SK2195A3 - Liquid cleaning product - Google Patents

Abstract

A substantially non-aqueous liquid cleaning product composition comprises a substantially non-aqueous liquid phase and also comprises a certain kind of polymer. The total composition is shear-thinning (viscosity decreases with shear rate). The equivalent composition without the solids is also shear-thinning but to a lesser or equal extent.

Description

Liquid cleaning product

Technical field

The invention relates to substantially non-aqueous liquid cleaning products comprising a non-aqueous liquid phase, optionally with a dispersed particulate solid material. Non-aqueous liquids are those that contain little or no water. The non-aqueous liquid phase may comprise a liquid surfactant and / or a liquid surfactant suitable for use in the cleaning product.

BACKGROUND OF THE INVENTION

Most generally, particulate solids are those having useful additive effects in use, for example, for fabric washing, they may contain detergent ingredients against water hardness as well as bleaches. In hard surface cleaning applications, the solids may include abrasive particles.

It is also often desirable to add one or more ingredients to these systems in order to achieve one or more of the following benefits:

(a) improve the solid suspension properties of the system, (b) reduce the formation of a clear storage layer, (c) reduce the need for additional stabilizing materials, (d) reduce ash in fabric washing applications, (e) reduce product density, (f) provide increased tolerance for high levels of solids in the system, and (g) reduce system solidification during storage.

We have now found that improved performance properties, such as one or more of the types from (a) to (g), listed above, can be obtained in non-aqueous liquid detergent compositions comprising a specific kind of polymeric material.

EP-A-0,413,616 discloses non-aqueous liquids comprising carboxypolymers to achieve stability and improved water dispersibility.

EP-A-0,359,491 and EP-A-0,359,492 disclose non-aqueous liquids comprising low and high molecular weight vinyl pyrrolidone polymers.

EP-A-0.028.849 discloses non-aqueous liquids comprising a stabilizing polymer which is at least partially hydrolyzed a maleic anhydride copolymer with ethylene or vinyl methyl ether.

GB-A-2,228,944 discloses non-aqueous liquids comprising polymeric materials that may contain acrylamide monomers.

Unpublished EP-A-2,228,944 discloses non-aqueous liquids comprising polymers which may contain 2-acrylamide-2-methylpropanesulfonic acid as monomer B.

SUMMARY OF THE INVENTION

The polymers of the present invention have the property that when added to the non-aqueous liquid phase in the absence of solids, the viscosity of the liquid phase decreases with shear force, and when the same liquid phase is added in the presence of solid material, said change in shear force, which, at least in the shear thinning region (typically less than 400 cm @ -1), is greater than for the liquid phase in the presence of solids or the polymer itself.

Thus, in one aspect, the invention provides a substantially non-aqueous liquid product comprising a substantially non-aqueous liquid phase, a composition further comprising a polymer which (a) when added to the substantially non-aqueous liquid phase in the absence of solid material causes the viscosity of said liquid phase to decrease. and (b) when added to a substantially non-aqueous liquid phase in the presence of a solid material causes the viscosity of the nominal liquid phase to decrease with the shear force, but such that the gradient of the viscosity versus shear force curve is greater than or equal to the shear force. in case (a).

Rheological properties

In principle, any solid may be suspended without sedimentation in the non-aqueous liquid phase if a sufficiently strong structure is formed in the liquid phase. By analogy, it will be appreciated that aqueous liquids may be adapted to suspend particulate solids either by adding a crosslinking thickening polymer such as Carbopol (trademark) or by forming a suitable liquid crystalline phase using the functional ingredients of the composition alone.

However, for the mixtures (either aqueous or non-aqueous) to be liquid, the structure must at least partially disintegrate or modify with shear (pressure). In other words, the viscosity must decrease with increasing shear force. In some aqueous systems, where the structure consists of multi-layered vesicles of surfactant molecules, only the pouches need to be deformed and rolled in order to achieve this effect.

We have found that in non-aqueous systems, the desired shear thinning behavior can be achieved by incorporating the aforementioned polymeric materials.

Without wishing to be bound by any theory or explanation, the Applicants believed that suitable polymeric materials are self-bonding thickeners. That is, when incorporated in the composition in a suitable amount, it increases its viscosity without perceptible absorption into the solid particles. Thus, it is the interaction between the polymer molecules themselves that gives rise to the desired properties. For example, such interactions may be strongly caused by crosslinking by covalent bonds or may be the result of weaker forces such as hydrogen bonds or van der Vaals interactions.

The crosslinking may result directly from the reaction of the functional groups present on the side chains of the polymer molecules and / or from the incorporation of specific crosslinking reagents added for this purpose. Although such cross-linking reagents will usually have a lower molecular weight than the molecular weight of the polymer (s), it will still be relatively high (e.g., > 1000).

Since the essence of the present invention is the discovery of the general principle and not only of certain combinations of defined ingredients, the Applicants do not wish to limit the scope of protection defined in the appended claims to the combinations set forth in the examples, either generically or specifically. For this purpose, the present invention is defined above, and also in the claims, in the sense of polymers selected for providing a liquid phase, with or without solid ingredients, certain properties.

However, the above requirement is primarily aimed at selecting the ingredients of a specific novel composition in accordance with the present invention in advance of preparation for the first time. It is also desirable to have a test to determine whether the prepared composition is in accordance with the present invention. The following is a non-limiting example of such a test. That is, if the nonaqueous solids containing the composition provides a positive result in such a test, it is the composition of the invention, although it is possible that some compositions of the invention, particularly those with a high solids fraction (e.g. greater than 0.3) , may give a tie or a negative result in this test.

The principle of the test is that most non-aqueous dispersions of particulate solids contain a relatively high solids fraction. In the sedimentation caused by the clear layer formed, smaller solid particles will be collected downstream with the sedimentation of larger particles. Any polymeric structure in the liquid phase, especially if dissolved, will also tend to sediment with the solids.

Thus, according to the test, the mixture should be diluted with the same or substantially the same component (s) of its liquid phase and either left to settle for a period of time or is still finely centrifuged. If the viscosity of the remainder of the clear metal layer decreases (typically more than 10 mPas) with increasing shear force (e.g., somewhere in the range of 0.01 to 200 s ^-1 ) and contains at least some polymer, then the polymer is a polymer specified as a component of the composition of the invention .

polymer

Preferred polymers for use as polymeric components of the compositions of the present invention are block copolymers that can be randomly arranged, containing at least one group soluble in the non-aqueous liquid phase, and which is also capable of self-association with a similar group of another polymer molecule when the polymer is dissolved in said polymer. liquid phase. Examples of such soluble self-linking groups are amines, amides and C1-C22 alkyl groups. Of these, amines and amides are particularly preferred.

The polymers also contain at least one other group soluble in the non-aqueous liquid phase, a group that binds two or more self-bonding groups together, and is substantially unabsorbed on solid particles. Typical other groups are homopolymers such as polyethylene oxide, polyvinylpyrrolidone and copolymers of commercially available vinyl monomers such as acrylic acid, maleic acid, vinylpyrrolidone, vinylalkylethoxylates, vinyl alcohol, vinylalkylates and vinylethoxyalkylates.

Generally speaking, the interconnected groups will comprise from 0.001 to 20% by weight of the average molecular weight, preferably from 0.01 to 10% by weight, and most preferably from 0.02 to 5% by weight.

The polymer as a whole will usually be used in 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and most preferably from 0.5 to 2% by weight of the total composition of the invention.

Thus, preferred polymers include polymers that include:

(i) 2 groups A which exhibit self-bonding when the polymer is dissolved in a non-aqueous liquid medium having a dielectric constant of from 1 to 20; (ii) from 10 to 1000 groups B which is a monomeric or polymeric group soluble in the non-aqueous liquid phase and (iii) 0 or from 1 to 15 BA groups.

Polymers of the invention include polymers of formula (I)

A- (B) _χ - (BA) _y N (I)

Where x is from 10 to 1000 y is 0 or still y is from 1 to 15

A is a group that exhibits self-bonding when the polymer is dissolved in a non-aqueous liquid medium having a dielectric constant of from 1 to 20,

B is a monomeric or polymeric group soluble in the non-aqueous liquid phase.

Most preferably, y is less than 8, especially from 0 to 3. Preferably, x is from 20 to 200.

7

Preferred units of group A include -NH ₂ , -CONR R, where R and R are independently selected from hydrogen and alkyl groups of less than 20 carbon atoms, C 1 -C 22 alkyl groups (preferably C 1 -C 22), ^and mixtures thereof. More preferred Group A units are -NH ₂ , -COR ¹ R ² .

9

Preferably R and R are independently selected from hydrogen and ^C 1 ^-C 10 alkyl groups, and more preferably from hydrogen and C 1 -C 8 alkyl-19 groups. Preferably, R + Rs contain less than 12 carbon atoms in total

Preferred units of Group B include - (CH ₂ -CH ₂ O) -, especially when n is from 20 to 200, vinylpyrrolidone, polyvinylpyrrolidone (ie [vinylpyrrolidone] where n is from 15 to 300), vinyl acetate, vinyl alcohol, acrylic acid, methacrylic acid, and maleic anhydride semi-esters, especially when copolymerized with acrylic acid in a molar ratio of from 1: 1 to 0.2: 1.

The average molecular weight of the polymeric material as determined by aqueous goal chromatography using polyacrylate standards is preferably from 1000 to 100000, more preferably from 2000 to 80000, and most preferably from 5000 to 50000. The assay method is based on eluent from aqueous phosphate buffer using Toya Soda and Polymer Laboratories aqueous GPC column with ultraviolet detector set at 215 nm, refractive detector can also be used.

Preferably, the polymer is prepared in situ in one or more or all of the components of the non-aqueous liquid phase. This can be achieved using methods known in the art, for example as described by F. Billmeyer, Textbook of Polymer Science, Viley Interscience.

Alternatively, the polymer may be prepared in isolation and subsequently pre-dissolved in the non-aqueous liquid phase before solids are added.

Post-dosing of the separately prepared polymer after incorporation of some or all of the solids into the non-aqueous liquid phase is also possible, especially if the composition also contains a deflocculating agent (see below).

Product form

All compositions of the present invention are liquid cleaning products. In the context of this specification, all references to liquid cleaning products refer to these materials which are liquid at 15 ° C and atmospheric pressure. They can be prepared in a wide range of specific forms, depending on the intended use. They can be prepared as cleaners for hard surfaces (with or without abrasives) or as a means of washing equipment (washing dishes, cutlery, etc.) either by hand or by mechanical means, as well as in the form of specialized cleaning products such as surgical instruments or artificial dentures. Preferably, the compositions of the invention are formulated as a fabric washing and / or fabric care composition.

Thus, the compositions will contain at least one component that promotes the cleaning and / or conditioning of the product concerned, selected according to the intended application. Typically, this component will be selected from surfactants, enzymes, bleaches, detergents, buffers, microbiocides, (for fabrics) fabric softeners, and (for hard surface cleaning) abrasives. Of course, in many cases more than one of these ingredients will be present as well as other ingredients commonly used in the relevant product forms.

When the compositions of the invention are fabric cleaners, preferably comprise a liquid phase comprising a nonionic surfactant and a solid phase dispersed in the liquid phase, said solid phase comprising one or more of the following bleach ingredients, bleach activators, detergent builders and solid surfactants.

When the compositions of the invention are intended for other uses, for example for mechanical washing of the device, the liquid phase will sometimes contain a solvent material other than a nonionic surfactant, for example glycerol triacetate, paraffin, low molecular weight polyethylene glycol or ethoxylated polyethylene glycol. The solid phase of the product will then generally comprise one or more detergent builders, abrasive materials and solid surfactant materials.

Surfactant

If the surfactants are solids, they will usually be dissolved or dispersed in the liquid phase. If they are liquids, they will usually form all or part of the liquid phase. However, in some cases, surfactants may undergo phase conversion in the composition.

In general, the surfactants for use in the compositions of the invention may be selected from any of the classes, subclasses and specific materials described in Surface Active Agents Vol. I, Schvartz & Perry, Interscience 1949 and Surface Active Agents Vol.II, Schwartz, Perry & Berch. , Interscience 1958, in an ongoing edition of McCutcheon's Emusi Fiers & Detergents published by the McCutcheon Division of Manufacturing Confectioners Company or in Tensid-Taschenbuch, H. Stache, 2nd Edition, Carl Hanser Verlag, Munchen & Vien, 1981.

Non - ionic surfactants

Nonionic detergent surfactants are well known. Normally they consist of a water-solubilizing polyalkoxylene or 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 it contains from about 6 to about 12 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-covered derivatives) having preferably from 8 to 20 carbon atoms, monocarboxylic acids having from 10 to 24 carbon atoms in the alkyl group, and polyoxypropylenes.

Also common are fatty acids of 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 has from 1 to 3 carbon atoms. In any of the mono- and dialkanolamide derivatives, optionally, there may be a polyoxyalkylene group linking the latter to the hydrophobic portion of the molecule.

In all surfactants containing polyalkoxylene, the polyalkoxylene group preferably contains from 2 to 20 ethylene oxide groups or ethylene oxide and propylene oxide groups. Of the latter class, those described in Applicants EP-A-225,654 are particularly preferred, especially for use as all or part of the liquid phase of a non-aqueous liquid composition. Also preferred are those ethoxylated nonionic surfactants which are the condensation products of C 9 -C 15 fatty alcohols condensed with 3 to 11 moles of ethylene oxide. Examples of these are the condensation products of alcohols

Cl-13 with 3 to 7 moles of ethylene oxide. These may be used as the only nonionic surfactant or in combination with those described in the above-mentioned European application, in particular as all or part of the liquid phase of the non-aqueous liquid composition.

Another class of suitable nonionic surfactants includes polysaccharides (polyglycosides / oligosaccharides), for example as described in any of the documents:

US 3,640,998; US 3,346,558; US 4,223,129; EP-A-92.355; EP-A99,183; EP 70,074; EP 70,075; EP 70,076; EP 70,077; EP 75,994; EP 75,995; EP 75,996.

Mixtures of various nonionic detergent surfactants may also be used. Particularly preferred is the combined use of detergent nonionic surfactants and non-detergent nonionic surfactants, for example mixtures of alkoxylated fatty alcohols containing from 5 to 10 EO groups and alkoxylated alcohols containing from 2 to 4 EO groups.

Mixtures of nonionic detergent surfactants with other detergent surfactants such as anionic, cationic or ampholytic detergent surfactants and soaps may also be used.

Preferably, the level of nonionic surfactants is from 1 to 90% by weight of the composition, more preferably from 5 to 75% by weight, most preferably from 20 to 60% by weight.

Anionic surfactants

Examples of suitable anionic detergent surfactants are alkali metal, ammonium or alkylamine salts with alkoxybenzene sulfonates having from 10 to 18 carbon atoms in the alkyl group, alkyl and alkyl ether sulfates having from 10 to 24 carbon atoms in the alkyl group, alkyl ether sulfates having 1 to 10 carbon atoms. and up to 5 ethylene oxide groups, and olefin sulfonates prepared by sulfonating the C10-24 alpha-olefins followed by neutralization and hydrolysis of the sulfonation reaction product, and all stable free acid forms of these anionic surfactants.

Non-aqueous organic solvents

As a general rule, the most suitable liquids selected to form the liquid phase are those organic materials that have polar molecules. Particularly suitable will be those having a relatively lipophilic portion and a relatively hydrophilic portion, especially a hydrophilic portion rich in free electron vapors. This is entirely consistent with the observation that liquid surfactants, especially polyalkoxylated nonionic surfactants, are a preferred class of liquid phase materials.

Surfactants which are suitable for use as the liquid phase include those having the preferred molecular form mentioned above, although other species may also be used, especially when used in combination with the previous, more preferred types. In general, non-surfactant solvents may be used alone or in combination with liquid surfactants. Non-surfactant solvents having a molecular structure that falls within the previous more preferred category include ethers, polyethers, alkylamines and fatty amines (especially di- and tri-alkyls or fatty-N-substituted amines), alkyl (or fatty) amides and their mono- and di-N-substituted derivatives, lower alkyl (or fatty) carboxylic acid esters, ketones, aldehydes and glycerides. Particular examples include dialkyl ethers, polyethylene glycols, alkyl ketones (e.g. acetone) and glyceryltrialkyl carboxylates (e.g. glyceryl triacetate), glycerol, propylene glycol and sorbitol.

Several light solvents with little or no hydrophilic character are unsuitable in most systems, examples of which are lower alcohols, for example ethanol, or higher alcohols, for example dodecanol, as well as alkanes and olefins. However, these may be combined with other liquid materials.

Proportion of liquid phase

Preferably, the compositions of the invention comprise a liquid phase (containing or not containing a liquid surfactant) in an amount of at least 10% by weight of the total composition. The amount of liquid phase present in the composition may be up to about 90% by weight, but in most cases the practical amount will lie between 20 and 70% by weight and preferably between 35 and 60% by weight of the composition.

Solids content

The compositions of the invention may comprise a solid phase dispersed in a liquid phase. The term solid as used herein is formed to correspond to solid phase materials that are added to and dispersed in the solid form in the mixture, those solids that dissolve in the liquid phase and those in the liquid phase that solidify (subject to phase conversion) in the mixture in which they are then dispersed.

When solids are present, generally their content in non-aqueous liquid compositions can be very wide, for example from 10 to 90% by weight, usually from 30 to 80% by weight, and preferably from 40 to 65% by weight of the final composition. The solid phase should be in particulate form and have an average particle size of less than 300 gm, preferably less than 200 µm, more preferably less than 100 gm, especially less than 10 gm. The particle size may also be sub-micron.

For the purposes of this invention, references to the mean particle diameter correspond to D (3,2) particle size, which is the surface, volume mean diameter calculated as described in M. Alderliesen, Anal. Proc. Vol. 21, May, 1984, 167-172. Further, herein, any reference to an average or medium particle size or diameter corresponds to a D (3,2) diameter, unless explicitly stated otherwise.

Appropriate particle sizes may be obtained by using materials of appropriate size or by grinding the total product in a suitable grinding apparatus. In order to control the solid phase aggregation which leads to the non-dispersible settling or solidification of the mixture, it is preferably to include a deflocculant therein.

Other ingredients

In addition to the ingredients already discussed, there are many other ingredients that can be incorporated into liquid cleaning products.

There are very many such other ingredients and are selected according to the intended use of the product. However, the greatest variety is in laundry and / or fabric treatment products. Many of the ingredients intended for this purpose will also find application in products for other applications (e.g. hard surface cleaners and dishwashing liquids).

Hydrophobically modified materials

Surprisingly, it has been found that the physical stability of non-aqueous liquid detergent compositions can be further improved and / or settling problems can be minimized when using hydrophobically modified dispersants (hereinafter referred to as HM materials).

For the purposes of the present invention, a dispersing material is a material whose main purpose is to stabilize the mixture. Hydrophobically modified materials are particulate materials whose outer surface has been chemically treated to reduce its hydrophilic character.

Preferred HM materials have a weight average particle size of from 0.005 to 5 µm, more preferably from 0.01 to 3 µm, most preferably from 0.02 to 0.5 µm. Quantity HM. % of the material is preferably from 0.1 to 10% by weight of the mixture, more preferably from 0.3 to 5% by weight, most preferably from 0.5 to 3% by weight.

Preferably, the number of hydroxy and / or acid groups on the surface of the particles is reduced by hydrophobic treatment. Suitable reactions include esterification or etherification of hydrophilic groups. Preferably, the hydrophilic modification treatment comprises at least 10% hydrophilic groups on the particle surface, more preferably from 40 to 95%, most preferably from 50 to 90%.

Partial hydrophobization is preferable to a completely hydrophobic modification.

HM silica gel containing dispersants are preferably used. The hydrophobic modification of silica gel particles preferably involves the substitution of free hydroxy groups on the outer surface of the silica gel particles with a short alkyl or silyl group. More preferably, the surface hydroxy groups are substituted with a methyl group.

It has been found that to further reduce the separation of the clear layer of the liquid detergent composition of the invention, the use of particulate metal oxides is particularly preferred. Preferably, the suspended metal oxides have a density of from 200 to 1000 g / l, more preferably from 250 to 800 g / l, particularly preferably from 300 to 700 g / l, most preferably from 400 to 650 g / l.

Preferably, the metal oxide is selected from calcium oxide, magnesium oxide and alumina, most preferably magnesium oxide.

The average weight particle size of the metal oxide is preferably from 0.1 to 200 gm, more preferably from 0.5 to 100 gm, most preferably from 2 to 70 gm. The level of metal oxide is preferably from 0.1 to 7% by weight of the composition, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight.

Detergent ingredients

Detergent ingredients are those materials that counteract the effect of calcium or other ions, water hardness either by precipitation or sequestering effect. They include both inorganic and organic detergent ingredients. They can also be divided into phosphorus-containing and phosphorus-free types, the latter being preferred if environmental considerations are important.

In general, inorganic detergent builders include various phosphate, carbonate, silicate, borate and aluminosilicate types of materials, particularly in the form of alkali metal salts. Mixtures thereof may also be used.

Examples of phosphorus-containing inorganic components, if present, include water-soluble salts, especially pyrophosphates, orthophosphates, polyphosphates and phosphonates of alkali metals. Particular examples of inorganic phosphate components are sodium and potassium tripolyphosphates, phosphates and hexametaphosphates.

Examples of phosphorus-free inorganic components, if present, include water-soluble carbonates, bicarbonates, borates, silicates, metasilicates, and crystalline and amorphous alkali metal aluminosilicates. Specific examples include sodium carbonate (with or without calcite embryos), potassium carbonate, sodium and potassium bicarbonate, silicates and zeolites.

Examples of organic ingredients include citrates, succinates, malonates, fatty acid sulfonates, carboxymethoxysuccinates, ammonium polyacetates, carboxylates, polycarboxylates, aminopolycarboxylates, polyacetyl carboxylates and polyhydroxysulfonates of alkali metals, ammonium and substituted ammonium. Specific examples include sodium, potassium, Utne, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, and citric acid. Other examples are organic phosphonates of the sequestering reagent type, for example sold by Monsanto under the trade name of Dequest series, and alkane hydroxyphosphonates.

Other suitable organic detergent builders include high molecular weight polymers and copolymers known to have detergent builder properties, for example, suitable polyacrylic acid, polymaleic acid and polyacrylic / polymaleic acid copolymer and salts thereof, such as sold by BASF under the trademark Sokolan. Preferably, the level of these components is from 1 to 40% by weight of the composition, more preferably from 5 to 40% by weight.

deflocculants

Preferably, the compositions of the invention also contain one or more deflocculation materials. In principle, any material can be used as a deflocculant if it meets the deflocculation test described in EP-A-66199 (Unilever). The ability of a substance to act as a deflocculant will depend in part on the solid / liquid phase combination. However, acids are particularly preferred.

The deflocculants are preferably selected from Bronsted acids and Lewis acids. Examples thereof are transition metals, anhydrides, organic acids, inorganic mineral acids and salts, C 8 -C 20 fatty acids and salts, C 1 -C 6 alkanoic acids, substituted anhydrous alkali metal aluminosilicates, alkyl, alkenyl aryl, aralkyl and aralkenyl sulfonic acids. or carboxylic acids and salts and their halogenated derivatives, zwitterionic surfactants and anionic surfactants of the formula RLAY as defined in EP-A-266,199. Preferably, the acid form is used.

Some typical examples of novel acids such as α stearic, and their halogenated deflocculants include acetic acid, propionic derivatives such as trichloroacetic or trifluoroacetic acid, as well as alkyl (e.g. methane) sulfonic acids and aralkyl (e.g. paratoluene) sulfonic acids.

Examples of suitable inorganic mineral acids and their salts are hydrochloric, carbonic, sulfuric, sulfuric and phosphoric acid; potassium hydrogen sulphate, sodium hydrogen sulphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, potassium dihydrogen pyrophosphate, tetrasodium hydrogen triphosphate.

Organic acids such as formic, lactic, aminoacetic, benzoic, salicylic, violet, nicotinic, ascorbic, ethylenediaminetetraacetic and aminophosphonic acids, as well as long-chain fatty carboxylates and triglycerides such as oleic, stearic, stearic, stearic, stearic and stearic acids Similarly. Peroxyacids such as percarboxylic and persulfonic acids may also be used.

The acid deflocculant class further extends to Lewis acids, including anhydrides of inorganic and organic acids. Examples are acetic, maleic, phthalic and succinic anhydrides, sulfur trioxide, phosphorus pentoxide, boron trifluoride, antimony chloride.

Fatty anions are very suitable deflocculants, and a particularly preferred class of deflocculants includes anionic surfactants. Although anionic surfactants that are salts of alkali and other metals may be used, the free acid forms of these surfactants (wherein the metal ion is replaced by the H ⁺ cation, i.e., the proton) are particularly preferred. These anionic surfactants include all classes, subclasses and specific forms described in the general surfactant references above, cf. Schwartz & Perry, Schwartz & Perry & Berch, McCutcheon's, Tensid-Taschenbuch; and their free acid forms. Several anionic surfactants have been described herein. In the role of deflocculants, their free acid forms are generally preferred.

Particularly, some preferred subclasses and examples are C10 to C22 fatty acids and dimers thereof, C8 to C18 alkylbenzenesulfonic acids, monoesters of C10 to C18 alkyl or alkyl ether sulfuric acids, C12 to C18 paraffin sulfonic acids, sulfonic acids of fatty acids, benzene, toluene, xylene and cumenesulfonic acids and the like. Of particular interest are linear C12 to C18 alkylbenzene sulfonic acids.

Like the anionic surfactants, zwitterionic agents can also be used as deflocculants. These may be some of the substances described in the above-mentioned general references to surfactants. One example is lecithin.

The level of deflocculation material in the composition can be optimized as described in EP-A-266199 above, but in very many cases it is at least 0.01% by weight, usually 0.1% by weight, preferably at least 1% by weight, and can be up to 15% weight.

For most practical applications, this amount ranges from 2 to 12% by weight, preferably from 4 to 10% by weight, based on the final composition. Surprisingly, however, it has been found that, in order to obtain stability, in the composition of the invention, the presence of a polymeric material generally reduces the need for high levels of deflocculating material.

bleach

Bleaching agents include halogen, in particular chlorine bleaches, for example bleaches provided in the form of alkali metal halides, for example hypochlorites. When used for fabric washing, oxygen bleaches are preferred, for example in the form of inorganic peroxy salts, preferably with a bleach precursor, or as a peracid.

In the case of inorganic peroxy salt bleaches, the activator makes bleaching more efficient at low temperatures, i.e. in the range of ambient temperature to about 60 ° C, so such bleaching systems are commonly known as low temperature bleaching systems and are well known in the art. An inorganic peroxy salt, for example sodium perborate, monohydrate or tetrahydrate, causes the release of active oxygen in solution, and the activator, which is usually an organic substance _c having one or more reactive acyl residues that cause peroxyacids, the latter provides a more effective bleaching effect at low temperatures. as peroxy-whitening agents themselves. The weight ratio of peroxy bleach to activator is from about 20: 1 to about 2: 1, preferably from about 10: 1 to about 3.5: 1. While the amount of bleach system, i.e., peroxy bleach and activator, may be varied between about 5% and about 35% by weight of the total liquid, it is preferable to use from about 6% to about 30% by weight of the ingredients of the bleaching system. The preferred level of peroxy bleach in the composition is between about 5.5% and about 27% by weight, while the preferred level of activator is between about 0.5% and about 14% by weight, most preferably between about 1% and about 7% by weight.

Typical examples of suitable peroxy bleach compounds are alkali metal perborates, tetrahydrates and monohydrates, percarbonates, persilicates, and alkali metal perphosphates, of which perborate is preferred.

It is particularly preferred to include a bleach stabilizer or bleach system, for example, ethylenediaminetetramethylene phosphonate and diethylenetriaminepentamethylene phosphonate or other suitable organic phosphonates or salts thereof, such as those described in the Dequest series described above. These stabilizers may be used in the form of an acid or a salt, for example in the form of a calcium, magnesium, zinc or aluminum salt. The stabilizer may be present at a level of up to about 1% by weight, preferably between about 0.1% and about 0.5% by weight.

It has been found that liquid bleach precursors such as glycerol triacetate and ethylidene heptanoate acetate, isopropenyl acetate and the like also function well as both the liquid phase forming material and eliminate or reduce the need for additional relatively volatile solvents such as lower alcohols, paraffins, glycols and glycol ethers for example to control viscosity. However, solid bleach precursors such as N, N, N ¹ , N -tetraacetyl ethylenediamine (TAED) can also be used.

Various other ingredients

Other ingredients that include the remaining ingredients that can be used in liquid cleaning products, such as fabric conditioning agents, enzymes, perfumes (including deoparfum), microbiocides, coloring agents, fluorescent agents, sludge suspending agents (anti-redeposition agents), inhibitors corrosion, enzyme stabilizers, bleach catalysts and suds suppressors.

Among the fabric conditioning agents that can be used, either in fabric wash liquids or in rinse conditioners, are fabric softening materials, quaternary ammonium salts, imidazolinium salts, fatty amines, and cellulases.

Enzymes that can be used in the liquids of the invention include proteolytic enzymes, amylolytic enzymes, and lipolitic enzymes (lipases). Various types of proteolytic enzymes and amylolytic enzymes are known and are commercially available. They may be incorporated, for example, as prills, marums or suspensions.

Fluorescent agents that can be used in the liquid cleaning products of this invention are well known and many such fluorescent reagents are commercially available. Usually, these fluorescent substances are supplied and used in the form of alkali metal salts, for example sodium salts. The total amount of fluorescent reagent (s) used in the detergent composition is generally from 0.02 to 2% by weight.

If it is desired to include anti-redeposition agents in the cleaning liquid products, their amount 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, for example sodium carboxymethylcellulose (SCMC), anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.

Water

The compositions are substantially non-aqueous, i. contain little or no free water, preferably not more than 5% by weight, more preferably less than 3%, particularly preferably less than 1% by weight of the total mixture. It has been found that the higher the water content, the more likely the viscosity of the non-aqueous liquids is too high or even causes settling.

The use

Compositions in accordance with the present invention can be used for a variety of detergent purposes, for example, for cleaning surfaces and washing fabrics. For washing fabrics, preferably an aqueous liquid containing 0.1 to 10% by weight, more preferably 0.2 to 2% by weight, of the non-aqueous detergent composition of the invention is used.

Production

A suitable stage for incorporating the polymer has been discussed above. The following is a description of a preferred method of adding and treating solids and a non-aqueous liquid phase.

During the manufacture of non-aqueous liquid compositions, it is preferred that all raw materials are dry and (in the case of hydratable salts) in a low hydration state, for example, anhydrous phosphate components, sodium perborate monohydrate and dry calcite abrasive when used in the composition. In a preferred process, the dry, substantially anhydrous solids are mixed with the liquid phase in a dry vessel. If a deflocculation material has been used, it should preferably - at least partially - be mixed with the liquid phase, rather than adding solids. In order to minimize the sedimentation rate of the solids, it is passed through a friction mill or a combination of mills, for example a colloid mill, corundum disk mill, horizontal or vertical ball mill, to achieve a particle size of 0.1 to 100 μτη, preferably 0.5 up to 50 µm, ideally from 1 to 10 µm.

However, compositions having a Bingham resistance to movement of 5 Pa or more may be prepared with large particulate solids, for example, grains or spheres to render the composition aesthetically pleasing, or large functional solids such as abrasives if required to prepare a liquid abrasive. cleaner. The above value of 5 Pa as a Bingham resistance to movement corresponds to its determination in the range of shear force from 0.1 to 400 s -1 at 25 ° C after one minute stabilization.

A preferred combination of such mills to achieve particle sizes of from 0.1 to 100 µm is a colloid mill followed by a horizontal ball mill as these can operate under the desired conditions to provide a narrow size distribution of the final product. Of course, a particulate material that already has the desired particle sizes does not need to undergo this procedure and, if desired, can be incorporated during a later stage of manufacture.

During this grinding process, the energy input causes an increase in the temperature of the product and the release of air trapped in or between the particles of the solid ingredients. Therefore, it is very necessary to add any thermally sensitive ingredients to the product after the grinding step and subsequent cooling step. It may also be desirable to deaerate the product before adding these ingredients (usually added in small quantities) and optionally, at any stage of the manufacturing process. Typical additives that can be added at this stage are perfumes and enzymes, but could also be high temperature sensitive bleaching components or volatile solvent components that may be desired in the final blend. It is particularly preferred that the volatile material enters after any deaeration step. Suitable devices for cooling (e.g. heat exchangers) and deaeration will be well known to those skilled in the art.

It is to be understood that all equipment used in this process should preferably be completely dry, with particular care being taken after any cleaning operations. The same applies to the following storage and packaging facilities.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

component % weight Vista 1012-62 (D 22.9 Synperonic A3 (2) 19 glycerol 5 Silicone oil anti - foaming substance 1.2 Marlon AS (3) 6 Sodium carbonate 16.7 Calcite, Soca'l U 3 (4) 6 Verse TL 3 (5) 1.5 Sipernat D 17 (6) 3 TAED 5 Sodium perborate (monohydrate) 10.5 SCMC 1.5 Tinopal CBS-X, Fluorescent 0.15

perfume

polymer

1.05

0.5

Example 1 - Result **** Clear top layer after one month storage at 37 ° C Polymer viscosity mPa at 21 sec ^- ^ **** without polymer

980 7mm

Rheovis CRX (dry, solid) ex Allied Colloids 1120 4 mm A = NH 2> B = ethylene oxide Ratio 2: 1, M = 4000 w 1300 2.5 mm A = NH2, B = ethylene oxide Ratio 2: 1, M = 8000 1280  3 mm A = NH 2> B = ethylene oxide 2: 1 ratio, M _w = 15000 1104 3 mm AB-Al-BA polymer A = NH 2, B = ethylene oxide M _w = 8000, A1 = CO ₂ CH ₂ CH ₂ NH ₂ CH ₂ CO 2 - 1420 1 mm Poly (acrylic acid co-acrylamide) random copolymer, Monomer ratio 5: 1, M, 10,000 1240 2 mm Poly (acrylic acid co-acrylamide) random copolymer, 5: 1 monomer ratio, M1, 20,000 w 1510 1 mm Hydrolyzed polyvinyl acetate co-acrylamide, 10: 1 monomer ratio, M _w 15000 1200 3.5 mm

Comparative examples

Polyacrylic acid

M _w 20000 (GB-A-2,228,944) 1010 7,5 i Polyvinyl alcohol, M _w 10000, 1080 6.5 i Polyvinylpyrrolidone M _w 40000, (EP-A-359492) 1103 6.5 i Gantrez AN-119 dodecanol semi-ester (EP-A-413 616) 1130 6 mm

mm mm mm

Example 2

% By weight

Marlipal 013/60 (7) 26.2 Marlipal 013/30 (7) 26.2 Anti-foaming substance (8) 2 Sodium carbonate 10 Verse TL 3 (5) 1.5 Sipernat D 17 (6) 3 TAED 2 Sodium perborate (Monohydrate) 5 SCMC 1 Tinopal CBS-X, Fluorescent 0.2 Sodium stearate 2.0 perfume 1.05 polymer 0.5

Time to form a 1 cm clear topsheet at 37 ° C in 11 specimens in a 10 cm diameter container

The results

Polymer without polymer

Rheovis CRX (dry, solid) ex Allied Colloids days days

A = NH 2> B = ethylene oxide Ratio 2: 1, M _w = 4000 10 days A = NH2, B = ethylene oxide Ratio 2: 1, M = 8000 W 8 days A = NH 2> B = ethylene oxide The ratio of 2: 1, _Mw = 15,000 16 days

A-B-Al-B-A polymer

A = NH 2> B = ethylene oxide

M. = 8000. A1 = COoCHoCH2NHCHnCHnCO0- 35 days

Poly (acrylic acid random copolymer,

5: 1 monomer ratio, M w

Poly (acrylic acid random copolymer,

5: 1 monomer ratio, M '' what acrylamide)

10000 20 days what about acrylamide) 20000 40 days

Raw materials (1) Narrow-range ethoxylated non-ionic surfactants ex Vista (2) C13-C15 alcohol alkoxylated with an average of 3 ethylene oxime groups ex ICI (3) Anionic detergent in acid form ex Huls (4) Calcium carbonate with large surface area (5) Copolymer of sulphonated styrene and maleic anhydride, sodium salt, ex National Starch & Chemical Co.

(6) Hydrophobically modified silica dispersing agent ex Degussa (7) Marlipal 013 are ethoxylated isotridecanols, 013/30 contains 30% by weight of ethylene oxide, Ex Hoechst (8) DBIOO®, ex Dow Corning

Claims (5)

A liquid cleaning product comprising a substantially non-aqueous liquid phase, further comprising a polymer, characterized in that the polymer has the formula (I) A- (B) _χ - (BA) _y -A (I) where x is from 10 to 1000 y is 0 to 15 A is a group that exhibits self-bonding when the polymer is dissolved in a non-aqueous liquid medium having a dielectric constant of from 1 to 20, A constitutes from 0.001 to 20% by weight of the average molecular weight, and comprises units selected from -N1 · 4, -CONR R, wherein R and R are independently selected from hydrogen and alkyl groups of less than 10 carbon atoms, C 1 -C 22 alkyl groups (preferably And mixtures thereof. B is a monomeric or polymeric group soluble in the non-aqueous liquid phase. A composition according to claim 1, characterized in that B is polyethoxy, vinylpyrrolidone, polyvinylpyrrolidone, vinyl acetate, vinyl alcohol, acrylic acid, methacrylic acid, and maleic anhydride semi-esters, especially when copolymerized with acrylic acid in a molar ratio of 1 : 1 to 0.2: 1. A composition according to claims 1 to 2, characterized in that the average molecular weight of the polymer is from 1000 to 100000. 4. A composition according to claims 1 to 3 wherein the amount of polymer is from 0.1 to 10% by weight of the total composition. A composition according to claims 1 to 4, characterized in that the particulate solid material is dispersed in phase.