Irritation Reducing Surfactants

Abstract

Furan-based surfactants are used in detergents for the purpose of reducing or preventing irritation during use.

Description

[0001] The present invention relates to the use of furan-based compounds.

[0002] WO 2015 / 084813 (P&G) discloses furan-based chemicals comprising a furan group, a hydrophilic group and a hydrophobic group, wherein the hydrophilic group may be ionic, zwitterionic or nonionic, and further, wherein the hydrophobic group may be an alkyl or alkenyl, linear or branched moiety.

[0003] WO 2015 / 094970 (Archer Daniels Midland Co) discloses linear mono- and di-alkyl ethers of furan-2,5-dimethanol (FDM) and / or 2,5-bis(hydroxymethyl)tetrahydrofuran (bHMTHF), describes their preparation methods, and their derivative compounds.

[0004] George Kraus et al. "A Direct Synthesis of Renewable Sulfonate-Based Surfactants" Journal of Surfactants and Detergents vol. 16, no. 3, 1 May 2013 (2013-05-01), pp. 317-320 discloses furan-based surfactants with ester and ether linkages of β-hydroxysulfonic acid head groups. The compositions are described as being unstable in the alkaline pH range.

[0005] Despite the prior art, there remains a need for more effective cleaning compositions that contain raw materials of environmental origin and that are suitable for use in a wide range of commercially useful detergent formulations and provide mildness benefits during use.

[0006] Thus, in a first aspect there is provided the use of a furan-based surfactant in a detergent for reducing or preventing irritation during use.

[0007] In a second aspect, there is provided a method for treating a substrate, the method comprising forming a wash liquor comprising 0.1 to 5 g / l of a furan-based surfactant. Preferably, the wash liquor comprises 0.1 to 2 g / l of a furan-based surfactant.

[0008] Preferably, the method for treating a substrate is a method for hand washing fabrics, hand washing dishes or cleaning hard surfaces.

[0009] Preferably, the furan-based surfactant comprises a head group, furan, and a hydrophobic portion connected to the furan via a linker.

[0010] Preferably, the head group is selected from the group consisting of beta-sulfonate, beta-hydroxysulfonate, beta-sulfate, beta-hydroxysulfate, alpha-sulfonate, alpha-hydroxysulfonate, alpha-sulfate, alpha-hydroxysulfonate, alpha-sulfate, alpha-hydroxysulfate, and mixtures thereof.

[0011] Preferably, the linker is selected from direct alkyl, carbonyl alkyl, hydroxyalkyl, carbonyl ether, hydroxy ether, carbonyl amide, hydroxy amide and ester.

[0012] The furan-based surfactants described herein are shown to have mildness benefits when used in detergent compositions. Detergent compositions include compositions whose primary purpose is to clean substrates, where the substrate is a fabric (e.g., a laundry detergent), a household item (e.g., a dishware or kitchen surface), etc. More preferably, however, the detergent is a laundry detergent, a dishwashing detergent, or a hard surface cleaner.

[0013] In use, the detergent composition preferably comprises 0.01 to 7 wt % of the furan-based surfactant, but this depends on the nature of the detergent composition and the presence of other surfactants in the composition. More preferably, the detergent composition comprises 0.01 to 5 wt % of the furan-based surfactant, more preferably 0.01 to 4.0 wt % of the furan-based surfactant, and more preferably 0.1 to 2.0 wt %.

[0014] In a more preferred embodiment, the furan-based surfactant comprises a beta sulfonate head group, furan, and a C10-20 hydrophobe attached to the furan either directly or by means of a linker.

[0015] We have surprisingly found that the material claimed in claim 1 provides mildness benefits in addition to adequate cleaning power. This is very unusual in general, where cleaning power is usually at the expense of higher irritation and vice versa.

[0016] Preferably, the linker in the furan-based surfactant is selected from the group consisting of carbonyl alkyl, hydroxyalkyl, carbonyl ether, hydroxy ether, carbonyl amide, hydroxy amide and ester.

[0017] Preferably, the hydrophobic group is an alkyl chain. More preferably, it is a linear alkyl chain, and most preferably, it contains 12 to 18 carbon atoms.

[0018] Preferably, the hydrophobic group can be attached to the linker at any point, but preferably, the hydrophobic group comprises a linear alkyl chain attached at the midpoint along its length. Midpoint means that the alkyl chains on either side of the attachment point are the same or within 6, preferably 4 and more preferably 2 carbons. The most preferred alkyl chain length is one where they are attached so that the number of carbon atoms of both chains is equal.

[0019] Preferably, the hydrophobic group is saturated.

[0020] Preferably, the detergent composition is selected from a laundry liquid composition, a powdered laundry composition, a hard surface cleaning composition, a toilet cleaning composition and a hand dishwashing cleaning composition. More preferably, the detergent composition is a laundry liquid composition or a laundry powder composition.

[0021] Regardless of the detergent form, it is preferred that the furan-based surfactant is a co-surfactant along with the additional anionic or nonionic surfactants as described below.

[0022] In a third aspect, there is provided the use of a detergent composition comprising 0.01 to 8 wt % of a furan-based surfactant as described above to prevent or reduce irritation, wherein the furan-based surfactant comprises an alpha sulfonate head group, furan, a linker and a C10-20 hydrophobic group.

[0023] liquid

[0024] Liquid laundry detergent

[0025] Examples of liquid laundry detergents include heavy duty liquid laundry detergents for use in the wash cycle of an automatic washing machine, and liquid delicates and liquid color care detergents, such as those suitable for washing delicate garments (e.g., garments made of silk or wool) by hand or in the wash cycle of an automatic washing machine.

[0026] In the context of the present invention, the term "liquid" means that the continuous phase or major part of the composition is liquid, and the composition is flowable at 15°C and above. Thus, the term "liquid" may include emulsions, suspensions and compositions with a flowable but hard consistency, known as gels or pastes. The viscosity of the composition is 25°C and 21 seconds. -1 The shear rate of 1000 mPa.s may suitably be in the range of about 200 mPa.s to about 10,000 mPa.s. This shear rate is the shear rate normally applied to the liquid when pouring from a bottle. Pourable liquid detergent compositions typically have a viscosity of 200 to 1,500 mPa.s, preferably 200 to 500 mPa.s.

[0027] The liquid detergent composition as a pourable gel generally has a viscosity of 1,500 to 6,000 mPa.s, preferably 1,500 to 2,000 mPa.s.

[0028] The liquid composition according to the present invention may suitably have an aqueous continuous phase. "Aqueous continuous phase" refers to a continuous phase based on water. Compositions having an aqueous continuous phase typically contain 15 to 95%, preferably 20 to 90%, more preferably 25 to 85% water (by weight based on the total weight of the composition).

[0029] The liquid composition according to the invention may also have a low water content, for example when the composition is intended for packaging in a polymer film soluble in wash water. Low water content compositions generally contain no more than 20%, preferably no more than 10%, for example 5-10% water (by weight based on the total weight of the composition).

[0030] The liquid composition of the present invention having an aqueous continuous phase preferably has a pH in the range of 5 to 9, more preferably 6 to 8, measured when the composition is diluted to 1% with demineralized water.

[0031] The liquid composition of the present invention suitably comprises 3-60%, preferably 5-40%, more preferably 6-30% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof.

[0032] In the context of the present invention, the term "detersive surfactant" means a surfactant that provides a detersive (ie cleaning) effect on laundry treated as part of a domestic laundry process.

[0033] In addition to the above-mentioned furan-based surfactants, other non-soap anionic surfactants used in liquid compositions are typically salts of organic sulfuric and sulfonic acids having an alkyl group containing about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of the higher acyl group. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, α-olefin sulfonates, and mixtures thereof. The alkyl group preferably contains 10-18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain 1-10 ethylene oxide or propylene oxide units per molecule, preferably 1-3 ethylene oxide units per molecule. The counter ions of the anionic surfactants are typically alkali metals such as sodium or potassium; or ammonia counter ions such as monoethanolamine (MEA), diethanolamine (DEA) or triethanolamine (TEA). Mixtures of these counter ions may also be used.

[0034] Before, a class of preferred non-soap anionic surfactants for liquid compositions includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of 10-18 carbon atoms. Commercially available LAS is a mixture of closely related isomers and homologues of alkyl chain homologues, each containing an aromatic ring that is sulfonated in the "para-position" and is connected to a linear alkyl chain at any position except the terminal carbon. The linear alkyl chain has a chain length of 11 to 15 carbon atoms, and the main material has a chain length of about C12. Each alkyl chain homologue is composed of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is usually formulated into compositions in the form of acid (i.e. HLAS), then at least partially in situ neutralization.

[0035] In addition to the furan-based surfactants as described above, the compositions according to the invention may contain some alkylbenzene sulfonate. Typical ratios between benzene-based surfactants and furan-based surfactants are from 99:1 to 0:100% by weight of the composition (before in-situ neutralization), more preferably from 50:50 to 0:100, especially preferably from 5:95 to 0:100, most preferably from 0.1:99.9 to 0:100.

[0036] Also suitable are alkyl ether sulfates having a linear or branched alkyl group containing 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES), in which the predominantly C12 lauryl alkyl groups are ethoxylated with an average of 3 EO units per molecule.

[0037] Some alkyl sulfate surfactants (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulfates having an alkyl chain length of 10-18.

[0038] Mixtures of any of the above materials may also be used. Preferred mixtures of non-soap anionic surfactants for use in the present invention comprise linear alkyl benzene sulfonates (preferably C 11 -C 15 linear alkylbenzene sulfonate) and sodium lauryl ether sulfate. (preferably C 10 -C 18 alkyl sulfate).

[0039] In the liquid compositions of the present invention the total level of non-soap anionic surfactant may suitably be in the range of 4 to 20%, preferably 6 to 16% by weight based on the total weight of the composition.

[0040] The nonionic surfactant used for liquid compositions is generally a polyoxyalkylene compound, i.e., a reaction product of an oxyalkylene (such as ethylene oxide or propylene oxide or a mixture thereof) with a starting molecule having a hydrophobic group and a reactive hydrogen atom (which is reactive with the oxyalkylene). Such starting molecules include alcohols, acids, amides, or alkylphenols. When the starting molecule is an alcohol, the reaction product is referred to as an alcohol alkoxylate. The polyoxyalkylene compound can have a variety of block and mixed (random) structures. For example, they can contain a single oxyalkylene block, or they can be a diblock alkoxylate or a triblock alkoxylate. Within the block structure, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain mixed mixtures of oxyalkylenes. Examples of such materials include C8 to C 22 Alkylphenol ethoxylates having an average of 5 to 25 moles of ethylene oxide per mole of alkylphenol; and aliphatic alcohol ethoxylates such as C8-C 18Primary or secondary straight or branched chain alcohol ethoxylates having an average of 2 to 40 moles of ethylene oxide per mole of alcohol.

[0041] Preferred classes of nonionic surfactants for use in liquid compositions include aliphatic C8-C 18 , more preferably C 12 -C 15 Straight chain primary alcohol ethoxylates have an average of 3 to 20, more preferably 5 to 10, moles of ethylene oxide per mole of alcohol.

[0042] Mixtures of any of the above materials may also be used.

[0043] In the liquid composition of the present invention, the total content of nonionic surfactant is suitably in the range of 1 to 15% (by weight based on the total weight of the composition).

[0044] Examples of suitable mixtures of non-soap anionic and / or nonionic surfactants for use in liquid compositions include linear alkylbenzene sulfonates (preferably C 11 To C 15 linear alkylbenzene sulfonate) (if present) with a furan-based surfactant as described above, with sodium lauryl ether sulfate (preferably C 10 To C 18 alkyl sulfates) and / or ethoxylated aliphatic alcohols (preferably C 12 To C 15 The level of furan-based surfactant in such mixtures is preferably at least 50%, such as 50 to 95% (by weight based on the total weight of the mixture).

[0045] The weight ratio of total non-soap anionic surfactant to total nonionic surfactant in the compositions of the present invention is suitably in the range of from about 3:1 to about 1:3, more preferably from about 2.5:1 to 1.1:1.

[0046] Non-aqueous carrier

[0047] The liquid compositions of the present invention may incorporate non-aqueous carriers such as hydrotropes, cosolvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids, such as C1 to C5 monohydric alcohols (such as ethanol and n-propanol or isopropanol); C2 to C6 diols (e.g., monopropylene glycol and dipropylene glycol); C3 to C9 triols (e.g., glycerol); weight average molecular weight (M w ) ranges from about 200 to 600; C1-C3 alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (e.g., sodium and potassium xylene, toluene, ethylbenzene, and cumene (cumene) sulfonates).

[0048] Mixtures of any of the above materials may also be used.

[0049] When a non-aqueous carrier is included, it may be present in an amount ranging from 0.1 to 20%, preferably from 1 to 15%, more preferably from 3 to 12% (by weight based on the total weight of the composition).

[0050] Co-surfactant

[0051] In addition to the non-soap anionic and / or nonionic detersive surfactants described above, the liquid compositions of the present invention may comprise one or more co-surfactants (eg amphoteric (zwitterionic) and / or cationic surfactants).

[0052] Specific cationic surfactants include C8-C18 alkyl dimethyl ammonium halides and derivatives thereof, wherein one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof. When cationic surfactants are included, they may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0053] Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkyl sultaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycocinates, alkylamidopropyl hydroxysultaines, acyl taurates and acyl glutamates having an alkyl group containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. When included, the amphoteric (zwitterionic) surfactant may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0054] Mixtures of any of the above materials may also be used.

[0055] Polyamine

[0056] Ethoxylated polyamines (EPEI) are typically linear or branched poly(>2) amines. The amines may be primary, secondary or tertiary amines. Single or multiple amine functional groups react with one or more alkylene oxide groups to form polyalkylene oxide side chains. The alkylene oxide may be a homopolymer (e.g., ethylene oxide) or a random or block copolymer. The end groups of the alkylene oxide side chains may be further reacted to impart anionic properties to the molecule (e.g., imparting carboxylic acid or sulfonic acid functionality).

[0057] The liquid composition comprises from about 0.5% to about 4%, more preferably 2.0 to 3.5% by weight of the composition of the polyamine. Preferably, the polyamine is a soil release agent comprising a polyamine backbone corresponding to the formula:

[0058]

[0059] A modified polyamine having the formula V(n+1)WmYnZ, or

[0060] The polyamine backbone corresponds to the following formula:

[0061]

[0062] A modified polyamine having the formula V(nk+1)WmYnY'kZ,

[0063] where k is less than or equal to n,

[0064] Preferably, the polyamine backbone has a molecular weight greater than about 200 Daltons prior to modification.

[0065] Preferably,

[0066] i) The V unit is a terminal unit having the formula:

[0067]

[0068] ii) The W unit is a backbone unit having the formula:

[0069]

[0070] iii) the Y unit is a branching unit having the formula:

[0071]

[0072] iv) The Z unit is a terminal unit having the formula:

[0073]

[0074] Preferably, the backbone-linked R units are selected from C2-C12 alkylene, -(R1O)xR3(OR1)x-, -(CH2CH(OR2)CH2O)z(R1O)yR1(OCH2CH(OR2)CH2)w-, -CH2CH(OR2)CH2- and mixtures thereof,

[0075] Provided that when R comprises a C1-C12 alkylene group, R further comprises at least one -(R1O)xR3(OR1)x-, -(CH2CH(OR2)CH2O)z(R1O)yR1-(OCH2CH(OR2)CH2)w- or -CH2CH(OR2)CH2- unit;

[0076] Preferably, R1 is C2-C6 alkylene and mixtures thereof;

[0077] Preferably, R2 is hydrogen, (R1O)xB and mixtures thereof;

[0078] Preferably, R3 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -C(O)-, -C(O)NHR5NHC(O)-, C(O)(R4)rC(O)-, -CH2CH(OH)CH2O(R1O)yR1O-CH2CH(OH)CH2-, and mixtures thereof;

[0079] Preferably, R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene and mixtures thereof;

[0080] Preferably, R5 is C2-C12 alkylene or C6-C12 arylene;

[0081] Preferably, the E unit is selected from (CH2)p-CO2M, -(CH2)qSO3M, -CH(CH2CO2M)CO2M, (CH2)pPO3M, -(R1O)xB and mixtures thereof,

[0082] Preferably, B is hydrogen, -(CH2)qSO3M, -(CH2)pCO2M, -(CH2)qCH(SO3M)CH2SO3M, -(CH2)qCH(SO2M)CH2SO3M, -(CH2)pPO3M, -PO3M and mixtures thereof,

[0083] Preferably, M is hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance;

[0084] Preferably X is a water-soluble anion;

[0085] Preferably k has a value from 0 to about 20;

[0086] Preferably m has a value from 4 to about 400;

[0087] Preferably n has a value from 0 to about 200;

[0088] Preferably p has a value from 1 to 6,

[0089] Preferably q has a value from 0 to 6;

[0090] Preferably r has a value of 0 or 1;

[0091] Preferably w has a value of 0 or 1;

[0092] Preferably x has a value from 1 to 100;

[0093] Preferably y has a value from 0 to 100; and

[0094] Preferably z has a value of 0 or 1.

[0095] Builder

[0096] The liquid compositions of the present invention may contain one or more builders. Builders enhance or maintain the cleaning efficiency of surfactants primarily by reducing water hardness. This is achieved by sequestration or chelation (keeping hardness minerals in solution), by precipitation (forming insoluble materials) or by ion exchange (exchanging charged particles).

[0097] Builders used in liquid compositions can be organic or inorganic type, or mixtures thereof.

[0098] Suitable inorganic builders include hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites and mixtures thereof. Specific examples of these materials include sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.

[0099] Suitable organic builders include polycarboxylates in acid and / or salt form. When used in salt form, alkali metals (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium citrate and potassium citrate, sodium tartrate and potassium tartrate, sodium and potassium salts of tartrate monosuccinic acid, sodium and potassium salts of tartrate disuccinic acid, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylenediaminetriacetate, sodium and potassium nitrilotriacetate, and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetate. Polymeric polycarboxylates may also be used, such as polymers of unsaturated monocarboxylic acids (e.g., acrylic acid, methacrylic acid, vinyl acetic acid, and crotonic acid) and / or unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid and anhydrides thereof). Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic acid and maleic acid. The polymer may be in acid, salt or partially neutralized form and may suitably have a molecular weight (Mw) ranging from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, more preferably from about 2,500 to about 75,000.

[0100] Mixtures of any of the above materials may also be used.Preferred builders for use herein may be selected from polycarboxylic acids (eg citric acid) in acid and / or salt form, and mixtures thereof.

[0101] When included, builders may be present in amounts ranging from about 0.1 to about 20%, preferably from about 0.5 to about 15%, more preferably from about 1 to about 10% by weight, based on the total weight of the composition.

[0102] Transition metal ion chelators

[0103] The liquid compositions of the present invention may contain one or more chelating agents for transition metal ions such as iron, copper and manganese. Such chelating agents may help improve the stability of the composition and prevent, for example, the decomposition of certain ingredients catalyzed by the transition metals.

[0104] Suitable transition metal ion chelators include phosphonates in acid and / or salt form. When used in salt form, alkali metals (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotris(methylenephosphonic acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP) and diethylenetriamine penta(methylenephosphonic acid) (DTPMP) and their corresponding sodium or potassium salts. HEDP is preferred. Mixtures of any of the above materials may also be used.

[0105] When included, the transition metal ion chelating agent may be present in an amount ranging from about 0.1 to about 10%, preferably from about 0.1 to about 3%, by weight based on the total weight of the composition.

[0106] fatty acid

[0107] Liquid compositions according to the present invention preferably contain one or more fatty acids and / or salts thereof.

[0108] In the context of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, most preferably 12 to 18 carbon atoms and 0 or 1 double bonds. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures, wherein 50-100% by weight (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures can typically be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

[0109] The fatty acids may be present in the form of their sodium, potassium or ammonium salts and / or in the form of soluble salts with organic bases such as mono-, di- or triethanolamine.

[0110] Mixtures of any of the above materials may also be used.

[0111] When included, fatty acids and / or their salts may be present in an amount ranging from about 0.25-5%, more preferably 0.5-5%, most preferably 0.75-4% by weight based on the total weight of the composition.

[0112] For the purpose of formulation, fatty acids and / or their salts (as defined above) are not included in the level of surfactant or in the level of builder in the formulation.

[0113] Polymer cleaning enhancers

[0114] In order to further improve the environmental profile of liquid laundry detergents, it may be preferred in some cases to reduce the volume of laundry detergent charged per wash load and to add various weight efficient ingredients to the composition to enhance cleaning performance. In addition to the soil release polymers of the present invention described above, the compositions of the present invention will preferably contain one or more additional polymeric cleaning enhancers, such as anti-redeposition polymers.

[0115] Anti-redeposition polymers stabilize soil in the washing solution, thereby preventing soil redeposition. Anti-redeposition polymers suitable for use in the present invention include alkoxylated polyethyleneimines. Polyethyleneimines are materials composed of ethyleneimine units -CH2CH2NH-, and in the case of branching, the hydrogen on the nitrogen is replaced by another chain of ethyleneimine units. Preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (MW) of about 300 to about 10,000. w ). The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of the two. When the nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10-30, preferably 15-25 alkoxy groups per modification. The preferred material is ethoxylated polyethyleneimine, wherein the average degree of ethoxylation is 10-30, preferably 15-25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.

[0116] Mixtures of any of the above materials may also be used.

[0117] When included, the compositions of the present invention preferably comprise from 0.25 to 8%, more preferably from 0.5 to 6% (by weight based on the total weight of the composition) of one or more anti-redeposition polymers, such as the alkoxylated polyethyleneimines described above.

[0118] Soil Release Polymers

[0119] Soil release polymers help improve the release of soil from fabrics by modifying the fabric surface during the wash process. The adsorption of SRPs on the fabric surface is promoted by the affinity between the chemical structure of the SRPs and the target fibers.

[0120] The SRPs used in the present invention may include a variety of charged (e.g., anionic) and uncharged monomer units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include end-capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (M) of the SRP is w ) may suitably be in the range of about 1000 to about 20,000, preferably in the range of about 1500 to about 10,000.

[0121] The SRP used in the present invention can be suitably selected from copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), diols (e.g. ethylene glycol or propylene glycol) and polyglycols (e.g. polyethylene glycol or polypropylene glycol). The copolyesters can also include monomer units substituted with anionic groups, such as sulfonated isophthaloyl units. Examples of such materials include oligoesters produced by transesterification / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and poly(ethylene glycol") ("PEG"); partially and fully anionically terminated oligoesters, such as oligomers from ethylene glycol ("EG"), PG, DMT, and Na-3,6-dioxa-8-hydroxyoctanesulfonic acid; non-ionically terminated block polyester oligomeric compounds, such as those produced from DMT, Me-terminated PEG and EG and / or PG, or a combination of DMT, EG, and / or PG, Me-terminated PEG and Na-dimethyl-5-sulfoisophthalic acid, and copolymerized blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0122] Other types of SRPs useful in the present invention include cellulose derivatives, such as hydroxyether cellulose polymers, C1-C4 alkyl celluloses, and C4 hydroxyalkyl celluloses; polymers having poly(vinyl ester) hydrophobic segments, such as graft copolymers of poly(vinyl esters), such as C1-C6 vinyl esters (e.g., poly(vinyl acetate)) grafted onto a polyalkylene oxide backbone; poly(vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

[0123] Preferred SRPs for use in the present invention include end-capped copolyesters formed by condensation of terephthalate and a diol, preferably 1,2-propylene glycol, and also include end-capped copolyesters formed from repeating units of alkyl-terminated alkylene oxides. Examples of such materials have structures corresponding to formula (I):

[0124]

[0125] Where R 1 and R 2 Independently of each other, X-(OC2H4) n -(OC3H6) m ;

[0126] Where X is C 1-4 Alkyl, preferably methyl;

[0127] n is a number from 12 to 120, preferably from 40 to 50;

[0128] m is a number from 1 to 10, preferably from 1 to 7; and

[0129] a is a number from 4 to 9.

[0130] Because they are average values, m, n and a are not necessarily integers for a large number of polymers.

[0131] Mixtures of any of the above materials may also be used.

[0132] When included, the overall level of SRPs may range from 0.1-10%, preferably 0.3-7%, more preferably 0.5-2% (by weight based on the total weight of the composition).

[0133] Suitable soil release polymers are described in more detail in U.S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO2007 / 079850 and WO2016 / 005271. If used, soil release polymers are typically incorporated into the liquid laundry detergent compositions herein at a concentration ranging from 0.01% to 10%, more preferably 0.1% to 5%, by weight of the composition.

[0134] Polymer thickener

[0135] The compositions of the present invention may include one or more polymeric thickeners. Suitable polymeric thickeners for use in the present invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by addition polymerization of a monomer mixture comprising at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e., methacrylic acid and / or acrylic acid); and at least one associative monomer. In the context of the present invention, the term "associative monomer" means a monomer having an ethylenically unsaturated portion (for addition polymerization with other monomers in the mixture) and a hydrophobic portion. A preferred type of associative monomer includes a polyoxyalkylene portion between the ethylenically unsaturated portion and the hydrophobic portion. Preferred HASE copolymers for use in the present invention include those prepared by addition polymerization of (meth)acrylic acid with (i) at least one selected from a linear or branched C8-C 40 Alkyl (preferably straight chain C 12 -C 22 The invention relates to a linear or crosslinked copolymer prepared by addition polymerization of an associative monomer of (i) a polyethoxylated (meth)acrylate (C1-C4 alkyl) polyethoxylated (meth)acrylate; and (ii) at least one other monomer selected from C1-C4 alkyl (meth)acrylate, a polyacid vinyl monomer (e.g., maleic acid, maleic anhydride and / or its salts) and mixtures thereof. The polyethoxylated portion of the associative monomer (i) generally comprises from about 5 to about 100, preferably from about 10 to about 80, and more preferably from about 15 to about 60 oxyethylene repeating units.

[0136] Mixtures of any of the above materials may also be used.

[0137] When included, the compositions of the present invention preferably comprise 0.1 to 5 wt. % (by weight based on the total weight of the composition) of one or more polymeric thickeners, for example, the HASE copolymers described above.

[0138] Fluorescent agent

[0139] It may be advantageous to include a fluorescent agent in the composition. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts, such as sodium salts. The total amount of one or more fluorescent agents used in the composition is typically 0.005-2 wt%, more preferably 0.01-0.5 wt%.

[0140] Preferred classes of fluorescent agents are: distyrylbiphenyl compounds such as Tinopal (Trade Mark) CBS-X, diaminostilbene disulfonic acid compounds such as Tinopal DMS pure Xtra, Tinopal 5BMGX and Blankophor (Trade Mark) HRH, and pyrazoline compounds such as Blankophor SN.

[0141] Preferred fluorescent agents are: sodium 2(4-phenylvinyl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N-methyl-N-2-hydroxyethyl)amino1,3,5-triazin-2-yl)]amino}stilbene-2-2'disulfonate, disodium 4,4'-bis{[(4-phenylvinyl-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2-2'disulfonate and disodium 4,4'-bis(2-sulfostyryl)biphenyl.

[0142] Color dye

[0143] Shading dyes can be used to improve the performance of the composition. Preferred dyes are violet or blue. It is believed that low levels of deposition of dyes of these shades on fabrics mask the yellowing of the fabric. A further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.

[0144] Suitable and preferred classes of dyes are discussed below.

[0145] Direct dyes:

[0146] Direct dyes (otherwise known as affinity dyes) are the class of water-soluble dyes which have an affinity for the fibers and are directly absorbed. Preferred are direct violet and direct blue dyes.

[0147] Preferably, disazo or trisazo dyes are used.

[0148] Most preferably, the direct dye is direct violet of the following structure:

[0149]

[0150]

[0151] in:

[0152] Rings D and E may independently be naphthyl or phenyl as shown;

[0153] R1 is selected from: hydrogen and C1-C4-alkyl, preferably hydrogen;

[0154] R2 is selected from the group consisting of: hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;

[0155] R3 and R4 are independently selected from: hydrogen and C1-C4-alkyl, preferably hydrogen or methyl;

[0156] X and Y are independently selected from: hydrogen, C1-C4-alkyl and C1-C4-alkoxy; preferably the dye has X=methyl; and Y=methoxy and n is 0, 1 or 2, preferably 1 or 2.

[0157] Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51 and direct violet 99. Disazo copper containing dyes may be used, for example direct violet 66. Benzidene based dyes are less preferred.

[0158] Preferably the direct dye is present in an amount of from 0.000001 to 1 wt %, more preferably from 0.00001 wt % to 0.0010 wt % of the composition.

[0159] In another embodiment, the direct dye may be covalently linked to a photobleach, for example as described in WO2006 / 024612.

[0160] Acid dyes:

[0161] Cotton direct acid dyes impart benefits to cotton containing garments. Preferred dyes and dye mixtures are blue or violet. Preferred acid dyes are:

[0162] (i) Azine dyes, wherein the dyes have the following core structure:

[0163]

[0164] Where R a , R b , R c and Rd is selected from: H, branched or linear C1-C7-alkyl chains, benzyl, phenyl and naphthyl;

[0165] The dye is at least one SO3 - or -COO - Group substitution;

[0166] Ring B does not carry a negatively charged group or its salt; and

[0167] The A ring may be further substituted to form a naphthyl group; the dye is optionally substituted with a group selected from the group consisting of amine, methyl, ethyl, hydroxy, methoxy, ethoxy, phenoxy, Cl, Br, I, F and NO2.

[0168] Preferred azine dyes are: Acid Blue 98, Acid Violet 50 and Acid Blue 59, more preferably Acid Violet 50 and Acid Blue 98.

[0169] Other preferred non-azine acid dyes are Acid Violet 17, Acid Black 1 and Acid Blue 29.

[0170] Preferably, the acid dye is present at 0.0005 wt % to 0.01 wt % of the formulation.

[0171] Hydrophobic dyes:

[0172] Composition can comprise one or more hydrophobic dyes selected from benzodifuran, methine, triphenylmethane, naphthalimide (napthalimide), pyrazole, naphthoquinone, anthraquinone and monoazo or disazo dye chromophore.Hydrophobic dye is the dyestuff that does not contain any charged water solubilizing group.Hydrophobic dye can be selected from disperse dye and solvent dye.Preferred is blue and violet anthraquinone and monoazo dye.

[0173] Preferred dyes include Solvent Violet 13, Disperse Violet 27, Disperse Violet 26, Disperse Violet 28, Disperse Violet 63 and Disperse Violet 77.

[0174] Preferably, the hydrophobic dye is present at 0.0001 wt % to 0.005 wt % of the formulation.

[0175] Basic dyes:

[0176] Basic dyes are organic dyes with a net positive charge. They deposit on cotton. They have a particular use in compositions containing primarily cationic surfactants. The dye may be selected from the basic violet and basic blue dyes listed in the Color Index International.

[0177] Preferred examples include triarylmethane basic dyes, methane basic dyes, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.

[0178] Reactive dyes:

[0179] Reactive dyes are dyes that contain organic groups that react with cellulose and link the dye to cellulose through covalent bonds. They deposit on cotton.

[0180] Preferably, the reactive groups are hydrolysed, or the reactive groups of the dye have been reacted with an organic substance, such as a polymer, thereby attaching the dye to that substance.The dye may be selected from the reactive violet and reactive blue dyes listed in the International Colour Index.

[0181] Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.

[0182] Dye conjugates:

[0183] Dye conjugates are formed by combining direct, acid or basic dyes with polymers or particles by physical forces. Depending on the choice of polymer or particle, they are deposited on cotton or synthetic fabrics. A description is given in WO2006 / 055787.

[0184] Particularly preferred dyes are: Direct Violet 7, Direct Violet 9, Direct Violet 11, Direct Violet 26, Direct Violet 31, Direct Violet 35, Direct Violet 40, Direct Violet 41, Direct Violet 51, Direct Violet 99, Acid Blue 98, Acid Violet 50, Acid Blue 59, Acid Violet 17, Acid Black 1, Acid Blue 29, Solvent Violet 13, Disperse Violet 27, Disperse Violet 26, Disperse Violet 28, Disperse Violet 63, Disperse Violet 77 and mixtures thereof.

[0185] The hueing dye may be used in the absence of a fluorescent agent, but it is particularly preferred to use a hueing dye in combination with a fluorescent agent, for example to reduce yellowing due to chemical changes in the adsorbed fluorescent agent.

[0186] External structurants

[0187] The compositions of the present invention can further modify their rheology by using one or more external structurants that form a structured network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose, and citrus pulp fibers. The presence of an external structurant can provide shear thinning rheology and also enable materials such as encapsulates and visual cues to be stably suspended in the liquid.

[0188] Enzymes

[0189] The composition of the present invention may comprise an effective amount of one or more enzymes selected from pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzyme is preferably present together with a corresponding enzyme stabilizer.

[0190] Fragrance

[0191] Examples of aromatic components include aromatic, aliphatic and araliphatic hydrocarbons having a molecular weight of about 90 to about 250; aromatic, aliphatic and araliphatic esters having a molecular weight of about 130 to about 250; aromatic, aliphatic and araliphatic nitriles having a molecular weight of about 90 to about 250; aromatic, aliphatic and araliphatic alcohols having a molecular weight of about 90 to about 240; aromatic, aliphatic and araliphatic ketones having a molecular weight of about 150 to about 270; aromatic, aliphatic and araliphatic lactones having a molecular weight of about 130 to about 290; aromatic, aliphatic and araliphatic aldehydes having a molecular weight of about 90 to about 230; aromatic, aliphatic and araliphatic ethers having a molecular weight of about 150 to about 270; and condensation products of aldehydes and amines having a molecular weight of about 180 to about 320.

[0192] Specific examples of fragrance components useful in the present invention include:

[0193] i) hydrocarbons, such as D-limonene, 3-carene, α-pinene, β-pinene, α-terpinene, γ-terpinene, p-cymene, bisabolene, camphene, caryophyllene, cedrene, farnesene, longifolene, myrcene, ocimene, valencene, (E,Z)-1,3,5-undecatriene, styrene and diphenylmethane;

[0194] ii) aliphatic and araliphatic alcohols, for example benzyl alcohol, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol, 2-phenylpropanol, 2-phenoxyethanol, 2,2-dimethyl-3-phenylpropanol, 2,2-dimethyl-3-(3-methylphenyl)propanol, 1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-3-phenylpropanol, 1-ethyl-1-methyl-3-phenylpropanol, 2-methyl-5-phenylpentanol, 3-methyl-5-phenylpentanol, 3-phenyl-2-propen-1-ol, 4-methoxybenzyl alcohol, 1-(4-isopropylphenyl)propanol, ) ethanol, hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E)-2-hexenol, a mixture of (E)- and (Z)-3-hexenol, 1-octen-3-ol, 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol, (E,Z)-2,6-nonadienol, 3,7-dimethyl-7-methoxyoctan-2-ol, 9-decenol, 10-undecenol and 4-methyl-3-decen-5-ol;

[0195] iii) cyclic and cycloaliphatic alcohols, for example 4-tert-butylcyclohexanol, 3,3,5-trimethylcyclohexanol, 3-isocamphylcyclohexanol, 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, α,3,3-trimethylcyclohexylmethanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butanol, penten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol, 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-2-ol, 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol, 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol, 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol and 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;

[0196] iv) aliphatic aldehydes and their acetals, for example hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, 2-methylundecanal, (E)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptenal, 10-undecenal, (E)-4-decenal, 2-dodecenal, 2,6,10-trimethyl-5,9-undecadienal, heptaldehyde-diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene and citronellyloxyacetaldehyde;

[0197] v) aliphatic ketones and their oximes, for example 2-heptanone, 2-octanone, 3-octanone, 2-nonanone, 5-methyl-3-heptanone, 5-methyl-3-heptanone oxime and 2,4,4,7-tetramethyl-6-octen-3-one;

[0198] vi) aliphatic sulfur-containing compounds, for example 3-methylthiohexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol, 3-mercaptohexyl acetate, 3-mercaptohexyl butyrate, 3-acetylthiohexyl acetate and 1-menthene-8-thiol;

[0199] vii) aliphatic nitriles, for example 2-nonenenitrile, 2-tridecenenitrile, 2,12-tridecenenitrile, 3,7-dimethyl-2,6-octadienenitrile and 3,7-dimethyl-6-octenenitrile;

[0200] viii) aliphatic carboxylic acids and esters thereof, for example (E)- and (Z)-3-hexenyl carboxylate, ethyl acetoacetate, isoamyl acetate, hexyl acetate, 3,5,5-trimethylhexyl acetate, 3-methyl-2-butenyl acetate, (E)-2-hexenyl acetate, (E)- and (Z)-3-hexenyl acetate, octyl acetate, 3-octyl acetate, 1-octen-3-yl acetate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexyl butyrate, (E)- and (Z)-3-hexenyl acetate alkenyl isobutyrate, hexyl crotonate, ethyl isovalerate, ethyl-2-methyl valerate, ethyl hexanoate, allyl hexanoate, ethyl heptanoate, allyl heptanoate, ethyl octanoate, ethyl-(E,Z)-2,4-decadienoate, methyl-2-octinate, methyl-2-noninate, allyl-2-isopentyloxyacetate and methyl-3,7-dimethyl-2,6-octadienoate;

[0201] ix) acyclic terpene alcohols, for example citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters and 3-methyl-2-butenoates;

[0202] x) acyclic terpene aldehydes and ketones, for example geranal, neral, citronellal, 7-hydroxy-3,7-dimethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, α-neral, β-neral, geranylacetone and the dimethyl and diethyl acetals of geranal, neral and 7-hydroxy-3,7-dimethyloctanal;

[0203] xi) cyclic terpene alcohols, for example menthol, isopulegol, α-terpineol, terpinen-4-ol, menth-8-ol, menth-1-ol, menth-7-ol, borneol, isoborneol, linalool oxide, nopol, cedryl alcohol, ambroxol, vetiverol, guaiacol, and the formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters and 3-methyl-2-butenoic acid esters of α-terpineol, terpinen-4-ol, methan-8-ol, methan-1-ol, methan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedryl alcohol, ambroxol, vetiverol and guaiacol;

[0204] xii) cyclic terpene aldehydes and ketones, for example menthone, isomenthone, 8-mercaptomenth-3-one, carvone, camphor, fenchone, α-ionone, β-ionone, α-n-methylionone, β-n-methylionone, α-isomethylionone, β-isomethylionone, α-irone, α-damascone, β-damascone, β-damascone, δ-damascone, γ-damascone, 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-naphthone-8(5H)-one, nootkatone, nootkatone and methyl cedryl ketone;

[0205] xiii) cyclic and cycloaliphatic ethers, for example eucalyptol, cedarwood methyl ether, cyclododecyl methyl ether, (ethoxymethoxy)cyclododecane; α-cedarene epoxide, 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan, 1,5,9-trimethyl-13-oxabicyclo[10.1.0]-trideca-4,8-diene, rose oxide and 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

[0206] xiv) cyclic ketones, for example 4-tert-butylcyclohexanone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-heptylcyclopentanone, 2-pentylcyclopentanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one, 3-methyl-2-pentyl-2-cyclopenten-1-one, 3-methyl-4-cyclopentadecenone, 3-methyl-5-cyclopentenone, 3-methyl-2-penten-1-yl-2-cyclopenten-1-one, 3-methyl-2-pentyl-2-cyclopenten-1-one, 3-methyl-4-cyclopentadecenone, 3-methyl-2-penten-1-yl-2-cyclopenten-1-one, 3-methyl-2-penten-1-yl-2-cyclopent cyclopentadecanone, 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, 4-tert-pentylcyclohexanone, 5-cyclohexadecene-1-one, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 5-cyclohexadecene-1-one, 8-cyclohexadecene-1-one, 9-cycloheptadecene-1-one and cyclopentadecanone;

[0207] xv) cycloaliphatic aldehydes and ketones, for example 2,4-dimethyl-3-cyclohexenecarboxaldehyde, 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde, 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde, 1-(3,3-dimethylcyclohexyl)-4-penten-1-one, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthylmethyl-ketone, methyl-2,6,10-trimethyl-2,5,9-cycloeicosatrienyl ketone and tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl)ketone;

[0208] xvi) Esters of cyclic alcohols, for example 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, 2-tert-pentylcyclohexyl acetate, 4-tert-pentylcyclohexyl acetate, decahydro-2-naphthyl acetate, 3-pentyltetrahydro-2H-pyran-4-yl acetate, decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl acetate, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl propionate, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5- or 6-indenyl isobutyrate and 4,7-methanooctahydro-5- or 6-indenyl acetate;

[0209] xvii) esters of cycloaliphatic carboxylic acids, for example allyl 3-cyclohexylpropionate, allyl cyclohexyloxyacetate, methyl dihydrojasmonate, methyl jasmonate, methyl 2-hexyl-3-oxocyclopentanecarboxylate, ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate, ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate and ethyl 2-methyl-1,3-dioxolane-2-acetate;

[0210] xviii) esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, for example benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, α-trichloromethylbenzyl acetate, α,α-dimethylphenethyl acetate, α,α-dimethylphenethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate and 4-methoxybenzyl acetate;

[0211] xix) aromatic aliphatic ethers and their acetals, for example 2-phenylethyl methyl ether, 2-phenylethyl isopentyl ether, 2-phenylethyl cyclohexyl ether, 2-phenylethyl-1-ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, 2-phenylpropionaldehyde dimethyl acetal, phenylacetaldehyde glycerol acetal, 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 4,4a,5,9b-tetrahydroindeno[1,2-d]-dioxin and 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-dioxin;

[0212] xx) Aromatic and aromatic aliphatic aldehydes and ketones, for example benzaldehyde; phenylacetaldehyde, 3-phenylpropanal, 2-phenylpropanal, 4-methylbenzaldehyde, 4-methylphenylacetaldehyde, 3-(4-ethylphenyl)-2,2-dimethylpropanal, 2-methyl-3-(4-isopropylphenyl)propanal, 2-methyl-3-(4-tert-butylphenyl)propanal, 3-(4-tert-butylphenyl)propanal, cinnamaldehyde, α-butylcinnamaldehyde, α-amylcinnamaldehyde, α-hexylcinnamaldehyde, 3-methyl-5-phenylpentanal, 4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 4-hydroxy-3-ethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 2-methyl-3-(4-methoxy phenyl)propanal, 2-methyl-3-(4-methylenedioxyphenyl)propanal, acetophenone, 4-methylacetophenone, 4-methoxyacetophenone, 4-tert-butyl-2,6-dimethylacetophenone, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, 1-(2-naphthyl)ethanone, benzophenone, 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone, 6-tert-butyl-1,1-dimethyl-4-indanylmethyl ketone, 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methyl-ethyl)-1H-5-indenyl]ethanone and 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-naphthylacetonone;

[0213] xxi) aromatic and araliphatic carboxylic acids and esters thereof, for example benzoic acid, phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methyl phenylacetate, ethyl phenylacetate, geranyl phenylacetate, phenylethyl phenylacetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, cinnamyl cinnamate, allyl phenoxyacetate, methyl salicylate, isopentyl salicylate, hexyl salicylate, cyclohexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenylethyl salicylate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl 3-phenylglycidate and ethyl 3-methyl-3-phenylglycidate;

[0214] xxii) nitrogen-containing aromatic compounds, for example 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene, 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone, cinnamonitrile, 5-phenyl-3-methyl-2-pentenenitrile, 5-phenyl-3-methylvaleronitrile, methyl anthranilate, methyl-N-methyl anthranilate, the Schiff base of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde, 6-isopropylquinoline, 6-isobutylquinoline, 6-sec-butylquinoline, indole, methylindole, 2-methoxy-3-isopropylpyrazine and 2-isobutyl-3-methoxypyrazine;

[0215] xxiii) phenols, phenyl ethers and phenyl esters, for example estragole, anethole, eugenol, eugenol methyl ether, isoeugenol, isoeugenol methyl ether, thymol, carvacrol, diphenyl ether, β-naphthyl methyl ether, β-naphthyl ethyl ether, β-naphthyl isobutyl ether, 1,4-dimethoxybenzene, eugenyl acetate, 2-methoxy-4-methylphenol, 2-ethoxy-5-(1-propenyl)phenol and p-tolyl phenylacetate;

[0216] xxiv) heterocyclic compounds, for example 2,5-dimethyl-4-hydroxy-2H-furan-3-one, 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one, 3-hydroxy-2-methyl-4H-pyran-4-one, 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0217] xxv) lactones, for example 1,4-octanolactone, 3-methyl-1,4-octanolactone, 1,4-nonanolactone, 1,4-decanolactone, 8-decene-1,4-lactone, 1,4-undecanolactone, 1,4-dodecanolactone, 1,5-decanolactone, 1,5-dodecanolactone, 1,15-pentadecanolactone, cis- and trans-1′-pentadecen-1,15-lactone, cis- and trans-1′-pentadecen-1,15-lactone, 2-pentadecen-1,15-lactone, 1,16-hexadecanolide, 9-hexadecanolide, 10-oxa-1,16-hexadecanolide, 11-oxa-1,16-hexadecanolide, 12-oxa-1,16-hexadecanolide, ethylene-1,12-dodecanedioic acid, ethylene-1,13-tridecanedioic acid, coumarin, 2,3-dihydrocoumarin and octahydrocoumarin.

[0218] Naturally occurring exudates such as essential oils extracted from plants can also be used as aromatic components in the present invention. Essential oils are usually extracted by steam distillation, solid phase extraction, cold pressing, solvent extraction, supercritical fluid extraction, water distillation or simultaneous distillation-extraction processes. Essential oils can be derived from several different parts of a plant, including, for example, leaves, flowers, roots, buds, twigs, rhizomes, heartwood, bark, sap, seeds and fruits. The main plant families from which essential oils are extracted include Asteraceae, Myrtaceae, Lauraceae, Lamiaceae, Myrtaceae, Rutaceae and Zingiberaceae. Oils are "essential" in the sense that they carry a plant-specific fragrance or essence.

[0219] Those skilled in the art will appreciate that essential oils are complex mixtures that are typically composed of tens or hundreds of components. Most of these components have an isoprenoid backbone containing 10 carbon atoms (monoterpenes), 15 carbon atoms (sesquiterpenes) or 20 carbon atoms (diterpenes). Other components of smaller amounts may also be found, such as alcohols, aldehydes, esters and phenols. However, in the case of practical aromatic preparations, separate essential oils are typically considered to be single ingredients. Therefore, for purposes of the present invention, separate essential oils may be considered to be single aromatic components.

[0220] Specific examples of the essential oils used as the fragrance component in the present invention include cedar oil, juniper oil, cumin oil, cinnamon bark oil, camphor oil, rosewood oil, ginger oil, basil oil, eucalyptus oil, lemongrass oil, peppermint oil, rosemary oil, spearmint oil, tea tree oil, frankincense oil, chamomile oil, clove oil, jasmine oil, lavender oil, rose oil, ylang-ylang oil, bergamot oil, grapefruit oil, lemon oil, lime oil, orange oil, fir needle oil, galbanum oil, geranium oil, grapefruit essential oil, pine needle oil, caraway oil, labdanum oil, lovage oil, oregano oil, orange peel oil, clary sage oil, nutmeg oil, myrtle oil, clove oil, neroli oil, patchouli oil, sandalwood oil, thyme oil, verbena oil, vetiver oil, and wintergreen oil.

[0221] The number of different fragrance components contained in the fragrance preparation (f1) is usually at least 4, preferably at least 6, more preferably at least 8, most preferably at least 10, for example 10-200, more preferably 10-100.

[0222] Typically, no single fragrance component accounts for more than 70% by weight of the total weight of the fragrance formulation (f1). Preferably, no single fragrance component accounts for more than 60% by weight of the total weight of the fragrance formulation (f1), and more preferably, no single fragrance component accounts for more than 50% by weight of the total weight of the fragrance formulation (f1).

[0223] In the context of the present invention, the term "fragrance preparation" means a fragrance component as defined above plus any optional excipients. Excipients may be included in fragrance preparations for various purposes, such as solvents for insoluble or poorly soluble components, diluents for more effective components, or control of vapor pressure and evaporation characteristics of fragrance preparations. Excipients may have many features of fragrance components, but they do not have strong odors themselves. Therefore, excipients may be distinguished from fragrance components because they may be added to fragrance preparations in high proportions, such as 30% or even 50% by weight of the total weight of the fragrance preparation, without significantly changing the odor quality of the fragrance preparation. Some examples of suitable excipients include ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, and triethyl citrate. A mixture of any of the above materials may also be suitable.

[0224] Suitable fragrance formulations (f1) for use in the present invention comprise a blend of at least 10 fragrance components selected from the group consisting of: hydrocarbons i); aliphatic and aromatic aliphatic alcohols ii); aliphatic aldehydes and their acetals iv); aliphatic carboxylic acids and their esters viii); acyclic terpene alcohols ix); cyclic terpene aldehydes and ketones xii); cyclic and cycloaliphatic ethers xiii); esters of cyclic alcohols xvi); esters of aromatic aliphatic alcohols and aliphatic carboxylic acids xviii); aromatic aliphatic ethers and their acetals xix); aromatic and aromatic aliphatic aldehydes and ketones xx) and aromatic and aromatic aliphatic carboxylic acids and their esters xxi); as further described and exemplified above.

[0225] The content of the fragrance component is preferably in the range of 50 to 100% by weight, more preferably 60 to 100% by weight and most preferably 75 to 100% by weight, based on the total weight of the fragrance preparation (f1); with one or more excipients (as described above) constituting the balance of the fragrance preparation (f1) as required.

[0226] The fragrance agent (f1) is in the form of free droplets dispersed in the composition. In the context of the present invention, the term "free droplets" refers to droplets that are not trapped within discrete polymer microparticles.

[0227] In a typical liquid laundry detergent composition according to the present invention, the content of fragrance formulation (f1) is generally in the range of 0.1 to 0.75%, and preferably in the range of 0.3 to 0.6% by weight based on the total weight of the composition.

[0228] Microcapsules

[0229] One type of microparticle suitable for use in the present invention is a microcapsule. Microencapsulation can be defined as the process of surrounding or encapsulating one substance within another substance at a very small scale, thereby producing a capsule with a size ranging from less than 1 micron to several hundred microns. The encapsulated material can be referred to as a core, an active ingredient or agent, a filler, a payload, a core, or an inner phase. The material encapsulating the core can be referred to as a coating, a membrane, a shell, or a wall material.

[0230] Microcapsules typically have at least one generally spherical continuous shell surrounding a core. Depending on the materials and encapsulation techniques employed, the shell may contain pores, vacancies or interstitial openings. Multiple shells may be made of the same or different encapsulating materials and may be arranged in layers of varying thickness around the core. Alternatively, microcapsules may be asymmetrically and variably shaped, with a certain amount of smaller core material droplets embedded throughout the microcapsule.

[0231] The shell may have a barrier function to protect the core material from the environment outside the microcapsule, but may also be used as a means of regulating the release of the core material, such as a fragrance. Thus, the shell may be water-soluble or water-swellable and may initiate fragrance release in response to exposure of the microcapsule to a humid environment. Similarly, if the shell is temperature-sensitive, the microcapsule may release fragrance in response to elevated temperatures. The microcapsule may also release fragrance in response to shear forces applied to the surface of the microcapsule.

[0232] A preferred type of polymer microparticle suitable for use in the present invention is a polymer core-shell microcapsule in which at least one generally spherical continuous shell of polymer material surrounds a core containing a fragrance agent (f2). The shell typically accounts for up to 20% by weight based on the total weight of the microcapsule. The fragrance agent (f2) typically accounts for about 10 to about 60% by weight, preferably about 20 to about 40% by weight, based on the total weight of the microcapsule. The amount of the fragrance agent (f2) can be determined by obtaining a slurry of the microcapsule, extracting it into ethanol and measuring it by liquid chromatography.

[0233] The polymer core-shell microcapsules used in the present invention can be prepared using methods known to those skilled in the art, such as coacervation, interfacial polymerization, and polycondensation.

[0234] Coacervation methods generally involve encapsulating a core material, which is usually water-insoluble, by precipitating a colloidal material onto the surface of a droplet of material. Coacervation can be simple, for example using one colloid such as gelatin, or where two or possibly more colloids of opposite charge are used under carefully controlled conditions of pH, temperature and concentration, such as a complex of gelatin and gum arabic or gelatin and carboxymethylcellulose.

[0235] Interfacial polymerization is usually carried out with the formation of a fine dispersion of oil droplets (containing core material) in an aqueous continuous phase. The dispersed droplets form the core of the future microcapsules, and the size of the dispersed droplets directly determines the size of the subsequent microcapsules. The microcapsule shell forming material (monomer or oligomer) is contained in both the dispersed phase (oil droplets) and the aqueous continuous phase, and they react together at the phase interface to build a polymer wall around the oil droplets, thereby encapsulating the droplets and forming core-shell microcapsules. An example of a core-shell microcapsule produced by this method is a polyurea microcapsule with a shell formed by the reaction of a diisocyanate or polyisocyanate with a diamine or polyamine.

[0236] The polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of a precondensate of the polymer material under appropriate stirring conditions to produce capsules of the desired size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, thereby causing the condensate to separate from the solution and surround the dispersed core material to produce a coherent film and the desired microcapsules. Examples of core-shell microcapsules produced by this process are aminoplast microcapsules having a shell formed from the polycondensation products of melamine (2,4,6-triamino-1,3,5-triazine) or urea with formaldehyde. Suitable crosslinking agents (e.g. toluene diisocyanate, divinylbenzene, butanediol diacrylate) may also be used, and secondary wall polymers such as polymers and copolymers of anhydrides and their derivatives, particularly maleic anhydride, may also be used as appropriate.

[0237] An example of a preferred polymer core-shell microcapsule for use in the present invention is an aminoplast microcapsule, wherein the aminoplast shell surrounds a core containing the fragrance agent (f2). More preferably, this aminoplast shell is formed from a polycondensation product of melamine and formaldehyde.

[0238] Polymer microparticles suitable for use in the present invention typically have an average particle size of 100 nanometers to 50 microns. Particles greater than this value enter the visible range. Examples of particles in the submicron range include latexes and microemulsions with a typical size range of 100-600 nanometers. Preferred particle size ranges are in the micrometer range. Examples of particles in the micrometer range include polymer core-shell microcapsules (such as those described further above) with a typical size range of 1 to 50 microns, preferably 5 to 30 microns. The average particle size can be measured by light scattering using a Malvern Mastersizer, where the average particle size takes the median particle size D (0.5) value. The particle size distribution can be narrow, wide or multi-mode. If desired, the initially produced microcapsules can be filtered or screened to produce a product with higher size uniformity.

[0239] Polymer microparticles suitable for use in the present invention may have a deposition aid on the outer surface of the microparticle. Deposition aids are used to modify the properties of the exterior of the microparticle, for example, to make the microparticle more compatible with a desired substrate. Desired substrates include cellulosics (including cotton) and polyesters (including those used to make polyester fabrics).

[0240] The deposition aid may be suitably provided on the outer surface of the microparticle by means of covalent bonding, entanglement or strong adsorption. Examples include polymer core-shell microcapsules (such as those described further above) in which the deposition aid is preferably attached to the exterior of the shell by covalent bonding. Although it is preferred that the deposition aid is directly attached to the exterior of the shell, it may also be attached via a linking substance.

[0241] The deposition aid for use in the present invention may be suitably selected from polysaccharides having an affinity for cellulose. Such polysaccharides may be naturally occurring or synthetic and may have an inherent affinity for cellulose or may be derivatized or otherwise modified to have an affinity for cellulose. Suitable polysaccharides have a 1-4 linked beta glycan (a broad sugar) backbone structure having at least 4, preferably at least 10 β1-4 linked backbone residues, such as a glucan backbone (consisting of β1-4 linked glucose residues), a mannan backbone (consisting of β1-4 linked mannose residues) or a xylan backbone (consisting of β1-4 linked xylose residues). Examples of such β1-4 linked polysaccharides include xyloglucan, glucomannan, mannan, galactomannan, β(1-3),(1-4) glucan and the xylan family of combined glucuronyl, arabinosyl and glucuronylarabinoxylans. Preferred β1-4 linked polysaccharides for use in the present invention may be selected from plant-derived xyloglucans, such as pea xyloglucan and tamarind xyloglucan (TXG) (which have a β1-4 linked glucan backbone with α-D xylopyranose and β-D-galactopyranosyl-(1-2)-α-D-xylopyranose side chains, both linked 1-6 to the backbone); and plant-derived galactomannans, such as locust bean gum (LBG) (which have a mannan backbone of β1-4 linked mannose residues with single unit galactose side chains α1-6 linked to the backbone).

[0242] Also suitable are polysaccharides which upon hydrolysis acquire an affinity for cellulose, such as cellulose monoacetate, or modified polysaccharides having an affinity for cellulose, such as hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylguar, hydroxyethylethylcellulose and methylcellulose.

[0243] The deposition aid for use in the present invention may also be selected from phthalate-containing polymers having an affinity for polyesters. Such phthalate-containing polymers may have one or more nonionic hydrophilic segments containing oxyalkylene groups (such as ethylene oxide, polyoxyethylene, propylene oxide or polyoxypropylene groups), and one or more hydrophobic segments containing terephthalate groups. Typically, the degree of polymerization of the oxyalkylene groups is from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. Suitable examples of phthalate-containing polymers of this type are copolymers having random blocks of ethylene terephthalate and polyethylene oxide terephthalate.

[0244] Mixtures of any of the above materials may also be suitable.

[0245] The weight average molecular weight (M) of the deposition aid used in the present invention is w) is generally in the range of about 5 kDa to about 500 kDa, preferably about 10 kDa to about 500 kDa, and more preferably about 20 kDa to about 300 kDa.

[0246] An example of a particularly preferred polymer core-shell microcapsule for use in the present invention is an aminoplast microcapsule having a shell formed by polycondensation of melamine and formaldehyde; surrounding a core containing the fragrance formulation (f2); wherein the deposition aid is attached to the outside of the shell by covalent bonding. Preferred deposition aids are selected from β1-4 linked polysaccharides, in particular xyloglucans of plant origin, as further described above.

[0247] Therefore, the total amount of fragrance agent (f1) and fragrance agent (f2) in the laundry liquid composition of the present invention is suitably in the range of 0.5-1.4%, preferably 0.5-1.2%, more preferably 0.5-1%, most preferably 0.6-0.9% (by weight based on the total weight of the composition).

[0248] The weight ratio of fragrance agent (f1) to fragrance agent (f2) in the laundry liquid composition of the present invention is preferably in the range of 60:40 to 45:55. Particularly good results are obtained when the weight ratio of fragrance agent (f1) to fragrance agent (f2) is about 50:50.

[0249] Fragrance preparation (f1) and fragrance preparation (f2) are usually incorporated at different stages of the formation of the composition of the present invention. Usually, discrete polymer particles (e.g. microcapsules) encapsulating fragrance preparation (f2) are added in the form of a slurry to a warm base preparation containing other components of the composition (e.g. surfactants and solvents). Fragrance preparation (f1) is usually post-added after the base preparation has cooled.

[0250] Other optional ingredients

[0251] The laundry liquid composition of the present invention may contain other optional ingredients to enhance performance and / or consumer acceptance. Examples of such ingredients include foam boosters, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosives, drape imparting agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or sunscreens, and hueing dyes. Each of these ingredients exists in an amount that effectively achieves its purpose. Typically, these optional ingredients are individually included in an amount of up to 5% (based on the gross weight of the composition by weight).

[0252] Packaging and filling

[0253] The laundry liquid composition of the present invention can be packaged as a unit dose in a polymer film soluble in the wash water. Alternatively, the composition of the present invention can be provided in a multi-dose plastic package with a top or bottom closure. The dosing means can be provided as part of the cover or as an integrated system with the package.

[0254] A method of laundering fabrics using the compositions of the present invention generally comprises diluting a dose of the detergent composition with water to obtain a wash liquor, and laundering fabrics with the wash liquor so formed.

[0255] The dilution step preferably provides a wash liquor comprising, inter alia, from about 3 to about 20 g / wash of detersive surfactant (as further defined above).

[0256] In automatic washing machines, the detergent composition of the dosage is usually placed in a distributor, and is rinsed from the distributor into the washing machine by the water flowing into the washing machine, thereby forming washing liquid. According to the structure of the washing machine, 5 liters to about 65 liters of water can be used to form washing liquid. The dosage of the detergent composition can be adjusted accordingly to obtain a suitable washing liquid concentration. For example, the dosage range for a typical front-loading washing machine (using 10 to 15 liters of water to form washing liquid) can be about 10ml to about 60ml, preferably about 15 to 40ml. The dosage for a typical top-loading washing machine (using 40-60 liters of water to form washing liquid) can be higher, for example, up to about 100ml.

[0257] A subsequent water rinsing step and drying of the laundry is preferred.

[0258] Granular laundry detergent

[0259] In the context of the present invention, the term "granular laundry detergent" means a free-flowing or compacted solid form, such as a powder, granules, pellets, flakes, bars, lumps or tablets, and which is intended for and capable of wetting and cleaning household laundry, such as clothing, linens and other household textiles. The term "linens" is commonly used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins and uniforms. Textiles may include woven fabrics, nonwoven fabrics and knitted fabrics; and may include natural or synthetic fibers, such as silk fibers, flax fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers and blends thereof, including cotton and polyester blends.

[0260] Examples of laundry detergents include heavy-duty detergents for use in the wash cycle of an automatic washing machine, and delicate and color care detergents such as those suitable for washing delicate garments (e.g., those made of silk or wool) by hand or in the wash cycle of an automatic washing machine.

[0261] A preferred form of the composition according to the invention is a free-flowing powdered solid having a loose (unpackaged) bulk density generally in the range of from about 200 g / l to about 1300 g / l, preferably from about 400 g / l to about 1,000 g / l, more preferably from about 500 g / l to about 900 g / l.

[0262] The granular composition of the present invention comprises 3 to 80%, preferably 10 to 60%, more preferably 15 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof.

[0263] In the context of granular detergent formulations, the term "detersive surfactant" means a surfactant that provides a detersive (ie cleaning) benefit to laundry treated as part of a domestic laundry process.

[0264] In addition to the furan-based surfactants described above, other non-soap anionic surfactants used in granular compositions are typically salts of organic sulfuric and sulfonic acids having an alkyl group containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of the higher acyl group. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, α-olefin sulfonates, and mixtures thereof. The alkyl group preferably contains 10-18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain 1-10 ethylene oxide or propylene oxide units per molecule, preferably 1-3 ethylene oxide units per molecule. The counter ions of the anionic surfactants are typically alkali metals such as sodium or potassium; or ammonia counter ions such as monoethanolamine (MEA), diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counter ions may also be used.

[0265] Before, a class of preferred non-soap anionic surfactants for granular compositions included alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of 10-18 carbon atoms. Commercially available LAS is a mixture of closely related isomers and homologous alkyl chain homologues, each containing an aromatic ring that is sulfonated in the "para-position" and is connected to a linear alkyl chain at any position except the terminal carbon. The linear alkyl chain has a chain length of 11 to 15 carbon atoms, and the main material has a chain length of about C12. Each alkyl chain homologue is composed of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is usually formulated into compositions in the form of acid (i.e. HLAS), then at least partially in situ neutralization.

[0266] In addition to the furan-based surfactants as described above, the granular composition according to the invention may also contain some alkylbenzene sulfonate. A typical ratio between the benzene-based surfactant and the furan-based surfactant is 99:1-0:100% by weight of the composition (before in-situ neutralization), more preferably 50:50-0:100, especially preferably 5:95-0:100, most preferably 0.1:99.9-0:100.

[0267] Mixtures of any of the above materials may also be used.

[0268] In a typical granular composition the total level of non-soap anionic surfactant may suitably be in the range 5 to 25% (by weight based on the total weight of the composition).

[0269] Nonionic surfactants can provide enhanced performance for removing very hydrophobic oily soils and cleaning hydrophobic polyester and polyester / cotton blend fabrics.

[0270] The nonionic surfactant used for the granular composition is usually a polyoxyalkylene compound, i.e., the reaction product of an oxyalkylene (such as ethylene oxide or propylene oxide or a mixture thereof) and a starting molecule having a hydrophobic group and an active hydrogen atom that reacts with the oxyalkylene. Such starting molecules include alcohols, acids, amides or alkylphenols. When the starting molecule is an alcohol, the reaction product is referred to as an alcohol alkoxylate. The polyoxyalkylene compound can have a variety of block and mixed (random) structures. For example, they can contain a single alkylene oxide block, or they can be a diblock alkoxylate or a triblock alkoxylate. In the block structure, the block can be all ethylene oxide or all propylene oxide, or the block can contain a mixed mixture of alkylene oxides. Examples of such materials include C8 to C 22 Alkylphenol ethoxylates having an average of 5 to 25 moles of ethylene oxide per mole of alkylphenol; and aliphatic alcohol ethoxylates such as C8 to C 18 Primary or secondary straight or branched chain alcohol ethoxylates having an average of 2 to 40 moles of ethylene oxide per mole of alcohol.

[0271] A preferred class of nonionic surfactants for use in granular compositions includes aliphatic C8-C 18 , more preferably C 12 -C 15 Straight chain primary alcohol ethoxylates have an average of 3 to 20, more preferably 5 to 10, moles of ethylene oxide per mole of alcohol.

[0272] Mixtures of any of the above materials may also be used.

[0273] In granular compositions, the total level of nonionic surfactant may suitably be in the range 1 to 10% (by weight based on the total weight of the composition).

[0274] Examples of suitable mixtures of non-soap anionic and / or nonionic surfactants for use in granular compositions include linear alkylbenzene sulfonates (preferably C 11 To C 15 linear alkylbenzene sulfonate) (if present) with a furan-based surfactant as described above, with sodium lauryl ether sulfate (preferably C 10 To C 18 Alkyl sulfate) and / or ethoxylated aliphatic alcohol (preferably C 12 To C 15 The furan-based surfactant level in such mixtures is preferably at least 50%, such as 50 to 95% (by weight based on the total weight of the mixture).

[0275] In addition to the non-soap anionic and / or nonionic detersive surfactants described above, the granular composition may also comprise one or more co-surfactants (eg amphoteric (zwitterionic) and / or cationic surfactants).

[0276] Specific cationic surfactants include C8-C 18 Alkyl dimethyl ammonium halides and derivatives thereof (in which one or two hydroxyethyl groups replace one or two methyl groups), and mixtures thereof. When a cationic surfactant is included, it may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0277] Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkyl sultaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycocinates, alkylamidopropyl hydroxysultaines, acyl taurates and acyl glutamates having an alkyl group containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl groups. When included, the amphoteric (zwitterionic) surfactant may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0278] The granular composition may also contain one or more builders. Builders are primarily used to reduce water hardness. This can be achieved by sequestration or chelation (keeping hardness minerals in solution), by precipitation (forming insoluble materials), or by ion exchange (exchanging charged particles). Builders can also provide and maintain alkalinity, which helps with cleaning, especially acidic soils; help keep removed soils from redeposition during washing; and emulsify oily and greasy soils.

[0279] Builders for use in granular compositions can be organic or inorganic types, or mixtures thereof.Preferred are non-phosphate builders.

[0280] Inorganic non-phosphate builders for granular compositions include carbonates, silicates, zeolites and mixtures thereof.

[0281] Suitable carbonate builders for use in granular compositions include the anhydrous or partially hydrated alkali metal carbonates, bicarbonates or sesquicarbonates, either mixed or singly.Preferably, the alkali metal is sodium and / or potassium, particularly preferred is sodium carbonate.

[0282] Suitable silicate builders include amorphous and / or crystalline forms of alkali metal (e.g. sodium) silicates. Preferred are crystalline layered sodium silicates (phyllosilicates) of formula (I):

[0283] NaMSi x O 2x+1 .yH2O (I)

[0284] wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2 or 3, and y is a number from 0 to 20. Particularly preferred is sodium disilicate of the above formula wherein M is sodium and x is 2. Such material can be prepared with different crystal structures, known as alpha, beta, gamma and delta phases, with delta-sodium disilicate being most preferred.

[0285] Zeolite is composed of (SiO4) 4- and (AlO4) 5- A naturally occurring or synthetic crystalline aluminosilicate composed of tetrahedra, which share oxygen bridging vertices and form a cage-like structure in crystalline form. The ratio between oxygen, aluminum and silicon is O:(Al+Si)=2:1. The framework obtains its negative charge by replacing some Si with Al. The negative charge is neutralized by cations, and under normal conditions, the framework is open enough to contain mobile water molecules. Zeolite builders suitable for the present invention can be defined by the general formula (II):

[0286] Na x [(AlO2) x (SiO2) y ]·zH2O (II)

[0287] wherein x and y are integers of at least 6, the molar ratio of x to y is in the range of about 1 to about 0.5, and z is an integer of at least 5, preferably about 7.5 to about 276, more preferably about 10 to about 264.

[0288] Suitable organic non-phosphate builders for granular compositions include polycarboxylates in acid and / or salt form. When used in salt form, alkali metals (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium citrate and potassium citrate, sodium and potassium tartrate, sodium and potassium tartrates of tartrate monosuccinic acid, sodium and potassium tartrates of tartrate disuccinic acid, sodium and potassium ethylenediaminetetraacetic acid, sodium and potassium N-(2-hydroxyethyl)-ethylenediaminetriacetic acid, sodium and potassium nitrilotriacetic acid, and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetic acid. Polymeric polycarboxylates may also be used, such as polymers of unsaturated monocarboxylic acids (e.g., acrylic acid, methacrylic acid, vinyl acetic acid, and crotonic acid) and / or unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid and anhydrides thereof). Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic acid and maleic acid. The polymer may be in acid, salt or partially neutralized form and may suitably have a molecular weight (Mw) ranging from about 1,000 to 100,000, preferably from about 2,000 to about 85,000, more preferably from about 2,500 to about 75,000.

[0289] Mixtures of any of the above materials may also be used.Preferred builders for granular compositions may be selected from zeolite (of general formula (II) above), sodium carbonate, sodium delta-disilicate and mixtures thereof.

[0290] Preferably, the level of phosphate builder in the granular composition is less than 1% (by weight based on the total weight of the composition).The term "phosphate builder" denotes alkali metal, ammonium and alkanolammonium (eg sodium tripolyphosphate) salts of polyphosphoric acid, orthophosphate and / or metaphosphate.

[0291] When included, builders may be present in a total amount ranging from about 10 to about 80%, preferably from about 15 to 50%, by weight based on the total weight of the composition.

[0292] The granular composition may also include one or more fillers to help provide the desired density and volume to the composition. Fillers suitable for use in the present invention may generally be selected from neutral salts having a solubility in water of at least 1 gram / 100 grams of water at 20°C, such as alkali metal, alkaline earth metal, ammonium or substituted ammonium chlorides, fluorides, acetates and sulfates, and mixtures thereof. Preferred fillers for use in the present invention include alkali metal (more preferably sodium and / or potassium) sulfates and chlorides and mixtures thereof, most preferably sodium sulfate and / or sodium chloride.

[0293] When fillers are included, they may be present in a total amount ranging from about 1 to about 80%, preferably from about 5 to about 50%, by weight based on the total weight of the composition.

[0294] The compositions of the present invention may contain one or more fatty acids and / or salts thereof.

[0295] In the context of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, most preferably 12 to 18 carbon atoms and 0 or 1 double bonds. Preferred examples of such materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures of which 50-100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may typically be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

[0296] The fatty acids may be present in the form of their sodium, potassium or ammonium salts and / or in the form of soluble salts with organic bases such as mono-, di- or triethanolamine.

[0297] Mixtures of any of the above materials may also be used.

[0298] When included, fatty acids and / or their salts may be present in an amount ranging from about 0.25-5%, more preferably 0.5-5%, most preferably 0.75-4% by weight based on the total weight of the composition.

[0299] For the purpose of formulation, fatty acids and / or their salts (as defined above) are not included in the level of surfactant or in the level of builder in the formulation.

[0300] The granular composition may also contain one or more polymeric cleaning boosters, such as soil release polymers, anti-redeposition polymers and mixtures thereof.

[0301] Soil release polymers adsorb onto fabric surfaces to aid in soil removal. Suitable soil release polymers for use in granular compositions include copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid, or terephthalic acid), diols (e.g., ethylene glycol or propylene glycol), and polyglycols (e.g., polyethylene glycol or polypropylene glycol). Examples of such materials have a midblock formed from repeating units of trimethylene terephthalate and one or two endblocks of capped polyalkylene oxide, typically methyl capped PEG 750-2000. The weight average molecular weight (M) of such materials is 1.347 W / m. w ) is generally in the range of about 1000 to about 20,000, preferably about 1500 to about 10,000.

[0302] Mixtures of any of the above materials may also be used.

[0303] When included, the compositions of the present invention preferably comprise from 0.05% to 6%, more preferably from 0.1% to 5% (by weight based on the total weight of the composition) of one or more soil release polymers, such as the copolyesters described above.

[0304] Anti-redeposition polymers stabilize soil in the washing solution, thereby preventing soil redeposition. Anti-redeposition polymers suitable for use in the present invention include alkoxylated polyethyleneimines. Polyethyleneimines are materials composed of ethyleneimine units -CH2CH2NH-, and in the case of branching, the hydrogen on the nitrogen is replaced by another chain of ethyleneimine units. Preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (MW) of about 300 to about 10,000. w ). The polyethyleneimine backbone can be straight or branched. It can be branched to the extent that it is a dendritic polymer. Alkoxylation can generally be ethoxylation or propoxylation, or a mixture of the two. When the nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10-30, preferably 15-25 alkoxy groups per modification. The preferred material is ethoxylated polyethyleneimine, wherein the average degree of ethoxylation is 10-30, preferably 15-25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone. Suitable anti-redeposition polymers for another type of the present invention include cellulose esters and ethers, such as sodium carboxymethylcellulose.

[0305] Mixtures of any of the above materials may also be used.

[0306] When included, the granular compositions of the present invention preferably comprise 0.05-6%, more preferably 0.1-5% (by weight based on the total weight of the composition) of one or more anti-redeposition polymers, such as the alkoxylated polyethyleneimines and / or cellulose esters and ethers described above.

[0307] The granular composition of the present invention may also include an oxidant to facilitate removal of thorny food stains and other organic stains by chemical oxidation. The oxidant may, for example, oxidize polyphenolic compounds commonly found in coffee, tea, wine, and fruit stains. Oxidation by the oxidant may also assist in bleaching, whitening, and disinfecting fabrics, and may also provide additional washing machine cleanliness and odor prevention. Oxidants suitable for use in the present invention include peroxy bleaching compounds such as sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.

[0308] When included, the granular compositions preferably comprise 5-35%, preferably 8-20% (by weight based on the total weight of the composition) of one or more oxidising agents, for example the peroxygen bleaching compounds described above.

[0309] Bleach activators such as N,N,N',N'-tetraacetylethylenediamine (TAED) or sodium nonanoyloxybenzene sulfonate (NOBS) may be included in combination with one or more oxidizing agents to improve bleaching at low wash temperatures.

[0310] In addition to or in place of the bleach activator, a bleach catalyst may be included. Typical bleach catalysts include complexes of heavy metal ions such as cobalt, copper, iron, manganese, or combinations thereof with organic ligands such as 1,4,7-triazacyclononane (TACN), 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN), 1,5,9-trimethyl-1,5,9-triazacyclononane, 1,5,9-triazacyclododecane, 1,4,7-triazacycloundecane, tris[2-(salicylideneamino)ethyl]amine, or combinations thereof.

[0311] The granular composition may also contain one or more chelating agents for transition metal ions. Such chelating agents may also have calcium and magnesium chelating capabilities, but preferentially bind heavy metal ions such as iron, manganese and copper. Such chelating agents may help improve the stability of the composition and prevent, for example, transition metal-catalyzed decomposition of certain ingredients.

[0312] Suitable transition metal ion chelators include phosphonic acids in acid and / or salt form. When used in salt form, alkali metals (e.g., sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include aminotri(methylenephosphonic acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP), and diethylenetriamine penta(methylenephosphonic acid) (DTPMP) and their respective sodium or potassium salts. HEDP is preferred. Mixtures of any of the above materials may also be used.

[0313] When included, the transition metal ion chelator may be present in an amount ranging from about 0.1 to about 10%, preferably from about 0.1 to about 3%, by weight based on the total weight of the composition. Mixtures of any of the foregoing materials may also be used.

[0314] The granular composition may further comprise an effective amount of one or more enzymes selected from the group consisting of pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzyme is preferably present together with a corresponding enzyme stabilizer.

[0315] The granular composition may include further optional ingredients to enhance performance and / or consumer acceptance. Examples of such ingredients include dye transfer inhibitors (e.g., polyvinyl pyrrolidone), foam control agents, preservatives (e.g., bactericides), anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosive agents, drape imparting agents, antistatic agents, ironing aids, colorants, fluorescent agents, pearlescent agents and / or sunscreens, and tinting dyes. Each of these ingredients will exist in an amount that effectively achieves its purpose. Typically, these optional ingredients are included individually in an amount of up to 5% (based on the gross weight of the composition by weight).

[0316] Packaging and filling

[0317] The composition of the present invention can be packaged in a unit dose in a polymer film that is soluble in wash water. Alternatively, the composition of the present invention can be provided in a multi-dose plastic package with a top or bottom closure. The dosing means can be provided as part of the cover or as an integrated system with the package.

[0318] The method of washing fabrics using the composition of the present invention generally comprises diluting the dosage of the detergent composition with water to obtain a washing liquid and washing the fabrics with the washing liquid thus formed. In an automatic washing machine, the detergent composition of the dosage is generally placed in a dispenser and is rinsed from the dispenser into the washing machine by water flowing into the washing machine, thereby forming the washing liquid. Depending on the configuration of the washing machine, 5 liters to about 65 liters of water can be used to form the washing liquid. The dosage of the detergent composition can be adjusted accordingly to obtain a suitable washing liquid concentration.

[0319] The dilution step preferably provides a wash liquor comprising, inter alia, from about 3 to about 20 g of detersive surfactant (as further defined above) per wash. The wash liquor preferably has a pH of greater than 7 to less than 13, preferably greater than 7 to less than 10.5.

[0320] A subsequent water rinsing step and drying of the laundry is preferred.

[0321] Dishwashing compositions

[0322] Dishware refers to hard surfaces intended to be cleaned using a hand dishwashing composition and includes dishes, glasses, pots, pans, bakeware and flatware made from any material or combination of hard surface materials commonly used in making articles for eating and / or cooking.

[0323] Surfactants for dishwashing compositions

[0324] The surfactant (detergent active) is typically selected from anionic and nonionic detergent actives.The cleaning composition may further or alternatively comprise cationic, amphoteric and zwitterionic surfactants.

[0325] Suitable synthetic (non-soap) anionic surfactants are water-soluble salts of organic sulfuric acid monoesters and sulfonic acids having in their molecular structure a branched or straight chain alkyl group containing 6 to 22 carbon atoms in the alkyl portion.

[0326] Examples of such anionic surfactants are water-soluble salts of alkylbenzene sulfonic acids, for example those in which the alkyl group contains 6 to 20 carbon atoms; (primary) long-chain (e.g. 6-22 carbon atoms) alcohol sulfates (hereinafter referred to as PAS), especially those obtained by sulfation of fatty alcohols produced by reducing the glycerides of tallow or coconut oil; secondary alkane sulfonates; and mixtures thereof.

[0327] Also suitable are the salts of alkyl glyceryl ether sulfates, in particular the salts of ethers of fatty alcohols derived from tallow and coconut oil; fatty acid monoglyceride sulfates; sulfates of ethoxylated aliphatic alcohols containing 1 to 12 ethyleneoxy groups; alkylphenol vinyloxy-ether sulfates having 1 to 8 ethyleneoxy units per molecule and in which the alkyl group contains 4 to 14 carbon atoms; reaction products of fatty acids esterified with isethionates and neutralized with a base, and mixtures thereof.

[0328] Previously, preferred water-soluble synthetic anionic surfactants were alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of alkylbenzene sulfonic acid and mixtures with olefin sulfonates and alkyl sulfates, and fatty acid monoglyceride sulfates. However, it is preferred that the composition comprises less than 5 wt%, more preferably less than 1 wt%, most preferably less than 0.1 wt% of alkylbenzene sulfonate surfactant.

[0329] When synthetic anionic surfactants (including furan-based surfactants) are used, they will be present in the cleaning compositions of the present invention at a level of at least 5%, preferably at least 10% by weight.

[0330] Nonionic surfactants tend to reduce the foam generated when using the composition. Consumers often associate high foam with strong cleaning, so they may wish to avoid the use of nonionic surfactants altogether. For compositions where this is not a problem, suitable types of nonionic surfactants can be broadly described as compounds produced by condensation of simple alkylene oxides that are hydrophilic in nature with aliphatic or alkyl-aromatic hydrophobic compounds having reactive hydrogen atoms. The hydrophilicity or length of the polyoxyalkylene chain connected to any particular hydrophobic group can be easily adjusted to produce a compound with a desired balance between the hydrophilic and hydrophobic elements. This enables the selection of nonionic surfactants with an appropriate HLB. Specific examples include: condensation products of aliphatic alcohols having 8 to 22 carbon atoms in a straight chain or branched configuration with ethylene oxide, such as coconut alcohol / ethylene oxide condensates having 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensations of alkylphenols having a C6-C15 alkyl group with 5-25 moles of ethylene oxide per mole of alkylphenol; and condensations of the reaction products of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing 40 to 80 weight percent ethyleneoxy groups and having a molecular weight of 5000 to 11,000.

[0331] Other types of nonionic surfactants are: tertiary amine oxides of the structure R1R2R3N-O, wherein R1 is an alkyl group of 8-20 carbon atoms, and R2 and R3 are each an alkyl group or a hydroxyalkyl group of 1-3 carbon atoms, such as dimethyldodecylamine oxide; tertiary phosphine oxides of the structure R1R2R3P-O, wherein R1 is an alkyl group of 8-20 carbon atoms, and R2 and R3 are each an alkyl group or a hydroxyalkyl group of 1-3 carbon atoms, such as dimethyl-dodecylphosphine oxide; dialkyl sulfoxides of the structure R1R2S=O, wherein R1 is an alkyl group of 10 to 18 carbon atoms and R2 is a methyl group or an ethyl group, such as methyl-tetradecyl sulfoxide; fatty acid alkanolamides, such as ethanolamide; alkylene oxide condensates of fatty acid alkanolamides; and alkyl mercaptans.

[0332] If used, nonionic surfactants are typically present in the cleaning compositions of the present invention in an amount of at least 0.1 wt%, preferably at least 0.5 wt%, more preferably at least 1.0 wt%, but not more than 20 wt%, preferably up to 10 wt%, more preferably not more than 5 wt%.

[0333] Amphoteric, cationic or zwitterionic surfactants may also optionally be included in the composition.

[0334] Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 20 carbon atoms and an aliphatic group substituted with an anionic water-solubilizing group, for example sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane-sulfonate and sodium N-2-hydroxy-dodecyl-N-methyltaurate.

[0335] Examples of suitable cationic surfactants may be found in quaternary ammonium salts having one or two alkyl or aralkyl groups of 8 to 20 carbon atoms and two or three small aliphatic (eg methyl) groups, such as cetyltrimethylammonium chloride.

[0336] A specific group of surfactants are tertiary amines obtained by condensation of ethylene oxide and / or propylene oxide with long chain aliphatic amines. The compounds behave like nonionic surfactants in alkaline media and like cationic surfactants in acidic media.

[0337] Examples of suitable zwitterionic surfactants can be found in derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium compounds having an aliphatic group of 8 to 18 carbon atoms and an aliphatic group substituted with an anionic water-solubilizing group, for example betaines and betaine derivatives such as alkyl betaines, in particular C12-C16 alkyl betaines, 3-(N,N-dimethyl-N-hexadecyl ammonium)-propane 1-sulfonate betaine, 3-(dodecylmethyl-sulfonium)-propane 1-sulfonate betaine, 3-(hexadecylmethyl-phosphonium)-propane-1-sulfonic acid betaine and N,N-dimethyl-N-dodecyl-glycine. Other well-known betaines are alkylamidopropyl betaines, for example those in which the alkylamide group is derived from coconut fatty acids.

[0338] Further examples of suitable surfactants are the compounds commonly used as surface-active agents which are given in the well-known textbooks: 'Surface Active Agents' Vol. 1, by Schwartz and Perry, Interscience 1949; 'Surface Active Agents' Vol. 2 by Schwartz, Perry and Berch, Interscience 1958; the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company; 'Tenside-Taschenbuch', H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.

[0339] Optional ingredients for dishwashing compositions

[0340] The compositions may contain optional ingredients such as abrasive particles and additional ingredients that aid in formulation, stability and cleaning performance.

[0341] To ensure the desired rheological properties, a magnesium sulfate content of 0.5-5% by weight is desirable.

[0342] Preservative systems are also desirable, such as a mixture of CIT and MIT. BIT can also be used. The amount of preservative varies depending on the expected storage temperature and the quality of the raw materials. Typically 0.0001-0.1 wt %.

[0343] Sodium EDTA chelating agent is advantageously included in the composition at a level of 0.01-0.5 wt%. DMDMH (glydant) may also be included in the composition at a level of 0.005-1 wt%.

[0344] When the composition contains one or more anionic surfactants, the composition may preferably contain a detergent builder, more preferably in an amount of 0.1-25 wt%. Suitable inorganic and organic builders are well known to those skilled in the art. Citric acid is a preferred buffer / builder and may suitably be included at a level of 0.01 to 0.5 wt%.

[0345] The compositions may also contain ingredients such as colorants, brighteners, fluorescent whitening agents, soil suspending agents, detersive enzymes, compatible bleaches (especially peroxides and active chlorine-releasing compounds), solvents, co-solvents, gel control agents, freeze-thaw stabilizers, bactericides, preservatives, hydrotropes, polymers and perfumes.

[0346] Examples of optional enzymes include lipase, cellulase, protease, mannanase and pectate lyase.

[0347] Viscosity for dishwashing compositions

[0348] The liquid composition according to the present invention preferably has a viscosity of 100 to 10,000 mPa.s, more preferably 200 to 8,000 mPa.s, even more preferably 400 to 6,500 mPa.s, and still even more preferably 800 to 5,000 mPa.s, such as at 20 s -1 The results are measured at a shear rate of 1.000 % and a temperature of 25°C.

[0349] Packaging for dishwashing compositions

[0350] The liquid composition may be packaged in any suitable form of container. Preferably, the composition is packaged in a plastic bottle with a detachable closure / pour spout. The bottle may be rigid or deformable. Deformable bottles allow the bottle to be squeezed to aid dispensing. If transparent bottles are used, they may be formed from PET. Polyethylene or transparent polypropylene may be used. Preferably, the container is sufficiently transparent so that the liquid with any visual cues therein is visible from the outside. The bottle may be provided with one or more labels, or provided with a shrink wrap, which is ideally at least partially transparent, for example 50% of the wrap area is transparent. The adhesive used for any transparent label should preferably not adversely affect transparency.

[0351] The invention will now be further described with reference to the following non-limiting examples. Example

[0352] The following are methods for preparing the furan-based surfactants described herein and using the various linker groups described. For each example, the order of steps can be interchanged and alternative reagents may provide optimal conditions.

[0353] Direct Alkyl

[0354] Starting with chloromethylfuran, the sulfonated head group was introduced using the Strecker reaction with sodium sulfite.

[0355] Friedel-Crafts alkylation of sulfonated furans using the corresponding alkyl halides gives directly alkylated furans using strong Lewis acids such as aluminum chloride as catalysts.

[0356] Exemplary Structure

[0357]

[0358] (5-Tetradecylfuran-2-yl)methanesulfonate

[0359]

[0360] (5-(Tetradec-7-yl)furan-2-yl methanesulfonate

[0361] Carbonyl alkyl

[0362] Starting with chloromethylfurfural, the sulfonic head group was introduced using the Strecker reaction with sodium sulfite.

[0363] The Grignard reaction of an alkyl magnesium halide with the aldehyde portion of furfural produces a 2° alcohol. This is then oxidized in a second step to produce a carbonyl alkyl derivative. A solution of the Grignard reagent is prepared from an alkyl bromide and magnesium in a dry solvent. Furfural is added under cooling. The resulting reaction mixture is quenched, the hydroxyalkyl derivative is extracted and dried. Subsequent oxidation with manganese dioxide gives the product under heating within 4 hours.

[0364] Exemplary Structure

[0365]

[0366] (5-Tetradecanoylfuran-2-yl) methanesulfonate

[0367]

[0368] (5-(2-Hexyloctanoyl)furan-2-yl)methanesulfonate

[0369] Hydroxyalkyl

[0370] Starting with chloromethylfurfural, the sulfonated head group was introduced using the Strecker reaction with sodium sulfite.

[0371] The Grignard reaction of alkyl magnesium halide with the aldehyde portion of furfural produces 2° alcohol. A solution of the Grignard reagent is prepared from alkyl bromide and magnesium in a dry solvent. Furfural is added under cooling. The resulting reaction mixture is quenched and the product is extracted and dried.

[0372] Exemplary Structure

[0373]

[0374] (5-(1-Hydroxytetradecyl)furan-2-yl)methanesulfonate

[0375]

[0376] (5-(2-Hexyl-1-hydroxyoctyl)furan-2-yl)methanesulfonate

[0377] Carbonyl ether

[0378] Linear and branched carbonyl ether derivatives are prepared from chloromethyl furfural according to the typical 4-step route and method described below. The acid chloride is reacted with the appropriate alcohol to form the carbonyl ether. Sulfonation is achieved by the Strecker reaction.

[0379]

[0380]

[0381] Examples of sodium (5-((tetradec-2-yloxy)carbonyl)furan-2-yl)methanesulfonate

[0382] General Procedure - Step 1: 5-(Chloromethyl)furfural (25.0 g, 172.9 mmol) and tert-butyl hypochlorite (93.35 g, 859.8 mmol, 5 equivalents) were vigorously stirred at room temperature for 24 hours. The volatiles were evaporated under reduced pressure at room temperature to give the crude product 5-(chloromethyl)furan-2-carbonyl chloride (CMFCC) (38 g, 72% yield, by 1 H NMR spectroscopy). The product was used in the subsequent reaction as a crude mixture with calculated purity.

[0383] General Procedure - Step 2: CMFCC (62% CMFCC w / w, 5.9 g, 33.3 mmol) was added to 2-tetradecanol (ROH) (10.72 g, 50 mmol, 1.5 equiv). The mixture was stirred at 50 °C overnight (to ensure melting of the solid alcohol) under a dry atmosphere until the reaction was complete as determined by TLC. Excess alcohol can be removed under high vacuum, and the resulting dark residue is purified by column chromatography (silica gel, ethyl acetate: hexane (1: 9), Rf = 0.24) to give the furanyl ester (7.65 g, 64% yield) as a yellow oil.

[0384] General Procedure - Step 3:Alkyl chloride (2.0 g, 5.6 mmol), sodium iodide (1.7 g, 1.1 mmol, 2 eq.) and acetone (20 ml) were added to the flask. The system was refluxed and stirred for 1 hour. Thereafter, the solution was filtered through a short path diatomaceous earth. The solvent was evaporated from the filtrate under reduced pressure. The resulting orange residue was ground with ethyl acetate (50 ml) and filtered through diatomaceous earth. The resulting solution was washed with sodium pyrosulfite solution (10% w / w aqueous solution, 2×50 ml), water (50 ml) and brine (50 ml). The combined organic phases were dried (MgSO ), filtered and evaporated to give alkyl iodide furan (2.3 g, 93%) as a yellow solid.

[0385] General Procedure - Step 4: Methyl iodide furanyl ester (9.28 g, 20.69 mmol), sodium sulfite (3.91 g, 31.04 mmol, 1.5 eq.), tetrabutylammonium iodide (764.4 mg, 2.07 mmol, 0.1 eq.) and acetonitrile / water mixture (1:1, v:v; 50 ml) were added to a flask. After stirring at 80°C for 10 hours, the solvent was removed and the resulting product was extracted with methanol (100 ml) and sonicated at 50°C for 5 minutes. The supernatant was obtained from the resulting suspension after centrifugation (3500 rpm, 5 minutes). The methanol extraction of the residue was repeated twice. The combined methanol fractions were evaporated to dryness, and the resulting solid was washed with ethyl acetate (100 ml), and collected by filtration to obtain the sodium salt (5.5 g, 57% yield) as a white solid.

[0386] Exemplary Structure

[0387]

[0388] (5-((Tetradecyloxy)carbonyl)furan-2-yl)methanesulfonate

[0389]

[0390] (5-(Tetradec-7-yloxy)furan-2-yl)methanesulfonate

[0391] Carbonyl amide

[0392] Starting with chloromethylfurfural, the sulfonated head group was introduced using the Strecker reaction with sodium sulfite.

[0393] The aldehyde group is oxidized to the carboxylic acid or forms an acid chloride moiety. The corresponding alkylamine is then reacted directly with the acid chloride or with an acid using coupling chemistry such as N,N'-carbonyldiimidazole (CDI) and an alkylamine.

[0394] CDI was added to a stirred suspension of furanic acid (until gas evolution subsided). Amine was added and the reaction was stirred overnight. The product was extracted and purified by chromatography.

[0395] Exemplary Structure

[0396]

[0397] (5-(Tetradecylcarbamoyl)furan-2-yl)methanesulfonate

[0398]

[0399] (5-(Tetradec-7-ylcarbamoyl)furan-2-yl)methanesulfonate

[0400] ester

[0401] Starting with chloromethylfurfural, the sulfonated head group was introduced using the Strecker reaction with sodium sulfite.

[0402] The aldehyde moiety of furfural is first reduced using sodium borohydride to form a hydroxymethyl functionality. In a second step, the hydroxymethyl furan is then esterified using the corresponding alkyl acid (plus a coupling agent) such as CDI or an alkyl acid chloride in dichloromethane (with triethylamine) with cooling.

[0403] Exemplary Structure

[0404]

[0405] (5-((Tetradecanoyloxy)methyl)furan-2-yl)methanesulfonate

[0406]

[0407] (5-(((2-pentylnonanoyl)methyl)furan-2-yl)methanesulfonate

[0408] Ether (near furan ring)

[0409] Chloromethylfuran is used as the starting material. Ether-linked alkyl chains can be prepared by bromination of the furan ring (eg using N-bromosuccinimide or bromine) followed by reaction of a hydroxyalkane with titanium isopropoxide in refluxing toluene.

[0410] The product was then sulfonated via the Strecker reaction using sodium sulfite.

[0411] Exemplary Structure

[0412]

[0413] (5-(Tetradecyloxy)furan-2-yl)methanesulfonate

[0414]

[0415] (5-(Tetradec-7-yloxy)furan-2-yl)methanesulfonate

[0416] Ether (removal of 1C from furan ring)

[0417] Starting with chloromethylfurfural, the sulfonated head group was introduced using the Strecker reaction with sodium sulfite.

[0418] Starting with chloromethylfurfural, the aldehyde is first partially reduced to hydroxymethylfuran using sodium borohydride. In a second step, the alcohol is deprotonated with a strong base such as sodium hydride to form an alkoxide, which is trapped with a suitable alkyl bromide.

[0419] Exemplary Structure

[0420]

[0421] (5-((Tetradecyloxy)methyl)furan-2-yl)methanesulfonate

[0422]

[0423] (5-((Tetradec-7-yloxy)methyl)furan-2-yl)methanesulfonate

[0424] Hydroxyl ether

[0425] Starting with chloromethylfurfural, the sulfonated head group was introduced using the Strecker reaction with sodium sulfite.

[0426] The furfural is then reacted with a hydroxyalkane (which may need to be activated as an alkoxide) to produce the product.

[0427] Exemplary Structure

[0428]

[0429] (5-(Hydroxy(tetradecyloxy)methyl)furan-2-yl)methanesulfonate

[0430]

[0431] (5-(Hydroxy(tetradec-7-yloxy)methyl)furan-2-yl)methanesulfonate

[0432] Hydroxylamine

[0433] The aforementioned carbonyl amides can be selectively hydrogenated using a suitable catalyst.

[0434] Example structure:

[0435]

[0436] (5-(Hydroxy(tetradecylamino)methyl)furan-2-yl)methanesulfonate

[0437]

[0438] (5-(Hydroxy(tetradec-7-ylamino)methyl)furan-2-yl)methanesulfonate

[0439] Material

[0440] The following materials were used to demonstrate the efficacy of the claimed furan-based surfactants:

[0441] C12LEFS-C12 straight chain ester furan sulfonate

[0442] C14LEFS-C14 straight chain ester furan sulfonate

[0443] C12GEFS-C12 Guerbet Ester Furan Sulfonate

[0444] C14MEFS-C14 Methyl Ester Furan Sulfonate

[0445] The following images are in the same order as the names / abbreviations above.

[0446]

[0447] Mildness

[0448] The mildness of the surfactants was tested by colorimetric measurement of the solubility of zein (corn protein) mixed with a blue dye and dried to the bottom of a 96-well plate; the greater the solubility, the greater the absorbance.

[0449] Measurements were performed at 10, 5 and 1 g / l, SDS was used as positive control (harsh), and rhamnolipid (RL) and water were used as negative controls (mild).

[0450] The concentrations of furanic surfactants reflect normal levels up to and above which one might use in detergent compositions. The use of 10 g / l is included as a parameter stretch rather than the actual amount used in detergents.

[0451] Of all the detergents considered for furan surfactants, handwash detergents are the most concentrated in use, typically using about 1 to 2 g / l of total detergent in the wash liquor.

[0452] The samples were mixed, incubated at 40°C for 30 minutes with stirring, and then read on a UV-Vis spectrophotometer at 590 nm.

[0453] Figure 1 , 2 and 3 illustrate the improved mildness performance exhibited by furan-based surfactants.

Claims

1. Use of a furan-based surfactant in a detergent for reducing or preventing irritation during use, wherein the detergent comprises 0.01 to 7% by weight of the furan-based surfactant, wherein the furan comprises a head group, a furan, and a hydrophobic portion connected to the furan by a linker, wherein the head group is selected from β-sulfonate, β-hydroxysulfonate, β-sulfate, β-hydroxysulfate, α-sulfonate, α-hydroxysulfonate, α-sulfonate, α-hydroxysulfonate, α-sulfate, α-hydroxysulfonate and mixtures thereof, and wherein the linker is selected from direct alkyl, carbonyl alkyl, hydroxyalkyl, carbonyl ether, hydroxy ether, carbonyl amide, hydroxy amide and ester.

2. The use according to claim 1, wherein the hydrophobic part is a C10-20 hydrophobic group.

3. Use according to claim 1 or 2, wherein the head group is a β-sulfonate.

4. The use according to claim 1 or 2, wherein the linker is a carbonyl ether.

5. The use according to claim 1 or 2, wherein the detergent is a laundry detergent.

6. The use according to claim 1 or 2, wherein the detergent is a hand-washing laundry detergent.

7. The use according to claim 1 or 2, wherein the detergent is a hand dishwashing detergent.

8. Use according to claim 1 or 2, wherein the detergent is a hard surface cleaner.

9. The use according to claim 1 or 2, wherein the detergent comprises 0.01 wt% to 4.0 wt% of the furan-based surfactant.

10. Use according to claim 1 or 2, wherein the detergent comprises additional anionic surfactants and / or nonionic surfactants.

Images