Laundry detergent composition containing MONO alcohol
By adding C10-C16 mono alcohols and specific polymers to liquid detergents, the issues of low sudsing and temperature-dependent viscosity are addressed, resulting in a stable and user-friendly detergent formulation.
Patent Information
- Application Number
- PCT/CN2024/096040
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-05-29
- Publication Date
- 2025-12-04
AI Technical Summary
Existing liquid detergent products often exhibit low sudsing profiles and high viscosity, which are undesirable for consumers, particularly in regions using handwashing or top-loading machines, and have temperature-dependent viscosity issues.
Incorporating C10-C16 linear or branched mono alcohols, polyalkylene imine polymers, and polyalkylene oxide polymers into liquid detergent compositions to achieve a desirable sudsing profile and reduced viscosity temperature dependence.
The composition provides an appropriate viscosity and stable sudsing profile, making it easier to handle and effective in various temperature conditions.
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Figure PCTCN2024096040-FTAPPB-I100003
Abstract
Description
LAUNDRY DETERGENT COMPOSITION CONTAINING MONO ALCOHOLFIELD OF THE INVENTION
[0001] The present invention relates to a laundry detergent composition containing a mono alcohol.BACKGROUND OF THE INVENTION
[0002] As detergent products are evolving, consumer needs in the term of cleaning have been well met. However, there are still some other unmet consumer needs in the field of laundry. Usually, consumers from different regions may have different needs in various performances of detergent products, e.g. anti-bac effect, malodor performances and / or sudsing profile. One of the unmet needs is to provide a desirable sudsing profile for consumers from specific regions. Sudsing profile is important for a cleaning composition, particularly laundry detergents, where the appropriate volume and speed of suds formation, retention and disappearance in the wash and rinse cycles are considered key benchmarks of performance by the consumers. In particular, for consumers accustomed to handwashing or top-loading washing machines (e.g., in developing countries) , high suds is desirable.
[0003] However, compared to powder detergent products containing builders, liquid detergent products containing common surfactants, e.g. C6-C20 linear alkylbenzene sulfonates (LAS) , C6-C20 alkyl sulfates (AS) , C6-C20 alkyl alkoxy sulfates (AAS) , C6-C20 alkoxylated alcohol, usually show a low suds. As such, there is a need for providing a liquid detergent composition having a desirable sudsing profile.
[0004] On the other hand, another unmet need is to manage viscosity of liquid detergent products. Managing viscosity is one of important aspects in laundry detergent formulation work so as to provide products with consumer desirable viscosity and processible in the plant. And, in some regions, consumers prefer liquid detergent products which have relatively low viscosity because consumers in these regions believe high viscosity corresponds to “messy” and difficult to manipulate. Too high viscosity also makes it hard to agitate and fill into bottles during product making. Furthermore, it is desirable that the viscosity of liquid detergent products can remain relatively stable at various temperatures, i.e., does not vary too much depending on temperatures. However, liquid detergent products in market often have a viscosity temperature dependence, i.e., to be significantly more viscous at low temperatures.SUMMARY OF THE INVENTION
[0005] It was discovered by the present inventors that the addition of long-chain fatty alcohols (e.g. C10-C16 linear or branched mono alcohol) as well as the combination of a polyalkylene imine polymer and a polyalkylene oxide polymer in a liquid detergent composition can provide both a desirable sudsing profile and a reduced viscosity temperature dependence.
[0006] Correspondingly, the present invention in one aspect relates to a liquid laundry detergent composition, comprising:
[0007] 1) from 0.02%to 10%, by weight of the composition, of a C10-C16 linear or branched mono alcohol;
[0008] 2) from 0.1%to 10%, by weight of the composition, of a polyalkylene imine polymer,
[0009] 3) from 0.1%to 10%, by weight of the composition, of a polyalkylene oxide polymer, and
[0010] 4) from 4%to 60%, by weight of the composition, of a surfactant system.
[0011] In some embodiments, the composition comprises from 5%to 50%, preferably from 6%to 40%, more preferably from 10%to 30%, by weight of the composition of the surfactant system. Preferably, the surfactant system comprises an anionic surfactant and optionally a non-ionic surfactant.
[0012] In some embodiments, the composition comprises from 0.1%to 10%, preferably from 0.15%to 8%, more preferably from 0.18%to 5%, yet more preferably from 0.2%to 2%, by weight of the composition of a C10-C16 linear or branched mono alcohol. Preferably, the C10-C16 linear or branched mono alcohol is selected from the group consisting of decyl alcohol, dodecyl alcohol, tetradecyl alcohol, cetyl alcohol and any combinations thereof. More preferably, the C10-C16 linear or branched mono alcohol is dodecyl alcohol.
[0013] In some embodiments, the anionic surfactant is selected from the group consisting of C6-C20 linear alkylbenzene sulfonates (LAS) , C6-C20 alkyl sulfates (AS) , C6-C20 alkyl alkoxy sulfates (AAS) , C6-C20 methyl ester sulfonates (MES) , C6-C20 alkyl ether carboxylates (AEC) , or any combinations thereof. Preferably, the anionic surfactant comprises C10-C16 LAS and / or C10-C16 alkyl ethoxy sulfate (AES) .
[0014] In some embodiments, the composition comprises less than 4%, preferably less than 3%, more preferably less than 2%, most preferably less than 1%, by weight of the composition of the non-ionic surfactant.
[0015] In some embodiments, the nonionic surfactant is selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combinations thereof. Preferably, the nonionic surfactant comprises a C6-C20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10.
[0016] In some embodiments, the composition comprises from 4%to 35%, preferably 5%to 30%, by weight of the composition, of C10-C16 AES having a weight average degree of ethoxylation ranging from 1 to 5; and from 1%to 10%, preferably 2%to 8%, by weight of the composition, of C10-C16 LAS.
[0017] In some embodiments, the weight ratio of C10-C16 AES to the C10-C16 linear or branched mono alcohol is from 1 to 60, preferably from 5 to 55, more preferably from 10 to 50, and / or the weight ratio of C10-C16 LAS to the C10-C16 linear or branched mono alcohol is from 5 to 100, preferably from 6 to 50, more preferably from 7 to 30.
[0018] In some embodiments, the polyalkylene imine polymer is present at a level of from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition; and / or the polyalkylene oxide polymer is present at a level of from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition.
[0019] In another aspect, the present invention relates to a method of managing viscosity of a liquid detergent product comprising contacting adding a polyalkylene imine polymer and a polyalkylene oxide polymer into the liquid detergent product.
[0020] It is an advantage of the laundry detergent composition to provide an appropriate viscosity, especially which is desirable for consumers.
[0021] It is another advantage of the laundry detergent composition to provide a reduced viscosity temperature dependence of a liquid detergent composition.
[0022] It is another advantage of the laundry detergent composition to provide a desirable sudsing profile.DETAILED DESCRIPTION OF THE INVENTION
[0023] Definitions
[0024] As used herein, the articles including “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
[0025] As used herein, the terms “comprise” , “comprises” , “comprising” , “include” , “includes” , “including” , “contain” , “contains” , and “containing” are meant to be non-limiting, i.e., other steps and other ingredients which do not affect the end of result can be added. The above terms encompass the terms “consisting of” and “consisting essentially of” .
[0026] As used herein, when a composition is “substantially free” of a specific ingredient, it is meant that the composition comprises less than a trace amount, alternatively less than 0.1%, alternatively less than 0.01%, alternatively less than 0.001%, by weight of the composition, of the specific ingredient.
[0027] As used herein, the term “laundry detergent composition” means a composition for cleaning soiled materials, including fabrics. Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation. The laundry detergent composition compositions may have a form selected from liquid, powder, unit dose such as single-compartment or multi-compartment unit dose, pouch, tablet, gel, paste, bar, or flake. Preferably, the laundry detergent composition is a liquid or a unit dose composition. The term of “liquid laundry detergent composition” herein refers to compositions that are in a form selected from the group consisting of pourable liquid, gel, cream, and combinations thereof. The liquid laundry detergent composition may be either aqueous or non-aqueous, and may be anisotropic, isotropic, or combinations thereof. The term of “unit dose laundry detergent composition” herein refers to a water-soluble pouch containing a certain volume of liquid wrapped with a water-soluble film.
[0028] As used herein, the term "fatty alcohol" means a type of alcohol that is derived from natural fats and oils. It is characterized by having a long hydrocarbon chain, typically containing 8 to 22 carbon atoms, preferably 10 to 16 carbon atoms.
[0029] As used herein, the term "C10-C16 linear or branched mono alcohols" or “C10-C16 linear or branched monohydric alcohols” means a type of alcohol compounds having only one hydroxyl group which comprise a C10-C16 hydrocarbon chain.
[0030] As used herein, the term "alkyl" means a hydrocarbyl moiety which is branched or unbranched, substituted or unsubstituted. Included in the term "alkyl" is the alkyl portion of acyl groups.
[0031] As used herein, the term “washing solution” refers to the typical amount of aqueous solution used for one cycle of laundry washing, preferably from 1 L to 50 L, alternatively from 1 L to 20 L for hand washing and from 20 L to 50 L for machine washing.
[0032] As used herein, the term “soiled fabric” is used non-specifically and may refer to any type of natural or artificial fibers, including natural, artificial, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations.
[0033] Anionic Surfactant
[0034] The laundry detergent composition of the present invention may comprise an anionic surfactant. Particularly, the laundry detergent composition of the present invention may comprise from 0.1%to 50%by weight of the composition, of an anionic surfactant.
[0035] The C6-C20 linear alkylbenzene sulfonate surfactant (LAS) is a required anionic surfactant for the laundry detergent composition of the present invention. In one embodiment, LAS is C10-C16 LAS, preferably C12-C14 LAS.
[0036] The LAS is normally prepared by sulfonation (using SO2 or SO3) of alkylbenzenes followed by neutralization. Suitable alkylbenzene feedstocks can be made from olefins, paraffins or mixtures thereof using any suitable alkylation scheme, including sulfuric and HF-based processes. By varying the precise alkylation catalyst, it is possible to widely vary the position of covalent attachment of benzene to an aliphatic hydrocarbon chain. Accordingly, the LAS herein can vary widely in 2-phenyl isomer and / or internal isomer content.
[0037] In some embodiments of the laundry detergent composition, C6-C20 LAS may be present in an amount ranging from 10%to 100%, preferably from 20%to 99%, more preferably from 30%to 95%, most preferably from 40%to 90%, for example 50%, 60%, 70%, 80%, 90%or any ranges therebetween, by weight of the surfactant system.
[0038] In some embodiments of the laundry detergent composition, the level of LAS is preferably higher than that of any other anionic surfactant contained by such composition, i.e., the LAS is the main anionic surfactant in such composition.
[0039] The anionic surfactant suitable for use in the present disclosure may further comprise C6-C20 alkyl sulfates (AS) , C6-C20 alkyl alkoxy sulfates (AAS) , C6-C20 methyl ester sulfonates (MES) , C6-C20 alkyl ether carboxylates (AEC) , or any combinations thereof. For example, the laundry detergent composition may contain a C6-C20 alkyl alkoxy sulfates (AAxS) , wherein x is about 1-30, preferably about 1-15, more preferably about 1-10, most preferably x is about 1-3. The alkyl chain in such AAxS can be either linear or branched, with mid-chain branched AAxS surfactants being particularly preferred. A preferred group of AAxS include C12-C14 alkyl alkoxy sulfates with x of about 1-3. The amount of AAxS surfactant (s) in the laundry detergent composition of the present invention may range from about 0.05%to about 30%, preferably from about 0.1%to about 20%, more preferably from about 0.5%to about 15%, most preferably from about 1%to about 5%, by weight of the composition.
[0040] In some embodiments, the weight ratio of LAS to AAxS is at least 0.6, preferably at least 0.8, more preferably at least 0.9, most preferably at least 1, for example 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 2, 2.5, 3, 4, 5, 8, 10 or any ranges therebetween.
[0041] In some embodiments of the present disclosure, the anionic surfactant in the composition according to the present disclosure may comprise less than 30%, preferably less than 20%, more preferably less than 10%, most preferably less than 5%, of soap by weight of the surfactant system.
[0042] Nonionic Surfactants (NI)
[0043] The laundry detergent composition of the present invention may comprise a nonionic surfactant. The nonionic surfactant may comprise a nonionic surfactant selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combinations thereof. Preferably, the nonionic surfactant may comprise a C6-C20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10. More preferably, the nonionic surfactant may comprise a C8-C18 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10.
[0044] Non-limiting examples of nonionic surfactants suitable for use herein include: C12-C18 alkyl ethoxylates, such as nonionic surfactants available from Shell; C6-C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethylene oxide / propylene oxide block alkyl polyamine ethoxylates such as available from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from about 1 to about 30; alkylpolysaccharides, specifically alkylpolyglycosides; polyhydroxy fatty acid amides; and ether capped poly (oxyalkylated) alcohol surfactants. Also useful herein as nonionic surfactants are alkoxylated ester surfactants such as those having the formula R1C (O) O (R2O) nR3 wherein R1 is selected from linear and branched C6-C22 alkyl or alkylene moieties; R2 is selected from C2H4 and C3H6 moieties and R3 is selected from H, CH3, C2H5 and C3H7 moieties; and n has a value between about 1 and about 20. Such alkoxylated ester surfactants include the fatty methyl ester ethoxylates (MEE) and are well-known in the art.
[0045] In a particular embodiment, the alkoxylated nonionic surfactant contained by the laundry detergent composition of the present invention is a C6-C20 alkoxylated alcohol, preferably C8-C18 alkoxylated alcohol, more preferably C10-C16 alkoxylated alcohol. The C6-C20 alkoxylated alcohol is preferably an alkyl alkoxylated alcohol with an average degree of alkoxylation of from about 1 to about 50, preferably from about 3 to about 30, more preferably from about 5 to about 20, even more preferably from about 5 to about 9. The alkoxylation herein may be ethoxylation, propoxylation, or a mixture thereof, but preferably is ethoxylation. In one embodiment, the alkoxylated nonionic surfactant is C6-C20 ethoxylated alcohol, preferably C8-C18 alcohol ethoxylated with an average of about 5 to about 20 moles of ethylene oxides, more preferably C10-C16 alcohol ethoxylated with an average of about 5 to about 9 moles of ethylene oxides. The most preferred alkoxylated nonionic surfactant is C12-C14 alcohol ethoxylated with an average of about 7 or 9 moles of ethylene oxide, or C12-C15 alcohol ethoxylated with an average of about 7 moles of ethylene oxide, e.g., 25-7 commercially available from Shell.
[0046] Amphoteric Surfactant
[0047] The amphoteric surfactant suitable for use in the present invention can be selected from the group consisting of C6-C20 alkyldimethyl amine oxides (AO) and combinations thereof.
[0048] Preferably, the amphoteric surfactant is characterized by the following structure:
[0049] where R1 is a C6-20 alkyl, a C6-20 hydroxyalkyl, or a C6-20 alkyl phenyl group; each R2 is a C2-5 alkylene, or a C2-5 hydroxyalkylene group; x is from 0 to about 3; and each R3 is a C1-3 alkyl, a C1-3 hydroxyalkyl, or a polyethylene oxide containing from about 1 to about 3 ethoxylene (EO) units. Preferably, the amphoteric surfactant may be a C8-18 alkyldimethyl amine oxide, preferably a C10-16 alkyldimethyl amine oxide.
[0050] Preferably, the amphoteric surfactant is selected from the group consisting of dodecyldimethyl amine oxide, tetradecyldimethyl amino oxide, and a combination thereof. More preferably, the amphoteric surfactant contains dodecyldimethyl amino oxide having the following formula (III) :
[0051] Such a compound is also referred to as lauryldimethyl amine oxide or dodecydimethyl amine-N-oxide (DDAO) . It is commercially available from Huntsman under the tradename LO.
[0052] The amphoteric surfactant (e.g., amine oxides) in the composition according to the present disclosure may be present in an amount ranging from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%or any ranges therebetween, by weight of the composition.
[0053] The laundry detergent composition of the present invention may further comprise another amphoteric surfactant (i.e., besides AO) . Non-limiting examples of other amphoteric surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Preferred examples include: betaine, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, sulfo and hydroxy betaines, such as N-alkyl-N, N-dimethylammino-1-propane sulfonate where the alkyl group can be C8-C18 or C10-C14.
[0054] Polyalkylene imine polymers
[0055] The liquid detergent composition may comprise a polyalkylene imine polymer which comprising a core structure and a plurality of alkoxylate groups. The core structure may comprise either i) a polyalkylenimine structure comprising, in condensed form, repeating units of formulae (I) , (II) , (III) and (IV) :
[0056] wherein #in each case denotes one-half of a bond between a nitrogen atom and the free binding position of a group A1 of two adjacent repeating units of formulae (I) , (II) , (III) or (IV) ; *in each case denotes one-half of a bond to one of the alkoxylate groups; and A1 is independently selected from linear or branched C2-C6-alkylene; wherein the polyalkylenimine structure consists of 1 repeating unit of formula (I) , x repeating units of formula (II) , y repeating units of formula (III) and y+1 repeating units of formula (IV) , wherein x and y in each case have a value in the range of from 0 to about 150; where the average weight average molecular weight, Mw, of the polyalkylenimine core structure is a value in the range of from about 60 to about 10,000 g / mol; or ii) a polyalkanolamine structure of the condensation products of at least one compound selected from N- (hydroxyalkyl) amines of formulae (I. a) and / or (I. b) ,
[0057] wherein A are independently selected from C1-C6-alkylene; R1, R1*, R2, R2*, R3, R3*, R4, R4*, R5 and R5*are independently selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted; and R6 is selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted. The the plurality of alkylenoxy groups are independently selected from alkylenoxy units of the formula (V)
[0058] wherein: *in each case denotes one-half of a bond to the nitrogen atom of the repeating unit of formula (I) , (II) or (IV) ; A2 is in each case independently selected from 1, 2-propylene, 1, 2-butylene and 1, 2-isobutylene; A3 is 1, 2-propylene; R is in each case independently selected from hydrogen and C1-C4-alkyl; m has an average value in the range of from 0 to about 2; n has an average value in the range of from about 10 to about 50; and p has an average value in the range of from about 0 to about 50.
[0059] In some embodiments, n has an average value in the range of from about 20 to about 50; and p has an average value in the range of from about 10 to about 50.
[0060] Polyalkylene oxide polymers
[0061] The liquid detergent composition may comprise a polyalkylene oxide polymer.
[0062] In some embodiments, the polyalkylene oxide polymer is a polyalkylene graft copolymer comprising
[0063] a) polyalkylene oxide component as a graft base, which has a number average molecular weight of from 1000 to 20,000 Daltons and is based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof,
[0064] b) polyvinyl ester component as side chains, which is derived from a saturated monocarboxylic acid containing from 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic or methacrylic acid, and
[0065] c) polyvinyl five-membered nitrogen heterocycle as side chains.
[0066] In some embodiments, five-membered nitrogen heterocycle is selected from the group consisting of pyrrole, imidazole, pyrazole, oxazole, thiazole, triazole, pyrrolidone and any combinations thereof. Preferably, the polyalkylene oxide polymer comprises polyvinylpyrrolidone or polyvinylimidazole as side chains.
[0067] Particularly, the polyalkylene oxide polymer comprises:
[0068] a) polyalkylene oxide component as a graft base, which has a number average molecular weight of from 1000 to 20,000 Daltons and is based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof,
[0069] b) polyvinyl ester component as side chains, which is derived from a saturated monocarboxylic acid containing from 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic or methacrylic acid, and
[0070] c) polyvinylpyrrolidone or polyvinylimidazole as side chains.
[0071] In some embodiments, the polyalkylene oxide polymer comprises:
[0072] a) polyalkylene oxide component as a graft base, which has a number average molecular weight of from 1000 to 20,000 Daltons and is based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof,
[0073] b) polyvinyl ester component as side chains, which is derived from a saturated monocarboxylic acid containing from 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic or methacrylic acid, and
[0074] c) polyvinylpyrrolidone as side chains,
[0075] wherein the weight ratio of (a) : (c) is from 1: 0.1 to 1: 2, and
[0076] wherein the amount, by weight, of (a) is greater than the amount of (b) .
[0077] In some embodiments, in the polyalkylene oxide polymer
[0078] a) the polyalkylene oxide comprises and preferably consists of ethylene oxide units or ethylene oxide units and propylene oxide units, and
[0079] b) the polyvinyl ester component comprises and preferably consists of vinyl acetate.
[0080] In some embodiments, in the polyalkylene oxide polymer, the polyalkylene oxide has a number average molecular weight of from 2000 to 15,000 Daltons.
[0081] In some embodiments, in the polyalkylene oxide polymer, the weight ratio of (a) : (c) is from 1.0: 0.1 to 1.0: 0.99, preferably from 1.0: 0.3 to 1.0: 0.9.
[0082] In some embodiments, the polyalkylene oxide polymer has a weight average molecular weight of from 4,000 Da to 100,000 Da, preferably 5,000 Da to 100,000 Da, more preferably from 5,000 Da to 50,000 Da, most preferably from 8,000 Da to 20,000 Da.
[0083] The polyalkylene oxide backbone of the graft copolymer of the present invention, which is also referred to herein as the graft base, may comprise repeated units of C2-C10, preferably C2-C6, and more preferably C2-C4, alkylene oxides. For example, the polyalkylene oxide backbone may be: a polyethylene oxide (PEO) backbone; a polypropylene oxide (PPO) backbone; a polybutylene oxide (PBO) backbone; a polymeric backbone that is a linear block copolymer of PEO, PPO, and / or PBO; and combinations thereof. Preferably, the polyalkylene oxide backbone is a PEO backbone. Such a polyalkylene oxide backbone preferably has a number average molecular weight (Mn) from about 1,000 to about 20,000 g / mol, preferably from about 2,000 to about 15,000 g / mol, more preferably from about 3,000 to about 13,000 g / mol, and most preferably from about 5,000 to about 10,000 g / mol.
[0084] The one or more side chains of the graft copolymers of the present invention are formed by polymerizations of a vinyl ester component in the presence of the graft base. Suitable vinyl ester components may be selected from C2-C10 vinyl esters, preferably C2-C6 vinyl esters, and more preferably C2-C4 vinyl carboxylates. For example, the one or more side chains may be selected from the group consisting of polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate, and combinations thereof, while polyvinyl acetate is preferred. The side chains may also be formed by copolymerizing vinyl acetate and / or vinyl propionate with a further ethylenically unsaturated monomer (e.g., methyl acrylate, ethyl acrylate, and n-butyl acrylate) . The fraction of such further ethylenically unsaturated monomer in the total content of the vinyl ester component may be up to 30%by weight. The polyvinyl ester side chains may further be partially saponified, for example, to an extent of up to 15%.
[0085] Such side chains may be present in an amount ranging from about 30%to about 85%, preferably from about 40%to abuot 75%, by total weight of the graft copolymer.
[0086] The graft copolymers of the present invention may have an overall weight average molecular weight (Mw) of from about 3,000 to about 100,000, preferably from about 10,000 to about 50,000, and more preferably from about 20,000 to about 40,000.
[0087] The graft copolymers of the present invention may further feature a narrow molar mass distribution represented by a polydispersity Mw / Mn of generally ≤ about 3, preferably ≤ about 2.8, more preferably ≤ about 2.5, and even more preferably ≤ about 2.3. Most preferably, their polydispersity Mw / Mn is in the range from about 1.5 to about 2.2.
[0088] The vinyl ester component (B) may consist advantageously of (B1) vinyl acetate or vinyl propionate or of mixtures of vinyl acetate and vinyl propionate, particular preference being given to vinyl acetate as the vinyl ester component (B) .
[0089] However, the side chains of the graft polymer can also be formed by copolymerizing vinyl acetate and / or vinyl propionate (B1) and a further ethylenically unsaturated monomer (B2) . The fraction of monomer (B2) in the vinyl ester component (B) may be up to 30%by weight, which corresponds to a content in the graft polymer of (B2) of 24%by weight. Suitable comonomers (B2) are, for example, monoethylenically unsaturated carboxylic acids and dicarboxylic acids and their derivatives, such as esters, amides and anhydrides, and styrene. It is of course also possible to use mixtures of different comonomers. Specific examples include: (meth) acrylic acid, C1-C12-alkyl and hydroxy-C2-C12-alkyl esters of (meth) acrylic acid, (meth) acrylamide, N-C1-C12-alkyl (meth) acrylamide, N, N-di (C1-C6-alkyl) (meth) acrylamide, maleic acid, maleic anhydride and mono (C1-C12-alkyl) esters of maleic acid.
[0090] In a particularly embodiment, the polyalkylene oxide graft copolymer comprises: (a) polyalkylene oxide which has a number average molecular weight of from 1000 to 20,000 Daltons and is based on ethylene oxide, propylene oxide, and / or butylene oxide, (b) polyvinyl ester component as side chains, and (c) polyvinylpyrrolidone or polyvinylimidazole as side chains. Particularly, the polyvinyl ester component is derived from a saturated monocarboxylic acid containing from 1 to 6 carbon atoms.
[0091] Suitable polyalkylene oxides may be based on homopolymers or copolymers, with homopolymers being preferred. Suitable polyalkylene oxides may be based on homopolymers of ethylene oxide or ethylene oxide copolymers having an ethylene oxide content of from 40 mol%to 99 mol%. Suitable comonomers for such copolymers may include propylene oxide, n-butylene oxide, and / or isobutylene oxide. Suitable copolymers may include copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and / or copolymers of ethylene oxide, propylene oxide, and at least one butylene oxide. The copolymers may include an ethylene oxide content of from 40 to 99 mol%, a propylene oxide content of from 1.0 to 60 mol%, and a butylene oxide content of from 1.0 to 30 mol%. The graft base may be linear (straight-chain) or branched, for example a branched homopolymer and / or a branched copolymer.
[0092] Branched copolymers may be prepared by addition of ethylene oxide with or without propylene oxides and / or butylene oxides onto polyhydric low molecular weight alcohols, for example trimethylol propane, pentoses, or hexoses.
[0093] The alkylene oxide unit may be randomly distributed in the polymer or be present therein as blocks.
[0094] The polyalkylene oxides of component (a) may be the corresponding polyalkylene glycols in free form, that is, with OH end groups, or they may be capped at one or both end groups. Suitable end groups may be, for example, C1-C25-alkyl, phenyl, and C1-C14-alkylphenyl groups. The end group may be a C1-alkyl (e.g., methyl) group. Suitable materials for the graft base may include PEG 1000, PEG 2000, PEG 4000, PEG 6000, PEG 8000, PEG 10000, PEG 12000, and / or PEG 20000, which are polyethylene glycols, and / or MPEG 2000, MPEG 4000, MPEG 6000, MPEG 8000 and MEG 10000 which are monomethoxypolyethylene glycols that are commercially available from BASF under the tradename PLURIOLand / or block copolymers made from ethylene oxide-propylene oxide-ethylene oxide (EO-PO-EO) or from propylene oxide-ethylene oxide-propylene oxide (PO-EO-PO) such as PE 6100, PE 6800 or PE 3100 commercially available from BASF under the tradename PLURONIC.
[0095] The polyalkylene oxides may be grafted with N-vinylpyrrolidone or N-vinylimidazole as the monomer of component (c) . Without wishing to be bound by theory, it is believed that the presence of the N-vinylpyrrolidone ( “VP” ) or N-vinylimidazole monomer in the graft copolymers according to the present disclosure provides water-solubility and good film-forming properties compared to otherwise-similar polymers that do not contain the N-vinylpyrrolidone or N-vinylimidazole monomer. The vinyl pyrrolidone or vinyl imidazole repeat unit has amphiphilic character with a polar amide group that can form a dipole, and a non-polar portion with the methylene groups in the backbone and the ring, making it hydrophobic.
[0096] The polyalkylene oxides may be grafted with a vinyl ester as the monomer of component (b) . The vinyl ester may be derived from a saturated monocarboxylic acid, which may contain 1 to 6 carbon atoms, or from 1 to 3 carbon atoms, or from 1 to 2 carbon atoms, or 1 carbon atom. Suitable vinyl esters may be selected from the group consisting of vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl iso-valerate, vinyl caproate, or mixtures thereof. Preferred monomers of component (b) include those selected from the group consisting of vinyl acetate, vinyl propionate, or mixtures thereof, preferably vinyl acetate.
[0097] Conventionally, molecular weights are expressed by their “K-values, ” which are derived from relative viscosity measurements. The graft copolymers may have a K value of from 5.0 to 200, optionally from 5.0 to 50, determined according to H. Fikentscher in 2%strength by weight solution in dimethylformamide at 25C.
[0098] An example of such polyalkylene oxide polymers is disclosed in WO2020 / 005476. Another example of such polyalkylene oxide polymers is disclosed in WO2023 / 017061, e.g. Ex. 1 to Ex. 9 in WO2023 / 017061.
[0099] Other ingredients
[0100] The laundry detergent composition of the present invention may further comprise a cationic surfactant. Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylate quaternary ammonium (AQA) surfactants; dimethyl hydroxyethyl quaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; and amino surfactants, specifically amido propyldimethyl amine (APA) .
[0101] The laundry detergent composition herein may comprise adjunct ingredients. Suitable adjunct materials include but are not limited to: builders, chelating agents, rheology modifiers, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, photobleaches, perfumes, perfume microcapsules, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents, hueing agents, structurants and / or pigments. The precise nature of these adjunct ingredients and the levels thereof in the laundry detergent composition will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used.
[0102] In some embodiments, the laundry detergent composition according to the present disclosure may further comprise from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition, of a fatty acid.
[0103] Composition Preparation
[0104] The laundry detergent composition of the present invention is generally prepared by conventional methods such as those known in the art of making laundry detergent compositions. Such methods typically involve mixing the essential and optional ingredients in any desired order to a relatively uniform state, with or without heating, cooling, application of vacuum, and the like, thereby providing laundry detergent compositions containing ingredients in the requisite concentrations.
[0105] Method of Use
[0106] Another aspect of the present invention is directed to a method of using the laundry detergent composition to treat a fabric. Such method can deliver a color protection benefit. The method comprises the step of administering from 5 g to 120 g of the above-mentioned laundry detergent composition into a laundry washing basin comprising water to form a washing solution. The washing solution in a laundry washing basin herein preferably has a volume from 1 L to 50 L, alternatively from 1 L to 20 L for hand washing and from 20 L to 50 L for machine washing. The temperatures of the laundry washing solution preferably range from 5℃ to 60℃.
[0107] The dosing amount in the method herein may be different depending on the washing type. In one embodiment, the method comprises administering from about 5 g to about 60 g of the laundry detergent composition into a hand washing basin (e.g., about 2-4 L) . In an alternative embodiment, the method comprises administering from about 5 g to about 100 g, preferably from about 10 g to about 65 g of the laundry detergent composition into a washing machine (e.g., about 30-45 L) .
[0108] Test Method
[0109] Test 1: The suds mileage of detergents at the soiled condition
[0110] The suds mileage of detergents compositions at the soiled condition is determined by the SITA instrument (SITA Messtechnik GmbH, Germany) with the method described hereinafter.
[0111] 1. Measuring samples preparation.
[0112] 1.1. Weigh 10g detergent compositions and dissolve in 90g deionized (DI) water to make a 10%w / w sample solution A.
[0113] 1.2. Weigh 1.5L DI water and add 0.21g CaCl2 and 0.09g MgCl2.6H2O and mix it homogeneously to make 4gpg hardness water B.
[0114] 1.3. Weigh 5g TBS (Lubrizol) and 45g peanut oil (brand Luhua) , mix them in a glass bottle and keep in a water bath set at 45 Celsius degrees to get the homogeneous oil solution C.
[0115] 2. Measuring the suds mileage by SITA
[0116] 2.1. SITA measuring program setting.
[0117] Open “Device>Measurement Parameter” on SITA software interface. Set parameter as:
[0118] -Fill (solution) : volume in ml 250mL (check)
[0119] -Wait: Time span in s: 30s
[0120] -Loop1: repetitions 1 (check)
[0121] -Stirrer speed in rpm: 500rpm, duration in s: 20s
[0122] -Loop2: repetitions 3 (check)
[0123] -Stirrer speed in rpm: 1000rpm, duration in s: 60s
[0124] -Wait: Time span in s: 30s
[0125] -Foam volume brightness 255
[0126] -Loop3: repetitions 4 (check)
[0127] -Stirrer speed in rpm: 1000rpm, duration in s: 60s
[0128] -Wait: Time span in s: 30s
[0129] -Foam volume brightness 255
[0130] -Loop4: repetitions 4 (check)
[0131] -Stirrer speed in rpm: 1000rpm, duration in s: 60s
[0132] -Wait: Time span in s: 30s
[0133] -Foam volume brightness 255
[0134] -Loop5: repetitions 7 (check)
[0135] -Stirrer speed in rpm: 1000rpm, duration in s: 60s
[0136] -Wait: Time span in s: 30s
[0137] -Foam volume brightness 255
[0138] -Cleaning: Normal (use hot water and dishwashing detergent with cotton brush to removal of soil residues)
[0139] -Temperature control (depends on actual needs)
[0140] 2.2. Fill in 250ml 4gpg hardness water B in the measuring container of SITA.
[0141] 2.3. Pipette 0.43ml sample solution A in the measuring container.
[0142] 2.4. Start the SITA program set in 2.1
[0143] 2.5. Pipette 0.25ml oil solution C in the measuring container of SITA after the end of the loop 1.
[0144] 2.6. Pipette 0.1ml oil solution C in the measuring container of SITA after the end of the loop 2.
[0145] 2.7. Pipette 0.1ml oil solution C in the measuring container of SITA after the end of the loop 3.
[0146] 2.8. After test finished, right click the data, and select “Result” to download result.
[0147] 3.Average the seven suds volume data point measured in the Loop 4 and the Loop
[0148] 5 set in the 2.1 as the suds mileage index.
[0149] The higher suds milage index represents the stronger capability of the detergent sample to maintain the suds volume at the dirty water bearing with more soils for a prolonged period.
[0150] EXAMPLES
[0151] Example 1: Improved Suds Mileage by Adding Dodecanol in the Liquid Laundry Detergent
[0152] Liquid laundry detergent compositions were prepared containing the ingredients as shown in Table 1 below, in which Sample 1A contains 0.5%dodecanol while Sample 1B contains no dodecanol.
[0153] Table 1
[0154] a C11-13LAS
[0155] b C12-14AE1-3S
[0156] c 25-7 which is C12-C15 alcohol ethoxylated with an average of 7 moles of ethylene oxide as a nonionic surfactant, available from Shell
[0157] d Polyalkylene imine polymer: Polyethyleneimines (PEI) polymer ethoxylated and propoxylated, available from BASF
[0158] e Polyalkylene oxide copolymer with PVP / PVAc-g-PEG at a weight ratio of 20: 30: 50 ratio with a weight average molecular weight 16, 800 Dalton available from BASF
[0159] f Dodecanol from Musim Mas.
[0160] Then, the suds mileage index of the above samples was measured in accordance with Test 1: The suds mileage of detergents at the soiled condition. The results are shown below.
[0161] Table 2
[0162] As the data shown above, it is surprising and unexpected that the addition of dodecanol can deliver a very high suds mileage index compared with nil-dodecanol formula (i.e. Sample 1B) .
[0163] Example 2: Reduced Viscosity Temperature Dependence by the Combination of Polyalkylene Imine Polymer and Polyalkylene Oxide Polymer in the Liquid Laundry Detergent
[0164] Liquid laundry detergent compositions were prepared containing the ingredients as shown in Table 3 below, in which Sample 1A comprises a combination of a polyalkylene imine polymer and a polyalkylene oxide polymer, while Sample 1C and Sample 1D contain a single polymer (i.e. a polyalkylene imine polymer or a polyalkylene oxide polymer alone) respectively. The Sample 1E contains none of the polymers.
[0165] Table 3
[0166] a C11-13LAS
[0167] b C12-14AE1-3S
[0168] c 25-7 which is C12-C15 alcohol ethoxylated with an average of 7 moles of ethylene oxide as a nonionic surfactant, available from Shell
[0169] d Polyalkylene imine polymer: Polyethyleneimines (PEI) polymer ethoxylated and propoxylated, available from BASF
[0170] e Polyalkylene oxide copolymer with PVP / PVAc-g-PEG at a weight ratio of 20: 30: 50 ratio with a weight average molecular weight 16, 800 Dalton available from BASF
[0171] f Dodecanol from Musim Mas.
[0172] Then, the viscosity of the above samples was measured by the rheometer (DHR2, TA Instruments) at 20℃, 22.5℃, 25℃, 27.5℃, 30℃, 33℃ and 35℃ at the shear rate of 20 / s. The results are shown below in which the viscosity unit is cps.
[0173] Table 4
[0174] The temperature dependence of the viscosity can be represented a temperature dependence factor FTr that is defined as the ratio of the viscosity μT at a relative low temperature T to the reference viscosity μTr at a relative high temperature Tr. Here the viscosity at 35℃ is set at the reference viscosity and the temperature dependence factor F30℃ is calculated in the following equation:
[0175] Then, the temperature dependence factor F30℃ of the samples in Table 1 was calculated as the following Table 5.
[0176] Table 5
[0177] As the data shown above, it is surprising and completely unexpected that the combination of a polyalkylene imine polymer and a polyalkylene oxide polymer can achieve the lowest temperature dependence factor. On the contrary, the polyalkylene oxide polymer alone enlarges the temperature dependence factor, while the polyalkylene imine polymer alone can only reduce the temperature dependence to a lower extent. In other words, Sample 1A has the best capability to maintain a constant viscosity when the temperature spans a broader range.
[0178] Example 3: Exemplary Formulations of Liquid Laundry Detergent Compositions
[0179] The following liquid laundry detergent compositions Samples A to F shown in Table 4 are made comprising the listed ingredients in the listed proportions (weight %) .
[0180] Table 4
[0181] 1 Polyalkylene oxide graft copolymer with PVP / PVAc-g-PEG at a weight ratio of 20: 30: 50 ratio with a weight average molecular weight 16, 800 Dalton
[0182] 2 Polyalkylene imine polymer: Polyethyleneimines (PEI) polymer ethoxylated and propoxylated, available from BASF
[0183] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm. ”
[0184] Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
[0185] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims
1.A liquid laundry detergent composition, comprising:1) from 0.02%to 10%, by weight of the composition, of a C10-C16 linear or branched mono alcohol;2) from 0.1%to 10%, by weight of the composition, of a polyalkylene imine polymer,3) from 0.1%to 10%, by weight of the composition, of a polyalkylene oxide polymer, and4) from 4%to 60%, by weight of the composition, of a surfactant system.2.The liquid laundry detergent composition according to Claim 1, wherein the composition comprises from 5%to 50%, preferably from 6%to 40%, more preferably from 10%to 30%, by weight of the composition of the surfactant system,preferably, wherein the surfactant system comprises an anionic surfactant and optionally a non-ionic surfactant.3.The liquid laundry detergent composition according to Claim 1 or 2, wherein the composition comprises from 0.1%to 10%, preferably from 0.15%to 8%, more preferably from 0.18%to 5%, yet more preferably from 0.2%to 2%, by weight of the composition of a C10-C16 linear or branched mono alcohol,preferably, wherein the C10-C16 linear or branched mono alcohol is selected from the group consisting of decyl alcohol, dodecyl alcohol, tetradecyl alcohol, cetyl alcohol and any combinations thereof,more preferably, wherein the C10-C16 linear or branched mono alcohol is dodecyl alcohol.4.The liquid laundry detergent composition according to any one of claims 1 to 3, wherein the anionic surfactant is selected from the group consisting of C6-C20 linear alkylbenzene sulfonates (LAS) , C6-C20 alkyl sulfates (AS) , C6-C20 alkyl alkoxy sulfates (AAS) , C6-C20 methyl ester sulfonates (MES) , C6-C20 alkyl ether carboxylates (AEC) , or any combinations thereof,preferably, wherein the anionic surfactant comprises C10-C16 LAS and / or C10-C16 alkyl ethoxy sulfate (AES) .5.The liquid laundry detergent composition according to any one of claims 1 to 4, wherein the composition comprises less than 4%, preferably less than 3%, more preferably less than 2%, most preferably less than 1%, by weight of the composition of the non-ionic surfactant.6.The liquid laundry detergent composition according to any one of claims 1 to 5, wherein the nonionic surfactant is selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combinations thereof,preferably, wherein the nonionic surfactant comprises a C6-C20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10.7.The liquid laundry detergent composition according to any one of claims 1 to 6, wherein the composition comprises from 4%to 35%, preferably 5%to 30%, by weight of the composition, of C10-C16 AES having a weight average degree of ethoxylation ranging from 1 to 5; and from 1%to 10%, preferably 2%to 8%, by weight of the composition, of C10-C16 LAS.8.The liquid laundry detergent composition according to Claim 7, wherein the weight ratio of C10-C16 AES to the C10-C16 linear or branched mono alcohol is from 1 to 60, preferably from 5 to 55, more preferably from 10 to 50, and / or wherein the weight ratio of C10-C16 LAS to the C10-C16 linear or branched mono alcohol is from 5 to 100, preferably from 6 to 50, more preferably from 7 to 30.9.The liquid laundry detergent composition according to any of preceding claims, wherein the polyalkylene imine polymer is present at a level of from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition; and / or the polyalkylene oxide polymer is present at a level of from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition.10.The liquid laundry detergent composition according to Claim 9, wherein the polyalkylene imine polymer comprises a core structure and a plurality of alkoxylate groups, wherein:the core structure comprisesi) a polyalkylenimine structure comprising, in condensed form, repeating units of formulae (I) , (II) , (III) and (IV) :wherein #in each case denotes one-half of a bond between a nitrogen atom and the free binding position of a group A1 of two adjacent repeating units of formulae (I) , (II) , (III) or (IV) ; *in each case denotes one-half of a bond to one of the alkoxylate groups; and A1 is independently selected from linear or branched C2-C6-alkylene; wherein the polyalkylenimine structure consists of 1 repeating unit of formula (I) , x repeating units of formula (II) , y repeating units of formula (III) and y+1 repeating units of formula (IV) , wherein x and y in each case have a value in the range of from 0 to about 150; where the average weight average molecular weight, Mw, of the polyalkylenimine core structure is a value in the range of from about 60 to about 10,000 g / mol; orii) a polyalkanolamine structure of the condensation products of at least one compound selected from N- (hydroxyalkyl) amines of formulae (I.a) and / or (I.b) ,wherein A are independently selected from C1-C6-alkylene; R1, R1*, R2, R2*, R3, R3*, R4, R4*, R5 and R5*are independently selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted; and R6 is selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted; andthe plurality of alkylenoxy groups are independently selected from alkylenoxy units of the formula (V)wherein: *in each case denotes one-half of a bond to the nitrogen atom of the repeating unit of formula (I) , (II) or (IV) ; A2 is in each case independently selected from 1, 2-propylene, 1, 2-butylene and 1, 2-isobutylene; A3 is 1, 2-propylene; R is in each case independently selected from hydrogen and C1-C4-alkyl; m has an average value in the range of from 0 to about 2; n has an average value in the range of from about 10 to about 50; and p has an average value in the range of from about 0 to about 50.11.The liquid laundry detergent composition according to Claim 10, wherein n has an average value in the range of from about 20 to about 50; and p has an average value in the range of from about 10 to about 50.12.The liquid laundry detergent composition according to Claim 9, wherein said polyalkylene oxide polymer is a polyalkylene graft copolymer comprisinga) polyalkylene oxide component as a graft base, which has a number average molecular weight of from 1000 to 20,000 Daltons and is based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof,b) polyvinyl ester component as side chains, which is derived from a saturated monocarboxylic acid containing from 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic or methacrylic acid, andc) polyvinyl five-membered nitrogen heterocycle as side chains.13.The liquid laundry detergent composition according to Claim 12, wherein five-membered nitrogen heterocycle is selected from the group consisting of pyrrole, imidazole, pyrazole, oxazole, thiazole, triazole, pyrrolidone and any combinations thereof.14.The liquid laundry detergent composition according to Claim 12, wherein the polyalkylene oxide polymer comprisesa) polyalkylene oxide component as a graft base, which has a number average molecular weight of from 1000 to 20,000 Daltons and is based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof,b) polyvinyl ester component as side chains, which is derived from a saturated monocarboxylic acid containing from 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic or methacrylic acid, andc) polyvinylpyrrolidone as side chains,wherein the weight ratio of (a) : (c) is from 1: 0.1 to 1: 2, andwherein the amount, by weight, of (a) is greater than the amount of (b) .15.The liquid laundry detergent composition according to any of preceding claims, wherein the composition further comprises a treatment adjunct which is preferably selected from the group consisting of fatty acids and / or salts thereof, enzymes, encapsulated benefit agents, soil release polymers, hueing agents, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzyme stabilizers, anti-oxidants, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersing agents, soil removal / anti-redeposition agents, polymeric grease cleaning agents, amphiphilic copolymers, brighteners, suds suppressors, dyes, hueing agents, perfume, structure elasticizing agents, fabric softeners, carriers, fillers, hydrotropes, solvents, anti-microbial agents and / or preservatives, neutralizers and / or pH adjusting agents, processing aids, rheology modifiers and / or structurants, opacifiers, pearlescent agents, pigments, anti-corrosion and / or anti-tarnishing agents, and mixtures thereof.
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