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EP0659205B1 - Ameliorations apportees a des produits de nettoyage de surfaces dures - Google Patents

Ameliorations apportees a des produits de nettoyage de surfaces dures Download PDF

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Publication number
EP0659205B1
EP0659205B1 EP94908829A EP94908829A EP0659205B1 EP 0659205 B1 EP0659205 B1 EP 0659205B1 EP 94908829 A EP94908829 A EP 94908829A EP 94908829 A EP94908829 A EP 94908829A EP 0659205 B1 EP0659205 B1 EP 0659205B1
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EP
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Prior art keywords
composition according
surfactant
electrolyte
mixtures
product
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EP94908829A
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German (de)
English (en)
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EP0659205A1 (fr
Inventor
Alexander Allan
Alan John 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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP97116919A priority Critical patent/EP0829530B1/fr
Publication of EP0659205A1 publication Critical patent/EP0659205A1/fr
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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.
  • GB-A-2108996 (Bristol Myers, 1981) discloses liquid abrasive cleaners (LAC's) in which the surfactant system comprises, as anionic detergent, alkyl benzene sulphonate (ABS).
  • LAC's liquid abrasive cleaners
  • ABS alkyl benzene sulphonate
  • the nonionic detergents are present at low levels with a typical ABS:nonionic ratio of around 3.5:1.
  • EP-A-0362916 (Unilever, 1988) discloses LAC's in which the surfactant system is again ABS in combination with lesser levels of nonionics.
  • 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
  • EP-A-0086614 discloses non-abrasive fluid detergent compositions which comprise effective levels of builder. Builders must be soluble in water whereas the particulate abrasives used in LAC's are generally insoluble. However, if an excess of builder is present then solid builder remains present in a saturated solution of electrolyte. Compositions are disclosed which comprise both ABS and PAS together with a nonionic surfactant, but there are no examples of compositions containing a suspended abrasive.
  • Non-suspending systems comprising 1-1.2% PAS, 0.1-1.5% of a mixed non-ionic system and low molecular weight nonthickening 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&C: 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 electrolytefree, 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.
  • 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, 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 2-25%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 1-20% wt dissolved multivalent electrolyte on product, CHARACTERISED IN THAT, said particulate phase comprises calcium carbonate, dolomite, sodium hydrogen carbonate, potassium sulphate, alumina, hydrated alumina, feldspar, talc or silica and in that the ethoxylated alcohol nonionic surfactant (ii) has 1-5 moles of ethoxylation per mole of
  • 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 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 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 ethoxylated alcohols are 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.
  • 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.
  • 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 selected from calcium carbonate, mixtures of calcium and magnesium carbonates, sodium hydrogen carbonate, potassium sulphate, alumina, hydrated alumina, feldspar, talc and 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.
  • 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.
  • Calcite calcium carbonate
  • dolomite a mixture of calcium and magnesium carbonate
  • 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.
  • 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.
  • 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.
  • 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:
  • Figure 4 shows the lamellar regions for formulations containing PAS with a 3.0 EO nonionic surfactant at varying di-valent electrolyte levels
  • 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.
  • 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 Dobanol23-6.5 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 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.
  • Example 22 and the towerying figure 4 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 process routes used to obtain the compositions of example 22 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 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.
  • 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.
  • non-ionic ethylene oxide chain surfactant such as Synperonic A3: 3EO, as in example 25 and example 26
  • electrolyte salts comprising multivalent anionic species such as carbonates
  • PAS irrespective of the type of PAS
  • the level of electrolyte need not exceed the total surfactant level when shorter chain ethylene oxide non-ionics are used.
  • nonionic, surfactants such as Dobanol 23-6.5EO are used, (see Examples 24C and 25A).

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  • Polishing Bodies And Polishing Tools (AREA)

Claims (15)

  1. Composition liquide, structurée, stable, de nettoyage de surfaces dures, comprenant une phase aqueuse continue, une phase lamellaire dispersée et 1-80% pds par rapport au produit d'une phase particulaire dispersée en suspension, ledit produit comprenant 2-25% pds par rapport à la phase aqueuse d'agent tensio-actif, ledit agent tensio-actif comprenant un sulfate d'alcool primaire (i) et un agent tensio-actif non ionique de type alcool éthoxylé (ii), dans laquelle le rapport pondéral (i)/(ii) est compris dans l'intervalle allant de 5/1 à 0,45/1, ladite composition comprenant en outre 1-20% pds d'électrolyte multivalent dissous par rapport au produit, caractérisé en ce que ladite phase particulaire comprend du carbonate de calcium, de la dolomite, de l'hydrogénocarbonate de sodium, du sulfate de potassium, de l'alumine, de l'alumine hydratée, du feldspath, du talc ou de la silice, et en ce que l'agent tensio-actif non ionique de type alcool éthoxylé (ii) a 1-5 moles d'éthoxylation par mole d'agent tensio-actif.
  2. Composition selon la revendication 1, dans laquelle le rapport de (i)/(ii) est de 2/1 à 0,6/1.
  3. Composition selon la revendication 2, dans laquelle le rapport de (i)/(ii) est de 1,5/1 à 0,75/1.
  4. Composition selon la revendication 1, dans laquelle le sulfate d'alcool primaire comprend un mélange de substances de formule générale : ROSO3X dans laquelle R représente un groupe alkyle primaire en C8-18 et X représente un cation solubilisant.
  5. Composition selon la revendication 1, dans laquelle l'agent tensio-actif non ionique préféré (ii) est choisi dans l'ensemble comprenant des alcools éthoxylés de formule générale : R-(OCH2CH2)m-OH dans laquelle R représente un groupe alkyle en C8-18 linéaire ou ramifié et le degré moyen d'éthoxylation m est de 1-14.
  6. Composition selon la revendication 5, dans laquelle m vaut 1-10.
  7. Composition selon la revendication 6, dans laquelle m vaut 5-10.
  8. Composition selon la revendication 1, dans laquelle l'électrolyte comprend 25-100 % en mole d'anions multivalents par rapport à la quantité totale d'anions.
  9. Composition selon la revendication 11, dans laquelle l'anion multivalent est choisi dans l'ensemble comprenant des carbonates, des citrates, des sulfates et des mélanges de ceux-ci.
  10. Composition selon la revendication 1, dans laquelle la phase particulaire dispersée en suspension comprend un abrasif ayant une taille de particule moyenne comprise dans l'intervalle allant de 0,5 à 200 microns.
  11. Composition selon la revendication 1, dans laquelle la phase particulaire dispersée en suspension est présente à une concentration de 20-40%.
  12. Composition selon la revendication 1, dans laquelle la phase particulaire comprend une ou plusieurs substances choisies parmi la calcite, le bicarbonate et des mélanges de ceux-ci, ladite composition comprenant :
    a) 2-15% de sulfate d'alcool primaire comprenant un mélange de substances de formule générale : ROSO3X dans laquelle R représente un groupe alkyle primaire en C8-18 et X représente un cation solubilisant choisi dans l'ensemble comprenant le sodium, le magnésium, le potassium, l'ammonium et des mélanges de ceux-ci,
    b) 2-15% d'alcools éthoxylés de formule générale : R1-(OCH2CH2)m-OH dans laquelle R1 représente un groupe alkyle en C8-18 linéaire ou ramifié et le degré moyen d'éthoxylation m est compris entre 1 et 5, et dans laquelle le rapport a/b est compris dans l'intervalle 1/2 à 2/1, et
    c) 1-20% en poids d'électrolyte par rapport à la phase aqueuse, ledit électrolyte comprenant 25-100% en mole d'anions multivalents choisis dans l'ensemble comprenant des carbonates, des citrates, des sulfates et des mélanges de ceux-ci, par rapport à la quantité totale d'anions.
  13. Composition selon la revendication 1, qui est stable lorsqu'on la stocke sans agitation pendant 12 semaines à une température de 4°Celsius dans une boite froide thermostatée, et pendant 12 semaines à une température de 37°Celsius dans un four thermostaté, et pendant dix cycles de température, chacun d'une durée de vingt-quatre heures et consistant chacun en huit heures à -5 degrés Celsius suivies de seize heures à 25 degrés Celsius.
  14. Composition selon la revendication 1, comprenant en outre 0,01-2% d'un polymère hydrophile ayant une masse moléculaire moyenne supérieure à 500 000 Dalton.
  15. Composition selon la revendication 14, dans laquelle le polymère est choisi dans l'ensemble comprenant des polyacrylates réticulés, des polyméthacrylates réticulés, et des mélanges de ceux-ci.
EP94908829A 1992-09-09 1993-09-07 Ameliorations apportees a des produits de nettoyage de surfaces dures Expired - Lifetime EP0659205B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97116919A EP0829530B1 (fr) 1992-09-09 1993-09-07 Améliorations apportées à des produits de nettoyage de surfaces dures

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB929219042A GB9219042D0 (en) 1992-09-09 1992-09-09 Improvements to hard surface cleaners
GB9219042 1992-09-09
GB939302991A GB9302991D0 (en) 1993-02-15 1993-02-15 Improvements to hard surface cleaners
GB9302991 1993-02-15
PCT/GB1993/001892 WO1994005757A1 (fr) 1992-09-09 1993-09-07 Ameliorations apportees a des produits de nettoyage de surfaces dures

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP97116919A Division EP0829530B1 (fr) 1992-09-09 1993-09-07 Améliorations apportées à des produits de nettoyage de surfaces dures

Publications (2)

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EP0659205A1 EP0659205A1 (fr) 1995-06-28
EP0659205B1 true EP0659205B1 (fr) 1998-08-12

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EP94908829A Expired - Lifetime EP0659205B1 (fr) 1992-09-09 1993-09-07 Ameliorations apportees a des produits de nettoyage de surfaces dures
EP97116919A Expired - Lifetime EP0829530B1 (fr) 1992-09-09 1993-09-07 Améliorations apportées à des produits de nettoyage de surfaces dures

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EP (2) EP0659205B1 (fr)
JP (1) JP3516449B2 (fr)
AU (1) AU679454B2 (fr)
BR (1) BR9307025A (fr)
CA (1) CA2144065C (fr)
DE (2) DE69329782T2 (fr)
ES (2) ES2122243T3 (fr)
WO (1) WO1994005757A1 (fr)

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US8394361B1 (en) 2001-12-21 2013-03-12 Rhodia Operations Stable surfactant compositions for suspending components

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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 (fr) * 1995-03-13 1999-02-03 Unilever N.V. Compositions détergentes
CO4770890A1 (es) * 1996-03-06 1999-04-30 Colgate Palmolive Co Composiciones cristalinas liquidas que contienen particulas de madera o abrasivo
ES2174243T3 (es) * 1996-03-06 2002-11-01 Colgate Palmolive Co Composiciones detergentes de cristal liquido.
EP0798372A3 (fr) * 1996-03-29 1999-12-08 Unilever N.V. Composition détergente
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
US6511953B1 (en) 1998-06-09 2003-01-28 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Hard surface cleaners
WO2000018868A1 (fr) * 1998-09-25 2000-04-06 Unilever N.V. Composition detergente
AU2001262090A1 (en) * 2000-04-05 2001-10-23 Unilever Plc 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
ATE521332T1 (de) 2004-07-21 2011-09-15 Colgate Palmolive Co Strukturierte körperwaschlotion
CA2605432C (fr) 2005-04-21 2011-04-12 Colgate-Palmolive Company Composition detergente liquide pour perles en suspension
GB2434586A (en) * 2006-01-24 2007-08-01 Henkel Uk Structured liquid abrasive composition
PT2308957E (pt) 2006-12-15 2013-05-21 Colgate Palmolive Co Composição detergente líquida
BRPI0809314A2 (pt) 2007-03-23 2014-10-14 Rhodia Composições de tensoativo estruturado
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
EP3374481A1 (fr) 2015-11-13 2018-09-19 The Procter and Gamble Company Compositions détergentes
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 (fr) 2015-11-13 2017-05-18 The Procter & Gamble Company Composition de nettoyage contenant un tensioactif de type sulfate d'alkyle ramifié avec peu ou pas de sulfate d'alkyle alcoxylé
CA3065556C (fr) * 2017-06-08 2022-11-08 The Procter & Gamble Company Compositions non homogenes
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

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EP0125711A1 (fr) * 1983-04-19 1984-11-21 Unilever N.V. Composition de nettoyage à tout usage

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Publication number Priority date Publication date Assignee Title
US8394361B1 (en) 2001-12-21 2013-03-12 Rhodia Operations Stable surfactant compositions for suspending components

Also Published As

Publication number Publication date
DE69320355D1 (de) 1998-09-17
DE69329782D1 (de) 2001-01-25
ES2154867T3 (es) 2001-04-16
DE69329782T2 (de) 2001-05-03
WO1994005757A1 (fr) 1994-03-17
EP0659205A1 (fr) 1995-06-28
CA2144065A1 (fr) 1994-03-17
EP0829530B1 (fr) 2000-12-20
ES2122243T3 (es) 1998-12-16
JP3516449B2 (ja) 2004-04-05
EP0829530A1 (fr) 1998-03-18
CA2144065C (fr) 2003-11-11
BR9307025A (pt) 1999-06-29
JPH08501120A (ja) 1996-02-06
DE69320355T2 (de) 1999-02-11
AU4976193A (en) 1994-03-29
AU679454B2 (en) 1997-07-03

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