GB2217727A - Liquid cleaning products - Google Patents

Liquid cleaning products Download PDF

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Publication number
GB2217727A
GB2217727A GB8909801A GB8909801A GB2217727A GB 2217727 A GB2217727 A GB 2217727A GB 8909801 A GB8909801 A GB 8909801A GB 8909801 A GB8909801 A GB 8909801A GB 2217727 A GB2217727 A GB 2217727A
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weight
composition
liquid phase
alkali metal
composition according
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GB8909801D0 (en )
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Frederik Jan Schepers
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Unilever PLC
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Unilever PLC
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0004Non aqueous liquid compositions comprising insoluble particles
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3956Liquid compositions

Abstract

A substantially non-aqueous liquid cleaning product composition comprising solid particles such as zeolite or sodium perborate dispersed in a liquid solvent phase and from 2% to 40% by weight of the total composition of alkali metal soap, provided that at least 5% by weight of said liquid solvent phase is dissolved alkali metal soap, the viscosity of said composition at 25 DEG C being no greater than 2.5 Pas at a shear rate of 21s<-1>. The solvent phase comprises a di-C1-4 alkylene glycol or polyethylene glycol; dodecyl benzene sulphonic acid and oleic acid can also be present.

Description

LIQUID CLEANING PRODUCTS The present invention is concerned with substantially non-aqueous liquid cleaning compositions of the kind comprising solid particles dispersed in a liquid phase.

In recent years, the technology of aqueous detergent liquids has progressed considerably. Research into non-aqueous detergents has also continued due to interest in the possibility of incorporating components incompatible with the aqueous systems, for example bleaches. However, the state of the art in the non-aqueous area is less advanced than in the field of aqueous systems. For non-aqueous systems, recent publications have been mainly concerned with basic rheology and stability.

Thus, there is now a need to progress the non-aqueous technology into the realms of performance currently realisable for powder and aqueous liquid products.

Therefore, the applicants have sought to provide detergency and fabric softening benefits by incorporating soaps in non-aqueous systems.

French Patent 2 069 073 (Unilever N.V.) describes non-aqueous detergent liquids in which quite high levels of alkali metal soap are incorporated. It is stated that in these systems, some of the soap is dissolved and some not. These compositions also contain dispersed particles of builder, and optionally bleach. It is believed that the insoluble soap may act to inhibit settling of these particles. Unfortunately, the particular combinations of soaps and liquid phases used in those systems, limit the amount of soap which is actually dissolved. That in turn is a restriction on the fabric softening and/or non-phosphate building capacity of the compositions (the avoidance of phosphates being preferred for environmental reasons). Accordingly, these known systems require high solids levels to compensate, which can be detrimental to rheology of the liquid product.

European Patent Specification EP-A-253 151 (Henkel KG) describes non-aqueous detergent compositions comprising nonionic surtactant, an anionic surfactant or a soap and a polyethyleneglycol of molecular weight about 200-600. Although termed 'liquids' the viscosity of these products is very high so that effectively they are pastes.

Typically they contain very high levels of non-soap anionic surfactants.

The applicants have now discovered that detergency and fabric softening properties can be endowed to the non-aqueous products at relatively low viscosities by incorporating effective amounts of alkali metal soap, provided that at least some of the liquid phase is dissolved alkali metal soap. This objective is achieved by including in the liquid phase a solvent selected from certain glycols and polyethylene glycols.Thus, according to the invention there is provided a substantially non-aqueous liquid cleaning composition comrpising a liquid phase and a particulate solid phase dispersed in the liquid phase, wherein the liquid phase includes a solvent selected from di-C 1-4 alkylene glycols and polyethylene glycols of molecular weight of up to 1000 and at least 5t, based on the weight of the liquid phase, of dissolved alkali metal soap, the total level of soap in the composition being from 2% to 40% by weight and the composition having a viscosity at 250C of no more than 2.5 Pas at a shear rate of 21s 1. Most preferably, the viscosity is 1.75 Pas or less at the latter temperature and shear rate.

Preferably, the dissolved alkali metal soap is 7.58 to 30% by weight of the liquid phase, especially from 10% to 20%. Typically, the total alkali metal soap will constitute from 5% to 20% by weight of the total composition, especially from 7.5% to 10%. Such soaps are the salts of alkali metals, especially sodium-or potassium, and fatty acids, for example those containing from 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. It is preferred to use mixtures comprising at least one alkali metal soap of a Cm~14 saturated fatty acid and at least one alkali metal soap of a Cl6 22 mono- and/or di-unsaturated fatty acid in a weight ratio of from 9:1 to 1:9.A specific preferred combination is a mixture of oleate and laurate soaps in an approximately 1:1 mole ratio. For this combination, and indeed for the soaps in general, the potassium salts are preferred.

It is also advantageous to include in the compositions of the present invention, a fatty acid in a weight ratio relative to the alkali metal soap, of 1:5 to 1.5:1. Here, fatty acid refers to the substance as it is incorporated into the liquid during manufacture. It should be realised that in some cases, where the dispersed solid particles comprise--a high proportion of alkaline inorganic salts, analysis of the ensuing product may only reveal a corresponding alkali metal soap. That may be due, for example, to the fact that such analytical methods often involve dissolving the product in water, whereupon the alkaline salts and fatty acid can react to form the soap.In some systems, particularly those containing high proportions of nonionic surfactant, and optionally, trace impurities of water, it may also be possible for some of the fatty acid to react with the alkaline salts at the particle surfaces in situ.

Typically, the dispersed solid particles may constitute from 5% to 30% by weight of the total composition, preferably from 5% to 208. In such systems, it is possible to incorporate high levels of particulate solid bleaches and omitting builders other than the soap which itself functions as a builder, especially when incorporated at levels of 208 or above.

For greasy soil removal and to aid viscosity reduction, it is possible to formulate the compositions of the present invention such that the liquid phase comprises a nonionic surfactant in addition to the non-surfactant solvent. The latter is chosen from di-C 1-4 alkylene glycols and polyethylene glycols of molecular weight up to 1000. In general, the non-surfactant solvent may be incorporated at from 1% to 15% by weight of the total composition. However, the non-surfactant solvents can advantageously be incorporated at higher levels such as from 10% to 20% by weight, the soap being incorporated at from 30% to 50% by weight of the total composition which may then be substantially free of nonionic surfactant.

Other non-surtactant solvents may also be included in the compositions, such as fatty alcohols, ethers, polyethers, alkylamines and fatty amines, (especially diand tri-alkyl- and/or fatty- N- substituted amines), alkyl (or fatty) amides and mono- and di- N-alkyl substituted derivatives thereof, alkyl (or fatty) carboxylic acid lower alkyl esters, ketones, aldehydes, and glycerides.

Specific examples include respectively, liquid fatty alcohols having from 8 to 15 carbon atoms, di-alkyl ethers, liquid polyethylene glycols of molecular weight over 1000, alkyl ketones (such as acetone) and glyceryl trialkylcarboxylates (such as glyceryl tri-acetate), glycerol, propylene glycol, and sorbitol.

Suitable light solvents with little or no hydrophilic character include lower alcohols, such as ethanol, or higher alcohols, such as dodecanol, as well as alkanes and olefins, and such materials may also be included.

As indicated above, the liquid cleaning products according to the present invention are non-aqueous dispersions comprising a non-aqueous liquid phase which as well as the soap, can optionally comprise a liquid non-soap surfactant. Many do contain a non-soap surfactant as a dispersed or dissolved solid, or more often, as part of said liquid phase. These synthetic surfactant compositions are liquid detergent products, e.g. for fabrics washing, machine warewashing or general or hard surface cleaning (with or without abrasives in the product). However, the wider term 'liquid cleaning composition' also includes liquids which although containing no non-soap surfactant, are still useful in cleaning, for example non-aqueous bleach products or those in which the liquid phase consists of one or more non-surfactant solvents for greasy stain pre-treatment of fabrics prior to washing.Such pre-treatment products can contain solid bleaches, dispersed enzymes and the like.

As well as the liquid phase, such non-aqueous dispersions also contain dispersed particulate solids.

These are small (e.g. 10 microns) particles of solid material which are useful in cleaning and could be solid surfactants, builders, bleaches, enzymes or anv other such solids known to those skilled in the art.

The particles can be maintained in dispersion (i.e.

resist settling, even if not perfectly) by any means known in the art or as described in the applicants' European Patent Specification EP 266199-A to which the reader's attention is directed. For example, settling may be inhibited purely by virtue of the relative small size of the particles and the relatively high viscosity of the solvent phase. In other words, the particles settle very slowly at a rate predicted by Stokes' law, or due to the formation of a loosely aggregated network of particle flocs. This effect is utilised in the compositions described in patent specifications EP-A-30 096 (ICI) and GB 2 158 838 A (Colgate). However, there have been several proposals to utilise additional means to enhance solid-suspending properties in such non-aqueous liquids.

These are somewhat analogous to so-called external structuring techniques used in aqueous systems; i.e., in addition to the particulate solids and the liquid solvent phase in which they are to be suspended, an additional dispersant is used which by one means or another, acts to aid stable dispersion or suspension of the solids for a finite period.

Another known means by which such dispersions can be stabilised is the use of a dispersant material which has been termed 'a deflocculant', according to the aforementioned EP 266199. As described there, for deflocculation to occur, an appropriate combination of solids, solvent and deflocculant must be identified. The deflocculant can be solid or liquid before it is added to the remainder of the composition. It can be mono-functional (i.e. act only to deflocculate the particulate solids) or it can be bi-functional (i.e. also have properties beneficial in the relevant cleaning application, e.g. a surfactant). Many of the-deflocculants described are inorganic or organic acids (including the free acid form of anionic surfactants). Two mentioned as particularly preferred are dodecyl benzene sulphonic acid (as the free acid) and lecithin.

All 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.

In the case of hard-surface cleaning, the compositions may be formulated as main cleaning agents, or pre-treatment products to be sprayed or wiped on prior to removal, e.g. by wiping off or as part of a main cleaning operation.

In the case of warewashing, the compositions may also be the main cleaning agent or a pre-treatment product, e.g applied by spray or used for soaking utensils in an aqueous solution and/or suspension thereof.

Those products which are formulated for the cleaning and/or conditioning of fabrics constitute an especially preferred form of the present invention because in that role, there is a very great need to be able to incorporate substantial amounts of various kinds of solids. These compositions may for example, be of the kind used for pre-treatment of fabrics (e.g. for spot 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.Within the context of the present invention, 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').

The soap in the compositions according to the present invention is capable of acting as a cleaning agent, a conditioner and optionally also a builder. The relative balance of these functions will depend on the particular application.

The compositions will be substantially free from agents which are detrimental to the article(s) to be treated. For example, 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.

All ingredients before incorporation will either be liquid, in which case, in the composition they will constitute all or part of the liquid phase, or they will be solids, in which case, in the composition they will either be dispersed as solid particles in the solvent or they will be dissolved in the solvent. Thus as used herein, the term "solid phase" is to be construed as referring to materials in the solid phase which are added as such to the composition and are dispersed therein in solid form and those in the liquid phase which solidify (undergo a phase change) in the composition, wherein they are then dispersed.

When the liquid phase contain two or more liquids it is preferred that they should be mutually miscible or at least one should be dispersible in the other in the form of droplets.

When non-soap surfactants are present, they will be dissolved or dispersed in the liquid phase. Where they are liquids, they will constitute part of the liquid phase. Also, as mentioned earlier above, some non-soap surfactants are also eminently suitable as deflocculants.

In general, non-soap surfactants 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' Viol. II by Schwartz, Perry & Berch (Interscience 1958), in the current edltion of cCutcheon's Emulsifiers & Detergents" published by the McCutcheon division of Manufacturing Confectioners Company or in 'Tensid-Taschenbuch', H.

Stache, 2nd Edn., Carl Hanser Verlag, M5nchen & Wien, 1981.

When it is desired to have a deflocculated system, as a general rule, it is preferable to choose as part of the liquid phase, organic materials having polar molecules.

In particular, those comprising a relatively lipophilic part and a relatively hydrophilic part, especially a hydrophilic part rich in electron lone pairs, tend to be well suited.

Nonionic detergent surfactants are incorporated in many (but not all) compositions of the present invention and 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.

Also common are tatty 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. In any of the mono- and di- alkanolamide derivatives, optionally, there may be a polyoxyalkylene moiety joining the latter groups and the hydrophobic part of the molecule. In all polyalkoxylene containing surfactants, the polyalkoxylene moiety preferably consists of from 2 to 20 groups of ethylene oxide or of ethylene oxide and propylene oxide groups.

Amongst the latter class, particularly preferred are those described in the applicants' published European specification EP-A-225,654, especially for use as all or part of the solvent. Also preferred are those 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. Examples of these are the condensation products of C1l 13 alcohols with (say) 3 or 7 moles of ethylene oxide. These 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 solvent phase.

Another class of 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 normally have molecular weights of from about 300 to about 11,000.

Mixtures of different nonionic detergent surfactants may also be used. Mixtures of nonionic detergent surfactants with other detergent surfactants such as anionic, cationic and ampholytic detergent surfactants may also be used. If such mixtures are used, the mixture must be liquid at room temperature.

Examples of suitable synthetic 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.

Yet again, it is also possible two utilise cationic, zwitterionic and amphoteric surfactants such as referred to in the general surfactant texts referred to hereinbefore. Examples of 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.

Preferably, 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 20 and 508 by weight of the composition.

In the most preferred embodiments, the compositions of the present invention contain a deflocculant (as hereinbefore defined) which may be any of those referred to in the published prior art or any described in EP 266199 as related above.

The level of the detlocculant material in the composition can be optimised by the means hereinbefore described but in very many cases is at least 0.01t, usually 0.1% and preferably at least 18 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.

The compositions according to the present invention preferably also contain one or more other functional ingredients, for example selected from detergency builders, bleaches or bleach systems, and (for hard surface cleaners) abrasives.

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.

In general, the inorganic builders comprise the various phosphate-, carbonate-, silicate-, borate- and aliminosilicate-type materals, 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.

Examples of non-phosphorus-containing inorganic builders, when present, include water-soluble alkali metal carbonates, bicarbonates, borates, silicates, metasilicates, and crystalline and amorphous alumino silicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.

Examples of organic builders include the alkali metal, ammonium and substituted, citrates, succinates, malonates, fatty acid sulphonates, carboxymethoy succinates, ammonium polyacetates, carboxylates, polycarboxylates, aminopolycarboxylates, polyacetyl carboxylates and polyhydroxsulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts ot ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid. Other examples are organic phosphonate type sequestering agents such as those sold by Monsanto under the tradename of the Dequest range and alkanehydroxy phosphonates.

Other 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 aluminosilicates are an especially preferred class of non-phosphorus inorganic builders. These for example are crystalline or amorphous materials having the general formula: Naz (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 285 by weight water content), the water level can lead to network formation.

Below this level (e.g. from 0 to about 6% by weight water content), trapped gas in pores of the material can be displaced which causes gassing and tends to lead to a viscosity increase also. However, anhydrous materials (i.e. with 0 to about 6% by weight of water) can be used as structurants. The preferred range of aluminosilicate is from about 12% to about 30% on an anhydrous basis, although it will usually be 20% or less by weight of the composition when other solids are also present. The aluminosilicate preferably has a particle size of from 0.1 to 100 microns, ideally betweeen 0.1 and 10 microns and a calcium ion exchange capacity of at least 200 mg calcium carbonate/g.

Suitable bleaches include the halogen, particularly chlorine bleaches such as are provided in the form of alkalimetal hypohalites, e.g. hypochlorites. In the application of fabrics washing, the oxygen bleaches are preferred, for example in the form of an inorganic persalt, preferably with an precursor, or as a peroxy acid compound.

In the case of the inorganic persalt bleaches, the precursor makes the bleaching more effective at lower temperatures, i.e. in the range from ambient temperature to about 600C, 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 peroxy bleach compound to the precursor is from about 15:1 to about 2:1, preferably from about 10:1 to about 3.5:1. Whilst the amount of the bleach system, i.e. peroxy bleach compound and precursor, may be varied between about 5% and about 30% by weight of the total liquid, it is preferred to use from about 68 to about 20% of the ingredients forming the bleach system.

Thus, the preferred level of the peroxy bleach compound in the composition is between about 5.5% and about 12% by weight, while the preferred level of the precursor is between about 0.5% and about 18%, most preferably between about 18 and about 5% by weight.

Typical examples of the suitable peroxybleach compounds are alkalimetal peroborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.

Precursors for peroxybleach compounds have been amply described in the literature, including in British patent specifications 836,988, 855,735, 907,356, 907,358, 907,950, 1,003,310, and 1,246,339, US patent specifications 3,332,882, and 4,128,494, Canadian patent specification 844,481 and South African patent specification 68/6,344.

The exact mode of action of such precursors is not known, but it is believed that peracids are formed by reaction of the precursors with the inorganic peroxy compound, which peracids then liberate active-oxygen by decomposition.

They are generally compounds which contain N-acyl or O-acyl residues in the molecule and which exert their activating action on the peroxy compounds on contact with these in the washing liquor.

Typical examples of precursors within these groups are polyacylated alkylene diamines, such as N,N,N1,N -tetraacetylethylene diamine (TAED) and N,N,N,N -tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylgylcoluril (TAGU); triacetylcyanurate and sodium sulphophenyl ethyl carbonic acid ester.

A particularly preferred precursor is 11 N,N,N ,N -tetra- acetylethylene diamine (TAED).

The organic peroxyacid compound bleaches are preferably those which are solid at room temperature and most preferably should have a melting point of at least 50"C. ost commonly, they are the organic peroxyacids and water-soluble salts thereof having the general formula <img class="EMIRef" id="026809961-00170001" />

wherein R is an alkylene or substituted alkylene group containing 1 to 20 carbon atoms or an arylene group containing from 6 to 8 carbon atoms, and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.

Another preferred class of peroxygen compounds which can be incorporated to enhance dispensing/dispersibility in water are the anhydrous perborates described for that purpose in the applicants' European patent specification EP-A-217,454.

When the composition contains abrasives for hard surface cleaning (i.e. 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 applicants' patent specifications EP-A-50,887; EP-A-80,221; EP-A-140,452; EP-A-214,540 and EP 9,942, which relate to such abrasives when suspended in aqueous media. Water soluble abrasives may also be used.

The 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, fluorescers, soil-suspending agents (anti-redeposition agents), corrosion inhibitors, enzyme stabilizing agents, and lather depressants.

In general, the average particle size of the dispersed solids should be 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.

The compositions are substantially non-aqueous, i.e.

they 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 by the applicants that the higher the water content, the more likely it is for the viscosity to be too high, or even for setting to occur. However, this may at least in part be overcome by use of higher amounts of, or more effective deflocculants or other dispersants.

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 accidental 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.

Thus during manufacture, it is preferred that 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. In a preferred process, the dry, substantially anhydrous solids are blended with the liquid phase 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, e.g. a colloid mill, a corundum disc mill, a horizontal or vertical agitated ball 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. Of course 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.

During this milling procedure, the energy input results in a temperature rise in the product and the liberation of air entrapped in or between the particles of the solid ingredients. It is therefore highly desirable to mix any heat sensitive ingredients into the product after the milling stage and a subsequent cooling step. It may also be desirable to de-aerate the product before addition of these (usually minor) ingredients and optionally, at any other stage of the process. Typical ingredients which might be added at this stage are perfumes and enzymes, but might also include highly temperature sensitive bleach components or volatile solvent components which may be desirable in the final composition. However, it is especially preferred that volatile material be introduced after any step of aeration.Suitable equipment for cooling (e.g. heat exchangers) and de-aeration will be known to those skilled in the art.

It follows that all equipment used in this process should be completely dry, special care being taken after any cleaning operations. The same is true for subsequent storage and packing equipment.

The invention will now be illustrated by way of the following examples.

Examples 1 to 9 The following compositions were prepared and their appearance at 200C was judged by the eye.

Example No: 1* 2 3 4 5* 6 7* 8* 9 Ingredients (parts by wt) Non ionic surfactant 95.2 90.9 82.0 82.6 90.9 75.0 75.0 83.3 76.0 Diethylene glycol - 4.6 8.6 - - 12.5 - Polyethylene glycol 200 - - - 8.7 - - - Potassium oleate 4.8 4.6 9.4 8.7 9.1 12.5 12.5 12.5 12.0 Particulate zeolite 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Oleic acid - - - - - - - - 12.0 Dodecanol - - - - - - 12.5 - Glycerol - - - - - - - 4.2 2 Appearance T C T/C T/C T C VT T C * Comparative example 1 Imbentin-C-91/35 OFA 2 C = clear T = turbid T/C = slightly turbid VT = very turbid Examples 10 and 11 Two further compositions were prepared with dodecyl benzene (free) sulphonic acid (ABSA) at 2% by weight of the solvent phase, as deflocculant.

Example No Ingredients % wt 10 Nonionic 71.1 Potassium oleate 7.3 ABSA 1.6 Zeolite 20.0 11 Nonionic 64.4 Potassium oleate 7.0 Polyethylene glycol 200 7.0 ABSA 1.6 Sodium Perborate 20.0 Monohydra te In both compositions, the nonionic surfactant was Imbentin-C-91/35 OFA

Claims (10)

  1. Claims 1. A substantially non-aqueous liquid cleaning composition comprising a liquid phase and a particulate solid phase dispersed in the liquid phase, wherein-the liquid phase includes a solvent selected from di-Cl 4 alkylene glycols and polyethylene glycols of molecular weight up to 1000 and at least 5%, based on the weight of the liquid phase, of dissolved alkali metal soap, the total level of soap in the composition being from 28 to 40% by weight and the composition having a-viscosity at -1 25 C of no more than
  2. 2.5 Pas at a shear rate of 21s 2. A composition according to claim 1, having a viscosity at 250C of no greater than 1.75 Pas at a shear rate of 21s 1.
  3. 3. A composition according to either preceding claim, wherein said dissolved alkali metal soap is from 7.58 to 30% by weight of the liquid phase.
  4. 4. A composition according to claim 3, wherein said dissolved alkali metal soap is from 10% to 20% by weight ot the liquid phase.
  5. 5. A composition according to claim 1, further comprising a fatty acid, the weight ratio of said fatty acid to said alkali metal soap being from 1:5 to 1.5:1.
  6. 6. A composition according to claim 1, wherein the amount of dispersed particulate solid phase is from 5% to 30% by weight of the total composition.
  7. 7. A composition according to claim 6, wherein the amount ot dispersed particulate solid phase is from 5% to 20% by weight of the total composition.
  8. 8. A composition according to claim 1, which is substantially free of builder other than the soap and in which the particulate solid phases comprise a bleach.
  9. 9. A composition according to any preceding claim, wherein the liquid phase comprises a mixture of a nonionic surfactant and said solvent.
  10. 10. A composition according to any preceding claim, comprising from 10% to 208 by weight of said solvent and from 30% to 50% by weight of said alkali metal soap, said composition being substantially free of nonionic surfactant.
GB8909801A 1988-04-29 1989-04-28 Liquid cleaning products Withdrawn GB2217727A (en)

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GB8909801A Withdrawn GB2217727A (en) 1988-04-29 1989-04-28 Liquid cleaning products

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992002610A1 (en) * 1990-08-02 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Liquid washing agent
EP0534298A1 (en) * 1991-09-25 1993-03-31 Henkel Kommanditgesellschaft auf Aktien Liquid or pasty washing or cleaning composition
WO2001007557A1 (en) * 1999-07-27 2001-02-01 Henkel Kommanditgesellschaft Auf Aktien Bleaching compositions
EP1614741A1 (en) * 2004-07-06 2006-01-11 JohnsonDiversey, Inc. Stable nonaqueous bleaching detergent composition dispersion

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992002610A1 (en) * 1990-08-02 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Liquid washing agent
EP0534298A1 (en) * 1991-09-25 1993-03-31 Henkel Kommanditgesellschaft auf Aktien Liquid or pasty washing or cleaning composition
WO1993006201A1 (en) * 1991-09-25 1993-04-01 Henkel Kommanditgesellschaft Auf Aktien Washing or cleaning agent in liquid or paste form
US5441661A (en) * 1991-09-25 1995-08-15 Henkel Kommanditgesellschaft Auf Aktien Non-aqueous liquid detergent preparations containing a hydrated zeolite a stabilized by a polar deactivating agent
WO2001007557A1 (en) * 1999-07-27 2001-02-01 Henkel Kommanditgesellschaft Auf Aktien Bleaching compositions
EP1614741A1 (en) * 2004-07-06 2006-01-11 JohnsonDiversey, Inc. Stable nonaqueous bleaching detergent composition dispersion
WO2006014223A1 (en) * 2004-07-06 2006-02-09 Johnsondiversey, Inc. Stable nonaqueous bleaching detergent composition dispersion
CN100577786C (en) 2004-07-06 2010-01-06 约翰逊迪瓦西公司 Stable nonaqueous bleaching detergent composition dispersion

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Publication number Publication date Type
GB8909801D0 (en) 1989-06-14 application
GB8810190D0 (en) 1988-06-02 application

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