The present invention relates to detergent compositions which comprise a flocculating agent and an organophilic smectite clay whereof at least 30%, preferably at least 40% of the exchangeable cations in the clay is replaced by one or more long-chain organic cations, preferably having at least one long carbon chain of at least 10 or even 12 carbon atoms. The compositions provide improved fabric softening and deliver good cleaning.

The present invention relates to detergent compositions which comprise an organophilic smectite clay which comprises one or more long-chain organic cations which have replaced some or all of the exchangeable cations of normal smectite clay.
Various softening agent are known to have fabric conditioning or softening properties. They can be used in the form of fabric conditioners which are added during the rinse of the wash or incorporated in detergent compositions to provide softening during the wash itself.
Detergent compositions which comprise a softening agent have to provide excellent cleaning as well as softening. Detergents containing certain clays have been found to deliver good cleaning and softening. However, there is a desire to further improve the softening of such known detergent products.
Various alternatives are suggested in the art. For example, U.S. Pat. No. 4,764,292 suggest detergents containing quaternary ammonium softeners and organophilic clay material, present in the detergent in a ratio of 1:3 to 3:1.
It has been found that when such organophilic clay and quaternary ammonium softeners are used in detergents, the cleaning performance is reduced. Also, it has been found that the organophilic clays and quaternary ammonium softeners do not always provide sufficient softening to the fabrics.
It is believed that such quaternary ammonium softeners can have an adverse interaction with specific detergent actives, such as anionic surfactant and that this results in a reduced cleaning performance, which is not acceptable for the consumers.
The inventors have now found that when a hydrophilic clay flocculating agent is incorporated in detergent compositions comprising specific organophilic smectite clay good, softening and cleaning of the fabric is achieved. It is believed that the clay flocculating agent which can interact with normal hydrophilic clays, surprisingly also interact with the specific, more hydrophobic organophilic clays comprising specific long-chain organic cations. Without wishing to be bound by theory, it is believed that the flocculating agent not only aids the deposition onto the fabric of the specific organophilic clay, but it also reduces the interaction of the cations and other detergent actives, such as anionic surfactants. Thus, surprisingly improved softening is obtained, whilst a good cleaning performance of the detergent is maintained.
The invention relates to a detergent composition comprising a flocculating agent and an organophilic smectite clay whereof at least 30%, preferably at least 40% of the exchangeable cations is replaced by one or more long-chain organic cations which have at least one carbon chain of at least 10 carbon atoms.
The inventors also found that the cleaning performance and softening performance of the composition of the invention can be maximised when the ratio of flocculating agent to organophilic clay is preferably from 1:200 to 1:30 or even from 1:150 to 1:50.
Organophilic Smectite Clay
The compositions of the invention contain a smectite clay whereby at least 30% or even at least 40% or preferably at least 50% or even at least 60% of the exchangeable cations is replaced by a long-chain organic cations. Such clay will herein be referred to as organophilic or hydrophobic clay.
When used herein, a long-chain organic cation can be any compound which comprises at least one chain having at least 10 carbon atoms, preferably at least 12 carbon atoms, or in certain embodiments of the invention, at least 16 or even at least 18 carbon atoms. Preferred long-chain organic cations are described hereinafter.
For the purpose of the invention, it should be understood that the organophilic clays are formed prior to incorporation into the detergent composition. Thus, the cations, or part thereof, of the normal smectite clays are replaced by the long-chain organic cations to form the organophilic smectite clays herein, prior to further processing of the material to form the detergents of the invention.
When used herein, complexed long-chain organic cations refers to long-chain organic cations which replace the exchangeable cations the clay would normally contain.
The compositions herein may comprise additional long-chain organic cationic material or salts thereof, which are not in the form of a complex with clay. In one embodiment the detergent composition may be free of, or substantially free of, non-complexed long-chain organic cations.
Preferably, the organophilc clay is such that from 40%, or even 50% or even 60%, to 90% or even 95% or even 98% or preferably to 100% of exchangeable cations are replaced by one or more long-chain organic cations.
The organophilc smectite clay is preferably present in the detergent compositions of the invention at a level of from 0.05% to 40%, more preferably from 0.5% to 30%, most preferably from 2% to 20% by weight of the composition. For clarity, it is noted that the term clay mineral compound, as used herein, excludes sodium aluminosilicate zeolite builder compounds, which however, may be included in the compositions of the invention as optional components.
The weight ratio of organophilc clay to the flocculating polymer is preferably from 1000:1 to 1:1, more preferably from 500:1 to 1:1, most preferably from300:1 to 1:1, or even more preferably from 200:1 to 25:1, or even from 150:1 to 30:1 or in certain applications even from 80:1 to 40:1.
The term smectite clays herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice. The organophilc clay herein may be an expandable clay having a layered clay structure which has the ability to be swell or expand on contact with water.
The smectite clays used to make the organophilic clays of the present invention are commercially available. Highly preferred are smectite clays, which can be used to prepare the organophilic clays herein, are for example as disclosed in the U.S. Pat. Nos. 3,862,058 3,948,790, 3,954,632 and 4,062,647 and EP-A-299,575 and EP-A-313,146.
Specific examples of suitable smectite clays to be used to make the organophilic clays herein, include those selected from the classes of the bentonitesxe2x80x94also known as montmorillonites, hectorites, volchonskoites, nontronites, saponites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure. Preferably hectorites and montmorillonites are used herein; sodium or calcium montmorillonite and hectonite are particularly preferred to make the organophilic clays herein.
It is to be recognised that such smectite clays can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable from use herein.
The organophilic clay is preferably in the form of a platelet or lath-shaped particle. Preferably the ratio of the width to the length of such a platelet is at least 1:2, preferably at least 1:4 or even at least 1:6 or even at least 1:8.
The organophilic clays can be made by any suitable method. For instance they can be prepared by making a slurry or dispersion of the untreated clay in a solvent, preferably water, together with a quantity of the appropriate long-chain organic cations, intended to be reacted or complexed with the clay, that is to provide the desired degree of ion exchange. The treated clay can then be separated from the liquor by known methods such as filtration or centrifuging. Preferred can be that the organophilc clays are made by replacing the exchangeable inorganic cations of smectite clay with the organic cations in an aqueous reactor and then drying and milling the resultant organophilic clay.
The cation exchange capacity of clays and the percentage of exchange of the cations with the long-chain organic cations can be measured in several ways known in the art, as for example fully set out in Grimshaw, The Chemistry and Physics of Clays, Interscience Publishers, Inc.,pp. 264-265 (1971).
The organophilc clay can be dry mixed with the other components of the detergent composition, or it may be dispersed or dissolved in water or other liquids, including for example liquid components of the detergent composition, e.g. the nonionic surfactant and than sprayed onto other detergent components or formed into a granule by any method of granulation, for example agglomeration, spray-drying, compaction and/ or extrusion, and then incorporated in the detergent compositions.
In a highly preferred embodiment of the invention, the organophilc clay is present in an intimate mixture or in a particle with a humectant and/or a hydrophobic compound, preferably a wax or oil, such as paraffin oil. Preferred humectants are organic compounds, including propylene glycol, ethylene glycol, dimers or trimers of glycol, most preferably glycerol. The particle is preferably an agglomerate. Alternatively, the particle may be such that the wax or oil and optionally the humectant form an encapsulate on the clay or alternatively, the clay be a encapsulate for the wax or oil and the humectant. It may be preferred that the particle comprises an organic salt or silica or silicate.
It may also or alternatively be preferred that the organophilic clay is mixed with one or more components which help dispersion of the clay into the wash water. Preferred may be that the organophilc clay is present as a mixture and/or is coated with surfactants and/or polymeric material, such as polymeric polycarboxylates, and optionally also mixed with other builders. Preferably, such a mixture is further processed in a spray-drying method or agglomeration method or extrusion method, to obtain a spray dried particle, agglomerate or extrudate, comprising the organophilic clay.
Highly preferred maybe that one or more fatty acids are present in the detergent composition, or even in a particle containing the organophilc clay. It has been found that this can provide further improved flocculation and/or improved softening of the fabrics.
It may be preferred that the flocculating agent is also comprised in the particle or granule comprising the clay.
It may also be preferred that the intimate mixture comprises a chelating agent or heavy metal ion sequestrants, described herein after.
Long-chain Organic Cations
The long-chain organic cations herein comprise at least one chain of at least 10 or even at least 12 or even at least 14 or even at least 16 or even at least 18 carbon atoms. It may be preferred that at least two of such long-chains are present in the cation.
Preferred cations are quaternary ammonium cations and immidazolinium cations of the above requirements.
Preferred organophilic clays herein clay are smectite clays, preferably hectorite clays and/or montmorillonite clays containing one or more organic cations of formulae:
where R1 represents an organic radical selected from R7, R7xe2x80x94COxe2x80x94Oxe2x80x94(CH2)n, or R7xe2x80x94COxe2x80x94NR8xe2x80x94 in which R7 is an alkyl, alkenyl or alkylaryl group with 12-22 carbon atoms, whereby R8 is hydrogen, C1-C4 alkyl, alkenyl or hydroxyalkyl, preferably xe2x80x94CH3 or xe2x80x94C2H5 or xe2x80x94H; n is an integer, preferably equal to 2 or 3; R2 represents an organic radical selected from R1 or C1-C4 alkyl, alkenyl or hydroxyalkyl,
preferably xe2x80x94CH3 or xe2x80x94CH2CH2OH; R3 and R4 are organic radicals selected from C1-C4 alkyl-aryl, C1-C4 alkyl, alkenyl or hydroxyalkyl, preferably xe2x80x94CH3, xe2x80x94CH2CH2OH, or benzyl group; R5 is an alkyl or alkenyl group with 12-22 carbon atoms; R6 is preferably xe2x80x94OH, xe2x80x94NHCOxe2x80x94R7, or xe2x80x94OCOxe2x80x94R7.
Highly preferred cations are quaternary ammonium cations having two C16-C28 or even C16-C24 alkyl chains. Highly preferred are one or more organic cations which have one or preferably two alkyl groups derived from natural fatty alcohols, the cations preferably being selected from dicocoyl methyl benzyl ammonium, dicocoyl ethyl benzyl ammonium, dicocoyl dimethyl ammonium, dicocoyl diethyl ammonium; more preferably ditallow diethyl ammonium, ditallow ethyl benzyl ammonium; more preferably ditallow dimethyl ammonium and/or ditallow methyl benzyl ammonium.
It may be highly preferred that mixtures of organic cations are present.
Preferably, the clay material is such that at least 80% or even 90% to 100% of the exchangeable cations are replaced by these preferred or highly preferred organic cations.
Highly preferred are organophilic clays as available from Rheox/Elementis, such as Bentone SD-1 and Bentone SD-3, which are registered trademarks of Rheox/Elementis.
Flocculating Agent
The compositions of the invention may contain a clay flocculating agent, preferably present at a level of from 0.005% to 10%, more preferably from 0.01% to 5%, most preferably from 0.05% or even 0.1% to 1% by weight of the composition.
Preferred as clay flocculating agents herein are organic polymeric materials having an average weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000.
Suitable organic polymeric materials comprise homopolymers or copolymers containing monomeric units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Homopolymers of, on particular, ethylene oxide, but also acrylamide and acrylic acid are preferred.
European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe preferred organic polymeric clay flocculating agents for use herein.
Highly preferred are polyethylene oxides of an average molecular weight from 150,000 to 3,000,000.
Inorganic clay flocculating agents are also suitable herein, typical examples of which include lime and alum.
The flocculating agent is preferably present in a detergent base granule such as a detergent agglomerate, extrudate or spray-dried particle, comprising generally one or more surfactants and builders.
Detergent Compositions
The compositions of the invention can be liquid compositions, but preferably they are solid, in the form of granules, extrudates, flakes, bars or tablets.
The compositions can be used in automatic washing or hand washing. Also, the compositions can be such that they are suitable for pre-treatment or soaking, or for conditioning of the fabric after the main wash.
The compositions in accord with the invention contains additional detergent actives. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional detergent components selected from surfactants, bleaches, bleach catalysts, alkalinity systems, builders, additional organic polymeric compounds, enzymes, suds suppressers, lime soap, dispersants, perfumes, brighteners, photo-bleaching agents, corrosion inhibitors, soil release polymers, cellulose based polymers, including carboxy methyl cellulose, cellulose ethers or ester or amine or amide modified celluloses, dispensing aids such as water-swellable polymers and effervescence sources, preferably based on carbonate and acid compounds, in particular citric acid, malic acid or maleic acid, dye transfer inhibitors, and process aids such as hydrotropes. These ingredients are described in more detail herein.
It may be preferred that additional softening agents are present. For example, it may be preferred that nonionic softening agents, additional (non organophilic) clay softening agents, and/or silicone derivative softeners are present in the invention.
Highly preferred are one or more anionic surfactants, as described herein after, preferably present at a level of 1-50% by weight or even 3 to 25% by weight.
Highly preferred are perfume components, preferably at least one component comprising a coating agent and/or carrier material, preferably an encapsulate of preferably starch or other cellulosic material. The inventors have found that the perfumes are more efficiently deposited onto the fabric in the compositions of the invention, comprising the organophilic clay and preferably a flocculating agent.
It may also be preferred that the composition herein comprises one or more cationic surfactants, which are not complexed with the clay herein, preferably at a level of from 0.1% or even 0.5% to about 5% by weight. It may be beneficial that they are not comprised in the same particle as the organophilic clays herein.
Anionic Surfactant
The detergent compositions of the invention comprise at least 1% by weight of the composition of an anionic surfactant. More preferably the anionic surfactant is present at a level of from 3% to 40%, more preferably from 3% or even 5% to 25% by weight of the composition.
Any anionic surfactant useful for detersive purposes is suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
Anionic sulfonates surfactants are preferably present as the anionic surfactant or part of the anionic surfactants.
Preferred amounts of the alkyl sulfate surfactant, including preferably branched alkyl sulphates, are from 0% to 25%, or more preferably 2% to 20%, or even 4% to 12% by weight of the detergent composition. Preferred amounts of the sulfonate surfactant, preferably the alkyl benzene sulfonate surfactant in the detergent composition are from at least 3%, preferably at least 5%, or even at least 8% or even at least 10% by weight, preferably up to 30% by weight.
Anionic Sulfate Surfactant
Anionic sulfate surfactants suitable for use in the compositions or components of the invention include the primary and secondary alkyl sulfates, having a linear or branched alkyl or alkenyl moiety having from 9 to 22 carbon atoms or more preferably C12 to C18 alkyl; alkyl ethoxysulfates; fatty oleoyl glycerol sulfates; alkyl phenol ethylene oxide ether sulfates; the C5-C17 acyl-Nxe2x80x94(C1-C4 alkyl) and xe2x80x94Nxe2x80x94(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C9-C22 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C11-C18, most preferably C11-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic Sulfonate Surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of a C5-C20, more preferably a C10-C16, more preferably a C11-C13 (linear) alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
The alkyl ester sulfonated surfactant are preferably of the formula
R1xe2x80x94CH(SO3M)xe2x80x94(A)xxe2x80x94C(O)xe2x80x94OR2
wherein R1 is a C6-C22 hydrocarbyl, R2 is a C1-C6 alkyl, A is a C6-C22 alkylene, alkenylene, x is 0 or 1, and M is a cation. The counterion M is preferably sodium, potassium or ammonium.
The alkyl ester sulfonated surfactant is preferably a xcex1-sulpho alkyl ester of the formula above, whereby thus x is 0. Preferably, R1 is an alkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x is preferably 0. R2 is preferably ethyl or more preferably methyl.
It can be preferred that the R1 of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or 3 double bonds. It can also be preferred that R1 of the ester is derived from a natural occurring fatty acid, preferably palmic acid or stearic acid or mixtures thereof.
Mid-chain Branched Alkyl Sulfates or Sulphonates
Mid-chain branched alkyl sulfates or sulphonates are also suitable anionic surfactants for use in the compositions or components of the inevntion. Preferred are the mid-chain branched alkyl sulfates.
Preferred mid-chain branched primary alkyl sulfate surfactants are of the formula
These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms. In compositions or components thereof of the invention comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5. Thus, the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5.
Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol sulfate, 8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methyl hexadecanol sulfate, 11-methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methyl hexadecanol sulfate, and mixtures thereof.
Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate, 2,5-methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2,8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyl tetecanol sulfate, 2,11-methyl tetradecanol sulfate, 2,12-methyl tetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methyl pentadecanol sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methyl pentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methyl pentadecanol sulfate, 2,11-methyl pentadecanol sulfate, 2,12-methyl pentadecanol sulfate, 2,13-methyl pentadecanol sulfate, and mixtures thereof.
Nonionic Surfactant System
The detergent composition may also comprise a nonionic surfactant system comprising at least two nonionic alkoxylated surfactants.
Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic alkoxylated fatty acid amides, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
Preferably, at least one of the nonionic surfactants is an alkoxylated alcohol surfactant as described herein after.
Also, preferred are nonionic alkoxylated fatty acid amides, which can provide even more additional softening to the fabric, or to the skin when the detergent is in contact with the skin.
Most preferred is a nonionic surfactant system which comprises at least two nonionic alkoxylated alcohol surfactants whereof preferably one surfactant has an average alkoxylation degree of 5 or less and one surfactant has an average alkoxylation degree of more than 5. Highly preferred are systems comprising at least a nonionic alkoxylated alcohol with an average alkoxylation degree of 3 or 5 and at least one nonionic alkoxylated alcohol having an average alkoxylation degree of from 7 to 15, preferably 7 or 9.
The nonionic surfactant system is preferably present at a level of 0.5% to 35% or even 25% by weight, preferably from 2% to 15% or even 10% by weight and more preferably from 5% to 15% or even 10% by weight or even from 6% to 15% or even 10% by weight.
The alkoxylation groups of the nonionic surfactants preferably are propoxylate groups, more preferably ethoxylate groups.
The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are preferred in the nonionic surfactant system herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms.
The nonioninc surfactant system of the invention may comprise an alkoxylated fatty acid amide, which comprises preferably a compound of the formula
wherein R1 is a C12-C18 alkyl or alkenyl group, R2 is a C2-C4 alkylene group, R3 is a hydrogen or a C1-C4 alkyl group, R4 is a C1-C4 alkyl group or hydrogen and n is a number from 3 to 12.
The detergent compositions herein may also comprise additionally alkyl-polysaccharides, such as are disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula:
R2O(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R3(OR4)xN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C10-C18 alkyl dimethylamine oxide, and C10-C18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, N.J.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. Preferred betaines are C12-C18 dimethyl-ammonio hexanoate and the C10-C18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Cationic Surfactants
The compositions of the invention may comprise additional cationic compounds which are not in the form of a complex with smectite clays. Suitable cationic surfactants to be used as additional compounds in the detergent herein include the quaternary ammonium surfactants, which can have up to 26 carbon atoms Preferably the quaternary ammonium surfactant is a mono C6-C16 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. xe2x80x94COOxe2x80x94) linkage and at least one cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in U.S. Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.
In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, xe2x80x94Oxe2x80x94Oxe2x80x94 (i.e. peroxide), xe2x80x94Nxe2x80x94Nxe2x80x94, and xe2x80x94Nxe2x80x94Oxe2x80x94 linkages are excluded, whilst spacer groups having, for example xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94 and xe2x80x94CH2xe2x80x94NHxe2x80x94CH2xe2x80x94 linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
Cationic Mono-alkoxylated Amine Surfactants
Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I:
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R2 and R3 are methyl groups; R4 is selected from hydrogen (preferred), methyl and ethyl; Xxe2x88x92 is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the xe2x80x94OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR4 groups are xe2x80x94CH2CH2OH, xe2x80x94CH2CH2CH2OH, xe2x80x94CH2CH(CH3)OH and xe2x80x94CH(CH3)CH2OH, with xe2x80x94CH2CH2OH being particularly preferred. Preferred R1 groups are linear alkyl groups. Linear R1 groups having from 8 to 14 carbon atoms are preferred.
Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably C10 and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
Cationic Bis-alkoxylated Amine Surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general formula II:
wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, Xxe2x88x92 is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and Axe2x80x2 can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., xe2x80x94CH2CH2Oxe2x80x94), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula
wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, preferably C10, C12, C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R1 is derived from (coconut) C12-C14 alkyl fraction fatty acids, R2 is methyl and ApR3 and Axe2x80x2qR4 are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
wherein R1 is C10-C18 hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
Perhydrate Bleaches
An preferred additional components of the compositions is a perhydrate bleach, such as metal perborates and percarbonates, particularly the sodium salts. Perborate can be mono or tetra hydrated. They may be coated with known coating agents.
Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
Organic Peroxyacid Bleaching System
A preferred feature of the composition is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include the N,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. The TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Water-Soluble Builder Compound
The compositions in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight of the composition.
The detergent compositions of the invention may comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
The compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight of the composition.
Preferred are aluminosilicates and/or crystalline layered silicates such as SKS-6, available from Clariant.
Suitable aluminosilicate zeolites have the unit cell formula NaZ[(AlO2)Z(SiO2)y].xH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, Zeolite MAP and mixtures thereof.
Heavy Metal Ion Sequestrant or Chelants
The compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions or component
Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta(methylene phosphonate), ethylene diamine tri(methylene phosphonate)hexamethylene diamine tetra(methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The xcex2-alanine-N,Nxe2x80x2-diacetic acid, aspartic acid-N,Nxe2x80x2-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
EP-A476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,Nxe2x80x2-disuccinic acid (GADS), ethylenediamine-N-Nxe2x80x2-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-Nxe2x80x2-disuccinic acid (HPDDS) are also suitable.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N,Nxe2x80x2-disuccinic acid (EDDS) and 1,1hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
Enzyme
Another preferred ingredient useful in the compositions herein is one or more additional enzymes.
Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in U.S. Pat. Nos. 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, xcex1-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.
Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
Additional Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the compositions herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent composition.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
Polymeric Soil Release Agent
Polymeric soil release agents, hereinafter xe2x80x9cSRAxe2x80x9d, can optionally be employed in the present compositions. If utilized, SRA""s will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
Preferred SRA""s typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
Preferred SRA""s include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
Suitable SRA""s include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. Pat, No. 4,968,451, Nov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (xe2x80x9cDMTxe2x80x9d) and 1,2-propylene glycol (xe2x80x9cPGxe2x80x9d) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA""s include the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. Pat. No. 4,711,730, Dec. 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) (xe2x80x9cPEGxe2x80x9d). Other examples of SRA""s include: the partly- and fully-anionic-end-capped oligomeric esters of U.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomers from ethylene glycol (xe2x80x9cEGxe2x80x9d), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA""s useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRA""s also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20xc2x0 C. as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Also highly preferred are polysaccheride polymers.
Additional classes of SRA""s include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918 Lagasse et al.; and (II) SRA""s with carboxylate terminal groups made by adding trimellitic anhydride to known SRA""s to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA""s may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. Pat. No. 4,525,524 Tung et al. Other classes include: (III) anionic terephthalate-based SRA""s of the urethane-linked variety, see U.S. Pat. No. 4,201,824, Violland et al.;
Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Pat. No. 4,968,451, Scheibel et al., and U.S. Pat. No. 5,415,807, Gosselink et al., and in particular according to U.S. application No.60/051517.
Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=1), n is at least about 12 with a typical range of from about 12 to about 42.
Other dispersants/anti-redeposition agents for use herein are described in EP-B-011965 and U.S. Pat. Nos. 4,659,802 and 4,664,848.
Suds Suppressing System
The detergent compositions of the invention, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term xe2x80x9csiliconexe2x80x9d as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
Polymeric Dye Transfer Inhibiting Agents
The compositions herein may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
Optical Brightener
The compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
Preferred brighteners include 4,4xe2x80x2,-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2xe2x80x2-stilbenedisulfonic acid and disodium salt, commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation; 4,4xe2x80x2-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2xe2x80x2-stilbenedisulfonic acid disodium salt, commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation; 4,4xe2x80x2-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2xe2x80x2-stilbenedisulfonic acid, sodium salt, commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.
Other Optional Ingredients
Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, in particular including encapsulated perfumes, the perfume oils preferably being present at a level of from 0.01% or even 0.05% or even 0.1% by weight of the composition.
Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid, malic acid, maleic acid, acetic acid, tartaric acid, glutaric acid or an aminoacid.
Also preferred may be neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, photo-bleaches, speckles, dyes, such as those described in U.S. Pat. No. 4,285,841 to Barrat et al., issued Aug. 25, 1981 (herein incorporated by reference).
The compositions herein can take a variety of physical forms including liquid, but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms. Solid composition of the invention can be made via a variety of methods, including dry-mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques.
The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
Detergent compositions herein, in particular laundry detergents, preferably have a bulk density of from 280 g/liter to 2000 g/liter, or preferably from 300 g/liter or even 350 g/liter or 420 g/liter to 1500 g/liter or more preferably to 1000 g/liter or even to 700 g/liter.
Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 10 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 65 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
The compositions herein can be useful in both conventional washing machines and low-water fill washing machines.
In a preferred use aspect the composition hand washing. In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
Abbreviations Used in Examples
In the detergent compositions, the abbreviated component identifications have the following meanings:

Solid detergent compositions comprising an organophilic smectite clay


Oral composition comprising a co-ground of at least two ingredients which are co-ground without the use of solvents and wherein the co-ground comprises each of at least two ingredients at a level of at least 5% by weight of the total weight of the co-ground, characterised in that the composition is an aqueous composition.

The present invention relates to an oral composition.
Co-ground products are known in the pharmaceutical field for providing improved solubility to particular agents. Such products have improved dissolution rates when the product is wetted. Typical products are described in EP 0 371 431 (Vectorpharma) where an active substance is mixed with a support substance and co-ground in a mill. The end product is then dried before it can be used.
Co-grounds have also been disclosed for topical cosmetic purposes. WO 99/17736 (Telos) describes how amorphisation results in much a higher solubilisation kinetics profile, in conditions of supersaturation, compared with using the crystalline forms of an active. The co-ground typically comprises a binary system of a carrier, which may or may not be inert, and a cosmetic active material which typically has poor solubility characteristics. The two materials are ground together in the absence of a solvent. The cosmetic actives proposed for co-grinding are solids, or have been rendered solid via absorption, inclusion or microcapsulation. Suitable carriers with which the actives can be co-ground include organic materials such as starches, polyvinyl pyrrolidone, and phospholidpids to name a few, while inorganic examples include, talc, titanium dioxide, zinc oxide, kaolin, zeolites, siO2, silica gel, calcium phosphate, calcium carbonate and the like. This prior art also discloses how the co-grounds can be made by milling, preferably in a high energy mill.
The prior art also discloses in U.S. Pat. No. 4,098,878 (Baines) that co-grinding is one of a number of possible routes by which an abrasive particle for use in toothpaste may be surface-modified with a fatty acid. The abrasive is disclosed to have different reactive properties when modified during the chosen process. Essentially, the surface modification is a means to mask the reactive groups on the abrasive particle and the surface modifying agent is added only in very small amounts, preferably as little as possible, to coat the abrasive particle. In a way it is a form of encapsulation. This patent also states that the modifying agent is added at from 0.1 to 5% by weight of the abrasive particle.
U.S. Pat. No. 4,346,072 (Baines) discloses a similar technology but states that the amount of surface-modifying agent is from 0.1 to 0.5% by weight of the abrasive.
We have surprisingly found that co-grinding technology can be successfully used in oral care formulations which comprise water and where the co-ground comprises at least two ingredients each of which are present at more than 5% by weight of the total co-ground. It is disclosed in the prior art (Telos) that the co-grounds have improved wettability so it is quite surprising that these can be included in hydrous formulations. In fact, a co-ground ingredient can be included in an oral care formulation with surprising stability despite the presence of water as well as surfactants and ionic materials which would typically interfere with the stability of a material. The prior art mainly teaches that powders can be formulated which, when put into contact with a wet surface, have improved solubility/wettability characteristics. The prior art also teaches that co-grinding may be used to apply small amounts of a surface modifying agent to an abrasive particle.
The invention is thus a particularly useful technological advance in oral care as regulatory affairs and consumer sensory perception play an enormous part in the selection of ingredients. For example, there exist many materials, which have a relatively high efficacy but are not used because they taste unacceptably to the consumer. For example, chlorhexidine is an efficacious anti-microbial material, which is hardly ever used in oral care compositions because of its poor taste, which obviously presents an overwhelming consumer negative. On the other hand, there are some materials, which are virtually essential in oral care technology but have a noticeable negative effect on some of the other materials which could provide a consumer benefit. For example, sodium lauryl sulphate (SLS) is a preferred foaming agent in oral care compositions. Unfortunately, SLS has a negative effect on the efficacy of cationic anti-microbial materials such as cetylpyridinium chloride. As such, these materials cannot be used to their fullest in oral care.
Accordingly, we have surprisingly found that the inclusion of co-ground products in oral care formulations can provide an improvement for the consumer, depending upon the ingredients chosen in the co-ground. For example, the use of flavours in a co-ground can provide improved or even prolonged flavour release. Actives which are unstable in the presence of common oral care ingredients such as surfactants can now be used in a co-ground to provide a previously unattainable benefit. This has the further advantage that ingredients which were unstable in the presence of each other but which were stored independently in separate chambers until use may now be formulated in a single tube thus providing a cheaper product. Further, ingredients which were not included in commercially available oral care products before now because of poor sensory perception, e.g. taste or low-foaming, may now be included in a co-ground form which alters the perception profile and provides an improved benefit to the consumer.
A first aspect of the invention thus provides an oral composition comprising a co-ground of at least two ingredients which are co-ground without the use of solvents and wherein the co-ground comprises each of at least two ingredients at a level of at least 5% by weight of the total weight of the co-ground, characterized in that the composition is an aqueous toothpaste composition.
The composition according to the invention is an aqueous composition and comprises from 1 to 80%, preferably from 3 to 50%, more preferably from 5 to 30% by weight water.
By xe2x80x98co-groundxe2x80x99 is meant that at least two materials (a carrier and an active) are ground in a mill without the use of solvents as is described in WO 99/17736 the contents of which are incorporated herein by reference, particularly with respect to the nature and the making of co-grounds. However, for the sake of clarity a co-ground is a ground particle, which comprises at least two ingredients, which have been milled together in the absence of a solvent.
The co-grinding process is carried out in a conventional apparatus, such as a ball mill, a cylinder mill, a rotary mill, a grinding mill or a vibrational mill, for times ranging from a few minutes to some hours, for example from 30 minutes to 8 hours. Preferably, the co-grinding process is carried out in a mill which translates vibrational energy to the materials in the co-ground.
The mill is composed of a cylindrical chamber in stainless steel with a polyurethane covering. Small highly packed grinding media made from a very hard material are placed inside the chamber.
The choice of the size and material of the grinding media depends on the properties of the material to be processed and the desired characteristics of the finished product.
The variation in some operating parameters results in a different energy transfer from the mill to the mixture and thus in different final characteristics of the product.
The vibratory mechanism is made up of a special electric motor linked to two xe2x80x9cout of balancexe2x80x9d counterweights. This entire group of components, attached directly to the base of the grinding chamber, is suspended by high-tension steel springs in order that energy is directly imparted to the grinding media.
The vibration created by the movement of this system is defined according to two physics-related measures: frequency and amplitude. The particularity lies in the fact that the vibration is of a tri-dimensional type, in that it is characterized by a horizontal as well as a vertical component. The former can be modified by changing the grinding angle i.e. by varying the position of one of the two counterweights.
In this way a different load movement is attained, and in addition the energy transmitted to the grinding media is regulated.
The effect of the co-grinding process in a vibrational mill is determined by a number of parameters which may be adjusted by the skilled person according to the desired objectives. Said parameters include the fill-level of the chamber, in addition to the shape, volume and density of the grinding media.
Another important factor in determining the specific energy used in the co-grinding process is the ratio between the mass of material to be ground and the mass of the grinding media. If the ratio is highly skewed towards the grinding media then the energy will be higher.
The correct duration of the process clearly depends on the chemical and physical characteristics of the materials to be co-ground, as well as on the above-described factors.
Finally, the choice of the weight ratio between the ingredients of the co-ground logically depends on the chemical and physical characteristics of the starting materials, and on the desired final objectives.
The co-ground of the invention comprises at least two materials, which are individually present at more than 5% by weight of the co-ground. This thus allows for the presence of the usual level of impurity often found in such ingredients. Preferably, at least one of the ingredients is present at a level ranging from 10 to 95% by weight of the co-ground, more preferably from 20 to 85%, especially from 30 to 75% and most preferably from 40 to 65% by weight of the co-ground. The co-grounds according to the invention thus form an agglomerate comprising said ingredients and it is this agglomerate which surprisingly does not disintegrate when used in a formulation comprising water.
It is also possible for the co-ground to comprise more than two ingredients not including any impurity. For example, the co-ground may comprise three, four or even five or six different ingredients. It is also possible to prepare one co-ground with two ingredients and then use this product in another co-grinding step to increase the number of ingredients and perhaps change the characteristics of the end result. Where the co-ground comprises more than two ingredients it is also possible for it to be prepared by co-grinding all the ingredients in one step.
Obviously, where more than two ingredients are to be used the third and subsequent ingredient may not necessarily be present at more than 5% by weight of the co-ground.
It is also possible to include an ingredient in the co-ground as well as the remainder of the oral care composition. A suitable example of an embodiment according to the invention would thus comprise an active such as example sodium fluoride in both the co-ground and also in the remainder of the formulation thus providing a burst of fluoride ions during brushing and also a longer, slow-release of fluoride for a period of time after brushing.
Typically the oral composition may comprise from 0.001 to 50% by weight of the co-ground. Preferably the oral composition will comprise from 0.01 to 25% by weight and most preferably from 0.1 to 10% by weight of the co-ground.
The ingredients used in the co-ground may be any which provide a benefit to the composition. These may be flavours, flavour enhancers, antimicrobial actives, abrasives, thickeners, slow-release agents, colors, and such like. The remainder of the oral composition may comprise any of the materials commonly used in oral care formulations whether as active in the co-ground or active in the remainder of the composition. These include:
antimicrobial agents, e.g. Triclosan, chlorhexidine, copper-, zinc- and stannous salts such as zinc citrate, zinc sulphate, zinc glycinate, sodium zinc citrate and stannous pyrophosphate, sanguinarine extract, metronidazole, quaternary ammonium compounds, such as cetylpyridinium chloride; bis-guanides, such as chlorhexidine digluconate, hexetidine, octenidine, alexidine; and halogenated bisphenolic compounds, such as 2,2xe2x80x2 methylenebis-(4-chloro-6-bromophenol);
anti-inflammatory agents such as ibuprofen, flurbiprofen, aspirin, indomethacin etc.;
anti-caries agents such as sodium-, calcium-, magnesium- and stannous fluoride, aminefluorides, disodium monofluorophosphate, sodium trimeta phosphate and casein;
plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates;
vitamins such as Vitamin C;
plant extracts;
desensitising agents, e.g. potassium citrate, potassium chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts;
anti-calculus agents, e.g. hypophosphite-containing polymers, organic phosphonates and phosphocitrates etc.;
gum protection agents, e.g. vegetable oils such as sunflower oil, rape seed oil, soybean oil and safflower oil; silicone oil; and hydrocarbon oil. The gum protection agent may be an agent capable of improving the permeability barrier of the gums. A complete description of agents capable of improving the permeability barrier of the gum is found in our co-pending application PCT/EP99/03368;
biomolecules, e.g. bacteriocins, antibodies, enzymes, etc.;
flavours, e.g. peppermint and spearmint oils;
preservatives;
opacifying agents;
coloring agents;
pH-adjusting agents;
sweetening agents;
pharmaceutically acceptable carriers, e.g. starch, sucrose, water or water/alcohol systems etc.;
surfactants, such as anionic, nonionic, cationic and zwitterionic or amphoteric surfactants;
particulate abrasive materials such as silicas, aluminas, calcium carbonates, dicalciumphosphates, calcium pyrophosphates, hydroxyapatites, trimetaphosphates, insoluble hexametaphosphates and so on, including agglomerated particulate abrasive materials;
humectants such as glycerol, sorbitol, propyleneglycol, xylitol, lactitol etc.;
binders and thickeners such as sodium carboxymethyl-cellulose, xanthan gum, gum arabic etc. as well as synthetic polymers such as polyacrylates and carboxyvinyl polymers such as Carbopol(copyright);
buffers and salts; and
other optional ingredients that may be included are e.g. bleaching agents such as peroxy compounds e.g. potassium peroxydiphosphate, effervescing systems such as sodium bicarbonate/citric acid systems, color change systems, and so on.
Particularly preferred ingredients in the co-ground include those actives which are unstable in the presence of alkali metal anionic surfactants. Such ingredients include triclosan, cetyl pyridinium chloride, chlorhexidine and other ionic substances.
Ingredients particularly suitable in the present invention include the silicas, hydrophilic or lipophilic polymers, such as crospovidone, pectin, dextran, polyvinylpyrrolidone, cellulose and its derivatives, starches and their derivatives, cyclodextrins, phospholipids, fatty acids, sugars and mixtures thereof. A preferred carrier is abrasive silica.
Further co-ground examples include:
Vitamin C co-ground with abrasive silica to improve the stability of Vitamin C over time. This may also include stannous pyrophosphate to improve the stability of the co-ground. Typical examples include:
50% vitamin C
25% abrasive silica
25 stannous pyrophosphate;
63% vitamin C
33% abrasive silica
4% stannous pyrophosphate
33% vitamin C
67% polyvinylpyrrolidone
20% vitamin C
10% stannous pyrophosphate
40% abrasive silica
30% polyvinylpyrrolidone
20% vitamin C
70% abrasive silica
10% stannous pyrophosphate
50% Vitamin C
9% stannous pyrophosphate
41% abrasive silica
50% Vitamin C
16.7% stannous pyrophsophate
33.3% abrasive silica
Glyceryl monooleate (GMO) with abrasive silica to prevent the inhibition of the sensitive teeth effect of GMO by SLS;
Anti-microbial actives with abrasive silica, such as Chlorhexidine, Triclosan, Zinc etc. to improve retention in the oral cavity and also to prevent their interaction with materials in the remainder of the composition;
SLS co-ground with abrasive silica to improve foaming effect of SLS;
Chalk co-ground with abrasive silica to improve the compatibility of chalk with other ingredients.
Particular embodiments of the invention are now illustrated with the following examples:

Unilever Home and Personal Care USA, a division of Conopco, Inc.