MXPA98000194A - Compositions non-aqueous detergents comprising efervescen systems - Google Patents

Abstract

A non-aqueous detergent composition which is in the form of a liquid, gel or paste, further characterized in that said composition further comprises an effervescent carbon dioxide formation system.

Description

NON-AQUEOUS DETERGENT COMPOSITIONS THAT COMPRISE EFFERVESCENT SYSTEMS FIELD OF THE INVENTION This invention relates to non-aqueous laundry detergent products, which are in the form of a liquid, a gel or a paste, comprising an effervescent system.

BACKGROUND OF THE INVENTION Detergent products in the form of liquid, gel or paste are often considered more convenient to use than dry or powder detergent products. Therefore, said detergents have found substantial favor with consumers. Such detergent products can be easily measured, they dissolve quickly in the wash water, they can be easily applied in concentrated solutions or dispersions to soiled areas in garments that are to be washed, and do not release dust. They also usually take up less storage space than granulated products. Additionally, these detergents may have incorporated in their formulations materials that could not withstand drying operations without deterioration, for example, operations that are frequently employed in the manufacture of particulate or granular detergent products. While said detergents have many advantages over granular detergent products, they inherently have several disadvantages. In particular, the components of the detergent composition which may be compatible with each other in the granulated products, may tend to interact or react with each other. Thus, components such as enzymes, surfactants, perfumes, brighteners, solvents and, especially, bleach and bleach activators, can be especially difficult to incorporate into liquid detergent products that have an acceptable degree of chemical stability. One approach to increasing the chemical compatibility of components of the detergent composition in detergent products has been to formulate non-aqueous (or anhydrous) detergent compositions. The formulation of such non-aqueous products gives rise to specific problems. In particular, the non-aqueous products may have relatively high viscosity which, in turn, slows down the rate of dissolution or dispersion in the wash liquor. The net result is that the general operation of the non-aqueous product is adversely affected, especially under strenuous conditions, for example, short wash cycles with little agitation, at low temperature. It is possible to add viscosity control agents to these products; however, they increase the cost and volume of the product without contributing to the washing / cleaning operation of said detergent products. Given the foregoing, it is clear that there remains a need to identify and provide detergent compositions in the form of non-aqueous products, with improved dispersibility and dissolution capability. It has now been found that the dissolution and dispersion of non-aqueous products can be substantially improved by using an effervescent carbon dioxide-forming system.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a non-aqueous detergent composition, which is in the form of a liquid, a gel or a paste; said composition comprising an effervescent carbon dioxide forming system.

DETAILED DESCRIPTION OF THE INVENTION The effervescent system according to the present invention is an effervescent carbon dioxide forming system. By dilution in the wash liquor, the effervescent system compounds dissolve rapidly and neutralize each other, thereby releasing carbon dioxide which, in turn, improves the dissolution and dispersibility of the product. The preferred effervescent system according to the present invention includes anhydrous citric acid and anhydrous sodium bicarbonate. Other suitable effervescent systems include tartaric acid and anhydrous sodium bicarbonate. The molar ratio of citric acid or tartaric acid to sodium bicarbonate varies from 1/2 to 1/10. The total amount of the effervescent system is from 2% to 20% by weight of the non-aqueous product. The non-aqueous detergent compositions of this invention may additionally comprise a surfactant and a liquid gel phase, which contains low polarity solvent, which has a bleach activating salt dispersed therein. The components of the liquid and solid phases of the detergent compositions herein, as well as the form of the composition, the preparation and the use, are described in detail in the following.

THE SURGICAL AGENT The amount of the surfactant ingredient mixture component of the detergent compositions herein may vary, depending on the nature and amount of the other components of the composition and depending on the desired rheological properties of the ultimately formed composition. In general, this mixture of surfactants will be used in an amount comprising about 10% to 90% by weight of the composition. Better still, the surfactant mixture will constitute about 15% to 50% by weight of the composition. A typical list of anionic, nonionic, ampholytic and hybrid (or amphoteric) classes and species of these surfactants is given in US Patent 3,664,961, issued to Norris on May 23, 1972. Preferred anionic surfactants include the alkyl sulfate surfactants, which are water-soluble salts or water-soluble acids of the formula ROSO3M, wherein R is preferably a hydrocarbyl of 10 to 24 carbon atoms, preferably an alkyl or hydroxyalkyl having an alkyl component from 10 to 18 carbon atoms, preferably an alkyl or hydroxyalkyl having an alkyl component of 10 to 18 carbon atoms, better still, an alkyl or hydroxyalkyl of 12 to 15 carbon atoms, and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium) or ammonium or substituted ammonium (quaternary ammonium cations such as tetramethylammonium and dimethylpyridinium cations) . The most preferred anionic surfactants include the alkoxylated alkyl sulfate surfactants, which are soluble or acid salts of the formula R0 (A) mS03M, wherein R is an unsubstituted alkyl or hydroxyalkyl group of 10 to 24 carbon atoms, having an alkyl component of 10 to 24 carbon atoms, preferably an alkyl or hydroxyalkyl of 12 to 18 carbon atoms, better still, alkyl or hydroxyalkyl of 12 to 15 carbon atoms; A is an ethoxy or propoxy unit; is greater than zero, typically between about 0.5 and 6, better yet, between about 0.5 and 3, and h1 is H or a cation which, for example, can be a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium or substituted ammonium cation. The alkyl ethoxylated sulfates, as well as the propoxylated alkyl sulfates are contemplated herein. Specific examples of substituted ammonium cations include quaternary ammonium cations, such as tetramethylammonium cations and dimethylpyridinium cations. Exemplary surfactants are: polyethoxylate (10) alkyl sulfate of 12 to 15 carbon atoms (Ci 2 -CidE (1.0) M), polyethoxylate sulfate (2,25) of alkyl of 12 to 15 carbon atoms (C 12 -C) ? sE (2.25) M), polyethoxylate sulfate (3.0) of alkyl of 12 to 15 carbon atoms (Ci2-C? sE (3.0) M) and polyethoxylate sulfate (4.0) of alkyl of 12 to 15 carbon atoms (C12 -Cis (4.0) M), where M is conveniently selected sodium and potassium. Other suitable anionic surfactants to be used are the alkyl ester sulphonate surfactants, which include linear esters of carboxylic acids of 8 to 20 carbon atoms (ie, fatty acids) which are sulfonated with gaseous SO3 of agreement The Journal of the American Oil Chemists Society, 52 (1975), pages 323-329. Suitable starting materials would include natural fatty substances, such as those derived from tallow, from palm oil, etc. The preferred alkyl ester sulphonate surfactant, especially for laundry applications, comprises alkyl ester sulfonate surfactants of the structural formula: R3 - CH .4. -OR *. O3M wherein R3 is a hydrocarbyl of 8 to 20 carbon atoms, preferably an alkyl, or a combination thereof; R 'is a hydrocarbyl of 1 to 6 carbon atoms, preferably an alkyl or a combination thereof; and M is a cation that forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals, such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations. Preferably, R3 is alkyl of 10 to 16 carbon atoms and R * is methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates in which R3 is alkyl of 10 to 16 carbon atoms. Also included in the laundry detergent compositions of the present invention are other anionic surfactants useful for detergent purposes. These may include the salts (including, for example, the sodium, potassium, ammonium and substituted ammonium salts, such as the mono-, di- and triethanolamine salts) of soap; linear alkylbenzene sulphonates of 9 to 20 carbon atoms, primary or secondary alkan sulfonates of 8 to 22 carbon atoms, olefin sulphonates of 8 to 24 carbon atoms, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of citrates metal alkaline earth, for example, as described in British Patent Specification No. 1,082,179; alkyl polyglycol ether sulfates of 8 to 24 carbon atoms (containing up to 10 moles of ethylene oxide), alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl sulfates-glycerol, alkyl phenol ether sulphonates of ethylene oxide; the paraffin sulfonates, the alkyl phosphates, the isethionates, such as the acyl isethionates; the N-acyltaurates, the succinamates and alkyl sulfosuccinates, the monoesters of sulfosuccinates (especially the monoesters of 12 to 18 carbon atoms especially saturated) and the diesters of sulfosuccinates (especially the diesters of 6 to 12 carbon atoms, saturated and unsaturated) ), the alkyl polysaccharide sulfates, such as the alkyl polyglycoside sulfates (the non-sulfate, nonionic compounds, described below) and the alkyl polyethoxycarboxylates, such as those having the formula RO (CH2CH2?)? -CH2COO-M +, wherein R is an alkyl of 8 to 22 carbon atoms; is an integer from 1 to 10 and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin; and the resin acids and the hydrogenated resin acids present in or derived from second distillation oil. Other examples are described in Surface Active Agents and Detergents (volumes I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin and co-inventors, in column 23, row 58, to column 29, line 23 (incorporated herein by reference). When included herein, the detergent compositions of the present invention typically comprise about 1% to 40%, preferably about 5% to 25%, by weight of said anionic surfactants. One class of nonionic surfactants, useful in the present invention, are the condensates of ethylene oxide with a hydrophobic portion to give a surfactant having an average hydrophilic-lipophilic balance (EHL) on the scale of 8 to 17, preferably from 9.5 to 14, better still, from 12 to 14. The hydrophobic (lipophilic) portion can be aliphatic or aromatic in nature and the length of the polyoxyethylene group that condenses with any particular hydrophobic group can be easily adjusted to produce a compound soluble in water having the desired degree of equilibrium between the hydrophilic and hydrophobic elements. Especially preferred nonionic surfactants of this type are the primary alcohol ethoxylates of 9 to 15 carbon atoms, containing from 3 to 12 moles of ethylene oxide per mole of alcohol, particularly the primary alcohols of 12 to 15. carbon atoms containing from 5 to 8 moles of ethylene oxide per mole of alcohol. Another class of nonionic surfactants comprises the alkyl polyglucoside compounds of the general formula: R0 (Cn H2 n 0) t Z? wherein Z is a portion derived from glucose; R is a hydrophobic, saturated alkyl group, containing from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4; the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglycosides. Compounds of this type and their use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118. Also suitable as nonionic surfactants are polyhydroxy acid amide surfactants of the Formula: R2 --C - N - Z 0 Rl wherein R1 is H or R1 is hydrocarbyl of 1 to 4 carbon atoms, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof; R2 is hydrocarbyl of 5 to 31 carbon atoms and Z is a polyhydroxyhydrocarbyl having a straight hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight chain alkyl or alkenyl chain, of 11 to 15 carbon atoms, such as cocoalkyl or mixtures thereof; and Z is derived from a reducing sugar, such as glucose, fructose, maltose, lactose, in a reductive amination reaction.

THE NON-AQUEOUS LIQUID DILUENT To form the liquid gel or paste phase of the detergent compositions, the surfactant (or mixture thereof) described above can be combined with a non-aqueous liquid diluent, such as a liquid alcohol alkoxylate material or an organic solvent non-aqueous, low polarity.

THE ALCOHOL ALCOHOLATES A component of the liquid diluent suitable for forming the compositions herein comprises an alkoxylated fatty alcohol material. Said materials themselves are also nonionic surfactants. These materials correspond to the general formula: Rl (CmH2 (n0) n0H wherein R1 is an alkyl group of 8 to 16 carbon atoms; m is from 2 to 4 and n varies from about 2 to 12. Preferably, Ri is an alkyl group which may be primary or secondary, containing about 9 to 15 carbon atoms, better still, about 10 to 14 atoms of carbon. Also preferably the ethoxylated fatty alcohols will be the ethoxylated materials containing about 2 to 12 ethylene oxide portions per molecule; Better yet, about 3 to 10 portions ethylene oxide per molecule. The alkoxylated fatty alcohol component of the liquid diluent will often have a hydrophilic-lipophilic balance (EHL) ranging from about 3 to 17. Better still, the EHL of this material will vary from about 6 to 15, most preferably about 8. to 15. Examples of fatty alcohol alkoxylates useful as one of the essential components of the non-aqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been sold commercially under the tradenames Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodoles include: Neodol 1-5, an ethoxylated fatty alcohol having an average of 11 carbon atoms in its alkyl chain, with about 5 moles of ethylene oxide; Neodol 23-9, a primary ethoxylated alcohol of 12 to 13 carbon atoms having about 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated primary alcohol of 9 to 11 carbon atoms, having about 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been sold by Shell Chemical Company under the Dobanol brand. Dobanol 91-5 is an ethoxylated fatty alcohol of 9 to 11 carbon atoms, with an average of 5 moles of ethylene oxide and Dobanol 25-7 is an ethoxylated fatty alcohol of 12 to 15 carbon atoms, with an average of 7 moles of ethylene oxide per mole of fatty alcohol. Other examples of suitable ethoxylated alcohols include: Tergitol 15-S-7 and Tergitol 15-S-9, both linear secondary alcohol ethoxylates, which have been sold commercially by Union Carbide Corporation. The first is a mixed ethoxylation product of linear secondary alcohol of 11 to 15 carbon atoms with 7 moles of ethylene oxide, and the latter is a similar product, but which was reacted with 9 moles of ethylene oxide. Other types of alcohol ethoxylates, useful in the compositions herein, are high molecular weight nonionics, such as Neodol 45-11, which are similar condensation products of ethylene oxide of higher fatty alcohols, having the fatty alcohol higher than 14 to 15 carbon atoms, and the number of ethylene oxide groups per mole being about 11. These products have also been sold commercially by Shell Chemical Company. When the alcohol alkoxylate component is used as part of the liquid diluent in the non-aqueous compositions herein, they will generally be present to the extent of from about 1% to 60% by weight of the composition. Better still, the alkoxylate alcohol component will comprise about 5% to 40% by weight of the compositions herein. Most preferably, the alcohol alkoxylate component will comprise about 10% to 25% by weight of the detergent compositions herein.

THE NON-AQUEOUS ORGANIC SOLVENT OF LOW POLARITY Another component of the liquid diluent that can be part of the detergent compositions herein, constitutes the non-aqueous organic solvent (s) of low polarity. The term "solvent", as used herein, carries the connotation of the non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and / or optional components of the compositions herein may actually be dissolved in the phase containing the "solvent"; the other components will be present as particulate material dispersed within the phase containing the "solvent". Thus, the term "solvent" is not intended to make it necessary for the solvent material to be capable of actually dissolving all the components of the detergent composition that are added to it. The non-aqueous organic materials used as solvents herein are those that are low polarity liquids. For purposes of this invention, "low polarity" liquids are those that have, if anything, little tendency to dissolve one of the preferred types of particulate material used in the compositions herein; that is, peroxygen bleaching agents, sodium perborate or sodium percarbonate. Therefore, relatively polar solvents, such as ethanol, should not be used. Suitable types of low polarity solvents useful in the non-aqueous liquid detergent compositions herein include the lower onoalkyl ethers of alkylene glycol, the low molecular weight polyethylene glycols, the low molecular weight methyl esters and amides, and the like. A preferred type of non-aqueous, low polarity solvent, useful herein, comprises the low molecular weight polyethylene glycols (PEG). Such materials are those that have molecular weights of at least about 150. PEGs of molecular weight ranging from about 200 to 600 are most preferred. Another preferred type of non-polar, non-aqueous solvent comprises the low molecular weight methyl esters. Such materials are those having the general formula: R 1 -C (0) -0CH 3, wherein R 1 ranges from 1 to 18. Examples of low molecular weight methyl esters include: methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate. The solvent or the non-aqueous organic solvents, of low polarity, used, of course must be compatible and not reactive with the other components of composition; for example, bleaches and / or activators, used in the liquid detergent compositions herein. Said solvent component will generally be used in an amount of about 1% to 60% by weight of the composition. Better still, the non-aqueous organic solvent, of low polarity, will comprise about 5% to 40% by weight of the composition, even better, from 10% to 25% by weight of the composition.

THE CONCENTRATION OF LIQUID DILUENT As with the concentration of the surfactant mixture, the amount of total liquid diluent in the compositions herein will be determined by the type and amounts of the other components of the composition and by the properties desired in the composition. In general, the liquid diluent will comprise about 20% to 80% by weight of the compositions herein. Better still, the liquid diluent will comprise about 40% to 60% by weight of the composition.

THE SOLID PHASE The non-aqueous detergent compositions herein may additionally comprise a solid phase of the particulate material, which is dispersed and suspended within the liquid phase. In general, said particulate material will vary in size from about 0.1 to 1500 microns. Better yet, said material will vary in size from about 5 to 200 microns. The particulate material used herein may comprise one or more types of detergent composition components, which, in particulate form, are substantially insoluble in the nonaqueous liquid phase of the composition. The types of particulate materials that can be used are described in detail as follows: THE SURGICAL AGENTS Another possible type of particulate material that may be suspended in the non-aqueous liquid detergent compositions herein includes the anionic surfactants depending on which are totally or partially insoluble in the non-aqueous liquid phase. The most common type of anionic surfactant with said solubility properties comprises the anionic surfactants of primary or secondary alkyl sulfate. Said surfactants are those produced by sulfation of higher fatty alcohols of 8 to 20 carbon atoms. Conventional primary alkyl sulfate surfactants have the general formula: ROS03-M + wherein R is typically a linear hydrocarbyl group of 8 to 20 carbon atoms, which may be straight chain or branched chain; and M is a cation solubilizer in water. Preferably R is an alkyl of 10 to 14 carbon atoms and M is an alkali metal. Most preferably, R has about 12 carbon atoms and M is sodium. Conventional secondary alkyl sulfates can also be used as the essential anionic surfactant component of the solid phase of the compositions herein. Conventional secondary alkyl sulfate surfactants are those materials that have the sulfate portion distributed randomly along the hydrocarbyl "skeleton" of the molecule. These materials can be illustrated by the structure: CH3 (CH2) n (CHOSO3 -M +) (CH2) mCH3 wherein m and n are integers of 2 or more, and the sum of m + n is typically from about 9 to 15, and M is a cation solubilizer in water. If used as the whole or as part of the required particulate material, the anionic surfactants dependent, such as alkyl sulfates will generally comprise about 1% to 10% by weight of the composition, better yet, about 1% to 5%. % by weight of the composition. Alkyl sulfate is prepared as all or part of the particulate material and added to the compositions herein from the non-alkoxylated alkyl sulfate material, which may be part of the alkyl ether sulfate surfactant component, essentially used as part of the liquid phase of the present.

THE IMPROVING MATERIAL OF ORGANIC DETERGENCE Another possible type of particulate material that can be suspended in the non-aqueous liquid detergent compositions herein comprises a builder material, of organic detergent, which serves to counteract the effects of the calcium ion or other ion, of water hardness found during use in the laundry / bleaching of the compositions herein. Examples of such materials include citrates, succinates, alkali metal aluminates; fatty acids, carboxymethylsuccinates, carboxylates, polycarboxylates and polyacetalcarboxylates of fatty acids. Specific examples include the sodium, potassium and lithium salts of oxydisuccinic, mellitic, benzenepolycarboxylic and citric acids. Other examples of organic phosphonate sequestering agents are those sold by Monsanto under the Dequest brand name and alkane hydroxyphosphonates. Citrate salts are much preferred. Other suitable organic builders include the high molecular weight polymers and copolymers known to have builder properties. For example, such materials include: appropriate copolymers of polyacrylic acid, polymaleic acid and polyacrylic / polylactic acid and their salts, such as those sold by BASF under the trademark Sokalan. Another suitable type of organic builder comprises the water soluble salts of higher fatty acids, ie, "soaps". These include alkali metal soaps, such as the sodium, potassium, ammonium and alkylammonium salts of higher fatty acids containing approximately 8 to 24 carbon atoms, and preferably from 12 to 18 carbon atoms, approximately. The soaps can be formed by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, ie, sodium and potassium tallow and coconut soap. If it is used as all or part of the necessary particulate material, the insoluble, detergent builders for detergent can generally constitute 2% to 20% by weight of the compositions herein. It is more preferred that said enhancer material can comprise from 4% to 10% by weight of the composition.

INORGANIC SOURCES OF ALKALINITY Another possible type of particulate material that can be suspended in the liquid, non-aqueous detergent compositions herein can comprise a material which serves to make aqueous the washing solutions formed from said compositions, generally of an alkaline nature. Such materials may or may not act as builders, that is, as materials that counteract the adverse effect of water hardness on detergency operation. Examples of suitable alkalinity sources include the water soluble alkali metal carbonates, bicarbonates, borates, silicates and ethosilicates. Although not preferred for ecological reasons, water-soluble phosphate salts can also be used as sources of alkalinity. These include alkali metal pyrophosphates, orthophosphates, polyphosphates and alkali metal phosphonates. Of these alkalinity sources, most preferred are alkali metal carbonates, such as sodium carbonate. The source of alkalinity, in the form of a hydratable salt can also serve as a dissector in the non-aqueous liquid detergent compositions herein. The presence of a source of alkalinity, which is also a desiccant, can provide benefits in terms of chemical stabilization of those components of the composition, such as the peroxygen bleaching agent, which may be susceptible to deactivation by water. If used as all or part of the component of the particulate material, the source of alkalinity will generally comprise about 1% to 15% by weight of the compositions herein. It is more preferred that the alkalinity source may comprise from about 2% to 10% by weight of the composition. Such materials, while soluble in water, will generally be insoluble in the non-aqueous detergent compositions herein. Thus, said materials will generally be dispersed in the non-aqueous liquid phase, in the form of discrete particles.

OPTIONAL COMPOSITION COMPONENTS In addition to the liquid phase and solid phase components of the composition, which were described above, the detergent compositions of the present invention may contain and, preferably will contain, various optional components. Such optional components may be in liquid form or in solid form. The optional components can be dissolved in the liquid phase or they can be dispersed within the liquid phase, in the form of fine particles or droplets. Some of the materials that may optionally be used in the compositions herein are described in greater detail as follows: OPTIONAL INORGANIC DETERGENT IMPROVERS The detergent compositions herein may also optionally contain one or more types of inorganic builders, in addition to those already mentioned above, which also function as alkalinity sources. These optional inorganic builders may include, for example, aluminosilicates, such as zeolites. The aluminosilicate zeolites and their use as builders are discussed more fully in Corkill and co-inventors, U.S. Patent No. 4,605,509, issued August 12, 1986, the disclosure of which is incorporated herein by reference. Also suitable for use in the detergent compositions herein are the crystalline layer silicates, such as those discussed in US Patent '509. If used, optional inorganic builders can comprise from 2% to 15% by weight of the compositions herein.

OPTIONAL ENZYMES The detergent compositions herein may also optionally contain one or more types of detergent enzymes. Such enzymes may include proteases, amylases, cellulases and lipases. Such materials are known in the art and can be obtained commercially. Nonaqueous liquid detergents herein can be incorporated in the form of suspensions, "lumps", or "Granules" Another suitable type of enzyme comprises those in the form of enzyme suspensions in nonionic surfactants. Enzymes have been sold in this form, in commerce, for example by Novo Nordisk, under the trademark "LDP". Enzymes added to the compositions herein, in the form of conventional enzyme granules are especially preferred for use herein. Said granules will generally have a size ranging from around 100 to 1,000 microns, better still, from 200 to 800 microns and will be suspended in the entire non-aqueous liquid phase of the composition. It has been found that the granules present in the compositions of the present invention, in comparison with other forms of enzyme, exhibit especially convenient enzyme stability, in terms of retention of enzymatic activity over time. Thus, compositions using enzyme granules do not need conventional enzyme stabilization, such as that which is often used when incorporating enzymes in aqueous liquid detergents. If used, the enzymes will normally be incorporated into the non-aqueous liquid compositions herein, at levels sufficient to give up to about 10 mg by weight, more typical, about 0.01 mg to about 5 mg, of active enzyme per gram of the composition. In other words, the non-aqueous liquid detergent compositions herein will typically comprise from 0.001% to 5%, preferably from about 0.01% to 1% by weight, of a commercial enzyme preparation. Protease enzymes, for example, are usually present in such commercial preparations at levels sufficient to give 0.005 to 0.1 Anson units (AU) of activity per gram of composition.

THE OPTIONAL CHELATING AGENTS The detergent compositions herein may optionally contain a chelating agent that serves to chelate metal ions, for example, iron and / or manganese, within the non-aqueous detergent compositions herein. These chelating agents thus serve to form complexes with metallic impurities in the composition which would otherwise tend to deactivate the components of the composition, such as the peroxygen bleaching agent. Useful chelating agents may include carboxylates, phosphonates, amino, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Amine carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetramine hexaacetates, diethylenetriamine pentaacetates, ethylene diamine disuccinates and ethanol glycines. The alkali metal salts of these materials are preferred. The aminophosphonates are also suitable for use as chelating agents in the compositions of this invention, when at least low levels of total phosphorus are allowed in the detergent compositions, and include tetrakis (methylenephosphonates) of ethylenediamine, such as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Preferred chelating agents include: hydroxyethyldiphosphonic acid (HEDP), diethylenetriamine pentaacetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic acid (DPA) and their salts. Of course, the chelating agent can also act as a builder during the use of the compositions herein for fabric washing / bleaching. The chelating agent, if employed, may comprise from 0.1% to 4% by weight of the compositions herein. Better still, the chelating agent will comprise from about 0.2% to 2% by weight of the detergent compositions herein.

THICKENER AGENTS. VISCOSITY CONTROL AND / OR OPTIONAL DISPERSANT The detergent compositions herein may also optionally contain a polymeric material which serves to increase the ability of the composition to keep its particulate solid components in suspension. These materials can act as thickeners, viscosity controlling agents and / or dispersing agents. Such materials are often polymeric polycarboxylates, but may also include other polymeric materials, such as polyvinylpyrrolidone (PVP). Polymeric polycarboxylate can be prepared by polishing or copolymerizing suitable unsaturated monomers, preferably in their acid form. The unsaturated monomeric acids which can be polymerized to form the suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene-alonic acid. The presence in the polymeric polycarboxylates of the present, of monomeric segments that do not contain carboxylate radicals, such as vinyl methyl ether, styrene, ethylene, etc., is suitable as long as said segments do not constitute more than about 40% by weight of the polymer . Particularly suitable polymeric polycarboxylates can be acrylic acid derivatives. Those acrylic acid-based polymers, which are useful herein, are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, better yet, from about 4,000 to 7,000 and, most preferred, about 4,000 to 5,000. The water-soluble salts of these acrylic acid polymers may include, for example, the alkali metal salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type has been described, for example, in Diehl, US Patent No. 3,308,067, issued March 7, 1967. These materials can also perform a detergency builder function. If used, optional thickeners, viscosity control and / or dispersing agents should be present in the compositions herein in the range of about 0.1% to 4% by weight. Better still, said materials may comprise about 0.5% to 2% by weight of the detergent compositions herein.

POLISHERS. SUPPRESSORS OF FOAM AND / OR PERFUMES. OPTIONAL The detergent compositions herein may also optionally contain conventional brighteners, suds suppressants, silicone oils, bleach catalysts and / or perfume materials. Such brighteners, suds suppressors, silicone oils, bleach catalysts and perfumes, of course, must be compatible and non-reactive with the other components of the composition, in a non-aqueous environment. If present, foam suppressors and / or perfumes will typically comprise from 0.1% to 2% by weight of the compositions herein. Suitable bleach catalysts include the manganese-based complexes described in US patents 5,246,621, 5,244,594, 5,114,606 and 5,114,611.

PREPARATION AND USE OF THE COMPOSITION The non-aqueous detergent compositions herein can be prepared by combining the bleach activating salts and their optional components, in any convenient order, and mixing, for example, by stirring, the resulting combination of components, to form the stable phase compositions of the I presented. The compositions of this invention, prepared as described hereinabove, can be used to form aqueous wash solutions for use in fabric washing and fabric bleaching. In general, an effective amount of said compositions is added to water, preferably in an automatic washing machine for conventional laundry, in order to form said aqueous washing / bleaching solutions. The aqueous washing / bleaching solution thus formed is brought into contact, preferably with agitation, with the fabrics which are to be washed and bleached with it. An effective amount of the liquid detergent compositions herein is added to water, to form aqueous wash / bleach solutions, which may comprise sufficient amounts to form about 500 to 7,000 ppm of the composition in the aqueous solution. Better still, about 1,000 to 3,000 ppm of the detergent compositions herein will be provided in the wash / bleach solution. It is intended that the following example exemplifies the compositions of the present invention, but is not necessarily intended to limit the scope of the invention.

EXAMPLE Propanediol 29.3 Ethoxylate 0E7 of C12-14 alcohol 12.2 Ethoxylate 0E5 of C12-14 alcohol 12.2 Amides of polyhydroxy fatty acid 8.1 C12-14 sodium alkyl sulfate 8.1 H3 B03 1.0 TPK fatty acids 10.6 NaOH (50% am ) 3.7 Citric acid monohydrate 3.1 Sodium bicarbonate 7.4 Sodium carbonate 4.3

Claims (5)

NOVELTY OF THE INVENTION CLAIMS

1. A non-aqueous detergent composition, which is in liquid, gel or paste form, characterized in that said composition additionally comprises an effervescent system that forms carbon dioxide.

2. A non-aqueous detergent composition according to claim 1, further characterized in that the effervescent system comprises anhydrous citric acid and anhydrous sodium bicarbonate.

3. A non-aqueous detergent composition according to claim 1, further characterized in that the effervescent system comprises tartaric acid and sodium bicarbonate.

4. A non-aqueous detergent composition according to claims 2 and 3, further characterized in that the molar ratio of citric acid or tartaric acid to sodium bicarbonate is from 1: 2 to 1:10.

5. A non-aqueous detergent composition according to claim 1, further characterized in that the effervescent system is present in a proportion of 2 to 20% by weight of the detergent composition.