WO2022122483A1

WO2022122483A1 - Composition

Info

Publication number: WO2022122483A1
Application number: PCT/EP2021/083628
Authority: WO
Inventors: Stephen Norman Batchelor; Matthew Lloyd Parry
Original assignee: Unilever Ip Holdings B.V.; Unilever Global Ip Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2020-12-07
Filing date: 2021-11-30
Publication date: 2022-06-16

Abstract

A liquid detergent composition comprising a C16/18 alcohol ethoxylate and/or a C16/18 alkyl ether sulphate and an external structuring system for liquid and gel-form laundry detergents comprising by weight percentage: a. from about 2 to about 10 percent of crystals of a glyceride, preferably hydrogenated castor oil, having a melting temperature of from 40 degrees centigrade to 100 degrees C; b. from about 2 to about 10 percent of an alkanolamine, preferably alkanolamine selected from: monoethanolamine; diethanolamine; triethanolamine, and mixtures thereof; and c. from about 5 to about 50 percent of the anion of an anionic surfactant; wherein said alkanolamine is present in an amount at least balancing the charge of the anion form of said anionic surfactant; and wherein said structuring system is free from any added inorganic cations.

Description

COMPOSITION

The present invention relates to liquid detergent compositions comprising external structuring systems.

Aqueous laundry detergent compositions which are stabilized through the use of external structuring system(s) (ESS) comprising hydroxyl-containing stabilizers have been described. Hydrogenated castor oil (HCO) is a non-limiting example of a useful hydroxyl- containing stabilizer. HCO may be formulated into laundry detergent compositions using sodium- neutralized linear alkylbenzenesulfonate (NaLAS), a common laundry detergent anionic surfactant. It is believed that NaLAS acts as an emulsifier for the HCO structuring system. The acid form of LAS (HLAS) for use in such systems may be neutralized for example, with sodium hydroxide to form NaLAS. The structurant system may be prepared by forming, separately from the balance of the detergent composition, a melt of HCO in aqueous Na- neutralized LAS, which may then be stirred to form an emulsion of molten HCO. This emulsion may then be cooled to crystallize the HCO. Upon crystallization, an external structurant in the form of a premix may be yielded. The premix may then be added to the balance of a liquid laundry detergent composition in order to structure it. Alternatively, the structurant may be crystallized in-situ by mixing the molten emulsified HCO premix with the balance of the detergent composition and then cooling.

It has now been discovered that such external structuring systems can be used with the next generation anionic and non-ionic surfactants to produce products of improved stability and with a wider formulation window, particularly as regards the presence of inorganic electrolytes such as sequestrants and organic acids.

The ESS is provided as a premix. As used herein, the term "external structuring system" or ESS refers to a selected compound or mixture of compounds which provide structure to a detergent composition independently from, or extrinsic from, any structuring effect of the detersive surfactants of the composition. Structuring benefits include arriving at yield stresses suitable for suspending particles having a wide range of sizes and densities. ESS of use may have chemical identities set out in detail hereinafter. External Structuring System

A suitable ESS is described in WO2011/031940 the contents of which, in particular as regards manufacture of the ESS are incorporated by reference. The ESS of the present invention comprise: (a) crystallizable glyceride(s); (b) alkanolamine; (c) anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail in WO2011/031940 and which remains the definitive guide as to manufacture and processing of ESS’s comprising hydrogenated castor oil.

Detergent compositions

The ESS used in the present invention is incorporated into a detergent composition or components thereof as described below. The detergent composition can take any suitable form and may be selected from liquid laundry detergent, unit dose detergent and/or hard surface cleaning compositions. Preferably, the detergent is a laundry liquid composition.

Any suitable means of incorporating the ESS of the present invention into a detergent composition or components thereof may be utilized. One of skill in the art is capable of determining at what point in the detergent manufacturing process that the ESS should be incorporated. Since ESS of the present invention may be shear sensitive, it may be desirable in some embodiments to add the ESS to the detergent composition or components of thereof as late in the manufacturing process as possible. However, in some embodiments, it may be desirable to add the ESS earlier in the manufacturing process to stabilize any non-homogeneity prior to finishing the detergent in a late product differentiation process. Thus in some embodiments, the systems may be added via a continuous liquid process, whereas in other embodiments, the systems may be added via late product differentiation.

In some embodiments, the present invention is directed to liquid laundry detergent compositions comprising the ESS of the present invention. The liquid laundry detergent compositions may be in any suitable form and may comprise any suitable components. Non- limiting examples of suitable components for use in the detergent are described in turn below. The C18 alkyl based surfactant, whether the alcohol ethoxylate or the alkyl ether sulphate is typically available as a mixture with C18 alkyl chain length raw material.

CC18 Alcohol Ethoxylate

The C18 alcohol ethoxylate is of the formula:

Ri-O-(CH₂CH₂O)_q-H where Ri is selected from saturated, monounsaturated and polyunsaturated linear C18 alkyl chains and where q is from 4 to 20, preferably 5 to 14, more preferably 8 to 12. The mono-unsaturation is preferably in the 9 position of the chain, where the carbons are counted from the ethoxylate bound chain end. The double bond may be in a cis or trans configuration (oleyl or elaidyl), preferably cis. The cis or trans alcohol ethoxylate CH₃(CH₂)7-CH=CH-(CH₂)₈O-(OCH₂CH₂)nOH, is described as C18:1(A9) alcohol ethoxylate. This follows the nomenclature CX.YfAZ) where X is the number of carbons in the chain, Y is the number of double bonds and AZ the position of the double bond on the chain where the carbons are counted from the OH bound chain end.

Preferably, R1 is selected from saturated C18 and monounsaturated C18. More preferably, R1 also includes C16 chains in addition to the C18 chains. Preferably, the saturated C16 alcohol ethoxylate is at least 90% wt. of the total C16 linear alcohol ethoxylate. As regards the C18 alcohol ethoxylate content, it is preferred that the predominant C18 moiety is C18:1 , more preferably C18:1(A9). The proportion of monounsaturated C18 alcohol ethoxylate constitutes at least 50% wt. of the total C16 and C18 alcohol ethoxylate surfactant. Preferably, the proportion of monounsaturated C18 constitutes at least 60% wt., most preferably at least 75 of the total C16 and C18 alcohol ethoxylate surfactant.

Preferably, the C16 alcohol ethoxylate surfactant comprises at least 2% wt. and more preferably, from 4% of the total C16 and C18 alcohol ethoxylate surfactant.

Preferably, the saturated C18 alcohol ethoxylate surfactant comprises up to 20% wt. and more preferably, up to 11% of the total C16 and C18 alcohol ethoxylate surfactant. Preferably the saturated C18 content is at least 2% wt. of the total C16 and C18 alcohol ethoxylate content.

Alcohol ethoxylates are discussed in the Non-ionic Surfactants: Organic Chemistry edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series published by CRC press. Alcohol ethoxylates are commonly referred to as alkyl ethoxylates.

Preferably the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1 , more preferably from 2 to 100, most preferably 3 to 30. 018 alcohol ethoxylate’ is the sum of all the C18 fractions in the alcohol ethoxylate and 016 alcohol ethoxylate’ is the sum of all the C16 fractions in the alcohol ethoxylate.

Linear saturated or mono-unsaturated C20 and C22 alcohol ethoxylate may also be present. Preferably the weight fraction of sum of 018 alcohol ethoxylate’ 1020 and C22 alcohol ethoxylate’ is greater than 10.

Preferably the C16/18 alcohol ethoxylate contains less than 15wt%, more preferably less than 8wt%, most preferably less than 5wt% of the alcohol ethoxylate polyunsaturated alcohol ethoxylates. A polyunsaturated alcohol ethoxylate contains a hydrocarbon chains with two or more double bonds.

C16/18 alcohol ethoxylates may be synthesised by ethoxylation of an alkyl alcohol, via the reaction:.

Ri-OH + q ethylene oxide - Ri-O-(CH2CH2O)_q-H

The alkyl alcohol may be produced by transesterification of the triglyceride to a methyl ester, followed by distillation and hydrogenation to the alcohol. The process is discussed in Journal of the American Oil Chemists' Society. 61 (2): 343-348 by Kreutzer, II. R. Preferred alkyl alcohol for the reaction is oleyl alcohol with in an iodine value of 60 to 80, preferably 70 to 75, such alcohol are available from BASF, Cognis, Ecogreen. Production of the fatty alcohol is futher discussed in Sanchez M.A. et al J.Chem.Technol.Biotechnol 2017; 92:27-92 and and Ullmann's Enzyclopaedie der technischen Chemie, Verlag Chemie, Weinheim, 4th Edition, Vol. 11 , pages 436 et seq.

Preferably the ethoxylation reactions are base catalysed using NaOH, KOH, or NaOCH₃. Even more preferred are catalyst which provide narrower ethoxy distribution than NaOH, KOH, or NaOCH₃. Preferably these narrower distribution catalysts involve a Group II base such as Ba dodecanoate; Group II metal alkoxides; Group II hyrodrotalcite as described in W02007/147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

Preferably the narrow ethoxy distribution has greater than 70 wt.%, more preferably greater than 80 w.t% of the alcohol ethoxylate R-O-(CH2CH2O)_q-H in the range R-O- (CH2CH2O)X-H to R-O-(CH2CH2O)_y-H where q is the mole average degree of ethoxylation and x and y are absolute numbers, where x = q-q/2 and y = q+q/2. For example when q=10, then greater than 70 wt.% of the alcohol ethoxylate should consist of ethoxylate with 5, 6, 7, 8, 9 10, 11 , 12, 13, 14 and 15 ethoxylate groups.

C16 and/or C18 Alcohol ether sulfates

Preferably, the composition comprises C16 and C18 ether sulfate of the formula:

R2-O-(CH₂CH₂O)pSO3H

Where R2 is selected from saturated, monounsaturated and polyunsaturated linear C16 and C18 alkyl chains and where p is from 3 to 20, preferably 4 to 12, more preferably 5 to 10. The mono-unsaturation is preferably in the 9 position of the chain, where the carbons are counted from the ethoxylate bound chain end. The double bond may be in a cis or trans configuration (oleyl or elaidyl), but is preferably cis. The cis or trans ether sulfate CH₃(CH2)7-CH=CH-(CH2)8O-(CH2CH2O)nSO₃H, is described as C18:1(A9) ether sulfate. This follows the nomenclature CX.YfAZ) where X is the number of carbons in the chain, Y is the number of double bonds and AZ the position of the double bond on the chain where the carbons are counted from the OH bound chain end. Preferably, R2 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, the saturated C16 is at least 90% wt. of the C16 content linear alkyl. As regards the C18 content, it is preferred that the predominant C18 moiety is C18: 1 , more preferably C18:1(A9). Preferably, the proportion of monounsaturated C18 constitutes at least 50% wt. of the total C16 and C18 alkyl ether sulphate surfactant.

More preferably, the proportion of monounsaturated C18 constitutes at least 60% wt., most preferably at least 75 of the total C16 and C18 alkyl ether sulphate surfactant.

Preferably, the C16 alkyl ether sulphate surfactant comprises at least 2% wt. and more preferably, from 4% of the total C16 and C18 alkyl ether sulphate surfactant.

Preferably, the saturated C18 alkyl ether sulphate surfactant comprises up to 20% wt. and more preferably, up to11 % of the total C16 and C18 alkyl ether sulphate surfactant. Preferably the saturated C18 content is at least 2% wt. of the total C16 and C18 alkyl ether sulphate content.

Where the composition comprises a mixture of the C16/18 sourced material for the alkyl ether sulphate as well as the more traditional C12 alkyl chain length materials it is preferred that the total C16/18 alkyl ether sulphate content should comprise at least 10% wt. of the total alkyl ether sulphate, more preferably at least 50%, even more preferably at least 70%, especially preferably at least 90% and most preferably at least 95% of alkyl ether sulphate in the composition.

Ether sulfates are discussed in the Anionic Surfactants: Organic Chemistry edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series published by CRC press.

Linear saturated or mono-unsaturated C20 and C22 ether sulfate may also be present. Preferably the weight fraction of sum of 018 ether sulfate’ 1 20 and C22 ether sulfate’ is greater than 10.

Preferably the C16 and C18 ether sulfate contains less than 15 wt.%, more preferably less than 8 wt.%, most preferably less than 4wt% and most preferably less than 2% wt. of the ether sulfate polyunsaturated ether sulfate. A polyunsaturated ether sulfate contains a hydrocarbon chains with two or more double bonds.

Ether sulfate may be synthesised by the sulphonation of the corresponding alcohol ethoxylate. The alcohol ethoxylate may be produced by ethoxylation of an alkyl alcohol. The alkyl alcohol used to produced the alcohol ethoxylate may be produced by transesterification of the triglyceride to a methyl ester, followed by distillation and hydrogenation to the alcohol. The process is discussed in Journal of the American Oil Chemists' Society. 61 (2): 343-348 by Kreutzer, II. R. Preferred alkyl alcohol for the reaction is oleyl alcohol with an iodine value of 60 to 80, preferably 70 to 75, such alcohol are available from BASF, Cognis, Ecogreen.

The degree of polyunsaturation in the surfactant may be controlled by hydrogenation of the triglyceride as described in: A Practical Guide to Vegetable Oil Processing (Gupta M.K. Academic Press 2017). Distillation and other purification techniques may be used.

Ethoxylation reactions are described in Non-lonic Surfactant Organic Chemistry (N. M. van Os ed), Surfactant Science Series Volume 72, CRC Press.

Preferably the ethoxylation reactions are base catalysed using NaOH, KOH, or NaOCHs. Even more preferred are catalyst which provide narrower ethoxy distribution than NaOH, KOH, or NaOCHs. Preferably these narrower distribution catalysts involve a Group II base such as Ba dodecanoate; Group II metal alkoxides; Group II hyrodrotalcite as described in W02007/147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

Preferably the narrow ethoxy distribution has greater than 70 wt.%, more preferably greater than 80 w.t% of the ether sulfate R2-O-(CH2CH2O)_PSO3H in the range R2-O-(CH2CH2O)_ZSO3H to R2-O-(CH2CH2O)WSO3H where q is the mole average degree of ethoxylation and x and y are absolute numbers, where z = p-p/2 and w = p+p/2. For example when p=6, then greater than 70 wt.% of the ether sulfate should consist of ether sulfate with 3, 4, 5, 6, 7, 8, 9 ethoxylate groups. The ether sulfate weight is calculated as the protonated form: R2-O-(CH2CH2O)_PSO3H. In the formulation it will be present as the ionic form R2-O-(CH2CH2O)_PSO3~ with a corresponding counter ion, preferred counter ions are group I and II metals, amines, most preferably sodium.

Source of alkyl chains

The alkyl chain of C16/18 surfactant whether an alcohol ethoxylate or an alkyl ether sulphate is preferably obtained from a renewable source, preferably from a triglyceride. A renewable source is one where the material is produced by natural ecological cycle of a living species, preferably by a plant, algae, fungi, yeast or bacteria, more preferably plants, algae or yeasts.

Preferred plant sources of oils are rapeseed, sunflower, maze, soy, cottonseed, olive oil and trees. The oil from trees is called tall oil. Most preferably Palm and Rapeseed oils are the source.

Algal oils are discussed in Energies 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges by Saad M.G. et al. A process for the production of triglycerides from biomass using yeasts is described in Energy Environ. Sci., 2019,12, 2717 A sustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents by Masri M.A. et al.

Non edible plant oils may be used and are preferably selected from the fruit and seeds of Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), Linseed, Pongamia pinnata (karanja), Hevea brasiliensis (Rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L.(castor), Simmondsia chinensis (Jojoba), Eruca sativa. L., Cerbera odollam (Sea mango), Coriander (Coriandrum sativum L.), Croton megalocarpus, Pilu, Crambe, syringa, Scheleichera triguga (kusum), Stillingia, Shorea robusta (sal), Terminalia belerica roxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, Rice bran, Hingan (balanites), Desert date, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, Alagae, Argemone mexicana L. (Mexican prickly poppy, Putranjiva roxburghii (Lucky bean tree), Sapindus mukorossi (Soapnut), M. azedarach (syringe), Thevettia peruviana (yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, B. napus, Zanthoxylum bungeanum.

Further non-ionic

Preferably, the composition comprises a non-ionic surfactant in addition to the surfactants described above. Preferably the composition comprises from 5 to 20% wt. non-ionic surfactant based on the total weight of composition including the C16/18 non-ionic surfactants and any other nonionic surfactants, for example, polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. The polyoxyalkylene compounds can have a variety of block and heteric (random) structures. For example, they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates. Within the block structures, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides. Examples of such materials include Cs to C22 alkyl phenol ethoxylates with an average of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol; and aliphatic alcohol ethoxylates such as Cs to Cis primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.

A preferred class of additional nonionic surfactant for use in the invention includes aliphatic C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.

The alcohol ethoxylate may be provided in a single raw material component or by way of a mixture of components.

Where the composition comprises a mixture of the C16/18 sourced material for the alcohol ethoxylate as well as the more traditional C12 alkyl chain length materials it is preferred that the total C16/18 alcohol ethoxylate content should comprise at least 10% wt. total alcohol ethoxylate, more preferably at least 50%, even more preferably at least 70%, especially preferably at least 90% and most preferably at least 95% of the alcohol ethoxylate in the composition.

A further class of non-ionic surfactants include the alkyl poly glycosides. Rhamnolipids are another preferred additional surfactant.

Preferably, the weight ratio of total non-ionic surfactant to total alkyl ether sulphate surfactant (wt. non-ionic I wt. alkyl ether sulphate) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably 0.9 to 1.1.

Preferably, the weight ratio of total C16/18 non-ionic surfactant, to total alkyl ether sulphate surfactant (wt. non-ionic I wt. alkyl ether sulphate) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably 0.9 to 1.1.

Preferably, the weight ratio of total non-ionic surfactant to total C16/18 alkyl ether sulphate surfactant (wt. non-ionic I wt. alkyl ether sulphate) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably 0.9 to 1.1.

Preferably, the weight ratio of total C18:1 non-ionic surfactant to total C18:1 alkyl ether sulphate surfactant (wt. non-ionic I wt. alkyl ether sulphate) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably 0.9 to 1.1.

Preferably, the weight ratio of total non-ionic surfactant to linear alkyl benzene sulphonate, where present, (wt. non-ionic/ wt. linear alkyl benzene sulphonate) is from 0.1 to 2, preferably 0.3 to 1 , most preferably 0.45 to 0.85.

Preferably, the weight ratio of total C16/18 non-ionic surfactant to linear alkyl benzene sulphonate, where present, (wt. non-ionic/ wt. linear alkyl benzene sulphonate) is from 0.1 to 2, preferably 0.3 to 1 , most preferably 0.45 to 0.85.

Additional anionic surfactants

The composition preferably comprises an anionic surfactant in addition to any C16/18 alkyl ether sulphate as described above. Non-soap anionic surfactants for use in the invention are typically salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Examples of such materials include alkyl sulfates, C12-C14 alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and mixtures thereof. The alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated. The C12-C14 alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule. Alkyl ether sulfates are also called alcohol ether sulfates. Anionic surfactants are described in anionic surfactants, volume 56 of the Surfactant Science Seried (H.W. Stache editor) Dekker 1995.

Commonly used in laundry liquid compositions are C12-C14 alkyl ether sulfates having a straight or branched chain alkyl group having 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3EO units per molecule.

The C12-C14 alkyl ether sulphate may be provided in a single raw material component or by way of a mixture of components.

The counterion for any of the anionic surfactants used in the compositions described herein is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as ammonium, monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed.

The compositions according to the invention may preferably include alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1-phenyl isomer. LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.

Some alkyl sulfate surfactant may be used, such as non-ethoxylated primary and secondary alkyl sulphates with an alkyl chain length of from 10 to 18.

Mixtures of any of the above described materials may also be used.

Preferably, linear alkyl benzene sulphonate surfactant is present at from 1 to 20% wt., more preferably from 2 to 15% wt. of the composition, most preferably 8 to 12 wt.%.

Weight ratios are calculated for the protonated form of the surfactant.

Preferably, the detergent composition with the EES comprises C16/18 alcohol ethoxylate and C16/18 alkyl ether sulphate.

Preferably, the level of surfactant in the detergent composition is from 4 to 40wt%.

The aqueous liquid carrier component of the liquid detergent products herein will generally comprise water present in concentrations ranging from about 0 percent to 90 percent, more preferably from about 5 percent to 70 percent, by weight of the composition.

The detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional laundry detergent composition components such as detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and/or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibiting agents, optical brighteners, perfumes and coloring agents. The various optional detergent composition ingredients, if present in the compositions herein, should be utilized at concentrations conventionally employed to bring about their desired contribution to the composition or the laundering operation. Frequently, the total amount of such optional detergent composition ingredients can range from 2 percent to 50 percent, more preferably from 5 percent to 30 percent, by weight of the composition. A few of the optional ingredients which can be used are described in greater detail as follows: i) Organic Detergent Builders.

The detergent compositions herein may also optionally contain low levels of an organic detergent builder material which serves to counteract the effects of calcium, or other ion, water hardness encountered during laundering/bleaching use of the compositions herein. Examples of such materials include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids C10-C22 fatty acids and citric acid. Other examples are organic phosphonate type sequestering agents such as those which have been sold by Monsanto under the Dequest tradename and alkanehydroxy phosphonates. Citrate salts and C12-C18 fatty acid soaps are highly preferred.

Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the Sokalan trademark. If utilized, organic builder materials will generally comprise from about 1 percent to 50 percent, more preferably from about 2 percent to 30 percent, most preferably from about 5 percent to 20 percent, by weight of the composition, ii) Detersive Enzymes.

The liquid detergent compositions herein may comprise one or more detersive enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta - glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and known amylases, or combinations thereof. A preferred enzyme combination comprises a cocktail of conventional detersive enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase. Detersive enzymes are described in greater detail in U.S. Patent No. 6,579,839. If employed, enzymes will normally be incorporated into the liquid detergent compositions herein at levels sufficient to provide up to 3 mg by weight, more typically from about 0.0001 mg to about 2.5 mg, of active enzyme per gram of the composition. Stated otherwise, the aqueous liquid detergent compositions herein can typically comprise from 0.001 percent to 5 percent, preferably from 0.005 percent to 3 percent by weight, of a commercial enzyme preparation. The activity of the commercial enzyme preparation is typically in the range of 10 to 50 mg active enzyme protein per gram of raw material, iii) Solvents, Hydrotropes and Phase Stabilizers.

The detergent compositions herein may also optionally contain low levels of materials which serve as phase stabilizers and/or co-solvents for the liquid compositions herein. Materials of this type include C1-C3 lower alkanols such as methanol, ethanol and/or propanol. Lower C1-C3 alkanolamines such as mono-, di- and triethanolamines can also be used, by themselves or in combination with the lower alkanols. If utilized, phase stabilizers/co-solvents can comprise from about 0.1 percent to 5.0 percent by weight of the compositions herein, iv) pH Control Agents.

The detergent compositions herein may also optionally contain low levels of materials which serve to adjust or maintain the pH of the aqueous detergent compositions herein at optimum levels. The pH of the compositions of this invention should range from about 6.0 to about 10.5, from about 7.0 to about 10.0, or from about 8.0 to about 8.5. Materials such as NaOH can be added to alter composition pH, if necessary, c. Unit Dose Detergent.

In some embodiments of the present invention, the liquid detergent compositions are packaged in a unit dose pouch, wherein the pouch is made of a water soluble film material, such as a polyvinyl alcohol. In some embodiments, the unit dose pouch comprises a single or multicompartment pouch where the present liquid detergent composition can be used in conjunction with any other conventional powder or liquid detergent composition. Examples of suitable pouches and water soluble film materials are provided in U.S. Patent Nos. 6,881,713, 6,815,410, and 7,125,828. The pouch is preferably made of a film material which is soluble or dispersible in water, and has a water- solubility of at least 50 percent, preferably at least 75 percent or even at least 95 percent, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns: 50 grams plus or minus 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker and 245ml plus or minus 1 ml of distilled water is added. This is stirred vigorously on a magnetic stirrer set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a folded qualitative sintered-glass filter with a pore size as defined above (max. 20 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed fraction). Then, the percentage solubility or dispersability can be calculated.

Preferred pouch materials are polymeric materials, preferably polymers which are formed into a film or sheet. The pouch material can, for example, be obtained by casting, blowmoulding, extrusion or blown extrusion of the polymeric material, as known in the art.

Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatin, natural gums such as xanthum and carragum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof. Preferably, the level of polymer in the pouch material, for example a PVA polymer, is at least 60 percent. The polymer can have any weight average molecular weight, preferably from about 1000 to 1 ,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.

Mixtures of polymers can also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartments or pouch, depending on the application thereof and the required needs. Suitable mixtures include for example mixtures wherein one polymer has a higher water-solubility than another polymer, and/or one polymer has a higher mechanical strength than another polymer. Also suitable are mixtures of polymers having different weight average molecular weights, for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of about 10,000- 40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000. Also suitable herein are polymer blend compositions, for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35 percent by weight polylactide and about 65 percent to 99 percent by weight polyvinyl alcohol. Preferred for use herein are polymers which are from about 60 percent to about 98 percent hydrolysed, preferably about 80 percent to about 90 percent hydrolysed, to improve the dissolution characteristics of the material.

Naturally, different film material and/or films of different thickness may be employed in making the compartments of the present invention. A benefit in selecting different films is that the resulting compartments may exhibit different solubility or release characteristics.

Most preferred pouch materials are PVA films known under the trade reference MonoSol M8630, as sold by Chris-Craft Industrial Products (Gary, IN), and PVA films of corresponding solubility and deformability characteristics. Other films suitable for use herein include films known under the trade reference PT film or the K-series of films supplied by Aicello (Koshikawa, Japan), or VF-HP film supplied by Kuraray (Tokyo, Japan).

The pouch material herein can also comprise one or more additive ingredients. For example, it can be beneficial to add plasticisers, for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof. Other additives include functional detergent additives to be delivered to the wash water, for example organic polymeric dispersants, etc.

For reasons of deformability pouches or pouch compartments containing a component which is liquid will preferably contain an air bubble having a volume of up to about 50 percent, preferably up to about 40 percent, more preferably up to about 30 percent, more preferably up to about 20 percent, more preferably up to about 10 percent of the volume space of said compartment. llnit dose pouches comprising liquid detergent compositions according to the present invention may be made using any suitable means. Non-limiting examples of such means are described in the patents listed above.

The pouch is preferably made of a film material which is soluble or dispersible in water, and has a water- solubility of at least 50 percent, preferably at least 75 percent or even at least 95 percent, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:

50 grams plus or minus 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker and 245ml plus or minus 1ml of distilled water is added. This is stirred vigorously on a magnetic stirrer set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a folded qualitative sintered-glass filter with a pore size as defined above (max. 20 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed fraction). The percentage solubility or dispersability can then be calculated, d. Hard Surface Cleaning Compositions.

In some embodiments, the ESS may be utilized in liquid hard surface cleaning compositions. Such compositions include, but are not limited to, forms selected from gels, pastes, thickened liquid compositions as well as compositions having a water-like viscosity. A preferred liquid hard surface cleaning composition herein is an aqueous, liquid hard surface cleaning composition and therefore, preferably comprises water more preferably in an amount of from 50 percent to 98 percent, even more preferably of from 75 percent to 97 percent and most preferably 80 percent to 97 percent by weight of the total composition.

Examples

Example 1 is an example of a liquid detergent composition according to the invention, wherein a premix comprising 4 percent HCO, 16 percent Linear Alkylbenzene Sulfonic acid neutralized by 3.1 percent Monoethanolamine (MEA), and water up to 100 parts is made and then added at 18.75 percent in a HDL comprising the rest of the ingredients, to give the detergent composition 1 in Table I. Table 1

C16/18 alcohol ethoxylate is commercially available from Clariant as Genopol 0-100.

Claims

1. A liquid detergent composition comprising a C18 alcohol ethoxylate and/or a C18 alkyl ether sulphate and an external structuring system for liquid and gel-form laundry detergents comprising by weight percentage: a. from about 2 to about 10 percent of crystals of a glyceride, preferably hydrogenated castor oil, having a melting temperature of from 40 degrees centigrade to 100 degrees C; b. from about 2 to about 10 percent of an alkanolamine, preferably alkanolamine selected from: monoethanolamine; diethanolamine; triethanolamine, and mixtures thereof; and c. from about 5 to about 50 percent of the anion of an anionic surfactant; wherein said alkanolamine is present in an amount at least balancing the charge of the anion form of said anionic surfactant; and wherein said structuring system is free from any added inorganic cations.

2. A detergent composition according to claim 1 wherein the external structuring system according to claim 1 wherein said crystals have a non- spherical elongated crystal habit with an aspect ratio of at least 5: 1 and a needle radius of at least about 20 nanometers.

3. A detergent composition according to claim 1 wherein the external structuring system according to claim 2 wherein said anionic surfactant is a synthetic anionic surfactant, the sodium salt which has a Krafft temperature below 50 degrees centigrade.

4. A detergent composition according to claim 1 wherein the external structuring system according to any of the preceding claims wherein said anionic surfactant has an HI value below 8.

5. A detergent composition according to claim 1 wherein the external structuring system according to claim 4 wherein said anionic surfactant is alkylbenzene sulfonate comprising a 2-phenyl isomer content of not more than 70 percent. A detergent composition according to claim 1 wherein the external structuring system according to any one of the preceding claims wherein said composition is substantially free from soap and/or divalent metal cations. A detergent composition according to claim 1 wherein the external structuring system according to claim 6 wherein said alkanolamine is present in said structuring system in stoichiometric excess over said anionic surfactant and the pH on dilution at 5 weight percent in water of said external structuring system is from about 7.5 to about 9.0. A detergent composition according to claim 1 wherein the external structuring system of claim 1 wherein said alkanolamine is monoethanolamine and said system is boron- free. A detergent composition according to claim 1 wherein the external structuring system of claim 8, comprising less than about 1 percent by weight of the external structuring system of sodium-neutralized linear alkyl benzene sulfonate. A detergent composition, preferably in a form selected from the group liquid and gel, comprising a C18 alcohol ethoxylate and/or a C18 alkyl ether sulphate and an external structuring system of any of the preceding claims. The detergent composition of claim 10 wherein said detergent is a liquid laundry detergent comprising from about 1 percent to about 20 percent external structuring system by weight of the liquid laundry detergent composition and wherein said external structuring system provides sufficient hydrogenated castor oil to achieve a finished detergent product level of from about 0.1 to about 10 by weight percent of the finished detergent product of hydrogenated castor oil. The detergent composition of claim 11 , wherein said detergent composition is a liquid laundry detergent composition comprising less than 2 percent by weight laundry detergent composition of monovalent inorganic cations. The laundry detergent composition according to any one of claims 10-12, wherein said detergent composition is a liquid enclosed in water-soluble film. The detergent composition of claim 13 wherein said detergent is a detergent selected from a hard surface cleaning composition and a liquid laundry detergent composition.