Unilever N.V. Flüssige Waschmittelzusammensetzungen
EP0544492A1 (de) * 1991-11-26 1993-06-02 Unilever Plc Teilchenförmige Waschmittelzusammensetzungen

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064553A1 (en) * 1998-06-09 1999-12-16 Unilever N.V. Hard surface cleaners
US6511953B1 (en) 1998-06-09 2003-01-28 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Hard surface cleaners
WO2000018868A1 (en) * 1998-09-25 2000-04-06 Unilever N.V. Detergent composition
WO2005049776A1 (en) * 2003-11-14 2005-06-02 The Procter & Gamble Company Liquid detergent composition comprising a solubilizing anionic surfactant
WO2017079958A1 (en) * 2015-11-13 2017-05-18 The Procter & Gamble Company Cleaning compositions containing a branched alkyl sulfate surfactant and a short-chain nonionic surfactant
US10266791B2 (en) 2015-11-13 2019-04-23 The Procter & Gamble Company Detergent compositions
US10647944B2 (en) 2015-11-13 2020-05-12 The Procter & Gamble Company Cleaning compositions containing branched alkyl sulfate surfactant with little or no alkoxylated alkyl sulfate
US10876072B2 (en) 2015-11-13 2020-12-29 The Procter & Gamble Company Cleaning compositions containing a branched alkyl sulfate surfactant and a short-chain nonionic surfactant
WO2018223368A1 (en) * 2017-06-08 2018-12-13 The Procter & Gamble Company Non-homogeneous compositions
US11975348B2 (en) 2019-12-16 2024-05-07 The Procter & Gamble Company Liquid dispensing system comprising an unitary dispensing nozzle

Also Published As

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WO1994005757A1 (en) 1994-03-17
EP0829530B1 (de) 2000-12-20
EP0659205A1 (de) 1995-06-28
DE69320355T2 (de) 1999-02-11
ES2154867T3 (es) 2001-04-16
CA2144065A1 (en) 1994-03-17
CA2144065C (en) 2003-11-11
ES2122243T3 (es) 1998-12-16
EP0659205B1 (de) 1998-08-12
DE69320355D1 (de) 1998-09-17
JPH08501120A (ja) 1996-02-06
BR9307025A (pt) 1999-06-29
AU4976193A (en) 1994-03-29
DE69329782T2 (de) 2001-05-03
DE69329782D1 (de) 2001-01-25
AU679454B2 (en) 1997-07-03
JP3516449B2 (ja) 2004-04-05

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