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EP0521863B1 - Produits de nettoyage liquides - Google Patents

Produits de nettoyage liquides Download PDF

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Publication number
EP0521863B1
EP0521863B1 EP91904091A EP91904091A EP0521863B1 EP 0521863 B1 EP0521863 B1 EP 0521863B1 EP 91904091 A EP91904091 A EP 91904091A EP 91904091 A EP91904091 A EP 91904091A EP 0521863 B1 EP0521863 B1 EP 0521863B1
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EP
European Patent Office
Prior art keywords
nonionic
detergency
weight
average
groups
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.)
Expired - Lifetime
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EP91904091A
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German (de)
English (en)
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EP0521863A1 (fr
Inventor
Cornelis Bernard Jellicoe Drive Donker
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Publication of EP0521863A1 publication Critical patent/EP0521863A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to non-aqueous liquid cleaning products, especially non-aqueous liquid detergent compositions containing particulate solid materials dispersed in a liquid phase.
  • Non-aqueous liquids are those containing little or no water.
  • Non-aqueous liquid cleaning products often comprise a liquid phase comprising a nonionic surfactant material.
  • these nonionic surfactant materials have as one of their main functions to clean objects such as fabrics to be washed or hard surfaces.
  • These detergency nonionics often comprise a fatty alcohol chain comprising from 9 to 15 carbon atoms, said chain being alkoxylated with on average more than 5 alkoxy groups such as ethoxy or propoxy groups or mixtures thereof.
  • a problem in using detergency nonionics in non-aqueous liquid detergent compositions is that they often generate high foam levels, specifically in the rinsing spinning cycles of washing machines.
  • One way of reducing the amount of foam is to incorporate foam control agents such as silicone-materials.
  • foam control agents such as silicone-materials.
  • silicone-materials For adequately reducing the foam-problem, hitherto it proved sometimes necessary to use relatively high levels of costly silicone anti-foam materials. Therefore there still exists a need for foam-control materials other than silicone anti-foam materials.
  • detergency nonionics Another problem in using detergency nonionics is sometimes the occurence of relatively high viscosities of the final product, especially at a relatively low temperature, for example 5 °C.
  • GB-A-2,011,942 describes aqueous liquid detergent compositions comprising a specific ternary nonionic mixture.
  • FR-A-2,393,846 and EP-0,158,464 describe non-aqueous liquid detergents that may comprise alkoxylated nonionic mixtures.
  • mixtures of relatively hydrophilic alkoxylated detergency nonionics and relatively hydrophobic nonionic ingredients having a relatively small hydrophilic headgroup are suitable for this purpose.
  • Preferred relatively hydrophilic alkoxylated detergency nonionics are selected from the group consisting of alkoxylated fatty alcohols, said alcohol comprising on average more than 9 and less than 12 carbon atoms and being alkoxylated with on average more than 5 and less than 10 alkoxy-groups selected from ethoxy and/or propoxy groups.
  • nonionic non-detergency ingredients do not have as their main function a detergency function if used in the absence of other detergency materials, therefore they are referred to as nonionic non-detergency ingredients.
  • Especially preferred non-detergency materials for use in compositions of the invention are nonionic ingredients which are selected from the groups of alkoxylated fatty alcohols, said alcohol comprising on average 12 to 16 carbon atoms and being alkoxylated with on average less than 5 alkoxy groups selected from ethoxy and/or propoxy groups and fatty alcohols having a carbon chain length of from 9 to 15.
  • the present invention relates to a liquid non-aqueous detergent composition
  • a liquid non-aqueous detergent composition comprising nonionic surfactant, characterised in that the nonionic surfactant is a mixture of:
  • detergency nonionic materials for the purpose of the present invention a distinction between detergency nonionic materials and nonionic non-detergency ingredients can be made by applying the following test: Six soiled test-cloths ( 2 x WFK 10C, 2 x WFK 20C and 2 x WFK 30C) are washed in a tergotometer at 40 °C for 15 minutes at 75 rpm in water of 24 °FH. The weight ratio of cloth to water is 1 : 40. The water contains 1.25 g/l of nonionic material and a buffering system of 0.15 g/l borax and 0.10 g/l of triethanolamine.
  • the cloths After washing, the cloths are centrifuged and dried, whereafter the reflectometer-score for the WFK 20 C cloths is measured in an Elrepho reflectometer at 460 nm.
  • Detergency nonionic materials will generally provide a reflectometer-score of more than 3.5, more preferred more than 4.0, most preferred more than 4.5.
  • Nonionic non-detergency ingredients will generally provide a reflectometerscore of less than 3.5, more preferred less than 2.5, most preferred less than 1.5.
  • the detergency nonionic material is the detergency nonionic material
  • compositions of the invention comprise one or more detergency nonionic materials selected from the group consisting of alkoxylated fatty alcohols having on average more than 9 and less than 12 carbon atoms and being alkoxylated with on average more than 5 and less than 10 alkoxy-groups selected from ethoxy and/or propoxy groups.
  • these nonionic materials additionally satisfy one or more of the following conditions:
  • the HLB value (the hydrophilic-lipophilic balance) is a well-known parameter for determining the hydrophilic character of nonionic ingredients. A higher HLB value indicates a more hydrophilic character of the nonionic material.
  • a preferred method for calculating the HLB of a material is to divide the average molecular weight of the hydrophilic portion of the molecule times 20, by the average molecular weight of the whole molecule. This method is especially suitable for calculating the HLB of ethoxylated fatty alcohols.
  • the HLB value of the detergency nonionic material is 12 or more, preferably from 12.5 to 14.
  • condition (b) is determined in accordance with the following method: the detergency nonionic material is mixed with Na Dobs in a weight ratio of 50 : 1 and the conductivity of the mixture is measured with a Hewlett Packard Impedantie-meter 4800A.
  • the conductivity of the mixture is more than 1 x 10 ⁇ 4 ohm ⁇ 1 m -1, more preferred between 1.5 x 10 ⁇ 4 and 2.5 x 10 ⁇ 4 ohm ⁇ 1 m -1.
  • the foam height in accordance with test (c) is determined in accordance with the following method: 250 ml of water of 16 °FH is mixed with 0.125 g of the detergency nonionic, the solution is stirred vigorously for 40 seconds in a pipe of 6.5 cm diameter and the foam height is determined.
  • the height of the developed foam is more than 40 mm, more preferred more than 45 mm, most preferably between 50 and 100 mm.
  • Nonionic detergency materials as specified above preferably additionally satisfy one or more of the above conditions. It is preferred that test (a), eventually in combination with tests (b) and/or (c) are satisfied.
  • a very preferred embodiment of the invention concerns the use of so-called narrow range ethoxylates as detergency nonionic materials.
  • the detergency nonionic is an ethoxylated alcohol having an average of from 5 to 8 ethylene oxide (EO) groups per molecule, at least 60% having a number of ethylene oxide groups within ⁇ 2EO of the average and the alkyl chain distribution being such that less than 2% has a chain length of 9 or less carbon atoms, at least 90% has a chain length between 10 and 12 carbon atoms and less than 10% has a chain length of 13 or more carbon atoms, said percentages being by weight of the ethoxylated alcohol.
  • EO ethylene oxide
  • Preferred narrow range ethoxylates are available from Vista.
  • the detergency nonionic material preferably is liquid at 20 °C and preferably has a pour point of less than 10 °C, more preferably less than 5 °C.
  • the level of the detergency nonionic material is preferably from 5 to 75 % by weight of the composition, more preferably from 10 to 40 %, most preferably from 25 to 35 %.
  • the nonionic non-detergency ingredient is used in compositions of the invention as a foam control agent and/or viscosity control agent and/or for the prevention of off-odours.
  • a foam control agent and/or viscosity control agent and/or for the prevention of off-odours.
  • these materials should be able to reduce the amount of foaming of the compositions when used in a washing machine and/or to reduce the viscosity of the product and/or they should not give rise to off-odours.
  • Suitable nonionic non-detergency materials are selected from the groups of alkoxylated fatty alcohols comprising on average from 12 to 16 carbon atoms and being alkoxylated with on average less than 5 alkoxy groups selected from ethoxy and/or propoxy groups and fatty alcohols having a carbon chain length of from 9 to 15.
  • C 13-15 alcohols ethoxylated with on average 2-4 ethoxy groups are used. Most prefered is the use of a C 13-15 alcohol ethoxylated with on average about 3 ethoxy groups.
  • suitable non-detergency nonionic ingredients preferably additionally satisfy one or more of the following tests:
  • the HLB value of the nonionic non-detergency ingredient is less than 12, more preferably from 4-11, most preferably from 5-10.
  • Preferably narrow range ethoxylates are used.
  • the nonionic non-detergency ingredient preferably is capable to reduce the conductivity of a standard solution.
  • the reduction of conductivity can be measured as follows: a mixture is made of the nonionic non-detergency ingredient, a nonionic material having the trade name Dobanol 91-6 and Na Dobs in weight ratios of 15 : 35 : 1.
  • the conductivity of this mixture should be less than the conductivity of a 50 : 1 mixture of Dobanol 91-6 and Na Dobs.
  • the reduction in conductivity is at least 10%, more preferred more than 30%, most preferred more than 50%.
  • Condition (c) can be tested as follows: 250 ml of water of 16 °FH is mixed with 0.125 g of a 1 : 1 (by weight) mixture of Dobanol 91-6 and the nonionic non-detergency ingredient, the solution is vigorously stirred for 40 seconds in a pipe of 6.5 cm diameter.
  • the foam height is determined.
  • the height of the developed foam is at least 30% less than the amount of foam generated when 0.125 g of pure Dobanol 91-6 is used, more preferably the foam reduction is at least 50%, most preferably from 70 to 100%.
  • Condition (d) can be tested by measuring the viscosity at 21s ⁇ 1 of the following composition:
  • the nonionic is Dobanol 91-6
  • the Nonionic is a 2 : 1 (by weight) mixture of Dobanol 91-6 and the nonionic non-detergency ingredient.
  • the viscosity reduction by substituting the Dobanol 91-6 by the mixture of nonionic materials is at least 100 mPa.s, more preferred more than 250 mPa.s, most preferred more than 500 mPa.s at 21 s ⁇ 1.
  • the nonionic non-detergency ingredient is liquid at 20 °C.
  • the pour point of the ingredient is les than 10 °C, more preferably less than 5 °C.
  • the level of the nonionic non-detergency ingredient is preferably from 1 to 30 % by weight of the composition, more preferably from 3 to 20 %, most preferably from 7 to 17 %.
  • the weight ratio of detergency nonionic material to nonionic non-detergency ingredient is preferably from 10 : 1 to 1 : 5, more preferably from 5 : 1 to 1 : 3, most preferably from 4 : 1 to 1 : 1.
  • compositions according to the present invention are non-aqueous liquid cleaning products.
  • liquids refer to materials which are liquid at 25°C at atmospheric pressure. 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.
  • compositions according to the invention will contain a detergency nonionic material.
  • the compositions may contain one or more agents which further promote the cleaning and/or conditioning of the article(s) in question, selected according to the intended application.
  • these agents 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 in the case of hard surface cleaning agents
  • abrasives in many cases, more than one of these agents will be present, as well as other ingredients commonly used in the relevant product form.
  • surfactants are solids, they will usually be dissolved or dispersed in the liquid phase. Where they are liquids, they will usually constitute all or part of the liquid phase. However, in some cases the surfactants may undergo a phase change in the composition.
  • surfactants for use in the compositions of the invention may be chosen from any of the classes, sub-classes and specific materials described in "Surface Active Agents” Vol. I, by Schwartz & Perry, Interscience 1949 and “Surface Active Agents” Vol. II by Schwartz, Perry & Berch (Interscience 1958), in the current edition of "McCutcheon's Emulsifiers & Detergents” published by the McCutcheon division of Manufacturing Confectioners Company or in "Tensid-Taschenbuch", H. Stache, 2nd Edn., Carl Hanser Verlag, München & Wien, 1981.
  • alkyl refers to a straight or branched alkyl moiety having from 1 to 30 carbon atoms, whereas lower alkyl refers to a straight or branched alkyl moiety of from 1 to 4 carbon atoms.
  • alkyl species however incorporated (e.g. as part of an aralkyl species).
  • Alkenyl (olefin) and alkynyl (acetylene) species are to be interpreted likewise (i.e.
  • alkylene in terms of configuration and number of carbon atoms
  • alkylene alkenylene and alkynylene linkages.
  • any reference to lower alkyl or C1 ⁇ 4 alkyl (unless the context so forbids) is to be taken specifically as a recitation of each species wherein the alkyl group is (independent of any other alkyl group which may be present in the same molecule) methyl, ethyl, iso -propyl, n -propyl, n -butyl, iso -butyl and t -butyl, and lower (or C1 ⁇ 4) alkylene is to be construed likewise.
  • 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 liquid phase and those in the liquid phase which solidify (undergo a phase change) in the composition, wherein they are then dispersed.
  • Suitable anionic detergent surfactants are alkali metal, ammonium or alkylolamine 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, and olefin sulphonates prepared by sulphonation of C10 ⁇ 24 alpha-olefins and subsequent neutralization and hydrolysis of the sulphonation reaction product.
  • the compositions of the invention contain the liquid phase (whether or not comprising liquid surfactant) in an amount of at least 10% by weight of the total composition.
  • the amount of the liquid phase present in the composition may be as high as about 90%, but in most cases the practical amount will lie between 20 and 70% and preferably between 35 and 50% by weight of the composition.
  • At least 50 % by weight of the liquid phase is composed of the detergency nonionic material and the nonionic non-detergency ingredient. More preferably at least 70 % of the liquid phase is composed of these two ingredients, most preferably from 80 to 100 %.
  • the solids content of the product may be within a very wide range, for example from 10-90%, usually from 30-80% and preferably from 50-65% by weight of the final composition.
  • the solid phase should preferably be in particulate form and preferably have a weight average particle size of less than 300 microns, preferably less than 200 microns, more preferably less than 100 microns, especially less than 10 microns.
  • the particle size may even be of sub-micron size.
  • the proper particle size can be obtained by using materials of the appropriate size or by milling the total product in a suitable milling apparatus.
  • HM hydrophobically modified
  • a dispersant material is a material, of which the main purpose is to stabilise the composition.
  • Hydrophobically modified dispersant materials are particulate materials, of which the outer surface has chemically been treated to reduce the hydrophilic nature thereof.
  • HM materials have a weight average particle size of from 0.005 to 5 micrometer, more preferred 0.01 to 3 micrometer, most preferred from 0.02 to 0.5 micrometer.
  • the level of the HM material is preferably from 0.1 to 10 % by weight of the composition, more preferred 0.3 to 5 %, most preferred from 0.5 to 3 %.
  • the number of hydroxy- and/or acid- groups at the surface of the particles is reduced by the hydrophobing treatment.
  • Suitable reactions include esterification or etherfication of the hydrophilic groups.
  • the hydrophobing treatment involves at least 10 % of the hydrophilic groups at the surface of the particle, more preferably from 40 to 95 %, most preferably from 50 to 90 %. Partial hydrophobing is preferred over complete hydrophobation.
  • HM silica containing dispersants are used.
  • the hydrophobation of the silica particles preferably involves the substitution of the free hydroxy-groups at the outer surface of the silica particles by a short alkyl group. More preferably the surface hydroxy-groups are substituted by methyl groups.
  • HM particles and particulate metal oxides have a bulk density of 200 to 1,000 g/l, more preferred 250 to 800 g/l, especially preferably 300 to 700 g/l, most preferably from 400 to 650 g/l.
  • the metal oxide is selected from calcium oxide, magnesium oxide and aluminium oxide, most preferably magnesium oxide is used.
  • the weight average particle size of the metal oxide is preferably from 0.1 to 200 micrometer, more preferably from 0.5 to 100 micrometer, most preferred from 2 to 70 micrometer.
  • the level of metal oxide is preferably from 0.1 to 7 % by weight of the composition, more preferred from 0.5 to 5 %, most preferred from 1 to 4 %.
  • the 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 latter being preferred when environmental considerations are important.
  • the inorganic builders comprise the various phosphate-, carbonate-, silicate-, borate- and aluminosilicates-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 tripolyphosphates, phosphates and hexametaphosphates.
  • 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.
  • 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.
  • the level of builder materials is preferably from 5-60 % by weight of the composition, more preferred 10-50 % by weight, most preferred 20-40 %.
  • compositions of the invention also comprise a deflocculant material.
  • a deflocculant material any material may be used as a deflocculant provided it fulfils the deflocculation test described in European Patent Specification EP-A-266199 (Unilever).
  • EP-A-266199 Unilever
  • the capability of a substance to act as a deflocculant will partly depend on the solids/liquid phase combination. However, especially preferred are acids.
  • deflocculants include the alkanoic acids such as acetic, propionic and stearic and their halogenated counterparts such as trichloracetic and trifluoracetic as well as the alkyl (e.g. methane) sulphonic acids and aralkyl (e.g. paratoluene) sulphonic acids.
  • alkanoic acids such as acetic, propionic and stearic and their halogenated counterparts such as trichloracetic and trifluoracetic as well as the alkyl (e.g. methane) sulphonic acids and aralkyl (e.g. paratoluene) sulphonic acids.
  • suitable inorganic mineral acids and their salts are hydrochloric, carbonic, sulphurous, sulphuric and phosphoric acids; potassium monohydrogen sulphate, sodium monohydrogen sulphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, sodium monohydrogen phosphate, potassium dihydrogen pyrophosphate, tetrasodium monohydrogen triphosphate.
  • organic acids may also be used as deflocculants, for example formic, lactic, amino acetic, benzoic, salicylic, phthalic, nicotinic, ascorbic, ethylenediamine tetraacetic, and aminophosphonic acids, as well as longer chain fatty carboxylates and triglycerides, such as oleic, stearic, lauric acid and the like.
  • Peracids such as percarboxylic and persulphonic acids may also be used.
  • the class of acid deflocculants further extends to the Lewis acids, including the anhydrides of inorganic and organic acids. Examples of these are acetic anhydride, maleic anhydride, phthalic anhydride and succinic anhydride, sulphur-trioxide, diphosphorous pentoxide, boron trifluoride, antimony pentachloride.
  • fatty anions are very suitable deflocculants, and a particularly preferred class of deflocculants comprises anionic surfactants.
  • anionics which are salts of alkali or other metals may be used, particularly preferred are the free acid forms of these surfactants (wherein the metal cation is replaced by an H+ cation, i.e. proton).
  • These anionic surfactants include all those classes, sub-classes and specific forms described in the aforementioned general references on surfactants, viz, Schwartz & Perry, Schwartz Perry and Berch, McCutcheon's, Tensid-Taschenbuch; and the free acid forms thereof. Many anionic surfactants have already been described hereinbefore. In the role of deflocculants, the free acid forms of these are generally preferred.
  • some preferred sub-classes and examples are the C10-C22 fatty acids and dimers thereof, the C8-C18 alkylbenzene sulphonic acids, the C10-C18 alkyl- or alkylether sulphuric acid monoesters, the C12-C18 paraffin sulphonic acids, the fatty acid sulphonic acids, the benzene-, toluene-, xylene- and cumene sulphonic acids and so on.
  • Particularly are the linear C12-C18 alkylbenzene sulphonic acids.
  • zwitterionic-types can also be used as deflocculants. These may be any described in the aforementioned general surfactant references.
  • lecithin is lecithin.
  • the level of the deflocculant material in the composition can be optimised by the means described in the aforementioned EP-A-266199, but in very many cases is at least 0.01%, usually 0.1% and preferably at least 1% by weight, and may be as high as 15% by weight. For most practical purposes, the amount ranges from 2-12%, preferably from 4-10% by weight, based on the final composition.
  • compositions of the invention contain one or more bleach ingredients.
  • Bleaches include the halogen, particularly chlorine bleaches such as are provided in the form of alkalimetal hypohalites, e.g. hypochlorites.
  • the oxygen bleaches are preferred, for example in the form of an inorganic persalt, preferably with a bleach precursor, or as a peroxy acid compound.
  • the activator makes the bleaching more effective at lower temperatures, i.e. 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 activator 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 activator is from about 20:1 to about 2:1, preferably from about 10:1 to about 3.5:1. Whilst the amount of the bleach system, i.e. peroxybleach compound and activator, may be varied between about 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. Thus, 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 activator is between about 0.5% and about 14%, most preferably between about 1% and about 10% by weight.
  • Suitable peroxybleach compounds are alkalimetal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.
  • a stabiliser for the bleach or bleach system for example ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate or other appropriate organic phosphonate or salt thereof, such as the Dequest range hereinbefore described.
  • These stabilisers can be used in acid or salt form, such as the calcium, magnesium, zinc or aluminium salt form.
  • the stabiliser may be present at a level of up to about 2% by weight, preferably between about 0.1% and about 1.0 % by weight.
  • liquid bleach precursors such as glycerol triacetate and ethylidene heptanoate acetate, isopropenyl acetate and the like, also function suitably as a material for the liquid phase, thus obviating or reducing any need of additional relatively volatile solvents, such as the lower alkanols, paraffins, glycols and glycolethers and the like,. e.g. for viscosity control.
  • ingredients comprise those remaining ingredients which may be used in liquid cleaning products, such as fabric conditioning agents, enzymes, perfumes (including deoperfumes), micro-biocides, colouring agents, fluorescers, soil-suspending agents (anti-redeposition agents), corrosion inhibitors, enzyme stabilising agents, and lather depressants.
  • fabric conditioning agents such as fabric conditioning agents, enzymes, perfumes (including deoperfumes), micro-biocides, colouring agents, fluorescers, soil-suspending agents (anti-redeposition agents), corrosion inhibitors, enzyme stabilising agents, and lather depressants.
  • fabric conditioning agents which may be used, either in fabric washing liquids or in rinse conditioners, are fabric softening materials such as fabric softening clays, quaternary ammonium salts, imidazolinium salts, fatty amines and cellulases.
  • Enzymes which can be used in liquids according to the present invention include proteolytic enzymes, amylolytic enzymes and lipolytic enzymes (lipases).
  • proteolytic enzymes amylolytic enzymes and lipolytic enzymes (lipases).
  • lipolytic enzymes lipolytic enzymes
  • proteolytic enzymes and amylolytic enzymes are known in the art and are commercially available. They may be incorporated as “prills", “marumes” or suspensions e.g.
  • the fluorescent agents which can be used in the liquid cleaning products according to the invention are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in a detergent composition is generally from 0.02-2% by weight.
  • anti-redeposition agents When it is desired to include anti-redeposition agents in the liquid cleaning products, the amount thereof is normally from about 0.1% to about 5% by weight, preferably from about 0.2% to about 2.5% by weight of the total liquid composition.
  • Preferred anti-redeposition agents include carboxy derivatives of sugars and celluloses, e.g. sodium carboxymethyl cellulose, anionic poly-electrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.
  • compositions are substantially non-aqueous, i.e. 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.
  • compositions in accordance with the invention comprise:
  • the viscosity of the product is preferably less than 2,500 mPa.s at 21 s ⁇ 1, more preferred less than 2,000, most preferred from 500 to 1,500 mPa.s.
  • Compositions of the invention preferably are free from nonionic materials containing propoxy groups.
  • Composition in accordance with the present invention may be used for several detergency purposes, for example the cleaning of surfaces and the washing of fabrics.
  • an aqueous liquor containing 0.1 to 10 %, more preferably 0.2 to 2% of the non-aqueous detergent composition of the invention is used.
  • all raw materials should be dry and (in the case of hydratable salts) in a low hydration state, e.g. anhydrous phosphate builder, sodium perborate monohydrate and dry calcite abrasive, where these are employed in the composition.
  • a low hydration state e.g. 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 liquid phase in a dry vessel. If deflocculant materials are used, these should preferably -at least partly- be mixed with the liquid phase, prior to the addition of the solids. In order to minimise the rate of sedimentation of the solids, this blend is passed through a grinding mill or a combination of mills, e.g.
  • 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.
  • compositions (percent by weight) were prepared by mixing the ingredients in the order stated. The ingredients were milled after mixing to give a mean particle size of 5 ⁇ m.

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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)

Abstract

On décrit une composition détergente liquide non aqueuse, comportant une ou plusieurs substances non ioniques détergentes, et un ou plusieurs ingrédients non détergents non ioniques.

Claims (8)

  1. Une composition détergente liquide non aqueuse contenant des agents tensioactifs non ioniques, caractérisée en ce que l'agent tensioactif non ionique est un mélange de :
    (a) un ou plusieurs matériaux non ioniques détergents sélectionnés parmi le groupe comprenant des alcools gras alkoxylés, ledit alcool contenant en moyenne plus de 9 et de moins de 12 atomes de carbone, et étant alkoxylé avec en moyenne plus de 5 et moins de 10 groupes alkoxy, sélectionnés parmi des groupes éthoxy et/ou propoxy ; et
    (b) un ou plusieurs ingrédients non détergents non ioniques, qui sont sélectionnés parmi les groupes d'alcools gras alkoxylés, ledit alcool contenant en moyenne 12 à 16 atomes de carbone et étant alkoxylé avec en moyenne moins de 5 groupes alkoxy sélectionnés parmi des groupes éthoxy et/ou propoxy et des alcools gras ayant une longueur de chaîne de carbone allant de 9 à 15.
  2. Une composition selon la Revendication 1, dans laquelle le matériau non ionique détergent satisfait en outre à une ou plusieurs des conditions suivantes :
    (a) le matériau a une valeur HLB de plus de 12 ;
    (b) le matériau présente une conductivité de plus de 10 x 10⁻⁴ ohm⁻¹ m⁻¹ ;
    (c) le matériau génère une mousse de hauteur standard supérieure à 40 mm.
  3. Une composition selon la Revendication 1, dans laquelle le matériau non ionique détergent contient un alcool éthoxylaté ayant une moyenne de 5 à 8 groupes d'oxydes d'éthylène (EO) par molécule, au moins 60 % ayant un nombre de groupes d'oxyde d'éthylène à l'intérieur de +/- 2EO de la moyenne et la distribution de chaîne alkyle étant telle que moins 2 % ont une longueur de chaîne de 9 atomes de carbone, ou moins, au moins 90 % ont une longueur de chaîne située entre 10 et 12 atomes de carbone, et moins de 10 % ont une longueur de chaîne de 13 atomes de carbone ou plus, lesdits pourcentages étant des pourcentages en masse de l'alcool éthoxylaté.
  4. Une composition selon la Revendication 1, dans laquelle le matériau non ionique non détergent satisfait en outre à une ou plusieurs des conditions suivantes :
    (a) l'ingrédient a une valeur HLB de moins de 12 ;
    (b) l'ingrédient fournit une réduction de conductivité standard d'au moins 10 % ;
    (c) l'ingrédient génère une réduction de hauteur de mousse standard d'au moins 30 % ;
    (d) I'ingrédient fournit une réduction de viscosité standard d'au moins 100 mPa.s à 21s-1.
  5. Une composition selon la Revendication 1, dans laquelle le matériau non ionique non détergent est sélectionné parmi le groupe composé d'alcools gras alkoxylés contenant une chaîne alkyle en C₁₀-C₁₄ éthoxylatée avec 2 à 4 groupes éthoxy et des alcools gras contenant de 10 à 14 atomes de carbone ou des mélanges de ceux-ci.
  6. Une composition selon la Revendication 1, dans laquelle le rapport en masse du matériau non ionique détergent à l'ingrédient non détergent non ionique va de 10:1 à 1:5.
  7. Une composition selon une ou plusieurs des Revendications précédentes contenant :
    (a) au moins 10 % en masse d'une phase liquide, de préférence 80 à 100 % en masse de celle-ci étant un mélange d'un matériau non ionique détergent et d'un ingrédient non détergent non ionique ;
    (b) 10 à 90 % en masse de solides en suspension ;
    (c) 0,1 à 15 % en masse d'un matériau défloculant ;
    (d) 5,5 à 27 % en masse d'un composé de blanchiment peroxy ;
    (e) de 0,5 à 14 % en masse d'un activateur de blanchiment.
  8. Utilisation d'un ingrédient non détergent non ionique sélectionné parmi les groupes d'alcools gras alkoxylés, ledit alcool contenant en moyenne 12 à 16 atomes de carbone et étant alkoxylé avec en moyenne moins de S groupes alkoxy sélectionnés parmi des groupes éthoxy et/ou propoxy et des alcools gras ayant une longueur de chaîne de carbone allant de 9 à 15, en tant qu'agent de contrôle de mousse et/ou de viscosité dans une composition détergente liquide non aqueuse.
EP91904091A 1990-03-28 1991-02-14 Produits de nettoyage liquides Expired - Lifetime EP0521863B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP90200745 1990-03-28
EP90200745 1990-03-28
PCT/EP1991/000295 WO1991014765A1 (fr) 1990-03-28 1991-02-14 Produits de nettoyage liquides

Publications (2)

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EP0521863A1 EP0521863A1 (fr) 1993-01-13
EP0521863B1 true EP0521863B1 (fr) 1994-05-18

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EP91904091A Expired - Lifetime EP0521863B1 (fr) 1990-03-28 1991-02-14 Produits de nettoyage liquides

Country Status (11)

Country Link
EP (1) EP0521863B1 (fr)
JP (1) JPH05505633A (fr)
AU (1) AU651961B2 (fr)
BR (1) BR9106283A (fr)
CA (1) CA2078789A1 (fr)
DE (1) DE69102064T2 (fr)
ES (1) ES2052373T3 (fr)
FI (1) FI924296A0 (fr)
NZ (1) NZ237545A (fr)
WO (1) WO1991014765A1 (fr)
ZA (1) ZA912378B (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9110720D0 (en) * 1991-05-17 1991-07-10 Unilever Plc Detergent composition
ES2106546T5 (es) * 1993-06-11 2001-05-16 Unilever Nv Composicion detergente.
EP0907711B2 (fr) † 1996-06-28 2007-01-10 The Procter & Gamble Company Compositions detergentes non aqueuses et comprenant un tensioactif specifique de sulfonate alkylbenzene

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2011944A (en) * 1978-01-09 1979-07-18 Unilever Ltd Liquid nonionic detergent composition

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1600981A (en) * 1977-06-09 1981-10-21 Ici Ltd Detergent composition
NO781898L (no) * 1977-06-09 1978-12-12 Ici Ltd Flytende vaskemiddelblanding.
US4264466A (en) * 1980-02-14 1981-04-28 The Procter & Gamble Company Mulls containing chain structure clay suspension aids
EG16786A (en) * 1984-03-23 1991-08-30 Clorox Co Low-temperature effective composition and delivery systems therefor
NZ221555A (en) * 1986-09-09 1989-08-29 Colgate Palmolive Co Detergent composition containing inorganic bleach and a liquid activator
GB8904415D0 (en) * 1989-02-27 1989-04-12 Unilever Plc Liquid detergent products

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2011944A (en) * 1978-01-09 1979-07-18 Unilever Ltd Liquid nonionic detergent composition

Also Published As

Publication number Publication date
DE69102064T2 (de) 1994-09-01
NZ237545A (en) 1993-11-25
FI924296A7 (fi) 1992-09-25
BR9106283A (pt) 1993-03-30
CA2078789A1 (fr) 1991-09-29
FI924296L (fi) 1992-09-25
ES2052373T3 (es) 1994-07-01
JPH05505633A (ja) 1993-08-19
FI924296A0 (fi) 1992-09-25
DE69102064D1 (de) 1994-06-23
AU7243091A (en) 1991-10-21
AU651961B2 (en) 1994-08-11
EP0521863A1 (fr) 1993-01-13
ZA912378B (en) 1992-11-25
WO1991014765A1 (fr) 1991-10-03

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