BR112021001856A2 - liquid detergent composition for laundry and fabric washing method - Google Patents

Abstract

LIQUID DETERGENT COMPOSITION FOR LAUNDRY AND METHOD FOR WASHING FABRICS. The invention provides a liquid laundry detergent composition comprising ethoxylated polyethyleneimine (EPEI) for an improved product viscosity profile without compromising cleaning performance; wherein the detergent composition comprises: a) from 6 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from non-soap anionic surfactants, non-ionic surfactants and mixtures thereof, and b) from 2 to 15% of an ethoxylated polyethyleneimine (EPEI) having a polyethyleneimine backbone derived from a polyethylene starting material and formed of -[(CH 2 CH 2 )N]- repeating subunits; and one or more polyoxyethylene side chains that are attached to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone; wherein the polyethyleneimine starting material has an average molecular weight (M w ) ranging from 1800 to 5000 g/mol (before ethoxylation), and the polyoxyethylene side chains have an average of 25 to 40 ethoxy units per side chain linked to the polyethyleneimine backbone.

Description

Invention Patent Descriptive Report

LIQUID DETERGENT COMPOSITION FOR LAUNDRY AND METHOD

FOR WASHING FABRICS Field of Invention

[0001] The present invention relates to liquid laundry detergents comprising ethoxylated polyethyleneimine (EPEI) for an improved product viscosity profile without compromising cleaning performance. Background of the Invention

[0002] There is a continuing need to improve the cleaning performance of laundry liquids as consumers tend to use lower wash temperatures and look for products with improved environmental credentials. One way to improve the environmental profile of liquid laundry detergents is to add multifunctional or highly weight efficient materials to replace traditional materials, eg surfactants, resulting in less overall use of chemicals.

[0003] One such component is ethoxylated polyethyleneimine (EPEI), which is known to improve the removal of particulate dirt from fabrics. However, the inclusion of EPEI can reduce the viscosity of the resulting liquid, leading to lower consumer acceptability and therefore the need to include additional viscosity enhancing technology.

[0004] The present invention addresses this problem. Invention Summary

[0005] The present invention provides a liquid laundry detergent composition comprising ethoxylated polyethyleneimine (EPEI) for an improved product viscosity profile without compromising cleaning performance; wherein the detergent composition comprises: a) from 6 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, and b) of 0, 5 to 10% of an ethoxylated polyethyleneimine (EPEI) having a polyethyleneimine backbone formed by repeating subunits of -[(CH2CH2)N]-; and one or more polyoxyethylene side chains that are attached to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone; wherein the polyethyleneimine backbone is derived from a polyethyleneimine starting material which is ethoxylated to produce EPEI; wherein the polyethyleneimine starting material has an average molecular weight (Mw) ranging from 1800 to 5000 g/mol (before ethoxylation), and the polyoxyethylene side chains have an average of 25 to 40 ethoxy units per side chain attached. to the polyethyleneimine backbone. Detailed Description of the Invention Ethoxylated Polyethyleneimine (EPEI)

[0006] The ethoxylated polyethyleneimine (EPEI) for use in the invention includes, among other things, a polyethyleneimine backbone formed by repeating subunits of -[(CH2CH2)N]-. The backbone is derived from a polyethyleneimine starting material (as defined above) which is ethoxylated to produce EPEI.

[0007] More preferably, the polyethyleneimine starting material (before ethoxylation) has an average molecular weight (Mw) ranging from 1800 to 2400 g/mol, and most preferably from 1800 to 2200 g/mol, for example, 1900 to 2100 g/mol, determined by gel permeation chromatography (GPC) with 1.5% by weight aqueous formic acid as eluent and cross-linked polyhydroxyethyl methacrylate as stationary phase (TSKgel GMPWXL column) and using a detector RI and Pullulan standards (PSS GmbH, Mainz, Germany) for calibration.

[0008] A polyethyleneimine starting material suitable in the context of the present invention may, for example, be an ethyleneimine homopolymer according to the (empirical) formula: -(CH2-CH2-NH)n-; where n ranges from about

40 to about 120. Preferably, n ranges from about 40 to about 60.

[0009] The polyethyleneimine starting material may vary in terms of shape, including, for example, linear, branched, dendritic (hyper-branched) or comb-like structure structures, depending on the method of manufacture. The manufacturing methods for these materials are generally acid-catalyzed reactions to open the ring of ethyleneimine, also known as aziridine.

[0010] Examples of polyethyleneimine starting materials suitable for use in the invention have a branched structure comprising three types of subunits, which can be randomly distributed. The subunits that form the polymer are primary amine units having the formula (I): [H2N-CH2CH2]- and -NH2 (I) which terminate the main polymer chain and any branch chains; secondary amine units having the formula (II): -[N(H)CH2CH2]- (II) and tertiary amine units having the formula (III): -[N(B)CH2CH2]- (III) which are the polymer branch points, where B represents a continuation of the chain structure by branching.

[0011] The branches can be ethyleneamino groups, for example groups -CH2CH2-NH2; or longer groups, for example, groups -(CH2CH2)-N(CH2CH2NH2)2 or -(CH2CH2)-N(H)CH2CH2NH2. The mixture of primary, secondary and tertiary amine units, respectively, can be in any molar ratio, including, for example, in a molar ratio of from about 1:1:1 to about 1:2:1. The molar ratio of primary, secondary and tertiary amine units, respectively, can, for example, be determined by C-NMR or N-NMR spectroscopy, preferably in D2O. The degree of branching can be defined as follows: DB = D+T/D+T+L, where D

(dendritic) corresponding to the fraction of tertiary amine units, L (linear) corresponding to the fraction of secondary amine units and T (terminal) corresponding to the fraction of primary amine units. Suitably the DB ranges from 0.25 to 0.95, preferably from 0.30 to 0.80, and more preferably from 0.5 to 0.8.

[0012] In the polyethyleneimine starting material above, each hydrogen atom of the primary or secondary amine represents a reactive site for subsequent ethoxylation. Preferably, most or all of these hydrogen atoms are replaced with polyoxyethylene side chains to form the ethoxylated polyethyleneimine for use in the invention. The polyoxyethylene side chains may suitably correspond to the formula R-(EO)n-, wherein (EO)n represents an ethylene oxide block; n is a number from 25 to 40, preferably from 25 to 35; and R is hydrogen.

[0013] Preferred polyethyleneimine starting materials, in the context of the present invention, have a polydispersity Q = M w/Mn of at most 3.4, for example in the range of 1.1 to 3.0, more preferably in the range from 1.3 to 2.5 and most preferably from 1.5 to 2.0.

Preferred polyethyleneimine starting materials in the context of the present invention have a primary amine value in the range of 1 to 1000 mg KOH/g, preferably 10 to 500 mg KOH/g, most preferably from 50 to 300 mg KOH/g. The primary amine value can be determined in accordance with ASTM D2074-07.

Preferred polyethyleneimine starting materials in the context of the present invention have a secondary amine value in the range of 10 to 1000 mg KOH/g, preferably 50 to 500 mg KOH/g, most preferably from 50 to 500 mg KOH/g. Secondary amine value can be determined in accordance with ASTM D2074-07.

Preferred polyethyleneimine starting materials in the context of the present invention have a tertiary amine value in the range of 1 to 300 mg KOH/g, preferably 5 to 200 mg KOH/g, most preferably from 10 to 100 mg KOH/g. The tertiary amine value can be determined in accordance with ASTM D2074-07.

[0017] The polyethyleneimine starting material can be pretreated (eg with a combination of water removal and degassing) before the start of the ethoxylation stage.

[0018] A standard procedure for the ethoxylation stage involves reacting the polyethyleneimine starting material with at least enough ethylene oxide to provide 2-hydroxyethyl groups at each reactive site (eg, 1 ethylene oxide (EO) group per primary or secondary amine hydrogen atom in the polyethyleneimine molecule). The reaction product thus obtained is then condensed with the remaining amount of ethylene oxide, typically in the presence of a basic catalyst.

[0019] A preferred procedure for the ethoxylation stage is a two-step procedure that requires adjusting the amount of ethylene oxide that is added in the first (and second) step to a certain range. This preferred procedure (hereinafter referred to as the "strong subethoxylation process") involves reacting, in a first step (1), the polyethyleneimine starting material with ethylene oxide in an amount significantly less than one molar equivalent, for example, in an amount of from 0.01 to 0.85, preferably from 0.1 to 0.7, more preferably from 0.1 to 0.6 and most preferably from 0.1 to 0.5 EO groups per atom of primary or secondary amine hydrogen in the polyethyleneimine molecule.

[0020] Preferably, step (1) is carried out in the absence of a catalyst and in an aqueous solution (which may be a 50 to 99% solution, preferably 75 to 99% by weight of the polyethylene starting material in water ). Step (1) can also be carried out in the absence of a catalyst and in the absence of water. The temperature during step (1) is normally in the range from about 90 to 180°C, preferably from 100 to 170°C, more preferably from 110 to 160°C and most preferably from 120 to 145°C.

[0021] In a second step (2), the reaction product obtained from step (1), that is, partially ethoxylated polyethyleneimine, is reacted with the remaining amount of ethylene oxide in the presence of a basic catalyst. The second step (2) is preferably carried out at a temperature of 100 to 250 °C, and more preferably 120 to 180 °C.

[0022] Examples of suitable base catalysts include alkali metal hydroxides (eg sodium or potassium); alkali metal alkoxides (for example sodium or potassium), for example potassium methylate (KOCH 3), potassium tert-butoxide, sodium ethoxide and sodium methylate (NaOCH3); alkali metal or alkaline earth metal hydrides, for example sodium hydride and calcium hydride, and alkali metal carbonates (for example sodium or potassium), for example sodium carbonate and potassium carbonate. Potassium hydroxide is preferred.

[0023] The final product obtained is ethoxylated polyethyleneimine (EPEI). The total degree of ethoxylation per reactive site can be determined according to the following formula: E/(AR), where E is the total number of moles of condensed ethylene oxide (including hydroxyethylation), A is the number of moles of the polyethyleneimine starting material, and R is the number of reactive sites for the polyethyleneimine starting material.

[0024] Ethoxylated polyethyleneimines (EPEI) for use in the invention may generally have a weight average molecular weight (Mw) of from 25000 to 120000 g/mol, preferably from 30000 to 100000 g/mol, more preferably from 35000 at 90000 g/mol and most preferably from 40000 to 50000 g/mol, determined by gel permeation chromatography (GPC) with 0.05% by weight of potassium trifluoroacetate in hexafluorisopropanol (HFIP) as eluent and polystyrene/divinylbenzene crosslinked as stationary phase (PL HFIPGel column; MALLS detector).

[0025] Preferred ethoxylated polyethyleneimines for use in the invention correspond to the following general formula (IV): [E2N-CH2CH2]w[N(E)CH2CH2]x[N(B)CH2CH2]y-NE2(IV) where E represents a polyoxyethylene side chain corresponding to the formula R-(EO)n- is as described above; B represents a continuation of the chain structure by branching; w, x and y each independently range from about 1 to 100, and (w + x + y) ranges from about 40 to about 120. Preferably, (w + x + y) ranges from about 40 to about of 60. The subunits that make up the polymer of formula (IV) can be randomly distributed. Generally speaking, w:x:y ranges from about 1:1:1 to about 1:2:1.

Particularly preferred ethoxylated polyethyleneimines for use in the invention and corresponding to general formula (IV) above can be produced using the strong subethoxylation process as is further described above.

[0027] Mixtures of any of the materials described above can also be used.

In the composition of the invention, the EPEI level (b) preferably ranges from 0.5 to 10%, more preferably from 0.7 to 5% (by weight based on the total weight of the composition). Liquid laundry detergents

[0029] The term "laundry detergent", in the context of the present invention, denotes formulated compositions intended for and capable of wetting and cleaning in household washing, for example, clothing, bed and table linen and other household textiles. The term “bed and table linen” is generally used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, table napkins and uniforms. Textiles can include woven fabrics, non-woven fabrics and knitted fabrics; and may include natural or synthetic fibers, for example silk fibers, fabric fibers, cotton fibers, polyester fibers, polyamide fibers, for example nylon, acrylic fibers, acetate fibers and mixtures thereof, including cotton blends and polyester.

[0030] Examples of liquid laundry detergents include liquid laundry detergents for heavy use in the wash cycle of automatic laundry washers, as well as liquid detergents for fine washing and color care, for example those suitable for washing clothes delicate (for example, those made of silk or wool) either by hand or in the wash cycle of automatic clothes washers.

[0031] The term "liquid", in the context of the present invention, denotes that a continuous phase or predominant part of the composition is liquid and that the composition is flowable at 15 °C and above. Consequently, the term "liquid" can encompass emulsions, suspensions and compositions having a flowable but more rigid consistency known as gels or pastes. The viscosity of the composition may suitably range from about 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 s-1. This shear rate is the shear rate that is generally exerted on the liquid when poured from a bottle. Liquid pourable detergent compositions generally have a viscosity of 200 to 2,500 mPa.s, preferably 200 to 1500 mPa.s. Liquid detergent compositions which are pourable gels generally have a viscosity of

1,500 mPa.s to 6,000 mPa.s, preferably from 1,500 mPa.s to 2,000 mPa.s.

A composition of the invention may generally comprise from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% water (by weight based on the total weight of the composition). The composition can also incorporate non-aqueous vehicles, for example, hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight organic liquids, soluble in water or miscible in water, for example, C1 to C5 monohydric alcohols (for example, ethanol and n- or i-propanol); C2 to C6 diols (for example, monopropylene glycol and dipropylene glycol); C3 to C9 triols (for example, glycerol); polyethylene glycols having an average molecular weight (Mw) ranging from about 200 to 600; C 1 to C 3 alkanolamines, for example mono, di and triethanolamines; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (for example, the sodium and potassium xylene, toluene, ethylbenzene and isopropylbenzene (cumene) sulfonates).

[0033] Mixtures of any of the materials described above can also be used.

[0034] Non-aqueous vehicles, when included, may be present in an amount ranging from 0.1 to 20%, preferably from 1 to 15%, and more preferably from 3 to 12% (by weight based on the total weight of the composition).

[0035] The composition of the invention preferably has a pH in the range of 5 to 9, more preferably of 6 to 8, when measured in diluting the composition to 1% using demineralized water.

[0036] The composition of the invention comprises from 6 to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants (a) selected from non-soap anionic surfactants, non-ionic surfactants and mixtures thereof.

[0037] The term "detersive surfactant", in the context of the present invention, denotes a surfactant that provides a detersive (i.e., cleaning) effect to washes treated as part of a household washing process.

[0038] The non-soap anionic surfactants for use in the invention are typically salts of organic sulfates and sulfonates that have alkyl radicals containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl radicals. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and mixtures thereof. Alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated. Alkyl ether sulfates can contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain from one to three ethylene oxide units per molecule. The counterion for anionic surfactants is usually an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions can also be used.

[0039] A preferred class of non-soap anionic surfactant for use in the invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and alkyl chain homologues, each containing a sulfonated aromatic ring at the “para” position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all possible sulfophenyl isomers, except for the 1-phenyl isomer. LAS is typically formulated into compositions in acid form (ie HLAS) and then at least partially neutralized in situ.

Also suitable are alkyl ether sulfates having a straight or branched chain alkyl group having from 10 to 18, more preferably from 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 lauryl C 12 alkyl group has predominantly been ethoxylated with an average of 3 EO units per molecule.

[0041] Some alkyl sulfate surfactant (PAS) can be used, such as non-ethoxylated primary and secondary alkyl sulfates with an alkyl chain length of 10 to 18.

[0042] Mixtures of any of the materials described above can also be used. A preferred blend of non-soap anionic surfactants for use in the invention comprises linear alkylbenzene sulfonate (preferably C11 to C15 linear alkylbenzene sulfonate) and alkyl ether sulfate (preferably ethoxylated C10 to C18 alkyl sulfate with an average of 1 to 3 EO) .

[0043] The total level of non-soap anionic surfactant can suitably range from 5 to 30% (by weight based on the total weight of the composition).

[0044] Nonionic surfactants for use in the invention are typically polyoxyalkylene compounds, that is, the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starting molecules having a hydrophobic group and a reactive hydrogen atom that is reactive with alkylene oxide. Such starting molecules include alcohols, acids, amides or alkyl phenols. Where the starting molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. Polyoxyalkylene compounds can have a variety of block and etheric (random) structures. For example, they can comprise a single alkylene oxide block or they can be two-block alkoxylates or three-block alkoxylates. Within the block structures, the blocks can be all ethylene oxide or all propylene oxide or the blocks can contain an etheric mixture of alkylene oxides. Examples of such materials include aliphatic alcohol ethoxylates, for example linear or branched primary or secondary C 8 to C 18 alcohol ethoxylates with an average of 2 to 40 moles of ethylene oxide per mole of alcohol.

[0045] A preferred class of nonionic surfactant for use in the invention includes aliphatic primary linear alcohol ethoxylates C8 to C18, more preferably C12 to C15, with an average of 3 to 20, more preferably 5 to 10 moles of ethylene oxide per mole of alcohol.

[0046] Mixtures of any of the materials described above can also be used.

[0047] The total level of nonionic surfactant can suitably range from 0 to 25% (by weight based on the total weight of the composition).

[0048] A preferred mixture of non-soap anionic and nonionic surfactants for use in the invention comprises linear alkylbenzene sulfonate (preferably C11 to C15 linear alkylbenzene sulfonate), sodium lauryl ether sulfate (preferably ethoxylated C10 to C18 alkyl sulfate with a average of 1 to 3 EO) and ethoxylated aliphatic alcohol (preferably C12 to C15 linear primary alcohol ethoxylate with an average of 5 to 10 moles of ethylene oxide per mole of alcohol). Optional components

[0049] A composition of the invention may contain other optional components to enhance performance and/or consumer acceptability, as follows: Co-surfactants

[0050] A composition of the invention may contain one or more co-surfactants (for example, amphoteric (zwitterionic) and/or cationic surfactants), in addition to the anionic and/or non-ionic detersive surfactants described above.

[0051] Specific cationic surfactants include C8 to C18 alkyldimethyl ammonium halides and derivatives thereof, in which one or two hydroxyethyl groups replace one or two of the methyl groups and mixtures thereof. The cationic surfactant, when included, can be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0052] Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkylbetaines, alkylamidopropyl betaines, alkyl sulphobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl tachytases, alkyl amphopropionates sulfates acyl and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher acyl radicals. The amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0053] Mixtures of any of the materials described above can also be used. complexing agents

[0054] A composition of the invention may contain one or more complexing agents. Complexing agents intensify or maintain the cleaning efficiency of the surfactant, mainly by reducing water hardness. This is accomplished by sequestration or chelation (keeping hard minerals in solution), precipitation (forming an insoluble substance), or ion exchange (exchanging electrically charged particles).

[0055] The complexing agents for use in the invention may be of the organic or inorganic type, or a mixture thereof.

Suitable inorganic complexing agents include hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites and mixtures thereof. Specific examples of such materials include sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.

Suitable organic complexing agents include polycarboxylates in acid and/or salt form. When used in salt form, alkali metal (eg sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrates, sodium and potassium tartrates, the sodium and potassium salts of tartaric acid monosuccinate, the sodium and potassium salts of tartaric acid disuccinate, sodium and potassium ethylenediaminetetraacetates, N(2 - hydroxyethyl)-ethylenediamine sodium and potassium triacetates, sodium and potassium nitrilotriacetates and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetates. Polymeric polycarboxylates can also be used, for example polymers of unsaturated monocarboxylic acids (eg acrylic, methacrylic, vinylacetic and crotonic acids) and/or unsaturated dicarboxylic acids (eg maleic, fumaric, itaconic, mesaconic and citraconic acids and their anhydrides). Specific examples of such materials include polyacrylic acid, polymaleic acid and copolymers of acrylic and maleic acid. The polymers 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, and more preferably from about 2,500 to about 75,000.

[0058] Mixtures of any of the materials described above can also be used. Preferred complexing agents for use in the invention may be selected from polycarboxylates (eg citrates) in acid and/or salt form and mixtures thereof.

[0059] The complexing agent, when included, may be present in an amount 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). Transition metal ion chelating agents

[0060] A composition of the invention may contain one or more chelating agents for transition metal ions, for example iron, copper and manganese. These chelating agents can help to improve the stability of the composition and protect, for example, against transition metal catalyzed decomposition of certain components.

Suitable transition metal ion chelating agents include phosphonate in acid and/or salt form. When used in salt form, alkali metal (eg sodium and potassium) or alkanolammonium salts are preferred. Specific examples of these materials include aminotris(methylenephosphonic) acid (ATMP), 1-hydroxyethylidenediphosphonic acid (HEDP), and diethylenetriaminepenta(methylenephosphonic) acid (DTPMP) and their respective sodium or potassium salts. HEDP is preferred. Mixtures of any of the materials described above can also be used.

Transition metal ion chelating agents, when included, may be present in an amount ranging from about 0.1 to about 10%, preferably from about 0.1 to about 3% (in weight based on the total weight of the composition). Fatty acid

[0063] A composition of the invention may, in some cases, contain one or more fatty acids and/or salts thereof.

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

[0065] Fatty acids can be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.

[0066] Mixtures of any of the materials described above can also be used.

[0067] Fatty acids and/or their salts, when included, may be present in an amount ranging from about 0.25 to 5%, more preferably from 0.5 to 5%, most preferably from 0.75 to 4% (by weight based on the total weight of the composition).

[0068] For formula accounting purposes, in the formula, fatty acids and/or their salts (as defined above) are not included in the level of surfactant or level of complexing agents. Dirt Release Polymers

[0069] A composition of the invention will preferably include one or more soil release polymers (SRPs) which help to improve soil release from fabric by modifying the fabric surface during laundering. Adsorption of an SRP onto the tissue surface is promoted by an affinity between the chemical structure of the SRP and the target fiber.

[0070] The SRPs for use in the invention may include various charged (i.e., anionic) and uncharged monomeric units and the structures may be linear, branched or star-shaped. The structure of the

SRP can also include termination groups to control molecular weight or to alter polymer properties, eg surface activity. The average molecular weight (Mw) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.

[0071] The SRPs for use in the invention may be suitably selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol ). The copolyester can also include monomeric units substituted by anionic groups, for example, sulphonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification/oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG") and poly(ethylene glycol) ("PEG"); partially and fully anionic end capped oligomeric esters such as ethylene glycol ("EG"), PG, DMT, and Na-3,6-dioxa-8-hydroxyoctane sulfonate oligomers; non-ionic capped block polyester oligomeric compounds such as those made from Me capped DMT, PEG and EG and/or PG or a combination of DMT, EG and/or PG, Me capped PEG and Na-dimethyl-5-sulfoisophthalate and copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide.

[0072] Other types of SRP for use in the invention include cellulosic derivatives, for example, hydroxyether cellulosic polymers, C1-C4 alkylcelluloses and C4 hydroxyalkylcelluloses; polymers with hydrophobic segments of poly(vinyl ester), eg poly(vinyl ester) graft copolymers, eg C1-C6 vinyl esters (eg poly(vinyl acetate)) grafted onto oxide backbones. polyalkylene; poly(vinyl caprolactam) and related monomer copolymers, for example vinylpyrrolidone and/or dimethylaminoethyl methacrylate; and polyester polymers-

polyamide prepared by the condensation of adipic acid, caprolactam and polyethylene glycol.

Preferred SRPs for use in the invention include copolyesters formed by condensing terephthalic acid ester and diol, preferably 1,2-propanediol, and further comprise a terminus formed from alkylene oxide repeating units with an alkyl group at termination. Examples of these materials have a structure that corresponds to the general formula (V):

O O O O 1

C O R 2 (V) (I) R O C O C3H6 O C a wherein R1 and R2 independently of one another are X-(OC2H4)n-(OC3H6)m; wherein X is C1-4 alkyl and preferably methyl; n is a number from 12 to 120, preferably from 40 to 50; m is a number from 1 to 10, preferably from 1 to 7; and a is a number from 4 to 9. Since they are means, m, n, and a are not necessarily integers for the block polymer.

[0074] Mixtures of any of the materials described above can also be used.

[0075] When included, a composition of the invention will generally comprise from 0.1 to 10%, preferably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the composition) of one or more SRPs (for example, the copolyesters of general formula (V) as described above). rheology modifiers

[0076] A composition of the invention may comprise one or more rheology modifiers. Examples of such materials include polymeric thickeners and/or builders such as hydrophobically modified alkaline swellable emulsion copolymers (HASE). Exemplary HASE copolymers for use in the invention include linear or crosslinked copolymers which are prepared by addition polymerization of a monomeric mixture including at least one acidic vinylic monomer, e.g., (meth)acrylic acid (e.g., methacrylic acid and/or acid acrylic); and at least one associative monomer. The term "associative monomer" in the context of the present invention denotes a monomer having an ethylenically unsaturated section (for addition polymerization with the other monomers in the mixture) and a hydrophobic section. A preferred type of associative monomer includes a polyoxyalkylene section between the ethylenically unsaturated section and the hydrophobic section. Preferred HASE copolymers for use in the invention include linear or crosslinked copolymers which are prepared by addition polymerization of (meth)acrylic acid with (i) at least one associative monomer selected from polyethoxylated C8-C40 alkyl (meth)acrylates (preferably linear or branched C12-C22 alkyl; and (ii) at least one additional monomer selected from C1-C4 alkyl (meth)acrylates, polyacid vinyl monomers (e.g. maleic acid, maleic anhydride and/or salts thereof) and mixtures thereof. The polyethoxylated portion of the associative monomer (V) generally comprises from about 5 to about 100, preferably from about 10 to about 80, and more preferably from about 15 to about 60 repeating oxyethylene units.

[0077] Mixtures of any of the materials described above can also be used.

[0078] When included, a composition of the invention will preferably comprise from 0.1 to 5% (by weight based on the total weight of the composition) of one or more polymeric thickeners, for example the HASE copolymers which are described above.

[0079] The compositions of the invention can also have their rheology modified by the use of one or more external structurants that form a structuring network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose and citrus pulp fiber. The presence of an external structuring agent can provide pseudo-plasticity rheology and also allow materials such as encapsulates and visual indicators to be stably suspended in the liquid. Enzymes

[0080] A composition of the invention may comprise an effective amount of one or more enzymes selected from the group comprising pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. Enzymes are preferably present with corresponding enzyme stabilizers. Other optional components

[0081] A composition of the invention may contain other optional components to enhance performance and/or consumer acceptability. Examples of these components include foam reinforcing agents, preservatives (eg, bactericides), polyelectrolytes, anti-shrink agents, anti-wrinkling agents, antioxidants, sunscreens, anti-corrosive agents, trim agents, antistatic agents, ironing aids, dyes, pearls and/ or opacifiers as well as colorant. Each of these components will be present in an amount effective to accomplish this purpose. These optional components are generally included individually in an amount of up to 5% (by weight based on the total weight of the composition). Packing and Dosing

[0082] A composition of the invention can be packaged as unit doses in wash water-soluble polymeric film. Alternatively, a composition of the invention may be provided in multi-dose plastic packages with a top or bottom closure. A dose meter can be supplied with the package either as part of the cap or as an integrated system.

[0083] A method of washing fabric using a composition of the invention will generally involve diluting the dose of detergent composition to obtain a washing liquid and washing fabrics with the washing liquid thus formed. The fabric washing method can be properly performed in an automatic washing machine with top loading or front loading, or it can be done manually.

[0084] In automatic clothes washers, the dose of detergent composition is typically placed in a dispenser and, from it, is inserted into the machine by the water flowing into the machine, thus forming the washing liquid. Dosages for a typical front loading washing machine (using 10 to 15 liters of water to form the washing liquid) can range from about 10 ml to about 100 ml, preferably from about 15 to 75 ml. Dosages for a typical top loading washing machine (using 40 to 60 liters of water to form the washing liquid) may be larger, eg 100 ml or more. Smaller dosages of detergent (eg 50 mL or less) can be used for manual washing methods (using approximately 1 to 10 liters of water to form the wash liquor).

[0085] A subsequent aqueous rinse and laundry drying step is preferred.

[0086] The invention will now be further described with reference to the following non-limiting Examples. Examples

[0087] All percentages by weight are by weight based on the total weight of the formulation, unless otherwise specified. Examples according to the invention are indicated by a number; whereas comparative examples (not according to the invention) are indicated by a letter.

[0088] Viscosity measurements were performed using an Anton Paar rheometer at room temperature (25 °C).

[0089] Liquid laundry detergent formulations were prepared having the components shown in Table 1. Table 1 % BY WEIGHT

COMPONENT (ACTIVE COMPONENT) Control Example A Alcohol ethoxylate C12-15 (7 EO) 2.04 2.04 Triethanolamine 3.52 3.52 Linear alkylbenzenesulfonic acid (LAS) C12-14 2.72 2.72 Fatty acids, C12 -18 0.4 0.4 1-Hydroxyethane-1,1-diphosphonic acid (HEDP) 0.7 0.7 SLES (3 EO) 2.04 2.04 Polyester SRP 0.47 0.47 Copolymer HASE 1, 05 1.05 EPEI (Sokalan®HP20, ex BASF) - 1.00 Water, dashes qsp up to 100

[0090] The viscosities of the control formulation and the formulation of Example A are shown in Table 2. It can be seen how the inclusion of EPEI in Example A initiates a reduction in the viscosity of the formulation compared to the control. Table 2 Formulation Viscosity at 21s-1 (mPa.s) Control 1230 Example A 537

[0091] A number of other formulations were prepared using a number of different grades of EPEI in a detergent base equivalent to that shown in Table 1. The formulations are shown in Table 3. Table 3

EXAMPLE BCDE 4 5 6 7 8 Component % by weight (active component) Alcohol C12-15 (7 2.04 2.04 2.04 2.04 2.04 2.04 2.04 2.04 2.04 EO) Triethanolamine 3.52 3.52 3.52 3.52 3.52 3.52 3.52 3.52 3.52 LAS 2.72 2.72 2.72 2.72 2.72 2.72 2.72 2.72 2.72 Fatty acids, 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 C12-18 HEDP 0.7 0.7 0.7 0 0.7 0.7 0.7 0.7 0.7 0.7 SLES (3 EO) 2.04 2.04 2.04 2.04 2.04 2.04 2.04 2.04 2.04 Polyester SRP 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 Copolymer 1.05 1.05 1.05 1.05 1.05 1.05 1.05 1.05 1.05 1.05

HASE EPEI (B) 1.00 - - - - - - - - EPEI (C) - 1.00 - - - - - - - EPEI (D) - - 1.00 - - - - - - EPEI (E) - - - 1.00 - - - - - EPEI (4) - - - - 1.00 - - - EPEI (5) - - - - - 1.00 - - - EPEI (6) - - - - - - 1.00 - - EPEI (7) - - - - - - - 1.00 - EPEI (8) - - - - - - - - 1.00 Water, dashes qsp up to 100 (B) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 800 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 15 units of ethoxy per side chain attached to the polyethyleneimine backbone; (C) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (Mw) of 1300 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of

25 ethoxy units per side chain attached to the polyethyleneimine backbone; (D) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 2000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 15 ethoxy units by side chain attached to the polyethyleneimine backbone; (E) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 2000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 20 ethoxy units by side chain attached to the polyethyleneimine backbone; (4) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (Mw) of 2000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 25 ethoxy units per side chain attached to the polyethyleneimine backbone; (5) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 2000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 30 ethoxy units by side chain attached to the polyethyleneimine backbone; (6) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 5000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 20 ethoxy units by side chain attached to the polyethyleneimine backbone; (7) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 5000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of

25 ethoxy units per side chain attached to the polyethyleneimine backbone; (8) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (Mw) of 5000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 30 ethoxy units per side chain attached to the polyethyleneimine backbone;

[0092] The viscosities of the above formulations are shown in Table 4.

Table 4 Formulation Viscosity at 21 s-1 (mPa.s) Example B 389 Example C 726 Example D 542 Example E 746 Example 4 851 Example 5 933 Example 6 802 Example 7 939 Example 8 977

[0093] It can be seen how Examples 4 to 8 (according to the invention) have a higher product viscosity compared to both Example A and Examples B to E (not according to the invention).

[0094] Liquid laundry detergent formulations were prepared using different grades of EPEI in a liquid detergent base thickened with HASE. The formulations are shown in Table 5. Table 5 EXAMPLE F 9 10 11 12 Alcohol C12-15 (7 EO) 2.04 2.04 2.04 2.04 2.04

Triethanolamine 3.52 3.52 3.52 3.52 3.52 LAS 2.72 2.72 2.72 2.72 2.72 Fatty acids, C12-18 0.4 0.4 0.4 0.4 0.4 SLES (3 EO) 2.04 2.04 2.04 2.04 2.04 HASE Copolymer 0.75 0.75 0.75 0.75 0.75 EPEI (Sokalan®HP20, ex BASF) 1 .45 - - - - EPEI (9) - 1.45 - - - EPEI (10) - - 1.45 - - EPEI (11) - - - 1.45 - EPEI (12) - - - - 1.45 water, lines qsp up to 100 (9) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 2000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 32. 5 ethoxy units per side chain attached to the polyethyleneimine backbone (prepared by standard ethoxylation process); (10) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 2000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 32.5 units of ethoxy by side chain attached to the polyethyleneimine backbone (prepared by preferential ethoxylation process); (11) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 5000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 30 ethoxy units by side chain attached to the polyethyleneimine backbone (prepared by standard ethoxylation process); (12) EPEI with polyethyleneimine backbone derived from a polyethyleneimine starting material having an average molecular weight (M w) of 5000 g/mol (before ethoxylation), and polyoxyethylene side chains having an average of 30 ethoxy units by side chain attached to the polyethyleneimine backbone (prepared by preferential ethoxylation process);

[0095] The viscosities of the above formulations are shown in Table 6.

Table 6 Formulation Viscosity at 21s-1 (mPa.s) Example F 185 Example 9 316 Example 10 356 Example 11 352 Example 12 373

[0096] It can be seen how Examples 9 to 12 (according to the invention) have a higher product viscosity compared to Example F (not according to the invention).

[0097] It can also be seen how Example 10, which uses EPEI prepared by the preferential ethoxylation process (described above) provides particularly good results, with a viscosity performance that is superior to that of Example 9 which uses a structure-size EPEI equivalent principal and degree of ethoxylation, but prepared by a standard process.

[0098] It can also be seen how Example 12, which uses EPEI prepared by the preferential ethoxylation process (described above) provides particularly good results, with a viscosity performance that is superior to that of Example 11 which uses a structure-size EPEI equivalent principal and degree of ethoxylation, but prepared by a standard process.

[0099] Liquid laundry detergent formulations were prepared using different grades of EPEI in a salt thickened detergent base. The formulations are shown in Table 7.

Table 7 CONTROL G FORMULATION 13 Component % by weight (active component)

Fluorescent agent 0.1 0.1 0.1 Triethanolamine 1 1 1 NaOH 0.34 0.34 0.34 Citric acid 0.27 0.27 0.27 LAS 3 3 3 SLES (3 EO) 9 9 9 CAPB 3 .15 3.15 3.15 Polyester polymer for 0.5 0.5 0.5 dirt release EPEI (Sokalan®HP20, ex BASF) - 1.55 - EPEI (5) - - 1.55 NaCl 1, 25 1.25 1.25 Fragrance, preservative, water eq up to 100

[0100] The viscosities of the above formulations are shown in Table 8. Table 8 Formulation Viscosity at 21s-1 (mPa.s) Control 5325 Example G 4866 Example 13 5683

[0101] It can be seen as Example 13 (according to the invention) has a higher product viscosity compared to both the control and Example G (not according to the invention).

[0102] Liquid laundry detergent formulations were prepared using different grades of EPEI in a salt thickened detergent base. The formulations are shown in Table 9. Table 9 EXAMPLE H 14 15 16 17

Triethanolamine 1 1 1 1 1 NaOH 0.34 0.34 0.34 0.34 0.34 LAS 3 3 3 3 3 Citric acid 0.27 0.27 0.27 0.27 0.27 SLES (3 EO) 2.04 2.04 2.04 2.04 2.04 CAPB 2 2 2 2 2

EPEI (Sokalan®HP20, ex 1.55 - - - BASF) EPEI (9) - 1.55 - - EPEI (10) - - 1.55 - - EPEI (11) - - - 1.55 - EPEI (12 ) - - - - 1.55 Water, dashes qsp up to 100

[0103] The viscosities of the above formulations are shown in Table 10. Table 10 Formulation Viscosity at 21s-1 (mPa.s) Example H 236 Example 14 328 Example 15 402 Example 16 339 Example 17 392

[0104] It can be seen how Examples 14 to 17 (according to the invention) have a higher product viscosity compared to Example H (not according to the invention).

[0105] It can also be seen how Example 15, which uses EPEI prepared by the preferential ethoxylation process (described above) provides particularly good results, with a viscosity performance that is superior to that of Example 14 which uses a structure-size EPEI equivalent principal and degree of ethoxylation, but prepared by a standard process.

[0106] It can also be seen how Example 17, which uses EPEI prepared by the preferential ethoxylation process (described above) provides particularly good results, with a viscosity performance that is superior to that of Example 15 which uses a structure-size EPEI equivalent principal and degree of ethoxylation, but prepared by a standard process. cleaning performance

[0107] Liquid laundry detergent formulations were prepared having the components shown in Table 11. Table 11 FORMULATION I 18 Component % by weight (active ingredient) MPG 4 4 Citric acid 1 1 Triethanolamine 8 8 alcohol C12-15 (7 EO) 7.5 7.5 LAS 10 10 SLES (3 EO) 7.5 7.5 Fatty acids, C12-18 3 3 EPEI (Sokalan®HP20, ex BASF) 2.5 - (5) EPEI - 2.5 Water , dashes qsp up to 100

[0108] The cleaning performance of the above formulations was evaluated on various stains on white cotton or polyester test fabrics. The stained test fabrics were washed using a 30 ml dosage of test formulation on the cotton cycle at 40°C from an automatic clothes washer with a 26° French hardness water supply.

[0109] After washing, the fabrics were rinsed, dried and then the color was measured by a reflectometer and expressed as the post-wash SRI, which is post-wash SRI = 100 - ΔE

[0110] where ΔE is the color difference of the stained test fabric compared to an unstained control fabric. A higher SRI value indicates cleaner fabrics.

[0111] Each experiment was repeated 6 times and the statistical difference was calculated using a Tukey test. The results are shown in Table 12. Table 12 SRI for SRI for Stain and Fabric 95% NC Example I Example 18 red pottery clay on polyester 76.0 76.2 2.9 red pottery clay on cotton 66, 5 66.1 2.7 garden dirt on cotton 79.5 80.0 2.7 yellow pottery clay on polyester 80.9 83.4 5.4

[0112] It can be seen that the cleaning performance of Example 18 (according to the invention) is at least equivalent to that of Example I (not according to the invention).

Claims (9)

Claims 1. Liquid laundry detergent composition, characterized by comprising ethoxylated polyethyleneimine (EPEI) for an improved product viscosity profile without compromising cleaning performance, wherein the detergent composition comprises: a) from 6% to 50% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from non-soap anionic surfactants, non-ionic surfactants and mixtures thereof, and b) from 0.5% to 10% of an ethoxylated polyethyleneimine (EPEI) having a backbone structure of polyethyleneimine formed by repeating subunits of -[(CH2CH2)N]-; and one or more polyoxyethylene side chains that are attached to internal and/or terminal nitrogen atoms in the polyethyleneimine backbone; wherein the polyethyleneimine backbone is derived from a polyethyleneimine starting material which is ethoxylated to produce EPEI; wherein the polyethyleneimine starting material has an average molecular weight (Mw) ranging from 1800 g/mol to 5000 g/mol (before ethoxylation), and the polyoxyethylene side chains have an average of 25 to 40 ethoxy units per side chain attached to the backbone of the polyethyleneimine. Composition according to claim 1, characterized in that the polyethyleneimine starting material has an average molecular weight (M w) ranging from 1800 g/mol to 2200 g/mol and preferably from 1900 g/mol to 2100 g/mol (before ethoxylation). Composition according to claim 1 or 2, characterized in that the polyoxyethylene side chains have an average of 25 to 35 ethoxy units per side chain attached to the polyethyleneimine backbone. 4. Composition according to claim 1, characterized in that the EPEI (b) corresponds to the following general formula (IV): [E2N-CH2CH2]w[N(E)CH2CH2]x[N(B)CH2CH2]y-NE2 (IV) wherein E represents a polyoxyethylene side chain corresponding to the formula R-(EO)n-, wherein ( EO)n represents an ethylene oxide block; n is a number from 25 to 40, and R is hydrogen; B represents a continuation of the chain structure by branching; w, x and y each range independently from 1 to 100 and (w + x + y) range from 40 to 120. Composition according to claim 4, characterized in that (w + x + y) ranges from 40 to 60. Composition according to any one of claims 1 to 5, characterized in that the EPEI level (b) ranges from 0.7% to 7.5% (by weight based on the total weight of the composition). 7. Composition according to any one of the preceding claims, characterized in that the total level of non-soap anionic surfactants varies from 5% to 30% (by weight based on the total weight of the composition); and in that the total level of nonionic surfactant ranges from 0 to 25% (by weight based on the total weight of the composition). 8. Composition according to any one of the preceding claims, characterized in that it additionally comprises from 0.1% to 5% (by weight based on the total weight of the composition) of one or more soil release polymers (SRPs) selected from copolyesters of dicarboxylic acids, diols and polydiols. A method of washing fabric using a composition as defined in any one of claims 1 to 8, characterized in that the method comprises diluting a dose of the composition to obtain a washing liquid and washing fabrics with the washing liquid thereby formed.