EP0359491A2 - Flüssige Reinigungsmittel - Google Patents
Flüssige Reinigungsmittel Download PDFInfo
- Publication number
- EP0359491A2 EP0359491A2 EP89309173A EP89309173A EP0359491A2 EP 0359491 A2 EP0359491 A2 EP 0359491A2 EP 89309173 A EP89309173 A EP 89309173A EP 89309173 A EP89309173 A EP 89309173A EP 0359491 A2 EP0359491 A2 EP 0359491A2
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- EP
- European Patent Office
- Prior art keywords
- liquid
- polymer
- composition according
- molecular weight
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
Definitions
- the present invention is concerned with liquid cleaning compositions of the kind comprising solid particles, such as detergency builders, bleaches, abrasives and mixtures thereof, dispersed in a liquid solvent phase, which phase comprises a liquid polyalkoxylated material.
- EP-A-266 199 (Unilever) claims and discloses a range of deflocculants for stabilising such suspensions. These deflocculants are believed to act by inhibiting aggregation of the individual particles so that they do not combine to form larger flocs which could sediment more rapidly. Some of the deflocculants described in the latter reference also inhibit network-formation by the particles in the longer term. This phenomenon eventually manifests itself in "setting" of the composition. That effect is sometimes referred to as "Ostwald ripening".
- Network formation by the particles is generally undesirable because it affects the rheology of the product during storage in a variable and somewhat unpredictable manner.
- the ultimate rheology should be determined solely at the time of manufacture, and governed by the chosen ingredients and manner of processing.
- Such network formation can occur when sufficiently small particles are present, less than 10 ⁇ particle diameter, but mainly when less than 1 ⁇ , especially less than 0.1 ⁇ . This may be achieved by use of particles of functional ingredients having a size distribution such that at least some are below the required threshold, for example by milling them such that the volume average particle size is below 10 ⁇ , as disclosed in patent specification EP-A-30,096 (ICI).
- the small particles may be added in the form of an auxiliary dispersant comprising a highly voluminous metal oxide or metalloid oxide, such as silica, for example as described in British patent specifications GB 1,205,711 (Unilever) and GB 1,270040 (Unilever). Best known amongst these small-particle silica-type materials are those sold under the trade name "Aerosil".
- the problems of network formation can be particularly acute when such auxiliary dispersants are used.
- a substantially non-aqueous liquid cleaning composition comprising solid particles dispersed in a liquid solvent phase, which phase comprises a liquid polyalkoxylated material, characterised in that the composition further comprises a network inhibiting amount of vinylpyrrolidone polymer, or a derivative thereof, said polymer having a viscosity average molecular weight of less than 30,000 and being dissolved in said liquid solvent phase.
- polymer molecules to be associated with the surfaces they must be in equilibrium with at least some of the polymer which is in solution in the liquid solvent phase.
- Higher molecular weight polymers are less weight efficient, requiring a higher total concentration for saturation of the particle surfaces.
- a viscosity average molecular weight of less than 30,000 is required, although the best results are obtained with viscosity average molecular weights no greater than 24,000, most preferably no greater than 15,000.
- the amount of polymer material required will depend in part on the other components of the composition, in particular on the type(s) and volume fraction of the dispersed solids. However, the molecular weight of the polymer material is of importance also. For consumer preferred flow behaviour, it is usually required that the viscosity of the product is no higher than 2.5 Pas, most preferably no greater than 1 Pas when measured at a shear rate of 21s ⁇ 1. Network inhibition by an effective amount of the polymer materials should prevent the product viscosity from rising to unacceptable levels during storage. If an insufficient amount of polymer material is used though, it can result in a rapid viscosity increase. If this is observed, more must be added to achieve the desired effect.
- the amount of polymer dissolved in the liquid solvent phase will itself unnecessarily raise the viscosity.
- the higher the molecular weight of a given amount of the polymer the greater the resultant viscosity.
- the upper molecular weight limit of 30,000 one finds that the amount of polymer at which the viscosity of the liquid solvent phase begins to be undesirable, is significantly reduced. In other words, the usable range of polymer level contracts as one exceeds the upper molecular weight limit.
- polyvinylpyrrolidones are readily commercially available, in the light of the present teaching, the man skilled in the art will now appreciate that derivatives thereof with minor structural variations may be substituted therefor with expectation of achieving the same effect, provided that any such derivative is soluble in the liquid solvent phase.
- such derivatives may be co-polymers containing minor amounts of other monomer units.
- Such derivatives may be any of those described in said GB 1,348,212, the text of which is incorporated herein by reference.
- polymer molecular weight there is a wide range of possible ways of expressing polymer molecular weight, varying according to the particular assay used and how the average is calculated (e.g. number average, weight average etc.).
- the term 'viscosity average molecular weight' when used in respect of polyvinylpyrrolidones (or soluble derivatives thereof) will readily be understood by those skilled in the art and is widely used by manufacturers to characterise such polymer products.
- the liquid solvent phase must contain at least some of a liquid polyalkoxylated material and must be such that the polymer material is soluble therein, although it is permissible for a portion of the polymer material to be present as dispersed solid.
- the polyalkoxylated liquids are chosen in particular for their ability to dissolve the polymer material although co-solvents may also be present, provided that the polymer is soluble in the resultant mixture.
- a polyalkoxylated material is any which has a molecule which contains two or more alkoxylene groups, whether the same or different, bonded directly to one another. All references to liquids refer to materials which are liquid at 25°C at atmospheric pressure.
- liquid solvent phase it is particularly preferred for a major amount, e.g. 50% by weight or greater, of the liquid solvent phase to consist of one or more liquid polyalkoxylated materials.
- liquid polyalkoxylated nonionic surfactants such as are disclosed in our aforementioned EP-A-266,199, relevant parts of which are incorporated herein by reference.
- these will be chosen from liquids which are the condensation products of fatty alcohols with lower (C1 ⁇ 4) alkylene oxides, especially ethylene oxide and/or propylene oxides.
- suitable polyalkoxylated liquids are poly-lower (C1 ⁇ 4) alkylene glycols, especially liquid polyethylene glycols and liquid polypropylene glycols.
- the polyethylene glycols may be chosen from those which are liquid and have molecular weights in the range of from 200 to 600.
- alkylene glycol mono- or di-alkyl ethers are also suitable.
- Such mono-alkyl ethers are disclosed in British patent specification GB 2,169,613 (Colgate).
- Typical such di-alkyl ethers are diethylene glycol di-ethyl or di-butyl ether (di-ethyl and di-butyl Carbitol, respectively), most preferably di-ethylene glycol dimethyl ether (diglyme).
- the polymer material is insoluble in the latter liquid but when the diglyme is mixed with a polyalkoxylated nonionic surfactant liquid or a liquid polyalkylene glycol, especially a polyethylene glycol, then the polymer can be dissolved.
- the polymer can be dissolved in mixtures of diglyme and polyethylene glycol, molecular weight 200, in weight ratios from at least 1:3 to 3:1.
- non-polyalkoxylated co-solvents are also included, these may be selected from any co-solvent which is miscible with the liquid polyalkoxylated materials yet does not cause insolubility of the polymer material to the extent that the network inhibition effect is lost. Suitable co-solvents are disclosed in said EP-A-266,199.
- compositions according to the present invention are liquid cleaning products. They may be formulated in a very wide range of specific forms, according to the intended use. They may be formulated as cleaners for hard surfaces (with or without abrasive) or as agents for warewashing (cleaning of dishes, cutlery etc) either by hand or mechanical means, as well as in the form of specialised cleaning products, such as for surgical apparatus or artificial dentures. They may also be formulated as agents for washing and/or conditioning of fabrics. When additional ingredients are selected to adapt the basic formulation for the intended purpose, these will be chosen to be compatible therewith, ie. so as not to destroy the required network inhibiting effect.
- compositions may be formulated as main cleaning agents, or pre-treatment products to be sprayed or wiped on prior to removal, eg. by wiping off or as part of a main cleaning operation.
- compositions may also be the main cleaning agent or a pre-treatment product, eg. applied by spray or used for soaking utensils in an aqueous solution and/or suspension thereof.
- compositions may for example, be of the kind used for pre-treatment of fabrics (eg. for pot stain removal) with the composition neat or diluted, before they are rinsed and/or subjected to a main wash.
- the compositions may also be formulated as main wash products, being dissolved and/or dispersed in the water with which the fabrics are contacted. In that case, the composition may be the sole cleaning agent or an adjunct to another wash product.
- the term 'cleaning product' also embraces compositions of the kind used as fabric conditioners (including fabric softeners) which are only added in the rinse water (sometimes referred to as 'rinse conditioners').
- compositions will contain at least one agent which promotes the cleaning and/or conditioning of the article(s) in question, selected according to the intended application.
- this agent will be selected from surfactants, enzymes, bleaches, microbiocides, (for fabrics) fabric softening agents and (in the case of hard surface cleaning) abrasives.
- surfactants for fabrics
- bleaches for fabrics
- microbiocides for fabrics
- fabric softening agents for fabrics
- abrasives in the case of hard surface cleaning
- compositions will be substantially free from agents which are detrimental to the article(s) to be treated.
- they will be substantially free from pigments or dyes, although of course they may contain small amounts of those dyes (colourants) of the kind often used to impart a pleasing colour to liquid cleaning products, as well as fluorescers, bluing agents and the like.
- solids are to be construed as referring to materials in the solid phase which are added to the composition and are dispersed therein in solid form, those solids which dissolve in the solvent and those in the liquid phase which solidify (undergo a phase change) in the composition, wherein they are then dispersed.
- surfactants are solids, they will usually be dissolved or dispersed in the liquid solvent phase. Where they are liquids, they will usually constitute all or part of the liquid solvent phase. However, in some cases the surfactants may undergo a phase change in the composition. In general, they may be chosen from any of the classes, sub-classes and specific materials described in 'Surface Active Agents' Vol. I, by Schwartz & Perry, Interscience 1949 and 'Surface Active Agents' Vol.
- Nonionic detergent surfactants both liquid and solid, are well-known in the art. They normally consist of a water-solubilizing polyalkoxylene or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 to 12 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof), preferably having from 8 to 20 carbon atoms, monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylenes.
- alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms
- dialkylphenols in which each alkyl group contains from 6 to 12 carbon atoms
- primary, secondary or tertiary aliphatic alcohols or alkyl-capped derivative
- fatty acid mono- and dialkanolamides in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms.
- the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms.
- the polyalkoxylene moiety preferably consists of from 2 to 20 groups of ethylene oxide or of ethylene oxide and propylene oxide groups.
- European patent specification EP-A-225,654 Unilever
- ethoxylated nonionics which are the condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with from 3 to 11 moles of ethylene oxide.
- condensation products of C11 ⁇ 13 alcohols with (say) 3 or 7 moles of ethylene oxide may be used as the sole nonionic surfactants or in combination with those of the described in the last-mentioned European specification, especially as all or part of the liquid solvent phase.
- Suitable nonionics comprise the alkyl polysaccharides (polyglycosides/oligosaccharides) such as described in any of specifications US 3,640,998; US 3,346,558; US 4,223,129; EP-A-92,355; EP-A-99,183; EP-A-70,074, '75, '76, '77; EP-A-75,994, '95, '96.
- nonionic detergent surfactants may also be used, provided the mixture is liquid at room temperature.
- Mixtures of nonionic detergent surfactants with other detergent surfactants such as anionic, cationic or ampholytic detergent surfactants and soaps may also be used. If such mixtures are used, the mixture must be liquid at room temperature.
- Suitable anionic detergent surfactants are alkali metal, ammonium or alkylolamaine salts of alkylbenzene sulphonates having from 10 to 18 carbon atoms in the alkyl group, alkyl and alkylether sulphates having from 10 to 24 carbon atoms in the alkyl group, the alkylether sulphates having from 1 to 5 ethylene oxide groups, olefin sulphonates prepared by sulphonation of C10-C24 alpha-olefins and subsequent neutralization and hydrolysis of the sulphonation reaction product.
- surfactants which may be used include alkali metal soaps of a fatty acid, preferably one containing 12 to 18 carbon atoms.
- Typical such acids are oleic acid, ricinoleic acid and fatty acids derived from caster oil, rapeseed oil, groundnut oil, coconut oil, palmkernal oil or mixtures thereof.
- the sodium or potassium soaps of these acids can be used.
- soaps can act as detergency builders or fabric conditioners, other examples of which will be described in more detail hereinbelow. It can also be remarked that the oils mentioned in this paragraph may themselves constitute part of the solvent, whilst the corresponding low molecular weight fatty acids (triglycerides) can be dispersed as solids or function as structurants.
- cationic detergent surfactants are aliphatic or aromatic alkyl-di(alkyl) ammonium halides and examples of soaps are the alkali metal salts of C12-C24 fatty acids.
- Ampholytic detergent surfactants are e.g. the sulphobetaines. Combinations of surfactants from within the same, or from different classes may be employed to advantage for optimising structuring and/or cleaning performance.
- compositions according to the present invention preferably also contain one or more other functional ingredients, for example selected from other detergency builders, bleaches or bleach systems, and (for hard surface cleaners) abrasives.
- Detergency builders are those materials which counteract the effects of calcium, or other ion, water hardness, either by precipitation or by an ion sequestering effect. They comprise both inorganic and organic builders. They may also be sub-divided into the phosphorus-containing and non-phosphorus types.
- the inorganic builders comprise the various phosphate-, carbonate-, silicate-, borate- and aliminosilicate-type materials, particularly the alkali-metal salt forms. Mixtures of these may also be used.
- Examples of phosphorus-containing inorganic builders when present include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
- Specific examples of inorganic phosphate builders include sodium and potassium phosphates and hexametaphosphates, as well as sodium and potassium tripolyphosphate.
- non-phosphorus-containing inorganic builders when present, include water-soluble alkali metal carbonates, bicarbonates, borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates.
- specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
- the aluminosilicates are an especially preferred class of non-phosphorus inorganic builders. These for example are crystalline or amorphous materials having the general formula: Na Z (AlO2) Z )(SiO2) Y x H2O wherein Z and Y are integers of at least 6, the molar ratio of Z to Y is in the range from 1.0 to 0.5, and x is an integer from 6 to 189 such that the moisture content is from about 4% to about 20% by weight (termed herein, 'partially hydrated'). This water content provides the best rheological properties in the liquid. Above this level (e.g. from about 19% to about 28% by weight water content), the water level can lead to network formation. Below this level (e.g.
- aluminosilicate preferably has a particle size of from 0.1 to 100 microns, ideally between 0.1 to 10 microns and a calcium ion exchange capacity of at least 200 mg calcium carbonate/g.
- organic builders include the alkali metal, ammonium and substituted ammonium, citrates, succinates, malonates, fatty acid sulphonates, carboxymethoxy succinates, ammonium polyacetates, carboxylates, polycarboxylates, aminopolycarboxylates, polyacetyl carboxylates and polyhydroxsulphonates.
- Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid.
- organic phosphonate type sequestering agents such as those sold by Monsanto under the tradename of the Dequest range and alkanehydroxy phosphonates.
- suitable organic builders include the higher molecular weight polymers and co-polymers known to have builder properties, for example appropriate polyacrylic acid, polymaleic acid and polyacrylic/polymaleic acid co-polymers and their salts, such as those sold by BASF under the Sokalan Trade Mark.
- Suitable bleaches include the halogen, particularly chlorine bleaches such as are provided in the form of alkalimetal hypohalites, eg. hypochlorites.
- the oxygen bleaches are preferred, for example in the form of an inorganic persalt, preferably with an precursor, or as a peroxy acid compound.
- the precursor makes the bleaching more effective at lower temperatures, ie. in the range from ambient temperature to about 60°C, so that such bleach systems are commonly known as low-temperature bleach systems and are well known in the art.
- the inorganic persalt such as sodium perborate, both the monohydrate and the tetrahydrate, acts to release active oxygen in solution, and the precursor is usually an organic compound having one or more reactive acyl residues, which cause the formation of peracids, the latter providing for a more effective bleaching action at lower temperatures than the peroxybleach compound alone.
- the ratio by weight of the peroxybleach compound to the precursor is from about 15:1 to about 2:1, preferably from about 10 1 to about 3.5:1.
- the amount of the bleach system ie. peroxybleach compound and precursor
- the amount of the bleach system may be varied between 5% and about 35% by weight of the total liquid, it is preferred to use from about 6% to about 30% of the ingredients forming the bleach system.
- the preferred level of the peroxybleach compound in the composition is between about 5.5% and about 27% by weight, while the preferred level of the precursor is between about 0.5% and about 40%, most preferably between about 1% and about 5% by weight.
- Suitable peroxybleach compounds are alkalimetal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.
- Cationic peracid bleach precursors such as those described in United States patent specifications US 4,751,015 and US 4,397,757 (Lever Bros.) can be included.
- compositions contain abrasives for hard surface cleaning (ie. is a liquid abrasive cleaner), these will inevitably be incorporated as particulate solids.
- abrasives for hard surface cleaning ie. is a liquid abrasive cleaner
- these will inevitably be incorporated as particulate solids.
- They may be those of the kind which are water insoluble, for example calcite. Suitable materials of this kind are disclosed in the patent specifications EP-A-50,887; EP-A-80,221; EP-A-140,452; EP-A-214,540 and EP 9,942 (all Unilever) which relate to such abrasives when suspended in aqueous media. Water soluble abrasives may also be used.
- compositions which contain finely divided silica or other finely divided metal or metaloid oxides as referred to in British patent specifications GB 1,205,711 and GB 1,270,040
- the compositions may alternatively or additionally contain other auxiliary dispersants such as fine particulate chain-structure clay as described in European specification EP-A-34,387 (Procter). They may also contain one or more of the deflocculants disclosed in EP-A-266,199, for example dodecyl benzene sulphonic acid (added in the free acid form) or lecithin.
- compositions of the invention optionally may also contain one or more minor ingredients such as fabric conditioning agents, enzymes, perfumes (including deoperfumes), micro-biocides, colouring agents, viscosity modifiers, fluorescers, soil-suspending agents (anti-redeposition agents), corrosion inhibitors, enzyme stabilizing agents, and lather depressants.
- minor ingredients such as fabric conditioning agents, enzymes, perfumes (including deoperfumes), micro-biocides, colouring agents, viscosity modifiers, fluorescers, soil-suspending agents (anti-redeposition agents), corrosion inhibitors, enzyme stabilizing agents, and lather depressants.
- compositions are substantially non-aqueous, ie. they contain little or no free water, preferably no more than 5%, preferably less than 3%, especially less than 1% by weight of the total composition. It has been found that the higher the water content, the more likely it is for the viscosity to be too high, or even for setting to occur.
- non-aqueous liquid Since the objective of a non-aqueous liquid will generally be to enable the formulator to avoid the negative influence of water on the components, e.g. causing incompatibility of functional ingredients, it is clearly necessary to avoid the accidential or deliberate addition of water to the product at any stage in its life. For this reason, special precautions are necessary in manufacturing procedures and pack designs for use by the consumer.
- all raw materials should be dry and (in the case of hydratable salts) in a low hydration state, eg. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
- a low hydration state eg. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
- the dry, substantially anhydrous solids are blended with the solvent in a dry vessel. In order to minimise the rate of sedimentation of the solids, this blend is passed through a grinding mill or a combination of mills, eg.
- a colloid mill to achieve a particle size of 0.1 to 100 microns, preferably 0.5 to 50 microns, ideally 1 to 10 microns.
- a preferred combination of such mills is a colloid mill followed by a horizontal ball mill since these can be operated under the conditions required to provide a narrow size distribution in the final product.
- particulate material already having the desired particle size need not be subjected to this procedure and if desired, can be incorporated during a later stage of processing.
- model systems were formulated with Aerosil 380 finely divided silica auxiliary dispersant in liquid nonionic as Dobanol 91/6T, a C9 ⁇ 11 fatty alcohol alkoxylated with an average of 6 moles of ethylene oxide per molecule (ex Shell).
- Dobanol 91/6T a C9 ⁇ 11 fatty alcohol alkoxylated with an average of 6 moles of ethylene oxide per molecule
- zeolite was included as an additional dispersed solid.
- Polymer materials were polyvinyl pyrrolidone, viscosity average molecular weights 2,500 (PVP 2.5K) and 10,000 (PVP 10K).
- composition 1 2 3 4 5 6 7 Aerosil 1.25 1.25 1.25 1.25 2.5 2.5 2.5 2.5 Zeolite 12.0 12.0 12.0 12.0 - - - PVP 2.5K - 0.5 - - - - PVP 10K - - 0.2 1.0 0.1 0.5 1.0 Nonionic balance
- composition 1 the polymer was omitted, whilst in composition 5, the polymer was found to be insufficient and particle aggregation appeared to be progressive leading to thickening, increasing on storage.
- compositions 2, 3, 6 and 7 lack of particle aggregation was evident by visual inspection but composition 4 showed some evidence of a viscosity increase due to the use of too much polymer.
- Example 2 Fully formulated composition wt % Dobanol 91/6T (1) 37.35 Glycerol tri-acetate 5.0 Aerosil 380 (2) 1.25 PVP (3) 1.0 STP (4) 30.0 Sodium carbonate 0aq 4.0 Na Perborate monohydrate 15.0 EDTA (5) 0.15 SCMC (6) 1.0 TAED (7) 4.0 Dequest 2041 0.1 Fluorescer (Tinopal DMS-X) 0.3 Tylose MH20 0.5 Silicone DB100 0.25 Savinase 8.0 SL 0.6 (1) (2) (3) : as Example 1. (4) Sodium tripolyphosphate (5) Ethylene diamine tetraacetic acid (6) Sodium carboxymethylcellulose (7) Tetraacetyl ethylenediamine
- a 51% by weight dispersion of zeolite (having a water content of 21.5% by weight and a particle size of approximately 4 microns) in Dobanol 91-6T was prepared in a Silverson mixer. Equal weights (15g) of this dispersion and solutions of PVP (having a molecular weight of 2.5K, 10K, 24K and 40K) in Dobanol 91-6T were mixed overnight on a bottle roller to give a range of samples containing 25.5% by weight zeolite and from 0 to 5% PVP.
- the sediment volume results after 40 days were as follows. Molecular Weight PVP Concentration Sediment Volume (%) (%) 2,500 0.05 44 0.1 44 0.25 42 0.5 42 1.0 42 2.5 41 5.0 41 10,000 0.05 42 0.1 42 0.25 39 0.5 31 1.0 30 2.5 30 5.0 30 24,000 0.05 43 0.1 41 0.25 29 0.5 30 1.0 29 2.5 29 5.0 30 40,000 0.05 43 0.1 36 0.25 30 0.5 30 1.0 29 2.5 30 5.0 32
- the samples using PVP with a molecular weight of 40K were measurably more viscous than the other samples.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8821282 | 1988-09-12 | ||
GB888821282A GB8821282D0 (en) | 1988-09-12 | 1988-09-12 | Liquid cleaning products |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0359491A2 true EP0359491A2 (de) | 1990-03-21 |
EP0359491A3 EP0359491A3 (de) | 1990-09-05 |
Family
ID=10643406
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890309173 Withdrawn EP0359491A3 (de) | 1988-09-12 | 1989-09-11 | Flüssige Reinigungsmittel |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0359491A3 (de) |
JP (1) | JPH02120400A (de) |
AU (1) | AU4125389A (de) |
BR (1) | BR8904563A (de) |
GB (1) | GB8821282D0 (de) |
ZA (1) | ZA896939B (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0576777A1 (de) * | 1992-06-29 | 1994-01-05 | The Procter & Gamble Company | Polyvinylpyrrolidon und schmutzabweisendes Polymer auf Basis von Polyterephthalate enthaltende konzentrierte wässrig-flüssige Waschmittelzusammensetzungen |
EP0576778A1 (de) * | 1992-07-03 | 1994-01-05 | The Procter & Gamble Company | Konzentriertes, wässeriges, flüssiges Reinigungsmittel |
WO1994001524A1 (en) * | 1992-07-08 | 1994-01-20 | Unilever N.V. | Liquid cleaning products |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8821280D0 (en) * | 1988-09-12 | 1988-10-12 | Unilever Plc | Thickened liquids |
KR20180041812A (ko) * | 2016-10-14 | 2018-04-25 | 오씨아이 주식회사 | 액상 표백제 조성물 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0017149A1 (de) * | 1979-03-31 | 1980-10-15 | Henkel Kommanditgesellschaft auf Aktien | Verwendung eines flüssigen Mittels zur Reinigung harter Oberflächen |
EP0256343A1 (de) * | 1986-08-12 | 1988-02-24 | MIRA LANZA S.p.a. | Aus zwei getrennten Hauptzusammensetzungen bestehendes, nicht wässeriges, flüssiges Detergensprodukt |
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1988
- 1988-09-12 GB GB888821282A patent/GB8821282D0/en active Pending
-
1989
- 1989-09-11 AU AU41253/89A patent/AU4125389A/en not_active Withdrawn
- 1989-09-11 BR BR898904563A patent/BR8904563A/pt not_active Application Discontinuation
- 1989-09-11 EP EP19890309173 patent/EP0359491A3/de not_active Withdrawn
- 1989-09-12 JP JP1236799A patent/JPH02120400A/ja active Pending
- 1989-09-12 ZA ZA896939A patent/ZA896939B/xx unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0017149A1 (de) * | 1979-03-31 | 1980-10-15 | Henkel Kommanditgesellschaft auf Aktien | Verwendung eines flüssigen Mittels zur Reinigung harter Oberflächen |
EP0256343A1 (de) * | 1986-08-12 | 1988-02-24 | MIRA LANZA S.p.a. | Aus zwei getrennten Hauptzusammensetzungen bestehendes, nicht wässeriges, flüssiges Detergensprodukt |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0576777A1 (de) * | 1992-06-29 | 1994-01-05 | The Procter & Gamble Company | Polyvinylpyrrolidon und schmutzabweisendes Polymer auf Basis von Polyterephthalate enthaltende konzentrierte wässrig-flüssige Waschmittelzusammensetzungen |
EP0576778A1 (de) * | 1992-07-03 | 1994-01-05 | The Procter & Gamble Company | Konzentriertes, wässeriges, flüssiges Reinigungsmittel |
WO1994001524A1 (en) * | 1992-07-08 | 1994-01-20 | Unilever N.V. | Liquid cleaning products |
Also Published As
Publication number | Publication date |
---|---|
GB8821282D0 (en) | 1988-10-12 |
EP0359491A3 (de) | 1990-09-05 |
AU4125389A (en) | 1990-03-15 |
JPH02120400A (ja) | 1990-05-08 |
ZA896939B (en) | 1991-05-29 |
BR8904563A (pt) | 1990-04-24 |
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