WO2025180874A1 - Substituted 1,3-dioxolane sulfates and their use - Google Patents

Abstract

Substituted 1,3-dioxolane sulfates and their use This invention deals with substituted 1,3-dioxolane sulfates according to Formula (I), their manufacture, methods and uses, for example in laundry or dishwashing.

Description

Substituted 1 ,3-dioxolane sulfates and their use

This invention deals with specific 1 ,3-dioxolane sulfates (in this present invention abbreviated as “inventive compound” or “compound of the invention” whenever the inventive compounds are meant) comprising a structure according to Formula (I), their manufacture, methods, their uses and compositions including the inventive compound, particularly laundry detergent compositions.

Anionic surfactants, particularly the sulphonates such as linear alkylbenzene sulphonate (LAS) and the sulphates such as primary alkyl sulphate (PAS), are the key ingredients of modern laundry detergents, providing excellent detergency performance on a wide range of soils and stains.

However, detergent formulators are continuously faced with the task to improve the environmental “footprint” of any product, be it in terms of its origin like being from natural or renewable resources, or compared to previous products, its production in terms of production efficiency and thus reduced usage of energy, its efficiency in usage such as reduced amounts for the same performance or higher performance at the same amount levels used, its persistence in the natural environment after its usage, especially its biodegradation, since recycling is technically very challenging and therewith economically not attractive.

Hence, due to the climate change, one of the most important targets of the detergent and cleaner (D&C) industry today is to significantly lower the CO2 emission per wash. Surfactants, such as LAS and PAS are based on fossil carbon sources and therefore their production is incompatible with the environmental-friendly aims of the D&C industry. To overcome this problem, alternative surfactants that provide significant wash performance and which are (or can potentially be) based on non-fossil carbon sources are of interest for the D&C industry.

One such alternative group of surfactants that roughly resembles the structure of LAS are 1 ,3- dioxolane sulfates.

In the following, a summary of the current knowledge and most relevant publications in the field of the present invention, the synthesis and use of 1 ,3-dioxolane sulfates and similar compounds is given.

US10822323 A describes acid labile surfactants comprising 1 ,3-dioxane- or 1 ,3-dioxolane-based surfactants. In detail, the application discloses the advantage of acid labile surfactants and suggests a use in protein gel separation (SDS-PAGE). In contrast to the present compounds, US10822323 A describes compounds with a sulfated linker of two carbon atoms, however, this linker is attached at position 2 of the 1 ,3-dioxolane ring. A longer alkyl group is attached at position 4 but contains heteroatoms, such as O, S and NH.

US3948953 A discloses 1 ,3-dioxolane derivatives with surfactant properties. For these compounds a role is described as components of detergent compositions and as organic intermediates, particularly pharmaceutical intermediates. They are obtained by the reaction of a ketone with glycerol followed by further modification (sulfation or ethoxylation). Therefore, these compounds are different from the inventive compounds of the present application as they do not comprise at least two carbon atoms in the linker carrying the sulfate group which is located on the position 4 of the 1 ,3-dioxolane ring.

US20230174897 A and US20230174897 A describe liquid hand dishwashing detergent composition comprising a mixture of sulfated 1 ,3-dioxane- and sulfated 1 ,3-dioxolane-based surfactants, which are obtained by conversion of a fatty aldehyde with glycerol followed by sulfation. Also, these compounds comprise a sulfated linker at position 4 of the 1 ,3-dioxolane ring which contains only one carbon atom.

In contrast to US3948953 A, US20230174897 A and US20230174897 A the compounds of the present invention are not synthesized by reacting a ketone with glycerol but with a linear triol comprising 4 to 12 carbon atoms, wherein hydroxy groups are in the 1 -, 2- and omega position. Reacting this triol with an aldehyde or ketone results in surfactants having a linker at position 4 of the dioxolane ring that comprise at least two carbon atoms. Compared to the prior art compounds containing a linker with only one carbon atom, the present compounds demonstrate significantly improved foamability and dynamic surface tension as experimentally shown.

Thus, the present inventors surprisingly found that elongating the sulfated alkyl linker in position 4 results in increased wash performance of sulfated 1 ,3-dioxolane based surfactants while maintaining the possibility to synthesize these compounds with renewable and commercially available educts.

Therefore, the object of the present invention is to provide novel compounds having a structure according to Formula (I)

Formula (I) wherein R1 is C8 to C27 alkyl or C8 to C27 alkenyl,

R4 is hydrogen, C2 to C18 alkyl or C2 to C18 alkenyl,

R2 is (i) wherein M is selected from the group consisting of hydrogen, Na, K, ammonia, protonated amine and protonated amino alcohol; m is an integer having a value of 1 to 4; the dotted line indicates the bond to the oxygen atom of Formula (I), and n is an integer having a value of 1 to 9.

In another aspect, the present invention relates to a process to prepare the inventive compound comprising i) reacting an aldehyde or ketone according to Formula (II)

O

R3 - L

^R4

Formula (II), wherein R3 is C8 to C27 alkyl or C8 to C27 alkenyl and

R4 is hydrogen, C2 to C18 alkyl or C2 to C18 alkenyl, with a linear triol comprising 4 to 12 carbon atoms, wherein hydroxy groups are in the 1 -, 2- and omega position in presence of an acidic catalyst to obtain the inventive compound, wherein R2 is " ' "^H and the dotted line is defined as above, and optionally ii) sulfating or sulfonating the compound of reaction step i) and subsequent neutralization with a base selected from the group consisting of sodium hydroxide or potassium hydroxide, ammonia, amines and amino alcohols to obtain the inventive compound, wherein R2 is or and wherein M, m and the dotted line are defined as above.

Further, a (cleaning) composition comprising the inventive compounds is also part of the invention. In addition, the invention is directed to a cleaning method and uses of the inventive compounds in (cleaning) compositions.

Thus, subjects of the present invention are the following Embodiments 1 to 15 as defined and further explained with further embodiments hereinafter and further exemplified in the experimental section:

Embodiment 1

A compound having the structure according to Formula (I)

Formula (I) wherein

R1 is C8 to C27 alkyl or C8 to C27 alkenyl,

R4 is hydrogen, C2 to C18 alkyl or C2 to C18 alkenyl, wherein M is selected from the group consisting of hydrogen, Na, K, ammonia, protonated amine and protonated amino alcohol; m is an integer having a value of 1 to 4; the dotted line indicates the bond to the oxygen atom of Formula (I), and n is an integer having a value of 1 to 9.

The inventive compound according to Formula (I) may be synthesized by reacting a linear triol comprising 4 to 12 carbon atoms, wherein hydroxy groups are in the 1 -, 2- and omega position and an aldehyde (resulting in R4 being hydrogen) or a ketone (resulting in R4 being C2 to C18 alkyl or C2 to C18 alkenyl). In preferred embodiments, R4 is hydrogen meaning that the triol is reacted with an aldehyde.

In preferred embodiments, R1 is at least C9, at least C10, at least C11 , at least C12, at least C13, at least C14, at least C15, at least C16 or at least C17 alkyl or alkenyl and not more than C26, not more than C25, not more than C24, not more than C23, not more than C22, not more than C21 , not more than C20, not more than C19 or not more than C18 alkyl or alkenyl.

In preferred embodiments, R4 is at least C3, at least C4, at least C5, at least C6, at least C7, at least C8, at least C9, at least C10 or at least C11 alkyl or alkenyl and not more than C17, not more than C16, not more than C15, not more than C14, not more than C13, not more than C12 alkyl or alkenyl.

The skilled person will know that the inventive compounds can form the basis for further reactions, in particular reactions to modify the inventive compounds by substitution of a hydrogen atom with functional groups, such as additional alkyl or alkylene groups, nitrogen containing groups, -OH groups, -CHO groups, -COOH groups, -SO4 groups or variations or combinations thereof.

In preferred embodiments, the inventive compounds do not comprise any such functional modifications, in particular functional groups such as nitrogen containing groups, -OH groups, -CHO groups, -COOH groups, sulfur containing groups or variations or combinations thereof.

“Pronated amine”, as used herein, means any protonated amine, namely ammonium, primary, secondary and tertiary amines. Amines that can be protonated and can form a salt with the inventive compounds include methylamine, ethylmethylamine and trimethylamine.

The term "amino alcohol", as used herein, refers to a chemical entity containing both an amino group and a hydroxyl moiety. The skilled person knows that the amino groups of these compounds can be protonated.

The substructure“-OM” of Formula (I) may refer to a salt and the interaction of an anion and a cation. In case the inventive compounds are salts, “M” is the cation, whereas the “O” is negatively charged and therefore forms the anion. Alternatively, the “O” may be covalently bound to a hydrogen atom and therefore does not form a salt.

“m” is an integer having a value of 1 to 4, preferably m is 1 , 2, 3 or 4, more preferably m is 1 or 2.

The term “at least one”, as used herein, includes but is not limited to 1 , 2, 3, 4, 5, 6, 7, 8, 9 and more.

Embodiment 2 The compound of the invention, wherein R1 is C10 to C17 alkyl or C10 to C17 alkenyl, preferably C10 to C17 alkyl.

In preferred embodiments, R1 is linear or non-cyclic branched, more preferably R1 is linear. Further, R1 is at least C9, at least C10, at least C1 1 , at least C12, at least C13, at least C14, at least C15, at least C16 or at least C17 alkyl or alkenyl, preferably alkyl, and not more than C26, not more than C25, not more than C24, not more than C23, not more than C22, not more than C21 , not more than C20, not more than C19 or not more than C18 alkyl or alkenyl, preferably alkyl.

Embodiment 3 o

. S - OM o

The inventive compound, wherein R2 is and the dotted line and M are defined as above, preferably M is Na or hydrogen, preferably Na.

Embodiment 4

The inventive compound, wherein i) n is an integer having a value of 1 to 3; and ii) R4 is hydrogen.

In preferred embodiments, n is 1 , 2 or 3, preferably 1 .

Embodiment 5

The compound of the invention, wherein M is selected from the group consisting of hydrogen, Na, K and ammonia.

In preferred embodiments, M is hydrogen or Na.

In more preferred embodiments, the compounds of the invention are 2-llndecyl-4-hydroxyethyl- 1 ,3-dioxolane according to Formula (III) and 2-Undecyl-4-ethylsulfate-1 ,3-dioxolane sodium salt according to Formula (IV):

(III), and

Embodiment 6

In another aspect, the present invention is directed to a process to prepare the inventive compound comprising i) reacting an aldehyde or ketone according to Formula (II)

O

R3 - L

^R4

Formula (II), wherein R3 is C8 to C27 alkyl or C8 to C27 alkenyl and

R4 is hydrogen, C2 to C18 alkyl or C2 to C18 alkenyl, with a linear triol comprising 4 to 12 carbon atoms, wherein hydroxy groups are in the 1 -, 2- and omega position in presence of an acidic catalyst to obtain the inventive compound, wherein R2 is " ' "^H and the dotted line is defined as above, and optionally ii) sulfating or sulfonating the compound of reaction step i) and subsequent neutralization with a base selected from the group consisting of sodium hydroxide or potassium hydroxide, ammonia, amines and amino alcohols to obtain the inventive compound, wherein R2 is or and wherein M, m and the dotted line are defined as above.

In preferred embodiments, R3 is linear or non-cyclic branched, more preferably R3 is linear. Further, R3 is at least C9, at least C10, at least C1 1 , at least C12, at least C13, at least C14, at least C15, at least C16 or at least C17 alkyl or alkenyl, preferably alkyl, and not more than C26, not more than C25, not more than C24, not more than C23, not more than C22, not more than C21 , not more than C20, not more than C19 or not more than C18 alkyl or alkenyl, preferably alkyl. In preferred embodiments, the linear triol may be selected from the group consisting of 1 ,2,4- butanetriol, 1 ,2,5-pentanetriol, 1 ,2,6-hexanetriol, 1 ,2,7-heptanetriol, 1 ,2,8-octanetriol, 1 ,2,9-non- anetriol and 1 ,2,10-decanetriol, more preferably the linear triol is 1 ,2,4-butanetriol.

The term “neutralization”, as used herein, relates to raising the pH of the reaction system after sulfation via the addition of an appropriate base. The amount of the base will be adapted in a way that the final pH is between 5 to 9 and preferably 6 to 8. The skilled person is well-aware of appropriate bases.

In further embodiments, the inventive compound is purified (by distillation). After this purification, the inventive compound has a purity level of at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 99% or at least 99.5% based on the mole fraction (i.e. amount of the inventive compound expressed in moles divided by the total amount of all constituents in the mixture also expressed in moles). In particular, the purification step is carried out to isolate the inventive compound from non-reacted substrates, in particular the linear triol and the aldehyde or ketone.

In addition, the inventive compound may be further submitted to the following process steps of a) purification using standard means such as steam distillation, thermal distillation, vacuum evaporation, including removal of all solvent, dialysis and/or b) drying using standard drying means such as spray-, drum, paddle-, vacuum-drying means including agglomeration methods such as fluidized-bed-drying, to obtain a purified solution, a purified liquid, a solid, e.g., granulated or co -granulated or a purified solid, respectively.

In case that after the reaction leading to the inventive compound residual substrates are present to a non-desirable extent, the resulting product mixture containing the inventive compound may be further purified by standard means to reduce the content of residual substrates, but also to reduce the amount of possible by-products, reduce the amount(s) of the solvent(s) employed (i.e., to concentrate) or replace solvent(s) with other solvents. Such processes are known to a person of skill in this field.

Preferably, undesirable amounts of residual substrates are removed, preferably by means of dis- tillative processes, more preferably by thermal distillative processes, which may additionally comprise the application of reduced pressure to increase the speed and/or the effectiveness of the removal. In a preferred embodiment only the additional process step a) is employed.

In further embodiments, the linear triol and the aldehyde or ketone are renewable compounds, preferably directly isolated from an organism such as bacteria, algae, fungi or plants or are prepared from preceding compounds obtained from bacteria, algae, fungi or plants. In preferred embodiments, all of the above-mentioned substrates are renewable compounds. A renewable triol may be 1 ,2,4-butanetriol which is synthesized by biotechnological synthesis using genetically engineered Escherichia coliand Pseudomonas fragi as described by Cao et al. (Yujin Cao, Wei Niu, Jiantao Guo, Mo Xian, Huizhou Liu: Biotechnological production of 1 ,2,4-butanetriol: An efficient process to synthesize energetic material precursor from renewable biomass. Scientific Reports, issue 5, Nr. 1 , 2015, page 18149).

Long-chained carboxylic acids are well-known metabolites of bacteria, fungi or plants. These compounds are therefore naturally based and renewable. Several different protocols have been developed for their isolation and thus such carboxylic acids are frequently available on the market. Moreover, these carboxylic acids can also be used to produce aldehydes and ketones. Therefore, the skilled person also knows how naturally based and renewable aldehydes and ketones can be synthesized.

Suitable linear triols to prepare the reaction of the invention are 1 ,2,4-butanetriol, 1 ,2,5-penta- netriol, 1 ,2,6-hexanetriol, 1 ,2,7-heptanetriol, 1 ,2,8-octanetriol, 1 ,2,9-nonanetriol and 1 ,2,10-dec- anetriol, preferably 1 ,2,4-butanetriol.

Embodiment 7

The process of the invention, wherein the acidic catalyst is selected from the group consisting of alkylbenzene sulfonic acid, methane sulfonic acid, sulfuric acid, phosphoric acid, hypophosphoric acid and hydrochloric acid.

In preferred embodiments, the acidic catalyst is an alkylbenzene sulfonic acid according to the formula CI O-CI S-Ph-SOsH.

The reaction between the linear triol and the aldehyde or ketone may be carried out for at least 1 hour at at least 30°C. Preferably the reaction takes place for 1 .5 to 2.5 hours at a temperature between 40°C to 60°C. In more preferred embodiments, the reaction conditions are 2 hours at 50°C.

Embodiment 8 The inventive process, wherein

(i) R3 is C10 to C17 alkyl or C10 to C17 alkenyl, preferably C10 to C17 alkyl; and

(ii) R4 is hydrogen.

Embodiment 9

The inventive process, wherein the linear triol comprises 4 to 6 carbon atoms.

Embodiment 10

The process of the invention, wherein the sulfating step comprises i) sulfation with sulfur trioxide on a falling film reactor; ii) sulfation with chlorosulfuric acid; or iii) sulfation with sulfamic acid in presence of urea.

The above described sulfur containing have the following chemical structures: sulfur trioxide (SO3), chlorosulfuric acid (CISO3H) and sulfamic acid (H3NSO3).

In a preferred embodiment, the sulfation reaction based on sulfur trioxide is carried out using a falling film reactor. Such falling film reactors and their use for sulf(on)ation are well-known in the art and include Stepan’s Falling Film Reactor (for example, as described in US3169142A) and Chemithon’s Annular Film Reactor (for example, as described in US3427342A).

Embodiment 1 1

Use of the inventive compound in cleaning compositions, in fabric and home care products, in cosmetic formulations, as crude oil emulsion breaker, as surfactant in enhanced oil recovery, as surfactant in corn oil separation, as surfactant in fermentation processes, as surfactant in flotation of mineral ores, in pigment dispersions for ink jet inks, in formulations for electro plating, in cementitious compositions, as dispersant for agrochemical formulations.

A subject matter of the present invention is the use of the above-mentioned substituted 1 ,3-diox- olane sulfates in fabric and home care products, in cosmetic formulations, as crude oil emulsion breaker, in pigment dispersions for ink jet inks, in formulations for electro plating, in cementitious compositions and/or as dispersant for agrochemical formulations, preferably in cleaning compositions and/or in fabric and home care products, in particular cleaning compositions for improved clay removal or oily and fatty stain removal, wherein the cleaning composition is preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation. The substituted 1 ,3-dioxolane sulfates can be added to cosmetic formulations, as crude oil emulsion breaker, in pigment dispersions for ink jet inks, formulations for electro plating, in cementitious compositions. However, the inventive compounds can also be added to (used in) washing or cleaning compositions.

Another subject-matter of the present invention is, therefore, a cleaning composition, fabric and home care product, industrial and institutional cleaning product, cosmetic formulation, crude oil emulsion breaker, pigment dispersion for ink jet inks, formulation for electro plating, cementitious composition and/or dispersant for agrochemical formulations, comprising at least one substituted 1 ,3-dioxolane sulfate, as defined above.

Preferably, it is a cleaning composition and/or fabric and home care product, comprising at least one substituted 1 ,3-dioxolane sulfate, as defined above, preferably for improved clay removal or oily and fatty stain removal, preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

In another preferred embodiment of the present invention, the cleaning composition may be used for soil removal of particulate stains and/or oily and fatty stains, and additionally for whiteness maintenance, preferably in laundry care.

In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass.

In another embodiment, the cleaning composition of the present invention is a liquid or solid automatic dish wash detergent composition, preferably a solid automatic dish wash detergent composition, that may be used for cleaning dish ware, e.g., dish ware such as glasses, wherein the inventive substituted 1 ,3-dioxolane sulfate is improving the removal of stubborn soils.

In another embodiment, the cleaning composition is designed to be used in personal care and pet care compositions such as shampoo compositions, body wash formulations, liquid or solid soaps.

In this invention, a preferred area of application for the use of the substituted 1 ,3-dioxolane sulfate is the field of fabric and home care products and cleaning compositions, preferably cleaning compositions for industrial and institutional use and the use by consumers in their household. Embodiment 12

The inventive use in cleaning compositions and/or in fabric and home care products, preferably in cleaning compositions for i) improved removal of oily/fatty stains, and/or ii) improved removal of sebum, and/or iii) clay removal, and/or iv) soil removal of particulate stains, and/or v) dispersion and/or emulsification of soils, and/or vi) modification of treated surface to improve removal upon later re-soiling, and/or vii) whiteness improvement and/or preferably in cleaning compositions for removal of oily/fatty stains, each of the before mentioned options i) to vii) preferably for use in a laundry detergent formulation and/or a manual dish wash detergent formulation and/or in a formulation suitable for (pre) -treatment of textiles and/or soap bars, more preferably in a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

Embodiment 13

Cleaning composition, fabric and home care product, industrial and institutional cleaning product, cosmetic formulation, crude oil emulsion breaker, oil recovery formulation, formulation for corn oil separation, formulation for fermentation process, flotation agent of mineral ores, pigment dispersion for ink jet inks, formulation for electro plating, cementitious composition, dispersant for agrochemical formulations, comprising at least one compound ac -cording to any of claims 1 to 5, preferably cleaning composition and/or fabric and home care product and/or industrial and institutional cleaning product, comprising at least one inventive compound.

Embodiment 14

Cleaning composition of the invention further comprising i) at least one cleaning polymer or soil release polymer, and/or ii) at least one further surfactant selected from the group consisting of anionic surfactants and/or non-ionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants, and/or iii) an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4’- dichoro 2-hydroxydiphenylether; preferably comprising 2-phenoxyethanol in an amount ranging from 2ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol or preferably comprising 4,4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, more preferably 0.002 to 1 %, even more preferably 0.01 to 0.6%, each by weight of the composition, and/or iv) at least one enzyme selected from the list consisting of lipases, hydro-lases, amylases, DNases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xy- lanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme being selected from proteases, and/or v) at least one compound selected from the group consisting of builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, dye fixation agent and perfumes, vi) cosolvent selected from groups of aliphatic alcohols, diols (preferably propylene glycole), or triols comprising 2 to 5 carbon atoms or selected from group of ethylene glycole or diethylene glycol mono alkyl ether comprising 2 to 5 carbon atoms in alkyl moiety or selected from group of propylene glycole or dipropylene glycol mono alkyl ether comprising 2 to 5 carbon atoms in alkyl moiety, and/or vii) water.

Embodiment 15

A cleaning method comprising contacting a cleaning composition of the invention with an object that requires cleaning, preferably a laundry or a hard surface household item. The term “cleaning”, as used herein, refers to performing or aiding in any soil removal, bleaching, microbial population reduction, or combination thereof. This includes to rinse a fabric with water or to wash the fabric with the inventive liquid cleaning composition by means of a washing machine, automatic dish washer or by hand. It is preferred that the cleaning is carried out at a temperature of 60 °C or less, more preferably at a temperature of 40 °C or less, most preferably at a temperature of 30 °C or less. In other preferred embodiments, the cleaning method is performed under water conserving conditions. This means that not more than 60%, not more than 70%, not more than 80%, not more than 90% or not more than 95% of the water generally recommended for a given cleaning procedure is used for the cleaning method of the present invention.

The following examples shall further illustrate the present invention without restricting the scope of the invention.

The specific embodiments as described throughout this disclosure are encompassed by the present invention as part of this invention; the various further options being disclosed in this present specification as “optional”, “preferred”, “more preferred”, “even more preferred” or “most preferred” (or “preferably” etc.) options of a specific embodiment may be individually and independently (unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded) selected and then combined within any of the other embodiments (where other such options and preferences can be also selected individually and independently unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded), with each and any and all such possible combinations being included as part of this invention as individual embodiments.

As used herein, the articles “a” and “an” when used in a claim or an embodiment, are understood to mean one or more of what is claimed or described. As used herein, the terms “include(s)” and “including” are meant to be non-limiting, and thus encompass more than the specific item mentioned after those words.

The compositions of the present disclosure can “comprise” (i.e. , contain other ingredients), “consist essentially of” (comprise mainly or almost only the mentioned ingredients and other ingredients in only very minor amounts, mainly only as impurities), or “consist of” (i.e., contain only the mentioned ingredients and in addition may contain only impurities not avoidable in a technical environment, preferably only the ingredients) the components of the present disclosure.

The term “at least one”, as used herein, includes but is not limited to 1 , 2, 3, 4, 5, 6, 7, 8, 9 and more. Similarly, the terms “substantially free of ...” or “substantially free from ...” or “(containing/com- prising) essentially no ...” may be used herein; this means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1 %, or even less than 0.1 %, or even more less than 0.01%, or even 0%, by weight of the composition.

The term “about”, as used herein, encompasses the exact number “X” mentioned as e.g., “about X%” etc., and small variations of X, including from minus 5 to plus 5 % deviation from X (with X for this calculation set to 100%), preferably from minus 2 to plus 2 %, more preferably from minus 1 to plus 1 %, even more preferably from minus 0,5 to plus 0,5 % and smaller variations. Of course, if the value X given itself is already “100%” (such as for purity etc.) then the term “about” clearly can and thus does only mean deviations thereof which are smaller than “100”.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. Unless otherwise specified, all measurements herein are conducted at 20°C and under atmospheric pressure. In all embodiments of the present disclosure, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise.

Description of cleaning compositions, formulations and their ingredients

The phrase "cleaning composition" as used herein includes compositions and formulations designed for cleaning soiled material. Such compositions and formulations include those designed for cleaning soiled material or surfaces of any kind.

Compositions for “industrial and institutional cleaning” includes such cleaning compositions being designed for use in industrial and institutional cleaning, such as those for use of cleaning soiled material or surfaces of any kind, such as hard surface cleaners for surfaces of any kind, including tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, lacquered surfaces. “Compositions for Fabric and Home Care” include cleaning compositions and formulations including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein and detailed herein below when describing the compositions. Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation, preferably during the wash cycle of the laundering or dish washing operation, and as further detailed herein below when describing the use and application of the inventive compounds and compositions comprising such polymers.

The cleaning compositions of the invention may be in any form, namely, in the form of a liquid; a solid such as a powder, granules, agglomerate, paste, tablet, pouches, bar, gel; an emulsion; types delivered in dual- or multi-compartment containers; single-phase or multi-phase unit dose; a spray or foam detergent; premoistened wipes (i.e., the cleaning composition in combination with a nonwoven material such as that discussed in US 6, 121 ,165, Mackey, et al.); dry wipes (i.e., the cleaning composition in combination with a nonwoven materials, such as that discussed in US 5,980,931 , Fowler, et al.) activated with water by a user or consumer; and other homogeneous, non-homogeneous or single-phase or multiphase cleaning product forms.

The liquid cleaning compositions of the present invention preferably have a viscosity of from 50 to 10000 mPa*s; liquid manual dish wash cleaning compositions (also liquid manual “dish wash compositions”) have a viscosity of preferably from 100 to 10000 mPa*s, more preferably from 200 to 5000 mPa*s and most preferably from 500 to 3000 mPa*s at 20 1/s and 20°C; liquid laundry cleaning compositions have a viscosity of preferably from 50 to 3000 mPa*s, more preferably from 100 to 1500 mPa*s and most preferably from 200 to 1000 mPa*s at 20 1/s and 20°C.

The liquid cleaning compositions of the present invention may have any suitable pH -value. Preferably the pH of the composition is adjusted to between 4 and 14. More preferably the composition has a pH of from 6 to 13, even more preferably from 6 to 10, most preferably from 7 to 9. The pH of the composition can be adjusted using pH modifying ingredients known in the art and is measured as a 10% product concentration in demineralized water at 25°C. For example, NaOH may be used and the actual weight% of NaOH may be varied and trimmed up to the desired pH such as pH 8.0. In one embodiment of the present invention, a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

Cleaning compositions such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, are known to a person skilled in the art. Any composition etc. known to a person skilled in the art, in connection with the respective use, can be employed within the context of the present invention by including at least one inventive compound, preferably at least one polymer in amounts suitable for expressing a certain property within such a composition, especially when such a composition is used in its area of use.

One aspect of the present invention is also the use of the inventive compounds as additives for detergent formulations, particularly for liquid detergent formulations, preferably concentrated liquid detergent formulations, or single mono doses for laundry.

The cleaning compositions of the invention may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as “adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.

Suitable adjunct cleaning additives include builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, dye fixation agent and perfumes.

Liquid cleaning compositions additionally may comprise - and preferably do comprise at least one of - rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.

Solid compositions additionally may comprise - and preferably do comprise at least one of - fillers, bleaches, bleach activators and catalytic materials. Suitable examples of such cleaning adjuncts and levels of use are found in WO 99/05242, U.S.

Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

Hence, the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above and below in more detail.

The surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

The cleaning compositions of the invention preferably comprise a surfactant system in an amount sufficient to provide desired cleaning properties. In some embodiments, the cleaning composition comprises, by weight of the composition, from about 1% to about 70% of a surfactant system. In other embodiments, the liquid cleaning composition comprises, by weight of the composition, from about 2% to about 60% of the surfactant system. In further embodiments, the cleaning composition comprises, by weight of the composition, from about 5% to about 30% of the surfactant system. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

(a) Laundry compositions

In laundry formulations, anionic surfactants contribute usually by far the largest share of surfactants within such formulation. Hence, preferably, the inventive cleaning compositions for use in laundry comprise at least one anionic surfactant and optionally further surfactants selected from any of the surfactant classes described herein, preferably from non-ionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants in addition to the inventive surfactant. Nonlimiting examples of anionic surfactants - which may be employed also in combinations of more than one surfactant - useful herein include C9-C20 linear alkylbenzenesulfonates (LAS), C10- C20 primary, branched chain and random alkyl sulfates (AS); C10-C18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefin sulfonate (AOS).

Preferred examples of suitable anionic surfactants are alkali metal and ammonium salts of Cs- Ci 2-alkyl sulfates, of Ci2-Ci8-fatty alcohol ether sulfates, of Ci2-Ci8-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-Ci2-alkylphenols (ethoxylation: 3 to 50 mol of ethylene oxide/mol), of Ci2-Ci8-alkylsulfonic acids, of C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, of C -C -alkylarylsulfonic acids, preferably of n-C -Cis- alkylbenzene sulfonic acids, of C10-C18 alkyl alkoxy carboxylates and of soaps such as for example C8-C24-carboxylic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.

In one embodiment of the present invention, anionic surfactants are selected from n-C -Cis-al- kylbenzene sulfonic acids and from fatty alcohol polyether sulfates, which, within the context of the present invention, are in particular sulfuric acid half-esters of ethoxylated Ci2-Ci8-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), preferably of n-Ci2-Ci8-alkanols.

In one embodiment of the present invention, also alcohol polyether sulfates derived from branched (i.e., synthetic) Cn-C -alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol) may be employed.

Preferably, the alkoxylation group of both types of alkoxylated alkyl sulfates, based on C12-C18- fatty alcohols or based on branched (i.e., synthetic) Cn-C -alcohols, is an ethoxylation group and an average ethoxylation degree of any of the alkoxylated alkyl sulfates is 1 to 5, preferably 1 to 3.

In a further embodiment of the present invention, anionic surfactants are selected from rhamnolipids and/or sophorolipids. Preferably, the laundry detergent formulation of the present invention comprises from at least 1 wt.% to 50 wt.%, preferably in the range from greater than or equal to about 2 wt.% to equal to or less than about 30 wt.%, more preferably in the range from greater than or equal to 3 wt.% to less than or equal to 25 wt.%, and most preferably in the range from greater than or equal to 5 wt.% to less than or equal to 25 wt.% of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.

In a preferred embodiment of the present invention, anionic surfactants are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1 -5 ethoxy units and C10-C18 alkylsulfates.

Non-limiting examples of non-ionic surfactants - which may be employed also in combinations of more than one other surfactant - include: Cs-C alkyl ethoxylates, such as, NEODOL® nonionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as discussed in U.S. 4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as discussed in US 5,332,528; and ether capped poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO 01/42408.

Preferred examples of non-ionic surfactants are in particular alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides).

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (A)

[formula (A)] in which the variables are defined as follows:

R¹ is selected from linear Ci-C -alkyl, preferably ethyl and particularly preferably methyl, R² is selected from C8-C22-alkyl, for example n-CsHi?, n-CioH₂i, n-Ci2H₂5, n-Ci4H₂9, n-C Hss or n-Ci₈H₃₇,

R³ is selected from Ci-C -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl, m and n are in the range from zero to 300, where the sum of n and m is at least one. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

Here, compounds of the general formula (A) may be block copolymers or random copolymers, preference being given to block copolymers.

Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (B)

[formula (B)] in which the variables are defined as follows:

R¹ is identical or different and selected from linear Ci-C4-alkyl, preferably identical in each case and ethyl and particularly preferably methyl,

R⁴ is selected from C6-C2o-alkyl, in particular n-CsHi?, n-CioH₂i, n-Ci2H₂5, n-Ci4H₂9, n- C16H33, n-C Hs?, a is a number in the range from zero to 6, preferably 1 to 6, b is a number in the range from zero to 20, preferably 4 to 20, d is a number in the range from 4 to 25.

Preferably, at least one of a and b is greater than zero.

Here, compounds of the general formula (B) may be block copolymers or random copolymers, preference being given to block copolymers.

Further suitable non-ionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable non-ionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of suitable further non-ionic surfactants can be found in EPA 0851 023 and in DE-A 198 19 187. Mixtures of two or more different non-ionic surfactants may of course also be present.

In a preferred embodiment of the present invention, non-ionic surfactants are selected from C12/14 and C16/18 fatty alkoholalkoxylates, C13/15 oxoalkoholalkoxylates, C -alkoholalkoxylates, and 2- propylheptylalkoholalkoxylates, each of them with 3 - 15 ethoxy units, preferably 4-10 ethoxy units, or with 1 -3 propoxy- and 2-15 ethoxy units.

Non-limiting examples of amphoteric surfactants - which may be employed also in combinations of more than one other surfactant - include: water-soluble amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681 ,704, and US 4,133,779. Suitable surfactants include thus so-called amine oxides, such as lauryl dimethyl amine oxide (“lauramine oxide”).

Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amido propyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coco dimethyl amino oxides. Amine oxides may have a linear or midbranched alkyl moiety. Typical linear amine oxides include water-soluble amine oxides containing one R¹ = Cs-18 alkyl moiety and two R² and R³ moieties selected from the group consisting of C1- C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide is characterized by the formula

R¹-N(R²)(R³)-O wherein R¹ is a Cs-is alkyl and R² and R³ are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl. The linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferred amine oxides include linear C10, linear C10- C12, and linear C12-C14 alkyl dimethyl amine oxides. As used herein "mid-branched" means that the amine oxide has one alkyl moiety having n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching for the amine oxide is also known in the art as an internal amine oxide. The total sum of n1 and n2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16. The number of carbon atoms for the one alkyl moiety (n1 ) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric. As used herein "symmetric" means that (n1 -n2) is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt.%, more preferably at least 75 wt.% to 100wt.% of the mid-branched amine oxides for use herein. The amine oxide further comprises two moieties, independently selected from a C1-C3 alkyl, a C1-C3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups. Preferably the two moieties are selected from a C1-C3 alkyl, more preferably both are selected as a Ci alkyl.

In a preferred embodiment of the present invention, amphoteric surfactants are selected from Cs- C18 alkyl-dimethyl aminoxides and Cs-Cis alkyl-di(hydroxyethyl)aminoxide.

Cleaning compositions may also contain zwitterionic surfactants - which may be employed also in combinations of more than one other surfactant.

Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the phosphobetaines. Examples of suitable betaines and sulfobetaines are the following (designated in accordance with INCI): Almond amidopropyl of betaines, Apricotamidopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenamidopropyl betaines, Behenyl of betaines, Canol amidopropyl betaines, Capryl/Capramidopropyl betaines, Carnitine, Cetyl of betaines, Cocamidoethyl of betaines, Cocamidopropyl betaines, Cocamidopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl of PG-betaines, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow of betaines, Isostearamidopropyl betaines, Lau ram idopropyl betaines, Lauryl of betaines, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl betaines, Minkamidopro- pyl of betaines, Myristamidopropyl betaines, Myristyl of betaines, Oleamidopropyl betaines, Oleamidopropyl Hydroxysultaine, Oleyl of betaines, Olivamidopropyl of betaines, Palmamidopro- pyl betaines, Palmitamidopropyl betaines, Palmitoyl Carnitine, Palm Kernelamidopropyl betaines, Polytetrafluoroethylene Acetoxypropyl of betaines, Ricinoleam idopropyl betaines, Sesamidopro- pyl betaines, Soyamidopropyl betaines, Stearamidopropyl betaines, Stearyl of betaines, Tal- lowamidopropyl betaines, Tallowamidopropyl Hydroxysultaine, Tallow of betaines, Tallow Dihydroxyethyl of betaines, Undecylenamidopropyl betaines and Wheat Germamidopropyl betaines.

Preferred betaines are, for example, Ci2-Ci8-alkylbetaines and sulfobetaines. The zwitterionic surfactant preferably is a betaine surfactant, more preferably a Cocoamidopropylbetaine surfactant. Non-limiting examples of cationic surfactants - which may be employed also in combinations of more than one other surfactant - include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as discussed in US patents Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and amino surfactants as discussed in US 6,221 ,825 and WO 00/47708, specifically amido propyldimethyl amine (APA).

Compositions according to the invention may comprise at least one builder. In the context of the present invention, no distinction will be made between builders and such components elsewhere called “co-builders”. Examples of builders are complexing agents, hereinafter also referred to as complexing agents, ion exchange compounds, and precipitating agents. Builders are selected from citrate, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates.

In the context of the present invention, the term citrate includes the mono- and the dialkali metal salts and in particular the mono- and preferably the trisodium salt of citric acid, ammonium or substituted ammonium salts of citric acid as well as citric acid. Citrate can be used as the anhydrous compound or as the hydrate, for example as sodium citrate dihydrate. Quantities of citrate are calculated referring to anhydrous trisodium citrate.

The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. Preferably, however, the composition according to the invention is free from phosphates and polyphosphates, with hydrogenphosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate (“phosphate -free”). In connection with phosphates and polyphosphates, “free from” should be understood within the context of the present invention as meaning that the content of phosphate and polyphosphate is in total in the range from 10 ppm to 0.2% by weight of the respective composition, determined by gravimetry.

The term “carbonates” includes alkali metal carbonates and alkali metal hydrogen carbonates, preferred are the sodium salts. Particularly preferred is Na2COs. Examples of phosphonates are hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, the 1 -hydroxyethane-1 ,1 -diphosphonate (HEDP) is of particular importance as builder. It is preferably used as sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkanephosphonates are preferably ethylene diaminetetramethylenephosphonate (EDTMP), diethylenetriamine- pentamethylenephosphonate (DTPMP), and also their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g., as hexasodium salt of EDTMP or as hepta- and octa-sodium salts of DTPMP.

Examples of amino carboxylates and polycarboxylates are nitrilotriacetates, ethylene diamine tetraacetate, diethylene triamine pentaacetate, triethylene tetraamine hexaacetate, propylene diamines tetraacetic acid, ethanol-diglycines, methylglycine diacetate, and glutamine diacetate. The term amino carboxylates and polycarboxylates also include their respective non-substituted or substituted ammonium salts and the alkali metal salts such as the sodium salts, in particular of the respective fully neutralized compound.

Silicates in the context of the present invention include in particular sodium disilicate and sodium metasilicate, alumosilicates such as for example zeolites and sheet silicates, in particular those of the formula a-Na2Si20s, p-Na2Si20s, and 5-Na2Si20s.

Compositions according to the invention may contain one or more builder selected from materials not being mentioned above. Examples of builders are a-hydroxypropionic acid and oxidized starch.

In one embodiment of the present invention, builder is selected from polycarboxylates. The term “polycarboxylates” includes non-polymeric polycarboxylates such as succinic acid, C2-Ci6-alkyl disuccinates, C2-Ci6-alkenyl disuccinates, ethylene diamine N,N’-disuccinic acid, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid.

Oligomeric or polymeric polycarboxylates are for example polyaspartic acid or in particular alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

Suitable co-monomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has a weight-average molecular weight Mw in the range from 2000 to 40000 g/mol, preferably 2000 to 10000 g/mol, in particular 3000 to 8000 g/mol. Further suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid.

It is also possible to use copolymers of at least one monomer from the group consisting of mo- noethylenically unsaturated Cs-C -mono- or C4-C -dicarboxylic acids or anhydrides thereof, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilically or hydrophobically modified co -monomer as listed below.

Suitable hydrophobic co-monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with ten or more carbon atoms or mixtures thereof, such as, for example, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1 -eicosene, 1 -do- cosene, 1 -tetracosene and 1 -hexacosene, C22-a-olefin, a mixture of C2o-C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.

Suitable hydrophilic co-monomers are monomers with sulfonate or phosphonate groups, and also non-ionic monomers with hydroxyl function or alkylene oxide groups. By way of example, mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxy- poly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (methacrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. Polyalkylene glycols here can comprise 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

Particularly preferred sulfonic-acid-group-containing monomers here are 1 -acrylamido-1 -propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesul- fonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-pro- pene-1 -sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of said acids, such as sodium, potassium or ammonium salts thereof.

Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.

Moreover, amphoteric polymers can also be used as builders. Compositions according to the invention can comprise, for example, in the range from in total 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight, of builder(s), especially in the case of solid formulations. Liquid formulations according to the invention preferably comprise in the range of from 0.1 to 8% by weight of builder.

Formulations according to the invention can comprise one or more alkali carriers. Alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired. Of suitability are, for example, the alkali metal carbonates, the alkali metal hydrogen carbonates, and alkali metal metasilicates mentioned above, and, additionally, alkali metal hydroxides. A preferred alkali metal is in each case potassium, particular preference being given to sodium. In one embodiment of the present invention, a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

In one embodiment of the present invention, the composition or laundry formulation according to the invention comprises additionally at least one enzyme.

In one embodiment, the composition according to the present invention additionally comprises at least one enzyme.

Preferably, the at least one enzyme is a detergent enzyme.

In one embodiment, the enzyme is classified as an oxidoreductase (EC 1 ), a transferase (EC 2), a hydrolase (EC 3), a lyase (EC 4), an isomerase (EC 5), or a ligase (EC 6). The EC-numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999. Preferably, the enzyme is a hydrolase (EC 3).

In a preferred embodiment, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pento- sanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohydrases, galactanases, xantha- nases, xyloglucanases, oxidoreductase, perhydrolases, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alpha-galacto- sidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersins, and combinations of at least two of the foregoing types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types. Most preferably, the enzyme is a protease, preferably, a serine protease, more preferably, a subtilisin protease.

Preferably, the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101 E (according to BPN’ numbering). Preferably, the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881 A1.

The composition of the present invention can comprise one type of enzyme or more than one enzyme of different types, e.g., an amylase and a protease, or more than one enzyme of the same type, e.g., two or more different proteases, or mixtures thereof, e.g. , an amylase and two different proteases.

The enzyme(s) can be incorporated into the composition at levels sufficient to provide an effective amount for achieving a beneficial effect, preferably for primary washing effects and/or secondary washing effects, like anti-greying or antipilling effects (e.g., in case of cellulases). Preferably, the enzyme is present in the composition at levels from about 0.00001 % to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001 % to about 1%, or even more preferably from about 0.001 % to about 0.5% enzyme protein by weight of the composition.

The skilled person will understand that the above-described enzymes may also be part of microorganisms, probiotics and/or prebiotics.

Preferably, the enzyme-containing composition further comprises an enzyme stabilizing system.

Preferably, the enzyme-containing composition described herein comprises from about 0.001% to about 10%, from about 0.005% to about 8%, or from about 0.01% to about 6%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.

Preferably, the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2-propane- diol, or sorbitol), inorganic salts (preferably, CaC , MgCl2, or NaCI), short chain (preferably, Ci- C3) carboxylic acids or salts thereof (preferably, formic acid, formate (preferably, sodium formate), acetic acid, acetate, or lactate), borate, boric acid, boronic acids (preferably, 4-formyl phenyl- boronic acid (4-FPBA)), peptide aldehydes (preferably, Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrosulfite adducts. Preferably, the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. In particular, if proteases are present in the composition, protease inhibitors may be added, preferably selected from borate, boric acid, boronic acids (preferably, 4-FPBA), peptide aldehydes (preferably, peptide aldehydes like Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrosulfite adducts.

Compositions according to the invention may comprise one or more bleaching agent (bleaches). Preferred bleaches are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term “persulfate” in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate.

In this connection, the alkali metal salts can in each case also be alkali metal hydrogen carbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulfate. However, the dialkali metal salts are preferred in each case.

Formulations according to the invention can comprise one or more bleach catalysts. Bleach catalysts can be selected from oxaziridinium-based bleach catalysts, bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.

Formulations according to the invention can comprise one or more bleach activators, for example tetraacetyl ethylene diamine, tetraacetylmethylene diamine, tetraacetylglycoluril, tetraacetylhexylene diamine, acylated phenolsulfonates such as for example n-nonanoyl- or isononanoyloxybenzene sulfonates, (S)NOBS, LOBS, DOBA, PAP, N-methylmorpholinium-ace- tonitrile salts (“MMA salts”), trimethylammonium acetonitrile salts, N -acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts). As precursors of H2O2 peroxides come into consideration, i. e. every compound which is capable of yielding hydrogen peroxide in aqueous solutions, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C.

Preferably, however, inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates. They are typically used in an amount of 2-80 wt-%, preferably of 4- 30 wt-%, based on the weight of the composition.

O

I I

Typically, the compound of formula (1 ) , as described in more detail below, is present in the composition in an amount of 0.05-15 wt-%, preferably from 0.1 to 10 wt-%, based on the weight of the total composition.

Examples of suitable inorganic peroxides are sodium perborate tetrahydrate or sodium perborate monohydrate, sodium percarbonate, inorganic peroxyacid compounds, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-80 wt-%, preferably from 4-30 wt-%, based on the weight of the composition.

The organic peroxides are, for example, mono- or poly-peroxides, urea peroxides, a combination of a Ci-C4alkanol oxidase and Ci-C4alkanol (Such as methanol oxidase and ethanol as described in WO95/07972), alkylhydroxy peroxides, such as cumene hydroperoxide and t-butyl hydroperoxide.

The peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.

As oxidants, peroxo acids can also be used. One example are organic mono peracids of formula O

... R -C -O-OM

(1 ) wherein

M signifies hydrogen or a cation,

R19 signifies unsubstituted Ci -Ci salkyl ; substituted Ci-C alkyl; unsubstituted aryl; substituted aryl; -(Ci-C6alkylene)-aryl, wherein the alkylene and/or the alkyl group may be substituted; and phthalimidoCi-Csalkylene, wherein the phthalimide and/or the alkylene group may be substituted.

O

__L R C -O-OM

Preferred mono organic peroxy acids and their salts are those of formula wherein

M signifies hydrogen or an alkali metal, and

R’ signifies unsubstituted Ci-C4alkyl; phenyl;-Ci-C2alkylene-phenyl or phthalimidoCi-Csalkylene.

Especially preferred is CH₃COOOH and its alkali salts.

Especially preferred is also e-phthalimido peroxy hexanoic acid and its alkali salts (PAP).

Also suitable are diperoxyacids, for example, 1 ,12-diperoxydodecanedioic acid (DPDA), 1 ,9-di- peroxyazelaic acid, diperoxybrassilic acid, diperoxysebasic acid, diperoxyisophthalic acid, 2- decyldiperoxybutane-1 ,4-diotic acid and 4,4'-sulphonylbisperoxybenzoic acid.

In some cases, the use of an additional bleach activator may be of advantage.

The term bleach activator is frequently used as a synonym for peroxyacid bleach precursor. All the above mentioned peroxy compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor.

Such precursors are the corresponding carboxyacid or the corresponding carboxyanhydride or the corresponding carbonylchlorid, or amides, or esters, which can form the peroxy acids on perhydrolysis. Such reactions are commonly known.

Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1 ,003,310 and 1 ,519,351 ; German Patent 3,337,921 ; EP-A- 0185522; EP-A-0174132; EP-A-0120591 ; and U.S. Pat. Nos. 1 ,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

Suitable bleach activators include the bleach activators, that carry O- and/or N-acyl groups and/or unsubstituted or substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED); acylated glycolurils, especially tetraacetyl glycol urea (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU); sodium-4-benzoyloxy benzene sulphonate (SBOBS); sodium-1 -methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl- 3-benzoloxy benzoate; trimethyl ammonium toluyloxy-benzene sulphonate;acylated triazine derivatives, especially 1 ,5-diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT); compounds of formula (10): wherein R22 is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R21 is linear or branched (C?-Ci5)alkyl, especially activators known under the names SNOBS, SLOBS and DOBA; acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran; and also acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use the combinations of conventional bleach activators known from German Patent Application DE-A-4443 177. Nitrile compounds that form perimine acids with peroxides also come into consideration as bleach activators.

Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Pat. Nos. 4,751 ,015 and 4,397,757, in EP-A0284292 and EP-A-331 ,229. Examples of peroxyacid bleach precursors of this class are: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride - (SPCC), N- octyl,N,N-dimehyl-N10 -carbophenoxy decyl ammonium chloride - (ODC), 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.

It is also possible to use additional bleach catalysts, which are commonly known, for example transition metal complexes as disclosed in EP 1194514, EP 1383857 or W004/007657.

Formulations according to the invention can comprise one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the present invention, formulations according to the invention comprise in total in the range from 0.1 to 1 .5% by weight of corrosion inhibitor. Formulations according to the invention may also comprise further cleaning polymers and/or soil release polymers.

The additional cleaning polymers may include, without limitation, “multifunctional alkoxylated polyethylene imines” (for example BASF’s Sokalan® HP20), “multifunctional alkoxylated diamines” (for example BASF’s Sokalan® HP96), BASF’s Sokalan® SR400 A and also terephthalic acidbased polyesters like Clariant’s TexCare®, such as TexCare® SRN 170, TexCare® SRN 172, TexCare® SRN 260, TexCare® SRN 260 SG Terra and TexCare® SRA 300 as well as distinct combinations of all of the before mentioned polymers.

Suitable multifunctional alkoxylated polyethylene imines are typically ethoxylated polyethylene imines with a weight-average molecular weight Mw in the range from 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000, and most preferably 10000 to 20000 g/mol. Suitable multifunctional alkoxylated polyethylene imines have 80 wt.% to 99 wt.%, preferably 85 wt.% to 99 wt.%, more preferably 90 wt.% to 98 wt.%, most preferably 93 wt.% to 97 wt.% or 94 wt.% to 96 wt.% ethylene oxide side chains, based on the total weight of the materials. Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell. Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5000 g/mol. Preferably employed is a molecular weight from 500 to 1000 g/mol, even more preferred is a Mw of 600 to 800 g/mol. The ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH- functional group.

Suitable multifunctional alkoxylated diamines are typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated (wherein the diamine is not ethylenediamine). Typical multifunctional alkoxylated diamines have a weight-average molecular weight Mw in the range from 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g/mol. In a preferred embodiment of the invention, ethoxylated hexamethylene diamine, furthermore quaternized and sulfated, may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.

Suitable polymers also comprise graft polymer comprising (A) a polyalkylene oxide backbone (A) which comprises at least one structural unit derived from the group of monomers consisting of ethylene oxide, 1 ,2-propylene oxide, 1 ,2-butylene oxide, 2,3-butylene oxide, 1 ,2-pentene oxide and 2,3-pentene oxide, and

(B) polymeric sidechains (B) grafted onto the polyalkylene oxide backbone (A), wherein said polymeric sidechains (B) comprise at least one vinyl ester monomer (B1 ) and optionally N-vi- nylpyrrolidone as further monomer (B2).

It is noted that the cleaning compositions of the invention can also comprise at least one propox- ylated ethylenediamine of the invention and in addition at least one propoxylated diamine that does not form part of the claims, such as propoxylated ethylenediamines having on average less than 28 PO units per mol EDA or having on average more than 52 PO units per mol EDA.

In a preferred embodiment of the present invention, the cleaning compositions may contain at least one multifunctional alkoxylated polyethylene imine and/or at least one multifunctional alkox- ylated diamine to improve the cleaning performance, such as preferably improve the stain removal ability, especially the primary detergency of particulate stains on polyester fabrics of laundry detergents. The multifunctional polyethylene imines or multifunctional diamines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15wt.%, preferably from 0.1 to 10 wt.% and more preferably from 0.25 to 5 wt.% and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents.

In another preferred embodiment of the present invention, the cleaning compositions may contain at least one terephthalic acid-based polyester, employed as soil release polymer, to improve the whiteness of the fabrics after the wash, especially the whiteness of polyester fabrics.

Thus, one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive compound and (ii) at least one compound selected from multifunctional alkoxylated polyethylene imines, multifunctional alkoxylated diamines and terephthalic acid-based polyesters, and mixtures thereof.

In one embodiment of the present invention, the ratio of the at least one inventive compound and (ii) the at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof, is from 10:1 to 1 :10, preferably from 5:1 to 1 :5 and more preferably from 3:1 to 1 :3. Laundry formulations comprising the inventive compound may also comprise at least one antimicrobial agent (also often named preservatives).

The composition may contain one or more antimicrobial agents and/or preservatives as listed in patent WO2021/115912 A1 on pages 35 to 39.

Especially of interest are the following antimicrobial agents and/or preservatives:

4,4’-dichloro 2-hydroxydiphenyl ether (CAS-No. 3380-30-1 ), further names: 5-chloro-2-(4-chloro- phenoxy) phenol, Diclosan, DCPP, which is commercially avail-able as a solution of 30 wt% of 4,4’-dichloro 2-hydroxydiphenyl ether in 1 ,2 propyl-eneglycol under the trade name Tinosan® HP 100 (BASF); 2-Phenoxyethanol (CAS-no. 122-99-6, further names: Phenoxyethanol, Methylphenylglycol, Phenoxetol, ethylene glycol phenyl ether, Ethylene glycol monophenyl ether, Protectol® PE); 2-bromo-2-nitropropane-1 ,3-diol (CAS-No. 52-51 -7, further names: 2-bromo-2- nitro-1 ,3-propanediol, Bronopol®, Protectol® BN, Myacide AS); Glutaraldehyde (CAS-No. 11 1 - 30-8, further names: 1 -5-pentandial, pentane-1 ,5-dial, glutaral, glutardialdehyde, Protectol® GA, Protectol® GA 50, Myacide® GA); Glyoxal (CAS No. 107-22-2; further names: ethandial, oxylal- dehyde, 1 ,2-ethandial, Protectol® GL); 2-butyl-benzo[d]isothiazol-3-one (BBIT, CAS No. 4299- 07-4); 2-methyl-2H-isothiazol-3-one (MIT, CAS No 2682-20-4); 2-octyl-2H-isothiazol-3-one (OIT, CAS No. 26530-20-1 ); 5-Chloro-2-methyl-2H-isothiazol-3-one (CIT, CMIT, CAS No. 26172-55-4); Mixture of 5-chloro-2-methyl-2H- isothiazol-3-one (CMIT, EINECS 247-500-7) and 2-methyl-2H- isothiazol-3-one (MIT, EINECS 220-239-6) (Mixture of CMIT/MIT, CAS No. 55965-84-9); 1 ,2-ben- zisothiazol-3(2H)-one (BIT, CAS No. 2634-33-5); Hexa-2,4-dienoic acid (Sorbic acid, CAS No. 1 10-44-1 ) and its salts, e.g. calcium sorbate, sodium sorbate, potassium (E,E)-hexa-2,4-dienoate (Potassium Sorbate, CAS No. 24634-61 -5); Lactic acid and its salts; L-(+)-lactic acid (CAS No. 79-33-4); Benzoic acid and its sodium salt (CAS No 65-85-0, CAS No. 532-32-1 ) and salts of benzoic acid e.g. ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate; Salicylic acid and its salts, e.g. calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate; Benzalkonium chloride, bromide and saccharinate, e.g. benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate (CAS Nos 8001 -54-5, 63449-41 -2, 91080-29-4, 68989-01 -5, 68424-85-1 , 68391 - 01 -5, 61789-y71 -7, 85409-22-9); Didecyldimethylammonium chloride (DDAC, CAS No. 68424- 95-3 and CAS No. 7173-51 -5); N-(3-aminopropyl)-N-dodecylpropane-1 ,3-diamine (Diamine, CAS No. 2372-82-9); Peracetic acid (CAS No. 79-21 -0); Hydrogen peroxide (CAS No. 7722-84-1).

The antimicrobial agent is added to the composition in a concentration of 0.001 to 10% relative to the total weight of the composition. Preferably, the composition contains 2-Phenoxyethanol in a concentration of 0.1 to 2% or 4,4’- dichloro 2-hydroxydiphenyl ether (DCPP) in a concentration of 0.005 to 0.6%.

The invention thus further encompasses a method of preserving an aqueous composition according to the invention against microbial contamination or growth, which method comprises addition of 2-Phenoxyethanol. The invention thus further encompasses a method of providing an antimicrobial effect on textiles after treatment with a solid laundry detergent e.g., powders, granulates, capsules, tablets, bars etc.), a liquid laundry detergent, a softener or an after rinse containing 4,4’-dichloro 2-hydroxydiphenyl ether (DCPP).

In a further embodiment, this invention also encompasses a composition comprising an inventive compound as descried herein before, further comprises an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.

In a further embodiment, this invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition comprising an inventive compound as described herein before, such composition being preferably a detergent composition, such method comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents as disclosed hereinafter, such antimicrobial agent preferably being 2-phenoxyethanol.

In a further embodiment, this invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising an inventive compound as described herein before, such composition further comprising 4,4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition.

In a further embodiment, this invention also encompasses a method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising an inventive compound as described herein before, such composition further comprising 4,4’-dichoro 2-hydroxydiphenylether. The term „dye fixation agent”, as used herein, relates to compounds that attenuate or even terminate dye bleeding of colored fabrics during the washing process. Dye fixation agents include, but are not limited to cationic dye fixation agents, crosslinking fixation agents and formaldehyde- based fixation agents. The skilled person is well-aware of these compounds and may purchase commercially available products from BASF SE, Huntsman, Archroma, Fineotex, Biotex Malaysia or Dystar. Exemplified, but not limiting dye fixation agents are Basilen Fixing Agent F-RP, Albafix ECO, Finofix NF, poly DADMAC, Polyamine (DCDA-DETA, Epichloro-DMA, Epichloro-DETA, etc.).

Formulations according to the invention may also comprise water and/or additional organic solvents, e.g., ethanol or propylene glycol.

Further optional ingredients may be but are not limited to viscosity modifiers, cationic surfactants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.

(b) General cleaning compositions and formulations

The liquid formulations disclosed in this chapter may comprise 0 to 2 % 2-phenoxyethanol, preferably about 1 %, in addition to all other mentioned ingredients.

The above and below disclosed liquid formulations may comprise 0-0,2% 4,4’-dichoro 2-hy- droxydiphenylether, preferably about 0,15 %, in addition to all other mentioned ingredients. The bleach-free solid laundry compositions may comprise 0-0,2% 4,4’-dichoro 2-hydroxydiphe- nylether, preferably about 0,15 %, in addition to all other mentioned ingredients.

The formulations disclosed in this chapter may - in addition to all other mentioned ingredients - comprise one or more enzymes selected from those disclosed herein above, more preferably a protease and/or an amylase, wherein even more preferably the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921 147B1 and having the amino acid substitution R101 E (according to BPN’ numbering) and wherein the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881 A1 , such enzyme(s) preferably being present in the formulations at levels from about 0.00001 % to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001 % to about 1%, or even more preferably from about 0.001 % to about 0.5% enzyme protein by weight of the composition. The following compositions shown below including those in the tables disclose general cleaning compositions of certain types, which correspond to typical compositions correlating with typical washing conditions as typically employed in various regions and countries of the world. The at least one inventive compound may be added to such formulation(s) in suitable amounts as outlined herein.

When the shown composition does not comprise an inventive compound, such composition is a comparative composition. When it comprises an inventive compound, especially in the amounts that are described herein as preferred, more preferred etc. ranges, such compositions are considered to fall within the scope of the present invention.

In a preferred embodiment the at least one substituted 1 ,3-dioxolane sulfate (as defined in any of the embodiments herein, especially the Embodiments 1 to 11 ; in this section also named “inventive compound”) is used in a laundry detergent.

Liquid laundry detergents according to the present invention are composed of:

0,05 - 20% of at least one inventive compound

1 - 50% of additional surfactants

0,05 - 50% of polymers

0,1 - 40% of builders, cobuilders and/or chelating agents

0,1 - 50% other adjuncts water to add up 100%.

Preferred liquid laundry detergents according to the present invention are composed of:

0,2 - 15 % of at least one inventive compound

2 - 40% of anionic surfactants selected from C10-C15- LAS and C10-C18 alkyl ether sulfates containing 1 -5 ethoxy-units

1 ,5 - 10% of nonionic surfactants selected from C -C -alkyl ethoxylates containing 3 - 10 ethoxy-units

2 - 20% of soluble organic builders/ cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxy-di- and hydroxytricaboxylic acids and polycarboxylic acids

0,05 - 5% of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system

0,5 - 20% of mono- or diols selected from ethanol, isopropanol, ethylene glycol, or propylene glycol

0,1 - 20% other adjuncts 0 - 20% of alkoxylated polyethylene amine or polyamide water to add up to 100%.

Solid laundry detergents (like e.g., powders, granules or tablets) according to the present invention are composed of:

0,05 - 20% of at least one inventive compound

1 - 50% of additional surfactants

0,1 - 80% of builders, cobuilders and/or chelating agents

0-50% fillers

0 - 40% bleach actives

0,1 - 30% other adjuncts and/or water

0 - 50% of polymers wherein the sum of the ingredients adds up 100%.

Preferred solid laundry detergents according to the present invention are composed of:

0,2 - 15 % of at least one inventive compound

5 - 30% of anionic surfactants selected from C10-C15- LAS, C10-C18 alkyl sulfates and C10- C alkyl ether sulfates containing 1 -5 ethoxy-units

1 ,5 - 7,5% of non-ionic surfactants selected from C -C -alkyl ethoxylates containing 3 - 10 ethoxy-units

5 - 50% of inorganic builders selected from sodium carbonate, sodium bicarbonate, zeolites, soluble silicates, sodium sulfate

0,5 - 15% of cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids and polycarboxylic acids

0,1 - 5% of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system

0,1 - 20% other adjuncts

0,1 - 20% of alkoxylated polyethylene amine or polyamide water to add up to 100%.

In a preferred embodiment the polymer according to the present invention is used in a manual dish wash detergent.

Liquid manual dish wash detergents according to the present invention are composed of:

0,05 - 10%of at least one inventive compound

1 - 50% of additional surfactants

0,1 - 50% of other adjuncts water to add up 100%.

Preferred liquid manual dish wash detergents according to the present invention are composed of:

0,2 - 5% of at least one inventive compound

5 - 40% of anionic surfactants selected from C10-C15- LAS, C10-C18 alkyl ether sulfates containing 1 -5 ethoxy-units, and C10-C18 alkyl sulfate

0 - 10% of Cocamidopropylbetaine

0 - 10% of Lauramine oxide

0 - 2% of a non-ionic surfactant, preferably a Cw-Guerbet alcohol alkoxylate

0 - 5% of an enzyme, preferably Amylase, and preferably also an enzyme stabilizing system

0,5 - 20% of mono- or diols selected from ethanol, isopropanol, ethylene glycol, or propylene glyclol

0,1 - 20% other adjuncts water to add up to 100%

As the surfactants of the invention may be biodegradable, and especially the cleaning formulations typically have a pH of about 7 or higher, and additionally often contain also enzymes - which are included into such cleaning formulations to degrade biodegradable stuff such as grease, proteins, polysaccharides etc. which are present in the stains and dirt which shall be removed by the cleaning compositions - some consideration is needed to be taken to formulate those potentially bio-degradable surfactants of the invention. Such formulations suitable are in principle known, and include the formulation in solids - where the enzymes and the surfactants can be separated by coatings or adding them in separate particles which are mixed - and liquids and semi-liquids, where the surfactants and the enzymes can be separated by formulating them in different compartments, such as different compartments of multi-chamber-pouches or bottles having different chambers, from which the liquids are poured out at the same time in a predefined amount to assure the application of the right amount per individual point of use of each component from each chamber. Such multi-compartment-pouches and bottles etc. are known to a person of skill as well.

The following table shows general cleaning compositions of certain types, which correspond to typical compositions correlating with typical washing conditions as typically employed in various regions and countries of the world. The at least one inventive compound may be added to such formulation(s) in suitable amounts as outlined herein. Table 1 : General formula for laundry detergent compositions according to the invention:

Table 2: Liquid laundry frame formulations according to the invention:

*Without inventive compound the formulations are comparative examples.

Table 2 - continued: Liquid laundry frame formulations according to the invention:

*Without inventive compound the formulations are comparative examples.

Table 3: Laundry powder frame formulations according to the invention:

Table 3 - continued: Laundry powder frame formulations according to the invention:

Table 4: Liquid manual dish wash frame formulations according to the invention:

The following examples shall further illustrate the present invention without restricting the scope of the invention.

The specific embodiments as described throughout this disclosure are encompassed by the present invention as part of this invention; the various further options being disclosed in this present specification as “optional”, “preferred”, “more preferred”, “even more preferred” or “most preferred” (or “preferably” etc.) options of a specific embodiment may be individually and independently (unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded) selected and then combined within any of the other embodiments (where other such options and preferences can be also selected individually and independently unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded), with each and any and all such possible combinations being included as part of this invention as individual embodiments.

Examples

I) Synthesis:

General

A long-chain aliphatic aldehyde is reacted with a triol, comprising at least four carbon atoms and hydroxy groups in the 1 - and 2-position, in presence of an acidic catalyst. The obtained acetale is sulfated with sulfur trioxide on a falling film reactor and neutralized with a base (e.g. aqueous sodium hydroxide), or with chloro sulfonic acid (optionally in presence of a solvent) and neutralized with a base (e.g. aqueous sodium hydroxide), or reacted with sulfamic acid (in presence of urea and optionally in presence of a solvent). Optionally a buffer is added to keep the pH above 7. The sulfation degrees are at >90%.

Inventive example a) 2-Undecyl-4-hydroxyethyl-1 ,3 -dioxo lane inventive example 1 (IE1 ) n-Dodecanal is freshly distilled. Then dodecanal (46.2 g, 0.245 mol, 1 .0 eq), 1 ,2,4-butantriol (27.8 g, 0.262 mol, 1 .07 eq), and an alkylbenzene sulfonic acid (C10C13-Ph-SO3H, 0.34 g, 0.001 mol, 0.004 eq) are mixed in a 250 ml glas vessel and stirred for 2 hours at 50°C under a N₂ atmosphere. In order to quench the reaction, 150 ml of a solution of 5 wt% NaHCOs in water is added. The organic phase is separated. The aqueous phase is extracted with ethyl acetate (3 x 150 ml). All organic phases are combined, dried over sodium sulfate, and the solvent removed at 60°C and at 10 mbar. According to proton nmr the dodecanal is fully converted into the desired acetal. b) 2-Undecyl-4-ethylsulfate-1 ,3-dioxolane sodium salt inventive example 2 (IE2)

2-llndecyl-4-hydroxyethyl-1 ,3-dioxolane (20 g, 0.073 mol, 1.0 eq) was dissolved in dichloromethane (140 ml) in a 500 ml vessel and cooled to 5°C. Nitrogen was bubbled through the mixture. To reduce strength of the sulfation reagent and avoid unwanted side-reactions due to the longer stirring time, 1 ,4-dioxane (12.9 g, 0.146 mol, 2.0 eq) was added. Then, chloro sulfonic acid (8.5 g, 0.073 mol, 1 .0 eq) was added dropwise at 5 - 10°C within 20 minutes. Reaction mixture was warmed to 10°C and stirred for 30 minutes. The solution was added into a 2 liter vessel comprising 600 ml of 10°C cold water, which comprised NaOH (3.96 g, 0.099 mol, 1.36 eq). The pH was adjusted to a value of 10.3 and a buffer was added (NaHCO3/Na2COs). The solvent was removed at 60°C and 140 mbar. The sulfation degree was according to proton nmr at 90%. Optionally, the crude product was dissolved in water to obtain a solution of 20 wt% surfactant in water.

For a 1 ,4-dioxane-free route, SOs-NEts can be used as sulfation reagent as it is milder compared to chloro sulfonic acid. In a falling film reactor, the sulfation with sulfur trioxide can be adjusted in such a way (by temperature and reaction time) that side reactions are reduced.

Comparative examples The following structures are disclosed in US20230174895 and synthesized for comparison with inventive compounds. a) 2-Undecyl-4-hydroxymethyl-1 ,3-dioxolane (CE1) : 2-Undecyl-5-hydroxy-1 ,3-dioxane (CE2) = 67 : 33 or 43 : 57

The acetalization of dodecanal with glycerin in presence of an alkyl benzene sulfonic acid (C10- C13-Ph-SOsH) is done in a similar way as the synthesis of the inventive example 1 . The 67 : 33 mixture of CE1 : CE2 is obtained if reaction mixture is stirred only for 1 hour. The 43 : 57 mixture of CE1 : CE2 is obtained if reaction mixture is stirred for 5 hours. b) 2-Undecyl-4-methylsulfate-1,3-dioxolane sodium salt (CE3) : 2-Undecyl-5-sulfate-1 ,3-dioxane sodium salt (CE4) = 67 : 33 or 43 : 57

The mixture of CE1 and CE2 are sulfated in a similar way as previously described for the sulfation of inventive example 2. The sulfation degree was around 90%.

II) Functional tests:

As shown in table 1 , the compound IE1 (inventive) is liquid at 20°C while mixture of CE1 & CE2 is a solid at 20°C (comparative examples). In case of compound IE1 , the sulfation with sulfur trioxide on a falling film reactor is feasible at low temperatures such as 20°C, which can reduce energy costs and can reduce formation of side products. Table 1 : Appearance of acetale at 20°C

As shown in table 2, inventive example 2 demonstrates a significantly stronger foamability, namely 640 ml, at 40°C in hard water (10° dH) using 2 g of material per liter in a test regarding whipped foam (EN 12728, DIN 53902) compared to the mixture of CE3 and CE4, namely 160 ml or 470 ml. A strong foamability is of interest e.g. for hand dishwashing. In particular, in hard water, such as water containing high concentration of calcium ions.

Table 2: Foamability of 2 g surfactant per liter of hard water (10° dH) at 40°C using whipped foam method

Table 3 discloses that IE2 (inventive) shows a much lower dynamic surface tension, namely 45.1 mN/m, compared to the mixtures of CE3 and CE4, namely 66.6 mN/m or 63.4 mN/m, respectively. Such lower dynamic surface tension indicates that the surfactant is fast at interfaces e.g. at oil - water interface and can start the removal of e.g. oil earlier which is relevant for l&l processes, laundry, and dishwashing.

Table 3: Dynamic surface tension of 1 g surfactant per liter of hard water (10° dH) at room temperature after 0.1 s Table 4 discloses that IE2 (inventive) shows a much lower interfacial tension against olive oil or n-hexadecane, namely 0.8 and 1.5 mN/m, compared to the mixtures of compounds CE3 and CE4, namely 2.3 and 7.7 mN/m or 2.6 and 5.5 mN/m. Such lower interfacial tension indicates that the surfactant can remove oil in a better way. Olive oil is a triglyceride and thereby a model oil for soil in laundry or dishwashing; n-hexadecane is a model oil for aliphatic oils e.g. from the lubricant sector.

Table 4: Interfacial tension of 1 g surfactant per liter of hard water (10° dH) at room temperature after 3 min

Application test in Launder-O-meter

The washing performance for the inventive compound was determined as follows.

The L*, a* b* values of the single stains on multi soil monitors are measured before wash with a MACH 5 from CFT/Colour consult. Then the fabrics are washed together with cotton ballast fabric and 20 steel balls at 30 °C in water with defined water hardess. After the wash the fabrics are rinsed, spin-dried and dried in the air.

The washing performance for the single stains is determined by measuring the L*, a* b* values with a MACH 5 from CFT/Colour consult after drying. The dE value is calculated from the single values before and after wash. The 2 stains from the monitor are summed up. The higher the value, the better the performance.

Washing conditions:

Producer: wfk-Testgewebe, Christenfeld 10, 41379 Bruggen; Swissatest Testmaterialien AG, M6- venstraBe 12, CH-9015 St. Gallen

Table 5 shows results of primary detergency in a launder-o-meter test at 30°C. E 12 removes se- bum rich stains more efficiently than the control without surfactant.

Table 5: Primary detergency in a launder-o-meter test at 30°C using 2 sebum-rich stains fabrics after 60 min with and without surfactant in hard water

Claims

Claims

1 . A compound having the structure according to Formula (I)

Formula (I) wherein

R1 is C8 to C27 alkyl or C8 to C27 alkenyl,

R4 is hydrogen, C2 to C18 alkyl or C2 to C18 alkenyl,

R2 is (i) wherein M is selected from the group consisting of hydrogen, Na, K, ammonia, protonated amine and protonated amino alcohol; m is an integer having a value of 1 to 4; the dotted line indicates the bond to the oxygen atom of Formula (I), and n is an integer having a value of 1 to 9.

2. The compound according to claim 1 , wherein R1 is C10 to C17 alkyl or C10 to C17 alkenyl, preferably C10 to C17 alkyl.

3. The compound according to claim 1 or 2, wherein R2 is and the dotted line and M are defined as above, preferably M is Na.

4. The compound according to any one of claims 1 to 3, wherein i) n is an integer having a value of 1 to 3; and ii) R4 is hydrogen.

5. The compound according to any one of claims 1 to 4, wherein M is selected from the group consisting of hydrogen, Na, K and ammonia.

6. A process to prepare the compound according to any one of claims 1 to 5 comprising i) reacting an aldehyde or ketone according to Formula (II)

O

R3 - L

^R4

Formula (II), wherein R3 is C8 to C27 alkyl or C8 to C27 alkenyl and

R4 is hydrogen, C2 to C18 alkyl or C2 to C18 alkenyl, with a linear triol comprising 4 to 12 carbon atoms, wherein hydroxy groups are in the 1 -, 2- and omega position in presence of an acidic catalyst to obtain the compound of claims 1 to 5, wherein R2 is ‘ ‘^H and the dotted line is defined as in claim 1 , and optionally ii) sulfating or sulfonating the compound of reaction step i) and subsequent neutralization with a base selected from the group consisting of sodium hydroxide or potassium hydroxide, ammonia, amines and amino alcohols to obtain the compound of claims 1 to 5, wherein R2 is or

, wherein M, m and the dotted line are defined as in claim 1 .

7. The process according to claim 6, wherein the acidic catalyst is selected from the group consisting of alkylbenzene sulfonic acid, methane sulfonic acid, sulfuric acid, phosphoric acid, hypophosphoric acid and hydrochloric acid.

8. The process according to claim 6 or 7, wherein

(i) R3 is C10 to C17 alkyl or C10 to C17 alkenyl, preferably C10 to C17 alkyl ; and

(ii) R4 is hydrogen.

9. The process according to any one of claims 6 to 8, wherein the linear triol comprises 4 to 6 carbon atoms.

10. The process according to any one of claims 6 to 9, wherein the sulfating step comprises i) sulfation with sulfur trioxide on a falling film reactor; ii) sulfation with chlorosulfuric acid; or iii) sulfation with sulfamic acid in presence of urea.

1 1 . Use of the compound according to any one of claims 1 to 5 in cleaning compositions, in fabric and home care products, in cosmetic formulations, as crude oil emulsion breaker, as surfactant in enhanced oil recovery, as surfactant in corn oil separation, as surfactant in fermentation processes, as surfactant in flotation of mineral ores, in pigment dispersions for ink jet inks, in formulations for electro plating, in cementitious compositions, as dispersant for agrochemical formulations.

12. The use according to claim 11 in cleaning compositions and/or in fabric and home care products, preferably in cleaning compositions for i) improved removal of oily/fatty stains, and/or ii) improved removal of sebum, and/or iii) clay removal, and/or iv) soil removal of particulate stains, and/or v) dispersion and/or emulsification of soils, and/or vi) modification of treated surface to improve removal upon later re-soiling, and/or vii) whiteness improvement and/or preferably in cleaning compositions for removal of oily/fatty stains, each of the before mentioned options i) to vii) preferably for use in a laundry detergent formulation and/or a manual dish wash detergent formulation and/or in a formulation suitable for (pre) -treatment of textiles and/or soap bars, more preferably in a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

13. Cleaning composition, fabric and home care product, industrial and institutional cleaning product, cosmetic formulation, crude oil emulsion breaker, oil recovery formulation, formulation for corn oil separation, formulation for fermentation process, flotation agent of mineral ores, pigment dispersion for ink jet inks, formulation for electro plating, cementitious composition, dispersant for agrochemical formulations, comprising at least one compound according to any of claims 1 to 5, preferably cleaning composition and/or fabric and home care product and/or industrial and institutional cleaning product, comprising at least one compound according to any of claims 1 to 5.

14. Cleaning composition according to claim 13 further comprising i) at least one cleaning polymer or soil release polymer, and/or ii) at least one further surfactant selected from the group consisting of anionic surfactants and/or non-ionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants, and/or iii) an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4’- dichoro 2-hydroxydiphenylether; preferably comprising 2-phenoxyethanol in an amount ranging from 2ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol or preferably comprising 4,4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, more preferably 0.002 to 1 %, even more preferably 0.01 to 0.6%, each by weight of the composition, and/or iv) at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, DNases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xy- lanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme being selected from proteases, and/or v) at least one compound selected from the group consisting of builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, dye fixation agent and perfumes, vi) cosolvent selected from groups of aliphatic alcohols, diols (preferably propylene glycole), or triols comprising 2 to 5 carbon atoms or selected from group of ethylene glycole or diethylene glycol mono alkyl ether comprising 2 to 5 carbon atoms in alkyl moiety or selected from group of propylene glycole or dipropylene glycol mono alkyl ether comprising 2 to 5 carbon atoms in alkyl moiety, and/or vii) water.

15. A cleaning method comprising contacting a cleaning composition according to claim 13 or 14 with an object that requires cleaning, preferably a laundry or a hard surface household item.