Biodegradable alkoxylated polyols, their preparation, use and compositions comprising them

Abstract

The present invention relates to biodegradable alkoxylated polyols based on polyols having four to five -OH groups reacted with ethylene oxide and propylene oxide, their manufacture and use, for example in laundry or dishwashing.

Description

[0001] This invention relates to biodegradable alkoxylated polyols (in this invention, whenever referring to alkoxylated polyols of the invention, they are abbreviated as "compounds of the invention", "polymers of the invention", or "compounds of the invention"), their manufacture, and their use, particularly in cleaning compositions such as laundry detergent compositions, and specifically for improving clay removal and / or oily / greasy stain removal and / or body grime removal and / or whiteness maintenance in laundry care.

[0002] Detergent formulators are constantly faced with the task of developing and improving products to remove a broad spectrum of dirt and stains from fabrics and hard surfaces. Chemically and physicochemically, the spectrum of dirt and stains ranges from polar stains such as proteins, clays, and inorganic dirt to non-polar stains such as cooking fumes, carbon black, and byproducts of incomplete hydrocarbon combustion, and organic stains such as sebum and body grime. The removal of grease (i.e., oily / fatty) stains is particularly challenging. This challenge is exacerbated by the recent high interest and motivation to reduce the amount of surfactants in cleaning detergents for environmental, sustainability, and cost reasons. Typically, reducing the amount of surfactant added, especially anionic surfactants such as linear alkylbenzene sulfonates (LAS), has been found to lead to a decrease in the removal of oily / fatty stains. Additionally, the global trend of using washing conditions at lower temperatures further reduces the grease-removing ability of typical detergents, as these types of oily and fatty stains exhibit the greatest performance degradation at lower temperatures. On the other hand, although clay stains sometimes come into contact with fabric fibers with relatively little force, they present a specific type of stain removal problem due to the high charge density associated with the clay itself. This high surface charge density can act as a repulsion agent for some clothing components, so surfactants alone cannot remove clay or introduce it into the laundry detergent.

[0003] Another global trend is the compression of laundry detergents in order to improve sustainability in terms of water use and / or transportation costs, as well as to improve convenience for end consumers (e.g., single-dose products, tablets, sachets, etc.), which has led to high market demand for new raw materials with higher weight efficiency and significantly wider performance characteristics.

[0004] Another strong emerging trend is the desire to improve the “footprint” of any product, whether in terms of its source, such as from natural or renewable resources, or in terms of production efficiency and thus reduced energy consumption compared to previous products, usage efficiency such as reduced dosage for the same performance or improved performance at the same dosage level, persistence in the natural environment after use, and especially in terms of biodegradability, because recycling is technically very challenging and therefore not economically attractive.

[0005] Therefore, due to climate change, one of the most important goals for the detergent and cleaning products (D&C) industry today is to significantly reduce CO2 emissions per wash by improving cleaning efficiency at temperatures below 30°C and even lower, improving cold water conditions, reducing the amount of chemicals used per wash, and increasing the weight efficiency of cleaning technologies. Another important goal for the D&C industry is the need for biodegradable polymers to improve the sustainability of detergent formulations and avoid the potential accumulation of polymers or their degradation products in ecosystems due to incomplete biodegradation, thus reducing the material's persistence in nature after use.

[0006] Due to these trends, there is a strong need for new biodegradable cleaning polymers that offer excellent primary (i.e., dirt removal) and / or secondary (i.e., whiteness maintenance) cleaning benefits against both hydrophobic and hydrophilic stains, as well as improved biodegradability. These materials should exhibit good dirt removal from oily / greasy / sebum and particulate stains, and / or should also produce improved whiteness maintenance by minimizing the amount of suspended and emulsified oily / greasy / sebum and particulate stains to prevent redeposition on textile or hard surfaces. Preferably, these new components will also exhibit synergistic effects with other cleaning techniques known for individually improving the removal and / or whiteness of oily / greasy / sebum or particulate stains on fabrics and hard surfaces, such as other cleaning polymers, surfactants, and / or enzymes, resulting in further improved detergent compositions.

[0007] For example, alkoxylated polyalkylene imides and alkoxylated polyamine polymers, particularly alkoxylated hyperbranched polyethyleneimine (PEI) and alkoxylated linear polypropyleneimine (PPI) homopolymers and copolymers, are known in the literature to be helpful in the removal of particulate or oily / greasy dirt, especially at low surfactant levels and in cold water conditions (30°C and below). Furthermore, their biodegradability is generally poor and therefore unacceptable for current and future requirements. Ideally, these polymers are readily biodegradable, i.e., showing an oxygen consumption of equal to or greater than 60% after 28 days in the OECD 301F test, or moderately biodegradable when they show an oxygen consumption of equal to or greater than 40% after 28 days in the OECD 301F test. Alternatively, polymers are inherently biodegradable in the OECD 302 B test, i.e., showing a dissolved organic carbon (DOC) level of equal to or greater than 70%. Therefore, there is a need to find improved polymer structures with similar or superior performance characteristics, feasible preparation methods, and improved biodegradability.

[0008] The following provides an overview of the most relevant disclosures in the field of this invention, alkoxylated polyols.

[0009] JP 2022056680 A discloses glycerol with a total of 16 alkylene oxide units modified with ethylene oxide (EO) and propylene oxide (PO). The glycerol is randomly alkoxylated by EO and PO, wherein the ratio of PO to EO is less than 1. This compound is disclosed in the context of a flavor retainer. Based on experiments in this application, compounds having a propylene oxide content of less than 50% by weight relative to the total weight of the alkoxylated polyols are estimated to be not significantly biodegradable.

[0010] US 7938900 A discloses a) pentaerythritol reacting with 20 PO / OH and 5 EO / OH, having a calculated molecular weight of 5651 g / mol, and b) pentaerythritol reacting with 4 PO / OH and 16 EO / OH. As demonstrated in this application, the high molecular weight and the PO / EO ratio negatively impact the biodegradability of the aforementioned compounds.

[0011] Perstorp AB (Malmö, Sweden) distributes Polyol 4290, which is used as a chemically constructive block and as a crosslinking agent in polyurethanes. However, the polyol has a molecular weight of only 800 g / mol and therefore cannot provide excellent washing performance.

[0012] JP 408020795 A discloses diglycerides that react with 2.5 PO / OH and 2.5 EO / OH. The compound has a molecular weight of 1187.47 g / mol. As stated above, it is anticipated, and experimentally demonstrated in this application, that this compound, based on its low molecular weight, cannot provide superior detergency performance.

[0013] Surprisingly, the inventors of this invention have discovered that ethylene oxide and propylene oxide-modified polyols (alkoxylated polyols) exhibit excellent detergency and significant biodegradability when: i) they are based on polyols having 4 to 5 -OH groups; ii) they have a weight-average molecular weight (Mw) ranging from 1,500 to 4,500 g / mol; and iii) the propylene oxide content is at least 50% by weight relative to the total weight of the alkoxylated polyol. Based on experimentally generated data, these parameters can be established as key factors contributing to the detergency and biodegradability of alkoxylated polyols. It should be noted that the compounds of this invention exhibit superior detergency properties compared to alkoxylated polyols having a weight-average molecular weight (Mw) of less than 1,500 g / mol. Furthermore, the compounds of the present invention exhibit significant biodegradability (at least about 40% within 28 days according to OECD 301F), while compounds with a weight-average molecular weight (Mw) greater than 5,000 g / mol or a PO content of less than 50 wt.% show lower biodegradability. In addition, the compounds of the present invention also exhibit good stability in cleaning compositions, particularly in liquid cleaning compositions. This high stability of the compounds of the present invention in liquid cleaning compositions may be based on the lack of ester and / or amide bonds.

[0014] Therefore, the object of the present invention is to provide novel alkoxylated polyols comprising a polyol core having substantially four to five -OH groups, wherein i) at least one of these -OH groups is modified to form an alkylene oxide branch, ii) each of the at least one alkylene oxide branch comprises ethylene oxide and propylene oxide, iii) the weight-average molecular weight (Mw) of the alkoxylated polyol is in the range of 1,500 to 4,500 g / mol, and iv) the propylene oxide content is at least 50% by weight relative to the total weight of the alkoxylated polyol.

[0015] In the following text, any alkyl oxide is collectively referred to as "AO", ethylene oxide is sometimes referred to as "EO", and propylene oxide is sometimes referred to as "PO". "PEO" is sometimes used in this document to describe polyethylene oxide homopolymers or PEO blocks within a larger polymer structure; similarly, "PPO" describes polypropylene oxide homopolymers or polymer blocks within a larger polymer structure.

[0016] The method for producing the compounds of this invention is also part of this invention.

[0017] The present invention also covers the use of the compounds of the present invention in various applications in which the previously described polyamines, polyethyleneimine, polypropyleneimine, and their alkoxylated derivatives have been used.

[0018] Compositions containing such alkoxylated polyols of the present invention—which, in place of or in combination with such known compounds—are also part of the present invention, similar to those compositions which have employed previously known polyamines, polyethyleneimine, polypropyleneimine, and their alkoxylated derivatives.

[0019] As used herein, the terms “compound of the invention”, “compound of the invention”, or “polymer of the invention” refer to alkoxylated polyols / polyol alkoxylates prepared as described below and / or in the appended claims (they may be used interchangeably herein).

[0020] Therefore, the subject matter of the present invention is the following embodiments 1 to 28, as defined below and further explained by other examples and illustrated further in the experimental section:

[0021] Example 1

[0022] An alkoxylated polyol comprising a polyol core having substantially four to five -OH groups, wherein

[0023] At least one of these -OH groups is modified to form an epoxide branch.

[0024] - Each of the at least one alkyl oxide branch contains ethylene oxide and propylene oxide.

[0025] The weight-average molecular weight (Mw) of this alkoxylated polyol is in the range of 1,500 to 4,500 g / mol, and

[0026] - The propylene oxide content is at least 50% by weight relative to the total weight of the alkoxylated polyol.

[0027] The alkoxylated polyols of the present invention are based on polyols having a total of four to five -OH groups. The polyol core used to prepare the alkoxylated polyols of the present invention can be a monomer, or it can be an oligomer or polymer constructed through an assembly process comprising subunits containing -OH groups. Furthermore, in the case where the polyol core is based on an oligomer or polymer, the total number of -OH groups is also four to five. For clarity, this means that the number of -OH groups in the compounds of the present invention is not limited to four and five, but can be any decimal between four and five.

[0028] For example, diglycerides have four -OH groups and triglycerides have five -OH groups. Those skilled in the art will understand that a mixture of diglycerides and triglycerides (n = 2 to 3) of polyglycerols can be prepared, wherein the polyols (the group) have a total number of -OH groups between four and five. Depending on the ratio of diglycerides to triglycerides, any decimal between four and five can be adjusted. Therefore, in a preferred embodiment, the alkoxylated polyols of the present invention have 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5 -OH groups. In a more preferred embodiment, the number of -OH groups in the alkoxylated polyol refers to the average number of mixtures of alkoxylated polyols, each generally having four or five -OH groups.

[0029] Therefore, the alkoxylated polyols of the present invention can be based on homopolymers or heteropolymers of polyols having four to five -OH groups.

[0030] As used herein, the term "-OH group" refers to a hydroxyl group, particularly an alcohol group. This also includes -OH groups in the context of aromatic structures, such as phenols. The term encompasses all alcohol groups regardless of their carbon atom state. Therefore, in the sense of this invention, primary, secondary, and tertiary alcohols fall within the meaning of "-OH group." For example, the -OH group can also be a sugar, such as a hexose (e.g., glucose, fructose, etc.). However, in preferred embodiments, alkoxylated polyols have a linear backbone of carbon atoms. Excluded from the scope of the term "-OH group" are -OH groups that are part of a carboxylic acid.

[0031] In a preferred embodiment, the polyol core reacting with the epoxide does not contain any other functional groups (such as amines, amides, esters, carbonyl groups, carbonic acid groups, phosphate esters, sulfonate groups, etc. and their derivatives) other than the -OH group, or contains only one or two ether groups, as is seen in polyol cores found in polyglycerol compounds.

[0032] For clarity, the term "alkoxylated polyol" refers to a compound derived from a polyol (referred to herein as the "polyol core") but not necessarily having any unmodified -OH groups. In a preferred embodiment, all four to five -OH groups in the polyol core of the alkoxylated polyol of the present invention are modified with epoxide branching.

[0033] The compounds of this invention comprise side chains, namely alkyl oxide branches, which are attached via ether bonds (-O-) to oxygen atoms of -OH groups derived from the polyol core. The side chains consist of ethylene oxide and propylene oxide. Typically, the side chains have an average total of 8 to 24 AO units (EO units + PO units). More detailed examples describing different chain lengths are provided below.

[0034] The side chain comprises ethylene oxide and propylene oxide, and is preferably composed of ethylene oxide and propylene oxide. The side chain is preferably terminated with a -OH group, but may alternatively be terminated with a C1 to C20 alkyl group, preferably a C1 to C6 alkyl group, more preferably a C1 alkyl group.

[0035] It should be noted that all such values ​​are "average" values, meaning that such values ​​refer to the average number of such units for each -OH group calculated based on all -OH groups of the alkoxylated polyol.

[0036] It is important to emphasize that the reactions that produce the compounds of this invention are statistical reactions, meaning that there is never just one chemically precisely defined compound, but rather a mixture of slightly deviated structures, all stemming from the same reactions within a single reaction space. These structural differences arise explicitly from the fact that no single reaction occurs in exactly the same manner and at the same rate across all functional units, especially because the chemical reactivity of the functional units—primarily those with -OH groups—varies depending on their environment. This means that primary alcohols react differently than secondary alcohols, and that the chemical environments of these groups can also differ. This generally leads to the existence of slightly deviated structures, and therefore any compound of this invention, as defined in the various examples including numbered Examples 1 to 28, and exemplified in the examples, is never just one compound, but rather a mixture of slightly deviated compounds with a statistical distribution. Since the reactivity of these groups does not differ significantly, the deviations are relatively small. Therefore, defining the alkoxylated polyols of this invention by prototypical members is a feasible way to define the structures. Furthermore, defining the composition of the side chains by averages (including those variables defined in this embodiment and the following embodiments) based on the number of -OH groups present in the alkoxylated polyol is a useful way to define the overall composition of any mixture of which is defined herein as "alkoxylated polyol of the present invention".

[0037] Therefore, unless otherwise indicated, the values, ranges, and ratios given in the specification for the number of -OH groups and molecular weight (Mn) relate to the number averages in heterogeneous mixtures of synthetic alkoxylated polyols containing individual, slightly different chemical structures produced by the preparation method of the present invention. As is known in polymer science, the weight-average molecular weight (Mw) is thus a measure of the (in)homogeneity within the mixture of different substances in the "alkoxylated polyol".

[0038] Consistent with the above, it is preferred that all -OH groups in the polyol core are replaced by epoxide branches, and that the epoxide branches vary slightly in the amount of different alkoxylation. More preferably, the amount of EO units and / or PO units in different epoxide branches within a molecule deviates from the average chain length by no more than 20%, no more than 15%, no more than 10%, or no more than 5%, where the average chain length represents 100%.

[0039] The presence of epoxides within or adjacent to the (mainly) hydrophobic polyol core generates amphiphilic properties and thus produces the excellent cleaning properties of the compounds of the present invention in detergent applications. The compounds of the present invention with this modification are also referred to as "alkoxylated," "ethoxylated and propoxylated," and / or "modified."

[0040] As used herein, the term "epoxy alkane branch" refers to a substructure of the compounds of the present invention that comprises, is substantially composed of, or is composed of, multiple EO and PO units.

[0041] As may be used interchangeably herein, the terms “essentially having” or “having essentially” for polyol nuclei mean that the polyol nuclei may contain impurities or other types of polyols in amounts not exceeding 10% w / w, 7% w / w, 5% w / w, 3% w / w, 2% w / w, 1% w / w, 0.5% w / w, or 0.1% w / w.

[0042] Example 2

[0043] According to the alkoxylated polyol of Example 1, wherein the polyol core is a monomer, oligomer or polymer, wherein each of the oligomer and the polymer comprises a plurality of subunits, preferably the oligomer is a homooligomer or the polymer is a heteropolymer.

[0044] As used herein, the term "monomer" refers to a polyol that has not polymerized prior to its alkoxylation. As used herein, the term "oligomer" refers to a molecule consisting of up to five repeating units (including polyol repeating units), which may be all identical or composed of different repeating units. Therefore, oligomers include dimers, trimers, tetramers, and pentamers. Preferably, the oligomer is a "homogeneous oligomer," meaning an oligomer formed from the same monomer. Homogeneous oligomers are compounds formed by covalent bonding of a given polyol repeating unit. As used herein, the term "polymer" refers to a compound having at least six repeating units covalently linked by a polymerization reaction. As used herein, "hybrid" refers to an organic polymer containing two or more different repeating units (including at least one polyol unit). As used herein, the term "a plurality of" is defined as two or more, i.e., at least 2, 3, 4, 5, 6, 7, 8, 9, or more.

[0045] Example 3

[0046] According to the alkoxylated polyols described in Example 1 or 2, each of these epoxide branches typically comprises or consists of the following:

[0047] i) at least two ethylene oxide units (EO), preferably at least three EO, and more preferably at least four EO; and

[0048] ii) at least 6 polyoxypropylene units (PO), preferably at least 7 PO and more preferably at least 8 PO.

[0049] In even more preferred embodiments, the epoxide side chains typically contain at least 5 or more EO atoms. Alternatively, in more preferred embodiments, the epoxide side chains typically contain at least 9, 10, 11, 12, 13 or more PO atoms.

[0050] In a preferred embodiment, an epoxide branch has an average weight ranging from 430 to 2000 g / mol, preferably from 500 to 1500 g / mol, and more preferably from 600 to 1300 g / mol.

[0051] Example 4

[0052] According to any one of Examples 1 to 3, the propoxylated polyols, wherein each of these epoxide branches comprises, on average, the following or is composed of:

[0053] i) No more than 8 EOs, preferably no more than 7 EOs, and more preferably no more than 6 EOs; and

[0054] ii) No more than 16 POs, preferably no more than 15 POs and more preferably no more than 14 POs.

[0055] In even more preferred embodiments, the epoxide branches typically contain no more than 5 or fewer EO atoms. Alternatively, in more preferred embodiments, the epoxide branches typically contain no more than 15 or fewer PO atoms.

[0056] Example 5

[0057] The alkoxylated polyol according to any one of Examples 1 to 4, wherein the polyol core has a weight ranging from 90 to 500 g / mol, preferably from 100 to 300 g / mol and more preferably from 120 to 250 g / mol.

[0058] Methods for measuring the weight of polyols are well known in the art and include mass spectrometry, mass spectrometry, and static light scattering.

[0059] Example 6

[0060] The alkoxylated polyols according to any one of Examples 1 to 5, wherein the polyol core contains at least one ether bond, and preferably the functional chemical groups of the polyol core consist of four to five -OH groups (and an additional one or two ether bonds). Apart from these functional chemical groups or residues, the polyol core has no additional functional chemical groups or residues. This means that the alkoxylated polyols of the present invention also do not contain functional groups such as amines, amides, esters, carbonyl groups, carbonic acid groups, phosphate esters, sulfonate groups, and their derivatives.

[0061] In a preferred embodiment, the alkoxylated polyols of the present invention exhibit at least 40%, preferably at least 50%, or more preferably at least 60% biodegradability within 56 days, preferably within 28 days, according to standard OECD 301F.

[0062] For the purposes of this invention, aerobic biodegradation in wastewater, as measured by OECD 301F, is expressed as a percentage of theoretical oxygen demand (ThOD, measured by elemental analysis of the compound of interest), which is required for the complete biodegradation of the compound sample. Therefore, the amount of oxygen taken up by the microbial population during the biodegradation of the test substance (corrected for by blank inoculum, in parallel runs) is expressed as a percentage of ThOD. The obtained values ​​are preferably measured in triplicate using the OECD 301F barometric respiration measurement method. Oxygen consumption is determined by measuring pressure changes in an OxiTop® C (Xylem 35 Analytical GmbH, Germany) measuring device. Details of the tests performed are given in the following experimental sections.

[0063] This invention provides modified polyols that are ethoxylated and propoxylated. The combined core-shell products (i.e., alkoxylated polyols) (where the "core" is the polyol core and the "shell" is an epoxide branch) exhibit significant biodegradability values. Furthermore, these compounds of the present invention also demonstrate washing performance comparable to currently used products.

[0064] Example 7

[0065] The alkoxylated polyol according to any one of Examples 1 to 6, wherein the weight-average molecular weight (Mw) of the alkoxylated polyol is in the range of 2,000 to 4,300 g / mol, preferably in the range of 2,500 to 4,000 g / mol, more preferably in the range of 3,000 to 3,500 g / mol, 3,100 to 3,500 g / mol, 3,200 to 3,500 g / mol or even 3,300 to 3,500 g / mol.

[0066] Those skilled in the art know how to determine / measure the corresponding weight-average molecular weight (M). W This can be accomplished, for example, by using size exclusion chromatography (such as GPC, e.g., in combination with light scattering), by measuring the hydroxyl value, by mass spectrometry, by mass spectrometry, or by calculation based on the molar ratio of the starting materials used. Preferably, M W The value is determined by the following method: OECDTG 118 (1996), which specifies in detail...

[0067] OECD (1996), Test No. 118: Determination of the Number-Average Molecular Weight and the Molecular Weight Distribution of Polymers using Gel Permeation Chromatography, OECD Guidelines for the Testing of Chemicals, Section 1, OECD Publishing, Paris. It is also available online, for example, at [website address missing]. https: / / doi.org / 10.1787 / 9789264069848-en Down.

[0068] The molecular weight of the polyol starting material can be determined as described above. The molecular weight of the alkoxylated polyol can be determined by gel permeation chromatography (GPC). Sample preparation was as follows: approximately 15 mg of sample was dissolved in 10 ml of eluent (THF + 0.035 mol / L diethanolamine) at 50°C for 1 hour. All sample solutions were filtered through a ChromafilXtra PTFE filter (0.20 µm before injection). The sealed sample vials were placed in an autosampler. An Agilent 1200 HPLC system was used, consisting of an isocratic pump, a vacuum degasser, an autosampler, and a column oven. The Agilent system also included differential refractive index (DRI) and variable ultraviolet (UVW) detectors for detection. Data acquisition and processing of routine SEC data were performed using WinGPC Unichrom (build number 6999) at PSS (Polymer Standard Services, now part of Agilent). A combination of a PSS SDV protected column (7.5 × 50 mm) and three SDV columns (1000A, 100000A, and 1000000A, all 7.5 × 300 mm) was arranged in series at 60°C. THF + 0.035 mol / L diethanolamine was used as the eluent at a flow rate of 1 mL / min. 100 µL of each sample solution was injected. Calibration was obtained using polyepoxide (EO and PO mixture) standards (Agilent Technologies) with a narrow molar mass distribution ranging from M = 160 g / mol to M = 1,378,000 g / mol. Molar masses outside this range were extrapolated.

[0069] “Mw” is the weight-average molecular weight, and “Mn” is the number-average molecular weight. The corresponding values ​​of Mw and / or Mn can be determined as described in the following experimental sections.

[0070] The molar mass distribution Mw / Mn obtained by GPC is equal to the polydispersity index (PDI), which has no unit [g / mol / g / mol].

[0071] In other preferred embodiments, the molecular weight is determined by measuring the hydroxyl value of the alkoxylated polyol.

[0072] The hydroxyl value can be determined using the phthalic anhydride method and given in mg KOH / g. This method is based on the esterification of a polyol and the hydroxyl group in the polyol system (in this invention, the alkoxylated polyol) with phthalic anhydride at elevated temperatures, followed by titration of the excess phthalic anhydride with an aqueous sodium hydroxide solution. The determination is performed as follows:

[0073] A suitable amount of sample was dissolved in 10 ml of a solution of phthalic anhydride in pyridine (180 g / L) and stirred at 105°C for 70 minutes. Subsequently, the air condenser used was rinsed with 5 ml of pyridine and the sample was potentiometrically titrated with a 0.5 mol / L sodium hydroxide aqueous solution. A blank test was performed similarly, but without a sample. The hydroxyl value was calculated from the difference in volume consumed. Any acid or base in the sample must be taken into account. The hydroxyl value is expressed as mg potassium hydroxide / g sample. The molecular weight Mn of the polyol sample can then be calculated from the measured hydroxyl value according to the following equation: Molecular weight Mn (in g / mol) = [Number of hydroxyl groups in the starting material]

[56100] / [Measured hydroxyl value (in mgKOH / g)].

[0074] For the alkoxylated polyols described herein, the molecular weight (MW) can also be calculated from the molar ratio of the starting materials used. Typically, the molecular weight (MW) of alkoxylated polyols can be calculated using the following equation:

[0075] MW of alkoxylated polyols =

[0076] The total MW of the polyol core + the total MW of PO + the total MW of EO + the total MW of other monomers (if present).

[0077] Alkoxylated polyols can be described using the following nomenclature:

[0078] (Polyol core)1[(PO / OH)] x (EO / OH) y ] m ,

[0079] x refers to the average number of PO groups at each hydroxyl position of the polyol core, and y refers to the average number of EO groups at each hydroxyl position of the polyol core; m is the number of OH groups on the polyol core, typically 4 to 5, more preferably 4.

[0080] Use (glycerol)1 / [(PO / OH)] 12 [(EO / OH)5]3 As an illustrative example: the polyol core is glycerol, which contains 3 OH groups. Therefore, the total molar number of propoxylated (PO) is 36 (3 × 12), and the total molar number of ethoxylated (EO) is 15 (3 × 5). The molecular weight of this specific polymer is then calculated as follows:

[0081] MW = MW of glycerol + MW of 36 PO + MW of 15 EO

[0082] = 92.09 + (36 × 58.08) + (15 × 44.05)

[0083] = 2843.72 g / mol

[0084] The percentage of PO by weight, or the percentage of EO by weight, or the percentage of the polyol core in alkoxylated polyols can be calculated using the same principle.

[0085] The propylene oxide content is at least 50%, or 50% to 96%, preferably 56% to 90%, more preferably 59% to 85%, more preferably 62% to 80%, and most preferably between 65% and 75%, based on the weight of the alkoxylated polyol.

[0086] The wt% of PO relative to the total weight of the epoxide branches can also be calculated using the same principle. Preferably, the wt% of PO is between 50 wt% and 96%, more preferably between 56 wt% and 90%, even more preferably between 59 wt% and 85 wt%, even more preferably between 62 wt% and 80 wt%, and most preferably between 65 wt% and 75 wt%.

[0087] Those skilled in the art will understand that for the alkoxylated polyols of the present invention, the molecular weight measured by GPC, hydroxyl value, mass spectrometry or mass spectrometry and the calculated molecular weight are consistent in the following sense: the measured molecular weight results do not change significantly.

[0088] Example 8

[0089] According to any one of Examples 1 to 7, the alkoxylated polyol nucleus is selected from the group consisting of: meso-erythritol, D-threitol, L-threitol, 1,2,5,6-hexanetetrol, pentaerythritol, xylitol, ribitol, arabinitol, pentapentanol, diglycerides, triglycerides, and polyglycerides, and wherein the polyglycerides are preferably composed of two to three glycerol subunits.

[0090] In a preferred embodiment, as used herein, the term "polyglycerol" refers to a mixture primarily of diglycerol and triglycerol. The ratio of diglycerol to triglycerol can vary between 100:1 and 1:100. In a further preferred embodiment, the mixture may also contain glycerol, tetraglycerol, or pentaglycerol, all present in small amounts (not exceeding 5% w / w, 3% w / w, or 1% w / w of the polyglycerol mixture).

[0091] Those skilled in the art will understand that polyols can also be alkoxylated with other AOs besides ethylene oxide and propylene oxide. In this context, butyl oxide is mentioned. Furthermore, those skilled in the art are well aware of the beneficial modifications to alkoxy chains, such as modifications with lactones or hydroxycarbonates, as described in WO 2021165468 A.

[0092] It should be noted that the epoxides used to prepare the compounds of the present invention can be derived from fossil or non-fossil carbon sources, or even mixtures thereof. Preferably, the amount of non-fossil carbon atoms in the epoxide branches is at least 10%, at least 20%, at least 40%, at least 70%, at least 95%, or it contains only carbon atoms from non-fossil sources. Those skilled in the art are well aware of commercial epoxide products made from non-fossil carbon sources (these products are often sold as sustainable, renewable, or bio-based). For example, Croda International, Snaith, UK, sells ethylene oxide and related products as part of the ECO series of bioethanol-based products. Additionally, methods for preparing bio-based propylene oxide are also known (see Abraham, DS, “Production of propylene oxide from propylene glycol”, Master's Thesis, University of Missouri-Columbia (2007) (75 pages)).

[0093] It should be noted that, in the preferred embodiments, the polyol core contains at least two "terminal" primary alcohol groups. In addition to these two primary alcohols, the polyol may further have two or three secondary alcohol groups.

[0094] Example 9

[0095] According to any one of Examples 1 to 8, the alkoxylated polyols, wherein each of these alkyl oxide branches comprises a block or random structure of ethylene oxide and propylene oxide, preferably a block structure, more preferably an ethylene oxide and propylene oxide block.

[0096] In a more preferred embodiment, the epoxide branch has a block structure consisting of PO and EO blocks, wherein the PO blocks react with the -OH groups of the polyol core. Alternatively, the epoxide branch has a block structure consisting of EO and PO blocks, wherein the EO blocks react with the -OH groups of the polyol core.

[0097] Example 10

[0098] According to any one of Examples 1 to 9, the alkoxylated polyols wherein all epoxide branches attached to the -OH group of the polyol core have the same structure, in that sense, the number of EO and / or PO units in each epoxide branch is the same, or alternatively, the structures of these epoxide branches are slightly different.

[0099] Without being bound by the following interpretation, there exists a fundamental principle explaining the resulting structures of alkoxylated polyols: since the reactions discussed, necessary for the preparation of the structural sequences of the side chains and thus for the preparation of the specific compounds of this invention, are reactions of fairly reactive substances, which, under suitable conditions, can produce almost complete and even “substantially complete” conversions, if not 100%, but nearly 100%, the statistical deviation in the composition of the mixture of “alkoxylated polyols” discussed is not so high, which in turn means that the structural sequences of the side chains do not show significant deviations. Therefore, it is a plausible assumption, which in principle can be demonstrated by complex and therefore time-consuming and expensive analytical methods—such as multidimensional NMR analysis—that such a bias is generally accepted; thus, a “specific alkoxylated polyol” will not be “just a compound with a well-defined chemical structure,” but will specifically consist of: a) a mixture of slightly different compounds, such differences being b) a slight deviation in the structure of the compounds constituting the “(unmodified) polyol” used for further modification steps, and c) a slight deviation in the structural sequence of the side chains attached by d) a multi-step reaction, due to e) changes in the chemical reactivity of the -OH groups, and f) slight inhomogeneities arising in industrial-scale methods. All these factors a) to f)—to mention only a few important ones—result in a “specific alkoxylated polyol” that is not a single compound, but rather a mixture of slightly different compounds with generally very similar chemical structures; therefore, such a structure is best described by the average of the variables and the percentage of the amount of the dominant structural sequence.

[0100] Example 11

[0101] A method for preparing an alkoxylated polyol according to any one of Examples 1 to 10, wherein a polyol having substantially four to five -OH groups is reacted with (i) at least eight ethylene oxide molecules and (ii) at least 24 propylene oxide molecules to obtain the corresponding alkoxylated polyol.

[0102] In a more preferred embodiment, a polyol containing four -OH groups is reacted with at least 16 ethylene oxide molecules, and a polyol containing five -OH groups is reacted with at least 20 ethylene oxide molecules. Additionally, a polyol containing four -OH groups is reacted with at least 36 propylene oxide molecules, and a polyol containing five -OH groups is reacted with at least 45 propylene oxide molecules. Typically, the amount of ethylene oxide molecules can be selected such that each -OH group of the polyol contains an average of at least 15 and no more than 30 ethylene oxide molecules.

[0103] All terms used in Example 11 have been defined and explained in detail in the descriptions of Examples 1 to 10 above, and such terms, definitions and other specifications naturally apply to Example 11.

[0104] The conversion rate of the reaction step can be monitored, and in a preferred embodiment, the conversion rate is at least 95%, preferably at least 99%, and even more preferably at least 99.5% or even higher. All other structural sequences of side chains as defined above, as well as undefined structures resulting from uncontrollable parameters, are produced in this defined manner, generating—based on statistical averages—a defined structural sequence directly derived from the manner in which this reaction is carried out.

[0105] The conversion rate of the reaction can be determined using methods known to those skilled in the art, such as NMR spectroscopy, including 13C NMR spectroscopy and / or 1H NMR spectroscopy.

[0106] The reaction conditions, such as catalyst, temperature, duration, purification, etc., for the reaction that produces the side chain of the alkoxylated polyol of the present invention are fully covered by reference in this most recent disclosure, as described in disclosures EP 3298120 A, JP 2022056680 A and US 7468348 B.

[0107] In this preferred embodiment, alkoxylation is carried out in the presence of at least one catalyst. In this single-step reaction of the alkoxylation step, the catalyst is preferably a basic catalyst. Examples of suitable catalysts are hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; alkali metal alkoxides, particularly C1-C4 alkoxides of sodium and potassium, such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; hydrides of alkali metals and alkaline earth metals such as sodium hydride and calcium hydride; and alkali metal carbonates such as sodium carbonate and potassium carbonate. Alkali metal hydroxides and alkali metal alkoxides are preferred, and potassium hydroxide and sodium hydroxide are particularly preferred. The typical amount of base used is 0.05% to 10% by weight of the final product, particularly 0.05% to 2% by weight, based on the total amount of polyol and epoxide.

[0108] Example 12

[0109] According to the method described in Example 11, the polyol having four to five -OH groups is selected from the group consisting of: meso-erythritol, D-threitol, L-threitol, 1,2,5,6-hexanetetrol, pentaerythritol, xylitol, ribitol, arabinitol, pentapentanol, diglycerides, triglycerides, and polyglycerides, preferably consisting of two to three glycerol subunits.

[0110] Example 13

[0111] According to the method described in Example 11 or 12, the alkoxylated polyol is further subjected to the following method steps:

[0112] a. Purification using standard methods such as steam distillation, hot distillation, vacuum evaporation (including removal of all solvents), dialysis, and / or

[0113] b. Drying is performed using standard drying methods such as spray drying, drum drying, paddle drying, and vacuum drying. These methods include agglomeration methods such as fluidized bed drying.

[0114] To obtain purified solutions, purified liquids, solid compounds, or purified solid compounds, respectively.

[0115] If, after the reaction that produces the compounds of the present invention, residual precipitates (polyols and / or epoxides) are present to an undesirable degree, the resulting mixture of products containing alkoxylated polyols can be further purified by standard means to reduce the content of residual precipitates, as well as the amount of possible byproducts, by reducing the amount of one or more solvents used (i.e., concentration), or by replacing one or more solvents with other solvents. Such methods are known to those skilled in the art.

[0116] Preferably, the unwanted amount of residual unreacted precipitates is removed by a distillation method, more preferably by a thermal distillation method, which may additionally include applying reduced pressure to improve the rate and / or efficiency of removal.

[0117] In a preferred embodiment, only additional method step a) is used.

[0118] Uses of the alkoxylated polyols of the present invention and compositions comprising the alkoxylated polyols of the present invention

[0119] Part of this invention is also the use of the alkoxylated polyols of this invention in various application areas, where they can replace similar structures currently known, but with improved biodegradation rates compared to those previously known structures.

[0120] Example 14

[0121] Use of at least one alkoxylated polyol according to any one of Examples 1 to 10 in cleaning compositions, in fabric and household care products, in cosmetic formulations, as a crude oil demulsifier, in pigment dispersions for inkjet inks, in formulations for electroplating, in adhesive compositions, and as a dispersant for agricultural chemical formulations.

[0122] One subject of the present invention is the use of the above-mentioned alkoxylated polyols in fabric and household care products, in cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in formulations for electroplating, in adhesive compositions and / or as dispersants for agricultural chemical formulations, preferably in cleaning compositions and / or in fabric and household care products, particularly in cleaning compositions for improved clay removal or removal of oily and greasy stains, wherein the cleaning composition is preferably a laundry detergent formulation and / or a hand dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation.

[0123] Alkoxylated polyols can be added to cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in formulations for electroplating, and in adhesive compositions. However, the compounds of this invention can also be added to washing or cleaning compositions.

[0124] Therefore, another subject of the present invention is a cleaning composition, fabric and household care product, industrial and institutional cleaning product, cosmetic formulation, crude oil demulsifier, pigment dispersion for inkjet ink, formulation for electroplating, adhesive composition and / or dispersant for agricultural chemical formulation, comprising at least one alkoxylated polyol as defined above.

[0125] Preferably, it is a cleaning composition and / or fabric and household care product (containing at least one alkoxylated polyol as defined above, preferably for improved clay removal or removal of oily and greasy stains, or removal of sebum and body grime), preferably a laundry detergent formulation and / or a detergent formulation for hand dishwashing, more preferably a liquid laundry detergent formulation and / or a liquid detergent formulation for hand dishwashing.

[0126] In another preferred embodiment of the invention, the cleaning composition can be used for the removal of particulate stains and / or oily and greasy stains, and additionally for whiteness maintenance, preferably in laundry care.

[0127] In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that can be used to clean various surfaces such as hardwood, tile, ceramic, plastic, leather, metal, and glass.

[0128] In another embodiment, the cleaning composition of the present invention is a liquid or solid detergent composition for automatic tableware washing, preferably a solid detergent composition for automatic tableware washing, which can be used to clean tableware, such as glassware, wherein the alkoxylated polyol of the present invention improves the removal of stubborn dirt.

[0129] In another embodiment, the cleaning composition is designed for use in personal care and pet care compositions such as shampoo compositions, shower gel formulations, liquid or solid soaps.

[0130] In this invention, the preferred application areas for the use of alkoxylated polyols are in the fields of fabric and home care products and cleaning compositions, preferably for cleaning compositions for industrial and institutional use, and for consumer use in their homes.

[0131] Example 15

[0132] According to the use described in Example 16, it is used in cleaning compositions and / or in fabric and household care products, preferably in liquid and solid detergent compositions, such detergent compositions being preferred.

[0133] a) Detergent compositions for manual and automatic dishwashing, each comprising the at least one alkoxylated polyol, and the at least one chelating agent and / or the at least one surfactant, or—more preferably—a chelating agent in the case of liquid or solid automatic dishwashing compositions, and a surfactant system in the case of liquid manual dishwashing compositions; and / or

[0134] b) A laundry detergent composition comprising at least one alkoxylated polyol and at least one surfactant or, preferably, a surfactant system.

[0135] In these preferred application areas, typical tasks must be performed, all of which are generally covered by the term "cleaning," but actually include various tasks such as clay removal or removal of oily and greasy residues, solid residues, amphiphilic residues, and hydrophilic residues. Other tasks include protecting the items to be cleaned from deterioration, such as protecting glass from corrosion, protecting silverware from oxidation, and protecting colors from fading. Other tasks include improving the overall appearance of the items to be cleaned, such as increasing or restoring color and whiteness, and imparting or increasing shine. For many of these applications, additional ingredients are typically added; for cleaning applications, important ingredients include, for example, enzymes, which help biodegrade residues.

[0136] Example 16

[0137] According to the uses described in Embodiment 14 or 15, for

[0138] i. Clay removal, and / or

[0139] ii. Improved removal of oily / greasy stains, and / or

[0140] iii. Removal of particulate stains, and / or

[0141] iv. Dispersion and / or emulsification of dirt, and / or

[0142] v. Modification of treated surfaces to improve re-contamination removal, and / or

[0143] vi. Improved whiteness, and / or

[0144] Most preferably used in cleaning compositions

[0145] i) Clay removal and / or ii) Oily / greasy stain removal,

[0146] Each of the preceding options i) to vi) is preferably used in laundry detergent formulations and / or detergent formulations for hand-washing dishes and / or formulations suitable for (pre)treating textiles and / or soap bars, more preferably in liquid laundry detergent formulations and / or liquid detergent formulations for hand-washing dishes.

[0147] Example 17

[0148] The use according to any one of Examples 14 to 16 is in a cleaning composition and / or in a fabric and household care product, preferably in a cleaning composition for fabric and household care, the cleaning composition being preferably a laundry detergent formulation or a dishwashing detergent formulation, even more preferably a liquid laundry detergent formulation or a liquid dishwashing detergent formulation.

[0149] Such ingredients are typically formulated together with other ingredients in formulations and compositions, which may also be referred to as “products” (because they are provided by the supplier as formulations to another consumer who uses such formulations directly for cleaning purposes or for the production of another formulation, which in turn may be sold to the consumer as a “product” to be used by the consumer).

[0150] Example 18

[0151] A composition comprising fabric and household care products, cleaning compositions, industrial and institutional cleaning products, cosmetic or personal care products, oilfield formulations such as crude oil demulsifiers, pigment dispersions for inks such as inkjet inks, electroplating products, adhesive compositions, varnishes, paints, agricultural chemical formulations, preferably laundry detergents, dishwashing compositions, cleaning compositions and / or fabric and household care products, each comprising at least one alkoxylated polyol obtained or available by any one of Examples 1 to 10 or by any one of Examples 11 to 13.

[0152] Example 19

[0153] The composition according to Example 18 is a solid or liquid laundry detergent composition or a solid or liquid hand dishwashing detergent composition, preferably a liquid laundry detergent or a liquid hand dishwashing detergent composition, more preferably a liquid laundry detergent composition, the detergent composition comprising at least one alkoxylated polyol obtained or obtainable by any one of Examples 1 to 10 or by any one of Examples 11 to 13.

[0154] Optionally, it further comprises at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersases, oxidoreductases, cutinases, pectin lyases, pectinases, lactases, pectinases, mannanases, and peroxidases, as well as combinations of at least two of the foregoing types, preferably at least one enzyme selected from proteases.

[0155] Optionally contains at least one antimicrobial agent.

[0156] At least one alkoxylated polyol is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5% relative to the total weight of the composition or product.

[0157] Such products or compositions further comprise, by weight, about 1% to about 70% of at least one surfactant, preferably an anionic surfactant, or even more preferably a surfactant system comprising at least one anionic surfactant.

[0158] Example 20

[0159] The composition according to Example 18 is a solid or liquid detergent composition for automatic tableware washing, preferably a solid detergent composition for automatic tableware washing, the detergent composition comprising at least one alkoxylated polyol obtained or available by any one of Examples 1 to 10 or by any one of Examples 11 to 13.

[0160] Optionally, it further comprises at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersases, oxidoreductases, cutinases, pectin lyases, pectinases, lactases, mannanases, and peroxidases, as well as combinations of at least two of the foregoing types, preferably at least one enzyme selected from proteases and amylases.

[0161] Optionally contains at least one antimicrobial agent.

[0162] Optionally, it contains at least one compound selected from alkali metal percarbonates, alkali metal perborates, and alkali metal persulfates.

[0163] Optionally contains at least one zinc salt.

[0164] The at least one alkoxylated polyol is present in a total amount ranging from about 0.001% to about 10%, preferably from about 0.005% to 5%, more preferably from about 0.01% to about 3%, and most preferably from about 0.1% to about 2%, and such a product or composition further comprises at least one chelating agent, which is present in a total amount ranging from about 1% to about 70%, preferably from 10% to about 60%, and even more preferably from 30% to about 50%.

[0165] Optionally, it may further comprise at least one surfactant or more preferably a surfactant system in a total amount of about 1% to about 70% by weight.

[0166] All weight percentages are relative to the total weight of the composition.

[0167] Example 21

[0168] The composition according to Example 20 is a solid detergent composition for automatic dishwashing, comprising at least one alkoxylated polyol obtained or obtainable according to any one of Examples 1 to 10 or by any one of Examples 11 to 13, and

[0169] Additionally, it contains at least one chelating agent selected from methylglycine diacetate (MGDA), glutamic acid diacetate (GLDA), citric acid, and their salts.

[0170] At least one enzyme selected from proteases and / or amylases,

[0171] At least one bleaching agent selected from alkali metal percarbonates, alkali metal perborates, and alkali metal persulfates, preferably alkali metal percarbonates.

[0172] At least one nonionic surfactant,

[0173] Optionally, at least one disintegrant, preferably a super-disintegrant, more preferably PVPP, and

[0174] Optionally contains at least one zinc salt.

[0175] Superdisintegrants are known to those skilled in the art, for example, from EP 1004661, EP 1263814 and EP1036839, and are also discussed in Pharmaceutical Technology, Vol. 2006, Supplement, No. 5, “A Comparative Study of Current Superdisintegrants”, October 1, 2006.

[0176] Example 22

[0177] The composition according to any one of Examples 18 and 19 is a detergent composition comprising at least one anionic surfactant as a surfactant.

[0178] Example 23

[0179] The composition according to any one of Examples 18 and 19 is a liquid detergent composition comprising at least one nonionic surfactant as a surfactant, and further comprising water.

[0180] Example 24

[0181] The composition according to any one of Examples 18, 19, 22 and 23 is a detergent composition comprising at least one polymer selected from polyfunctional alkoxylated polyethyleneimine, polyfunctional alkoxylated diamine or terephthalic acid-based detergency polyester or mixtures thereof.

[0182] Example 25

[0183] The composition according to any one of Examples 18, 19 and 22 to 24 is a liquid detergent composition comprising at least one 2-propylheptylethoxylated nonionic surfactant having an average degree of ethoxylation of 3 to 8 as a surfactant.

[0184] Example 26

[0185] The composition according to any one of Examples 18 to 25 further comprises an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether; preferably comprises 2-phenoxyethanol in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprises 0.1% to 2% phenoxyethanol or preferably comprises 0.001% to 3%, more preferably 0.002% to 1%, or even more preferably 0.01% to 0.6% of 4,4'-dichloro-2-hydroxydiphenyl ether, each by weight of the composition.

[0186] Example 27

[0187] The composition according to any one of Examples 18 to 26 further comprises at least one enzyme selected from the list of lipases, hydrolases, amylases, DNases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersases, oxidoreductases, keratinases, pectinases, 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 selected from proteases.

[0188] Example 28

[0189] A method for preserving an aqueous composition according to any one of Examples 18 to 27 from microbial contamination or growth, the method comprising adding an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether.

[0190] Example 29

[0191] In another aspect, the present invention relates to alkoxylated polyols comprising a polyol core having substantially three -OH groups.

[0192] in

[0193] At least one of these -OH groups is modified to form an epoxide branch.

[0194] - Each of the at least one alkyl oxide branch contains ethylene oxide and propylene oxide.

[0195] The weight-average molecular weight (Mw) of this alkoxylated polyol is in the range of 1,500 to 4,500 g / mol, and

[0196] - The propylene oxide content is at least 50% by weight relative to the total weight of the alkoxylated polyol.

[0197] As used herein, the term “polyol core having substantially three -OH groups” includes, but is not limited to, triols such as glycerol and trimethylolpropane (TMP) and triols having four, five or six carbon atoms (C4, C5 and C6 triols), preferably straight-chain C4, C5 and C6 triols. More preferably, the polyol nucleus, which substantially has three -OH groups, is selected from the group consisting of: 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,3-pentanetriol, 1,2,4-pentanetriol, 1,2,5-pentanetriol, 1,3,4-pentanetriol, 1,3,5-pentanetriol, 2,3,4-pentanetriol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol, 1,2,6-hexanetriol, 1,3,4-hexanetriol, 1,3,5-hexanetriol, 1,3,6-hexanetriol, 1,4,5-hexanetriol, and 2,3,4-hexanetriol.

[0198] All terms used in Example 29 have been defined and explained in detail in the descriptions of Examples 1 to 7 and 9 above, and such terms, definitions, and additional specifications naturally apply to Example 29. In particular, the terms and definitions given for epoxide branching also apply to alkoxylated polyols based on a polyol core having substantially three -OH groups as described above.

[0199] In another aspect, the present invention relates to a method for preparing alkoxylated polyols comprising a polyol core having substantially three -OH groups as described above, wherein the polyol having substantially three -OH groups is reacted with (i) at least eight ethylene oxide molecules and (ii) at least 24 propylene oxide molecules to obtain the corresponding alkoxylated polyol. All terms used in this preparation method have been defined and explained in detail above in the description of Examples 11 to 13, and such terms, definitions, and additional specifications naturally apply to the above-described preparation method.

[0200] In another aspect, the present invention relates to the use of at least one alkoxylated polyol comprising a polyol core substantially having three -OH groups, as described above, in cleaning compositions, in fabric and household care products, in cosmetic formulations, as a crude oil demulsifier, in pigment dispersions for inkjet inks, in formulations for electroplating, in adhesive compositions, and as a dispersant for agricultural chemical formulations. All terms used in such applications have been defined and explained in detail above in the description of Examples 14 to 17, and such terms, definitions, and additional specifications naturally apply to the above-described applications.

[0201] In another aspect, the present invention relates to a composition which is a fabric and household care product, a cleaning composition, an industrial and institutional cleaning product, a cosmetic or personal care product, an oilfield formulation such as a crude oil demulsifier, a pigment dispersion for inks such as inkjet inks, an electroplating product, an adhesive composition, a paint, an oil paint, an agricultural chemical formulation, preferably a laundry detergent, a dishwashing composition, a cleaning composition, and / or a fabric and household care product, each comprising at least one alkoxylated polyol comprising a polyol core substantially having three -OH groups as described above. All terms within such compositions have been defined and explained in detail in the description above in Examples 18 to 27, and such terms, definitions, and additional specifications naturally apply to the compositions described above.

[0202] Additional description

[0203] In this invention, it is also preferred that the cleaning composition additionally contains (in addition to at least one alkoxylated polyol as described above) at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersases, oxidoreductases, keratinases, pectinases, pectinases, lactases, and peroxidases, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the aforementioned types, more preferably at least one enzyme selected from proteases.

[0204] Preferably, the cleaning composition of the present invention is a fabric and household care product or an industrial and institutional (I&I) cleaning product, preferably a fabric and household care product, more preferably a laundry detergent or a hand dishwashing detergent, comprising at least one alkoxylated polyol of the present invention, and optionally further comprising at least one surfactant or surfactant system, providing improved removal, dispersion and / or emulsification of dirt and / or modification of treated surfaces and / or maintenance of the whiteness of treated surfaces.

[0205] At least one alkoxylated polyol of the present invention as described herein (such alkoxylated polyol as defined previously and especially in Examples 1 to 10 and 29, also referred to as "the compound of the present invention" in the following sections) is present in the cleaning composition of the present invention at a concentration of about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5% by weight relative to the total weight of such composition or product; such cleaning composition may—and preferably certainly—further comprise about 1% to about 70% by weight of a surfactant system.

[0206] Even more preferably, the cleaning compositions of the present invention, which contain at least one compound of the present invention and optionally further contain at least one surfactant or surfactant system, are for primary cleaning (i.e., stain removal) in laundry and manual dishwashing applications, and even more specifically for removing clay or oily and greasy stains (such as those on fabrics and tableware), and may additionally contain at least one enzyme selected from the list of enzymes of the following types: lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, DNase, mannanase, xylanase, dispersase, oxidoreductase, keratinase, pectinase, pectinase, lactase, and peroxidase, and combinations of at least two of the enzymes of the aforementioned types, more preferably at least one enzyme selected from proteases.

[0207] In a preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0208] In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (e.g., powder or tablet / unit dose) detergent composition for manual or automatic dishwashing, preferably a liquid detergent composition for manual dishwashing or a solid dishwashing composition for automatic dishwashing.

[0209] In one embodiment, the compound of the present invention can be used in a cleaning composition comprising a surfactant system containing C 10 -C 15 Alkylbenzene sulfonate (LAS) is used as the primary surfactant, along with one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0210] In another embodiment, the compounds of the present invention can be used in any kind of cleaning composition, such as laundry detergents, which contain C8-C4 compounds having 1-5 ethoxy units. 18 Linear or branched alkyl ether sulfates are used as the primary surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0211] In another embodiment, the compounds of the present invention can be used in any kind of cleaning composition, such as laundry detergent, etc., which contain C44 having 5-10 ethoxy units. 12 -C 18 Alkyl ethoxylated surfactants are used as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other nonionic surfactants, or mixtures thereof.

[0212] In other embodiments, the compounds of the present invention can be used in any kind of cleaning composition, such as laundry detergents, which contain bio-based surfactants such as rhamnolipids and / or sophorolipids as the main surfactant.

[0213] In one embodiment of the invention, the compound of the invention is a component of a cleaning composition such as preferably a laundry preparation or dishwashing preparation, more preferably a liquid laundry preparation or manual dishwashing preparation, each additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0214] The choice of additional surfactants in these embodiments may depend on the application and the desired benefits.

[0215] As used herein, when used in the claims or embodiments, the articles “a” and “an” should be understood to mean one or more of the claimed or described. As used herein, the terms “include” and “including” are non-limiting and therefore cover more than the specific entries mentioned after these words.

[0216] The compositions disclosed herein may “comprise” (i.e. contain other ingredients) the components disclosed herein, “consistently comprised of the components disclosed herein” (mainly or almost entirely comprised of the mentioned ingredients and only in very small amounts of other ingredients, mainly as impurities), or “composed of the components disclosed herein” (i.e. contain only the mentioned ingredients and may additionally contain only impurities unavoidable in the technical environment, preferably only those ingredients).

[0217] As used herein, the term "at least one" includes, but is not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

[0218] Similarly, the terms “substantially free of …”, “substantially free from …”, or “(containing / comprising) essentially no …” may be used herein; this means that the indicated material is present in a very small amount unintentionally added to the composition to form a part of it, or, preferably, not at an analytically detectable level. It means a composition comprising the indicated material only as an impurity in one of the other intentionally included materials. If present, the indicated material may be present at a level of less than 1%, or even less than 0.1%, or even much less than 0.01%, or even 0% by weight of the composition.

[0219] As used herein, the term "about" encompasses the exact number "X" referred to as, for example, "about X%", as well as small variations of X, including deviations from X by -5% to +5% (where X is set to 100% for such calculations), preferably -2% to +2%, more preferably -1% to +1%, even more preferably -0.5% to +0.5%, and smaller variations. Of course, if the given value X is already "100%" (e.g., for purity), then the term "about" can explicitly and indeed truly refer only to a deviation less than "100".

[0220] Unless otherwise stated, all component or composition levels refer to the active portion of the component or composition and do not include impurities that may be present in commercially available sources of such components or compositions, such as residual solvents or byproducts.

[0221] Unless otherwise indicated, all temperatures herein are in degrees Celsius (°C). Unless otherwise stated, all measurements herein were performed at 20°C and atmospheric pressure. In all embodiments disclosed herein, unless otherwise specified, all percentages are by weight of the total composition. Unless otherwise specified, all ratios are by weight.

[0222] Description of cleaning compositions, formulations and their ingredients

[0223] As used herein, the phrase "cleaning composition" includes compositions and formulations designed for cleaning soiled materials. Such compositions and formulations include those designed for cleaning any kind of soiled material or surface.

[0224] Compositions for “industrial and institutional cleaning” include such cleaning compositions designed for use in industrial and institutional cleaning, such as cleaning compositions for cleaning any kind of soiled materials or surfaces, such as hard surface cleaners for any kind of surfaces (including tile, carpet, PVC-coated surfaces, wood surfaces, metal surfaces, and painted surfaces).

[0225] "Compositions for fabric and household care" include cleaning compositions and formulations, including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric reinforcing compositions, fabric cleaning compositions, laundry pre-wash agents, laundry pretreatment agents, laundry additives, spray products, drying cleaners or compositions, laundry rinse additives, washing additives, post-rinse fabric treatment agents, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit-dose formulations, delayed-delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that will be apparent to those skilled in the art in light of the teachings herein and are detailed below in the description of the compositions. Such compositions can be used as pre-wash treatment agents, post-wash treatment agents, or can be added during the rinsing or washing cycle of a laundry operation, preferably during the washing cycle of a laundry or dishwashing operation, and are further detailed below in the description of the uses and applications of the compounds of the invention and compositions comprising such polymers.

[0226] The cleaning compositions of the present invention can be in any form, i.e., in the following forms: liquid; solid, such as powder, granules, agglomerates, pastes, tablets, sachets, sticks, gels; emulsions; delivered in dual-compartment or multi-compartment containers; single-phase or multi-phase unit doses; spray or foam detergents; pre-wet wipes (i.e., cleaning compositions combined with nonwoven materials, such as those discussed in US 6,121,165, Mackey et al.); dry wipes (i.e., cleaning compositions combined with nonwoven materials, such as those discussed in US 5,980,931, Fowler et al.), which are activated by water by the user or consumer; and other homogeneous, non-homogeneous, or single-phase or multi-phase cleaning product forms.

[0227] The liquid cleaning composition of the present invention preferably has a strength of 50 to 10000 mPa. The viscosity of the liquid manual dishwashing composition (also known as the liquid manual "dishwashing composition") is preferably 100 to 10000 mPa at 20 1 / s and 20°C. s, more preferably 200 to 5000 mPa s and most preferably 500 to 3000 mPa The viscosity of the liquid laundry cleaning composition is preferably 50 to 3000 mPa at 20 1 / s and 20°C. s, more preferably 100 to 1500 mPa s and most preferably 200 to 1000 mPa The viscosity of s.

[0228] The liquid cleaning composition of the present invention can 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 6 to 13, even more preferably 6 to 10, and most preferably 7 to 9. The pH of the composition can be adjusted using pH-modifying agents known in the art and measured at 25°C in demineralized water at a 10% product concentration. For example, NaOH can be used, and the actual weight percentage of NaOH can be varied and adjusted to a desired pH such as pH 8.0. In one embodiment of the invention, the pH is adjusted to > 7 by using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0229] Cleaning compositions, such as fabric and household care products and formulations for industrial and institutional cleaning, more specifically such as laundry detergents and hand dishwashing detergents, are known to those skilled in the art. Any compositions known to those skilled in the art, etc. (in conjunction with their respective uses), can be used in the context of this invention by comprising at least one compound of the invention, preferably at least one polymer, in an amount suitable for exhibiting certain properties in such compositions (especially when such compositions are used in their field of application).

[0230] Another aspect of the invention is the use of the compounds of the invention as additives for detergent formulations, particularly for liquid detergent formulations, preferably concentrated liquid detergent formulations, or for single-use, single-dose additives for laundry.

[0231] The cleaning compositions of the present invention may—and preferably certainly do—contain auxiliary cleaning additives (also referred to herein as “auxiliaries”), which are preferably in addition to surfactant systems as previously defined.

[0232] Suitable auxiliary cleaning additives include detergent builders, co-detergent builders, structuring agents or thickeners, clay stain removers / anti-redeposition agents, polymer detergents, dispersants such as polymer dispersants, polymer grease cleaners, solubilizers, chelating agents, enzymes, enzyme stabilizers, bleaching compounds, bleaching agents, bleaching activators, bleaching catalysts, brighteners, odor control agents, pigments, dyes, opacifiers, toning agents, dye transfer inhibitors, chelating agents, foaming agents, foam inhibitors (defoamers), color speckle removers, silver care products, anti-discoloration agents and / or preservatives, alkalinity sources, pH adjusters, pH buffers, water-soluble additives, detergent granules, antibacterial agents, antioxidants, softeners, carriers, processing aids, fragrance precursors, dye fixatives, and fragrances.

[0233] The liquid cleaning composition may additionally include—and preferably does include—at least one of a rheology control agent / modifier, emollient, humectant, skin rejuvenating active, and solvent.

[0234] The solid composition may additionally include—and preferably does include—at least one of filler, bleach, bleach activator, and catalytic material.

[0235] Suitable examples and levels of use of such cleaning aids can be found in WO 99 / 05242, U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

[0236] Those skilled in the art will understand that detergency surfactants encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0237] Therefore, the cleaning compositions of the present invention, such as fabric and household care products, as well as formulations for industrial and institutional cleaning, more specifically such as laundry detergents and hand dishwashing detergents, preferably additionally contain a surfactant system, and more preferably additional adjuvants, such as those described above and below in more detail.

[0238] A surfactant system may consist of a single surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures thereof. Those skilled in the art will understand that surfactant systems for detergents encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0239] The cleaning compositions of the present invention preferably comprise a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises about 1% to about 70% of the surfactant system by weight of the composition. In other embodiments, the liquid cleaning composition comprises about 2% to about 60% of the surfactant system by weight of the composition. In still other embodiments, the cleaning composition comprises about 5% to about 30% of the surfactant system by weight of the composition. The surfactant system may comprise detergency surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures thereof.

[0240] (a) Laundry composition

[0241] In laundry products, anionic surfactants typically constitute the largest proportion of the surfactants used. Therefore, preferably, the cleaning compositions of the present invention for laundry contain at least one anionic surfactant and optionally additional surfactants selected from any of the surfactant classes described herein, preferably from nonionic surfactants and / or amphoteric surfactants and / or amphoteric surfactants and / or cationic surfactants.

[0242] Non-limiting examples of anionic surfactants available in this article—which may also be used in combination with more than one surfactant—include C9-C. 20 Linear alkylbenzene sulfonates (LAS), C 10 -C 20 Primary, branched and random alkyl sulfates (AS); C 10 -C 18 secondary (2,3)alkyl sulfates; C 10 -C 18 Alkylalkoxy sulfates (AExS), where x is 1 to 30; C containing 1 to 5 ethoxy units. 10 -C 18 Alkyl alkoxycarboxylates; medium-chain branched alkyl sulfates, as discussed in US 6,020,303 and US 6,060,443; medium-chain branched alkyl alkoxy sulfates, as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonates (MLAS), as discussed in WO 99 / 05243, WO 99 / 05242 and WO 99 / 05244; methyl ester sulfonates (MES); and α-olefin sulfonates (AOS).

[0243] Preferred examples of suitable anionic surfactants are the following alkali metal salts and ammonium salts: C8-C 12 -Alkyl sulfate, C12 -C 18 - Fatty alcohol ether sulfate, C 12 -C 18 - Fatty alcohol polyether sulfate, ethoxylated C4-C 12 -Alkylphenol sulfate half-ester (ethoxylation: 3 to 50 mol ethylene oxide / mol), C 12 -C 18 -Alkyl sulfonic acid, C 12 -C 18 sulfonyl fatty acid alkyl esters, such as C 12 -C 18 sulfonyl fatty acid methyl ester, C 10 -C 18 -alkylarylsulfonic acid, preferably C 10 -C 18 -alkylbenzene sulfonic acid, C 10 -C 18 Alkyl alkoxycarboxylic esters and soaps, such as C8-C 24 -Carboxylic acid. Preferably, it is an alkali metal salt of the aforementioned compound, and particularly preferably a sodium salt.

[0244] In one embodiment of the present invention, the anionic surfactant is selected from C-type surfactants. 10 -C 18 - Alkylbenzene sulfonic acid and fatty alcohol polyether sulfate, in the context of this invention, particularly ethoxylated C 12 -C 18 -Alkyl alcohol (preferably C-1) 12 -C 18 Half-esters of alkyl alcohols (ethoxylated: 1 to 50 mol of ethylene oxide / mol).

[0245] In one embodiment of the invention, C derived from branched chains (i.e., synthetically produced) can also be used. 11 -C 18 - Alkyl alcohol polyether sulfate (ethoxylation: 1 to 50 mol ethylene oxide / mol).

[0246] Preferably, based on C 12 -C 18 - Fatty alcohols or branched (i.e. synthetic) C 11 -C 18 The alkoxylation group of the two types of alkoxylated alkyl sulfates of alcohols is an ethoxylation group, and the average degree of ethoxylation of any alkoxylated alkyl sulfate is 1 to 5, preferably 1 to 3.

[0247] In another embodiment of the invention, the anionic surfactant is selected from rhamnolipid and / or sophorolipid.

[0248] Preferably, the laundry detergent formulation of the present invention comprises at least 1 wt.% to 50 wt.%, preferably in the range of greater than or equal to about 2 wt.% to equal to or less than about 30 wt.%, more preferably in the range of greater than or equal to 3 wt.% to equal to or less than 25 wt.%, and most preferably in the range of greater than or equal to 5 wt.% to equal to or less than 25 wt.%, based on a specific overall composition (containing other components and water and / or solvent), one or more of the anionic surfactants as described above.

[0249] In a preferred embodiment of the present invention, the anionic surfactant is selected from C 10 -C 15 Straight-chain alkylbenzene sulfonates, C with 1-5 ethoxy units 10 -C 18 Alkyl ether sulfates and C 10 -C 18 Alkyl sulfates.

[0250] Non-limiting examples of nonionic surfactants—which may also be used in combination with more than one other surfactant—include: C8-C 18 Alkyl ethoxylates, such as NEODOL® nonionic surfactants from Shell; and ethylene oxide / propylene oxide block alkoxylates from BASF's PLURONIC®; C 14 -C 22 Medium-chain branched alkyl alkoxylates BAEx, wherein x is 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkyl polysaccharides, as discussed in US 4,565,647, published January 26, 1986 in Llenado; specifically, alkyl polyglycosides, 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-terminated poly(oxyalkylated) alcohol surfactants, as discussed in US 6,482,994 and WO 01 / 42408.

[0251] Preferred examples of nonionic surfactants include, in particular, alkoxylated alcohols and alkoxylated fatty alcohols, diblock and multiblock copolymers of ethylene oxide and propylene oxide, and reaction products of sorbitol with ethylene oxide or propylene oxide, as well as alkylphenol ethoxylates, alkyl glycosides, and polyhydroxy fatty acid amides (glucosamides).

[0252] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds having the general formula (A).

[0253] [Formula (A)]

[0254] The variables are defined as follows:

[0255] R 1 Selected from linear C1-C 10 -alkyl, preferably ethyl and particularly preferably methyl,

[0256] R 2 Selected from C8-C 22 -alkyl, for example, C8H 17 C 10 H 21 C 12 H 25 C 14 H 29 C 16 H 33 or positive C 18 H 37 ,

[0257] R 3 Selected from C1-C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodel,

[0258] m and n are in the range of 0 to 300, wherein the sum of n and m is at least one. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

[0259] Here, the compound having the general formula (A) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0260] Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds having the general formula (B).

[0261] [Formula (B)]

[0262] The variables are defined as follows:

[0263] R 1 They are the same or different and selected from straight-chain C1-C4-alkyl groups, preferably the same in each case and ethyl, and particularly preferably methyl.

[0264] R 4 Selected from C6-C 20-alkyl groups, especially C8H 17 C 10 H 21 C 12 H 25 C 14 H 29 C 16 H 33 C 18 H 37 ,

[0265] a is a number in the range of zero to 6, preferably 1 to 6.

[0266] b is a number in the range of zero to 20, preferably 4 to 20.

[0267] d is a number in the range of 4 to 25.

[0268] Preferably, at least one of a and b is greater than zero.

[0269] Here, the compound having general formula (B) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0270] Other suitable nonionic surfactants are selected from diblock and multiblock copolymers of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitol esters. Alkylphenol ethoxylates, alkyl polyglycosides, or polyhydroxy fatty acid amides (glucosamides) are also suitable. An overview of suitable other nonionic surfactants can be found in EP A 0 851 023 and DE-A 198 19 187.

[0271] Of course, a mixture of two or more different nonionic surfactants can also exist.

[0272] In a preferred embodiment of the present invention, the nonionic surfactant is selected from C 12 / 14 and C 16 / 18 Fatty alcohol alkoxylates, C 13 / 15 Oxy-ol alkoxylates, C 13 - Alcohol alkoxylates and 2-propylheptyl alcohol alkoxylates, each having 3-15 ethoxy units, preferably 4-10 ethoxy units, or having 1-3 propoxy units and 2-15 ethoxy units.

[0273] Non-limiting examples of amphoteric surfactants—which may also be used in combination with more than one other surfactant—include: a water-soluble amine oxide comprising an alkyl moiety having about 8 to about 18 carbon atoms and two portions selected from the group consisting of an alkyl moiety having about 1 to about 3 carbon atoms and a hydroxyalkyl moiety; and a water-soluble sulfoxide comprising an alkyl moiety having about 10 to about 18 carbon atoms and a portion selected from the group consisting of an alkyl moiety having about 1 to about 3 carbon atoms and a hydroxyalkyl moiety. See WO 01 / 32816, US 4,681,704 and US 4,133,779. Thus, suitable surfactants include so-called amine oxides, such as lauryl dimethylamine oxide (“laurylamine oxide”).

[0274] Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyl dimethylamine oxides or alkylamidopropyl dimethylamine oxides, more preferably alkyl dimethylamine oxides, and especially cocoyl dimethylamine oxides. Amine oxides may have a straight-chain or intermediate-branched alkyl moiety. Typical straight-chain amine oxides include water-soluble amine oxides containing an R... 1 = C 8-18 The alkyl moiety and the two Rs selected from the group consisting of C1-C3 alkyl and C1-C3 hydroxyalkyl. 2 and R 3 Partially. Preferably, the amine oxide is characterized by the following formula.

[0275] R 1 -N(R 2 (R) 3 )-O

[0276] Where R 1 It is C8- 18 Alkyl and R 2 and R 3 Selected from the group consisting of: methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. Straight-chain amine oxide surfactants may particularly include straight-chain C... 10 -C 18 Alkyl dimethylamine oxides and straight-chain C8-C 12 Alkoxyethyl dihydroxyethylamine oxide. Preferred amine oxides include straight-chain C... 10 Straight-chain C 10 -C 12 and straight chain C 12 -C 14Alkyl dimethylamine oxide. As used herein, “intermediate branch” means an amine oxide having an alkyl moiety having n1 carbon atoms, wherein an alkyl branch is present on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the α-carbon of nitrogen from the alkyl moiety. This type of branching of amine oxides is also referred to in the art as internal amine oxides. The sum of n1 and n2 is 10 to 24, preferably 12 to 20, and more preferably 10 to 16 carbon atoms. The number of carbon atoms (n1) of the alkyl moiety should be approximately the same as the number of carbon atoms (n2) of the alkyl branch, such that the alkyl moiety and the alkyl branch are symmetrical. As used herein, “symmetrical” means that in at least 50 wt.%, more preferably at least 75 wt.% to 100 wt.% of the intermediate branch amine oxides used herein, (n1-n2) is less than or equal to 5, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two moieties, each independently selected from C1-C3 alkyl, C1-C3 hydroxyalkyl, or polyoxyethylene alkyl groups containing an average of about 1 to about 3 ethylene oxide groups. Preferably, the two moieties are selected from C1-C3 alkyl, more preferably both are selected from C1 alkyl.

[0277] In a preferred embodiment of the present invention, the amphoteric surfactant is selected from C8-C. 18 Alkyl-dimethylamine oxides and C8-C 18 Alkyl-di(hydroxyethyl)amine oxide.

[0278] The cleaning composition may also contain amphoteric surfactants – which may also be used in combination with more than one other surfactant.

[0279] Suitable amphoteric surfactants include betaines, such as alkyl betaines, alkylamidobetaines, imidazolinium betaines, sulfobetaine (INCI sulfobetaine), and phosphate betaines. Examples of suitable betaines and sulfobetaines are as follows (according to INCI nomenclature): Almond amidopropyl betaine, Apricotamidopropyl betaine, avocadoamidopropyl betaine, babasamidopropyl betaine, betaine, betaine, octanoic acid amidopropyl betaine, capryloyl / decanoic acid amidopropyl betaine, carnitine, cetyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocamidopropyl betaine, and cocamidopropyl betaine. propyl hydroxysulfonyl betaine, cocobetaine, cocobetaine hydroxysulfonyl betaine, coco / oleamidopropyl betaine, cocobetaine sulfonyl betaine, decyl betaine, oleyl glycine dihydroxyethyl ester, daidzeinyl glycine dihydroxyethyl ester, stearyl glycine dihydroxyethyl ester, tallow glycine dihydroxyethyl ester, polydimethylsiloxanepropyl PG-betaine, erucamide propyl hydroxysulfonyl betaine, hydrogenated tallow betaine, isostearamide propyl betaine, and more. Laurethamide propyl betaine, lauryl betaine, lauryl hydroxysulfonyl betaine, lauryl sulfonyl betaine, milk amamidopropyl betaine, mink oil amamidopropyl betaine, myristoyl amamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysulfonyl betaine, oil-based betaine, olive oil amamidopropyl betaine, palm oil amamidopropyl betaine, palmitoyl carnitine, palmitoyl carnitine Palm kernel oleamidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, castor oil oleamidopropyl betaine, sesame oil oleamidopropyl betaine, soybean oil oleamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, butteramidopropyl betaine, butteramidopropyl hydroxysulfonyl betaine, butter betaine, butter dihydroxyethyl betaine, undecenoylamidopropyl betaine, and wheat germ oleamidopropyl betaine.

[0280] Preferred betaine is, for example, C 12 -C 18 -Alkyl betaine and sulfobetaine. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocamidopropyl betaine surfactant.

[0281] Non-limiting examples of cationic surfactants—which may also be used in combination with more than one other surfactant—include: quaternary ammonium surfactants that may have up to 26 carbon atoms, including: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; dimethylhydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethylhydroxyethyl 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 Patent Nos. 4,228,042, 4,239,660, 4,260,529, and US 6,022,844; and cationic ester surfactants as discussed in US The amino surfactant discussed in 6,221,825 and WO00 / 47708 is specifically amamidopropyl dimethylamine (APA).

[0282] The compositions according to the invention may contain at least one builder. In the context of this invention, no distinction will be made between a builder and such components elsewhere referred to as "co-builders". Examples of builders are complexing agents, also referred to hereinafter as complexing agents, ion exchange compounds, and precipitants. Builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates, and polycarboxylates.

[0283] In the context of this invention, the term citrate includes monoalkali metal salts and dialkali metal salts of citrate, and particularly monosodium salts and preferably trisodium salts of citrate, ammonium salts or substituted ammonium salts of citrate, and citrate itself. Citrates can be used as anhydrous compounds or as hydrates, for example as sodium citrate dihydrate. The amount of citrate is calculated with reference to anhydrous trisodium citrate.

[0284] The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogen phosphate, sodium pyrophosphate, and polyphosphates such as sodium tripolyphosphate. However, preferably, the compositions according to the invention are free of phosphates and polyphosphates, wherein hydrogen phosphate is included, for example, free of trisodium phosphate, pentasodium tripolyphosphate, and hexasodium metaphosphate (“phosphate-free”). In the context of this invention, “phosphate-free” should be understood to mean that the total content of phosphates and polyphosphates is in the range of 10 ppm to 0.2% by weight of the respective composition, determined by gravimetric analysis.

[0285] The term carbonate includes alkali metal carbonates and alkali metal bicarbonates, with sodium salts being preferred. Na₂CO₃ is particularly preferred.

[0286] Examples of phosphonates are hydroxyalkylphosphonates and aminoalkylphosphonates. Among hydroxyalkylphosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a detergent builder. It is preferably used as a sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkylphosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues. They are preferably used in the form of neutral reactive sodium salts, such as the hexasodium salt of EDTMP or the heptasodium and octasodium salts of DTPMP.

[0287] Examples of aminocarboxylates and polycarboxylates are hypotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, triethylenetetraaminehexaacetate, propylenediaminetetraacetate, ethanol-diglycine salt, methylglycine diacetate, and glutamine diacetate. The terms aminocarboxylates and polycarboxylates also include their respective unsubstituted or substituted ammonium salts and alkali metal salts, such as sodium salts, particularly sodium salts of their respective completely neutralized compounds.

[0288] In the context of this invention, silicates particularly include sodium disilicate and sodium metasilicate, aluminosilicates such as zeolites and layered silicates, especially those having the formula α-Na2Si2O5, β-Na2Si2O5 and δ-Na2Si2O5.

[0289] The compositions according to the invention may contain one or more detergent builders selected from materials not mentioned above. Examples of detergent builders are α-hydroxypropionic acid and oxidized starch.

[0290] In one embodiment of the invention, the detergent builder is selected from polycarboxylate salts. The term "polycarboxylate salt" includes non-polymerized polycarboxylate salts, such as succinic acid, C2-C... 16 -alkyl disuccinate, C2-C 16 -Alkenyl disuccinate, ethylenediamine N,N'-disuccinic acid, tartaric acid diacetate, alkali metal malonate, tartaric acid monoacetate, propane tricarboxylic acid, butane tetracarboxylic acid and cyclopentane tetracarboxylic acid.

[0291] Oligomeric or polymeric polycarboxylic acids are, for example, alkali metal salts of polyaspartic acid or, in particular, homopolymers or copolymers of (meth)acrylic acid.

[0292] Suitable comonomers are monoolefinically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Suitable polymers are particularly polyacrylic acid, preferably having a weight-average molecular weight (Mw) in the range of 2000 to 40,000 g / mol, preferably 2000 to 10,000 g / mol, and particularly 3000 to 8000 g / mol. Further suitable comonomers are, in particular, those of acrylic acid and methacrylic acid, and those of acrylic acid or methacrylic acid and maleic acid and / or fumaric acid.

[0293] Alternatively, C3-C monoolefin unsaturated compounds can be used. 10 -Single- or C4-C 10 A copolymer of at least one monomer of the group consisting of dicarboxylic acids or their anhydrides (such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid) with at least one hydrophilic or hydrophobic modified comonomer listed below.

[0294] Suitable hydrophobic comonomers are, for example, isobutylene, diisobutylene, butene, pentene, hexene, and styrene; olefins having 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-docodecene, 1-tetradecene, and 1-hexadecene, C 22 -α-olefin, C 20 -C 24 A mixture of -α-olefins and polyisobutylene having an average of 12 to 100 carbon atoms / molecule.

[0295] Suitable hydrophilic comonomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxyl or epoxyalkyl groups. Examples include: allyl alcohol, isoprene alcohol, methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, methoxy polybutylene glycol (meth)acrylate, methoxy poly(propylene oxide-copolymer-ethylene oxide) (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, ethoxy polypropylene glycol (meth)acrylate, ethoxy polybutylene glycol (meth)acrylate, and ethoxy poly(propylene oxide-copolymer-ethylene oxide) (meth)acrylate. The polyalkylene glycol may contain 3 to 50, particularly 5 to 40, and especially 10 to 30 epoxyalkyl units / molecules.

[0296] Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methylallylsulfonic acid, allyloxybenzenesulfonic acid, methylallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-acryloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethylacrylamide, and salts of said acids, such as their sodium, potassium, or ammonium salts.

[0297] The preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.

[0298] In addition, amphoteric polymers can also be used as detergent builders.

[0299] The compositions according to the invention may contain, for example, one or more builder agents in total of 0.1% to 70% by weight, preferably 10% to 50% by weight, and preferably up to 20% by weight, especially in the case of solid formulations. Liquid formulations according to the invention preferably contain builder agents in the range of 0.1% to 8% by weight.

[0300] The formulations according to the invention may contain one or more basic carriers. For example, if an alkaline pH is desired, the basic carrier ensures a pH of at least 9. Suitable carriers include, for example, the alkali metal carbonates, alkali metal bicarbonates, and alkali metal metasilicates mentioned above, and additionally, alkali metal hydroxides. In each case, the preferred alkali metal is potassium, and particularly preferred is sodium. In one embodiment of the invention, the pH is adjusted to > 7 by using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0301] In one embodiment of the invention, the composition or laundry preparation according to the invention additionally contains at least one enzyme.

[0302] In one embodiment, the composition according to the invention additionally contains at least one enzyme.

[0303] Preferably, the at least one enzyme is a detergent enzyme.

[0304] In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), transferase (EC 2), hydrolase (EC 3), lyase (EC 4), isomerase (EC 5), or ligase (EC 6). The EC numbers are based on the enzyme nomenclature recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (1992), including its supplements published between 1993 and 1999. Preferably, the enzyme is a hydrolase (EC 3).

[0305] In a preferred embodiment, the enzyme is selected from the group consisting of:

[0306] Protease, amylase, lipase, cellulase, mannanase, hemicellulase, phospholipase, esterase, pectinase, lactase, peroxidase, xylanase, keratinase, pectic acid lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, amylopectinase, tanninase, pentosanase, malic acid lyase, β-glucanase, arabinoside lyase, hyaluronidase, chondroitinase, laccase, nuclease, deoxyribonuclease, phosphodiester The enzyme comprises phytase, carbohydrate enzyme, galactanase, xanthan gumase, xyloglucanase, oxidoreductase, hydrolase, aminopeptidase, asparaginase, carbohydrate enzyme, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, α-galactosidase, β-galactosidase, glucosylamylase, α-glucosidase, β-glucosidase, invertase, ribonuclease, transglutaminase, and dispersin, as well as combinations of at least two of the aforementioned types. More preferably, the enzyme is selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, xylanase, deoxyribonuclease, dispersin, pectinase, oxidoreductase, and keratinase, as well as combinations of at least two of the aforementioned types. Most preferably, the enzyme is a protease, preferably a serine protease, and more preferably a subtilisin.

[0307] Preferably, the protease is a protease having at least 90% sequence identity with SEQ ID NO: 22 of EP 1921147 B1 and having an amino acid substitution R101E (according to the BPN number). Preferably, the amylase is an amylase having at least 90% sequence identity with SEQ ID NO: 54 of WO 2021032881A1.

[0308] The compositions of the present invention may contain one type of enzyme or more than one different type of enzyme, such as amylase and protease, or more than one enzyme of the same type, such as two or more different proteases, or a mixture thereof, such as amylase and two different proteases.

[0309] The enzyme may be incorporated into the composition in an effective amount sufficient to provide for achieving beneficial effects, preferably for primary and / or secondary washing effects, such as anti-ashing or anti-pilling effects (e.g., in the case of cellulase). Preferably, the enzyme is present in the composition at a level of about 0.00001% to about 5% by weight of the composition, preferably about 0.00001% to about 2%, more preferably about 0.0001% to about 1%, or even more preferably about 0.001% to about 0.5% of enzyme protein.

[0310] Preferably, the enzyme-containing composition further comprises an enzyme stabilizing system.

[0311] Preferably, the enzyme-containing composition described herein comprises about 0.001% to about 10%, about 0.005% to about 8%, or 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 compatible with the enzyme.

[0312] 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-propanediol, or sorbitol), inorganic salts (preferably CaCl2, MgCl2, or NaCl), short-chain (preferably C1-C3) carboxylic acids or their salts (preferably formic acid, formate (preferably sodium formate), acetic acid, acetate, or lactate), borates, boric acid, boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes (preferably Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde bisulfite adducts. Preferably, the enzyme stabilizing system comprises a combination of at least two compounds selected from the group consisting of salts, polyols, and short-chain carboxylic acids, and preferably one or more compounds selected from the group consisting of borates, boric acid, boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde bisulfite adducts. In particular, if a protease is present in the composition, a protease inhibitor may be added, preferably selected from borates, boric acid, boronic acid (preferably 4-FPBA), peptide aldehydes (preferably peptide aldehydes such as Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde bisulfite adducts.

[0313] The compositions according to the invention may contain one or more bleaching agents. Preferred bleaching agents are selected from sodium perborate, anhydrous or, for example, as a monohydrate or as a tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as a monohydrate, and sodium persulfate, wherein the term "persulfate" in each case includes salts of persulfate H2SO5 as well as perdisulfate.

[0314] In view of this, the alkali metal salt can also be an alkali metal bicarbonate, an alkali metal perborate, or an alkali metal persulfate in each case. However, in each case, a dialkali metal salt is preferred.

[0315] The formulations according to the invention may contain one or more bleaching catalysts. The bleaching catalyst may be selected from oxaziridinium-based bleaching catalysts, bleaching-promoting transition metal salts or transition metal complexes, such as manganese-, iron-, cobalt-, ruthenium-, or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, and copper complexes having nitrogen-containing tripod ligands, as well as cobalt-, iron-, copper-, and ruthenium-amine complexes, may also be used as bleaching catalysts.

[0316] The formulations according to the invention may contain one or more bleaching activators, such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycolurea, tetraacetylhexanediamine, acylated phenol sulfonates such as n-nonanoyloxybenzenesulfonate or isonanoyloxybenzenesulfonate, (S)NOBS, LOBS, DOBA, PAP, N-methylmorpholinium acetonitrile (“MMA salt”), trimethylammonium acetonitrile, N-imides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (“DADHT”), or nitrile quaternary ammonium (trimethylammonium acetonitrile).

[0317] As a precursor to H2O2, consider peroxides, which are every compound capable of producing hydrogen peroxide in aqueous solution, such as the organic and inorganic peroxides known in the literature and commercially available, which bleach textiles at conventional washing temperatures, such as 10°C to 95°C.

[0318] However, inorganic peroxides, such as persulfates, perborates, percarbonates, and / or persilicates, are preferably used. These peroxides are typically used in amounts of 2-80 wt%, preferably 4-30 wt%, based on the weight of the composition.

[0319] Typically, the following describes it in more detail as having equation (1) The compound is present in the composition in an amount of 0.05-15 wt% based on the total weight of the composition, preferably 0.1 to 10 wt%.

[0320] Suitable examples of inorganic peroxides are sodium perborate tetrahydrate or sodium perborate monohydrate, sodium percarbonate, and inorganic peroxyacid compounds, such as potassium persulfate (MPS). If an organic or inorganic peroxyacid is used as the peroxide compound, its amount is typically in the range of about 2-80 wt%, preferably 4-30 wt%, based on the weight of the composition.

[0321] Organic peroxides are, for example, single or multiple peroxides, urea peroxides, combinations of C1-C4 alkanol oxidases and C1-C4 alkanols (such as methanol oxidase and ethanol as described in WO 95 / 07972), and alkyl hydroxy peroxides, such as cumene hydroperoxide and tert-butyl hydroperoxide.

[0322] These peroxides can exist in various crystalline forms and have different water contents, and they can also be used with other inorganic or organic compounds to improve their storage stability.

[0323] Peroxy acids can also be used as oxidizing agents. One example is an organic monoperacid having formula (1). ,

[0324] in

[0325] M represents hydrogen or a cation.

[0326] R 19 Indicates unsubstituted C1-C 18 Alkyl; Substituted C1-C 18 Alkyl; unsubstituted aryl; substituted aryl; -(C1-C6 alkylene)-aryl, wherein the alkylene and / or the alkyl group may be substituted; and phthalimide C1-C8 alkylene, wherein the phthalimide and / or the alkylene group may be substituted.

[0327] Preferred single organic peroxy acids and their salts are those having the following formula: ,

[0328] in

[0329] M represents hydrogen or an alkali metal, and

[0330] R' 19 This indicates unsubstituted C1-C4 alkyl; phenyl; -C1-C2 alkylene-phenyl or

[0331] Phthalimide C1-C8 alkylene group.

[0332] CH3COOOH and its alkali metal salts are particularly preferred.

[0333] e-phthalimide peroxyhexanoic acid and its alkali metal salt (PAP) are particularly preferred.

[0334] Also suitable are diperoxic acids, such as 1,12-disperoxydodecanoic acid (DPDA), 1,9-disperoxyazeloic acid, diperoxadecanoic acid, diperoxadecanoic acid, diperoxisophthalic acid, 2-decyldisperoxybutane-1,4-diacid and 4,4'-sulfonylbisperoxybenzoic acid.

[0335] In some cases, the use of additional bleach activators can be advantageous.

[0336] The term bleaching activator is often used synonymously with peroxy acid bleaching precursor. All of the above-mentioned peroxy compounds can be used alone or in combination with peroxy acid bleaching precursors.

[0337] These precursors are the corresponding carboxylic acids, carboxylic anhydrides, carbonyl chlorides, amides, or esters, which can form peroxyacids upon hydrolysis. Such reactions are generally known.

[0338] Peroxyacid bleaching precursors are known and described in detail in the literature, such as in British Patents 836988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patents 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; and US Patents 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

[0339] Suitable bleaching activators include those with O- and / or N-acyl groups and / or unsubstituted or substituted benzoyl groups. Preferred are polyacylated alkylene diamines, especially tetraacetylethylenediamine (TAED); acylated glycoureas, especially tetraacetyldiol urea (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU); sodium 4-benzoyloxybenzenesulfonate (SBOBS); sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate; sodium 4-methyl-3-benzoyloxybenzoate; trimethylammonium tolueneoxybenzenesulfonate; acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); compounds having formula (10):

[0340]

[0341] Where R 22It is a sulfonate group, a carboxylic acid group, or a carboxylic ester group, and wherein R 21 Is it a straight chain or a branched chain (C7-C)? 15 Alkyl groups, especially activators known by the names SNOBS, SLOBS, and DOBA; acylated polyols, especially triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5-dihydrofuran; and also acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetyl glucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose, and octaacetyllactose, as well as acetylated, optionally N-alkylated glucosamine and gluconolactone. Combinations of conventional bleaching activators known from German patent application DE-A-44 43 177 may also be used. Nitrile compounds that form perimino acids with peroxides are also considered as bleaching activators.

[0342] Another class of useful peroxyacid bleaching precursors are cationic ones, namely quaternary ammonium-substituted peroxyacid precursors, such as those disclosed in U.S. Patent Nos. 4,751,015 and 4,397,757, EP-A0284292 and EP-A-331,229. Examples of such peroxyacid bleaching precursors are: 2-(N,N,N-trimethylammonium)ethyl-4-sulfophenyl carbonate sodium chloride-(SPCC), N-octyl,N,N-dimethyl-N10-carboxyphenoxydecyl ammonium chloride-(ODC), 3-(N,N,N-trimethylammonium)propyl-4-sulfophenylcarboxylate sodium salt, and N,N,N-trimethylammonium tolueneoxybenzenesulfonate.

[0343] Additional bleaching catalysts may also be used, such as transition metal complexes disclosed in EP1194514, EP 1383857 or WO 04 / 007657.

[0344] Formulations according to the invention may contain one or more corrosion inhibitors. In this case, this should be understood to include those compounds that inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, particularly benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, and phenol derivatives, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, or pyroglucinol.

[0345] In one embodiment of the invention, the formulation according to the invention comprises a total of 0.1% to 1.5% corrosion inhibitor by weight.

[0346] The formulations according to the invention may further comprise cleaning polymers and / or stain-removing polymers.

[0347] Additional cleaning polymers may include, but are not limited to: "multifunctional alkoxylated polyethyleneimine" (e.g., BASF's Sokalan® HP20), "multifunctional alkoxylated diamine" (e.g., BASF's Sokalan® HP96), BASF's Sokalan® SR400 A, and terephthalic acid-based polyesters, such as Clariant's TexCare®, including TexCare® SRN 170, TexCare® SRN 172, TexCare® SRN 260, TexCare® SRN260 SG Terra, and TexCare® SRA 300, as well as different combinations of all the aforementioned polymers.

[0348] Suitable polyfunctional alkoxylated polyethyleneimines are typically ethoxylated polyethyleneimines having a weight-average molecular weight (Mw) in the range of 3,000 to 250,000, preferably 5,000 to 200,000, more preferably 8,000 to 100,000, even more preferably 8,000 to 50,000, even more preferably 10,000 to 30,000, and most preferably 10,000 to 20,000 g / mol. Suitable polyfunctional alkoxylated polyethyleneimines have ethylene oxide side chains comprising 80 wt.% to 99 wt.%, preferably 85 wt.% to 99 wt.%, more preferably 90 wt.% to 98 wt.%, and most preferably 93 wt.% to 97 wt.% or 94 wt.% to 96 wt.% based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core and a polyethylene oxide shell. A suitable polyethyleneimine core molecule is a polyethyleneimine having a weight-average molecular weight Mw in the range of 500 to 5000 g / mol. Preferably, a molecular weight of 500 to 1000 g / mol is used, and even more preferably, a Mw of 600 to 800 g / mol is used. Then, the ethoxylated polymer has an average of 5 to 50, preferably 10 to 35, and even more preferably 20 to 35 ethylene oxide (EO) units / NH-functional groups.

[0349] Suitable polyfunctional alkoxylated diamines are typically ethoxylated C2 to C3. 12The alkylene diamine, preferably hexamethylene diamine, is further quaternized and optionally sulfated. Typical polyfunctional alkoxylated diamines have a weight-average molecular weight (Mw) in the range of 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, which is further quaternized and sulfated, may be used, containing an average of 10 to 50, preferably 15 to 40, and even more preferably 20 to 30 ethylene oxide (EO) groups / NH-functional groups, and preferably has two cationic ammonium groups and two anionic sulfate groups.

[0350] It should be noted that the cleaning composition of the present invention may also contain at least one alkoxylated polyol of the present invention and at least one other alkoxylated polyol that does not form part of the claims, such as alkoxylated polyols derived from polyols having six or more -OH groups (e.g., alkoxylated sorbitol).

[0351] In a preferred embodiment of the invention, the cleaning composition may contain at least one polyfunctional alkoxylated polyethyleneimine and / or at least one polyfunctional alkoxylated diamine to improve cleaning performance, such as preferably improving stain removal ability, especially the primary detergency of laundry detergents on particulate stains on polyester fabrics. The polyfunctional polyethyleneimine or polyfunctional diamine or mixture thereof described above may be added to the laundry detergent and cleaning composition in an amount typically 0.05 to 15 wt.%, preferably 0.1 to 10 wt.%, more preferably 0.25 to 5 wt.%, and even as low as up to 2 wt.%, based on the specific overall composition (containing other components and water and / or solvents).

[0352] In another preferred embodiment of the invention, the cleaning composition may contain at least one terephthalic acid-based polyester as a stain-removing polymer to improve the whiteness of the washed fabric, especially the whiteness of polyester fabrics.

[0353] Therefore, one aspect of the present invention is a laundry detergent composition, particularly a liquid laundry detergent, comprising (i) at least one compound of the present invention and (ii) at least one compound selected from polyfunctional alkoxylated polyethyleneimine, polyfunctional alkoxylated diamine and terephthalic acid-based polyesters, and mixtures thereof.

[0354] In one embodiment of the invention, the ratio of the at least one compound of the invention to (ii) the at least one compound selected from polyfunctional polyethyleneimine and polyfunctional diamine and mixtures thereof is 10:1 to 1:10, preferably 5:1 to 1:5 and more preferably 3:1 to 1:3.

[0355] Laundry products containing the compounds of the present invention may also contain at least one antimicrobial agent (also commonly referred to as a preservative).

[0356] The composition may contain one or more antimicrobial agents and / or preservatives as listed on pages 35 to 39 of patent WO 2021 / 115912 A1.

[0357] Of particular interest are the following antimicrobial agents and / or preservatives:

[0358] 4,4'-Dichloro-2-hydroxydiphenyl ether (CAS No. 3380-30-1), also known as 5-chloro-2-(4-chlorophenoxy)phenol, diclosan, DCPP, is commercially available as a 30 wt% solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propanediol under the trade name Tinosan® HP 100 (BASF); 2-phenoxyethanol (CAS No. 122-99-6, also known as phenoxyethanol, methylphenyl glycol, phenoxyethanol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, Protectol® PE); 2-bromo-2-nitropropane-1,3-diol (CAS No. 52-51-7, also known as 2-bromo-2-nitro-1,3-propanediol, Bronopol®, Protectol® BN, Myacide). AS); Glutaraldehyde (CAS No. 111-30-8, other names: 1-5-glutaraldehyde, pentyl-1,5-dialdehyde, glutaral, glutardialdehyde, Protectol® GA, Protectol® GA 50, Myacide® GA); Glyoxal (CAS No. 107-22-2; other names: ethandial, oxylaldehyde, 1,2-glyoxal, 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); 5-Chloro-2-methyl-2H-isothiazol-3-one (CMIT, EINECS 247-500-7) and 2-Methyl-2H-isothiazol-3-one (MIT, EINECS Mixtures of 220-239-6 (a mixture of CMIT / MIT, CAS No. 55965-84-9); 1,2-benzisothiazol-3(2H)-one (BIT, CAS No. 2634-33-5); hexano-2,4-dienoic acid (sorbic acid, CAS No. 110-44-1) and its salts, such as calcium sorbate, sodium sorbate, potassium (E,E)-hexano-2,4-dienoic acid (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 salts (CAS No. 65-85-0, CAS No. 532-32-1) and benzoates, such as ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate; salicylic acid and its salts, such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate; benzalkonium chloride, benzalkonium bromide and benzalkonium saccharin, such as benzalkonium chloride, benzalkonium bromide, benzalkonium saccharin (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; Didecyl dimethyl ammonium 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).

[0359] The antimicrobial agent is added to the composition at a concentration of 0.001% to 10% relative to the total weight of the composition.

[0360] Preferably, the composition contains 0.1% to 2% of 2-phenoxyethanol or 0.005% to 0.6% of 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP).

[0361] Therefore, the present invention further covers a method for preserving the aqueous composition according to the invention against microbial contamination or growth, the method comprising adding 2-phenoxyethanol. The present invention also further covers a method for providing antimicrobial action to textiles after treatment with a solid laundry detergent (e.g., powder, granules, capsules, tablets, sticks, etc.), liquid laundry detergent, softener, or post-rinse agent containing 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP).

[0362] In another embodiment, the present invention also covers a composition comprising the compounds of the present invention as described above, further comprising an antimicrobial agent disclosed below (preferably selected from the group consisting of 2-phenoxyethanol), more preferably comprising the antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; and even more preferably comprising 0.1% to 2% phenoxyethanol.

[0363] In another embodiment, the present invention also covers a method for preserving an aqueous composition against microbial contamination or growth, the composition comprising the compounds of the present invention as described above, preferably a detergent composition, the method comprising adding at least one antimicrobial agent selected from the antimicrobial agents disclosed below, preferably 2-phenoxyethanol.

[0364] In other embodiments, the present invention also covers 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 fabric softener composition for use in laundry, such composition comprising the compounds of the present invention as described above, and such composition further comprising 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6% by weight of the composition.

[0365] In another embodiment, the present invention also covers a method for washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand tableware composition, even more preferably a liquid laundry detergent composition or a liquid fabric softener composition for use in laundry, such composition comprising the compounds of the present invention as described above, such composition further comprising 4,4'-dichloro-2-hydroxydiphenyl ether.

[0366] As used herein, the term "dye fixative" refers to compounds that reduce or even stop dye penetration into colored fabrics during the washing process. Dye fixatives include, but are not limited to, cationic dye fixatives, crosslinking fixatives, and formaldehyde-based fixatives. These compounds are well-known to those skilled in the art and are commercially available from BASF SE, Huntsman, Archroma, Fineotex, Biotex Malaysia, or Dystar. Exemplary but not limiting dye fixatives include Basilen fixative F-RP, Albafix ECO, Finofix NF, poly DADMAC, and polyamines (DCDA-DETA, epichlorohydrin-DMA, epichlorohydrin-DETA, etc.).

[0367] The formulations according to the invention may also contain water and / or additional organic solvents, such as ethanol or propylene glycol.

[0368] Other optional ingredients may include, but are not limited to, viscosity modifiers, cationic surfactants, foam promoters or defoamers, fragrances, dyes, optical brighteners, and dye transfer inhibitors.

[0369] (b) General cleaning compositions and formulations

[0370] In addition to all other ingredients mentioned, the liquid formulations disclosed in this section may also contain 0 to 2%, preferably about 1%, of 2-phenoxyethanol.

[0371] In addition to all other ingredients mentioned, the liquid formulations disclosed above and below may also contain 0-0.2%, preferably about 0.15%, of 4,4'-dichloro-2-hydroxydiphenyl ether. In addition to all other ingredients mentioned, the bleach-free solid laundry compositions may also contain 0-0.2%, preferably about 0.15%, of 4,4'-dichloro-2-hydroxydiphenyl ether.

[0372] The formulations disclosed in this section may, in addition to all other ingredients mentioned, contain one or more enzymes selected from those disclosed above, more preferably proteases and / or amylases, wherein even more preferably the proteases are proteases having at least 90% sequence identity with SEQ ID NO: 22 of EP 1921147 B1 and having amino acid substitution R101E (according to the BPN number), and wherein the amylases are amylases having at least 90% sequence identity with SEQ ID NO: 54 of WO 2021032881 A1, wherein the one or more enzymes are preferably present in the formulation at a level of about 0.00001% to about 5% by weight of the composition, preferably about 0.00001% to about 2%, more preferably about 0.0001% to about 1%, or even more preferably about 0.001% to about 0.5% of the enzyme protein.

[0373] The following compositions (including those in the table) disclose certain types of general-purpose cleaning compositions corresponding to typical compositions associated with typical washing conditions typically employed in regions and countries around the world. At least one of the inventive compounds may be added to one or more formulations in suitable amounts as outlined herein.

[0374] When the illustrated composition does not contain any of the compounds of the present invention, it is a comparative composition. When it contains any of the compounds of the present invention, particularly in amounts described herein as preferred, more preferred, etc., such compositions are considered to fall within the scope of the present invention.

[0375] In a preferred embodiment, the at least one alkoxylated polyol (as defined in the embodiments herein, particularly any one of Examples 1 to 11; in this section, the alkoxylated polyol is also referred to as "the compound of the invention") is used in a laundry detergent.

[0376] The liquid laundry detergent according to the present invention comprises the following:

[0377]

[0378] The preferred liquid laundry detergent according to the present invention comprises the following:

[0379]

[0380] The solid laundry detergent (such as, for example, powder, granules, or tablets) according to the present invention comprises the following:

[0381]

[0382] The total of the components is 100%.

[0383] The preferred solid laundry detergent according to the present invention comprises the following:

[0384]

[0385] In a preferred embodiment, the polymer according to the invention is used in a detergent for manual dishwashing.

[0386] The liquid manual dishwashing detergent according to the present invention comprises the following:

[0387]

[0388] The preferred liquid manual dishwashing detergent according to the present invention comprises the following:

[0389]

[0390] Because the alkoxylated polyols of the present invention are biodegradable, and especially because cleaning formulations typically have a pH of about 7 or higher, and additionally often contain enzymes—which are included in such cleaning formulations to degrade biodegradable substances such as greases, proteins, polysaccharides, etc., present in stains and dirt that should be removed by the cleaning composition—several factors need to be considered when formulating those biodegradable polymers of the present invention. Suitable formulations of this kind are known in principle and include formulations in the following forms: solids—where enzymes and polymers can be separated by coating or by adding them as mixed individual particles—and liquids and semi-liquids—where polymers and enzymes can be separated by formulating them in different compartments, such as in the different compartments of a multi-compartment bag or bottle with different compartments, and liquids ensuring that a predetermined amount of each component from each compartment is applied at each individual point of use from each compartment is poured out simultaneously from these different compartments. Such multi-compartment bags and bottles, etc., are also known to those skilled in the art.

[0391] The following illustrates certain types of general-purpose cleaning compositions, corresponding to typical compositions associated with typical washing conditions typically employed in regions and countries around the world. At least one compound of the invention may be added to one or more formulations in suitable amounts as outlined herein.

[0392] Table 1: General formulations of laundry detergent compositions according to the present invention:

[0393]

[0394] Table 2: Liquid washing frame preparation according to the present invention:

[0395]

[0396] Formulations that do not contain the compounds of this invention are comparative examples.

[0397] Table 2 - Continued: Liquid washing frame preparations according to the present invention:

[0398]

[0399] Formulations that do not contain the compounds of this invention are comparative examples.

[0400] Table 3: Laundry powder frame formulation according to the present invention:

[0401]

[0402] Table 3-continued: Laundry powder frame formulation according to the present invention:

[0403]

[0404] Table 4: Liquid manual dishwashing frame preparation according to the present invention:

[0405]

[0406] The following examples are intended to further illustrate the invention but do not limit its scope.

[0407] This invention encompasses the specific embodiments described throughout this disclosure as part of the invention; various additional options are disclosed in the specification as “optional,” “preferred,” “more preferred,” “even more preferred,” or “most preferred” (or “preferred,” etc.), and options of specific embodiments may be selected individually and independently (unless such independent selection is impossible due to the nature of the feature or if such independent selection is explicitly excluded) and then combined with any other embodiment (where other such options and preferences may also be selected individually and independently, unless such independent selection is impossible due to the nature of the feature or if such independent selection is explicitly excluded), wherein each and any and all such possible combinations are included as separate embodiments as part of the invention. Example

[0408] The following is a list of compounds used for the data in the production cost application.

[0409] Table 5:

[0410]

[0411] synthesis:

[0412] Example 4 of the present invention illustrates this (meta-erythritol, alkoxylated with 12 moles of propylene oxide / hydroxyl and 5 moles of ethylene oxide / hydroxyl).

[0413] Example 4a: Meso-erythritol substituted with 3 moles of propylene oxide / hydroxypropoxylated

[0414] In a 2 L autoclave, 122.1 g of racemic erythritol and 1.6 g of potassium tert-butoxide were placed and the mixture was heated to 130°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. 696.9 g of propylene oxide was added over 13 hours. To complete the reaction, the mixture was allowed to react at 140°C for an additional 10 hours. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80°C. After filtration, 815.0 g of light brown oil was obtained.

[0415] Example 4: Meso-erythritol, alkoxylated with 12 moles of propylene oxide / hydroxyl group and 5 moles of ethylene oxide / hydroxyl group.

[0416] In a 2 L autoclave, 159.7 g of racemic erythritol (Example 4a) and 1.2 g of potassium tert-butoxide were placed and the mixture was heated to 80°C. The vessel was purged three times with nitrogen and the mixture was heated to 140°C. 422.8 g of propylene oxide was added over 7 hours. To complete the reaction, the mixture was allowed to react at 140°C for an additional 4 hours. 176.2 g of ethylene oxide was added over 2 hours. To complete the reaction, the mixture was allowed to react for 10 hours. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80°C. After filtration, 755.0 g of light brown oil was obtained. The elemental composition was 58.8% carbon, 30.8% oxygen, and 10.2% hydrogen.

[0417] Other examples and comparative examples were prepared in a similar manner.

[0418] Polymer biodegradability

[0419] The biodegradation of polymers in wastewater was tested in triplicate using the OECD 301F barometric respiration assay. The OECD 301F is an aerobic test that measures the biodegradation of a sample by measuring oxygen consumption. 100 mg / L of the test substance (which is nominally the only carbon source) along with inoculum (30 mg / L, aerated sludge from a wastewater treatment plant in Mannheim) was added to a measured volume of medium. This was then stirred in a sealed flask at a constant temperature (20°C or 25°C) for 28 or 56 days, respectively. Oxygen consumption was determined by measuring pressure changes in an OxiTop® C (Xylem 35 Analytical GmbH, Germany) measuring device. Released carbon dioxide was absorbed in a sodium hydroxide solution. A nitrification inhibitor was added to the flask to prevent oxygen consumption due to nitrification. The amount of oxygen taken up by the microbial population during the biodegradation of the test substance (corrected for by blank inoculum, in parallel runs) is expressed as a percentage of ThOD (Theoretical Oxygen Demand, measured by elemental analysis of the compound). For each cabinet, the positive control glucose / glucosamine was run together with the test sample.

[0420] The following is a list of polymers and their corresponding biodegradation after 28 days.

[0421] Table 6:

[0422]

[0423] Washing test

[0424] Polymer anti-redeposition properties in laundry detergents

[0425] The following liquid laundry detergent compositions (Table 7) were used as base detergents to test the polymer's resistance to receding. The polymer's resistance to receding was tested under the following conditions:

[0426] 3000 ppm clay, 1200 ppm base detergent / 25°C / 1 mM hardness / 34.2 ppm polymer.

[0427] Table 7. Liquid laundry detergents used for polymer anti-redeposition and cleaning tests.

[0428]

[0429] a The fluorescent brightener is 4,4'-bis{[4-anilino-6-morpholino-s-triazine-2-yl]-amino}-2,2'-stilbene disulfonate disodium salt or 2,2'-([1,1'-biphenyl]-4,4'-diyldi-2,1-vinyldiyl)bis-benzenesulfonate disodium salt.

[0430] b Methyl 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate [6386-38-5]

[0431] c Dow Corning supplies 80%-92% ethyl methyl, methyl (2-phenylpropyl)siloxane; 5%-14% MQ resin in octyl stearate; and 3%-7% modified silica defoamer blends.

[0432] Test preparation

[0433] The following fabrics are provided for whiteness benefit testing:

[0434] Knitted Cotton: Test fabric, cylindrical Inc 403 cotton double rib knit fabric

[0435] The CW120 is available from Empirical Manufacturing Company (Cincinnati, Ohio, USA).

[0436] Fabrics are prepared using the following two methods:

[0437] A) Wash 400 g of fabric twice with 18.6 g of Ariel™ compacted powder detergent at 60°C using a short program (45-minute wash cycle followed by three rinse cycles; total program is 90 minutes) in a WE Electrolux EWC1350 mini washing machine (3.5 liters of water), followed by two detergent-free washes at 60°C using a short program. Then dry the fabric in a tumble dryer using a cabinet dryer.

[0438] B) Place 400 g of fabric in a WE Electrolux EWC1350 mini washing machine (3.5 liters of water) on a short program (45-minute wash cycle followed by three rinse cycles; total program is 90 minutes) at 60°C with 18.6 g of Ariel. TM The compacted powder was washed twice with detergent, followed by two detergent-free washes at 60°C using a short program, and then with 8.2 g Lenor at 40°C using a short program. TM The concentrate (fabric reinforcing agent) is washed three times before entering its respective main wash. The fabric is then dried in a drum dryer using a cabinet dryer.

[0439] Test methods

[0440] In a 96-well plate simulated washing system using magnetized bearings to simulate the agitation of a typical full-size washer, each sample was run under the following conditions: 750 ppm detergent concentration, 150 µL water per well, 25°C, and 1.0 mM water hardness (3:1 Ca). +2 Mg +2 (Molar ratio), washing pH of 8.3, 3000 ppm Arizona test dust (supplied by PTI (Powder Technology Inc)).

[0441] Each fabric was washed for 60 minutes and dried in the dark under ambient conditions. For each washing condition, there were six 96-well plates, and each 96-well plate was subjected to eight internal replicates, for a total of 48 replicates.

[0442] When the samples were dry, L was measured at each well of the 96-well plate using a Spectrolino imaging system (Gretag Macbeth, Spectro Scan 3.273). a b And CIE WI. For each treatment, determine the average CIE WI. As reported in the table below, ΔCIE WI is the difference between the average CIE WI of the sample and the average CIE WI of the control sample (zero polymer) that does not contain the polymer being tested.

[0443] For the whiteness index, use the CIE whiteness index formula and calculate ΔWI as follows: ΔWI on substrate = WI technology - WI zero.

[0444] The results are shown in Table 8, demonstrating that the polymers of the present invention can provide clear resistance to redeposition.

[0445] Table 8: Polymer Anti-Redeposition Properties on Knitted Cotton (Washed and FE-treated)

[0446]

[0447] The cleaning properties of polymers in laundry detergents

[0448] The cleaning performance of polymers in laundry detergents was tested using the formulations described in Table 7, and the washing conditions for single-cycle performance can be summarized as follows:

[0449] Equipment: Launder-o-meter (color fastness to washing)

[0450] 500 mL of washing solution

[0451] Washing time 30 minutes

[0452] Washing temperature 25°C.

[0453] Detergent concentration 1.2 g / L

[0454] Water hardness 1 mmol / L; (Ca : Mg) : HCO3 (4 : 1) : 8

[0455] Soiled fabrics: WFK 20D (Sebum Bey) from CFT, PC-S-132 (High-Discrimination Sebum Bey) and PC-S-94 (ASTM Dust Sebum) from CFT, and GSRTBB001 (Caramelized Butter) from Equest.

[0456] After one cycle, rinse the soiled fabric twice with water, then briefly spin-dry and air dry at room temperature for 12 hours.

[0457] For each type of stain, the color fastness tester was run 3 times, with each run repeated 2 times, for a total of 6 repetitions.

[0458] To evaluate the primary detergency of the fabric, the Stain Removal Index (SRI) formula from ASTM D4265 was used to determine the soiled fabric before and after washing. Reflectance values ​​of the corresponding fabrics were obtained using a reflectometer (MACH5+, a multi-zone color measuring instrument from ColourConsult) before and after washing. A higher Δreflectance value indicates better primary detergency.

[0459] ASTM D4265-14: Evaluation of stain removal performance in household laundry

[0460] Stain Removal Ratio (SRI)

[0461] SRI = 100 x (((ΔE (Before washing - not dirty) - ΔE (After washing - not dirty) / ΔE (Before washing - not dirty)

[0462] ΔE = ((ΔL ) 2 + (Δa ) 2 + (Δb ) 2 ) ½

[0463] The cleaning properties of the polymers of this invention are summarized in Table 9. The polymers of this invention provide a significant improvement in the removal of sebum and grease stains.

[0464] Table 9. Cleaning performance of polymer sebum and grease stains (total of 4 types of stains).

[0465] .

Claims

1. An alkoxylated polyol comprising a polyol core having substantially four to five -OH groups, wherein, At least one of these -OH groups is modified to form an epoxide branch. - Each of the at least one alkyl oxide branch contains ethylene oxide and propylene oxide. The weight-average molecular weight (Mw) of this alkoxylated polyol is in the range of 1,500 to 4,500 g / mol, and - The propylene oxide content is at least 50% by weight relative to the total weight of the alkoxylated polyol.

2. The alkoxylated polyol according to claim 1, wherein, The polyol core is a monomer, oligomer, or polymer, wherein each of the oligomer and the polymer comprises a plurality of subunits, preferably the oligomer is a homooligomer or the polymer is a heteropolymer.

3. The alkoxylated polyol according to claim 1 or 2, wherein, Each of these epoxy alkane branches typically contains or consists of the following: i) at least two ethylene oxide units (EO), preferably at least three EO, and more preferably at least four EO; and ii) at least 6 polyoxypropylene units (PO), preferably at least 7 PO and more preferably at least 8 PO.

4. The alkoxylated polyol according to any one of claims 1 to 3, wherein, Each of these epoxy alkane branches typically contains or consists of the following: i) No more than 8 EOs, preferably no more than 7 EOs, and more preferably no more than 6 EOs; and ii) No more than 16 POs, preferably no more than 15 POs and more preferably no more than 14 POs.

5. The alkoxylated polyol according to any one of claims 1 to 4, wherein, The polyol core has a weight ranging from 90 to 500 g / mol, preferably from 100 to 300 g / mol, and more preferably from 120 to 250 g / mol.

6. The alkoxylated polyol according to any one of claims 1 to 5, wherein, The polyol core contains at least one ether bond.

7. The alkoxylated polyol according to any one of claims 1 to 6, wherein, The weight-average molecular weight (Mw) of the alkoxylated polyol is in the range of 2,000 to 4,300 g / mol, preferably in the range of 2,500 to 4,000 g / mol, and more preferably in the range of 3,000 to 3,500 g / mol.

8. The alkoxylated polyol according to any one of claims 1 to 7, wherein, The polyol nucleus is selected from the group consisting of: meso-erythritol, D-threitol, L-threitol, 1,2,5,6-hexanetetrol, pentaerythritol, xylitol, ribitol, arabinitol, pentapentyl alcohol, diglycerides, triglycerides, and polyglycerides, wherein the polyglyceride is preferably composed of two to three glycerol subunits.

9. The alkoxylated polyol according to any one of claims 1 to 8, wherein, Each of these alkyl oxide branches contains a block or random structure of ethylene oxide and propylene oxide, preferably a block structure, more preferably an ethylene oxide and propylene oxide block.

10. A method for preparing alkoxylated polyols according to any one of claims 1 to 9, wherein, A polyol having essentially four to five -OH groups is reacted with (i) at least eight ethylene oxide molecules and (ii) at least 24 propylene oxide molecules to obtain the corresponding alkoxylated polyol.

11. The method according to claim 12, wherein, The polyol having essentially four to five -OH groups is selected from the group consisting of: meso-erythritol, D-threitol, L-threitol, 1,2,5,6-hexanetetrol, pentaerythritol, xylitol, ribitol, arabinitol, pentapentanol, and polyglycerols, preferably consisting of two to three glycerol subunits.

12. The use of the alkoxylated polyol according to any one of claims 1 to 9 in laundry detergents, in cleaning compositions, in fabric and household care products, in cosmetic formulations, as a crude oil demulsifier, in pigment dispersions for inkjet inks, in formulations for electroplating, in adhesive compositions and / or as a dispersant for agricultural chemical formulations, preferably in cleaning compositions and / or in fabric and household care products.

13. The use according to claim 12, wherein it is used in cleaning compositions and / or in fabric and household care products, preferably in cleaning compositions. i) Sebum removal, and / or ii) Improved removal of oily / greasy stains, and / or iii) Removal of particulate stains, and / or iv) Dispersion and / or emulsification of dirt, and / or v) Modification of the treated surface to improve re-contamination removal, and / or vi) Whiteness improvement and / or Most preferably used in cleaning compositions i) Clay removal and / or ii) Oily / greasy stain removal, Each of the preceding options i) to vi) is preferably used in laundry detergent formulations and / or detergent formulations for hand-washing dishes and / or formulations suitable for (pre)treating textiles and / or soap bars, more preferably in liquid laundry detergent formulations and / or liquid detergent formulations for hand-washing dishes.

14. A laundry detergent, cleaning composition, fabric and household care product, cosmetic formulation, crude oil demulsifier, pigment dispersion for inkjet ink, formulation for electroplating, adhesive composition and / or dispersant for agricultural chemical formulation, comprising at least one alkoxylated polyol according to any one of claims 1 to 9, preferably a laundry detergent, cleaning composition and / or fabric and household care product comprising at least one alkoxylated polyol according to any one of claims 1 to 9.

15. The laundry detergent, cleaning composition, fabric or household care product of claim 14, further comprising... (a) An antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether; preferably comprising 2-phenoxyethanol in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1% to 2% phenoxyethanol or preferably comprising 0.001% to 3%, more preferably 0.002% to 1%, or even more preferably 0.01% to 0.6% of 4,4'-dichloro-2-hydroxydiphenyl ether, each by weight of the composition, and / or (b) At least one enzyme selected from the list consisting of lipases, hydrolases, amylases, DNases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersases, oxidoreductases, cutinases, pectinases, 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 selected from proteases, and / or (c) At least one surfactant, selected from the group consisting of anionic surfactants and nonionic surfactants, and / or (d) At least one chelating agent selected from the group consisting of methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), citric acid and its salts.

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