CN120835924A

CN120835924A - Composition

Info

Publication number: CN120835924A
Application number: CN202480021005.4A
Authority: CN
Inventors: S·N·巴切洛尔; 郑兆亮
Original assignee: Unilever IP Holdings BV
Current assignee: Unilever IP Holdings BV
Priority date: 2023-04-11
Filing date: 2024-04-02
Publication date: 2025-10-24
Also published as: WO2024213438A1

Abstract

包含芳香剂和醇醚硫酸盐的洗涤剂组合物，其中所述醇醚硫酸盐包含C12和C14烷基链并且具有摩尔平均2.0至4.0个乙氧基化物单元，其中所述醇醚硫酸盐包含小于10重量％的具有零个乙氧基化物基团的醇醚硫酸盐，并且其中所述芳香剂包含选自柠檬烯、吐纳麝香、八氢四甲基苯乙酮(OTNE)、仙客来醛、C8至C12直链和支链醛、β‑紫罗兰酮、二氢月桂烯醇、水杨酸己酯及其混合物的芳香剂组分。A detergent composition comprising a fragrance and an alcohol ether sulfate, wherein the alcohol ether sulfate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylate units, wherein the alcohol ether sulfate comprises less than 10% by weight of alcohol ether sulfate having zero ethoxylate groups, and wherein the fragrance comprises a fragrance component selected from limonene, musk tonalite, octahydrotetramethylacetophenone (OTNE), cyclamen aldehyde, C8 to C12 linear and branched aldehydes, β-ionone, dihydromyrcenol, hexyl salicylate, and mixtures thereof.

Description

Composition and method for producing the same

Technical Field

The present invention relates to detergent compositions comprising improved surfactants.

Background

In the supply chain from the manufacturing site bottling to liquid detergents used in the consumer's home, the product may be exposed to temperatures in excess of 40 ℃. This situation is becoming more pronounced due to global warming. Under such conditions, a significant amount of fragrance may be lost due to evaporation and escape from the package. The key way of fragrance loss is through the loss of fragrance in the headspace of the product above the liquid. This is especially true when there is a large head space, such as when the bottle is empty.

Desirably, the fragrance is stable in the bottle such that the fragrance in the headspace above the bottle is reduced.

Despite the prior art, there remains a need for improved anionic surfactants for use in detergent compositions.

Disclosure of Invention

Thus, in a first aspect, there is provided a detergent composition comprising a fragrance and an alcohol ether sulfate, wherein the alcohol ether sulfate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylate units, wherein the alcohol ether sulfate comprises less than 10 wt% of alcohol ether sulfate having zero ethoxylate groups, and wherein the fragrance comprises a fragrance component selected from the group consisting of limonene, musk, tetramethyl Octamonoacetophenone (OTNE), cyclamen, C8 to C12 linear and branched aldehydes, β -ionone, dihydromyrcenol, hexyl salicylate, and mixtures thereof.

Alcohol ether sulphates having a molar average of 2 to 4 ethoxylate groups are prepared by sulphation of the corresponding alcohol ethoxylates. The most widely used materials are based on linear or branched C12-C15 alcohols. Typically, the ethoxylation reaction to form the alcohol ethoxylate is base catalyzed using NaOH, KOH, or NaOCH ₃. This reaction produces a distribution of ethoxy chain lengths in the alcohol ethoxylate. Narrow range ethoxylation provides a narrower distribution of ethoxy chain lengths than NaOH, KOH or NaOCH ₃. Most notably, narrow range ethoxylation yields significantly lower fractions of materials with exactly 0 or 1 ethoxylation group.

We have surprisingly found that surfactants with a narrow range of ethoxylate distribution can improve the performance of fragrances incorporated into formulations.

Detailed Description

The alcohol ether sulfate has a molar average of 2.0 to 4.0 ethoxylate units and contains less than 10 weight percent alcohol ether sulfate having zero ethoxylate groups.

Preferably, the alcohol ether sulfate contains less than 5% by weight of alcohol ether sulfate having exactly zero ethoxylate groups.

Preferably, the alcohol ether sulfate contains less than 12% by weight of alcohol ether sulfate having exactly one ethoxylate group.

Preferably, the alcohol ether sulfate has a molar average of from 2.6 to 3.4, most preferably from 2.8 to 3.2 ethoxylate units.

Preferably, the composition comprises at least 60% water by weight of the composition.

Preferably, the alkyl ether sulfate is present at 5 to 30% by weight of the composition.

Preferably, the polyester-based soil release polymer is present at 0.1 to 2% by weight of the composition.

Preferably, the composition is a liquid detergent composition.

Preferably, the composition is a laundry liquid unit dose composition.

Preferably, the composition comprises a C12-14 alcohol ether sulfate, wherein the ratio of C12 to 14 is from 5:1 to 1:20. More preferably, the ratio of C12:14 is 4:1 to 1:10, most preferably the ratio of C12:14 is 3:1 to 5:4.

Preferably, the alcohol ether sulfate is present in 1-30% by weight of the composition.

Preferably, the composition comprises a salt. Preferably, the salt is selected from sodium chloride, potassium chloride and mixtures thereof.

Preferably, the salt is present at 0.1 to 5% by weight of the composition. More preferably, the salt is present at 0.8 to 4% by weight of the composition.

Preferably, the composition comprises 0.1-3 wt% betaine, preferably cocamidopropyl betaine.

Alcohol ether sulfate

Alcohol ether sulphates have the following form:

R2-O-(CH₂CH₂O)_pSO₃H。

wherein R2 is alkyl, and p is a molar average and is from 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, preferably the chains are linear.

The structure of the alcohol ether sulfate with exactly zero ethoxylate groups has the structure R2-O-SO ₃ H.

Alcohol ether sulphates are formed by the sulphation of the corresponding alcohol ethoxylates. Alcohol ethoxylates are formed by ethoxylating alcohols using a narrow range of ethoxylating catalysts.

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

Narrow-range ethoxylated 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. Oil chem. Soc. 1996, 73, 73-78 and WO2022/129374 (Unilever). Catalysts based on Ca or Ba are preferred, most preferably in combination with sulfuric acid.

Standard 3EO as described in the literature is not a disclosure of completely pure 3EO, in fact 100% pure 3EO is not commercially available. In contrast, described as 3EO is a mixture with different ethoxylation rates on average of about 3. This 3EO was ethoxylated with KOH. In order to obtain a narrow range of ethoxylation distribution, a dedicated catalyst must be used.

The following is a comparative standard 3EO and narrow range.

Preferably, the sum (n-1, n, n+1) is greater than 50%, more preferably greater than 55%, where n is 2 to 4 (n=average number of moles of ethoxy groups).

Preferably, the total level of 2EO, 3EO and 4EO in the total alkyl ether sulfate is greater than 50%, more preferably greater than 55%, of the total alcohol ether sulfate as measured by GC with Flame Ionization Detection (FID).

Preferably, the total proportion of 0EO and 1EO in the total alkyl ether sulfate is less than 25% of the total alcohol ether sulfate as measured by GC with Flame Ionization Detection (FID).

It should be appreciated that the alcohol ethoxylate was measured prior to sulfonation, but that sulfonation did not materially affect the ethoxylation ratio.

Alcohol ether sulfates are also known as alkyl ether sulfates.

Aromatic agent

The composition comprises a fragrance and preferably the fragrance is present at 0.01 to 5% by weight of the composition, more preferably 0.1 to 1% by weight.

Preferably, the fragrance comprises a fragrance component selected from the group consisting of limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched aldehydes, β -ionone, dihydromyrcenol, hexyl salicylate, and mixtures thereof.

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 15% by weight, particularly preferably from 6 to 10% by weight, of the fragrance component hexyl salicylate.

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 30% by weight, particularly preferably from 6 to 10% by weight, of the fragrance component limonene.

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 15% by weight, particularly preferably from 6 to 10% by weight, of the fragrance component β -ionone.

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 15% by weight, particularly preferably from 6 to 10% by weight, of the fragrance component octahydrotetramethyl acetophenone (OTNE).

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 15% by weight, particularly preferably from 6 to 10% by weight, of the fragrance component dihydromyrcenol.

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 15% by weight, particularly preferably from 6 to 10% by weight, of the fragrance component cyclamen aldehyde.

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 15% by weight, particularly preferably from 6 to 10% by weight, of the tertiary aldehyde MNA of the fragrance component.

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 15% by weight, particularly preferably from 6 to 10% by weight, of the C8-C12 linear and branched aldehydes of the fragrance component.

Preferably, the fragrance comprises from 0.5 to 30% by weight, more preferably from 2 to 15% by weight, particularly preferably from 6 to 10% by weight, of the fragrance component musk.

Preferably, the composition comprises at least two of the fragrance components selected from the group consisting of limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

Preferably, the composition comprises at least three of the fragrance components selected from the group consisting of limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

Preferably, the composition comprises at least four of the fragrance components selected from the group consisting of limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

Preferably, the composition comprises at least five of the fragrance components selected from limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

Preferably, the composition comprises at least six of the fragrance components selected from the group consisting of limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

Preferably, the composition comprises at least seven of the fragrance components selected from limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

Preferably, the composition comprises at least eight of the fragrance components selected from the group consisting of limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

Preferably, the composition comprises all nine of the fragrance components selected from limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

Preferably, the fragrance comprises one of the following mixtures of fragrance components:

-limonene, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

-Limonene, tolnaftate, octahydrotetramethyl acetophenone (OTNE), C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

-Limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, β -ionone, dihydromyrcenol and hexyl salicylate.

-Limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, dihydromyrcenol and hexyl salicylate.

-Limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched aldehydes, β -ionone and hexyl salicylate.

-Limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone and dihydromyrcenol.

-Limonene, tolnaftate, cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, beta-ionone, dihydromyrcenol and hexyl salicylate.

Cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, β -ionone, dihydromyrcenol and hexyl salicylate.

-Limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), β -ionone, dihydromyrcenol and hexyl salicylate.

-Limonene, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, β -ionone, dihydromyrcenol and hexyl salicylate.

-Limonene, tolazane, octahydrotetramethyl acetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched aldehydes and hexyl salicylate.

More preferably, the composition comprises OTNE, dihydromyrcenol and C8 to C12 straight and branched aldehydes, and optionally any remaining fragrance components.

Most preferably, the composition comprises OTNE, dihydromyrcenol, C8 to C12 straight and branched aldehydes and limonene, and optionally any remaining fragrance components.

Preferably, the above listed fragrance components are present in the final detergent composition at 0.0001 to 1% by weight of the composition.

Surface active agent

The liquid detergents of the invention preferably comprise from 2 to 60 wt%, most preferably from 4 to 30 wt% of total surfactant. Preferred are anionic and nonionic surfactants.

Anionic surfactants are discussed in Surfactant SCIENCE SERIES, published by Helmut W. Stache, edited Anionic Surfactants: organic Chemistry (MARCEL DEKKER 1995), CRC press. Preferred anionic surfactants are sulfonate and sulfate surfactants, preferably alkylbenzenesulfonates, alkyl sulfates and alkyl ether sulfates.

The anionic surfactant is preferably added to the detergent composition in the form of a salt. Preferred cations are alkali metal ions such as sodium and potassium. However, the salt form of the anionic surfactant may be formed in situ by neutralising the surfactant in the acid form with a base (such as sodium hydroxide) or an amine (such as monoethanolamine, diethanolamine or triethanolamine). The weight ratio is calculated for the protonated form of the surfactant. The ethoxy units in the anionic and nonionic surfactants may be partially replaced by propoxy units.

Other examples of suitable anionic surfactants are rhamnolipids, alpha-olefin sulfonates, alkene sulfonates, alkane-2, 3-diylbis (sulfates), hydroxyalkane sulfonates and disulfonates, fatty Alcohol Sulfates (FAS), paraffin sulfonates, ester sulfonates, sulfonated fatty acid glycerides, methyl ester sulfonate alkyl succinic acid or alkenyl succinic acid, dodecenyl/tetradecenyl succinic acid (DTSA), fatty acid derivatives of amino acids, DATEM's, CITREM's, and diesters and monoesters of sulfosuccinic acid.

Examples of preferred nonionic surfactants are alcohol ethoxylates and methyl ester ethoxylates. Preferably, the level of nonionic surfactant in the formulation is less than 2 wt%. Preferred alcohol ethoxylates are C12/14 alcohols having a molar average of from 7 to 9 ethoxylates and C16/C18:1 alcohol ethoxylates having a molar average of from 8 to 12 ethoxylates.

Linear alkylbenzene sulfonates are the preferred anionic surfactants other than alcohol ether sulfates.

Linear alkylbenzene sulfonate

LAS (linear alkylbenzene sulfonate) is a preferred anionic surfactant.

The key intermediate compounds in LAS production are related alkenes. These olefins (olefins) may be produced by any of the methods described above and may be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, marine carbon, and the like.

Whereas in the above process the olefin is instead processed by hydroformylation and oxidation to form a linear alcohol, the olefin is reacted with benzene and then with a sulfonate to form LAS.

Linear alkylbenzene sulfonates having alkyl chain lengths of 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologs of alkyl chains, each containing an aromatic ring sulfonated in the "para" position and attached to a linear alkyl chain at any position other than the terminal carbon. The linear alkyl chain preferably has a chain length of 11 to 15 carbon atoms, with the primary material having a chain length of about C12. Each alkyl chain homolog consists of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is typically formulated into the composition in the form of 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 wt%, more preferably 2 to 15 wt%, most preferably 8 to 12 wt% of the composition.

Branched surfactants

The compositions of the present invention preferably comprise branched C8-11 alcohol ether sulfate surfactants in the form of:

RO-(EO)_nSO₃X

Wherein R is preferably a branched C8 to C11 alkyl chain (R), preferably C9 or C10, n is 1 to 6, preferably 2.5 to 5, most preferably 3.5 to 4.5, and X is a cation, preferably sodium or an amine. The integer n is the molar average. EO represents an ethoxy group.

Preferably, the branched alcohol ether sulfate surfactant has the structure,

Where p and m are greater than 1, more preferably m is 4 and p is 2 or m=p+2.

Preferably, the branched alcohol ether sulfate is prepared from Guerbet alcohol. Preferably, the alcohols used to prepare the branched alcohol ether sulfate surfactant have a single alkyl chain length and configuration of greater than 80 mol%. Most preferred are the C10 branched alcohol ether sulfates on 2-propylheptanol having an average of 4 moles of ethoxylation.

Farbe et al discuss branched alcohols in section Alcohols of ALIPHATIC ULLMANN's Encyclopedia of Industrial Chemistry.

Branched alcohols are available from Sasol, exxon and BASF.

Preferably, the branched surfactant comprises from 1 to 20% by weight of the total surfactant in the composition.

Considering the typical surfactant loading of the composition as a whole, it is preferred that the branched surfactant content is 0.05 to 3 wt% of the composition.

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

Methyl Ester Ethoxylate (MEE)

Preferred nonionic surfactants include methyl ester ethoxylates. The methyl ester ethoxylate surfactant is in the form of:

R3(-C=O)-O-(CH₂CH₂-O)_n-CH₃

Wherein R3COO is a fatty acid moiety such as oleic acid, stearic acid, palmitic acid. Fatty acid nomenclature is described by the 2 numbers A: B, where A is the number of carbons in the fatty acid and B is the number of double bonds it contains. For example, oleic acid is 18:1, stearic acid is 18:0, and palmitic acid is 16:0. The position of the double bond on the chain can be given in brackets with oleic acid being 18:1 (9) and linoleic acid being 18:2 (9, 12), where 9 is the number of carbons starting from the COOH terminus.

The integer n is the molar average of ethoxylates.

Methyl Ester Ethoxylates (MEEs) are described in chapter 8 Synthesis, properties, and Applications, pages 287-301 (AOCS press 2019) of Biobased Surfactants (second edition) of G.A. Smith, J. Am. oil, chem. Soc, vol 74 (1997), pages 847-859, hreczuch et al, volume Tenside surf. Det. 28 (2001), pages 72-80, C.Kolano, household and Personal Care Today (2012), pages 52-55, J. Am. oil, chem. Soc, volume 72 (1995), pages 781-784 of A. Hama et al. MEE can be produced by reaction of methyl ester with ethylene oxide using a calcium or magnesium based catalyst. The catalyst may be removed or left in the MEE.

Alternative routes of preparation are transesterification of methyl esters or esterification of carboxylic acids with polyethylene glycols capped at one end of the chain with methyl groups.

Methyl esters can be prepared by transesterification of methanol with triglycerides or 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., month 6, volume 8, article 101) and references therein. Common catalysts for these reactions include sodium hydroxide, potassium hydroxide and sodium methoxide. Esterases and lipases may also be used. Triglycerides naturally occur in vegetable fats or oils, preferred sources being rapeseed oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high stearic/high oleic sunflower oil, inedible vegetable oils, tall oil and any mixtures thereof and any derivatives thereof. The oil from trees is known as tall oil. Used food cooking oil may be used. Triglycerides may also be obtained from algae, fungi, yeasts or bacteria. Plant sources are preferred.

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 containing less than 35% by weight polyunsaturated fatty acids in the oil prior to distillation, fractionation or hydrogenation.

Fatty acids and methyl esters are available from oleochemical suppliers such as Wilmar, KLK Oleo, unilever oleochemical Indonesia. Biodiesel is methyl ester and these sources can be used.

When the ESB is MEE, it preferably has a molar average of 8 to 30 ethoxylate groups (EO), more preferably 10 to 20. Most preferred ethoxylates comprise 12 to 18EO.

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 11EO, even more preferably at least 10% by weight is exactly 10EO. For example, when the MEE has a molar average of 10EO, then at least 10 wt% of the MEE should consist of ethoxylates having 9, 10 and 11 ethoxylate groups.

The methyl ester ethoxylate preferably has a molar average of 8 to 13 ethoxylate groups (EO). Most preferred ethoxylates have a mole average of 9 to 11EO, even more preferably 10EO. When the MEE has a molar average of 10EO then at least 10 wt% of the MEE should consist of ethoxylates having 9, 10 and 11 ethoxylate groups.

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

In addition, it is preferred that the MEE component further comprises some C16 MEEs.

Thus, it is preferred that the total MEE component comprises from 5 to 50 wt% of the C16 MEE of the total MEE. Preferably, the C16 MEE is greater than 90 wt%, more preferably greater than 95 wt% C16:0.

Furthermore, it is preferred that the total MEE component comprises less than 15wt%, more preferably less than 10 wt%, most preferably less than 5wt% of polyunsaturated c18, i.e. c18:2 and c18:3 of the total MEE. Preferably c18:3 is present at less than 1 wt%, more preferably less than 0.5 wt%, most preferably substantially absent. The level of polyunsaturated can be controlled by distillation, fractionation or partial hydrogenation of the feedstock (triglycerides or methyl esters) or MEE.

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

Furthermore, it is preferred that the component having a carbon chain of 15 or less comprises less than 4 wt% of the total MEE weight present.

Particularly preferred MEEs have 2 to 26 wt% C16:0 chains, 1 to 10 wt% C18:0 chains, 50 to 85 wt% C18:1 chains and 1 to 12 wt% C18:2 chains of the MEE.

Preferred sources of alkyl groups for MEE include methyl esters derived from distilled palm oil and methyl esters derived from palm kernel oil which are distilled, partially hydrogenated methyl esters of canola oil, methyl esters of high oleic sunflower oil, methyl esters of high oleic safflower oil and methyl esters of high oleic soybean oil.

High oleic oils are available from DuPont (Plenish high oleic soybean oil), monsanto (Visitive Gold soybean oil), dow (omega-9 canola oil, omega-9 sunflower oil), national Sunflower Association and Oilseeds International.

Preferably, greater than 80% by weight of the double bonds in the MEE are in the cis configuration.

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

The methyl group of the methyl ester may be replaced by ethyl or propyl. Methyl is most preferred.

Preferably, the methyl ester ethoxylate comprises 0.1 to 95 weight percent of the composition of methyl ester ethoxylate. More preferably the composition comprises from 2 to 40 wt% MEE, and most preferably from 4 to 30 wt% MEE.

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

The weight of anionic surfactant is calculated in protonated form.

Branched surfactants

The compositions of the present invention comprise branched C8-11 alcohol ether sulfate surfactants in the form of:

RO-(EO)_nSO₃X

Wherein R is preferably a branched C8 to C11 alkyl chain (R), preferably C9 or C10, n is 1 to 6, preferably 2.5 to 5, most preferably 3.5 to 4.5, and X is a cation, preferably sodium or an amine. The integer n is the molar average. EO represents ethoxy.

Preferably, the branched alcohol ether sulfate surfactant has the structure,

Where p and m are greater than 1, more preferably m is 4 and p is 2 or m=p+2.

Farbe et al discuss branched alcohols in section Alcohols, ALIPHATIC of Ullmann's Encyclopedia of Industrial Chemistry.

Branched alcohols are available from Sasol, exxon and BASF.

Zwitterionic surfactants

The composition may comprise 0 to 3wt% of a zwitterionic surfactant.

Examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines, including C10-C14 alkyl dimethyl betaines and coco dimethyl amidopropyl betaines, C10 to C14 amine oxides, and sulfo and hydroxy betaines, such as N-alkyl-N, N-dimethylamino-1-propane sulfonate, where alkyl may be C10 to C14.

Surfactant ratio

Preferably, the weight ratio of total ether sulfate surfactant to total anionic surfactant is from 1 to 0.5, preferably from 1 to 0.8.

Sources of alkyl chains

The alkyl chain of the surfactant is preferably obtained from a renewable source, preferably from a triglyceride. The renewable source is one in which the material is produced by natural ecological cycle of living species, preferably by plants, algae, fungi, yeast or bacteria, more preferably plants, algae or yeast.

Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil and tree. The oil from trees is known as tall oil. Most preferably palm kernel oil and coconut oil are sources. The desired C12:C14 ratio can be obtained by fractional distillation and mixing of the components.

Algal oil is discussed in Saad M.G. et al Energies 2019,12,1920 Algal Biofuels:Current Status AND KEY CHALLENGES. Masri m, a. 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 describes a method for producing triglycerides from biomass using yeast.

Inedible vegetable oils may be used and are preferably selected from fruits and seeds of Jatropha (Jatropha curcas), calophyllum inophyllum (Calophyllum inophyllum), sterculia aromatica (Sterculia feotida), cercis indicus (Madhuca indica) (cercis latifolia (mahua)), wampee hairless (Pongamia glabra) (koroch seeds), flaxseed, wampee (Pongamia pinnata) (kala Gu Shu (karanja)) Rubber tree (Hevea brasiliensis) (rubber seeds), neem tree (Azadirachta indica) (neem), camelina (CAMELINA SATIVA), lesquerella fendleri, tobacco (Nicotiana tabacum) (tobacco leaves), kenaf (DECCAN HEMP), castor (Ricinus communis l.) (castor (castor)), oil wax tree (Simmondsia chinensis) (Jojoba), tobacco (Nicotiana tabacum), Sesame seed (Eruca sativa.l.), lime tree (Cerbera odollam) (cerbera manghas (seamangos)), coriander (coriander seed (Coriandrum sativum l)), crotylon (Croton megalocarpus), pilu, crambe (Crambe), clove, long tree (SCHELEICHERA TRIGUGA) (kusum), black Socket (STILLINGIA), sal tree (Shorea robusta) (sal) and sal (sal)), Fructus Terminaliae Billericae (TERMINALIA BELERICA ROXB), flos Pitaamong (Cuphea), herba Camelliae Japonicae (Camellia), herba Kalimeridis (Champaca), quassia ramulus Et folium Picrasmae (Simarouba glauca), resina Garciniae (GARCINIA INDICA), testa oryzae, hingan (acorn wood (balanites)), fructus Elaeagni Angustifoliae (DESERT DATE), herba Cirsii (Cardoon), herba Sargassum (ASCLEPIAS SYRIACA) (herba Lactaricae (Milkweed)) Semen Abutili (Guizotia abyssinica), ejobi mustard (Radish Ethiopian mustard), jin Shankui (Syagrus), tung tree (Tung), idesia polycarpa (Idesia polycarpa var. Vestita), algae, argemone mexicana (Argemone mexicana L.) (Argemone mexicana (Mexican prickly poppy)), russian pseudo-yellow poplar (Putranjiva roxburghii) (lucky bean tree), tung tree (Tung), japanese apricot seed (Idesia polycarpa var. Sinensis (L.)), Soapberry (Sapindus mukorossi) (Soapnut), chinaberry (m. azedarach) (syringe), oleander (THEVETTIA PERUVIANA) (oleander), kubanba (Copaiba), white shea (Milk bush), bay (Laurel), winged bean (Cumaru), chinaberry (Andiroba), piqui, brassica napus (b. Napus), pricklyash (Zanthoxylum bungeanum).

C12C14 straight chain alcohols suitable as an intermediate step in the manufacture of C12C14 ether sulfates can be obtained from a number of different sustainable sources. These include:

Primary sugar

The primary sugars are obtained from sugar cane or sugar beets and the like and may be fermented to form bioethanol. Bioethanol is then dehydrated to form bioethylene, which is then subjected to olefin metathesis to form alkene. These olefins are then processed into linear alcohols by hydroformylation or oxidation.

Alternative methods may be used that also utilize primary sugars to form linear alcohols, and wherein the primary sugars are microbiologically converted by algae to form triglycerides. These triglycerides are then hydrolyzed to linear fatty acids, which are then reduced to form linear alcohols.

Biomass

Biomass, such as forestry products, rice hulls, straw, and the like, can be processed into syngas by gasification. These materials are processed into alkanes by the fischer-tropsch reaction, which are subsequently re-dehydrogenated to form olefins. These olefins may be treated in the same manner as the olefins described above for [ primary sugars ].

An alternative method converts the same biomass to polysaccharides by steam explosion, which can be enzymatically degraded to secondary sugars. These secondary sugars are then fermented to form bioethanol, which is subsequently dehydrated to form bioethylene. This bioethylene is then processed to linear alcohols as described above for [ primary sugars ].

Waste plastics

The waste plastics are pyrolyzed to form pyrolysis oil. It is then fractionated to form linear alkanes, which are then dehydrogenated to form alkenes. These alkenes are processed as described above for [ primary sugars ].

Or pyrolyzed oil is cracked to form ethylene which is then processed by olefin metathesis to form the desired alkene. These are then processed as described above for [ primary sugars ] to linear alcohols.

Urban solid waste

MSW is converted to synthesis gas by gasification. From the synthesis gas, it may be processed as described above for [ primary sugars ], or it may be converted to ethanol by an enzymatic process prior to dehydrogenation to ethylene. Ethylene can then be converted to a linear alcohol by Ziegler process.

MSW can also be converted to pyrolysis oil by gasification, which is subsequently fractionated to form alkanes. These alkanes are then dehydrogenated to form olefins, and then linear alcohols.

Ocean carbon

There are various carbon sources from marine communities such as seaweed and seaweed. From such marine communities, triglycerides may be separated from the source and subsequently hydrolyzed to form fatty acids, which are reduced to linear alcohols in the usual manner.

Or the feedstock may be separated into polysaccharides that are enzymatically degraded to form secondary sugars. These can be fermented to form bioethanol and then processed as described above for [ primary sugars ].

Waste oil

Waste oils (e.g., used cooking oil) may be physically separated into triglycerides, which are broken down into linear fatty acids, which then form linear alcohols as described above.

Or the used cooking oil may be subjected to a Neste process whereby the oil is catalytically cracked to form bioethylene. Which is then processed as described above.

Methane capture

Methane capture processes capture methane from landfill sites or fossil fuel production. Methane may be formed into synthesis gas by gasification. The synthesis gas may be treated as described above whereby the synthesis gas is converted to methanol (fischer-tropsch reaction) and then to olefins, followed by oxidation to linear alcohols by hydroformylation.

Or the synthesis gas may be converted to alkanes and then to olefins by fischer-tropsch and subsequent dehydrogenation.

Carbon capture

Carbon dioxide may be captured by any of a variety of known methods. The carbon dioxide may be converted to carbon monoxide by a reverse water gas shift reaction, and it may then be converted to synthesis gas using hydrogen in an electrolysis reaction. The synthesis gas is then processed as described above and converted to methanol and/or alkanes prior to reaction to form olefins.

Or the captured carbon dioxide is mixed with hydrogen prior to enzymatic treatment to form ethanol. This is the process developed by Lanzatech. Thus, ethanol is converted to ethylene, then processed to olefins and then processed to linear alcohols as described above.

The above process can also be used to obtain the C12/14 chain of the C12/14 ether sulfate.

Preferably, the composition is visually clear.

Preferably, the composition contains 10-80% by weight of water.

Preferably, the liquid detergent comprises 1 to 5wt% ethanol.

Liquid laundry detergents

In the context of the present invention, the term "laundry detergent" means a formulated composition intended for and capable of wetting and cleaning household clothing (such as clothing, linen and other household textiles). It is an object of the present invention to provide a composition which, upon dilution, is capable of forming a liquid laundry detergent composition in the manner now described.

In a preferred embodiment, the liquid composition is isotropic.

The term "linen" is commonly used to describe certain types of laundry items, including bedsheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles may include woven, nonwoven, and knit fabrics, and may include natural or synthetic fibers such as silk, linen, cotton, polyester, polyamide (e.g., nylon), acrylic, acetate, and blends thereof (including cotton and polyester blends).

Examples of liquid laundry detergents include heavy duty liquid laundry detergents used in the wash cycle of automatic washing machines, as well as liquid finishing and liquid color-protecting detergents, such as those suitable for washing delicate garments (e.g., those made of silk or wool) by hand or in the wash cycle of automatic washing machines.

In the context of the present invention, the term "liquid" means that the continuous phase or major portion of the composition is liquid and that the composition is flowable at 15 ℃ and higher. Thus, the term "liquid" may include emulsions, suspensions, and compositions having a flowable but harder consistency, referred to as gels or pastes. The viscosity of the composition is preferably 200 to about 10,000 mpa.s at 25 ℃ at a shear rate of 21 sec ^-1. The shear rate is the shear rate normally applied to a liquid when poured from a bottle. The pourable liquid detergent composition preferably has a viscosity of 200 to 1,500 mpa.s, preferably 200 to 700 mpa.s.

The composition according to the invention may suitably have an aqueous continuous phase. "aqueous continuous phase" refers to a continuous phase that is water-based. Preferably, the composition comprises at least 50% by weight water, more preferably at least 70% by weight water.

The alkyl ether sulfates may be provided in a single feed component or by way of a mixture of components.

When the composition comprises a mixture of C16/18 source materials for the alcohol ether sulfate and more conventional C12 alkyl chain length materials, it is preferred that the C16/18 alcohol ether sulfate should comprise at least 10% by weight of the total alcohol ether sulfate in the composition, more preferably at least 50%, even more preferably at least 70%, particularly preferably at least 90%, most preferably at least 95% of the alcohol ether sulfate.

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

Preferably, the surfactant is selected and in an amount such that the composition and diluted mixture are isotropic in nature.

Alkoxylated oligoamine cleaning enhancers

Preferably, the composition comprises an alkoxylated oligomeric amine cleaning enhancer.

The alkoxylated oligomeric amine cleaning enhancer is a polymer containing at least 2, preferably at least 4 nitrogen atoms, and most preferably at least 4 polyalkoxy groups, wherein the polyalkoxy groups contain 10 to 30 individual alkoxy units. Preferably, at least one polyalkoxy group is directly attached to the nitrogen atom. Preferably, the alkoxylate group is selected from ethoxy and propoxy groups, most preferably ethoxy. - [ CH ₂CH₂O]_n -H.

Preferably, the alkoxylated oligoamine contains from 2 to 40, more preferably from 2 to 10, most preferably from 3 to 8 nitrogen atoms.

Such polymers are described in 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).

The alkoxylated oligoamines preferably contain a permanent positive charge, wherein the positive charge is provided by quaternization of the nitrogen atom of the amine.

Preferably, the charge is present when the alkoxylated oligoamine contains from 2 to 10, preferably from 3 to 6 nitrogen atoms. When the alkoxylated oligoamine contains a permanent positive charge, it also contains anionic groups that are caused by sulfation or sulfonation of the alkoxylated groups.

Preferably, greater than or equal to 50 mol% of the nitrogen amine is quaternized, preferably with methyl groups. Preferably, the polymer contains 3 to 10, more preferably 3 to 6, most preferably 3 to 5 quaternized nitrogen amines. Preferably, the alkoxylate group is selected from ethoxy and propoxy groups, most preferably ethoxy.

Preferably, the alkoxylated oligoamine contains ester (COO) groups within the structure, preferably these groups are placed such that when all esters are hydrolysed, at least one, preferably all hydrolysed fragments have a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000.

Preferably, the alkoxylated oligoamine is selected from the group consisting of alkoxylated polyethyleneimines, zwitterionic alkoxylated oligoamines and tetra-ester alkoxylated oligoamines.

The alkoxylated polyethyleneimine is made from polyethyleneimine as a material consisting of ethyleneimine units-CH ₂CH₂ NH-and when branched, the hydrogen on the nitrogen is replaced by another ethyleneimine unit chain. Preferred alkoxylated polyethyleneimines for use in the present invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (M _w). The polyethyleneimine backbone may be linear or branched. Which can be branched to the extent of dendrimers. In the case of alkoxylation of the nitrogen atom, the preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25, alkoxy groups per modification. A preferred material is an ethoxylated polyethyleneimine wherein the average degree of ethoxylation of each ethoxylated nitrogen atom in the polyethyleneimine backbone is from 10 to 30, preferably from 15 to 25 ethoxy groups.

The zwitterionic alkoxylated oligoamine has the following form:

Wherein R ₁ is C3 to C8 alkyl, X is (C ₂H₄O)_n 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 SO ₃ ^-, and the number of SO ₃ ^- groups is greater than the number of OH groups.

Such polymers are described in WO2004/24858 (Procter and Gamble) and WO2021239547 (Unilever). Preferred exemplary polymers are the sulfated ethoxylated hexamethylenediamine of example 4 of WO2004/24858 and examples P1, P2, P3, P4, P5 and P6 of WO 2021239547. The ester groups may be included using lactones or sodium chloroacetate (modified Williamson synthesis), added to OH or NH groups, and then ethoxylated.

An exemplary reaction scheme for containing ester groups is

The addition of lactones is discussed in WO 2021/165468. Once the ester groups are included, the polyamine containing the alkoxylated esters may be methylated and sulfated, for example according to example P6 of WO 2021239547. Preferably, the product is neutralized to ph=7 at the end of the synthesis. If hydrolysis of the ester occurs to some extent, the hydrolysis product may be removed or re-esterified.

The tetraester alkoxylated oligoamines have the following form:

Wherein R ₁ is a polyalkoxy group, R is a polyalkoxy group, x is 0,1 or2, and b is 2, 3 or 4. They are described in WO 2023/287334 (DOW), WO 2023/287335 (DOW), WO 2023/287516 (DOW).

Preferably, the alkoxylated oligomeric amine cleaning enhancer is present at 0.01 to 8% by weight of the composition, more preferably 0.5 to 3% by weight.

Amino carboxylic acid salts

Preferably, the composition comprises an aminocarboxylate chelant. Preferably, the aminocarboxylate is selected from GLDA and MGDA.

Preferably, the aminocarboxylate is present in the composition from 0.1 to 15wt%, more preferably from 0.1 to 10 wt%, even more preferably from 0.3 to 5wt%, still more preferably from 0.8 to 3 wt%, and most preferably from 1 to 2.5 wt% (based on the weight of the composition).

Glutamic diacetic acid (GLDA)

GLDA may be present as a salt of GDLA or as a mixture of GDLA and GDLA salts. Preferred salt forms include mono-, di-, tri-or tetra-alkali metal salts and mono-, di-, tri-or tetra-ammonium salts of GLDA. The alkali metal salt of glutamic acid diacetic acid GDLA is preferably selected from lithium salt and potassium salt of GLDA, and more preferably sodium salt.

The glutamic diacetic acid can be partially or preferably completely neutralized with the corresponding base. Preferably, the average 3.5 to 4 COOH groups of GLDA are neutralized with an alkali metal, preferably sodium. Most preferably, the composition comprises the tetrasodium salt of GLDA.

GLDA is at least partially neutralized with alkali metal, more preferably with sodium or potassium, most preferably with sodium.

The GLDA salt may be an alkali metal salt of L-GLDA, an alkali metal salt of D-GLDA or an enantiomerically enriched isomer mixture.

Preferably, the composition comprises a mixture of L-and D-enantiomers of glutamic acid diacetic acid (GLDA) or corresponding mono-, di-, tri-or tetra-alkali metal or mono-, di-, tri-or tetra-ammonium salts or mixtures thereof, said mixture mainly containing the corresponding L-isomer, the enantiomeric excess being in the range of 10% to 95%.

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

Sodium salts of GLDA are preferred.

A suitable commercial source of GLDA in the form of the tetrasodium salt is DISSOLVINE GL, available from Nouryon.

Preferably, GLDA is present in the composition at 0.1 to 15 wt%, more preferably 0.1 to 10 wt%, even more preferably 0.3 to 5wt%, still more preferably 0.8 to 3 wt%, and most preferably 1 to 2.5 wt% (based on the weight of the composition).

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 salt is preferably selected from lithium and potassium salts of MGDA, more preferably sodium salt.

Sodium salts of methylglycine diacetic acid are preferred. Particularly preferred is the trisodium salt of MGDA.

MGDA may be partially or preferably fully neutralized with the corresponding alkali metal. Preferably, the average of 2.7-3 COOH groups per molecule of MGDA is neutralized with an alkali metal, preferably sodium.

The MGDA may be selected from the group consisting of racemic mixtures of alkali metal salts and racemic mixtures of pure enantiomers of MGDA, such as mixtures of alkali metal salts of L-MGDA, alkali metal salts of D-MGDA and enantiomerically enriched isomers.

Suitable commercial sources of MGDA in the form of the trisodium salt are TRILON cube M available from BASF and Dissolvine cube M-40 available from Nouryon.

Preferably, MGDA is present in the composition at 0.1 to 15 wt%, more preferably 0.1 to 10 wt%, even more preferably 0.3 to 5wt%, still more preferably 0.8 to 3 wt%, and most preferably 1 to 2.5 wt% (based on the weight of the composition).

Small amounts of aminocarboxylates may carry cations other than alkali metals. Thus, it is possible to carry alkaline earth cations, such as Mg ²⁺ or Ca ²⁺, or Fe (II) or Fe (III) cations, in small amounts (e.g. 0.01 to 5 mol%). GLDA may contain small amounts of impurities derived from its synthesis, such as lactic acid, alanine, propionic acid, etc. In this case, "small amount" means 0.1 to 1% by weight in total, referring to the chelating agent aminocarboxylate.

Organic acid

The composition preferably comprises an organic acid. Preferably, the organic acid has the general structure R-CH (OH) -COOH, wherein R is a linear C1-C5, more preferably C2-C4, most preferably C4 alkyl group.

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

Preferred examples are lactic acid, tartaric acid, gluconic acid, mucic acid, glucoheptonic acid. Most preferably, the organic acid is gluconic acid.

The organic acid may be in its D or L form.

The gluconic acid may be selected from racemic mixtures of salts (gluconate) of gluconic acid and pure enantiomers (e.g., alkali metal salts of L-gluconic acid, alkali metal salts of D-gluconic acid) and mixtures of enantiomerically enriched isomers. The D-isomer form is preferred.

Preferably, the organic acid is present in a range of from 0.1 to 15 wt%, more preferably from 0.1 to 10 wt%, even more preferably from 0.2 to 4 wt%, still more preferably from 0.5 to 3 wt%, and most preferably from 0.8 to 2 wt% (by weight of the composition). Measurements were made with respect to its protonated form.

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

External structurants

The composition of the present invention may further alter its rheology by using one or more external structurants that form a structured network within the composition. Examples of such materials include crystallizable glycerides, such as hydrogenated castor oil, microfibrillated cellulose and citrus pulp fibers. The presence of the external structurant may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be stably suspended in the liquid.

The composition preferably comprises a crystallisable glyceride.

The crystallizable glycerides may be used to form an external structuring system as described in WO2011/031940, the contents of which (particularly with respect to the manufacture of ESS) are incorporated by reference. When an ESS is present, it is preferred that 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 is discussed in detail below.

The crystallizable glycerides used herein preferably include "hydrogenated castor oil" or "HCO". HCO as used herein can most typically be any hydrogenated castor oil, provided that it is capable of crystallizing in an ESS premix. Castor oil may include glycerides, particularly triglycerides, which contain C10 to C22 alkyl or alkenyl moieties incorporating hydroxyl groups. The hydroconversion of castor oil to make HCO may be used as a double bond present in the feedstock oil as the ricinoleic moiety to convert the ricinoleic moiety to a saturated hydroxyalkyl moiety, e.g., hydroxystearyl. In some embodiments, the HCO herein may be selected from the group consisting of trihydroxystearin, dihydroxystearin, and mixtures thereof. HCO may be processed in any suitable starting form including, but not limited to, those selected from the group consisting of solids, melts, and mixtures thereof. HCO is typically present in the ESS of the present invention at a level of from about 2% to about 10%, from about 3% to about 8%, or from about 4% to about 6% by weight of the structuring system. In some embodiments, the corresponding percentage of hydrogenated castor oil delivered into the final laundry detergent product is less than about 1.0%, typically from 0.1% to 0.8%.

Useful HCOs can have a melting point of about 40 degrees celsius to about 100 degrees celsius, or about 65 degrees celsius to about 95 degrees celsius, and/or an iodine number in the range of 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357, both tests using DSC differential scanning calorimetry. HCOs for use in the present invention include those commercially available. Non-limiting examples of commercially available HCO for use in the present invention include THIXCIN (R) from Rheox, inc. Other examples of useful HCOs can be found in U.S. patent No. 5,340,390. The source of castor oil for hydrogenation to form HCO may have any suitable origin, such as from brazil or india. In one suitable embodiment, castor oil is hydrogenated using a noble metal (e.g., palladium catalyst) and the hydrogenation temperature and pressure are controlled to optimize hydrogenation of the double bonds of the natural castor oil while avoiding unacceptable levels of dehydroxylation.

The present invention is not intended to be directed solely to the use of hydrogenated castor oil. Any other suitable crystallizable glyceride may be used. In one example, the structuring agent is a triglyceride of substantially pure 12-hydroxystearic acid. This molecule represents the pure form of the fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is fairly constant, but may vary slightly. Likewise, the hydrogenation process may vary. Any other suitable equivalent material may be used, such as a mixture of triglycerides, at least 80% by weight of which is derived from castor oil. Exemplary equivalent materials consist essentially of or consist of triglycerides, or consist essentially of or consist of mixtures of diglycerides and triglycerides, or consist essentially of or consist of corresponding acid hydrolysates of any of the foregoing glycerides with a limited amount (e.g., less than about 20% by weight) of any of the glycerides. The precondition for this is that the major part (typically at least 80% by weight) of any of the glycerides is chemically identical to the glycerides of fully hydrogenated ricinoleic acid, i.e. the glycerides of 12-hydroxystearic acid. For example, it is known in the art to modify hydrogenated castor oil to have two 12-hydroxystearic acid moieties and one stearic acid moiety in a given triglyceride. Also, it is contemplated that hydrogenated castor oil may not be fully hydrogenated. In contrast, the present invention does not include poly (oxyalkylated) castor oil when it does not meet the melting criteria.

The crystallizable glycerides useful in the present invention may have a melting point of about 40 degrees celsius to about 100 degrees celsius.

Hydroxamic acid

Preferably, the composition comprises hydroxamic acid.

Whenever the term "hydroxamic acid" or "hydroxamate" is used, it encompasses hydroxamic acid and the corresponding hydroxamate (salts of hydroxamic acid) unless otherwise indicated.

Hydroxamic acids are a class of chemical compounds in which hydroxylamine is inserted into a carboxylic acid. The general structure of hydroxamic acid is as follows:

(1)

Wherein R ¹ is an organic residue, such as alkyl or alkenyl. The hydroxamic acid can be present as its corresponding alkali metal salt or hydroxamate. The preferred salt is the potassium salt.

Hydroxamates can be conveniently formed from the corresponding hydroxamic acid by substitution of the acid hydrogen atom with a cation:

(2)

L ⁺ is a monovalent cation, such as an alkali metal (e.g., potassium, sodium), or ammonium or substituted ammonium.

In the present invention, the hydroxamic acid or its corresponding hydroxamate has the following structure:

(3)

Wherein R ¹ is

Linear or branched C ₄-C₂₀ alkyl, or

A linear or branched substituted C ₄-C₂₀ alkyl group, or

Straight-chain or branched C ₄-C₂₀ alkenyl, or

Straight or branched substituted C ₄-C₂₀ alkenyl, or

An alkyl ether group CH ₃(CH₂)_n(EO)_m, where n is 2 to 20 and m is 1 to 12, or

A substituted alkyl ether group CH ₃(CH₂)_n(EO)_m, where n is 2 to 20 and m is 1 to 12, the substitution types including one or more of NH ₂, OH, S, -O-and COOH,

And R ² is selected from hydrogen and moieties that form part of a cyclic structure with the branched R ¹ group.

Preferred hydroxamates are those wherein R ² is hydrogen and R ¹ is C ₈ to C ₁₄ alkyl, preferably n-alkyl, most preferably saturated.

The general structure of hydroxamic acids in the context of the present invention is indicated in formula 3 and R ¹ is as defined above. When R ¹ is an alkyl ether group CH ₃(CH₂)_n(EO)_m, where n is 2 to 20 and m is 1 to 12, then the alkyl moiety blocks the pendant group. Preferably, R ¹ is selected from C ₄、C₅、C₆、C₇、C₈、C₉、C₁₀、C₁₁、C₁₂ and C ₁₄ n-alkyl, most preferably R ¹ is at least C _8-14 n-alkyl. When a C ₈ material is used, this is known as octyl hydroxamic acid. Potassium salts are particularly useful.

Octyl hydroxamate potassium salt

However, other hydroxamic acids, while less preferred, are also suitable for use in the present invention. Such suitable compounds include, but are not limited to, the following:

Such hydroxamic acids include lysine hydroxamate, methionine hydroxamate and norvaline hydroxamate, and are commercially available.

Hydroxamates are believed to act by binding to metal ions present in the soil on the fabric. This binding effect (which is in fact a known chelating agent property of hydroxamates) itself has no effect on the removal of soil from fabrics. The key is the "tail" of the hydroxamate, i.e., the group R ¹ minus any branching that folds back onto the acid salt (amate) nitrogen via the group R ². The tail is selected to have an affinity for the surfactant system. This means that the soil removal capacity of an already optimised surfactant system is further improved by the use of hydroxamates, since it in fact marks difficult to remove particulate matter (clay) as "soil" and is removed by the surfactant system acting on hydroxamate molecules now immobilized to the particles via their binding to metal ions embedded in the clay-type particles. The non-soap detersive surfactant adheres to the hydroxamate, resulting in more surfactant interacting with the fabric as a whole, resulting in better soil removal. Thus, the hydroxamic acid acts as a linking molecule, thereby facilitating the removal and suspension of particulate soil from the fabric into the wash liquor, and thus enhancing primary detergency.

Hydroxamates have a higher affinity for transition metals (such as iron) than alkaline earth metals (such as calcium and magnesium), and therefore hydroxamates act primarily to improve the removal of soil, especially particulate soil, from fabrics, and not otherwise act as builders for calcium and magnesium.

The preferred hydroxamate is 80% solids coco hydroxamic acid available from Axis House under the trade name RK 853. The corresponding potassium salt is available from Axis House under the trade name RK 852. Axis house also supplies cocohydroxamic acid as a 50% solids material under the trade name RK 858. 50% of the potassium cocohydroxamate salt was purchased as RK 857. Another preferred material is RK842, an alkyl hydroxamic acid prepared from palm kernel oil from Axis House.

Preferably, the hydroxamate is present at 0.1 to 3% by weight of the composition, more preferably 0.2 to 2% by weight of the composition.

Preferably, the weight ratio between hydroxamate and surfactant is from 0.05 to 0.3, more preferably from 0.75 to 0.2, most preferably from 0.8 to 1.2. The weight is calculated based on the protonated form.

Soil release polymers

Soil release polymers help improve the release of soil from fabrics by modifying the surface of the fabrics during the laundering process. The affinity between the chemical structure of the SRP and the target fibers promotes adsorption of the SRP on the fabric surface.

SRPs for use in the present invention may include various charged (e.g., anionic) as well as uncharged monomeric units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include end capping groups for controlling molecular weight or changing polymer properties (e.g., surface activity). The weight average molecular weight (M _w) of the SRP may suitably be in the range of about 1000 to about 20,000, and preferably in the range of about 1500 to about 10,000.

The SRP used in the present invention may be suitably 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 copolyesters may also include monomer units substituted with anionic groups, such as, for example, sulfonated isophthaloyl units. Examples of such materials include oligoesters produced by transesterification/oligomerization of poly (ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and polyethylene glycol ("PEG"), partially and fully anionically blocked oligoesters such as oligomers from ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa-8-hydroxyoctanesulfonate, nonionic blocked block polyester oligocompounds such as those produced from DMT, me blocked PEG and EG and/or PG, or combinations of DMT, EG and/or PG, me blocked PEG, and sodium 5-dimethyl sulfonate, and copolymer blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide.

Other types of SRPs useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, C ₁-C₄ alkyl celluloses, and C ₄ hydroxyalkyl celluloses, polymers having poly (vinyl ester) hydrophobic segments such as graft copolymers of poly (vinyl esters), e.g., C ₁-C₆ vinyl esters grafted onto a polyalkylene oxide backbone (such as poly (vinyl acetate)), poly (vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, and polyester polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

Preferred SRPs for use in the present invention include copolyesters formed by the condensation of terephthalic acid esters and diols, preferably 1,2 propanediol, and further comprise end-caps formed from repeating units of alkylene oxide end-capped with an alkyl group. Examples of such materials have a structure corresponding to the general formula (I):

Wherein R ¹ and R ² are independently of each other X- (OC ₂H₄)_n-(OC₃H₆)_m);

Wherein X is C _1-4 alkyl and preferably methyl;

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

m is a number from 1 to 10, preferably from 1 to 7, and

A is a number from 4 to 9.

Since they are average values, m, n and a are not necessarily integers for the overall polymer.

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

The total level of SRP based on polyester may be in the range of 0.1 to 10%, depending on the level of polymer intended for use in the final diluted composition, and it is desirably 0.3 to 7%, more preferably 0.5 to 5% (by weight based on the total weight of the diluted composition).

Suitable soil release polymers are described in more detail in U.S. patent No. 5,574,179;4,956,447;4,861,512;4,702,857;WO 2007/079850 and WO 2016/005271. If used, the soil release polymer is typically incorporated into the liquid laundry detergent compositions herein at a concentration in the range of from 0.01% to 10%, more preferably from 0.1% to 5% by weight of the composition.

Enzymes

The composition preferably comprises an enzyme selected from the group consisting of cellulases, proteases and amylase/mannanase mixtures.

Furthermore, additional enzymes may be present, such as those described below.

Preferably, the composition may comprise an effective amount of one or more enzymes, preferably selected from the group comprising lipases, hemicellulases, peroxidases, hemicellulases, xylanases, xanthanases, lipases, phospholipases, esterases, cutinases, pectinases, carrageenases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannase, pentosanases, malates (malanases), beta-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, tannase, nucleases (e.g. deoxyribonuclease and/or ribonuclease), phosphodiesterases, or mixtures thereof.

Preferably the enzyme is present in an amount of from 0.1 to 100, more preferably from 0.5 to 50, most preferably from 5 to 30 mg active enzyme protein per 100g of finished laundry liquid composition.

Examples of preferred enzymes are sold under the 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）、Lavergy®（BASF）.

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

Nucleases are enzymes capable of cleaving a phosphodiester bond between nucleotide subunits of a nucleic acid, and are preferably deoxyribonucleases or ribonucleases. Preferably, the nuclease is a deoxyribonuclease, preferably selected from any of the classes e.c.3.1.21.X, wherein x = 1, 2, 3, 4, 5, 6,7, 8 or 9, e.c.3.1.22.Y, wherein y = 1, 2, 4 or 5, e.c.3.1.30.Z, wherein z = 1, 2, e.c.3.1.31.1 and mixtures thereof.

Proteases hydrolyze peptides and bonds within proteins, which in the case of laundry washing results in enhanced removal of protein or peptide containing stains. Examples of suitable protease families include aspartic proteases, cysteine proteases, glutamic acid proteases, asparagine peptide lyases, serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http:// MEROPS sanger. Ac. Uk). Serine proteases are preferred. Subtilisin-type serine proteases are more preferred. The term "subtilase" refers to a subset 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 subset of proteases characterized by serine in the active site forming a covalent adduct with a substrate. Subtilases may be divided into 6 sub-parts, namely the subtilisin family, the thermophilic proteinase family, the proteinase K family, the lanthionin (Lantibiotic) peptidase family, the Kexin family and the Pyrolysin family.

Examples of subtilases are those derived from Bacillus such as Bacillus lentus (Bacillus lentus), bacillus alkalophilus (b. alkalophilus), bacillus subtilis (b. Subtilis), bacillus amyloliquefaciens (b. Amyloliquefaciens), bacillus pumilus (Bacillus pumilus) and Bacillus jie (Bacillus gibsonii), described in US7262042 and WO09/021867, and subtilisin lens, subtilisin Novo, subtilisin Carlsberg, bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168, described in WO89/06279, and proteinase PD138, described in (WO 93/18140). Other useful proteases may be those described in WO92/175177, WO01/016285, WO02/026024 and WO 02/016547. Examples of trypsin-like proteases are trypsin (e.g.of porcine or bovine origin) and Fusarium (Fusarium) proteases described in WO89/06270, WO94/25583 and WO05/040372, and chymotrypsin from Cellulomonas (Cellumonas) described in WO05/052161 and WO 05/052146.

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

Examples of subtilases are those derived from the genus Bacillus such as Bacillus lentus, bacillus alcalophilus, bacillus subtilis, bacillus amyloliquefaciens, bacillus pumilus and Bacillus gibsonii, described in U.S. Pat. No. 3, 7262042 and WO09/021867, and subtilisin lens, subtilisin Novo, subtilisin Carlsberg, bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168, described in WO89/06279, and proteinase PD138, described in (WO 93/18140). Preferably, the subtilisin is derived from the genus Bacillus, preferably Bacillus lentus, bacillus alcalophilus, bacillus subtilis, bacillus amyloliquefaciens, bacillus pumilus and Bacillus gibsonii, as described in U.S. Pat. No. 6,312,936 B1, U.S. Pat. No. 5,679,630, U.S. Pat. No. 4,760,025, U.S. Pat. No. 7,262,042 and WO 09/021867. Most preferably, the subtilisin is derived from bacillus gibsonii or bacillus lentus.

Suitable commercial proteases include those sold under the 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 can be sold as Ultra cubes or Evity cubes (Novozymes A/S).

Suitable amylases (α and/or β) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, such as the particular strain of Bacillus licheniformis described in more detail in GB 1,296,839, or the Bacillus strains disclosed in WO 95/026397 or WO 00/060060. Commercially available amylases are DuramylTM, termamylTM, termamyl UltraTM, NATALASETM, STAINZYMETM, FUNGAMYLTM and BANTM (Novozymes a/S), RAPIDASETM and PurastarTM (from Genencor International inc.).

Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, pseudomonas, humicola, fusarium (Fusarium), thielavia, acremonium (Acremonium), such as the fungal cellulases produced by Humicola insolens (Humicola insolens), thielavia terrestris (THIELAVIA TERRESTRIS), myceliophthora thermophila (Myceliophthora thermophila) and Fusarium oxysporum (Fusarium oxysporu) disclosed in U.S. Pat. No. 4,435,307, U.S. Pat. No. 5,648,263, U.S. Pat. No. 5,691,178, U.S. Pat. No. 5,776,757, WO89/09259, WO96/029397 and WO 98/0123307. Commercially available cellulases include CelluzymeTM, carezymeTM, cellucleanTM, endolaseTM, renozymeTM (Novozymes A/S), clazinaseTM and Puradax HATM (Genencor International Inc.) and KAC-500 (B) TM (Kao Corporation). CellucleanTM is preferred.

Lipase enzyme

Lipases are lipid esterases, and the terms lipid esterases and lipases are used synonymously herein.

The composition preferably comprises from 0.0005 to 0.5 wt%, preferably from 0.005 to 0.2 wt% lipase.

Cleaning lipid esterases are discussed in Enzymes IN DETERGENCY (1997 Marcel Dekker,New York) edited by Jan H, van Ee, onno Misset and Erik J. Baas.

The lipid esterase may be selected from lipases in e.c. class 3.1 or 3.2 or a combination thereof.

Preferably, the cleaning lipid esterase is selected from:

(1) Triacylglycerol lipase (E.C. 3.1.1.3)

(2) Carboxylic ester hydrolase (E.C. 3.1.1.1)

(3) Cutinase (E.C. 3.1.1.74)

(4) Sterol esterase (E.C. 3.1.1.13)

(5) Wax ester hydrolase (E.C. 3.1.1.50)

Most preferred is triacylglycerol lipase (e.c. 3.1.1.3).

Suitable triacylglycerol lipases may be selected from variants of Humicola lanuginosa (Humicola lanuginosa) (Thermomyces lanuginosus (Thermomyces lanuginosus)) lipases. Other suitable triacylglycerol lipases may be selected from variants of Pseudomonas lipases, for example from Pseudomonas alcaligenes (P. alcaligenes) or Pseudomonas alcaligenes (P. pseudoalcaligenes) (EP 218272), pseudomonas cepacia (P.cepacia) (EP 331 376), pseudomonas stutzeri (GB 1,372,034), pseudomonas fluorescens (P.fluoscens), pseudomonas strain SD 705 (WO 95/06720 and WO 96/27002), pseudomonas Weiss Kang Xinjia (P. wisconsinensis) (WO 96/12012), bacillus lipases, for example from Bacillus subtilis (Dartois et al (1993), biochemica et Biophysica Acta,1131, 253-360), bacillus stearothermophilus (B.stearothermophilus) (JP 64/744992) or Bacillus pumilus (WO 91/16422).

Suitable carboxylate hydrolases may be selected from wild-type or variant carboxylate hydrolases endogenous to bacillus gladiolus (b. gladioli), pseudomonas fluorescens, pseudomonas putida (p. Putida), bacillus acidocaldarius (b. acidocaldarius), bacillus subtilis, bacillus stearothermophilus, streptomyces flavus (Streptomyces chrysomallus), streptomyces chromogenes (s. diastatochromogenes) and saccharomyces cerevisiae (Saccaromyces cerevisiae).

Suitable cutinases may be selected from wild-type or variant of cutinases endogenous to aspergillus strains (in particular aspergillus oryzae), alternaria strains (in particular alternaria brassicae), fusarium strains (in particular fusarium putrescens, fusarium solani pisi, fusarium oxysporum, fusarium oxysporum cepa, fusarium martensii or Fusarium roseum sambucium), vermicularis strains (in particular Helminthosporum sativum), humicola strains (in particular humicola insolens), pseudomonas strains (in particular pseudomonas mendocina or pseudomonas putida), rhizoctonia strains (in particular rhizoctonia solani), streptomyces strains (in particular streptomyces scab), coprinus strains (in particular coprinus cinerea), wen Shuangqi bacterial strains (in particular thermobifida), megabase strains (in particular rice blast) or agaricus graciliatae strains (in particular Ulocladium consortiale).

In a preferred embodiment, the cutinase is selected from variants of Pseudomonas mendocina cutinase described in WO 2003/076580 (Genencor), such as variants having three substitutions at I178M, F V and S205G.

In another preferred embodiment, the cutinases are wild-type or variants of six cutinases endogenous to Coprinus cinereus described in H. Kontkanen et al, app.

In another preferred embodiment, the cutinase is a wild-type or variant of two cutinases endogenous to Trichoderma reesei described in WO2009007510 (VTT).

In a most preferred embodiment, the cutinase is derived from the humicola insolens strain, in particular humicola insolens strain DSM 1800. A specific Humicola insolens cutinase is described in WO 96/13580, which is incorporated herein by reference. The cutinase may be a variant, such as one of the variants disclosed in WO 00/34450 and WO 01/92502. Preferred cutinase variants include those listed in example 2 of WO 01/92502. Preferred commercial cutinases include Novozym 51032 (available from Novozymes, bagsvaerd, denmark).

Suitable sterol esterases may be derived from strains of the genus Serpentis (Ophiostoma), e.g., ophiostoma piceae, strains of the genus Pseudomonas, e.g., pseudomonas aeruginosa, or strains of Melanocarpus, e.g., melanocarpus albomyces.

In the most preferred embodiment, the sterol esterase is H. Kontkanen et al, enzyme Microb technology, 39, (2006), melanocarpus albomyces sterol esterase described in 265-273.

Suitable wax-ester hydrolases may be derived from the oil tree wax.

The lipid esterase is preferably selected from the group consisting of e.c. class 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably e.c.3.1.1.3 lipase.

Examples of EC 3.1.1.3 lipases include those described in WIPO publications WO 00/60063, WO 99/42566, WO 02/062973, WO 97/04078, WO 97/04079 and U.S. Pat. No. 5,869,438. Preferred lipases are prepared from Absidia reflexia (Absidia reflexa), absidia bevel (Absidia corymbefera), rhizomucor miehei (Rhizmucor miehei), rhizopus deleman, aspergillus niger, aspergillus tubingensis (Aspergillus tubigensis), fusarium oxysporum (Fusarium oxysporum), fusarium heterosporum (Fusarium heterosporum), aspergillus oryzae (Aspergillus oryzea), Kanga Bai Qingmei (Penicilium camembertii), aspergillus foetidus (Aspergillus foetidus), aspergillus niger, thermomyces lanuginosus (synonym: humicola lanuginosa) and LANDERINA PENISAPORA, in particular Thermomyces lanuginosus. Some preferred LIPASEs are provided by Novozymes under the trade names Lipolase, lipolase Ultra, lipoprime, lipoclean, and Lipex (registered trademark of Novozymes), and LIPASE P "AMANO", from Areario Pharmaceutical Co.Ltd., nagoya, japan, AMANO-CES, from Toyo Jozo Co., tagata, japan, and other Chromobacter viscosum LIPASEs from AMERSHAM PHARMACIA Biotech, piscataway, new Jersey, U.S. A, and Diosynth Co., netherlands, and other LIPASEs, such as Pseudomonas gladiolus (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 WO00/60063 and U.S. patent 6,939,702B1, preferably variants of SEQ ID No. 2, more preferably variants of SEQ ID No. 2 comprising substitution of an electrically neutral or negatively charged amino acid with R or K at any position of 3, 224, 229, 231 and 233, most preferably variants of SEQ ID No. 2 having at least 90% homology to SEQ ID No. 2 comprising T231R and N233R mutations, such most preferred variants being sold under the trade name Lipex (Novozymes).

The above lipases may be used in combination (any lipase mixture may be used). Suitable lipases are commercially available from Novozymes, bagsvaerd, denmark, areario Pharmaceutical co.ltd., nagoya, japan, toyo Jozo co., tagata, japan, AMERSHAM PHARMACIA biotech, piscataway, new Jersey, u.s.a., diosynth co., oss, the netherlands and/or prepared according to the examples contained herein.

As described in WO2007/087243, lipid esterases with reduced odor-generating potential and good relative properties are particularly preferred. These include lipoclean (Novozyme).

Preferred commercially available lipases include Lipolase ^TM and Lipolase Ultra ^TM、Lipex^TM and Lipoclean ^TM (Novozymes A/S).

Fluorescent agent

Preferably, the composition comprises a fluorescent agent. More preferably, the fluorescent agent comprises a sulphonated stilbene biphenyl fluorescent agent, such as those discussed in chapter 7 of Industrial Dyes (K. Hunger, edited, wiley VCH 2003).

Sulfonated distyryl biphenyl fluorescers are discussed in US5145991 (Ciba Geigy). Preferred is 4,4' -biphenylvinyl biphenyl. Preferably, the fluorescent agent contains 2 SO ₃ ^- groups. 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, most preferably Na or K.

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

Surfactants based on C16 and/or C18 alkyl groups, whether alcohol ethoxylates or alcohol ether sulphates, are generally available as mixtures of starting materials having C16 and C18 alkyl chain lengths.

Defoaming agent

The composition may also contain an antifoaming agent, but preferably does not. Defoamer materials are well known in the art and include silicones and fatty acids.

Preferably, the fatty acid soap is present at 0 to 0.5% by weight of the composition (as measured with reference to the acid added to the composition), more preferably 0 to 10% by weight and most preferably is absent.

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

The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as monoethanolamine, diethanolamine or triethanolamine.

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

For the purposes of formulation calculation, the fatty acid and/or salt thereof (as defined above) is not included in the surfactant content or builder content in the formulation.

Preferably, the composition comprises from 0.2 to 10% by weight of the composition of the cleaning polymer. Preferably, the cleaning polymer is selected from the group consisting of alkoxylated polyethylenimine, polyester soil release polymers and copolymers of PEG/vinyl acetate.

Preservative agent

Food preservatives are discussed in Food Chemistry (Belitz h.—d., grosch w., schieberle), 4 th edition Springer.

The formulation preferably contains a preservative or a mixture of preservatives selected from benzoic acid and salts thereof, alkyl esters of parahydroxybenzoic acid and salts thereof, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and salts thereof, most preferably sodium benzoate.

The optional preferred preservative is selected from sodium benzoate, phenoxyethanol, dehydroacetic acid, and mixtures thereof.

The preservative is present at 0.1 to 3wt%, preferably 0.3 to 1.5 wt%. Where appropriate, the weight is calculated for the protonated form.

Preferably, the composition comprises sodium benzoate in an amount of 0.1 to 3% by weight of the composition, preferably 0.3 to 1.5% by weight.

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

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

Preferably, the composition comprises less than 0.1 wt%, more preferably less than 0.05 wt% of an isothiazolinone-based preservative.

Hydrotrope

The compositions of the present invention may be blended with non-aqueous carriers such as hydrotropes, co-solvents 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 dihydric alcohols (e.g., monopropylene glycol and dipropylene glycol), C3 to C9 triols (e.g., glycerol), polyethylene glycols having a weight average molecular weight (M _w) ranging from about 200 to 600, C1 to C3 alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl groups (e.g., sodium and potassium xylene, toluene, ethylbenzene and cumene (cumene) sulfonates).

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

When included, the non-aqueous carrier may be present in an amount ranging from 0.1 to 3%, preferably from 0.5 to 1% (by weight based on the total weight of the composition). The amount of co-solvent used is related to the amount of surfactant and it is desirable to use the co-solvent content to control viscosity in such compositions. Preferred hydrotropes are monopropylene glycol and glycerol.

Cosurfactant

In addition to the non-soap anionic and/or nonionic detersive surfactants described above, the compositions of the present invention may also contain one or more cosurfactants (e.g., amphoteric (zwitterionic) and/or cationic surfactants).

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

Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkylamidopropylbetaines, alkyl sulfobetaines (sulfobetaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycinates, alkylamidopropylhydroxysulfobetaines, acyl taurates, and acyl glutamates having an alkyl group containing from about 8 to about 22 carbon atoms, preferably selected from the group consisting of C12, C14, C16, C18, and C18:1, the term "alkyl" being used for alkyl moieties including higher acyl groups. When included, the amphoteric (zwitterionic) surfactant can be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

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

Builder and chelating agent

The detergent composition may also optionally contain relatively low levels of organic detergent builder or chelant material. Examples include alkali metals, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetylcarboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, phenylhexaic acid, phenylpolycarboxylic acid and citric acid. Other examples are DEQUESTTM, organophosphonic chelating agents sold by Monsanto, and alkyl hydroxy phosphonates.

Other suitable organic builders include high molecular weight polymers and copolymers known to have builder characteristics. For example, such materials include suitable polyacrylic acid, polymaleic acid, and polyacrylic acid/polymaleic acid copolymers and salts thereof, such as those sold under the designation SOKALANTM by BASF. 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. Preferred builder levels are less than 10% by weight of the composition, and preferably less than 5% by weight of the composition.

More preferably, the liquid laundry detergent formulation is a non-phosphate-assisted laundry detergent formulation, i.e. contains less than 1 wt% phosphate. Most preferably, the laundry detergent formulation is non-builder, i.e. contains less than 1 wt% builder. Typically in liquids, the preferred chelating agent is HEDP (1-hydroxyethylidene-1, 1-diphosphonic acid), for example sold as Dequest 2010. Dequest (R) 2066 (diethylenetriamine penta (methylenephosphonic acid or DTPMP heptasodium) is also suitable, but less preferred because of its poor cleaning effect, however, it is preferred that the composition comprises less than 0.5 wt% phosphonate-based chelating agent, more preferably less than 0.1 wt% phosphonate-based chelating agent, most preferably the composition does not contain phosphonate-based chelating agent.

Polymeric thickeners

The compositions of the present invention may comprise one or more polymeric thickeners. Suitable polymeric thickeners for use in the present invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by addition polymerization of a monomer mixture comprising at least one acidic vinyl monomer, such as (meth) acrylic acid (i.e., methacrylic acid and/or acrylic acid), and at least one associative monomer. The term "associative monomer" in the context of the present invention means a monomer having an ethylenically unsaturated segment (for addition polymerization with other monomers in the mixture) and a hydrophobic segment. A preferred type of associative monomer includes a polyoxyalkylene segment between an ethylenically unsaturated segment and a hydrophobic segment. Preferred HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by the addition polymerization of (meth) acrylic acid with (i) at least one associative monomer selected from the group consisting of linear or branched C ₈-C₄₀ alkyl (preferably linear C ₁₂-C₂₂ alkyl) polyethoxylated (meth) acrylates, and (ii) at least one other monomer selected from the group consisting of C ₁-C₄ alkyl (meth) acrylates, polyacid vinyl monomers (such as maleic acid, maleic anhydride, and/or salts thereof), and mixtures thereof. The polyethoxylated portion of the associative monomer (i) generally comprises from about 5 to about 100, preferably from about 10 to about 80, more preferably from about 15 to about 60 ethylene oxide repeat units.

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

When included, the compositions of the present invention preferably comprise from 0.01 to 5% by weight of the composition, but depending on the amount intended for use in the final diluted product, and desirably from 0.1 to 3% by weight, based on the total weight of the diluted composition.

Shading dye

Hueing dyes may be used to improve the properties of the composition. Preferred hueing dyes are violet or blue. The deposition of low levels of these hues of dye on the fabric is believed to mask the yellowing of the fabric. A further advantage of hueing dyes is that they can be used to mask any yellow hue in the composition itself.

Hueing dyes are well known in the art of laundry liquid formulations.

Suitable and preferred classes of dyes 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 bound to ethoxylates or propoxylated polyethylenimines, as described in WO2011/047987 and WO2012/119859, alkoxylated mono-azothiophenes, dyes with CAS-No 72749-80-5, acid blue 59 and phenazine dyes, selected from:

wherein:

X ₃ is selected from the group consisting of-H, -F, -CH ₃;-C₂H₅;-OCH₃, and-OC ₂H₅;

X ₄ is selected from the group consisting of-H, -CH ₃;-C₂H₅;-OCH₃, and-OC ₂H₅;

Y ₂ is selected from the group consisting of-OH, -OCH ₂CH₂OH;-CH(OH)CH₂OH;-OC(O)CH₃, and C (O) OCH ₃.

Alkoxylated thiophene dyes are discussed in WO2013/142495 and WO 2008/087497.

The hueing dye is preferably present in the composition in the range of 0.0001 to 0.1% by weight. Depending on the nature of the hueing dye, there is a preferred range depending on the efficacy of the hueing dye (which depends on the class and the specific efficacy within any particular class).

Microcapsule

One type of microparticle suitable for use in the present invention is a microcapsule. Microencapsulation may be defined as the process of enclosing or encapsulating one substance within another substance in very small dimensions, resulting in capsules ranging in size from less than one micron to several hundred microns. The encapsulated material may be referred to as a core, active ingredient or agent, filler, payload, core or internal phase. The material that encapsulates the core may be referred to as a coating, film, shell, or wall material.

Microcapsules typically have at least one continuous shell, typically spherical, surrounding a core. Depending on the materials used and the encapsulation technique, the shell may contain voids, vacancies, or interstitial openings. The multiple shells may be made of the same or different encapsulating materials and may be arranged in layers of different thickness around the core. Or the microcapsules may be asymmetrically and variably shaped with a certain amount of smaller droplets of core material embedded in the whole microcapsule.

The shell may have a barrier function that protects the core material from the environment outside the microcapsule, but may also be used as a means to regulate the release of the core material (e.g. fragrance). Thus, the shell may be water-soluble or water-swellable and may initiate release of the fragrance in response to exposure of the microcapsules to a humid environment. Similarly, if the shell is temperature sensitive, the microcapsules may release fragrance in response to an elevated temperature. The microcapsules may also release fragrance in response to shear forces applied to the surface of the microcapsules.

A preferred type of polymeric microparticles suitable for use in the present invention are polymeric core-shell microcapsules in which at least one continuous shell of polymeric material, generally spherical, surrounds a core containing a fragrance formulation (f 2). The shell generally comprises up to 20% by weight, based on the total weight of the microcapsules. The perfume formulation (f 2) generally comprises from about 10 to about 60wt%, and preferably from about 20 to about 40 wt%, based on the total weight of the microcapsules. The amount of perfume (f 2) can be measured by taking a slurry of microcapsules, extracting into ethanol and measuring by liquid chromatography.

Further optional ingredients

The compositions of the present invention may contain further optional ingredients to enhance performance and/or consumer acceptance. Examples of such ingredients include foam enhancers, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkling agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, antistatic agents, ironing aids, colorants, pearlescers and/or opacifiers and hueing dyes. Each of these ingredients is present in an amount effective to achieve its purpose. Typically, these optional ingredients are contained individually in amounts up to 5% by weight (based on the total weight of the diluted composition) and are adjusted according to the dilution ratio using water.

Automatic quantitative feeding

In a further aspect, the compositions of the present invention are useful in automatic-dosing washing machines.

Accordingly, in a further aspect, there is provided a washing machine comprising a detergent reservoir containing from 80 ml to 3000 ml of the liquid detergent according to the first aspect.

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

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

In a still further aspect, there is provided a method for cleaning a first fabric, the method comprising filling a reservoir of a washing machine with a liquid detergent composition according to the first aspect of 80 ml to 3000 ml, and performing a first wash cycle by drawing a portion of the liquid detergent from the reservoir and combining with water to form a first wash liquor in the washing machine to form the first wash liquor and washing the first fabric;

optionally rinsing, and removing the first fabric from the washing machine, and

Performing a further wash cycle to clean the further fabric by withdrawing a portion of the liquid detergent from the reservoir and combining with water to form a further wash liquor and washing the further fabric;

optionally rinsing, and removing the further fabric from the washing machine;

Optionally repeating further wash cycles, and

Further liquid detergent is added to the reservoir.

80 The amount of ml to 3000 ml liquid detergent characterizes more than one dose of detergent. Preferably, the reservoir contains from 250 ml to 2500 ml, more preferably from 400 ml to 2000 ml, of liquid detergent.

The washing machine preferably comprises a detergent reservoir capable of storing up to 3000 ml detergent. Such washing machines are known in the market as automatic dosing washing machines and are capable of storing sufficient liquid detergent for more than one washing cycle, and preferably for a plurality of washing cycles. A typical example of such a washing machine is found in EP-a-3 071 742 (electroux). Preferably, the washing machine is a front-loading automatic washing machine.

Preferably, the washing machine comprises a housing, a washing tub (arranged inside the housing with its opening or mouth directly facing the laundry loading/unloading opening realized on the front wall of the housing), a detergent dispensing assembly (configured for supplying detergent into the washing tub), a main fresh water supply circuit (configured for connection to a water supply main and for selectively guiding a fresh water flow from the water supply main to the detergent dispensing assembly and/or the washing tub), and an appliance control panel (configured for allowing a user to manually select a desired washing cycle).

The washing machine detergent dispensing assembly further includes an auto-dosing detergent dispenser configured for auto-dosing an appropriate amount of detergent to be used during a selected washing cycle based on the selected washing cycle, and the auto-dosing detergent dispenser includes one or more detergent reservoirs each configured for receiving an amount of detergent for performing a plurality of washing cycles, and for each detergent reservoir, a respective detergent feed pump configured to selectively pump an amount of detergent for performing the selected washing cycle from the respective detergent reservoir and pump/direct the particular amount of detergent into a detergent collection chamber in fluid communication with the washing tub.

In addition to a reservoir capable of containing a desired amount of liquid detergent, the washing machine of the present invention also includes a motor for driving agitation of the drum. Water is flushed through the washing machine and a predetermined dose of detergent is added to the water to form a wash liquor.

With automatic dosing washing machines, the consumer can perform multiple wash cycles before further liquid detergent needs to be added to the reservoir. Typically, the reservoir is sufficient to perform five or more washes, and possibly as many as 20 or more washes, depending on the size of the reservoir in the washing machine and the dosage used per wash cycle.

Each wash cycle comprises drawing a volume of liquid laundry detergent from a reservoir sufficient to form a suitable wash liquor to clean the fabric.

Preferably, the volume is from 10 to 75 ml, but this may depend on the amount of fabric, stains to be cleaned and the amount of surfactant and other cleaning agents in the liquid laundry detergent composition.

After the first wash cycle is completed, the remaining liquid detergent remains in the washing machine until the next cycle begins, at which point a further dose is pumped from the reservoir and mixed with water to form a wash liquor.

It is also possible that the compositions described herein are loaded into a washing machine through a cartridge that is cooperable with the constituent parts of the washing machine. The cartridge may contain a desired volume of the desired liquid detergent composition, and it may be 200 ml to 3000 ml.

Examples

Example 1

A calcium catalyst was prepared according to EP1747183 having the following composition 73.5 wt% n-butanol, 15 wt% calcium hydroxide, 3.5 wt% 2-ethylhexanoic acid, and 7.8 wt% concentrated sulfuric acid from example 1 was used in this example to prepare narrow range ethoxylates.

915 G of C14 alcohol (c12=10% by weight, c14=89% by weight, c16=1% by weight) was added to a2 gallon stainless steel autoclave equipped with overhead stirrer, internal steam heating, water cooling and thermocouple. The C14 alcohol was dried under vacuum at 90 ℃, then 2.1 g catalyst was added and vacuum stripped at 90 ℃ until all solvent was removed (about 5 minutes). The reactor was heated to 140 ℃ and ethylene oxide was slowly added. After the induction period, a small exothermic reaction was observed, at which time the addition of ethylene oxide was continued at a pressure of 2 bar until a total of 3 moles of ethylene oxide were consumed. The temperature was controlled using water cooling and brought to 180 ℃. When the 3:1 molar ratio of ethylene oxide was reacted with a C14 alcohol to form an alcohol ethoxylate, the temperature was reduced to 90 ℃ and the product was vacuum stripped for 3 hours.

The narrow range ethoxylation procedure was repeated using the catalyst described in Ind. Eng. Chem. Res. 1992,31,2419-2421 (C ₁₁H₂₃COO)₂ Ba, methanesulfonic acid catalyst described in US10099964, and barium oxide/sulfuric acid catalyst described in WO2012028435 (Kolb)).

The ethoxylate distribution of the methanesulfonic acid catalyst was measured and compared to a fairly broad range of materials prepared with KOH as catalyst.

Narrow range materials have lower fractions of AE-O and AE-1 materials where AE-O is an unethoxylated alcohol (zero ethoxylate groups) and AE-1 is an alcohol ethoxylate having 1 ethoxylate group.

The resulting material was sulfated using SO ₃ in a falling film reactor to produce ether sodium sulfate salt.

Example 2

Resulting in a liquid laundry detergent containing a C12/14 ether sulfate. The C12/14 ether sulfate has a 3:1 molar ratio of C12 to C14 alkyl chains. The C12/14 ether sulfate was ethoxylated with either a standard ethoxylation catalyst (SLES) or with a narrow range ethoxylation catalyst (NRES) and both samples were present as Na salts. 0.65% fragrance was added to the formulation and the samples were mixed to ensure complete separation. To detect fragrance levels in the headspace when stored at elevated temperature, the samples were equilibrated for 15 minutes at 40 ℃. The fragrance level in the headspace was then measured using GCMS. The difference in fragrance intensity between NRES and SLES samples was calculated as NRES/SLES. Experiments were repeated three times and the average value of NRES/SLES is listed in the table below, along with a 95% confidence limit.

Surprisingly, the fragrance level in the headspace was lower for the NRES samples for a range of fragrance components, as listed in the present invention. This is indicated by a NRES/SLES value below 1. Even more surprisingly, β -ionone, benzene, (1-cyclohexylethyl) -, aldehyde MNA, cyclamen aldehyde, hexyl salicylate and musk showed the lowest NRES/SLES values (highest stability). Most surprisingly, a musk emetic with NRES/SLES value of 0.537 showed the highest stability.

Tuberone is similar in structure to iso E super (octahydrotetramethyl acetophenone (OTNE)),

Aldehyde MNA is part of the group of C8-C12 straight and branched chain aldehyde fragrances.

Example 3

Typical formulations include:

^1,2 Also prepared in C12-18 form

C12-14 Alkylethoxy (3) sulfate is a narrow range AES as described herein.

The perfume comprises a fragrance component selected from the group consisting of limonene, musk, tetramethyl Octaacetophenone (OTNE), cyclamen aldehyde, C8 to C12 straight and branched chain aldehydes, beta-ionone, dihydromyrcenol, hexyl salicylate, and mixtures thereof.

Claims

1. A detergent composition comprising a fragrance and an alcohol ether sulfate, wherein the alcohol ether sulfate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylate units, wherein the alcohol ether sulfate comprises less than 10 weight percent of alcohol ether sulfate having zero ethoxylate groups, and wherein the fragrance comprises a fragrance component selected from the group consisting of limonene, musk, tetramethyl Octamonoacetophenone (OTNE), cyclamate, C8 to C12 linear and branched aldehydes, β -ionone, dihydromyrcenol, hexyl salicylate, and mixtures thereof.

2. The composition of claim 1 which is a liquid detergent composition.

3. The composition of claim 1 or 2, comprising at least 60% water by weight of the composition.

4. The composition of claim 1 which is a laundry liquid unit dose composition.

5. The composition of any of the preceding claims, wherein the ratio of c12:14 is from 3:1 to 1:20.

6. The composition of any of the preceding claims, wherein the ratio of c12:14 is from 3:1 to 5:4.

7. The composition of any preceding claim, wherein the alcohol ether sulfate is present at 1-30% by weight of the composition.

8. The composition of any preceding claim, comprising a salt.

9. The composition of claim 8, wherein the salt is selected from the group consisting of sodium chloride, potassium chloride, and mixtures thereof.

10. The composition of claim 8 or 9, wherein the salt is present at 0.1-5% by weight of the composition.

11. The composition according to any of the preceding claims, wherein the alkoxylated polyamine is selected from the group consisting of propoxy and ethoxy groups, most preferably ethoxy groups.

12. The composition according to any of the preceding claims, having a pH of from 5 to 10, more preferably from 6 to 8, most preferably from 6.1 to 7.0.