Method for treating a fabric

Abstract

A method of treating a fabric with a washing liquid formed by diluting in water a detergent composition comprising at least one surfactant, an alkoxylated oligoamine cleaning synergist, and a fragrance, and contacting the fabric with the washing liquid for 10 to 25 minutes, preferably 10 to 20 minutes, prior to rinsing, wherein the fragrance comprises a fragrance component selected from the group consisting of p-tert-butylcyclohexyl acetate, an aldehyde MNA, dodecanal, 3-(4-isobutyl-2-methylphenyl) propionaldehyde, coumarin, amyl salicylate, and mixtures thereof.

Description

[0001] This invention relates to an improved method for washing fabrics.

[0002] WO 2020 / 216707 (Unilever) discloses a surfactant system for use in household detergent compositions, which is a mixture of (i) at least one sulfonate-functionalized alkyl polysaccharide glycoside, (ii) at least one ethoxylated fatty acid dehydrated sorbitan ester with an average ethoxylation of 15-25, and (iii) at least one fragrance component.

[0003] US 9765282 (Firmenich) discloses a polymer derived from a siloxane derivative and comprising at least one β-thiocarbonyl moiety capable of releasing an active molecule (e.g., an α,β-unsaturated ketone or aldehyde). It also discloses the use of the polymer in fragrances as a flavoring or anti-odor composition, and as a component of a flavoring composition or flavoring article containing the compound.

[0004] Despite existing technologies, there is still a need for improved compositions for treating fabrics in much shorter wash cycles than those conventionally used. We have found that fragrance deposition on fabrics is much more difficult when using rapid wash cycles (where fabrics are treated in the wash liquid for approximately 10 to 25 minutes). With less time to deposit from the wash liquid, any formulation that can deposit in greater quantities is highly desirable.

[0005] Therefore, in a first aspect, a method is provided for treating a fabric with a detergent solution formed by diluting a detergent composition in water and contacting the fabric with the detergent solution for a period of 10 to 30 minutes (preferably 10 to 20 minutes) before rinsing, the detergent composition comprising at least one surfactant, an alkoxylated polyamine cleaning synergist, and a fragrance, wherein the fragrance comprises a fragrance component selected from vertenex acetate, aldehyde MNA, dodecaneal, nympheal, coumarin, amyl salicylate, and mixtures thereof.

[0006] Preferably, the fabric is treated with a washing solution for 10 to 20 minutes.

[0007] Preferably, the detergent composition contains 0.01 to 5% by weight of a fragrance.

[0008] Preferably, the fragrance contains 0.01 to 30% by weight of the fragrance agent p-tert-butylcyclohexyl acetate.

[0009] Preferably, the fragrance contains 0.01 to 30% by weight of the fragrance aldehyde MNA.

[0010] Preferably, the fragrance contains 0.01 to 30% by weight of the fragrance agent dodecanealdehyde.

[0011] Preferably, the fragrance contains 0.01 to 30% by weight of the fragrance 3-(4-isobutyl-2-methylphenyl)propanal.

[0012] Preferably, the fragrance contains 0.01 to 30% by weight of the fragrance coumarin.

[0013] Preferably, the fragrance contains 0.01 to 30% by weight of fragrance amyl salicylate.

[0014] Preferably, the polyamine is a biodegradable alkoxylated oligoamine cleaning synergist.

[0015] surfactants The liquid detergent of the present invention preferably contains 2 to 60% by weight, most preferably 4 to 30% by weight of total surfactant. Anionic and nonionic surfactants are preferred.

[0016] Anionic surfactants are discussed in *Anionic Surfactants: Organic Chemistry*, edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series, CRC Press. Preferred anionic surfactants are sulfonate and sulfate surfactants, preferably alkylbenzene sulfonates, alkyl sulfates, and alkyl ether sulfates.

[0017] Anionic surfactants are preferably added to detergent compositions in the form of salts. Preferred cations are alkali metal ions, such as sodium and potassium. However, the salt form of anionic surfactants can be formed in situ by neutralizing the acidic form of the surfactant with a base (such as sodium hydroxide, or an amine such as monoethanolamine, diethanolamine, or triethanolamine). Weight ratios are calculated for protonated surfactants.

[0018] In anionic and nonionic surfactants, the ethoxy unit can be partially replaced by the propoxy unit.

[0019] Further examples of suitable anionic surfactants are rhamnolipids, α-olefin sulfonates, olefin sulfonates, chain olefin sulfonates, alkane-2,3-dimethylbis(sulfates), hydroxyalkane sulfonates and disulfonates, fatty alcohol sulfates (FAS), chain alkane sulfonates, ester sulfonates, sulfonated fatty acid glycerides, methyl ester sulfonates, alkyl- or alkenyl-succinic acid, dodecenyl / tetradecenylsuccinic acid (DTSA), fatty acid derivatives of amino acids, DATEMs, CITREMs, and diesters and monoesters of sulfosuccinic acid.

[0020] Examples of preferred nonionic surfactants are alcohol ethoxylates and methyl ester ethoxylates. Preferably, the nonionic surfactant is present in a concentration of less than 2% by weight in the formulation. Preferred alcohol ethoxylates are C12 / 14 alcohols having an average ethoxylate concentration of 7 to 9 moles and C16 / C18:1 alcohol ethoxylates having an average ethoxylate concentration of 8 to 12 moles.

[0021] Besides alcohol ether sulfates, linear alkylbenzene sulfonates are preferred anionic surfactants.

[0022] linear alkylbenzene sulfonates LAS (linear alkylbenzene sulfonate) is a preferred anionic surfactant.

[0023] The key intermediate compounds in LAS manufacturing are the relevant chain olefins. These chain olefins (olefins) can be produced by any of the methods mentioned above and can be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, marine carbon, etc.

[0024] In contrast to the method described above, where olefins are processed by hydroformylation and oxidation to form straight-chain alcohols, olefins react with benzene and then sulfonate to form LAS.

[0025] A linear alkylbenzene sulfonate with an alkyl chain length of 10 to 18 carbon atoms. Commercial LAS are mixtures of closely related isomers and homologues of alkyl chains, each containing an aromatic ring sulfonated in the "para" position and attached to the linear alkyl chain at any position except the terminal carbon. The linear alkyl chain preferably has a chain length of 11 to 15 carbon atoms, with the main material having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all possible sulfonylphenyl isomers except for the 1-phenyl isomer. LAS are typically formulated into the composition as an acid (i.e., HLAS) and then at least partially neutralized in situ. Preferably, the linear alkylbenzene sulfonate surfactant is present at 1 to 20% by weight of the composition, more preferably 2 to 15% by weight, and most preferably 8 to 12% by weight.

[0026] Methyl ester ethoxylate (MEE) Preferred nonionic surfactants include methyl ester ethoxylates. Methyl ester ethoxylate surfactants are available in the following forms: R3(-C=O)-O-(CH2CH2-O) n -CH3 R3COO represents the fatty acid portion, such as oleic acid, stearic acid, and palmitic acid. Fatty acid nomenclature uses two numbers, A:B, to describe fatty acids, where A is the number of carbon atoms and B is the number of double bonds. For example, oleic acid is 18:1, stearic acid is 18:0, and palmitic acid is 16:0. The position of the double bonds on the chain can be given in parentheses: oleic acid is 18:1(9), linoleic acid is 18:2(9,12), where 9 is the carbon number starting from the end of COOH.

[0027] The integer n is the molar average of the ethoxylate.

[0028] Methyl ester ethoxylate (MEE) is described in Chapter 8, Synthesis, Properties, and Applications, of GA Smith's Biobased Surfactants (2nd edition), pp. 287-301 (AOCS Press, 2019); Cox ME and Weerasooriva U, J. Am. Oil. Chem. Soc. vol 74 (1997), pp. 847-859; Hreczuch et al., Tenside Surf. Det. vol. 28 (2001), pp. 72-80; C. Kolano, Household and Personal Care Today (2012), pp. 52-55; and A. Hama et al., J. Am. Oil. Chem. Soc. vol. 72 (1995), pp. 781-784. MEE can be prepared by reacting methyl ester with ethylene oxide using calcium or magnesium-based catalysts. The catalyst can be removed or retained in the MEE.

[0029] Alternative preparation routes include transesterification of methyl esters or esterification of carboxylic acids with polyethylene glycol that is capped at one end of the chain with methyl groups.

[0030] Methyl esters can be prepared by transesterification of methanol with triglycerides or by esterification of methanol with fatty acids. Transesterification of triglycerides to fatty acid methyl esters and glycerol is discussed in Fattah et al. (Front. Energy Res., June 2020, Vol. 8, Article 101) and its references. Common catalysts used for these reactions include sodium hydroxide, potassium hydroxide, and sodium methoxide. Esterases and lipases can also be used. Triglycerides are naturally occurring in vegetable fats or oils, with preferred sources being rapeseed oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high-stearic acid / high-oleic acid sunflower oil, high-oleic acid sunflower oil, inedible vegetable oils, tall oil, any mixture thereof, and any derivative thereof. Oils derived from trees are called tall oils. Used cooking oils can be used. Triglycerides can also be obtained from algae, fungi, yeast, or bacteria. Plant sources are preferred.

[0031] Distillation and fractionation methods can be used to produce methyl esters or carboxylic acids to produce the desired carbon chain distribution. Preferred sources of triglycerides are those that contain less than 35% by weight of polyunsaturated fatty acids in the oil prior to distillation, fractionation, or hydrogenation.

[0032] Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, and Unileveroleochemical Indonesia. Biodiesel is a methyl ester and can be obtained from these sources.

[0033] When the ESB is a MEE, it preferably has a molar average of 8-30, more preferably 10-20 ethoxylated groups (EO). The most preferred ethoxylated group contains 12 to 18 EO.

[0034] Preferably, at least 10% by weight, more preferably at least 30% by weight, of the total C18:1 MEE in the composition has 9 to 11 EO, and even more preferably at least 10% by weight exactly 10 EO. For example, when the MEE has a molar average of 10 EO, then at least 10% by weight of the MEE should consist of ethoxylates having 9, 10, and 11 ethoxylate groups.

[0035] The methyl ester ethoxylate preferably has a molar average of 8 to 13 ethoxylate groups (EO). The most preferred ethoxylate has a molar average of 9 to 11 EO, and even more preferably 10 EO. When the MEE has a molar average of 10 EO, then at least 10% by weight of the MEE should consist of ethoxylates having 9, 10, and 11 ethoxylate groups.

[0036] In cases of broader MEE contribution, it is preferred that at least 40% by weight of the total MEE in the composition is C18:1.

[0037] Furthermore, it is preferable that the MEE component also contains some C16 MEE. Therefore, it is preferable that the total MEE component contains 5-50% by weight of C16 MEE as the total MEE. Preferably, the C16 MEE is greater than 90% by weight, more preferably greater than 95% by weight of C16:0.

[0038] Furthermore, it is preferred that the total MEE composition contains less than 15% by weight of total MEE, more preferably less than 10% by weight, and most preferably less than 5% by weight of polyunsaturated C18, namely C18:2 and C18:3. Preferably, C18:3 is present in amounts of less than 1% by weight, more preferably less than 0.5% by weight, and most preferably substantially absent. The degree of polyunsaturation can be controlled by distillation, fractionation, or partial hydrogenation of the feedstock (triglycerides or methyl esters) or MEE.

[0039] Furthermore, it is preferred that the C18:0 component is less than 10% by weight of the total MEE present.

[0040] Furthermore, it is preferred that the component having a carbon chain of 15 or shorter accounts for less than 4% of the total weight of the present MEE.

[0041] The particularly preferred MEE has 2 to 26% by weight of C16:0 chain, 1 to 10% by weight of C18:0 chain, 50 to 85% by weight of C18:1 chain and 1 to 12% by weight of C18:2 chain.

[0042] Preferred sources of alkyl groups in MEE include methyl esters derived from distilled palm oil and distilled high-oleic methyl esters derived from palm kernel oil, partially hydrogenated methyl esters from low-erucic rapeseed oil, methyl esters from high-oleic sunflower oil, methyl esters from high-oleic safflower oil, and methyl esters from high-oleic soybean oil.

[0043] High-oleic oils are available from DuPont (Plenish high-oleic soybean oil), Monsanto (Visitive Gold soybean oil), Dow (ω-9 canola oil, ω-9 sunflower oil), the National Sunflower Association, and Oilseeds International.

[0044] Preferably, the double bonds in the MEE are in the cis configuration, with a weight percentage greater than 80%.

[0045] Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0046] The methyl group of a methyl ester can be replaced by an ethyl or propyl group. Methyl is the preferred choice.

[0047] Preferably, the methyl ester ethoxylate comprises 0.1 to 95% by weight of the methyl ester ethoxylate in the composition. More preferably, the composition comprises 2 to 40% by weight of MEE, and most preferably 4 to 30% by weight of MEE.

[0048] Preferably, the composition contains at least 50% by weight of water, but this depends on the total surfactant content and is adjusted accordingly.

[0049] The weight of anionic surfactants is calculated in protonated form.

[0050] zwitterionic surfactants The composition may contain 0 to 3% by weight of a zwitterionic surfactant.

[0051] Examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphorus, or tertiary sulfonium compounds. Betaines include C10-C14 alkyldimethyl betaine and cocodimethylamidopropyl betaine, C10 to C14 amine oxides, and sulfonyl and hydroxy betaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonate, wherein the alkyl group can be C10 to C14.

[0052] NRE alcohol ether sulfate The composition preferably comprises a narrow-range ethoxylated (NRE) alcohol ether sulfate, which is in the following form: R2-O-(CH2CH2O) p SO3H R2 is an alkyl group, and p is a molar average value of 2.0 to 4.0. Preferably, more than 80% by weight, more preferably more than 95% by weight, of R2 is selected from C12 and C14 chains, and preferably the chains are straight chains.

[0053] The structure of an alcohol ether sulfate with exactly zero ethoxylated groups is as follows: R2-O-SO3H.

[0054] Alcohol ether sulfates are formed by the sulfation of the corresponding alcohol ethoxylates. Alcohol ethoxylates are formed by the ethoxylation of alcohols using a narrow-range ethoxylation catalyst.

[0055] Preferably, the alcohol ether sulfate contains less than 10% by weight, more preferably less than 4% by weight of chains other than C12 and C14, and most preferably less than 10% by weight of C16, C18 and C20 chains.

[0056] Narrow-range ethoxylation catalysts are described in EP3289790 (Procter & Gamble), EP1747183 (Hacros); Santacesatia et al., Ind. Eng. Chem. Res. 1992, 31, 2419-2421; US4239917 (Conoco); Li et al., ACS Omega. 2021 Nov 9; 6(44): 29774-29780; Hreczuch et al., J. Am. OilChem. Soc. 1996, 73, 73-78 and WO2022 / 129374 (Unilever). Ca or Ba-based catalysts are preferred, and most preferably in combination with sulfuric acid.

[0057] Alcohol ether sulfates are also known as alkyl ether sulfates.

[0058] Branched surfactants The compositions of the present invention comprise branched C8-11 alcohol ether sulfate surfactants in the following forms: RO-(EO) n SO3X Wherein R is preferably a branched C8 to C11 alkyl chain (R), more preferably C9 or C10; n is 1 to 6, more preferably 2.5 to 5, and most preferably 3.5 to 4.5; and X is a cation, preferably sodium or amine. The integer n is the molar average. EO represents ethoxy.

[0059] Preferably, the branched alcohol ether sulfate surfactant has the following structure: Where p and m are greater than 1, more preferably m is 4, and p is 2 or m = p+2.

[0060] Preferably, the branched alcohol ether sulfate is prepared from Guerbet alcohol. Preferably, the alcohol used to prepare the branched alcohol ether sulfate surfactant has a single alkyl chain length and configuration greater than 80 mol%. Most preferably, it is a C10 branched alcohol ether sulfate with 4 moles of average ethoxylated 2-propylheptanol.

[0061] Farbe et al. discussed branched alcohols in the chapter on Alcohols, Aliphatic in Ullmann's Encyclopedia of Industrial Chemistry.

[0062] Branched alcohols are available from Sasol, Exxon, and BASF.

[0063] Preferably, the branched surfactant accounts for 1 to 20% by weight of the total surfactant in the composition.

[0064] Considering the typical surfactant loading of the composition as a whole, it is preferred that the content of branched surfactant is 0.05 to 3% by weight of the composition.

[0065] Preferably, the weight ratio of total anionic and / or nonionic surfactant to C8 to C11 branched alcohol ether sulfate is 100:1 to 30:1, more preferably 80:1 to 40:1.

[0066] surfactant ratio Preferably, the weight ratio of total ether sulfate surfactant to total anionic surfactant is 1 to 0.5, more preferably 1 to 0.8.

[0067] Source of alkyl chains The alkyl chain of the surfactant is preferably obtained from a renewable source, more preferably from triglycerides. A renewable source is one in which the material is generated through the natural ecological cycle of a living species, preferably from plants, algae, fungi, yeast, or bacteria, more preferably from plants, algae, or yeast.

[0068] Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil, and tree oil. Oils from trees are known as tall oils. Palm kernel oil and coconut oil are the most preferred sources. The desired C12:C14 ratio can be obtained through fractional distillation / distillation and blending of the components.

[0069] Saad MG et al.'s Energies, 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges Algal oil was discussed in Masri MA et al., Energy Environ. Sci., 2019, 12, 2717. A sustainable, high-performance process for the economic production of waste- free microbial oils that can replace plant-based equivalents The paper describes a method for producing triglycerides from biomass using yeast.

[0070] Inedible vegetable oils may be used, preferably selected from the fruits and seeds of the following plants: Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (broadleaf mahua), Pongamia glabra (koroch seeds), flax seeds, Pongamia pinnata (karanja), Hevea brasiliensis (rubber seeds), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana atabacum (tobacco leaves), Deccan hemp, Ricinus communis L. (castor seeds), Simmondsia. chinensis (Jojoba), arugula (Eruca sativa. L.), sea mango (Cerbera odollam), coriander (Coriandrum sativum L.), croton megalocarpus, Pilu, sea cabbage (Crambe), clove (syringa), kusum (Scheleicheratriguga), stillingia (Stillingia), sal tree (Shorea robusta), Terminalia belerica roxb., Cupea (Cuphea), camellia (Camellia), Champaca (Champaca), Simarouba glauca (Simarouba glauca), Garcinia indica (Garcinia indica), rice bran, balanites (Hingan), desert jujube (Desert) date, artichoke (Cardoon), Syrian milkweed (Asclepiassyriaca), milkweed (Milkweed), small sunflower (Guizotia abyssinica), Ethiopian mustard (Radish Ethiopian mustard), golden sunflower (Syagrus), tung tree (Tung), hairy mountain pine (Idesia polycarpavar).Vesita), algae, thistle poppy (Argemone mexicana L.) (Mexican pricklypoppy), roxburghii boxwood (Putranjiva roxburghii), soapberry (Sapindus mukorossi), neem tree (M. azedarach) (syringe), yellow oleander (Thevettiaperuviana), yellow wine cup flower (Copaiba), milk bush, laurel (Laurel), fragrant two-winged bean (Cumaru), large bitter neem (Andiroba), Piqui, rapeseed (B. napus), Sichuan pepper (Zanthoxylum bungeanum).

[0071] Suitable C12-C14 straight-chain alcohols for use as an intermediate step in the preparation of C12-C14 ether sulfates can be obtained from many different sustainable sources. These include: Primary sugar Primary sugars are obtained from sucrose or sugar beets, and can be fermented to form bioethanol. Bioethanol is then dehydrated to form bioethylene, which then undergoes olefin metathesis to form alkenes. These alkenes are then processed into straight-chain alcohols by hydroformylation or oxidation.

[0072] An alternative method can be used, which also utilizes primary sugars to form straight-chain alcohols, wherein the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are then hydrolyzed into straight-chain fatty acids, which are then reduced to form straight-chain alcohols.

[0073] biomass Biomass, such as forest products, rice husks, and wheat straw, can be processed into syngas through gasification. Fischer Tropsc In the reaction, these are processed into alkanes, which are then dehydrogenated to form alkenes. These alkenes can be processed in the same way as the chain alkenes described above [primary sugars].

[0074] An alternative method is to convert the same biomass into polysaccharides via steam explosion, which can then be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol, which is further dehydrated to form bioethylene. This bioethylene is then processed into a straight-chain alcohol as described above [primary sugars].

[0075] waste plastics Waste plastics are pyrolyzed to form pyrolysis oil. This oil is then fractionated to form straight-chain alkanes, which are then dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].

[0076] Alternatively, the pyrolysis oil is cracked to form ethylene, which is then processed by olefin metathesis to form the desired chain olefins. These are then processed into straight-chain alcohols as described above [primary sugars].

[0077] Urban solid waste MSW is converted into syngas through gasification. From the syngas, it can be processed as described above [primary sugars], or it can be converted into ethanol via an enzymatic process before dehydrogenation to ethylene. Ethylene can then be... Ziegler The process converts it into a straight-chain alcohol.

[0078] MSW can also be converted into pyrolysis oil by gasification, and then fractionated to form alkanes. These alkanes are then dehydrogenated to form alkenes, and then straight-chain alcohols.

[0079] Ocean carbon There are various carbon sources from marine communities such as seaweed and giant kelp. From these marine communities, triglycerides can be separated from the source and then hydrolyzed to form fatty acids, which are then reduced to straight-chain alcohols in the usual way.

[0080] Alternatively, the raw materials can be separated into polysaccharides, which are then enzymatically degraded to form secondary sugars. These can be fermented to produce bioethanol, and then processed as described above for [primary sugars].

[0081] waste oil Waste oil, such as used cooking oil, can be physically separated into triglycerides, which are then broken down as described above to form straight-chain fatty acids and then straight-chain alcohols.

[0082] Alternatively, used cooking oil can undergo the Neste process, whereby the oil is catalytically cracked to produce bio-ethylene. It is then processed as described above.

[0083] Methane capture Methane capture methods capture methane from landfills or fossil fuel production. Methane can be gasified to form syngas. The syngas can then be processed as described above, thereby converting it to methanol before being converted to a straight-chain alcohol via hydroformylation oxidation. Fischer Tropsch (Reaction) and then olefins.

[0084] Alternatively, syngas can be obtained through... Fischer Tropsch Then it is dehydrogenated into alkanes and then alkenes.

[0085] Carbon capture Carbon dioxide can be captured by any of a number of well-known methods. Carbon dioxide can be converted to carbon monoxide via a reverse water-gas shift reaction, and it can then be converted to syngas using hydrogen in an electrolytic reaction. The syngas is then processed as described above and converted to methanol and / or alkanes before reacting to form olefins.

[0086] Alternatively, the captured carbon dioxide is mixed with hydrogen before being enzymatically treated to form ethanol. This is a process developed by Lanzatech. From this, ethanol is converted to ethylene, and then processed as described above into olefins and then straight-chain alcohols.

[0087] The above method can also be used to obtain the C12 / 14 chain of C12 / 14 ether sulfate.

[0088] Preferably, the composition is visually transparent.

[0089] Preferably, the composition contains 10 to 80% by weight of water.

[0090] Preferably, the liquid detergent contains 1 to 5% by weight of ethanol.

[0091] Liquid laundry detergent In the context of this invention, the term "laundry detergent" refers to a formulation intended for and capable of wetting and cleaning household garments such as clothing, linens, and other home textiles. The object of this invention is to provide compositions that, upon dilution, can form a liquid laundry detergent composition in the manner now described.

[0092] In a preferred embodiment, the liquid composition is isotropic.

[0093] The term "linen products" is commonly used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles can include woven, nonwoven, and knitted fabrics; and can include natural or synthetic fibers such as silk, linen, cotton, polyester, polyamide fibers such as nylon, acrylic, acetate, and their blends, including cotton and polyester blends.

[0094] Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine-wash and liquid color-protecting detergents, such as those suitable for hand washing or washing delicate garments (e.g., garments made of silk or wool) in the wash cycle of an automatic washing machine.

[0095] In the context of this invention, the term "liquid" means that the continuous phase or main component of the composition is liquid, and that the composition is flowable at 15°C and above. Therefore, the term "liquid" can encompass emulsions, suspensions, and compositions having a flowable but firmer consistency, referred to as gels or pastes. The viscosity of the composition is preferably at 25°C and 21 seconds. -1 The shear rate is from 200 to about 10,000 mPa·s. This shear rate is the shear rate typically applied to the liquid when poured from the bottle. The pourable liquid detergent composition preferably has a viscosity of 200 to 1,500 mPa·s, more preferably 200 to 700 mPa·s.

[0096] The compositions according to the invention may suitably have an aqueous continuous phase. "Aqueous continuous phase" refers to a water-based continuous phase. Preferably, the composition contains at least 50% by weight of water, more preferably at least 70% by weight of water.

[0097] Alkyl ether sulfates can be provided as a single feedstock component or as a mixture of components.

[0098] In the case where the composition comprises a mixture of C16 / 18 source materials for alkyl ether sulfates and more conventional C12 alkyl chain length materials, it is preferred that the C16 / 18 alkyl ether sulfates in the composition account for at least 10% by weight of the total alkyl ether sulfates, more preferably at least 50% by weight, even more preferably at least 70% by weight, particularly preferably at least 90% by weight, and most preferably at least 95% by weight of the alkyl ether sulfates.

[0099] Alcohol ethoxylates can be provided as a single feedstock component or as a mixture of components.

[0100] Preferably, the choice and amount of surfactant make the composition and the diluted mixture is isotropic in nature.

[0101] Fragrance The composition contains a fragrance, and preferably the fragrance is present in 0.01 to 5% by weight of the composition, more preferably 0.1 to 1% by weight.

[0102] In addition to the claimed fragrance components, the fragrance may contain further fragrance components as described below.

[0103] Preferably, the fragrance comprises a component selected from the following: ethyl-2-methylvalerate (matricyl ester), limonene, (4Z)-cyclopentadecano-4-en-1-one, dihydromyrcenol, dimethylbenzyl acetate carbonate, benzyl acetate, spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)], benzyl acetate, rose ether, geraniol, methylnonylacetaldehyde, decanal, octanal, undecyl, and verdyl acetate. Raw materials including acetate, tert-butylcyclohexyl acetate, cyclamal, β-ionone, hexyl salicylate, tonalid, [2-(cyclohexyloxy)ethyl]benzene, octahydrotetramethylacetophenone (OTNE), benzene, toluene, xylene (BTX), such as 2-phenylethanol, phenoxanol and mixtures thereof; cyclododecanone raw materials, such as habolonolide; phenolic raw materials, such as hexyl salicylate; C5 block or oxygen-containing heterocyclic raw materials, such as γ-decyl lactone, methyl dihydrojasmonate and mixtures thereof; terpene raw materials, such as dihydromyrcenol, linalool, terpinene, camphor, citronellol and mixtures thereof; alkyl alcohol raw materials, such as ethyl-2-methylbutyrate; diacid raw materials, such as ethylene glycol brassinate; and mixtures thereof.

[0104] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component ethyl-2-methylvalerate (chamomile ester).

[0105] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component limonene.

[0106] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component (4Z)-cyclopentadecano-4-en-1-one.

[0107] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component dimethyl benzyl acetate.

[0108] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component dihydromyrcene alcohol.

[0109] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component rose ether.

[0110] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component tert-butylcyclohexyl acetate.

[0111] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component tricyclodecenyl acetate.

[0112] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component benzyl acetate.

[0113] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)].

[0114] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component geraniol.

[0115] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component methylnonylacetaldehyde.

[0116] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component cyclamate.

[0117] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the aromatic component β-ionone.

[0118] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component hexyl salicylate.

[0119] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component, musk.

[0120] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, and particularly preferably 6 to 10% by weight of the fragrance component [2-(cyclohexyloxy)ethyl]benzene.

[0121] Preferably, the fragrance contains a component selected from benzene, toluene, and xylene (BTX) raw materials. More preferably, the fragrance component is selected from 2-phenylethanol, phenylamyl alcohol, and mixtures thereof.

[0122] Preferably, the fragrance contains a component selected from cyclododecyl ketone raw materials. More preferably, the fragrance component is habolonolide.

[0123] Preferably, the fragrance contains a component selected from phenolic raw materials. More preferably, the fragrance component is hexyl salicylate.

[0124] Preferably, the fragrance comprises a component selected from C5 block or oxygen-containing heterocyclic raw materials. More preferably, the fragrance component is selected from γ-decanolide, methyl dihydrojasmonate, and mixtures thereof.

[0125] Preferably, the fragrance contains a component selected from terpene raw materials. More preferably, the fragrance component is selected from linalool, terpinene, camphor, citronellol, and mixtures thereof.

[0126] Preferably, the fragrance contains a component selected from alkyl alcohol raw materials. More preferably, the fragrance component is ethyl-2-methylbutyrate.

[0127] Preferably, the fragrance contains a component selected from diacid raw materials. More preferably, the fragrance component is ethylene glycol brassinate.

[0128] Preferably, the fragrance components listed above are present in the final detergent composition at a weight percentage of 0.0001 to 1% of the composition.

[0129] Chelating agents Detergent compositions may also preferably contain detergent builders or chelating agents. Examples include alkali metals, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates, aminocarboxylates, and polyacetylated carboxylates. Specific examples include sodium, potassium, and lithium salts of oxadiosuccinic acid, benzohexanic acid, benzene polycarboxylic acids, and citric acid. Other examples include DEQUEST™, an organophosphonate chelating agent sold by Monsanto, and alkyl hydroxyphosphonates.

[0130] Other suitable organic builders include high molecular weight polymers and copolymers known to have builder properties. For example, such materials include suitable polyacrylic acid, polymaleic acid, and polyacrylic acid / polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALAN™. If used, the organic builder material may comprise from about 0.5% to 20% by weight of the composition, preferably from 1% to 10% by weight. Preferably, the builder content is less than 10% by weight of the composition, preferably less than 5% by weight.

[0131] More preferably, the liquid laundry detergent formulation is a non-phosphate-based laundry detergent formulation, i.e., containing less than 1% by weight of phosphate. Most preferably, the laundry detergent formulation is non-agent-based, i.e., containing less than 1% by weight of a detergent builder. Typically, in liquids, the preferred chelating agent is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), for example, sold as Dequest 2010. Also suitable but less preferred due to its poorer cleaning effect is Dequest® 2066 (diethylenetriaminepenta(methylenephosphonic acid) or DTPMP heptasodium). However, it is preferred that the composition contains less than 0.5% by weight of a phosphonate-based chelating agent, and more preferably less than 0.1% by weight of a phosphonate-based chelating agent. Most preferably, the composition does not contain a phosphonate-based chelating agent.

[0132] Preferably, the chelating agent is an aminocarboxylate chelating agent. Preferably, the aminocarboxylate is selected from GLDA and MGDA.

[0133] Preferably, the aminocarboxylate is present in the composition at 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, even more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

[0134] Glutamic acid diacetic acid (GLDA) GLDA can exist in the form of salts of GDLA or mixtures of salts of GDLA and GDLA. Preferred salt forms include mono-, di-, tri-, or tetra-alkali metal salts of GLDA and mono-, di-, tri-, or tetra-ammonium salts. The alkali metal salt of glutamate diacetate (GDLA) is preferably selected from lithium salts, potassium salts, and more preferably sodium salts of GLDA.

[0135] Glutamic acid diacetic acid (GLDA) can be partially or preferably completely neutralized with a corresponding base. Preferably, the average 3.5 to 4 COOH groups of GLDA are neutralized with an alkali metal, more preferably with sodium. Most preferably, the composition comprises a tetrasodium salt of GLDA.

[0136] GLDA is at least partially neutralized with an alkali metal, more preferably with sodium or potassium, and most preferably with sodium.

[0137] GLDA salts can be alkali metal salts of L-GLDA, alkali metal salts of D-GLDA, or mixtures of enantiomer-enriched isomers.

[0138] Preferably, the composition comprises a mixture of L- and D-enantiomers of glutamic acid diacetic acid (GLDA) or their corresponding mono-, di-, tri- or tetra-alkali metal salts or mono-, di-, tri- or tetra-ammonium salts or mixtures thereof, said mixture comprising primarily the corresponding L-isomer, with an enantiomer excess ranging from 10 to 95%.

[0139] Preferably, the GLDA salt is essentially L-glutamic acid diacetic acid that is at least partially neutralized with an alkali metal.

[0140] Sodium salts of GLDA are preferred.

[0141] A suitable commercial source of GLDA in the tetrasodium form is DISSOLVINE® GL, which is available from Nouryon.

[0142] Preferably, the amount of GLDA in the composition is 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, even more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

[0143] Methylglycine diacetic acid (MGDA) Preferred salt forms include mono-, di-, tri-, or tetra-alkali metal salts and mono-, di-, tri-, or tetra-ammonium salts of MGDA. The alkali metal salts are preferably selected from lithium and potassium salts of MGDA, and more preferably sodium salts.

[0144] Sodium salts of methylglycine diacetic acid are preferred. Trisodium salts of MGDA are particularly preferred.

[0145] MGDA can be partially or preferably completely neutralized with a corresponding alkali metal. Preferably, an average of 2.7 to 3 COOH groups per molecule of MGDA are neutralized with an alkali metal, and more preferably with sodium.

[0146] MGDA can be selected from racemic mixtures of alkali metal salts of MGDA and pure enantiomers (such as alkali metal salts of L-MGDA and alkali metal salts of D-MGDA), and mixtures enriched with enantiomers.

[0147] Suitable commercial sources of MGDA in the trisodium form are TRILON® M from BASF and Dissolvine® M-40 from Nouryon.

[0148] Preferably, the amount of MGDA in the composition is 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, even more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

[0149] Small amounts of aminocarboxylates can contain cations other than alkali metals. Therefore, it is possible that small amounts, such as 0.01 to 5 mol%, may contain alkaline earth metal cations, such as Mg. 2+ or Ca 2+GLDA may contain trace amounts of impurities derived from its synthesis, such as lactic acid, alanine, propionic acid, etc. In this case, "trace amounts" means a total of 0.1 to 1% by weight, referring to the chelating agent, aminocarboxylate.

[0150] Preferably, the chelating agent is a tertiary amine-based chelating agent in the form of NR1R2R3, which further contains secondary and / or primary amines selected from: HNR1R2, HNR1R3, HNR2R3, HNR1R1, HNR2R2, HNR3R3 (secondary amine); and H2NR1, H2NR2, and H2NR3 (primary amines).

[0151] The molar ratio of the tertiary amine to the sum of the primary and secondary amines is 3:1 to 100:1, preferably greater than 5:1 to 100:1, more preferably greater than 8:1 to 100:1, and most preferably greater than 20:1 to 1000:1.

[0152] R1, R2 and R3 are independently selected from aliphatic carboxylic acids containing a portion with a molecular weight of less than 150, preferably of the formula CH(X)COOH, wherein X is an organic group containing only C, H and O, more preferably selected from CH2COOH, CH(CH3)COOH, CH(COOH)CH2CH2COOH, and preferably R1=R2=CH2COOH.

[0153] The levels of secondary and primary amines can be controlled through synthetic chemistry, chromatographic separation, and careful process control using the Hoffmann method.

[0154] NR1R2R3 refers to the following chemical structures: organic acids The composition preferably contains an organic acid. Preferably, the organic acid has the general formula R-CH(OH)-COOH, wherein R is a straight-chain C1-C5, more preferably C2-C4, and most preferably C4 alkyl.

[0155] Preferably, at least two of the C1-4 straight-chain carbon atoms, more preferably all carbon atoms, are replaced by OH groups. Preferably, R contains a terminal COOH group.

[0156] Preferred examples are lactic acid, tartaric acid, gluconic acid, mucoic acid, and glucoheponic acid. Most preferably, the organic acid is gluconic acid.

[0157] Organic acids can be in their D or L form.

[0158] Gluconic acid can be selected from racemic mixtures of gluconic acid salts (glucuronides) and racemic mixtures of pure enantiomers (such as alkali metal salts of L-gluconic acid, alkali metal salts of D-gluconic acid) and enantiomer-enriched isomers. The D-isomer form is preferred.

[0159] Preferably, the organic acid is present in the range of 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 4% by weight, still more preferably 0.5 to 3% by weight, and most preferably 0.8 to 2% by weight (based on the weight of the composition). Its protonated form is measured.

[0160] In the most preferred embodiment, the composition comprises GLDA and / or MGDA and gluconic acid, more preferably GLDA and gluconic acid.

[0161] External structuring agent The compositions of the present invention can be further modified in terms of their rheological properties by using one or more external structuring agents that form a structured network within the composition. Examples of such materials include crystallizable glycerides, such as hydrogenated castor oil; microfibrillated cellulose; and citrus pomace fiber. The presence of external structuring agents can provide shear-thinning rheology and can also enable materials such as encapsulants and visual cues to be stably suspended in liquids.

[0162] The composition preferably contains crystallizable glycerides.

[0163] As described in WO2011 / 031940, crystallizable glycerides can be used to form externally structured systems, the contents of which, in particular, concerning the manufacture of ESS, are incorporated herein by reference. When an ESS is present, the ESS of the present invention preferably comprises: (a) a crystallizable glyceride; (b) an alkanolamine; (c) an anionic surfactant; (d) additional components; and (e) optional components. Each of these components will be discussed in detail below.

[0164] Crystallizable glycerides used herein preferably include “hydrogenated castor oil” or “HCO”. The HCO used herein can most generally be any hydrogenated castor oil, as long as it is capable of crystallizing in an ESS premix. Castor oil may include glycerides, particularly triglycerides, which contain a C10 to C22 alkyl or alkenyl moiety (which incorporates a hydroxyl group). The hydrogenation of castor oil to prepare HCO involves converting the double bond (which may be present in the feedstock oil such as the castor oil base moiety) to a saturated hydroxyalkyl moiety (e.g., hydroxystearyl). In some embodiments, the HCO herein may be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. HCO can be processed in any suitable starting form, including but not limited to those selected from solids, melts, and mixtures thereof. The level of HCO present in the ESS of the present invention is typically from about 2% to about 10% by weight, from about 3% to about 8% by weight, or from about 4% to about 6% by weight of the structured system. In some implementations, the percentage of hydrogenated castor oil delivered to the finished laundry detergent product is less than about 1.0%, typically 0.1% to 0.8%.

[0165] Useful HCO3 may have the following properties: a melting point of about 40°C to about 100°C, or about 65°C to about 95°C; and / or an iodine value ranging from 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of HCO3 can be measured using ASTM D3418 or ISO 11357; both tests utilize DSC: Differential Scanning Calorimetry. HCO3 used in this invention includes those commercially available. Non-limiting examples of commercially available HCO3 used in this invention include: THIXCIN(R) from Rheox, Inc. Further examples of useful HCO can be found in U.S. Patent 5,340,390. The castor oil source used for hydrogenation to form HCO can be any suitable origin, such as from Brazil or India. In a suitable embodiment, castor oil is hydrogenated using a precious metal (e.g., a palladium catalyst), and the hydrogenation temperature and pressure are controlled to optimize the hydrogenation of the double bonds in natural castor oil while avoiding unacceptable levels of dehydroxylation.

[0166] This invention is not intended to relate solely to the use of hydrogenated castor oil. Any other suitable crystallizable glycerides can be used. In one example, the structuring agent is a triglyceride of substantially pure 12-hydroxystearic acid. This molecule represents the pure form of a fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is fairly stable but can vary. Similarly, the hydrogenation process can vary. Any other suitable equivalent material can be used, such as a mixture of triglycerides, wherein at least 80% by weight is derived from castor oil. Exemplary equivalent materials consist primarily or substantially of triglycerides; or primarily or substantially of a mixture of diglycerides and triglycerides; or primarily or substantially of a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of the mixture of glycerides) of monoglycerides; or primarily or substantially of any of the aforementioned glycerides with a limited amount (e.g., less than about 20% by weight of the corresponding acid hydrolysis product of any of the glycerides). The aforementioned condition is that the major fraction of any of the glycerides, typically at least 80% by weight, is chemically identical to a fully hydrogenated glycerol ester of castor oil, i.e., a glycerol ester of 12-hydroxystearic acid. For example, it is known in the art to modify hydrogenated castor oil so that, in a given triglyceride, it has two 12-hydroxystearic acid fractions and one stearic acid fraction. Similarly, it is foreseeable that hydrogenated castor oil may not be fully hydrogenated. Conversely, this invention does not include poly(alkoxylated) castor oil when it does not meet the melt standard.

[0167] The melting point of the crystallizable glycerides used in this invention can be from about 40 degrees Celsius to about 100 degrees Celsius.

[0168] Hydroxamic acid Preferably, the composition comprises isohydroxamic acid.

[0169] Whenever the terms “hydroxamic acid” or “hydroxamic salt” are used, this covers both the hydroxamic acid and the corresponding hydroxamic salt (a salt of the hydroxamic acid), unless otherwise stated.

[0170] Hydroxamic acids are a class of compounds in which a hydroxylamine is inserted into a carboxylic acid. The general structure of hydroxamic acids is as follows: (Equation 1) Where R 1 These are organic residues, such as alkyl or alkenyl groups. Hydroxamic acids can exist as their corresponding alkali metal salts or hydroxamic acid salts. Preferred salts are potassium salts.

[0171] Hydroxamic acid salts can be conveniently formed from the corresponding hydroxamic acids by substituting the hydrogen atom with a cation: (Equation 2) L+ It is a monovalent cation, such as an alkali metal (e.g., potassium, sodium) or ammonium or substituted ammonium.

[0172] In this invention, isohydroxamic acid or its corresponding isohydroxamic acid salt has the following structure: (Equation 3) Where R 1 yes Straight or branched C4-C 20 alkyl, or Substitution of C4-C with straight or branched chains 20 alkyl, or Straight or branched C4-C 20 alkenyl, or Substitution of C4-C with straight or branched chains 20 alkenyl, or Alkyl ether group CH3(CH2) n (EO) m Where n is 2 to 20, m is 1 to 12, or a substituted alkyl ether group CH3(CH2). n (EO) m Where n is 2 to 20, m is 1 to 12, and the substitution type includes one or more of NH2, OH, S, -O- and COOH. And R 2 Selected from hydrogen and the formation and branching of R 1 A part of the cyclic structure of a group.

[0173] The preferred isohydroxamic acid is R. 2 It is hydrogen, R 1 It is C8-C 14 Alkyl groups, preferably n-alkyl groups, and most preferably saturated ones.

[0174] In the context of this invention, the general structure of isohydroxamic acid is indicated in Formula 3, and R 1 As defined above. When R 1 It is an alkyl ether group CH3(CH2). n (EO) m When n is 2 to 20 and m is 1 to 12, the alkyl portion is end-capped on this side. Preferably, R 1 Selected from C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 and C 14 n-alkyl, most preferably R 1 It is at least C 8-14 n-alkyl. When using C8 materials, this is called octylhydroxamic acid. Potassium salts are particularly useful.

[0175] Potassium octyl isohydroxamic acid However, other hydroxamic acids, while less preferred, are also suitable for use in this invention. These suitable compounds include, but are not limited to, the following: These hydroxamic acids include lysine hydroxamic acid salt, methionine hydroxamic acid salt, and valine hydroxamic acid salt, and are commercially available.

[0176] Hydroxamic acids are thought to work by binding with metal ions present in dirt on fabrics. This binding action (which is actually the known chelating property of hydroxamic acid salts) itself has no use in removing dirt from fabrics. The key is the "tail" of the hydroxamic acid, namely the R group. 1 Subtract the group R 2 Fold back to any branch on the oxime nitrogen. The tail is selected to have an affinity for the surfactant system. This means that the detergency of the already optimized surfactant system is further enhanced by the use of isohydroxamic acid, as it effectively marks stubborn particulate matter (clay) as “dirt” so that it can be removed by the surfactant system acting on isohydroxamic acid molecules now fixed to the particles by binding with metal ions embedded in clay-type particles. The non-soap-based detergency surfactant adheres to the isohydroxamic acid, resulting in more surfactant interaction with the fabric overall, leading to better detergency. Thus, the isohydroxamic acid acts as a linking molecule, thereby promoting the removal of particulate dirt from the fabric and suspending it in the washing liquid, and thus improving the primary detergency.

[0177] Hydroxamic acid has a higher affinity for transition metals (such as iron) than for alkaline earth metals (such as calcium and magnesium). Therefore, hydroxamic acid mainly functions to improve the removal of dirt from fabrics, especially particulate dirt, rather than acting as an adjuvant for calcium and magnesium.

[0178] A preferred hydroxamic acid is 80% solids cocoisoxamic acid, which is available from Axis House under the trade name RK853. The corresponding potassium salt is available from Axis House under the trade name RK852. Axis House also supplies cocoisoxamic acid as a 50% solids product under the trade name RK858. A 50% cocoisoxamic acid potassium salt is available as RK857. Another preferred material is RK842 from Axis House, an alkyl hydroxamic acid made from palm kernel oil.

[0179] Preferably, isohydroxamic acid is present in the composition at 0.1 to 3% by weight, more preferably 0.2 to 2% by weight.

[0180] Preferably, the weight ratio of hydroxamic acid to surfactant is 0.05 to 0.3, more preferably 0.75 to 0.2, and most preferably 0.8 to 1.2. The weight is calculated based on the protonated form.

[0181] Alkoxylated oligoamine cleaning synergists Alkoxylated oligoamine cleaning synergists are polymers containing at least two, preferably at least four, nitrogen atoms and most preferably at least four polyalkoxy groups, wherein the polyalkoxy groups contain 10-30 individual alkoxy units. Preferably, at least one polyalkoxy group is directly linked to a nitrogen atom. Preferably, the alkoxy group is selected from ethoxy and propoxy, most preferably ethoxy. -[CH2CH2O] n -H.

[0182] Preferably, the alkoxylated oligoamine contains 2 to 40, more preferably 2 to 10, and most preferably 3 to 8 nitrogen atoms.

[0183] Such polymers are described in WO2023 / 094275 (BASF), WO2023 / 287834 (DOW), WO2023 / 287835 (DOW), WO2023 / 287836 (DOW), WO2021 / 165493 (BASF), WO2021 / 165468 (BASF), WO2022 / 136389 (BASF), WO2022 / 136409 (BASF), WO2004 / 24858 (Procter and Gamble) and WO2021239547 (Unilever).

[0184] Alkoxylated oligoamines preferably contain a permanent positive charge, wherein the positive charge is provided by the quaternization of the nitrogen atoms of the amine. Preferably, the charge is present when the alkoxylated oligoamine contains 2 to 10, preferably 3 to 6, nitrogen atoms. When the alkoxylated oligoamine contains a permanent positive charge, it also contains anionic groups through sulfation or sulfonation of the alkoxylation groups.

[0185] Preferably, 50 mol% or more of the nitrogen-containing amine is quaternized, more preferably with methyl quaternization. Preferably, the polymer contains 3 to 10, more preferably 3 to 6, and most preferably 3 to 5 quaternized nitrogen-containing amines. Preferably, the alkoxy group is selected from ethoxy and propoxy, most preferably ethoxy.

[0186] Preferably, the alkoxylated oligoamine contains ester (COO) groups in its structure, and these groups are preferably placed such that when all the esters are hydrolyzed, at least one, preferably all, of the hydrolyzed fragments has a molecular weight of less than 4000, more preferably less than 2000, and most preferably less than 1000.

[0187] Preferably, the alkoxylated oligoamine is selected from alkoxylated polyethyleneimine, zwitterionic alkoxylated oligoamine, and tetraester alkoxylated oligoamine.

[0188] Alkoxylated polyethyleneimine is prepared from polyethyleneimine, which is a material composed of ethyleneimine units -CH2CH2NH-, and in the case of branching, the hydrogen on the nitrogen is replaced by another ethyleneimine unit chain. Preferred alkoxylated polyethyleneimines used in this invention have a weight-average molecular weight (M) of about 300 to about 10,000. w The polyethyleneimine backbone can be linear or branched. It can be branched to the point of being a dendritic polymer. When nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10-30 alkoxy atoms per modification, preferably 15-25 alkoxy atoms. A preferred material is ethoxylated polyethyleneimine, wherein the average degree of ethoxylation is 10-30 ethoxylated nitrogen atoms per ethoxylated nitrogen atom in the polyethyleneimine backbone, preferably 15-25 ethoxy atoms.

[0189] Zwitterionic alkoxylated oligoamines exist in the following forms: Where R1 is a C3 to C8 alkyl group, and X is (C2H4O). n The Y group, wherein n is 15 to 30, preferably 18 to 25, wherein m is 1 to 10, preferably 2, 3, 4 or 5, and wherein Y is selected from OH and SO3. - And SO3 - The number of functional groups is greater than the number of OH groups. Preferably, it has 0 or 1 OH groups. X and R1 may contain ester groups. X may contain a carbonyl group, preferably an ester group. Preferably, there is a C2H4O unit separating the ester group from N, such that the structural unit N-C2H4O-ester-(C2H4O) n-1 Y is the preferred option.

[0190] Such polymers are described in WO2004 / 24858 (Procter and Gamble) and WO 2021239547 (Unilever). Preferred exemplary polymers are sulfated ethoxylated hexamethylenediamine, Example 4 of WO2004 / 24858 and Examples P1, P2, P3, P4, P5, and P6 of WO2021239547. The ester group can be incorporated by adding a lactone or sodium chloroacetate (modified Williamson synthesis) to an OH or NH group, followed by ethoxylation.

[0191] An exemplary reaction scheme for containing ester groups is: The addition of lactones is discussed in WO2021 / 165468. Once the ester group is included, the polyamine containing the alkoxylated ester can be methylated and sulfated, for example, according to Example P6 of WO2021239547. Preferably, the product is neutralized to pH 7 at the end of the synthesis. If the ester undergoes some degree of hydrolysis, the hydrolyzed product can be removed or re-esterified.

[0192] Tetraester alkoxylated oligoamines exist in the following forms: Where R1 is a polyalkoxy group, R is a polyalkoxy group, x is 0, 1 or 2, and b is 2, 3 or 4. They are described in WO2023 / 287834 (DOW), WO2023 / 287835 (DOW), and WO2023 / 287836 (DOW).

[0193] Preferably, the alkoxylated oligoamine cleaning synergist is present in the composition at 0.01 to 8% by weight, more preferably 0.5 to 3% by weight.

[0194] Decontamination polymer Stain-removing polymers (SRPs) help improve the removal of dirt from fabrics by modifying the fabric surface during the washing process. The chemical structure of SRPs and the affinity between them and the target fibers promote the adsorption of SRPs on the fabric surface.

[0195] The SRP used in this invention can include a variety of charged (e.g., anionic) and uncharged monomer units, and the structure can be linear, branched, or star-shaped. The SRP structure can also include end-capping groups to control molecular weight or modify polymer properties, such as surface activity. The weight-average molecular weight (Mb) of the SRP is... w The range can suitably be from about 1,000 to about 20,000, preferably from about 1,500 to about 10,000.

[0196] The SRP used in this invention may suitably be selected from copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid, or terephthalic acid), glycols (e.g., ethylene glycol or propylene glycol), and polyglycols (e.g., polyethylene glycol or polypropylene glycol). The copolyester may also include monomer units substituted with anionic groups, such as, for example, sulfonated isophthaloyl units. Examples of such materials include oligomers produced by transesterification / oligopolymerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”), and poly(ethylene glycol”) (“PEG”); partially and fully anionic-terminated oligomers, such as oligomers derived from ethylene glycol (“EG”), PG, DMT, and sodium 3,6-dioxa-8-hydroxyoctanesulfonate; nonionic-terminated block polyester oligomers, such as those produced by DMT, Me-terminated PEG and EG and / or PG, or combinations of DMT, EG and / or PG, Me-terminated PEG and sodium dimethyl-5-sulfoisophthalate, and those produced by copolymerization blocks of polyethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0197] Other types of SRPs used in this invention include cellulose derivatives, such as hydroxy ether cellulose polymers, C1-C4 alkyl celluloses, and C4 hydroxyalkyl celluloses; polymers having hydrophobic segments of poly(vinyl ester), such as graft copolymers of poly(vinyl ester), for example, C1-C6 vinyl esters grafted onto a polyepoxide backbone (e.g., poly(vinyl caprolactam)); poly(vinyl caprolactam) and related copolymers with monomers such as vinylpyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensation of adipic acid, caprolactam, and polyethylene glycol.

[0198] Preferred SRPs used in this invention comprise copolyesters formed by the condensation of terephthalate and glycol, preferably 1,2-propanediol, and further comprise end caps formed from repeating alkylene oxide units. Examples of such materials have structures corresponding to general formula (I): Where R 1 and R 2 They are X-(OC2H4) independent of each other. n -(OC3H6) m ; Where X is C 1-4 Alkyl, 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 between 4 and 9.

[0199] Because they are averages, m, n, and a are not necessarily integers for the whole polymer.

[0200] A mixture of any of the above materials may also be used.

[0201] The total content of polyester-based SRP can range from 0.1% to 10%, depending on the amount of polymer intended for use in the final dilution composition, and ideally from 0.3% to 7%, more preferably from 0.5% to 5% (based on the total weight of the dilution composition by weight).

[0202] Suitable detergency polymers are described in more detail in U.S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO 2007 / 079850, and WO2016 / 005271. If used, the detergency polymer is typically incorporated into the liquid laundry detergent compositions herein at a concentration ranging from 0.01% to 10%, more preferably from 0.1% to 5% by weight of the composition.

[0203] enzymes The composition preferably contains an enzyme selected from cellulase, protease, and a mixture of amylase / mannanase.

[0204] In addition, further enzymes may be present, such as those described below.

[0205] Preferably, the composition may contain an effective amount of one or more enzymes, preferably selected from lipase, hemicellulase, peroxidase, xylanase, xantanase, lipase, phospholipase, esterase, keratinase, pectinase, carrageenase, pectic acid lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, amylopectinase, tannic acidase, pentosanase, malic acidase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, tanninase, nuclease (such as deoxyribonuclease and / or ribonuclease), phosphodiesterase, or mixtures thereof.

[0206] Preferably, the enzyme level is 0.1 to 100 mg per 100 g of the finished laundry liquid composition, more preferably 0.5 to 50 mg, and most preferably 5 to 30 mg of active enzyme protein.

[0207] Examples of preferred enzymes are sold under the following trade names: Purafect Prime®, Purafect®, Preferenz® (DuPont), Savinase®, Pectawash®, Mannaway®, Lipex®, Lipoclean®, Whitzyme®, Stainzyme®, Stainzyme Plus®, Natalase®, Mannaway®, Amplify®, Xpect®, Celluclean® (Novozymes), Biotouch (AB Enzymes), and Lavergy® (BASF).

[0208] Detergent enzymes are discussed in WO2020 / 186028 (Procter and Gamble), WO2020 / 200600 (Henkel), WO2020 / 070249 (Novozymes), WO2021 / 001244 (BASF) and WO2020 / 259949 (Unilever).

[0209] Nucleases are enzymes capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids, and are preferably deoxyribonucleases or ribonucleases. Preferably, the nuclease is a deoxyribonuclease, preferably selected from any one of EC3.1.21.x (where x = 1, 2, 3, 4, 5, 6, 7, 8 or 9), EC 3.1.22.y (where y = 1, 2, 4 or 5), EC3.1.30.Z (where z = 1 or 2), EC 3.1.31.1, and mixtures thereof.

[0210] Proteases hydrolyze bonds within peptides and proteins, leading to enhanced removal of stains containing proteins or peptides in the case of laundry. Examples of suitable protease families include aspartic proteases; cysteine ​​proteases; glutamate proteases; aspartic peptide lyases; serine proteases; and threonine proteases. These protease families are described in the MEROPS peptidase database (http: / / merops.sanger.ac.uk / ). Serine proteases are preferred. Substantia nigra-type serine proteases are more preferred. The term "substantia nigra enzyme" refers to a subgroup of serine proteases according to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al., Protein Science 6 (1997) 501-523. Serine proteases are a subgroup of proteases characterized by having a serine residue at the active site that forms a covalent adduct with the substrate. Substantiases can be divided into six subclasses: the substantiase family, the thermophilic protease family, the proteinase K family, the lanofibrillatin peptidase family, the Kexin family, and the Pyrolysin family.

[0211] Examples of subtilisinases are derived from the following: Bacillus species, such as *Bacillus tarda*, *Bacillus alkalophilus*, *Bacillus subtilis*, *Bacillus amyloliquefaciens*, *Bacillus pumilus*, and *Bacillus giganteus* as described in US7262042 and WO09 / 021867; and subtilisin proteases lentus, Novo, Carlsberg, *Bacillus licheniformis*, BPN', 309, 147, and 168 as described in WO 89 / 06279; and protease PD138 as described in (WO 93 / 18140). Other useful proteases may be those described in WO 92 / 175177, WO 01 / 016285, WO 02 / 026024, and WO 02 / 016547. Examples of trypsin-like proteases are trypsin (e.g., those of porcine or bovine origin) and Fusarium proteases described in WO 89 / 06270, WO 94 / 25583 and WO 05 / 040372, as well as chymotrypsin derived from Fibromospora described in WO 05 / 052161 and WO 05 / 052146.

[0212] Most preferably, the protease is subtilisin (EC 3.4.21.62).

[0213] Examples of subtilisinases are derived from the following: Bacillus species, such as Bacillus tarda, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus giganteus as described in US7262042 and WO09 / 021867; and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147, and subtilisin 168 as described in WO 89 / 06279; and protease PD138 as described in (WO 93 / 18140). Preferably, the subtilisin is derived from Bacillus species, particularly Bacillus tarda, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus giganteus as described in US 6,312,936 B1, US 5,679,630, US 4,760,025, US 7,262,042, and WO 09 / 021867. Most preferably, the subtilisin is derived from Bacillus giganteus or Bacillus tarda.

[0214] Suitable commercially available proteases include those sold under the following trade names: Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase®, and Esperase®, all of which are sold as Ultra® or Evity® (Novozymes A / S).

[0215] Suitable amylases (α and / or β) include those of bacterial or fungal origin. This includes chemically modified or protein-engineered mutants. Amylases include, for example, α-amylases obtained from Bacillus species, such as specific strains of Bacillus licheniformis described in more detail in GB 1,296,839, or Bacillus strains disclosed in WO 95 / 026397 or WO00 / 060060. Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™, and BAN™ (Novozymes A / S), Rapidase™, and Purastar™ (from Genencor International Inc.).

[0216] Suitable cellulases include those of bacterial or fungal origin. This includes chemically modified or protein-engineered mutants. Suitable cellulases include those from the genera *Bacillus*, *Pseudomonas*, *Pyrophyllus*, *Fusarium*, *Clostridium*, and *Apocytozoa*, for example, fungal cellulases produced by specific *Pyrophyllus*, *Clostridium*, *Thermophilus*, and *Fusarium* as disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89 / 09259, WO 96 / 029397, and WO 98 / 012307. Commercially available cellulases include Celluzyme™, Carezyme™, Celluclean™, Endolase™, Renozyme™ (Novozymes A / S), Clazinase™, Puradax HA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation). Celluclean™ is preferred.

[0217] Lipase Lipase is a lipid esterase, and the terms lipid esterase and lipase are used synonymously in this article.

[0218] The composition preferably contains 0.0005 to 0.5% by weight, preferably 0.005 to 0.2% by weight of lipase.

[0219] Clean lipases are discussed in Enzymes in Detergency (1997 Marcel Dekker, New York), edited by Jan H. Van Ee, Onno Misset, and Erik J. Baas.

[0220] The lipase can be selected from lipases in EC category 3.1 or 3.2 or a combination thereof.

[0221] Preferably, the clean lipase is selected from: (1) Triglyceride lipase (EC 3.1.1.3) (2) Carboxylester hydrolases (EC 3.1.1.1) (3) Keratinase (EC 3.1.1.74) (4) Sterol esterase (EC 3.1.1.13) (5) Wax-ester hydrolase (EC 3.1.1.50) Triglyceride lipase (EC 3.1.1.3) is the preferred option.

[0222] Suitable triacylglycerol lipases can be selected from variants of lipases from *Humicola lanuginosa* (*Thermomyces lanuginosus*). Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, such as those from *Pseudomonas alcaligenes* or *Pseudomonas pseudoalcaligenes* (EP 218 272), *Pseudomonas cepacia* (EP 331 376), *Pseudomonas stutzeri* (GB 1,372,034), *Pseudomonas fluorescens*, Pseudomonas strains SD 705 (WO 95 / 06720 and WO 96 / 27002), and *Pseudomonas wisconsinensis* (WO 96 / 12012); variants of Bacillus lipases, such as those from *Bacillus subtilis* (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, ...). 253-360), B. stearothermophilus (JP 64 / 744992) or B. pumilus (WO 91 / 16422).

[0223] Suitable carboxyl ester hydrolases can be selected from Burkholderia gladioli, Pseudomonas fluorescens, Pseudomonas putida, Bacillus acidocaldarius, Bacillus subtilis, Bacillus stearothermophilus, Streptomyces chrysomallus, Streptomyces diastatochromogenes, and wild-type carboxyl ester hydrolases or variants endogenous in Saccharomyces cerevisiae.

[0224] Suitable keratinases can be selected from endogenous wild-type keratinases or variants of the following strains: *Aspergillus*, especially *Aspergillus oryzae* strains; *Alternaria*, especially *Alternaria brassiciola* strains; *Fusarium*, especially *Fusarium solani pisi*, *Fusarium oxysporum*, *Fusarium cepa*, *Fusarium rosenbergii*, or *Fusarium roseum*. Strains of *Helminthosporum sativum*; strains of *Helminthosporum sativum*; strains of *Pyrophyte*, especially *Pyrophyte salivarius*; strains of *Pseudomonas*, especially *Pseudomonas mendoza* or *Pseudomonas putida*; strains of *Rhizoctonia*, especially *Rhizoctonia solani*; strains of *Streptomyces*, especially *Streptomyces scabies*; strains of *Coprinus*, especially *Coprinus gravidae*; strains of *Thermobifida*, especially *Thermobifida fusca*; strains of *Magnaporthe*, especially *Magnaporthe grisea*; or strains of *Ulocladium consortiale*.

[0225] In a preferred embodiment, the keratinase is selected from variants of the Mendoza Pseudomonas keratinase described in WO 2003 / 076580 (Genencor), such as variants having three substitutions at I178M, F180V and S205G.

[0226] In another preferred embodiment, the keratinases are wild-type or variants of the six endogenous keratinases of *Coprinus gracilis* described in H. Kontkanen et al., *App. Environ. Microbiology*, 2009, pp. 2148-2157.

[0227] In another preferred embodiment, the keratinase is a wild-type or variant of two endogenous keratinases from Trichoderma reesei described in WO2009007510 (VTT).

[0228] In the most preferred embodiment, the keratinase is derived from a strain of *Pyrophyllus*, particularly *Pyrophyllus* strain DSM1800. *Pyrophyllus* keratinase is described in WO 96 / 13580, which is incorporated herein by reference. The keratinase can be a variant, such as one of the variants disclosed in WO 00 / 34450 and WO 01 / 92502. Preferred keratinase variants include those listed in Example 2 of WO 01 / 92502. Preferred commercial keratinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

[0229] Suitable sterol esterases can be derived from strains of the genus *Ophiostoma*, such as *Ophiostomapiceae*; strains of the genus *Pseudomonas*, such as *Pseudomonas aeruginosa*; or strains of *Melanocarpus*, such as *Melanocarpus albomyces*.

[0230] In the most preferred embodiment, the sterol esterase is Melanocarpus albomyces sterol esterase as described in H. Kontkanen et al., Enzyme Microb Technol., 39, (2006), 265-273.

[0231] Suitable wax-ester hydrolases can be derived from Simmondsia chinensis.

[0232] The lipase is preferably selected from EC category 3.1.1.1 or 3.1.1.3 or a combination thereof, with EC 3.1.1.3 being the most preferred.

[0233] Examples of lipases in EC 3.1.1.3 include those described in WIPO publications WO 00 / 60063, WO 99 / 42566, WO 02 / 062973, WO 97 / 04078, WO 97 / 04079 and US 5,869,438. Preferred lipases are produced by *Absidia reflexa*, *Absidia corymbefera*, *Rhizmucormiehei*, *Rhizopus deleman*, *Aspergillus niger*, *Aspergillus tubigensis*, *Fusarium oxysporum*, *Fusarium heterosporum*, *Aspergillus oryzea*, *Penicilium camembertii*, *Aspergillus foetidus*, *Aspergillus niger*, *Landerina penisapora*, especially *Landerina penisapora*. Certain preferred lipases are provided by Novozymes under the trade names Lipolase®, Lipolase Ultra®, Lipoprime®, Lipoclean®, and Lipex® (registered trademarks of Novozymes); and LIPASE P "AMANO®", available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan; AMANO-CES®, commercially available from Toyo Jozo Co., Tagata, Japan; and additional Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, USA, and Diosynth Co., Netherlands; as well as other lipases such as Pseudomonas gladioli. Other useful lipases are described in WIPO publications WO 02062973, WO 2004 / 101759, WO 2004 / 101760 and WO 2004 / 101763.In one embodiment, suitable lipases include the “first-cycle lipase” described in WO 00 / 60063 and U.S. Patent 6,939,702 B1, preferably a variant of SEQ ID No. 2, more preferably a variant of SEQ ID No. 2 having at least 90% homology with SEQ ID No. 2, which includes the substitution of R or K for any of the electrically neutral or negatively charged amino acids at positions 3, 224, 229, 231, and 233, and most preferably a variant containing the T231R and N233R mutations, such most preferred variants being marketed under the trade name Lipex® (Novozymes).

[0234] The above-mentioned lipases can be used in combination (any mixture of lipases can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, USA; Diosynth Co., Oss, Netherlands, and / or prepared according to the examples contained herein.

[0235] As described in WO 2007 / 087243, lipases with reduced odor generation potential and good relative performance are particularly preferred. These include lipoclean® (Novozyme).

[0236] Preferred commercially available lipases include Lipolase™ and Lipolase Ultra™, Lipex™ and Lipoclean. TM (Novozymes A / S).

[0237] fluorescent agent Preferably, the composition contains a fluorescent agent. More preferably, the fluorescent agent includes sulfonated stilbene biphenyl fluorescent agents, such as those discussed in Chapter 7 of Industrial Dyes (edited by K. Hunger, Wiley VCH 2003).

[0238] Sulfonated stilbene biphenyl fluorescent agents are discussed in US5145991 (Ciba Geigy).

[0239] 4,4'-stilbene-based biphenyl is preferred. Preferably, the fluorescent agent contains two SO3 ions. - Group.

[0240] Most preferably, the fluorescent agent has the following structure: Wherein X is a suitable counter ion, preferably selected from metal ions, ammonium ions or amine salt ions, more preferably alkali metal ions, ammonium ions or amine salt ions, and most preferably Na or K.

[0241] Preferably, the fluorescent agent is present at a level of 0.01% to 1% by weight of the composition, more preferably 0.05% to 0.4% by weight, and most preferably 0.11% to 0.3% by weight.

[0242] C16 and / or C18 alkyl-based surfactants, whether alcohol ethoxylates or alkyl ether sulfates, are typically obtained as a mixture with feedstocks of C16 and C18 alkyl chain lengths.

[0243] Defoamer The composition may also contain a defoamer, but preferably it does not contain a defoamer. Defoamer materials are well known in the art and include siloxanes and fatty acids.

[0244] Preferably, the fatty acid soap is present in 0 to 0.5% by weight of the composition (as measured with reference to the acid added to the composition), more preferably 0 to 0.1% by weight, and most preferably zero.

[0245] In the context of this invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight-chain or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, and most preferably 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of these materials include saturated C12-18 fatty acids, such as lauric acid, myristic acid, palmitic acid, or stearic acid; and mixtures of fatty acids wherein 50 to 100% (by weight, based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures can typically be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil, or tallow).

[0246] Fatty acids can exist as their sodium, potassium, or ammonium salts, and / or as soluble salts of organic bases (such as monoethanolamine, diethanolamine, or triethanolamine).

[0247] A mixture of any of the above materials may also be used.

[0248] For formulation calculation purposes, fatty acids and / or their salts (as defined above) are not included in the content of surfactants or builder in the formulation.

[0249] Preferably, the composition comprises 0.2 to 10% by weight of a clean polymer.

[0250] Preferably, the cleaning polymer is selected from alkoxylated polyethyleneimine, polyester detergency polymers, and copolymers of PEG / vinyl acetate.

[0251] preservative Food preservatives are discussed in Food Chemistry (Belitz H.-D., Grosch W., Schieberle), 4th edition, Springer.

[0252] The formulation preferably contains a preservative or a mixture of preservatives selected from benzoic acid and its salts, alkyl esters of p-hydroxybenzoic acid and their salts, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and its salts, and most preferably sodium benzoate.

[0253] Optional preferred preservatives are selected from sodium benzoate, phenoxyethanol, dehydroacetic acid, and mixtures thereof.

[0254] The preservative is present in amounts of 0.1 to 3% by weight, preferably 0.3% to 1.5% by weight. Where appropriate, weight is calculated for the protonated form.

[0255] Preferably, the composition comprises 0.1 to 3% by weight of sodium benzoate, preferably 0.3% to 1.5% by weight.

[0256] Preferably, the composition comprises 0.1 to 3% by weight of phenoxyethanol, preferably 0.3% to 1.5% by weight.

[0257] Preferably, the composition comprises 0.1 to 3% by weight of the composition, preferably 0.3% to 1.5% by weight of dehydroacetic acid.

[0258] Preferably, the composition contains less than 0.1% by weight, more preferably less than 0.05% by weight of an isothiazolinone-based preservative.

[0259] Water-soluble substances The compositions of the present invention can be incorporated with non-aqueous carriers, such as water-soluble co-solvents, solubilizers, and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids, such as C1 to C5 monohydric alcohols (e.g., ethanol and n-propanol or isopropanol); C2 to C6 diols (e.g., monopropylene glycol and dipropylene glycol); C3 to C9 triols (e.g., glycerol); weight-average molecular weight (M... w The range is approximately 200 to 600 for polyethylene glycol; C1 to C3 alkanolamines, such as monoethanolamine, diethanolamine and triethanolamine; and alkyl aryl sulfonates (such as xylene, toluene, ethylbenzene and sodium and potassium cumene sulfonates) having up to 3 carbon atoms in the lower alkyl group.

[0260] A mixture of any of the above materials may also be used.

[0261] When a non-aqueous carrier is included, its presence can be from 0.1% to 3%, preferably from 0.5% to 1% (based on the total weight of the composition). The amount of the co-water-soluble agent used is related to the amount of surfactant, and ideally, the amount of the co-water-soluble agent is used to control the viscosity of this composition. Preferred co-water-soluble agents are monopropylene glycol and glycerin.

[0262] Co-surfactants In addition to the aforementioned non-soap anionic and / or nonionic detergency surfactants, the compositions of the present invention may contain one or more co-surfactants (such as amphoteric and / or cationic surfactants).

[0263] Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and their derivatives (one or two of which may replace one or two of the methyl groups), as well as mixtures thereof. When cationic surfactants are included, their presence may range from 0.1% to 5% (by weight based on the total weight of the composition).

[0264] Specific amphoteric (ampholy) surfactants include alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkyl sulfobetaine (sulfobetaine), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoteric acetates, alkyl amphoteric propions, alkyl amphoteric glycinates, alkylamidopropyl hydroxysulfobetaine, acyl taurates, and acyl glutamates, having an alkyl group containing about 8 to about 22 carbon atoms, preferably selected from C12, C14, C16, C18, and C18:1. The term "alkyl" is used for alkyl moiety comprising a higher acyl group. When an amphoteric (ampholy) surfactant is included, its presence may range from 0.1% to 5% (by weight based on the total weight of the composition).

[0265] A mixture of any of the above materials may also be used.

[0266] polymer thickener The compositions of the present invention may contain one or more polymer thickeners. Suitable polymer thickeners for use in the present invention include hydrophobically modified alkali-swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present invention comprise linear or crosslinked copolymers prepared by addition polymerization of a monomer mixture comprising at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e., methacrylic acid and / or acrylic acid); and at least one associating monomer. The term "associating monomer" in the context of the present invention refers to a monomer having an olefinically unsaturated segment (for addition polymerization with other monomers in the mixture) and a hydrophobic segment. A preferred type of associating monomer comprises a polyoxyethylene segment between the olefinically unsaturated segment and the hydrophobic segment. Preferred HASE copolymers for use in the present invention comprise linear or crosslinked copolymers prepared by (meth)acrylic acid with (i) at least one C8-C monomer selected from linear or branched monomers. 40 Alkyl (preferably straight-chain C) 12 -C 22 (i) An associating monomer of alkyl)polyethoxylated (meth)acrylate; and (ii) prepared by addition polymerization of at least one further monomer selected from C1-C4 alkyl esters of (meth)acrylate, polyoxovinyl monomers (such as maleic acid, maleic anhydride and / or salts thereof) and mixtures thereof. The polyethoxylated portion of the associating monomer (i) typically contains about 5 to about 100, preferably about 10 to about 80, more preferably about 15 to about 60 oxyethylene repeating units.

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

[0268] When included, the compositions of the present invention preferably comprise 0.01 to 5% by weight of the composition, but depending on the amount intended to be used in the final diluted product, ideally 0.1 to 3% by weight based on the total weight of the diluted composition.

[0269] Toning dyes Tinting dyes can be used to improve the properties of the composition. Preferred dyes are purple or blue. It is believed that depositing low levels of these tints on fabrics masks yellowing. A further advantage of tinting dyes is that they can be used to mask any yellow tints in the composition itself.

[0270] Color dyes are well-known in the field of laundry liquid formulations.

[0271] Suitable and preferred dye types include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes, and dye conjugates. Preferred examples are Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bonded to ethoxylated or propoxylated polyethyleneimine as described in WO2011 / 047987 and WO 2012 / 119859, alkoxylated monoazothiophenes, dyes of CAS-No 72749-80-5, Acid Blue 59, and phenazine dyes selected from the following: , in: X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and -OC2H5; X4 is selected from: -H; -CH3; -C2H5; -OCH3; and -OC2H5; Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and C(O)OCH3.

[0272] Alkoxylated thiophene dyes are discussed in WO2013 / 142495 and WO2008 / 087497.

[0273] The tinting dye is preferably present in the composition in the range of 0.0001 to 0.1% by weight. Depending on the properties of the tinting dye, there is a preferred range that depends on the potency of the tinting dye, which depends on the species and the specific potency within any particular species.

[0274] Microcapsules One type of microparticle suitable for this invention is a microcapsule.

[0275] Microencapsulation can be defined as the process of encapsulating or sealing one substance within another at a very small scale, resulting in capsules ranging in size from less than one micrometer to several hundred micrometers. The encapsulated material can be referred to as the core, active ingredient or drug, filler, payload, core, or internal phase. The material encapsulating the core can be referred to as a coating, membrane, shell, or wall material.

[0276] Microcapsules typically have at least one generally spherical continuous shell surrounding a core. Depending on the materials and encapsulation techniques used, the shell may contain pores, vacancies, or interstitial openings. Multiple shells may be made of the same or different encapsulation materials and may be arranged in layers of varying thicknesses around the core. Alternatively, microcapsules may be asymmetrically and variably shaped, in which a certain amount of smaller droplets of nuclear material are embedded throughout the microcapsule.

[0277] The shell can function as a barrier protecting the core material from the external environment of the microcapsule, but it can also be used as a means of regulating the release of the core material, such as fragrances. Therefore, the shell can be water-soluble or water-swellable and can initiate fragrance release in response to microcapsule exposure to a humid environment. Similarly, if the shell is temperature-sensitive, the microcapsule can release fragrance in response to an increase in temperature. The microcapsule can also release fragrance in response to shear forces applied to its surface.

[0278] The preferred type of polymer microparticles suitable for use in this invention are polymer core-shell microcapsules, wherein at least one continuous shell of polymeric material, typically spherical, surrounds a core containing the fragrance formulation (f2). The shell typically comprises at most 20% by weight based on the total weight of the microcapsules. The fragrance formulation (f2) typically comprises about 10 to about 60% by weight, preferably about 20 to about 40% by weight based on the total weight of the microcapsules. The amount of fragrance (f2) can be determined by taking a slurry of the microcapsules, extracting it into ethanol, and measuring it by liquid chromatography.

[0279] Further optional ingredients The compositions of the present invention may contain further optional ingredients to enhance performance and / or consumer acceptability. Examples of such ingredients include foam promoters, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, corrosion inhibitors, draping agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or opacifiers, and tinting dyes. Each of these ingredients is included in an amount that effectively achieves its purpose. Typically, these optional ingredients are included individually in amounts up to 5% (by weight based on the total weight of the diluted composition) and thus adjusted according to the dilution ratio with water.

[0280] Automatic quantitative feeding In a further aspect, the compositions of the present invention can be used in automatic metering washing machines.

[0281] Therefore, in a further aspect, a washing machine is provided that includes a detergent reservoir containing 80 ml to 3000 ml of liquid detergent according to the first aspect.

[0282] In a further aspect, a method for cleaning fabrics is provided, comprising filling a washing machine reservoir with 80 ml to 3000 ml of a liquid laundry detergent composition according to the first aspect, and performing at least two washing cycles before adding additional liquid detergent to the reservoir.

[0283] In a further aspect, a method for cleaning fabrics is provided, comprising filling a washing machine reservoir with 80 ml to 3000 ml of a liquid laundry detergent composition according to the first aspect, and performing a washing cycle that draws a portion of the liquid detergent from the reservoir and leaves at least 20 ml in the reservoir.

[0284] In a further aspect, a method for cleaning a first fabric is provided, the method comprising filling a tank of a washing machine with 80 ml to 3000 ml of a liquid detergent composition according to the first aspect, and forming a first washing liquid in the washing machine by drawing a portion of the liquid detergent from the tank and combining it with water to form a first washing liquid, and washing the first fabric to perform a first washing cycle. Optional rinsing; and removing the first fabric from the washing machine; and Another washing cycle is performed to clean the additional fabrics by drawing a portion of liquid detergent from the storage tank and combining it with water to form another washing solution. Optional rinsing; and removing the additional fabric from the washing machine; Optional, repeat additional washing cycles; and Add additional liquid detergent to the storage tank.

[0285] The amount of liquid detergent, from 80 ml to 3000 ml, indicates a quantity of more than one dose of detergent. Preferably, the reservoir contains 250 ml to 2500 ml, more preferably 400 ml to 2000 ml of liquid detergent.

[0286] The washing machine preferably includes a detergent reservoir capable of holding up to 3000 ml of detergent. Such washing machines are marketed as self-feeding washing machines and are capable of holding enough liquid detergent for more than one wash cycle, preferably for many wash cycles. Typical examples of such washing machines can be found in EP-A-3 071 742 (Electrolux). Preferably, the washing machine is a front-loading automatic washing machine.

[0287] Preferably, the washing machine includes a housing, a washing tub disposed within the housing with its opening or spout directly facing a clothes loading / unloading opening formed on the front wall of the housing; a detergent dispensing assembly configured to supply detergent to the washing tub; a main water supply circuit configured to connect to a main water pipe and to selectively direct water flow from the main water pipe to the detergent dispensing assembly and / or the washing tub; and an appliance control panel configured to allow a user to manually select the desired washing cycle.

[0288] The washing machine detergent dispensing assembly also includes an automatic metering detergent dispenser configured to automatically meter the appropriate amount of detergent to be used during the selected wash cycle based on a selected wash cycle, and includes: one or more detergent reservoirs, each configured to receive a certain amount of detergent for performing multiple wash cycles; and a corresponding detergent supply pump for each detergent reservoir, the detergent supply pump being configured to selectively draw an amount of detergent from the corresponding detergent reservoir for performing the selected wash cycle and pump / direct the specific amount of detergent into a detergent collection chamber in fluid communication with the wash tub.

[0289] In addition to a storage tank capable of holding a required amount of liquid detergent, the washing machine of the present invention also includes a motor for driving the drum agitation. Water is rinsed through the washing machine, and a predetermined dose of detergent is added to the water to produce a washing liquid.

[0290] With an automatic dispensing washing machine, consumers can run multiple wash cycles before needing to add additional liquid detergent to the tank. Typically, the tank is large enough for five or more washes, and possibly up to 20 or more, depending on the size of the tank in the washing machine and the dosage used for each wash cycle.

[0291] Each washing cycle involves drawing a certain volume of liquid laundry detergent from the reservoir, sufficient to form a suitable washing solution to clean the fabric.

[0292] Preferably, the volume is 10 to 75 ml, but this may depend on the amount of fabric, the stain to be cleaned, and the amount of surfactants and other detergents in the liquid laundry composition.

[0293] After the first wash cycle is completed, the remaining liquid detergent remains in the washing machine until the next cycle begins, at which point another dose is pumped out of the reservoir and mixed with water to form a washing solution.

[0294] The compositions described herein can also be loaded into a washing machine via a drum that operates in conjunction with components of the washing machine. The drum can contain the necessary volume of the desired liquid detergent composition, and can be from 200 ml to 3000 ml.

[0295] Example Prepare a control liquid laundry detergent using the following formulation.

[0296] The second formulation was prepared by adding 1% by weight of alkoxylated zwitterionic oligoamine.

[0297] The detergent was used to wash polyester and cotton fabrics at 1 g / L in linitester for 15 minutes at 25°C.

[0298] The fabric was rinsed once and dried, and then the fragrance content on the fabric was measured by GCMS. The results for the polyester are shown in the table below. Each result is the average of three measurements. The integrals of the GCMS peaks for the fragrance components are given in the table below. The integrals are proportional to the concentration of the component.

[0299] Data shows that, in the presence of polyamines, the fragrance component (bold) of the present invention deposits more on the fabric than other fragrances.

[0300] Coumarin and amyl salicylate have the greatest benefits and are preferred components of flavorings.

[0301] This suggests that alkoxylated zwitterionic oligoamines can be used to improve the deposition of certain fragrances on fabrics when using quick washes.

Claims

1. A method for treating a fabric with a detergent solution formed by diluting a detergent composition in water and contacting the fabric with the detergent solution for 10 to 25 minutes (preferably 10 to 20 minutes) before rinsing, the detergent composition comprising at least one surfactant, an alkoxylated oligoamine cleaning synergist, preferably an alkoxylated zwitterionic oligoamine cleaning synergist, and a fragrance, wherein the fragrance comprises a fragrance component selected from p-tert-butylcyclohexyl acetate, aldehyde MNA, dodecaldehyde, 3-(4-isobutyl-2-methylphenyl)propanal, coumarin, amyl salicylate, and mixtures thereof.

2. The method of claim 1, wherein the fabric is treated with the washing liquid for 10 to 20 minutes.

3. The method of claim 1 or 2, wherein the detergent composition comprises 0.01 to 5% by weight of a fragrance.

4. The method of any of the preceding claims, wherein the fragrance comprises 0.01 to 30% by weight of the fragrance p-tert-butylcyclohexyl acetate.

5. The method of any of the preceding claims, wherein the fragrance comprises 0.01 to 30% by weight of the fragrance aldehyde MNA.

6. The method of any of the preceding claims, wherein the fragrance comprises 0.01 to 30% by weight of the fragrance, dodecaneal.

7. The method of any of the preceding claims, wherein the fragrance comprises 0.01 to 30% by weight of the fragrance 3-(4-isobutyl-2-methylphenyl)propanal.

8. The method of any of the preceding claims, wherein the fragrance comprises 0.01 to 30% by weight of the fragrance coumarin.

9. The method of any of the preceding claims, wherein the fragrance comprises 0.01 to 30% by weight of the fragrance amyl salicylate.

10. The method of any of the preceding claims, wherein the alkoxylated oligoamine cleaning synergist is a biodegradable alkoxylated oligoamine cleaning synergist.

11. The method of any of the preceding claims, wherein the alkoxylated oligoamine comprises an alkoxylated zwitterionic oligoamine in the following forms: Where R1 is a C3 to C8 alkyl group, and X is (C2H4O). n The Y group, wherein n is 15 to 30, preferably 18 to 25, wherein m is 1 to 10, preferably 2, 3, 4 or 5, and wherein Y is selected from OH and SO3. - And SO3 - The number of functional groups is greater than the number of OH groups; preferably, there is 0 or 1 OH group; X and R1 may contain ester groups; X may contain carbonyl groups, preferably ester groups; preferably, there is one C2H4O unit separating the ester group from N, such that the structural unit N-C2H4O-ester-(C2H4O) n-1 Y is the preferred option.

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