Biodegradable polyol propoxylates, their preparation, use, and compositions containing them

Abstract

Biodegradable polyol propoxylates, their preparation, use, and compositions containing them. The present invention relates to biodegradable polyol propoxylates based on polyols having 4 to 5 -OH groups, their production, and their use, for example, in laundry or dishwashing.

Description

[Technical Field]

[0001] The present invention relates to biodegradable polyol propoxylates (in the present invention, whenever the inventive polyol propoxylate is intended, it will always be abbreviated as "inventive compound," "inventive polymer," or "compound of the present invention"), their manufacture, and their use in cleaning compositions, particularly laundry detergent compositions, specifically for use in laundry care to remove clay and / or oily / fatty stains and / or body stains and / or to improve the maintenance of whiteness. [Background technology]

[0002] Detergent manufacturers constantly face the challenge of developing improved products to remove a wide range of dirt and stains from fabrics and hard surfaces. Dirt and stains are diverse, ranging from polar stains such as proteinaceous substances, clay, and inorganic dirt, to nonpolar stains such as soot, carbon black, byproducts of incomplete combustion of hydrocarbons, and organic stains such as sebum and body grime. Removing oily (i.e., greasy / fatty) stains has been a particularly difficult challenge. This challenge has become more prominent due to the recent heightened interest and desire to reduce the concentration of surfactants in detergents for environmental, sustainability, and cost reasons. It has been found that reducing the amount of added surfactants, especially anionic surfactants such as linear alkylbenzene sulfonates (LAS), usually impairs the ability to remove oily / fatty stains. Furthermore, there is a global trend towards lowering washing temperatures, and the performance against stains classified as oily and fatty is the most affected by lower temperatures, further reducing the grease-removing ability of typical detergents. On the other hand, clay stains may have weak contact with the fabric fibers, but nevertheless, the high charge associated with the clay itself presents a certain type of stain removal problem. This high surface charge density can act to repel some laundry components, and therefore, surfactants alone cannot remove the clay or carry it away into the laundry solution.

[0003] Another global trend is the increasing compactness of laundry detergents, aimed at improving end-consumer convenience (e.g., individualized single-dose products, tablets, sachets, etc.) in addition to enhancing sustainability in terms of water usage and / or transportation costs. This has led to increased market demand for novel raw materials that are more weight-efficient and have a much wider range of performance characteristics.

[0004] Another emerging trend gaining momentum is the desire for improved "footprint" in all products. This "footprint" can be viewed from the perspective of its origin, such as whether it is derived from natural or renewable resources; from the perspective of its manufacturing efficiency, and therefore reduction in energy consumption, compared to conventional products; from the perspective of its usage efficiency, such as whether it can achieve equivalent performance with reduced quantity or higher performance with the same amount of use; and from the perspective of its persistence in the natural environment after use, particularly its biodegradability, as recycling is technically very difficult and not economically attractive.

[0005] Therefore, one of the most important goals in the detergent and cleaner (D&C) industry today, stemming from climate change, is to significantly reduce CO2 emissions per wash cycle by improving cold water conditions and enhancing washing efficiency at temperatures below 30°C, and to reduce the amount of chemicals used per wash cycle and improve the weight efficiency of washing technology. Another important goal in the D&C industry is to seek biodegradable polymers in order to improve the sustainability of detergent formulations and to avoid the accumulation of degradation products in ecosystems generated by polymers or incomplete biodegradation of polymers, thereby reducing the amount of material remaining in nature after use.

[0006] As a result of these trends, there is a strong need for novel biodegradable cleaning polymers that provide both excellent primary (i.e., stain removal) and secondary (i.e., whiteness maintenance) cleaning effects against both hydrophobic and hydrophilic stains, as well as improved biodegradability. This material needs to exhibit good stain removal properties against oily / fatty / sebum and particulate stains, while also providing improved whiteness maintenance and minimizing the amount of suspended and emulsified oily / fatty / sebum and particulate stains re-adhering to fabric or hard surfaces. Preferably, this novel component also exhibits synergistic effects with other cleaning technologies, such as other cleaning polymers, surfactants, and / or enzymes, known to improve only the removal of oily / fatty / sebum or particulate stains, and / or only the whiteness of fabrics and hard surfaces, thereby further improving the detergent composition.

[0007] For example, alkoxylated polyalkylene imine polymers and alkoxylated polyamine polymers, particularly alkoxylated superbranched polyethyleneimine (PEI) and alkoxylated linear polypropyleneimine (PPI) homopolymers and copolymers, are known in the literature to contribute to the removal of particulate or oily / fatty contaminants, especially at low surfactant levels and cold water conditions (below 30°C). Furthermore, their biodegradability is generally poor and therefore unacceptable to current and future requirements. Ideally, the polymers should be readily biodegradable, i.e., exhibiting an oxygen consumption of 60% or more after 28 days in the OECD 301F test, or exhibiting an oxygen consumption of 40% or more after 28 days in the OECD 301F test, and considered moderately biodegradable. Alternatively, in the OECD 302 B test, the polymers should be essentially biodegradable, i.e., exhibiting a dissolved organic carbon (DOC) level of 70% or more. Therefore, there is a need to find improved polymer structures, feasible preparation processes, and improved biodegradation behavior with equivalent or superior performance profiles. [Overview of the project] [Means for solving the problem]

[0008] Below is a summary of the most suitable publications in the field of polyol propoxylates, which is the technical area of ​​the present invention.

[0009] Japanese Patent Publication No. 2022056680A discloses glycerin modified with ethylene oxide and propylene oxide having a total of 16 alkylene oxide units. This compound is disclosed in the context of a fragrance retainer.

[0010] Furthermore, propoxylated sorbitol (CAS 52625-13-5) is commercially available from several companies, including the PCC Group (Dolny, Poland; https: / / www.products.pcc.eu / de / cas-numbers-2 / 52625-13-5 / ). These propoxylated sorbitol compounds are commonly used, for example, in the reaction with isocyanates, in the production of rigid polyurethane foam (PUR) and semi-rigid polyurethane foam.

[0011] In addition, several modified alkoxylated polyol compounds are known in the art. In this regard, European Patent No. 3802749A discloses propoxylated or butoxylated polyols, i.e., sorbitol further containing glycerol, trimethylolpropane, neopentyl glycol, and at least one fatty acid having 14 or more carbon atoms. These compounds are used as synthetic ester lubricating base oils. U.S. Patent No. 7468348B discloses alkoxylated polyols, i.e., propoxylated sorbitol terminally modified with a sulfate group, an aldehyde group, or a three-membered ring structure. U.S. Patent No. 7439219B discloses a cleaning composition comprising a surfactant and an ethoxy, propoxy, or butoxylated polyol having at least three hydroxy moieties, wherein at least one of the hydroxy moieties or at least one of the alkoxy moieties is substituted with a quaternary amine capping unit.

[0012] European Patent No. 3298120A discloses a detergent composition comprising propoxylated glycerin having a total of 1 to 10 propylene oxide units.

[0013] Surprisingly, the inventors found that propoxylated polyols having 4-5 -OH groups and propylene oxide (PO) branching shorter than 30 PO units exhibit excellent cleaning performance and significant biodegradability. Based on experimentally obtained data, we were able to establish a formula that can predict biodegradability based on (i) PO chain length, (ii) average number of -OH groups in the polyol, and (iii) average number of ether bonds in the polyol. It should be noted that the compounds of the present invention have superior cleaning properties compared to the above-mentioned propoxylated glycerol compounds having the same amount of propylene oxide units in the PO branching. Furthermore, as described above, the inventive compounds exhibit significant biodegradability (at least about 40% within 28 days according to OECD 301F), whereas propoxylated sorbitol known in the art exhibits less than 10% biodegradability within 28 days according to OECD 301F. Moreover, the inventive compounds exhibit good stability in cleaning compositions, particularly liquid cleaning compositions. The high stability of the inventive compound in the liquid cleaning composition can be attributed to the absence of ester and / or amide bonds.

[0014] Therefore, an object of the present invention is to provide a novel propoxylated polyol comprising a polyol core consisting of essentially 4 to 5 -OH groups, wherein at least one of the -OH groups is modified to form a polypropylene oxide branch, and the propoxylated polyol comprises a polypropylene oxide branch containing, on average, at least 4 polypropylene oxide units.

[0015] Hereinafter, all alkylene oxides are collectively referred to as "AO," ethylene oxide may be referred to as "EO," propylene oxide as "PO," and butylene oxide as "BuO." "PEO" is used in part herein to describe polyethylene oxide homopolymers or PEO blocks in larger polymer structures, and similarly, "PPO" describes polypropylene oxide homopolymers or polymer blocks in larger polymer structures.

[0016] The process for producing the inventive compound is also part of the present invention.

[0017] The use of the compounds of this invention is also encompassed by the invention in any type of application in which polyamines, polyethyleneimines, polypropyleneimines, and their alkoxylated derivatives have already been described.

[0018] Compositions containing such propoxylated polyols of the present invention, either as propoxylated polyols of the present invention in place of known compounds or in combination with such known compounds, are also part of the present invention, similar to those compositions using known polyamines, polyethyleneimines, polypropyleneimines, and alkoxylated derivatives thereof. [Modes for carrying out the invention]

[0019] As used herein, the terms “compound of the present invention,” “inventive compound,” or “polymer of the present invention” refer to propoxylated polyols / polyol propoxylates (which may be used interchangeably herein) prepared as described in the following and / or appended claims.

[0020] Accordingly, the subject matter of the present invention is the following embodiments 1 to 29, which are defined and further described together with the following further embodiments and are further illustrated in the Experimental section.

[0021] Embodiment 1 A propoxylated polyol comprising a polyol core comprising or essentially comprising 4 to 5 -OH groups, wherein at least one of the -OH groups is modified to form a polypropylene oxide branch, and the propoxylated polyol comprises a polypropylene oxide branch comprising, on average, at least 4 polypropylene oxide units.

[0022] The propoxylated polyols of the present invention are based on polyols having a total of 4 to 5 -OH groups. The polyol core used to prepare the propoxylated polyols of the present invention may be a monomer, or an oligomer or polymer constructed by an assembly process including -OH group-containing subunits. Furthermore, if the polyol core is based on an oligomer or polymer, the total number of -OH groups is also 4 to 5. To clarify, this means that the number of -OH groups in the inventive compound is not limited to 4 and 5, but may be any decimal between 4 and 5.

[0023] For example, diglycerol has 4 -OH groups, and triglycerol has 5 -OH groups. Those skilled in the art will understand that a polyglycerol (n=2-3) mixture of diglycerol and triglycerol can be prepared, and the polyol(group) will have a total number of -OH groups between 4 and 5. Any decimal between 4 and 5 can be adjusted depending on the ratio of diglycerol and triglycerol. Therefore, in a preferred embodiment, the propoxylated polyol of the present invention has 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 propoxylated polyol refers to the average number of a mixture of propoxylated polyols, each having mainly 4 or 5 -OH groups.

[0024] Therefore, the propoxylated polyol of the present invention may be a homomer or heteromer group of a polyol-based molecule having 4 to 5 -OH groups.

[0025] As used herein, the term "-OH group" refers to a hydroxyl group, particularly an alcohol group. This includes -OH groups associated with aromatic structures such as phenols. The term encompasses all alcohol groups, regardless of the state of their carbon atoms. Therefore, in the sense of the present invention, primary, secondary, and tertiary alcohols fall within the scope of "-OH group." For example, an -OH group may also be a sugar such as a hexose (e.g., glucose, fructose, etc.). However, in preferred embodiments, propoxylated polyols have a linear carbon-carbon skeleton. Not included in the scope of the term "-OH group" are -OH groups that are part of carboxylic acids.

[0026] In a preferred embodiment, the polyol reacted with propoxylen oxide does not contain any additional functional groups other than the -OH group (such as amine, ester, carbonyl, carbonate, phosphate, sulfonate groups, and their derivatives).

[0027] The compounds of the present invention include polypropylene oxide branching of the side chain bonded to the carbon atom of the -OH group of the polyol. The side chain is composed of propylene oxide. Typically, the side chain has an average of 4 to 30 PO units. More detailed embodiments illustrating different chain lengths are shown below.

[0028] It should be noted that all these figures are "averaged" figures, meaning they refer to the average number of such units per -OH group calculated based on the total -OH groups of the propoxylated polyol.

[0029] The reaction yielding the inventive compounds is a statistical reaction, meaning that there is never just one chemically strictly defined compound, and that the propoxylated polyols of the present invention are always a mixture of slightly deviant structures all originating from the same reaction in a single reaction space; these structural differences clearly stem from the fact that no reaction proceeds in exactly the same way and at the same rate on all functional units, in particular, because the chemical reactivity of the functional units (primarily the -OH groups in this specification) differs depending on their environment; that is, primary alcohol groups react differently from secondary alcohols, and furthermore, the chemical environment of these groups may differ; it should be emphasized that this leads to the overall insight that there are slightly deviant structures, and therefore none of the compounds of the present invention defined as in the various embodiments, including the numbered embodiments 1 to 29, and as illustrated in the examples, are ever just one chemical compound, but are always a mixture of slightly deviant structures with a statistical distribution. Since the reactivity of these groups does not vary greatly, the deviations are relatively small. Therefore, defining the propoxylated polyols of the present invention by prototype members is an effective way to define the structure. Furthermore, defining the side chain composition by average number (including a variable defined in this embodiment and the following embodiments based on the number of -OH groups present in the propoxylated polyol) is a useful way to define the overall composition of any mixture defined herein as "propoxylated polyol of the present invention".

[0030] Therefore, unless otherwise specified, the values, ranges, and ratios of the number of -OH groups and molecular weight (Mn) shown herein relate to the number-average values ​​in a heterogeneous mixture of synthesized propoxylated polyols, which include individual chemical structures that are slightly deviant from each other, resulting from the preparation method of the present invention. As is well known in polymer science, subsequently, the weight-average molecular weight (Mw) serves as an indicator of homogeneity (or heterogeneity) in a mixture of different types of "propoxylated polyols".

[0031] The presence of propylene oxide (primarily) within or adjacent to the hydrophobic polyol core results in amphiphilic properties, and therefore the excellent cleaning properties of the inventive compound in detergent applications. Inventive compounds having such modifications are also referred to as "alkoxylation," "propoxylation," and / or "modification."

[0032] With respect to polyols, the terms “essentially consisting of” or “essentially made from” as used interchangeably in this specification mean that the polyol may contain impurities or other types of polyols in amounts of 10% w / w or less, 7% w / w or less, 5% w / w or less, 3% w / w or less, 2% w / w or less, 1% w / w or less, 0.5% w / w or less, or 0.1% w / w or less.

[0033] Embodiment 2 The propoxylated polyol according to Embodiment 1, wherein the polyol core is a monomer, oligomer, or polymer, and each of the oligomer and polymer comprises a plurality of subunits, preferably the oligomer is a homooligomer or the polymer is a heteropolymer.

[0034] As used herein, the term “monomer” refers to a polyol that has not been polymerized before its propoxylation. As used herein, the term “oligomer” refers to a molecule consisting of up to five repeating units, each containing a polyol repeating unit, although all repeating units may be the same, or the oligomer may consist of different repeating units. Thus, oligomers include dimers, trimers, tetramers, and pentamers. Preferably, the oligomer is a “homooligomer,” which refers to an oligomer formed from the same monomer. A homooligomer is a compound formed by the 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 bonded by a polymerization reaction. As used herein, “heteropolymer” refers to an organic polymer containing two or more different repeating units, each containing at least one polyol unit. As used herein, the term “plural” is defined as two or more, i.e., at least two, three, four, five, six, seven, eight, nine, or more.

[0035] Embodiment 3 The propoxylated polyol is the propoxylated polyol according to Embodiment 1 or 2, comprising polypropylene oxide branches containing, on average, at least 5 polypropylene oxide units (PO), preferably at least 6 PO, and more preferably at least 8 PO. In a more preferred embodiment, the propylene oxide branches contain, on average, at least 9, 10, 11, 12, 13, 14, 15 or more PO.

[0036] In a preferred embodiment, one propylene oxide branch has an average weight in the range of 600 to 5500 g / mol, preferably 1000 to 4000 g / mol, and more preferably 1500 to 3000 g / mol.

[0037] Embodiment 4 The propoxylated polyol is the propoxylated polyol according to any one of Embodiments 1 to 3, comprising polypropylene oxide branches containing an average of at least 30 polypropylene oxide units (PO), preferably 25 or fewer PO, and more preferably 22 or fewer PO. In a further preferred embodiment, the propylene oxide branches contain an average of 21 or fewer, 20 or fewer, 19 or fewer, 18 or fewer, 17 or fewer, 16 or fewer, or fewer PO.

[0038] Embodiment 5 The propoxylated polyol according to any one of Embodiments 1 to 4, wherein the polyol core has a weight in the range of 90 to 500 g / mol, preferably 100 to 300 g / mol, and more preferably 120 to 250 g / mol.

[0039] Methods for measuring the weight of polyols are well known in the art and include mass spectrometry, mass photometry, and static light scattering.

[0040] Embodiment 6 For equation (I) and / or equation (II), F is greater than or equal to 0. Equation (I) is, F = 2.769PQ - 12.46P - 0.209QX + 0.524Q + 0.726X + 1, Equation (II) is, F = 0.1123PQ - 0.505P + 0.0027QX - 0.209Q - 0.018X + 1 (In the formula, X = average number of PO per propylene oxide branch. P = the average number of ether bonds in the polyol core. A propoxylated polyol according to any one of Embodiments 1 to 5, having a structure (Q = average number of -OH groups in the polyol core).

[0041] Formulas (I) and (II) are based on the biodegradability of approximately 30 compounds tested experimentally. It should be noted that a value of 0 or greater in formula (I) indicates at least 40% biodegradability within 28 days according to the OECD 301F test, and a value of 0 or greater in formula (II) indicates at least 60% biodegradability within 28 days according to the OECD 301F test.

[0042] As used herein, the term “average number of PO units per propylene oxide branch” refers to the calculated value of the number of PO units that should be present in one propoxylen oxide branch. As described in more detail above, those skilled in the art will be well aware of the fact that the synthesis of the compounds of the present invention will result in a mixture of slightly deviant compounds that form the basis of a statistical distribution. Thus, the “average number of PO units per propylene oxide branch” is calculated by dividing the total molar amount of PO units used per mole of polyol by the (average) number of -OH groups of the polyol (or mixture of polyols).

[0043] As used herein, the term “average number of ether bonds in a polyol core” refers to the calculated number of ether bonds present in one polyol molecule. Since a polyol may be a mixture of deviant compounds, “average number” may refer to the arithmetic mean derived from the polyols of the mixture. For example, diglycerol has one ether bond, and triglycerol has two ether bonds. A polyglycerol composed of 50% diglycerol and 50% triglycerol has an average of 1.5 ether bonds.

[0044] As used herein, the term “average number of -OH groups in a polyol core” refers to the calculated number of -OH groups that should be present in a single polyol molecule. Since a polyol may be a mixture of deviant compounds, “average number” may refer to the arithmetic mean derived from the polyols of the mixture.

[0045] In a preferred embodiment, the propoxylated polyol of the present invention exhibits at least 40%, preferably at least 50%, and more preferably at least 60% biodegradability within 56 days, preferably within 28 days, according to standard OECD 301F.

[0046] For the purposes of this invention, the aerobic biodegradability of wastewater according to OECD 301F is expressed as a percentage of the theoretical oxygen demand (ThOD, measured by elemental analysis of the target compound) required to completely biodegrade the compound sample. Therefore, the amount of oxygen taken up by the microbial population during the biodegradation of the test substance (corrected by the amount taken up by a blank inoculant performed in parallel) is expressed as a percentage of ThOD. Preferably, the obtained value is tested in three ways using the OECD 301F manometer respiratory measurement method. Oxygen consumption is determined by measuring the change in pressure inside the apparatus using OxiTop® C (Xylem 35 Analytics Germany Sales GmbH&Co KG). Details of the tests performed are described in the Experiments section below.

[0047] This invention provides propoxylated modified polyols. Combined core-shell products (i.e., propoxylated polyols), where the "core" is a polyol core and the "shell" is a polypropylene oxide branch, exhibit significant biodegradability. Furthermore, these inventive compounds also exhibit cleaning properties comparable to currently used products.

[0048] Embodiment 7 The propoxylated polyol according to any one of Embodiments 1 to 6, wherein the weight-average molecular weight (Mw) of the propoxylated polyol is in the range of 700 to 6,000 g / mol, preferably in the range of 1,500 to 4,000 g / mol, and more preferably in the range of 2,000 to 3,500 g / mol.

[0049] Each weight-average molecular weight (M WMethods for determining / measuring ) are known to those skilled in the art. This can be carried out, for example, by size exclusion chromatography (e.g., GPC combined with light scattering). Preferably, W The value is determined by the following method: OECD TG 118 (1996), which in detail refers to 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, and is also available on the internet, for example, https: / / doi.org / 10.1787 / 9789264069848-en.

[0050] The molecular weight of the polyol starting material can be determined as described above. The molecular weight of the propoxylated polyol can be measured by gel permeation chromatography (GPC). The sample was prepared as follows: Approximately 15 mg of the sample was dissolved in 10 ml of eluent (THF + 0.035 mol / L diethanolamine) and held at 50°C for 1 hour. The entire sample solution was filtered through Chromafil Xtra PTFE (0.20 μm filtration before injection). The sealed sample vial was placed in an autosampler. An Agilent 1200 HPLC system consisting of an isocratic pump, vacuum degasser, autosampler, and column oven was used. Furthermore, this Agilent system includes differential refractive index (DRI) and variable ultraviolet (UVW) detectors for detection. Data acquisition and processing of conventional SEC data were performed using WinGPC Unichrom (build 6999) from PSS (Polymer Standard Services, now part of Agilent). A combination of an SDV Guard column (7.5 x 50 mm) and three PSS SDV columns (1000A, 100000A, 1000000A, all 7.5 x 300 mm) was set up in series at 60°C. Diethanolamine with THF + 0.035 mol / L was used as the eluent at a flow rate of 1 mL / min. 100 μl was injected from each sample solution. Calibration was performed using a polyethylene oxide standard (Agilent) with a narrow molar mass distribution, where the molar mass range was M=160 to M=1,378,000 g / mol. Molar masses outside this range were extrapolated.

[0051] "Mw" is the weight-average molecular weight, and "Mn" is the number-average molecular weight. The values ​​of Mw and / or Mn can be determined as described in the experimental section below.

[0052] The molar mass distribution Mw / Mn obtained by GPC is equal to the polydispersity index (PDI), where PDI does not include units (g / mol / g / mol).

[0053] Embodiment 8 The polyol core is selected from the group consisting of meso-erythritol, D-threitol, L-threitol, 1,2,5,6-hexanetetrol, pentaerythritol, xylitol, ribitol, arabitol, pentitol, diglycerol, triglycerol, and polyglycerol, and the polyglycerol preferably consists of 2 to 3 subunits of glycerol, as described in any one of Embodiments 1 to 7.

[0054] In preferred embodiments, as used herein, the term “polyglycerol” primarily refers to a mixture of diglycerol and triglycerol. The ratio of diglycerol to triglycerol may vary between 100:1 and 1:100. In more preferred embodiments, the mixture may also contain glycerol, tetraglycerol, or pentaglycerol, all in trace amounts (less than 5, 3, or 1% w / w of the polyglycerol mixture).

[0055] Those skilled in the art will understand that polyols may be alkoxylated with AOs other than propoxylen oxide. In this regard, ethylene oxide and butylene oxide are mentioned. Furthermore, those skilled in the art are also well aware of useful modifications of alkoxy chains, such as modifications with lactones or hydroxycarbonates, as described in International Publication No. 2021165468A.

[0056] It should be noted that the alkylene oxides used to prepare the inventive compounds may be derived from fossil carbon sources, non-fossil carbon sources, or even mixtures thereof. Preferably, the amount of non-fossil carbon atoms in the alkoxy side chain is at least 10%, at least 20%, at least 40%, at least 70%, at least 95%, or consists solely of carbon atoms of non-fossil origin. Those skilled in the art are familiar with commercially available alkylene oxide products produced from non-fossil carbon sources (these products are often marketed as “sustainable,” “renewable,” or “bio-based”). For example, Croda International (Snaith, UK) sells bioethanol-based ethylene oxide and related products as the ECO Range. Furthermore, 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) (p. 75)).

[0057] Embodiment 9 A propoxylated polyol according to any one of Embodiments 1 to 8, wherein the amount of secondary alcohol groups in the propoxylated polyol is in the range of 30 to 100%, preferably 75 to 99%, and more preferably 95 to 98%.

[0058] The inventive compound comprises i) a primary alcohol group of a polyol modified with propoxylen oxide branching, or ii) a secondary alcohol derived from an unreacted secondary alcohol group of the polyol. As used herein, a secondary alcohol means an alcohol in which a hydroxyl carbon is bonded to two other carbon atoms. On the other hand, the inventive compound may also contain a tertiary alcohol derived from an unreacted tertiary alcohol group of the polyol. The primary alcohol group in the inventive compound, if present, is derived from an unreacted primary alcohol group of the polyol.

[0059] The amount of secondary alcohol groups in a propoxylated polyol can be measured by methods known to those skilled in the art, such as NMR spectroscopy, e.g., 13C-NMR spectroscopy and / or 1H-NMR spectroscopy. Furthermore, the amount of secondary alcohol groups can be measured by modifying the propoxylated polyol with trichloroacetyl isocyanate and identifying the modified secondary and primary alcohol groups in the 1H-NMR spectrum of CDCl3. This method is described in J. Loccufier et al., Polymer Bulletin 27, 201-204 (1991).

[0060] As used herein, “the amount of secondary alcohol groups in the propoxylated polyol” is defined as the percentage of the total amount of OH groups (i.e., the amount of secondary OH groups divided by the total amount of OH groups). For example, if the polymer has 4 secondary OH groups and 1 primary OH group, then “the amount of secondary alcohol groups in the propoxylated polyol” is 4 / (4+1)=80%.

[0061] Embodiment 10 The propoxylated polyol according to Embodiment 9, wherein the amount of secondary alcohol groups in the propoxylated polyol, based on the indicated polyol, is in the range of meso-erythritol: 50-100%; D-threitol: 50-100%; L-threitol: 50-100%; 1,2,5,6-hexanetetrol: 50-100%; pentaerythritol: 30-100%; xylitol: 60-100%; ribitol: 60-100%; arabitol: 60-100%; pentitol: 60-100%; and polyglycerol: 33-100%.

[0062] In preferred embodiments, it should be noted that the polyol core contains at least two "terminal" primary alcohol groups. In addition to these two primary alcohols, the polyol further has two or three secondary alcohol groups.

[0063] Embodiment 11 A propoxylated polyol according to any one of Embodiments 1 to 10, wherein all propoxylen oxide branches bonded to the -OH group of the polyol have the same structure in the sense that the number of PO units per propoxylen oxide branch is the same, or instead the propoxylen oxide branch structures are diverse.

[0064] While not bound by the following explanation, there is a theoretical basis for explaining the resulting structure of the propoxylated polyols. The reaction in question, which is necessarily used to prepare these structural orders of the side chains and, consequently, to prepare the specific inventive compound, is a highly reactive species of reaction, and under favorable conditions, this species can result in a nearly complete, if not 100%, and even "substantially complete" conversion. Therefore, the statistical deviation of the composition of the mixture of "propoxylated polyols" in question is not very high, meaning that the structural order of the side chains does not exhibit large deviations. Thus, this is a reliable assumption that can be proven in principle by sophisticated and therefore time-consuming and expensive analytical techniques such as multidimensional NMR analysis, and therefore, the existence of such deviations is generally accepted. Therefore, a "specific propoxylated polyol" is never "just one chemical compound consisting of a clearly defined chemical structure," but rather distinctly consists of a) a mixture of slightly different compounds, the differences of which lie in b) slight deviations that may already exist in the structure of the compounds constituting the "(unmodified) polyol" used for further modification steps, and c) slight deviations in the structural order of the side chains, which may be d) bonded by multi-step reactions, the multi-step reactions resulting from e) variations in the chemical reactivity of the -OH functional group, and h) slight heterogeneity that occurs in industrial-scale processes. All of these factors a) to f) (to name a few important ones) result in a "specific modified propoxylated polyol" that is not a single specific chemical compound, but in fact a mixture of slightly different compounds with a very similar overall chemical structure. Thus, such structures are best described by the average number of variables and the percentage of the amount of dominant structural order.

[0065] Embodiment 12 A process for preparing a propoxylated polyol according to any one of Embodiments 1 to 11, wherein a polyol consisting essentially of 4 to 5 -OH groups is reacted with at least 16 propylene oxide molecules to obtain each propoxylated polyol.

[0066] In more preferred embodiments, a polyol containing four -OH groups is reacted with at least 16 propylene oxide molecules, and a polyol consisting of five -OH groups is reacted with at least 20 propylene oxide molecules. Generally, the amount of propylene oxide molecules is selected such that each -OH group of the polyol contains, on average, at least four propylene oxide molecules.

[0067] All terms used in Embodiment 12 have already been defined and explained in detail in the descriptions of Embodiments 1 to 11, and such terms, definitions, and further specifications apply to Embodiment 12 as well.

[0068] The conversion rate of the reaction step can be monitored, and in a preferred embodiment, the conversion rate is at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99.5% or higher. Not only all other structural orders of the side chains defined above, but also undefined structures resulting from uncontrollable parameters are carried out in this defined manner, and the defined structural orders, which are derived directly from the way in which such reactions are carried out, are statistically averaged.

[0069] The conversion rate of the reaction can be determined by methods known to those skilled in the art, such as NMR spectroscopy, including 13C-NMR spectroscopy and / or 1H-NMR spectroscopy.

[0070] The catalyst, temperature, time, purification, and other reaction conditions for the reaction to produce the side chain units of the propoxylated polyol of the present invention are fully incorporated herein by reference by the information contained in European Patent No. 3298120A, Japanese Unexamined Patent Publication No. 2022056680A, and U.S. Patent No. 7468348B.

[0071] In this preferred embodiment, alkoxylation / propoxylation 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 preferred catalysts include alkali metal and alkaline earth metal hydroxides, e.g., sodium hydroxide, potassium hydroxide, and calcium hydroxide; alkali metal alkoxides, specifically sodium and potassium C1-C4 alkoxides, e.g., sodium methoxide, sodium ethoxide, and potassium tert-butoxide; alkali metal and alkaline earth metal hydrides, e.g., sodium hydride and calcium hydride; and alkali metal carbonates, e.g., sodium carbonate and potassium carbonate. Alkali metal hydroxides and alkali metal alkoxides are preferred, and potassium hydroxide and sodium hydroxide are particularly preferred. A typical amount of base used is 0.05-10% by weight of the final product, specifically 0.05-2% by weight, based on the total amount of polyol and propylene oxide.

[0072] Embodiment 13 The process according to Embodiment 12, wherein the polyol having 4 to 5 -OH groups is selected from the group consisting of meso-erythritol, D-threitol, L-threitol, 1,2,5,6-hexanetetrol, pentaerythritol, xylitol, ribitol, arabitol, pentitol, diglycerol, triglycerol, and polyglycerols consisting of preferably 2 to 3 glycerol subunits.

[0073] Embodiment 14 Propoxylated polyols are a. Purification by standard means such as steam distillation, thermal distillation, vacuum evaporation, and / or removal of the entire solvent. b. Further subjected to a drying process using standard drying methods such as spray drying, drum drying, and paddle vacuum drying, including agglomeration methods such as fluidized bed drying. The process according to Embodiment 12 or 13, which yields a purified solution, a purified liquid, a solid compound, or a purified solid compound, respectively.

[0074] If, after the reaction yielding the inventive compound, residual free matter (polyol and / or propylene oxide) is present in undesirable amounts, the resulting mixture of products containing the propoxylated polyol may be further purified by standard means, not only to reduce the content of residual free matter but also to reduce the amount of possible by-products, to reduce the amount of solvent used (i.e., to concentrate), or to replace the solvent with another solvent. Such processes are known to those skilled in the art.

[0075] Preferably, any undesirable amount of residual unreacted free material is removed, preferably by a distillation process, more preferably by a thermal distillation process, which may additionally include applying reduced pressure to increase the rate and / or efficiency of removal.

[0076] In a preferred embodiment, only the additional process step a) is used.

[0077] Use of the propoxylated polyol of the present invention and compositions containing the propoxylated polyol of the present invention Part of the present invention relates to the use of the propoxylated polyol of the present invention for various application fields, wherein the propoxylated polyol of the present invention can replace similar structures known to date, but with an improved rate of biodegradation compared to these already known structures.

[0078] Embodiment 15 Use of at least one propoxylated polyol described in any one of Embodiments 1 to 11 in a cleaning composition, in fabric care and home care products, in cosmetic formulations, as a crude oil emulsion disruptor, in pigment dispersions for inkjet inks, in electroplating formulations, in cement-based compositions, or as a dispersant for pesticide formulations.

[0079] The subject of the present invention is the use of the above-mentioned propoxylated polyol in fabric care and home care products, cosmetic formulations, as an emulsion disruptor for crude oil, in pigment dispersions for inkjet inks, in electroplating formulations, in cement-based compositions, and / or as a dispersant for pesticide formulations, preferably in cleaning compositions and / or fabric care and home care products, in particular in cleaning compositions for improving clay removal or the removal of oily and fatty stains, wherein the cleaning composition is preferably a laundry detergent formulation and / or a dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid dishwashing detergent formulation.

[0080] Propoxylated polyols can be added to cosmetic formulations, as crude oil emulsion disruptors, to pigment dispersions for inkjet inks, to electroplating formulations, and to cement-based compositions. On the other hand, the inventive compound can also be added (used) to washing or cleaning compositions.

[0081] Accordingly, other subjects of the present invention include cleaning compositions, fabric care and home care products, commercial cleaning products, cosmetic formulations, crude oil emulsion disruptors, pigment dispersions for inkjet inks, electroplating formulations, cement-based compositions, and / or dispersants for pesticide formulations, all comprising at least one propoxylated polyol as defined above.

[0082] Preferably, this is a cleaning composition and / or fabric care and home care product, preferably a laundry detergent formulation and / or dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or liquid dishwashing detergent formulation, comprising at least one propoxylated polyol as defined above, for improving the removal of clay or oily and fatty stains or sebum and body dirt.

[0083] In another preferred embodiment of the present invention, the cleaning composition may be used to remove particulate stains and / or oily and greasy stains, and more preferably to maintain whiteness in laundry care.

[0084] In other embodiments, the cleaning composition of the present invention is a hard surface cleaning composition that can be used to clean various surfaces such as hardwoods, tiles, ceramics, plastics, leather, metals, and glass.

[0085] In other embodiments, the cleaning composition of the present invention is a liquid or solid automatic dishwashing detergent composition, preferably a solid automatic dishwashing detergent composition that can be used to clean dishes, such as glasses, and the propoxylated polyol of the present invention improves the removal of stubborn stains.

[0086] In other embodiments, the cleansing composition is designed for use in personal care and pet care compositions such as shampoo compositions, body cleansing formulations, and liquid or solid soaps.

[0087] In the present invention, preferred application fields for the use of propoxylated polyols are the fields of fabric care and home care products and cleaning compositions, and more preferably the fields of cleaning compositions for commercial and consumer use in the home.

[0088] Embodiment 16 The use of a cleaning composition and / or fabric care and home care product, preferably a liquid and solid detergent composition, as described in Embodiment 15, wherein such a detergent composition is preferably a) A dishwashing and automatic dishwashing detergent composition comprising at least one propoxylated polyol and at least one chelating agent and / or at least one surfactant, more preferably a dishwashing and automatic dishwashing detergent composition comprising a chelating agent in the case of a liquid or solid automatic dishwashing detergent composition, and a surfactant system in the case of a liquid dishwashing detergent composition; and / or b) A laundry detergent composition comprising at least one propoxylated polyol and at least one surfactant, or preferably a surfactant system, for use.

[0089] In the preferred application areas of such use, typical tasks must be performed, all encompassed by the general term "cleaning," but in practice, they include different tasks, such as clay removal, or the removal of oily and fatty residues, solid residues, amphoteric residues, and hydrophilic residues. Other tasks include protecting the items to be cleaned from deterioration, such as protecting glass from corrosion, silverware from oxidation, and fading. Still other tasks include improving the overall appearance of the items to be cleaned, such as enhancing or restoring color and whiteness, or adding or increasing shine. In many of these applications, additional components are usually added, and those important for cleaning applications are, for example, enzymes that aid in the biological breakdown of residues.

[0090] Embodiment 17 The use described in Embodiment 15 or 16, i. To remove clay, and / or ii. To improve the removal of oily / fatty stains, and / or iii. To remove particulate stains, and / or iv. To disperse and / or emulsify the dirt, and / or v. To modify the treated surface in order to improve the removal of subsequent re-contamination, and / or vi. In order to improve whiteness, and / or Most preferably, in a cleaning composition, i) To remove clay, and / or ii) To remove oily / fatty stains, Each of the above options i) to vi) is preferably for use in laundry detergent formulations and / or dishwashing detergent formulations, and / or formulations suitable for (pre) treatment of fabrics and / or hand soaps, more preferably in liquid laundry detergent formulations and / or liquid dishwashing detergent formulations.

[0091] Embodiment 18 Uses of a cleaning composition and / or fabric care and home care products, preferably a cleaning composition for fabric care and home care, according to any one of Embodiments 15 to 17, wherein the cleaning composition is preferably a laundry detergent formulation or a dishwashing detergent formulation, and more preferably a liquid laundry detergent formulation or a liquid dishwashing detergent.

[0092] Such ingredients are typically incorporated together with other ingredients into formulations and compositions, which can be referred to as “products” (because such formulations are either supplied by suppliers to other customers as formulations for use as is, such as for cleaning purposes, or to manufacture other formulations that can then be sold to consumers as consumer “products”).

[0093] Embodiment 19 A composition comprising at least one propoxylated polyol obtained or obtainable by the process described in any one of Embodiments 1 to 11 or any one of Embodiments 12 to 14, wherein the composition is a fabric care and home care product, a cleaning composition, a commercial cleaning product, a cosmetic or personal care product, an oilfield formulation such as a crude oil emulsion disruptor, an ink pigment dispersion such as an inkjet ink, an electroplating product, a cement-based composition, a lacquer, a paint, a pesticide formulation, preferably a laundry detergent, a dishwashing composition, a cleaning composition, and / or a fabric care and home care product.

[0094] Embodiment 20 A solid or liquid laundry detergent composition, or a solid or liquid dishwashing detergent composition, preferably a liquid laundry detergent, or a liquid dishwashing detergent composition, more preferably a liquid laundry detergent composition, according to Embodiment 19, comprising at least one propoxylated polyol obtained or obtainable by the process described in any one of Embodiments 1 to 11, or any one of Embodiments 12 to 14, The material optionally further comprises, preferably, one or more enzymes selected from at least two combinations of the above types, including lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, DNase, mannanase, xylanase, dispersin, oxidoreductase, cutinase, pectinate lyase, pectinase, lactase, pectinate lyase, mannanase, and peroxidase, and preferably at least one enzyme selected from at least two combinations of the above types, and preferably at least one enzyme selected from proteases. It optionally contains at least one antibacterial agent, This at least one propoxylated polyol is present in an amount ranging from 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%, based on the total weight of such composition or product. Such a product or composition further comprises about 1% to about 70% by weight of a surfactant system comprising at least one surfactant, preferably an anionic surfactant, and more preferably at least one anionic surfactant.

[0095] Embodiment 21 A solid or liquid automatic dishwashing detergent composition, preferably a solid automatic dishwashing detergent composition, according to Embodiment 19, comprising at least one propoxylated polyol obtained or obtainable by the process described in any one of Embodiments 1 to 11 or any one of Embodiments 12 to 14, further comprising optionally, preferably one or more enzymes selected from at least two combinations of the above types, including lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, DNase, mannanase, xylanase, dispersin, oxidoreductase, cutinase, pectinate lyase, pectinase, lactase, pectinate lyase, mannanase, and peroxidase, and at least one enzyme selected from at least two combinations of the above types, preferably at least one enzyme selected from protease and amylase. It optionally contains at least one antibacterial agent, It optionally contains at least one compound selected from alkali metal percarbonates, alkali metal perborates, and alkali metal persulfates. It optionally contains at least one zinc salt, At least one propoxylated polyol is present in a total amount ranging from about 0.001% to about 10%, preferably about 0.005% to about 5%, more preferably about 0.01% to about 3%, most preferably about 0.1% to about 2%, and such product or composition further comprises at least one chelating agent present in a total amount ranging from about 1% to about 70%, preferably 10% to about 60%, and even more preferably 30% to about 50%. Optionally, further comprising at least one surfactant, more preferably a surfactant system, in a total amount of about 1% to about 70% by weight, All weight percentages are relative to the total weight of such compositions.

[0096] Embodiment 22 The composition according to Embodiment 21 is a solid automatic dishwashing detergent composition comprising at least one propoxylated polyol obtained or obtainable by the process described in any one of Embodiments 1 to 11 or any one of Embodiments 12 to 14, A chelating agent selected from methylglycine diacetic acid (MGDA), glutamate diacetic acid (GLDA), citric acid, and salts thereof, At least one enzyme selected from proteases and / or amylases, A bleaching agent selected from alkali metal percarbonates, alkali metal perborates, and alkali metal persulfates, preferably alkali metal percarbonates, At least one nonionic surfactant, Optionally, at least one disintegrant, preferably a super-disintergrant, more preferably a PVPP, A composition further comprising, optionally, at least one zinc salt.

[0097] Superdisintegrants are known to those skilled in the art, for example, from European Patent No. 1004661, European Patent No. 1263814, and European Patent No. 1036839, and are also described in Pharmaceutical Technology, Volume 2006 Supplement, Issue 5, “A Comparative Study of Current Superdisintegrants”, October 1, 2006.

[0098] Embodiment 23 The composition according to Embodiment 19 or 20, which is a detergent composition comprising at least one anionic surfactant as a surfactant.

[0099] Embodiment 24 The composition according to Embodiment 19 or 20, which is a liquid detergent composition comprising at least one nonionic surfactant as a surfactant, and further comprising water.

[0100] Embodiment 25 The composition according to any one of embodiments 19, 20, 23, and 24, which is a detergent composition comprising at least one polymer selected from a polyfunctional alkoxylated polyethyleneimine, a polyfunctional alkoxylated diamine, or a terephthalic acid-based stain-free polyester, or a mixture thereof.

[0101] Embodiment 26 The composition according to any one of embodiments 19, 20, and 23-25, which is a liquid detergent composition comprising at least one 2-propylheptylethoxylated nonionic surfactant having an average ethoxylation degree of 3 to 8.

[0102] Embodiment 27 The composition according to any one of Embodiments 19 to 26, further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichoro-2-hydroxydiphenyl ether, preferably comprising 2-phenoxyethanol in the range of 2 ppm to 5% by weight of the composition, more preferably comprising 0.1 to 2% of phenoxyethanol, or preferably comprising 4,4'-dichoro-2-hydroxydiphenyl ether, each at a concentration of 0.001 to 3% by weight, more preferably 0.002 to 1% by weight, and even more preferably 0.01 to 0.6% by weight based on the weight of the composition.

[0103] Embodiment 28 A composition according to any one of Embodiments 19 to 27, further comprising, preferably, one or more enzymes selected from a list consisting of lipase, hydrolase, amylase, DNase, protease, cellulase, hemicellulase, phospholipase, esterase, mannanase, xylanase, dispersin, oxidoreductase, cutinase, pectinate lyase, pectinase, lactase, and peroxidase, and at least one enzyme selected from a list consisting of at least two combinations of the above types, more preferably at least one enzyme selected from proteases.

[0104] Embodiment 29 A method for protecting an aqueous composition described in any one of Embodiments 19 to 28 from microbial contamination or growth, comprising adding an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dicolo-2-hydroxydiphenyl ether.

[0105] Furthermore, in the present invention, it is also preferable that the washing composition (in addition to the above-mentioned at least one propoxylated polyol) further preferably comprises one or more enzymes selected from lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, DNase, mannanase, xylanase, dispersin, oxidoreductase, cutinase, pectinate lyase, pectinase, lactase, and peroxidase, preferably one or more lipase, hydrolase, amylase, protease, cellulase, and at least one enzyme selected from a combination of at least two of the above types, more preferably at least one enzyme selected from proteases.

[0106] Preferably, such cleaning compositions of the present invention comprise at least one propoxylated polyol of the present invention and optionally further comprise at least one surfactant or surfactant system, and are fabric care and home care products or commercial (I&I) cleaning products, preferably fabric care and home care products, more preferably laundry detergents or dishwashing detergents, that have improved stain removal, dispersion and / or emulsification, and / or modify the treated surface and / or maintain the whiteness of the treated surface.

[0107] At least one of the propoxylated polyols of the present invention described herein (the propoxylated polyols defined above, particularly in Embodiments 1 to 11, are also referred to as “inventive compounds” in this section below) are present in the above-described cleaning compositions 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%, based on the total weight of such compositions or products, and such cleaning compositions may further contain, preferably about 1% to about 70% by weight, a surfactant system.

[0108] More preferably, the cleaning composition of the present invention, comprising at least one inventive compound and optionally further comprising at least one surfactant or surfactant system, is intended for primary cleaning (i.e., stain removal) in laundry and hand dishwashing applications, and more specifically, for the removal of clay or oily and fatty stains such as those on fabrics and tableware, and may further comprise at least one enzyme selected from a list consisting of lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, DNase, mannanase, xylanase, dispersin, oxidoreductase, cutinase, pectinate lyase, pectinase, lactase, and peroxidase, and at least two combinations of the above types of enzymes, more preferably at least one enzyme selected from proteases.

[0109] In one preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0110] In other preferred embodiments, the cleaning composition of the present invention is a liquid or solid (e.g., powder or tablet / unit dose) detergent composition for hand washing dishes or for use with automatic dishwashers, preferably a liquid hand washing detergent composition or a solid automatic dishwasher composition.

[0111] In one embodiment, the inventive compound of the present invention is C as the main surfactant agent. 10 ~C 15 It can be used in cleaning compositions comprising a surfactant system containing alkylbenzene sulfonate (LAS) and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic, or other anionic surfactants or mixtures thereof.

[0112] In further embodiments, the inventive compound has 1 to 5 ethoxy units as the main surfactant component, C8-C 18 It can be used in any type of cleaning composition, such as laundry detergent, comprising a linear or branched alkyl ether sulfate and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic, or other anionic surfactants, or mixtures thereof.

[0113] In further embodiments, the inventive compound contains 5 to 10 ethoxy units as a surfactant main component. 12 ~C 18 It can be used in any type of cleaning composition, such as a laundry detergent, comprising an alkyl ethoxylate surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic, or other nonionic surfactants or mixtures thereof.

[0114] In further embodiments, the inventive compound may be used in any type of cleaning composition, such as a laundry detergent, which contains a bio-based surfactant such as rhamnolipids and / or sophorolipids as the main surfactant component.

[0115] In one embodiment of the present invention, each of the inventive compounds is a component of a cleaning composition, preferably a laundry or dishwashing formulation, more preferably a liquid laundry or dishwashing detergent formulation, further comprising at least one surfactant, preferably at least one anionic surfactant.

[0116] The selection of additional surfactants in these embodiments may depend on the application and the desired benefits.

[0117] As used herein, the articles "a" and "an," as used in the claims or embodiments, are understood to mean one or more of the claims or descriptions. As used herein, the terms "include" and "including" are non-exclusive and therefore encompass more than the specific items referred to after the word.

[0118] The compositions of the present disclosure may "comprise" (i.e., contain other components) the components of the present disclosure, "consist essentially of" (mainly or almost solely of the components mentioned, with other components in very small amounts, mainly as impurities), or "consist of" (i.e., contain only the components mentioned, plus impurities that are unavoidable in the technical environment, preferably containing only those components).

[0119] As used herein, the term “at least one” includes, but is not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9, and more.

[0120] Similarly, the terms “substantially free of” or “substantially not containing” or “essentially (not containing / not containing)” may be used herein, meaning that the specified material is present in an extremely small amount, or preferably at a level detectable by analysis, that is not intentionally added to the composition to form part of the composition. This is intended to include compositions in which the specified material is present only as an impurity, among other materials that are intentionally included. If present, the specified material may be present at a level of less than 1% by weight of the composition, or even less than 0.1% by weight, or even less than 0.01% by weight, or even 0% by weight.

[0121] As used herein, the term “about” encompasses both an exact numerical value “X” referred to, for example, “about X%”, and smaller deviations of X, including deviations of minus 5 to plus 5%, preferably minus 2 to plus 2%, more preferably minus 1 to plus 1%, even more preferably minus 0.5 to plus 0.5%, and smaller deviations from X (for this calculation, setting X as 100%). Naturally, if the given numerical value X itself is already “100%” (for example, with respect to purity), the term “about” can obviously only mean deviations to less than “100”, and therefore only means that.

[0122] Unless otherwise stated, all concentrations of components or compositions refer to the active portion of that component or composition, excluding impurities that may be present in the commercially available source of such component or composition, such as residual solvents or by-products.

[0123] All temperatures in this specification are in degrees Celsius (°C) unless otherwise specified. Unless otherwise specified, all measurements in this specification are performed at atmospheric pressure at 20°C. In all embodiments of this disclosure, all percentages are based on the weight of the total composition unless otherwise specified. Unless otherwise specified, all ratios are weight ratios.

[0124] Description of cleaning compositions, formulations, and their components. As used herein, the term “cleaning composition” includes compositions and formulations designed for cleaning soiled materials. Such compositions and formulations include those designed to clean any type of soiled material or surface.

[0125] "Commercial cleaning" compositions include cleaning compositions designed for use in commercial cleaning, such as hard surface cleaners for any type of surface, including tiles, carpets, PVC surfaces, wood surfaces, metal surfaces, and lacquered surfaces, and for use in cleaning any type of soiled material or surface.

[0126] "Fabric care and home care compositions" include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric improving compositions, fabric freshening compositions, laundry pre-washing agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinsing additives, water 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 within porous substrates or nonwoven sheets, and other preferred forms that may become apparent to those skilled in the art with regard to the teachings herein and will be described in detail below when describing compositions herein. Such compositions may be used as laundry pre-treatment agents, laundry post-treatment agents, or added during the rinse or water wash cycle of a laundry operation, preferably during the water wash cycle of a laundry or dishwashing operation, as will be described in more detail below when describing the uses and applications of compositions containing the inventive compounds and such polymers.

[0127] The cleaning composition of the present invention may be in any form, namely, liquid form; solid form such as powder, granules, aggregates, paste, tablets, pouches, rods, gels; emulsion; type delivered in a container having two or more compartments; single-phase or multi-phase unit-dose articles; spray or foam detergent; wet wipe sheets (i.e., the cleaning composition combined with a nonwoven material such as described in U.S. Patent No. 6,121,165 by Mackey et al.); dry wipe sheets that are activated by wetting with water by the user or consumer (i.e., the cleaning composition combined with a nonwoven material such as described in U.S. Patent No. 5,980,931 by Fowler et al.); and other forms of homogeneous, heterogeneous, single-phase or multi-phase cleaning products.

[0128] The liquid cleaning composition of the present invention preferably has a viscosity of 50 to 10,000 mPa·s, the liquid dishwashing cleaning composition (also referred to as the liquid dishwashing composition (manual “dish wash composition”)) preferably has a viscosity of 100 to 10,000 mPa·s, more preferably 200 to 5,000 mPa·s, and most preferably 500 to 3,000 mPa·s at 20 1 / s and 20°C, and the liquid laundry cleaning composition preferably has a viscosity of 50 to 3,000 mPa·s, more preferably 100 to 1,500 mPa·s, and most preferably 200 to 1,000 mPa·s at 20 1 / s and 20°C.

[0129] The liquid cleaning composition of the present invention may have any suitable pH value. Preferably, the pH of the composition is adjusted to 4 to 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 adjusting components known in the art, which are measured at 25°C with a product concentration of 10% by weight in desalted water. For example, NaOH can be used, and the pH can be adjusted by changing the actual weight % of NaOH until a desired pH, for example, pH 8.0, is reached. In one embodiment of the present invention, the pH is adjusted to greater than 7 by using an amine, preferably an alkanolamine, more preferably a triethanolamine.

[0130] Fabric care and home care products, as well as commercial cleaning formulations, and more specifically, cleaning compositions such as laundry and dishwashing detergents, are known to those skilled in the art. Any composition known to those skilled in the art related to its respective use can be used in relation to the present invention, particularly when such composition is used in its field of use, by including at least one inventive compound, preferably at least one polymer in an amount suitable for exhibiting specific properties within such composition.

[0131] One aspect of the present invention is the use of the inventive compound as an additive for detergent formulations, particularly for liquid detergent formulations, preferably for concentrated liquid detergent formulations, or as a single-dose agent for laundry.

[0132] The cleaning composition of the present invention may contain, and preferably contains, a cleaning aid (which may be abbreviated as "aid" herein), and such an aid is preferably added to the surfactant system as defined above.

[0133] Suitable auxiliary cleaning additives include builders, co-builders, structuring agents or thickeners, clay stain removers / anti-re-adhesion agents, polymer stain release agents, polymer dispersants, polymer oil and fat cleaning agents, solubilizers, chelating agents, enzymes, enzyme stabilizers, bleaching compounds, bleaching agents, bleach activators, bleaching catalysts, whitening agents, odor suppressants, pigments, dyes, opacifiers, color correctors, dye migration inhibitors, chelating agents, foaming accelerators, anti-foaming agents (defoamers), color speckles, silverware cleaners, anti-tarnish and / or corrosion inhibitors, alkalizing agents, pH adjusters, pH buffers, hydrotropes, scrub particles, antibacterial agents, antioxidants, softeners, carriers, processing aids, fragrance precursors, dye fixatives, and fragrances.

[0134] The liquid cleaning composition may, preferably, further contain at least one of the following: a rheology control / modifier, a skin emollient, a moisturizer, a skin rejuvenating active substance, and a solvent.

[0135] The solid composition may, preferably, further contain at least one of the following: a filler, a bleaching agent, a bleaching activator, and a catalyst material.

[0136] Preferred examples of this type of cleaning aid and their amounts of use are described in International Publication No. 99 / 05242, U.S. Patent No. 5,576,282, U.S. Patent No. 6,306,812B1 and U.S. Patent No. 6,326,348B1.

[0137] Those skilled in the art will understand that a cleaning surfactant includes any surfactant or surfactant mixture that is beneficial for cleaning soiled materials, removing stains, or washing.

[0138] Therefore, the cleaning compositions of the present invention, such as fabric care and home care products and commercial cleaning formulations, and more specifically, laundry and dishwashing detergents, preferably further include the surfactant systems described above and described in more detail later, and more preferably also include further auxiliary agents.

[0139] The surfactant system can be composed of one type of surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those skilled in the art will understand that the surfactant system for detergents includes any surfactant or surfactant mixture beneficial for cleaning soiled materials, removing stains, or laundering.

[0140] The cleaning composition of the present invention preferably contains a surfactant system in an amount sufficient to impart the desired detergency. In some embodiments, the cleaning composition contains a surfactant system of about 1% to about 70% by weight of the composition. In other embodiments, the liquid cleaning composition contains a surfactant system of about 2% to about 60% by weight of the composition. In further embodiments, the cleaning composition contains a surfactant system of about 5% to about 30% by weight of the composition. The surfactant system may include a detergency surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof.

[0141] (a) Composition for laundry In laundry formulations, anionic surfactants usually account for the largest preponderant proportion among the surfactants contained in such formulations. Thus, preferably, the cleaning composition of the present invention for use in laundry contains at least one anionic surfactant and optionally at least one additional surfactant selected from any of the types of surfactants described herein, preferably nonionic surfactants and / or amphoteric surfactants and / or zwitterionic surfactants and / or cationic surfactants.

[0142] Non-limiting examples of anionic surfactants that can also be used in combinations of multiple surfactants useful herein include linear alkylbenzene sulfonates (LAS) of C9 - C 20 and primary branched-chain and random alkyl sulfates (AS) of C 10 -C 20 ; C 10 -C18 Secondary (2,3) alkyl sulfates of C, where x is between 1 and 30. 10 ~C 18 Alkylalkoxy sulfate (AExS); containing 1-5 ethoxy units. 10 ~C 18 Examples include alkylalkoxycarboxylates; medium-chain branched alkyl sulfates as described in U.S. Patent No. 6,020,303 and No. 6,060,443; medium-chain branched alkylalkoxy sulfates as described in U.S. Patent No. 6,008,181 and No. 6,020,303; modified alkylbenzene sulfonates (MLAS); methyl ester sulfonates (MES); and α-olefin sulfonates (AOS) as described in International Publication Nos. 99 / 05243, 99 / 05242, and 99 / 05244.

[0143] Preferred examples of suitable anionic surfactants are C8-C 12 Alkyl sulfate, C 12 ~C 18 Fatty alcohol ether sulfate, C 12 ~C 18 Fatty alcohol polyether sulfate, ethoxylated C4-C 12 Alkylphenol (ethoxylated: 3-50 moles of ethylene oxide / mol) sulfuric acid hemiester, C 12 ~C 18 Alkyl sulfonic acid, C 12 ~C 18 Sulfo fatty acid alkyl esters, for example, C 12 ~C 18 Sulfo fatty acid methyl ester, C 10 ~C 18 Alkylaryl sulfonic acid, preferably nC 10 ~C 18 Alkylbenzenesulfonic acid, C 10 ~C 18 Alkylalkoxycarboxylates and, for example, C8-C 24These are alkali metal and ammonium salts of soaps such as carboxylic acids. Alkali metal salts of the above compounds are preferred, and sodium salts are particularly preferred.

[0144] In one embodiment of the present invention, the anionic surfactant is nC 10 ~C 18 From alkylbenzene sulfonic acid and fatty alcohol polyether sulfate, in the context of the present invention, in particular ethoxylated C 12 ~C 18 Alkanol (ethoxylated: 1-50 moles of ethylene oxide / mol), preferably nC 12 ~C 18 Selected from sulfuric acid half-esters of alkanols.

[0145] In one embodiment of the present invention, branched (i.e., combined) C 11 ~C 18 -Alcohol polyether sulfates derived from alkanols (ethoxylated: ethylene oxide 1-50 mol / mol) can also be used.

[0146] Preferably, C 12 ~C 18 - Alkoxylation group or branching (i.e., synthetic) of alkoxylated alkyl sulfates based on fatty alcohols C 11 ~C 18 In both types of alcohol-based alkoxylated alkyl sulfates, the alkoxylated group is an ethoxylated group, and the average degree of ethoxylation of any alkoxylated alkyl sulfate is 1 to 5, preferably 1 to 3.

[0147] In further embodiments of the present invention, the anionic surfactant is selected from rhamnolipids and / or sophorolipids.

[0148] Preferably, the laundry detergent formulation of the present invention contains one or more of the anionic surfactants described above in an amount of at least 1% to 50% by weight, preferably about 2% to about 30% by weight, more preferably 3% to 25% by weight, and most preferably 5% to 25% by weight, based on the entire specific composition including the other components and water and / or solvent.

[0149] In a preferred embodiment of the present invention, the anionic surfactant is C 10 ~C 15 Linear alkylbenzene sulfonates containing 1 to 5 ethoxy units 10 ~C 18 Alkyl ether sulfates and C 10 ~C 18 Selected from alkyl sulfates.

[0150] Non-limiting examples of nonionic surfactants that can be used in combination with two or more other surfactants include C8-C 18 Alkyl ethoxylates, e.g., NEODOL® nonionic surfactant from Shell; ethylene oxide / propylene oxide block alkoxylate as PLURONIC® from BASF; C as discussed in U.S. Patent Nos. 6,153,577, 6,020,303 and 6,093,856. 14 ~C 22 Examples include medium-chain branched alkyl alkoxylates (BAEx) (wherein x is between 1 and 30); alkyl polysaccharides as discussed in Llenado's U.S. Patent No. 4,565,647, issued January 26, 1986; alkyl polyglycosides as discussed in particular in U.S. Patents No. 4,483,780 and No. 4,483,779; polyhydroxy fatty acid amides as discussed in U.S. Patent No. 5,332,528; and ether-terminated poly(oxyalkylated) alcohol surfactants as discussed in U.S. Patent No. 6,482,994 and International Publication No. 01 / 42408.

[0151] Preferred examples of nonionic surfactants include, in particular, alkoxylated alcohols and alkoxylated fatty alcohols, binary and multi-component block copolymers of ethylene oxide and propylene oxide, reaction products of sorbitan with ethylene oxide or propylene oxide, as well as alkylphenol ethoxylates, alkyl glycosides, and polyhydroxy fatty acid amides (glucamides).

[0152] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols include, for example, general formula (A) [ka] (In the formula, the variables are defined as follows: R 1 This is a linear C1-C 10 -Selected from alkyl groups, preferably ethyl, and particularly preferably methyl. R 2 C8~C 22 -alkyl, e.g., n-C8H 17 nC 10 H 21 nC 12 H 25 nC 14 H 29 nC 16 H 33 or nC 18 H 37 Selected from, R 3 C1~C 10 The compound is selected from alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, or isodecyl, where m and n are in the range of 0 to 300, and the sum of n and m is at least 1. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

[0153] In this specification, the compound of general formula (A) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0154] Other preferred examples of alkoxylated alcohols and alkoxylated aliphatic alcohols include, for example, those of general formula (B) [ka] (In the formula, the variables are defined as follows: R 1 These are either the same or different, selected from linear C1-C4 alkyl groups, preferably the same in each case, and are ethyl, particularly preferably methyl. R 4 C6~C 20 Alkyl, especially n-C8H 17 nC 10 H 21 nC 12 H 25 nC 14 H 29 nC 16 H 33 nC 18 H 37 Selected from, a is a number in the range of 0 to 6, preferably 1 to 6. b is a number in the range of 0 to 20, preferably 4 to 20. d is a compound (where d is a number in the range of 4 to 25).

[0155] Preferably, at least one of a and b is greater than 0.

[0156] In this specification, the compound of general formula (B) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0157] More preferred nonionic surfactants are selected from binary and multi-block copolymers composed of ethylene oxide and propylene oxide. More preferred nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of preferred further nonionic surfactants is described in EP 0851023 A and DE 19819187 A.

[0158] Mixtures of two or more different nonionic surfactants may of course also be present.

[0159] In a preferred embodiment of the present invention, the nonionic surfactant is a C 12 / 14 and C 16 / 18 fatty alcohol alkoxylate, a C 13 / 15 oxo alcohol alkoxylate, a C 13 - alcohol alkoxylate, and a 2-propylheptyl alcohol alkoxylate, each of which contains 3 to 15 ethoxy units, preferably 4 to 10 ethoxy units, or 1 to 3 propoxy units and 2 to 15 ethoxy units.

[0160] Non-limiting examples of amphoteric surfactants that can also be used in combination with two or more other surfactants include water-soluble amine oxides containing one alkyl moiety having from about 8 to about 18 carbon atoms and two moieties selected from the group consisting of an alkyl moiety and a hydroxyalkyl moiety containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety containing from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of an alkyl moiety and a hydroxyalkyl moiety having from about 1 to about 3 carbon atoms. See International Publication No. 01 / 32816 pamphlet, U.S. Patent No. 4,681,704 and U.S. Patent No. 4,133,779. Accordingly, preferred surfactants include so-called amine oxides, for example, lauryldimethylamine oxide ("lauramine oxide").

[0161] Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyldimethylamine oxides or alkylamidopropyldimethylamine oxides, more preferably alkyldimethylamine oxides, especially cocoalkyldimethylamino oxide. Amine oxides can have a straight-chain or medium-chain branched alkyl moiety. Typical straight-chain amine oxides include one R 1 =C 8~18 alkyl moiety and two R 2 and R 3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide has the formula: R 1 -N(R 2 )(R 3 )-O (wherein R 1 is C 8~18 alkyl, and R 2 and R 3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl). As straight-chain amine oxide surfactants, especially straight-chain C10 ~C 18 Alkyldimethylamine oxide and linear C8-C 12 Examples include alkoxyethyl dihydroxyethylamine oxide. Preferred amine oxides include linear C 10 , linear C 10 ~C 12 and linear C 12 ~C 14 Examples include alkyldimethylamine oxides. As used herein, “medium-chain branched” means that the amine oxide has one alkyl moiety having n1 carbon atoms, and on this alkyl moiety, one alkyl branch having n2 carbon atoms. This alkyl branch is located on the α-carbon relative to the nitrogen of the alkyl moiety. This type of branching of amine oxide is also known in the art as internal amine oxide. The sum of the number of carbon atoms in n1 and n2 is 10 to 24, preferably 12 to 20, more preferably 10 to 16. The number of carbon atoms in one alkyl moiety (n1) must be approximately equal to the number of carbon atoms in one alkyl branch (n2) so that this alkyl moiety and one alkyl branch are symmetrical. As used herein, “symmetrical” means that at least 50% by weight, more preferably at least 75% to 100% by weight of the medium-chain branched amine oxide for use herein, the number of carbon atoms in (n1-n2) is 5 or less, preferably 4 or less, most preferably 0 to 4. The amine oxide further comprises two portions independently selected from C1-C3 alkyl groups, C1-C3 hydroxyalkyl groups, or polyethylene oxide groups containing an average of about 1 to about 3 ethylene oxide groups. Preferably, these two portions are selected from C1-C3 alkyl groups, and more preferably both are C1 alkyl groups.

[0162] In a preferred embodiment of the present invention, the amphoteric surfactant is C8-C 18 Alkyl-dimethylamine oxide and C8~C 18 Selected from alkyl-di(hydroxyethyl)amine oxides.

[0163] The cleaning composition may also include zwitterionic surfactants, which can be used in combination with two or more other surfactants.

[0164] Suitable zwitterionic surfactants include betaines such as alkyl betaines, alkylamide betaines, amide azolinium betaines, sulfobetaines (INCI: sultaine), and phosphobetaines. Examples of suitable betaines and sulfobetaines are listed below (according to INCI): almondamidopropyl betaine, apricotamidopropyl betaine, avocadoamidopropyl betaine, babassuamidopropyl betaine, behenamidopropyl betaine, behenyl betaine, canolamidopropyl betaine, capryl / capramidopropyl betaine, carnitine, cetyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocamidopropyl Hydroxysultaine, Cocobetaine, Cocohydroxysultaine, Coco / Oleamidopropyl Betaine, Cocosultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Taro Glycinate, Dimethicone Propylene Glycol Betaine, Ercamidopropyl Hydroxysultaine, Hydrogenated Taro Betaine, Isostearamidopropyl Betaine, These include lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, lauryl sultaine, milk amidopropyl betaine, mink amidopropyl betaine, myristamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysultaine, oleyl betaine, olive amidopropyl betaine, coconut amidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, coconut kernel fatty acid amidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinol amidopropyl betaine, sesamidopropyl betaine, soy amidopropyl betaine, stearamidopropyl betaine, stearyl betaine, taro amidopropyl betaine, taro amidopropyl hydroxysultaine, taro betaine, taro dihydroxyethyl betaine, undecylenamidopropyl betaine, and wheat germ amidopropyl betaine.

[0165] A preferred betaine is, for example, C12 ~C 18 These are alkyl betaines and sulfobetaines. The zwitterionic surfactant is preferably a betaine surfactant, and more preferably a cocamidopropyl betaine surfactant.

[0166] Non-limiting examples of cationic surfactants that can be used in combination with two or more other surfactants include quaternary ammonium surfactants that may have up to 26 carbon atoms, such as the alkoxylated quaternary ammonium (AQA) surfactant described in U.S. Patent No. 6,136,769; dimethylhydroxyethyl quaternary ammonium described in U.S. Patent No. 6,004,922; dimethylhydroxyethyl laurylammonium chloride; International Publication No. 98 / 35002, International Publication No. 98 / 35003, International Publication Examples include polyamine cationic surfactants as described in U.S. Publication No. 98 / 35004, International Publication No. 98 / 35005, and International Publication No. 98 / 35006; cationic ester surfactants as described in U.S. Patent No. 4,228,042, U.S. Patent No. 4,239,660, U.S. Patent No. 4,260,529, and U.S. Patent No. 6,022,844; and amino surfactants as described in U.S. Patent No. 6,221,825 and International Publication No. 00 / 47708, specifically amidopropyldimethylamine (APA).

[0167] The compositions according to the present invention may include at least one builder. In relation to the present invention, no distinction is made between a builder and a component referred to elsewhere as a "co-builder." Examples of builders are complexing agents, ion exchange compounds, and precipitating agents, which are also referred to herein hereafter as complexing agents. Builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates, and polycarboxylates.

[0168] In relation to the present invention, the term citrate includes monoalkali metal salts and dialkali metal salts of citric acid, particularly monosodium salts and preferably trisodium salts, ammonium salts or substituted ammonium salts of citric acid, and citric acid. Citrate can be used as an anhydrous compound or as a hydrate, for example, sodium citrate dihydrate. The amount of citrate is calculated based on anhydrous trisodium citrate.

[0169] 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 present invention are free of phosphates and polyphosphates, including hydrogen phosphates, such as trisodium phosphate, pentasodium tripolyphosphate, and hexasodium metaphosphate ("phosphate-free"). The term "free" with respect to phosphates and polyphosphates in relation to the present invention should be understood to mean that the total content of phosphates and polyphosphates, as determined by gravimetric analysis, is in the range of 10 ppm to 0.2% by weight of each composition.

[0170] The term carbonate includes alkali metal carbonates and alkali metal bicarbonates, with sodium salts being preferred. Na2CO3 is particularly preferred.

[0171] Examples of phosphonates include hydroxyalkane phosphonates and aminoalkane phosphonates. Among hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a builder. It is preferably used as a sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues. They are preferably used in the form of neutral reactive sodium salts, for example, as the hexasodium salt of EDTMP or as the hepta and octasodium salts of DTPMP.

[0172] Examples of aminocarboxylates and polycarboxylates include nitrilotriacetate, ethylenediamine ethanol acetate, diethylenetriamine pentaacetate, triethylenetetraamine hexaacetate, propylenediaminetetraacetic acid, ethanol-diglycine, methylglycine diacetate, and glutamine diacetate. The terms aminocarboxylate and polycarboxylate also include their respective unsubstituted or substituted ammonium salts and alkali metal salts, such as sodium salts, and in particular, their fully neutralized compounds.

[0173] Silicates related to the present invention include, in particular, sodium disilicate and sodium metasilicate, aluminosilicate, such as zeolites and layered silicates, and especially those having the formulas α-Na2Si2O5, β-Na2Si2O5, and δ-Na2Si2O5.

[0174] The compositions according to the present invention may also include one or more builders selected from substances not mentioned above. Examples of builders include α-hydroxypropionic acid and oxidized starch.

[0175] In one embodiment of the present invention, the builder is selected from polycarboxylates. The term "polycarboxylate" refers to succinic acid, C2-C2 16 Alkyl disuccinate, C2~C 16 This includes non-polymerizable polycarboxylates such as alkenyl disuccinates, ethylenediamine N,N'-disuccinic acid, diacetate tartrate, alkali metal malonates, monoacetate tartrate, propanetricarboxylic acid, butanetetracarboxylic acid, and cyclopentanetetracarboxylic acid.

[0176] Oligomers or polymeric polycarboxylates are, for example, alkali metal salts of polyaspartic acid or, more specifically, (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

[0177] Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Suitable polymers are, specifically, preferably polyacrylic acid having a weight-average molecular weight Mw in the range of 2000 to 40000 g / mol, preferably 2000 to 10000 g / mol, and particularly 3000 to 8000 g / mol. Further preferred polycarboxylate copolymers are, in particular, copolymers of acrylic acid and methacrylic acid, and copolymers of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

[0178] Monoethylene unsaturated C3-C 10 -Mono or C4~C 10 It is also possible to use copolymers of at least one monomer from the group consisting of dicarboxylic acid or its anhydride, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, and citraconic acid, and at least one hydrophilic or hydrophobic modified comonomer listed below.

[0179] Suitable hydrophobic comonomers include, for example, isobutene, diisobutene, butene, pentene, hexene, and styrene, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, and 1-hexacocene, C 22 -α-olefin, C 20 ~C 24 - An olefin having 10 or more carbon atoms, such as a mixture of α-olefin and polyisobutene having an average of 12 to 100 carbon atoms per molecule, or a mixture thereof.

[0180] Suitable hydrophilic comonomers are monomers having a sulfonate or phosphonate group, and nonionic monomers having a hydroxyl functional group or an alkylene oxide group. Examples include allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide)(meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate, and ethoxypoly(propylene oxide-co-ethylene oxide)(meth)acrylate. In this specification, polyalkylene glycols may contain 3 to 50, specifically 5 to 40, and particularly 10 to 30 alkylene oxide units per molecule.

[0181] Particularly preferred sulfonic acid group-containing monomers in this specification 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, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of the above acids, such as sodium, potassium, or ammonium salts thereof.

[0182] Particularly preferred phosphate-containing monomers are vinylphosphonic acid and its salts.

[0183] Furthermore, amphoteric polymers can also be used as builders.

[0184] The compositions according to the present invention, particularly in the case of solid formulations, may contain, for example, 0.1 to 70% by weight, preferably 10 to 50% by weight, and preferably up to 20% by weight in total builder. Liquid formulations of the present invention preferably contain builder in the range of 0.1 to 8% by weight.

[0185] The formulation according to the present invention may contain one or more alkali carriers. The alkali carrier ensures a pH of at least 9, for example, when an alkaline pH is desired. For example, in addition to the alkali metal carbonates, alkali metal bicarbonates, and alkali metal metasilicates mentioned above, alkali metal hydroxides are also suitable. In any case, the preferred alkali metal is potassium, and sodium is particularly preferred. In one embodiment of the present invention, an amine, preferably an alkanolamine, more preferably triethanolamine, is used to adjust the pH to above 7.

[0186] In one embodiment of the present invention, the composition or laundry formulation according to the present invention further comprises at least one enzyme.

[0187] In one embodiment, the composition according to the present invention further comprises at least one enzyme.

[0188] Preferably, at least one of the enzymes is a detergent enzyme.

[0189] 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 numbering follows the Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology, including its supplements published between 1993 and 1999. Preferably, the enzyme is a hydrolase (EC 3).

[0190] In preferred embodiments, the enzymes include proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectinate lyases, keratinases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanases, maranases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNases, phosphodiesterases, and phytases. , selected from the group consisting of carbohydrase, galactanase, xanthanase, xyloglucanase, oxidoreductase, perhydrolase, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alpha-galactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersin, and combinations of at least two of the above types. More preferably, the enzyme is selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, xylanase, deoxyribonuclease, dispersin, pectinase, oxidoreductase, and cutinase, and combinations of at least two of the above types. Most preferably, the enzyme is a protease, preferably a serine protease, and more preferably a subtilisin protease.

[0191] Preferably, the protease is a protease having at least 90% sequence identity with Sequence ID No. 22 of European Patent No. 1921147B1 and having the amino acid substitution R101E (by BPN numbering). Preferably, the amylase is an amylase having at least 90% sequence identity with Sequence ID No. 54 of International Publication Brochure No. 2021032881A1.

[0192] The compositions of the present invention may contain one type of enzyme or two or more different types of enzymes, for example, amylase and protease, or two or more enzymes of the same type, for example, two or more different proteases, or a mixture thereof, for example, amylase and two different proteases.

[0193] The enzyme can be incorporated into the composition in a sufficient amount to provide a beneficial effect, preferably with respect to a primary washing effect and / or a secondary washing effect, such as an anti-graying or anti-pilling effect (for example, in the case of cellulase). Preferably, the enzyme is present in the composition at a level of enzyme protein of about 0.00001% to about 5%, 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% by weight of the composition.

[0194] Preferably, the enzyme-containing composition further comprises an enzyme stabilization system.

[0195] Preferably, the enzyme-containing compositions described herein contain 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 stabilization system. The enzyme stabilization system may be any stabilization system compatible with the enzyme.

[0196] Preferably, the enzyme stabilization system includes 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, citrate, or lactate), borate, boric acid, boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), peptaldehyde (preferably Z-VAL-H or Z-GAY-H), peptide acetals, and peptaldehyde bisulfite adducts. Preferably, the enzyme stabilization system includes 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)), peptaldehydes, peptide acetals, and peptaldehyde hydrosulfite adducts. In particular, if a protease is present in the composition, a protease inhibitor selected from borates, boric acid, boronic acid (preferably 4-FPBA), peptaldehydes (preferably peptaldehydes such as Z-VAL-H or Z-GAY-H), peptide acetals, and peptaldehyde hydrosulfite adducts may be added.

[0197] The composition according to the present invention may contain one or more bleaching agents. Preferred bleaching agents are selected from sodium perborate in anhydrous form or, for example, as monohydrate, tetrahydrate, or so-called dihydrate, sodium percarbonate in anhydrous form or, for example, as monohydrate, and sodium persulfate, in which case the term "persulfate" includes salts of peracid H2SO5 and peroxodisulfate.

[0198] In this regard, the alkali metal salt may be an alkali metal bicarbonate, alkali metal hydrogen perborate, or alkali metal hydrogen persulfate in any case. However, a dialkali metal salt is preferred in any case.

[0199] The formulation according to the present invention may contain one or more bleach catalysts. The bleach catalyst can be selected from oxaziridinium-based bleach catalysts, bleach-promoting transition metal salts, or transition metal complexes such as manganese-, iron-, cobalt-, ruthenium-, or molybdenum-salen complexes or carbonyl complexes. Complexes of nitrogen-containing tripod ligands with manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, and copper, as well as cobalt-, iron-, copper-, and ruthenium-amine complexes, can also be used as bleach catalysts.

[0200] The formulation according to the present invention may contain one or more bleaching activators, such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluryl, tetraacetylhexylenediamine, acylated phenol sulfonates, such as n-nonanoyl- or isononanoyloxybenzene sulfonates, (S)NOBS, LOBS, DOBA, PAP, N-methylmorpholinium acetonitrile salt ("MMA salt"), trimethylammonium acetonitrile salt, N-acylimide, such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT"), or nitrile quat (trimethylammonium acetonitrile salt).

[0201] Any compound capable of producing hydrogen peroxide in aqueous solution as a precursor to H2O2 peroxide is considered, such as organic and inorganic peroxides known in the literature and commercially available for bleaching fabric materials at conventional washing temperatures, e.g., 10-95°C.

[0202] However, preferably, inorganic peroxides such as persulfates, perborates, percarbonates and / or persilicates are used. They are usually used in amounts of 2 to 80% by weight, preferably 4 to 30% by weight, based on the weight of the composition.

[0203] Usually, the compound of formula (1) described in more detail below

Chemical formula

[0204] Examples of suitable inorganic peroxides are sodium perborate tetrahydrate or sodium perborate monohydrate, sodium percarbonate, inorganic peracid compounds such as potassium monopersulfate (MPS). When an organic or inorganic peracid is used as the oxygen compound, the amount is usually in the range of about 2 to 80% by weight, preferably 4 to 30% by weight, based on the weight of the composition.

[0205] Examples of organic peroxides include, for example, mono- or polyperoxides, urea peroxide, combinations of C1-C4 alkanol oxidases and C1-C4 alkanols (such as methanol oxidase and ethanol described in WO 95 / 07972 pamphlet), alkylhydroxy peroxides such as cumene hydroperoxide, and t-butyl hydroperoxide.

[0206] Peroxides can have various crystal forms and different water contents and may be used in combination with other inorganic or organic compounds to improve storage stability.

[0207] As the oxidizing agent, peroxy acids can also be used. An example is the compound of formula (1)

Chemical formula

[0208] Preferred monoorganic peracids and their salts are given by formula [ka] (In the formula, M stands for hydrogen or alkali metal. R' 19 (where C1-C4-alkyl;phenyl;-C1-C2-alkylene-phenyl, or phthalimide C1-C8-alkylene)

[0209] CH3COOOH and its alkali salts are particularly preferred.

[0210] Particularly preferred are e-phthalimide peroxyhexanoic acid and its alkali salts (PAP).

[0211] Diperoxy acids, such as 1,12-diperoxide decanedioic acid (DPDA), 1,9-diperoxyazelaic acid, diperoxyvaleric acid, diperoxybasic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-dioic acid, and 4,4'-sulfonylbisperoxybenzoic acid, are also suitable.

[0212] In some cases, using an additional bleach activator may be beneficial.

[0213] The term "bleach activator" is often used as a synonym for peroxy acid-based bleach precursor. All of the peroxy compounds mentioned above can be used alone or in combination with peroxy acid-based bleach precursors.

[0214] Such precursors are the corresponding carboxylic acids, or the corresponding carboxyanhydrides, or the corresponding carbonyl chlorides, amides, or esters, which can form peroxy acids upon hyperhydrolysis. Such reactions are generally known.

[0215] Peroxy acid-based bleach precursors are known and have been adequately described in documents such as British Patent Nos. 836988, 864,798, 907,356, 1,003,310 and 1,519,351; German Patent No. 3,337,921; European Patent Publication No. 0185522A, 0174132A and 0120591A; and U.S. Patent Nos. 1,246,339, 3,332,882, 4,128,494, 4,412,934 and 4,675,393.

[0216] Suitable bleaching agents include those having O- and / or N-acyl groups and / or unsubstituted or substituted benzoyl groups. These include polyacylated alkylenediamines, particularly tetraacetylethylenediamine (TAED); acylated glycoluryls, particularly tetraacetylglycolurea (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 toluyloxybenzenesulfonate; acylated triazine derivatives, particularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); and compounds of formula (10): [ka] (In the formula, R 22 R is a sulfonate group, a carboxylic acid group, or a carboxylate group. 21is a linear or branched (C7-C 15 ) alkyl, especially activators known by the names SNOBS, SLOBS and DOBA; acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran; furthermore acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated glucamine and gluconolactone). It is also possible to use combinations of conventional bleach activators known from German Patent Application Publication No. 4443177A. Nitrile compounds that form peracetic acid together with peroxides are also considered as bleach activators.

[0217] Another useful class of peroxyacid bleach precursors is the class of cationic, i.e., quaternary ammonium-substituted peroxyacid-based precursors disclosed in U.S. Patent Nos. 4,751,015 and 4,397,757, European Patent Application Publication Nos. 0284292A and 331,229A. Examples of this class of peroxyacid-based bleach precursors are: 2-(N,N,N-trimethylammonium)ethyl sodium-4-sulfonphenyl carbonate chloride-(SPCC), N-octyl, N,N-dimethyl-N10-carbophenoxydecylammonium chloride-(ODC), 3-(N,N,N-trimethylammonium)propyl sodium-4-sulfophenyl carboxylate, and N,N,N-trimethylammonium toluoyloxybenzenesulfonate.

[0218] It is also possible to use generally known additional bleach catalysts, such as transition metal complexes disclosed in European Patent No. 1194514, European Patent No. 1383857 or International Publication No. 04 / 007657 pamphlet.

[0219] The formulation according to the present invention may contain one or more corrosion inhibitors. In this case, this is understood to include compounds that inhibit metal corrosion. Examples of suitable corrosion inhibitors are triazoles, particularly benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and phenol derivatives such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, or pyrogallol.

[0220] In one embodiment of the present invention, the formulation according to the present invention contains a total amount of corrosion inhibitors in the range of 0.1 to 1.5% by weight.

[0221] The formulation of the present invention may also include further cleaning polymers and / or dirt-releasing polymers.

[0222] Additional cleaning polymers include, but are not limited to, "polyfunctional alkoxylated polyethyleneimines" (e.g., BASF's Sokalan® HP20), "polyfunctional alkoxylated diamines" (e.g., BASF's Sokalan® HP96), BASF's Sokalan® SR400 A, as well as terephthalic acid-based polyesters such as Clariant's TexCare®, e.g., TexCare® SRN 170, TexCare® SRN 172, TexCare® SRN 260, TexCare® SRN 260 SG Terra, and TexCare® SRA 300, and various combinations of all the aforementioned polymers.

[0223] Suitable polyfunctional alkoxylated polyethyleneimines are typically ethoxylated polyethyleneimines with a weight-average molecular weight Mw in the range of 3,000 to 250,000 g / mol, preferably 5,000 to 200,000 g / mol, more preferably 8,000 to 100,000 g / mol, more preferably 8,000 to 50,000 g / mol, more preferably 10,000 to 30,000 g / mol, and most preferably 10,000 to 20,000 g / mol. Suitable polyfunctional alkoxylated polyethyleneimines have ethylene oxide side chains in an amount of 80% to 99% by weight, preferably 85% to 99% by weight, more preferably 90% to 98% by weight, and most preferably 93% to 97% or 94% to 96% by weight, 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 polyethyleneimine with a molecular weight of 500 to 1000 g / mol is used, and more preferably, a polyethyleneimine with a Mw of 600 to 800 g / mol. In this case, the ethoxylated polymer has an average of 5 to 50, preferably 10 to 35, and more preferably 20 to 35 ethylene oxide (EO) units per NH functional group.

[0224] Suitable polyfunctional alkoxylated diamines are typically ethoxylated C2-C2. 12 The present invention uses alkylenediamines, preferably quaternized and optionally sulfated hexamethylenediamines. Typical polyfunctional alkoxylated diamines have a weight-average molecular weight Mw in the range of 2000 to 10000 g / mol, more preferably 3000 to 8000 g / mol, and most preferably 4000 to 6000 g / mol. In preferred embodiments of the present invention, ethoxylated hexamethylenediamines that are further quaternized and sulfated, containing an average of 10 to 50 ethylene oxide (EO) groups per NH functional group, preferably 15 to 40, and more preferably 20 to 30, and preferably having 2 cationic ammonium groups and 2 anionic sulfate groups, can be used.

[0225] It should be noted that the cleaning compositions of the present invention may also include at least one propoxylated polyol of the present invention, in addition to at least one propoxylated polyol that does not form part of the claims, for example, a propoxylated polyol derived from a polyol having three -OH groups (such as propoxylated glycerol) or six -OH groups (such as propoxylated sorbitol).

[0226] In preferred embodiments of the present invention, the cleaning composition may contain at least one polyfunctional alkoxylated polyethyleneimine and / or at least one polyfunctional alkoxylated diamine to improve the cleaning performance of the laundry detergent, for example, preferably to improve stain removal ability, particularly primary cleaning ability for particulate stains on polyester fabrics. The polyfunctional polyethyleneimines or polyfunctional diamines or mixtures thereof described above may be added to the laundry detergent and cleaning composition in amounts of generally 0.05 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.25 to 5% by weight, and even less than 2% by weight, based on the entire specific composition including the other components and water and / or solvent.

[0227] In another preferred embodiment of the present invention, the washing composition may contain at least one terephthalic acid-based polyester used as a dirt-free polymer to improve the whiteness of the fabric after washing, particularly the whiteness of polyester fabrics.

[0228] Accordingly, one aspect of the present invention is a laundry detergent composition, particularly a liquid laundry detergent, comprising (i) at least one inventive compound and (ii) at least one compound selected from polyfunctional alkoxylated polyethyleneimines, polyfunctional alkoxylated diamines, terephthalic acid-based polyesters, and mixtures thereof.

[0229] In one embodiment of the present invention, the ratio of (ii) at least one inventive compound to (ii) at least one compound selected from polyfunctional polyethyleneimines, polyfunctional diamines, and mixtures thereof is 10:1 to 1:10, preferably 5:1 to 1:5, and more preferably 3:1 to 1:3.

[0230] Laundry formulations containing the inventive compound may also contain at least one antimicrobial agent (sometimes referred to as a "preservative").

[0231] This composition may contain one or more antimicrobial agents and / or preservatives described on pages 35-39 of International Publication No. 2021 / 115912A1.

[0232] In particular, the following antimicrobial and / or preservatives are of interest: 4,4'-dichloro-2-hydroxydiphenyl ether (CAS No. 3380-30-1), also known as 5-chloro-2-(4-chlorophenoxy)phenol, diclosan, DCPP (commercially available as a 30% by weight solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propyl-eneglycol under the trade name Tinosan® HP 100 (BASF); 2-phenoxyethanol (CAS No. 122-99-6, also known as phenoxyethanol, methylphenyl glycol, phenoxetol, 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, also known as: 1-5-pentanedial, pentane-1,5-dial, glutaraldehyde, Protectol® GA, Protectol® GA) 50, Myacide (registered trademark) GA); Glyoxal (CAS number 107-22-2, also known as ethanedial, oxylaldehyde, 1,2-ethanedial, Protectol (registered trademark) GL); 2-butyl-benzo[d]isothiazol-3-one (BBIT, CAS number 4299-07-4); 2-methyl-2H-isothiazol-3-one (MIT, CAS number 2682-20-4); 2-octyl-2H-isothiazol-3-one (OIT, CAS number 26530-20-1); 5-chloro-2-methyl-2H-isothiazol-3-one (CIT, CMIT, CAS number 26172-55-4); 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT, EINECS247-500-7) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS A mixture of 220-239-6 (CMIT / MIT mixture, CAS number 55965-84-9); 1,2-benzisothiazole-3(2H)-one (BIT, CAS number 2634-33-5);Hexa-2,4-dienoic acid (sorbic acid, CAS number 110-44-1) and its salts, e.g., calcium sorbate, sodium sorbate, potassium (E,E)-hexa-2,4-dienoate (potassium sorbate, CAS number 24634-61-5); lactonic acid and its salts; L-(+)-lactonic acid (CAS number 79-33-4); benzoic acid and its sodium salts (CAS numbers 65-85-0, CAS numbers 532-32-1) and salts of benzoic acid, e.g., ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, potassium benzoate; salicylic acid and its salts, e.g., calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate TEA salicylate; benzalkonium chloride, bromide and saccharinates, e.g., benzalkonium chloride, benzalkonium bromide, benzalkonium saccharate (CAS numbers 8001-54-5, 63449-41-2, 91080-29-4, 68989-01-5, 68424-85-1, 68391-01-5, 61789-y71-7, 8 5409-22-9); Didecyldimethylammonium chloride (DDAC, CAS numbers 68424-95-3 and 7173-51-5); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (diamine, CAS number 2372-82-9); Peracetic acid (CAS number 79-21-0); Hydrogen peroxide (CAS number 7722-84-1).

[0233] The antibacterial agent is added to the composition at a concentration of 0.001 to 10% of the total weight of the composition.

[0234] Preferably, the composition contains 2-phenoxyethanol at a concentration of 0.1 to 2%, or 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP) at a concentration of 0.005 to 0.6%.

[0235] Therefore, the present invention also encompasses a method for protecting an aqueous composition according to the present invention from bacterial contamination or growth, the method comprising the addition of 2-phenoxyethanol. Therefore, the present invention also encompasses a method for imparting an antimicrobial effect to fabrics after treatment with a solid laundry detergent (e.g., powder, granules, capsules, tablets, rods, etc.), liquid laundry detergent, fabric softener, or post-rinse treatment agent containing 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP).

[0236] In further embodiments, the present invention also includes compositions comprising the inventive compounds described herein, which further comprises an antimicrobial agent disclosed below herein, preferably selected from the group consisting of 2-phenoxyethanol, more preferably the antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition, and even more preferably 0.1 to 2% phenoxyethanol.

[0237] In further embodiments, the present invention also encompasses a method for protecting an aqueous composition from microbial contamination or growth, wherein such composition comprises the inventive compounds described herein, and such composition is preferably a detergent composition, and such method comprises adding at least one antimicrobial agent selected from the antimicrobial agents of this disclosure disclosed below herein, wherein such antimicrobial agent is preferably 2-phenoxyethanol.

[0238] In further embodiments, the present invention also includes compositions, preferably cleaning compositions, more preferably liquid laundry detergent compositions or liquid hand dish compositions, even more preferably liquid laundry detergent compositions or liquid fabric softener compositions for use on laundry, such compositions comprising the inventive compounds described herein, and such compositions further comprising 4,4'-dicolo-2-hydroxydiphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, and more preferably 0.01 to 0.6%, based on the weight of the composition.

[0239] In further embodiments, the present invention also includes a method for washing fabrics or cleaning hard surfaces, the method comprising treating the fabric or hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid fabric softener composition for use with laundry, the composition comprising the inventive compounds described herein, the composition further comprising 4,4'-dicolo-2-hydroxydiphenyl ether.

[0240] As used herein, the term “dye fixative” refers to a compound that reduces or stops color bleeding in colored fabrics during the washing process. Examples of dye fixatives include, but are not limited to, cationic dye fixatives, crosslinking fixatives, and formaldehyde-based fixatives. Those skilled in the art are familiar with these compounds, which can be purchased commercially from BASF SE, Huntsman, Archroma, Fineotex, Biotex Malaysia, or Dystar. Examples of dye fixatives, but not limited to these, include Basilen Fixing Agent F-RP, Albafix ECO, Finofix NF, polyDADMAC, and polyamines (DCDA-DETA, epichloro-DMA, epichloro-DETA, etc.).

[0241] The formulation according to the present invention may also contain water and / or additional organic solvents, such as ethanol or propylene glycol.

[0242] Further optional components may include, but are not limited to, viscosity modifiers, cationic surfactants, foaming or defoaming agents, fragrances, dyes, fluorescent whitening agents, and dye migration inhibitors.

[0243] (b) General cleaning compositions and formulations The liquid formulations disclosed in this chapter may contain 0-2%, preferably about 1%, of 2-phenoxyethanol, in addition to all other ingredients mentioned.

[0244] The liquid formulations disclosed above and below may contain 0 to 0.2%, preferably about 0.15%, of 4,4'-dicolo-2-hydroxydiphenyl ether, in addition to all other components mentioned. The bleach-free solid laundry composition may contain 0 to 0.2%, preferably about 0.15%, of 4,4'-dicolo-2-hydroxydiphenyl ether, in addition to all other components mentioned.

[0245] The formulations disclosed in this chapter may, in addition to all other components mentioned, comprise one or more enzymes, more preferably proteases and / or amylases, selected from those disclosed above in this specification, the protease being a protease having at least 90% sequence identity to Sequence ID No. 22 of European Patent No. 1921147B1 and having the amino acid substitution R101E (by BPN' numbering), and the amylase being an amylase having at least 90% sequence identity to Sequence ID No. 54 of International Publication No. 2021032881A1, wherein such enzymes are preferably present in the formulation at a level of enzyme protein of about 0.00001% to about 5% by weight, preferably about 0.00001% to about 2% by weight, more preferably about 0.0001% to about 1% by weight, or even more preferably about 0.001% to about 0.5% by weight, based on the weight of the composition.

[0246] The compositions shown below, including those in the table, disclose typical compositions associated with typical cleaning conditions commonly adopted in various regions and countries around the world, as well as specific types of general cleaning compositions corresponding to those conditions. At least one of the inventive compounds may be added to such formulations in suitable amounts, as outlined herein.

[0247] If a composition shown does not contain the inventive compound, such a composition is a comparative example composition. If a composition shown contains the inventive compound in an amount particularly described herein as a preferred range, a more preferred range, etc., such a composition is considered to fall within the scope of the present invention.

[0248] In a preferred embodiment, at least one propoxylated polyol (as defined in any of the embodiments herein, particularly in embodiments 1 to 11; in this section, propoxylated polyol is also referred to as the “inventive compound”) is used in a laundry detergent.

[0249] The liquid laundry detergent according to the present invention is 0.05-20% of at least one inventive compound, 1-50% surfactant, 0.1-40% builder, co-builder and / or chelating agent, 0.1-50% of other adjuvants Water that makes up 100% in total, It consists of.

[0250] A preferred liquid laundry detergent according to the present invention is: 0.2-6% of at least one inventive compound, 5-40%, C 10 ~C 15 -LAS and C containing 1 to 5 ethoxy units 10 ~C 18 -LAS and C 10 ~C 18 An anionic surfactant selected from alkyl ether sulfates, 1.5-10% of C, containing 3-10 ethoxy units. 10 ~C 18 -A nonionic surfactant selected from alkyl ethoxylates, 2-20%, C 10 ~C 18 A soluble organic builder / cobuilder selected from fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, and polycarboxylic acids, An enzyme system comprising 0.05-5% of at least one enzyme suitable for detergent applications, and preferably an enzyme stabilization system, 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol, Other adjuvants in 0.1-20% concentrations, Water that makes up 100% in total, It consists of.

[0251] The solid laundry detergent according to the present invention (for example, powder, granules, or tablets) is 0.05-20% of at least one inventive compound, 1-50% surfactant, 0.1-80% builder, co-builder and / or chelating agent, A 0-50% bulking agent, 0-40% bleaching active substance, 0.1-30% of other adjuvants and / or water, Composed of, The total of the ingredients will be 100%.

[0252] A preferred solid laundry detergent according to the present invention is: 0.2-6% of at least one inventive compound, 5-30%, C 10 ~C 15 -LAS, C 10 ~C 18 Alkyl sulfate and C containing 1 to 5 ethoxy units 10 ~C 18 - An anionic surfactant selected from alkyl ether sulfates, 1.5-7.5% of C, containing 3-10 ethoxy units. 10 ~C 18 -A nonionic surfactant selected from alkyl ethoxylates, Inorganic builders selected from 5-50% sodium carbonate, sodium carbonate, sodium bicarbonate, zeolite, soluble silicate, and sodium sulfate, 0.5-15%, C 10 ~C 18 Cobuilders selected from fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, and polycarboxylic acids, An enzyme system containing 0.1-5% of at least one enzyme suitable for detergent applications, and preferably an enzyme stabilization system, Other adjuvants in 0.1-20% concentrations, Water that makes up 100% in total, It consists of.

[0253] In a preferred embodiment, the polymer according to the present invention is used in dishwashing detergent.

[0254] The liquid dishwashing detergent according to the present invention is: 0.05-10% of at least one inventive compound, 1-50% surfactant, Other adjuvants in 0.1-50% concentrations, Water that makes up 100% in total, It consists of.

[0255] A preferred liquid dishwashing detergent according to the present invention is: 0.2-5% of at least one inventive compound, 5-40%, C 10 ~C 15 -LAS, containing 1 to 5 ethoxy units 10 ~C 18 Alkyl ether sulfates and C 10 ~C 18 An anionic surfactant selected from alkyl sulfates, 0-10% cocamidopropyl betaine, 0-10% lauramine oxide and 0-2% of a nonionic surfactant, preferably C 10 -Gerbet alcohol alkoxylate and, 0-5% enzyme, preferably amylase, and preferably further an enzyme stabilization system, 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol, Other adjuvants in 0.1-20% concentrations, Water that makes up 100% in total, It consists of.

[0256] Since the polyalkylene imines or polyamine polymers of the present invention are biodegradable, and in particular the cleaning formulations typically have a pH of about 7 or higher, and additionally, in many cases contain enzymes that are included in such cleaning formulations to decompose biodegradable substances such as grease, proteins, polysaccharides, etc., present in stains and dirt and removed by the cleaning composition, some consideration is needed when formulating these biodegradable polymers of the present invention. Such suitable formulations are known in principle and include solid formulations (where the enzymes and polymers can be separated by coating or by adding them to individual particles mixed together) and liquid and semi-liquid formulations (where the polymers and enzymes can be separated by formulating them in different compartments, such as multi-chamber pouches or different compartments of a bottle having various chambers, so that the liquid is poured simultaneously in predetermined amounts from these compartments to ensure that the correct amount is applied at each individual time of use of each component in each chamber). Such multi-compartment pouches and bottles are also known to those skilled in the art.

[0257] The following table shows specific types of common cleaning compositions corresponding to typical cleaning conditions and associated compositions commonly adopted in various regions and countries around the world. At least one of the inventive compounds may be added to such formulations in suitable amounts as outlined herein.

[0258] [Table 1]

[0259] [Table 2]

[0260] [Table 3]

[0261] [Table 4]

[0262] [Table 5]

[0263] [Table 6]

[0264] [Table 7]

[0265] [Table 8]

[0266] [Table 9]

[0267] [Table 10]

[0268] The present invention will be further illustrated by the following embodiments, but these will not limit the scope of the invention.

[0269] Any particular embodiment described throughout this disclosure is incorporated into the Invention as part of the Invention, and any further options disclosed herein as “optional,” “preferred,” “more preferred,” “even more preferred,” or “most preferred” (or “preferred,” etc.) options of any particular embodiment may be individually and independently selected (only if such independent selection is possible due to the nature of its features or if such independent selection is not expressly excluded) and subsequently combined in any of the other embodiments (where other such options and preferences may also be individually and independently selected, but only if such independent selection is not possible due to the nature of its features or if such independent selection is expressly excluded), and any such possible combinations are included as part of the Invention as individual embodiments. [Examples]

[0270] Method for testing the biodegradability of polymers The biodegradation of wastewater was tested in three ways using the OECD 301F manometer respiratory measurement method. OECD 301F is an aerobic test that measures the biodegradation of a sample by measuring oxygen consumption. A 100 mg / L test substance, nominally the sole source of carbon, was added to the measured volume of culture medium along with an inoculant (30 mg / L, aerated sludge collected from the Mannheim wastewater treatment plant). This was 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 the change in pressure within the apparatus using OxiTop® C (Xylem 35 Analytics Germany Sales GmbH&Co KG). The released carbon dioxide was absorbed into a sodium hydroxide solution. A nitrification inhibitor was added to the flask to prevent oxygen consumption due to nitrification. The amount of oxygen absorbed by the microbial population during the biodegradation of the test substance (corrected for the amount absorbed by a blank inoculation conducted in parallel) is expressed as a percentage of ThOD (theoretical oxygen demand measured by elemental analysis of the compound). For each cabinet, the test sample is tested together with the positive control glucose / glutamic acid.

[0271] A method for evaluating the effect of polymers in laundry detergent on whiteness. Whiteness preservation, also known as whiteness retention, is the ability of detergents to protect white items from loss of whiteness when they are washed while dirty. With white clothing, dirt removed from the dirty garment floats in the wash water and reattaches to the garment, causing the whiteness of the garment to decrease with each wash, making it appear dirty or grimy over time.

[0272] The whiteness effect of the polymers of this disclosure is evaluated using an automated turgotometer equipped with 10 pots for laundry formulation testing.

[0273] SBL2004 test stain strips supplied by WFK Testgewebe GmbH are used to simulate consumer stain levels (a mixture of body grime, food, mud, etc.). Each SBL2004 strip has 8g of stain attached to it. The SBL2004 test stain strips were cut into 5x5cm squares for use in the test.

[0274] Warwick Equest Ltd.'s Black Todd clay powder is an additional dirt used to mimic particulate dirt. Add 0.25g with each wash cycle.

[0275] The white fabric samples listed in Table 5, purchased from WFK Testgewebe GmbH, were used as whiteness tracers. Before the washing test, the L, a, b, and WI CIE values ​​of all whiteness tracers were measured using a Konica Minolta CM-3610D spectrophotometer.

[0276] [Table 11]

[0277] To simulate fabric load and supply the mechanical energy during an actual washing process, additional ballast (background fabric samples) is also used. The ballast load consists of 5x5cm knit samples of cotton and polycotton.

[0278] Four cleaning cycles are required to complete the test: Cycle 1: Completely dissolve the desired amount of detergent and clay powder by mixing them with 1 liter of water (specified hardness) in the pot of each turgotometer. Wash and rinse 60 grams of cloth containing whiteness tracers (four types, including four copies of each), 10 pieces of 5 x 5 cm SBL2004, and ballast in the pot of the turgotometer under specified conditions.

[0279] In the test of the liquid laundry detergent composition, the washing concentration was 2500 ppm. The washing temperature was 30°C, and the water hardness was 7 gpg.

[0280] Cycle 2: Next, wash and rinse the whiteness tracer and ballast from each pot again with a new set of SBL2004 (5 x 5 cm, 10 sheets) and 0.25 g of clay powder, then follow the process of Cycle 1. All other conditions remain the same as in Cycle 1.

[0281] Cycle 3: Next, wash and rinse the whiteness tracer and ballast from each pot again with a new set of SBL2004 (5 x 5 cm, 10 sheets) and 0.25 g of clay powder, then follow the process of Cycle 1. All other conditions remain the same as in Cycle 1.

[0282] Cycle 4: Next, wash and rinse the whiteness tracer and ballast from each pot again with a new set of SBL2004 (5 x 5 cm, 10 sheets) and 0.25 g of clay powder, then follow the process of Cycle 1. All other conditions remain the same as in Cycle 1.

[0283] After cycle 4, all whiteness tracers and ballast are laid flat on a tray until dry, and then the tracers are measured again using a Konica Minolta CM-3610D spectrophotometer. The change in whiteness index (ΔWI(CIE)) is calculated based on the L, a, and b measurements before and after washing. ΔWI(CIE) = WI(CIE) (after washing) - WI(CIE) (before washing).

[0284] Method for evaluating the stain-removing effect of polymers in laundry detergent The cleaning effect of the polymer is evaluated using an automated turgotometer. Some of the suitable test stains for this test are as follows: Dust and sebum on polycotton without CFT A very specific type of sebum on polycotton that does not contain CFT.

[0285] Stains are analyzed before and after washing using an image analysis system for stain removal testing during laundry.

[0286] SBL2004 test stain strips supplied by WFK Testgewebe GmbH are used to simulate consumer stain levels (a mixture of body grime, food, mud, etc.). Each SBL2004 strip has 8g of stain attached to it. The SBL2004 test stain strips were cut into 5x5cm squares for use in the test.

[0287] To simulate fabric load and supply the mechanical energy during the actual washing process, additional ballast (background fabric samples) is also used. The ballast load consists of 5x5cm knit samples of cotton and polycotton. Four washing cycles are performed.

[0288] The desired amount of detergent is completely dissolved by mixing it with 1 liter of water (of the specified hardness) in each turgotometer pot. Add the specified amount of 5 x 5 cm SBL2004 and ballast to the fabric containing a total of 60 g of stains (two internal replicas of each stain in each pot), and wash and rinse in the turgotometer pot under the specified conditions.

[0289] All stains are tumble-dried at 60-65°C until dry, and then the stains are measured again using an image analysis system for laundry stain removal testing.

[0290] The Stain Removal Index (SRI) is automatically calculated from the L, a, and b values ​​using the formula shown below. A higher SRI indicates better stain removal. SRI = 100 * ((ΔE b -ΔE a ) / ΔE b ) ΔE b =√((L c -L b ) 2 +(a c -a b ) 2 +(b c -b b ) 2 ) ΔE a =√((L c -L a ) 2 +(a c -a a ) 2 +(b c -b a ) 2 ) The subscript "b" indicates data about the stain before washing. The subscript "a" indicates data about stains after washing. The subscript "c" indicates data for stain-free fabric.

[0291] Compound Synthesis Synthesis of the inventive compound Example IE1: Meso-erythritol propoxylated with 8 moles of propylene oxide per hydroxyl group. Example 1a: Meso-erythritol propoxylated with 3 moles of propylene oxide per hydroxyl group 122.1 g of meso-erythritol and 1.6 g of potassium tert-butoxide were placed in a 2-liter autoclave, and the mixture was heated to 130°C. The vessel was purged three times with nitrogen, and the mixture was heated to 140°C. Within 13 hours, 696.9 g of propylene oxide was added. To complete the reaction, the mixture was further reacted at 140°C for 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 a light brown oily substance was obtained.

[0292] Example 1b: Meso-erythritol propoxylated with 8 moles of propylene oxide per hydroxyl group 245.7 g of meso-erythritol propoxylated with 3 moles of propylene oxide per hydroxyl group (Example 1a) and 0.7 g of potassium tert-butoxide were placed in a 2 liter autoclave, and the mixture was heated to 80°C. The vessel was purged three times with nitrogen, and the mixture was heated to 140°C. Within 5 hours, 348.5 g of propylene oxide was added. To complete the reaction, the mixture was further reacted at 140°C for 7 hours. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. After filtration, 592.0 g of a light brown oily substance was obtained. The elemental composition was 60.6% carbon, 29.2% oxygen, and 10.4% hydrogen.

[0293] Synthesis of the inventive polymer example IE10: Polyglycerol propoxylated with 4 moles of propylene oxide per hydroxyl group Example 1a: Polyglycerol propoxylated with 4 moles of propylene oxide per hydroxyl group In a 2-liter autoclave, 150.0 g of polyglycerol (polyglycerol HT, obtained from Solvay Chemicals International, hydroxyl value: 1148 mg KOH / g, equivalent to 48.9 g per mole of hydroxyl groups) and 1.7 g of potassium tert-butoxide were added, and the mixture was heated to 130°C. The vessel was purged three times with nitrogen, and the mixture was heated to 140°C. Within 13 hours, 713.1 g of propylene oxide was added. To complete the reaction, the mixture was further reacted at 140°C for 10 hours. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum at 80°C. After filtration, 860.0 g of a pale yellow oily substance was obtained. Elemental analysis: Carbon = 59.0%, Oxygen = 31.5%, Hydrogen = 10.2%

[0294] Other inventive polymer examples (IE1-IE16) and comparative polymer examples (CE1-CE7) were synthesized following a similar procedure by adjusting the type of polyol core and the amount of propylene oxide. The chemical compositions of IE1-IE16 and CE1-CE7 are summarized in Table 6.

[0295] [Table 12]

[0296] [Table 13]

[0297] Table 7 summarizes the results of the biodegradability tests of the polymers using the above method, and the calculated values ​​of F from formulas (I) and (II) for the polymers IE1 to IE16 of the present invention and comparative polymers CE1 to CE2. The inventive polymers IE1 to IE16 exhibit improved biodegradability.

[0298] [Table 14]

[0299] Stain removal performance of polymers in liquid detergents: The liquid detergent compositions E and F described below are prepared by traditional means known to those skilled in the art by mixing the listed components (Table 8).

[0300] The stain-removing performance of the invented polymer is evaluated according to the method for evaluating the stain-removing effect of the polymer in the laundry detergent described above. The liquid detergent concentration was 2500 ppm, and the fabric was washed at 30°C for 12 minutes with a hardness of 7 gpg, followed by rinsing at 15°C for 5 minutes. Eleven SBL pieces (squares) were added as stains to simulate the level of soiling experienced by consumers.

[0301] By directly comparing the stain removal performance of illuminating composition E and test composition F, the ΔSRI of composition F versus composition E is reported in Table 9 as an indicator of the polymer's stain removal performance.

[0302] [Table 15]

[0303] [Table 16]

[0304] As shown in Table 9, the inventive polymer exhibits a significant stain-removing effect against sebum stains. In comparative samples containing only three polypropylene oxide units (PO), no significant stain-removing effect against sebum was observed.

[0305] [Table 17]

[0306] Liquid detergent compositions G and H are prepared by traditional means known to those skilled in the art by mixing the components described (Table 10), and evaluated according to a method for evaluating the stain-removing effect of polymers in laundry detergents.

[0307] The liquid detergent concentration was 2500 ppm. The fabric was washed at 30°C for 12 minutes with a hardness of 7 gpg, followed by rinsing at 15°C for 5 minutes. Eleven SBL pieces were added to simulate the level of dirt experienced by consumers.

[0308] Table 10 reports the ΔSRI of composition H versus composition G, showing that composition H, which contains the inventive polymer IE10 based on a polyglycerol core, exhibits statistically better sebum removal performance than composition G, which contains the comparative polymer CE5 based on a glycerol core.

[0309] [Table 18]

[0310] [Table 19]

[0311] The following liquid detergent compositions I and K are prepared by traditional means known to those skilled in the art by mixing the listed components (Table 11) and evaluated according to a method for evaluating the stain-removing effect of polymers in laundry detergents.

[0312] The liquid detergent concentration was 2500 ppm. The fabric was washed at 30°C for 12 minutes with a hardness of 7 gpg, followed by rinsing at 15°C for 5 minutes. Eleven SBL pieces were added to simulate the level of dirt experienced by consumers.

[0313] Table 11 reports the ΔSRI of composition K versus composition I. Composition K, which contains the inventive polymer IE3 based on a mesoerythritol core, exhibits statistically superior and outstanding sebum removal performance compared to composition G, which contains the comparative polymer CE4 based on a glycerol core.

[0314] [Table 20]

[0315] [Table 21]

[0316] The following liquid detergent compositions L and M are prepared by traditional means known to those skilled in the art by mixing the listed components (Table 12) and evaluated according to a method for evaluating the stain-removing effect of polymers in laundry detergents.

[0317] The liquid detergent concentration was 2740 ppm. The fabric was washed at 30°C for 40 minutes with a hardness of 7 gpg, followed by rinsing at 15°C for 2 x 5 minutes. Twenty SBL pieces were added to simulate the level of dirt experienced by consumers.

[0318] Table 12 reports the ΔSRI of composition M versus composition L. Composition M, which contains the inventive polymer IE3 based on a mesoerythritol core, exhibits statistically superior dust and sebum removal performance compared to composition L, which does not contain the polymer.

[0319] [Table 22]

[0320] [Table 23]

[0321] Polymer re-adhesion prevention performance in laundry detergents The polymer re-adhesion prevention performance was tested using the following liquid laundry detergent compositions (Table 13) as detergent bases. The polymer re-adhesion prevention performance was tested under the following conditions: 3000 ppm clay, 688 ppm detergent base / 25℃ / hardness 1 mM / 19.6 ppm polymer.

[0322] [Table 24]

[0323] [Table 25]

[0324] Exam preparation: For the whiteness effect test, prepare the following fabrics: Knit Cotton: Test fabric, Inc. 403 Cotton Interlock Circular Knit Available from CW120, Empirical Manufacturing Company (Cincinnati, OH, USA).

[0325] The fabric was prepared according to the following method: 400g of fabric was washed twice at 60°C using 18.6g of Ariel® Compact powder detergent on a short program (45-minute wash cycle followed by 3 rinse cycles; the total program is 90 minutes), twice at 60°C without detergent on a short program, and then three times at 40°C on a short program with 8.2g of Lenor® Concentrate (fabric enhancer) during each main wash, in a WE Miniwasher Electrolux EWC1350 (3.5 liters of water). The fabric was then dried in a tumble dryer on extra dry until dry.

[0326] Test method: Each sample was prepared under the following conditions: detergent concentration 750 ppm, 150 μL of water per well, 25°C, and 1.0 mM (3:1 Ca). +2 :Mg +2 The system is run on a 96-well plate simulated washing system that mimics the stirring of a typical full-scale washing machine, according to the water hardness (molar ratio), washing pH of 8.3, and 3000 ppm Arizona test dust (supplied by PTI, Powder Technology Inc.).

[0327] Each fabric was washed for 60 minutes and dried in the dark under ambient conditions. For each washing condition, there were 6 96-well plates for a total of 48 repeated tests, with 8 internal repeated tests per 96-well plate.

[0328] Once the sample is dry, use the Spectrolino imaging system (Gretag Macbeth, Spectro Scan 3.273) to scan each spot in the 96-well plate. * a * , b * The CIE WI is measured. For each treatment, the average CIE WI is measured. The ΔCIE WI reported in the table below is the difference between the average CIE WI of the sample and the average CIE WI of the control sample without the test polymer (polymer-free).

[0329] Regarding the whiteness index, the CIE whiteness index formula was used, and ΔWI was calculated as follows: ΔWI = WI Technology - WI No (for substrate)

[0330] The results are shown in Table 14, demonstrating that the inventive polymer can provide clear re-adhesion prevention performance.

[0331] [Table 26]

[0332] Polymer cleaning performance of laundry detergents The polymer cleaning performance of laundry detergents was tested using the formulations listed in Table 13, and the cleaning conditions for a single wash cycle can be summarized as follows: Device: Roundhometer Cleaning solution 500mL Washing time: 30 minutes Washing temperature 25℃ Detergent concentration: 0.688 g / L Water hardness 1 mmol / L:(Ca:Mg):HCO3(4:1):8 Dirty fabric: CFT WFK 20D

[0333] After one cycle, the soiled fabric was rinsed twice with water, then immediately centrifuged and air-dried at room temperature for 12 hours.

[0334] To evaluate the primary cleaning power of stains, the stain removal index (SRI) formula of ASTM D4265 was used to measure the reflectance of soiled fabrics before and after washing. A reflectometer (MACH5+, ColourConsult's multi-area color meter) was used to determine the reflectance of each fabric before and after washing. A higher delta reflectance value indicates better primary cleaning power.

[0335] ASTM D4265-14: Evaluation of stain removal performance in household laundry. Stain Removal Index = SRI SRI = 100 × (((ΔE * (Before washing - no stains) - ΔE * (After washing - no stains) / ΔE * (Before washing - no stains) ΔE*=((ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2 ) 1 / 2 Average ΔSRI = (Sum of ΔSRIs for all stains) / Number of stains

[0336] The cleaning performance of the invented polymer is summarized in Table 15. The invented polymer can provide a clear improvement in sebum stain removal (WFK 20D).

[0337] [Table 27]

[0338] Whiteness performance of polymers in liquid detergents: The liquid detergent compositions E and K described below were prepared by traditional means known to those skilled in the art by mixing the listed components (Table 16) and evaluated according to the method for evaluating the whiteness-retaining effect of polymers in laundry detergents. The ΔWI CIEs of composition K versus composition E are reported in Table 16, and composition K, which contains the inventive polymer IE3 based on a mesoerythritol core, shows significantly better whiteness-retaining performance than composition E.

[0339] Table 28

[0340] Table 29

Claims

1. A propoxylated polyol comprising essentially a polyol core consisting of 4 to 5 -OH groups, wherein at least one of the -OH groups is modified to form a polypropylene oxide branch, and the propoxylated polyol comprises, on average, a polypropylene oxide branch containing at least 4 polypropylene oxide units.

2. The propoxylated polyol according to claim 1, wherein the polyol core is a monomer, oligomer, or polymer, and 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 propoxylated polyol according to claim 1 or 2, wherein the propoxylated polyol comprises polypropylene oxide branches containing, on average, at least 5 polypropylene oxide units (PO), preferably at least 6 PO, and more preferably at least 8 PO.

4. The propoxylated polyol according to any one of claims 1 to 3, wherein the propoxylated polyol comprises polypropylene oxide branches containing an average of at least 30 or fewer polypropylene oxide units (PO), preferably 25 or fewer PO, and more preferably 22 or fewer PO.

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

6. In equation (I) and / or equation (II), F is 0 or greater, Equation (I) is, F = 2.769PQ - 12.46P - 0.209QX + 0.524Q + 0.726X + 1, Equation (II) is, F = 0.1123PQ - 0.505P + 0.0027QX - 0.209Q - 0.018X + 1 (In the formula, X = average number of PO per propylene oxide branch, P = the average number of ether bonds in the polyol core, A propoxylated polyol according to any one of claims 1 to 5, having a structure (Q = average number of -OH groups in the polyol core).

7. The propoxylated polyol according to any one of claims 1 to 6, wherein the weight-average molecular weight (Mw) of the propoxylated polyol is in the range of 700 to 6,000 g / mol, preferably in the range of 1,500 to 4,000 g / mol, and more preferably in the range of 2,000 to 3,500 g / mol.

8. The propoxylated polyol according to any one of claims 1 to 7, wherein the polyol core is selected from the group consisting of meso-erythritol, D-threitol, L-threitol, 1,2,5,6-hexanetetrol, pentaerythritol, xylitol, ribitol, arabitol, pentitol, diglycerol, triglycerol, and polyglycerol, and the polyglycerol preferably consists of two to three subunits of glycerol.

9. The propoxylated polyol according to any one of claims 1 to 8, wherein the amount of secondary alcohol groups in the propoxylated polyol is in the range of 30 to 100%, preferably 75 to 99%, and more preferably 95 to 98%.

10. The propoxylated polyol according to claim 9, wherein the amount of secondary alcohol groups in the propoxylated polyol, based on the indicated polyol, is in the range of meso-erythritol: 50-100%; D-threitol: 50-100%; L-threitol: 50-100%; 1,2,5,6-hexanetetrol: 50-100%; pentaerythritol: 30-100%; xylitol: 60-100%; ribitol: 60-100%; arabitol: 60-100%; pentitol: 60-100%; and polyglycerol: 33-100%.

11. A process for preparing a propoxylated polyol according to any one of claims 1 to 10, wherein a polyol consisting essentially of 4 to 5 -OH groups is reacted with at least 16 propylene oxide molecules to obtain each propoxylated polyol.

12. The process according to claim 11, wherein the polyol, which essentially consists of 4 to 5 -OH groups, is selected from the group consisting of meso-erythritol, D-threitol, L-threitol, 1,2,5,6-hexanetetrol, pentaerythritol, xylitol, ribitol, arabitol, pentitol, and polyglycerols, preferably consisting of 2 to 3 glycerol subunits.

13. Use of a propoxylated polyol according to any one of claims 1 to 10 in laundry detergents, cleaning compositions, fabric care and home care products, cosmetic formulations, crude oil emulsion disruptors, pigment dispersions for inkjet inks, electroplating formulations, cement-based compositions, and / or dispersants for pesticide formulations, preferably in cleaning compositions and / or fabric care and home care products.

14. Cleaning compositions and / or fabric care and home care products, preferably i) For the removal of sebum, and / or ii) To improve the removal of oily / fatty stains, and / or iii) To remove particulate stains, and / or iv) In order to disperse and / or emulsify the dirt, and / or v) To modify the treated surface in order to improve the removal of any subsequent re-contamination, and / or vi) To improve whiteness, and / or Most preferably, in a cleaning composition, i) To remove clay, and / or ii) To remove oily / fatty stains, The use of the cleaning composition according to claim 13, Each of the above options i) to vi) is preferably for use in laundry detergent formulations and / or dishwashing detergent formulations and / or formulations suitable for (pre) treatment of fabrics and / or hand soaps, more preferably in liquid laundry detergent formulations and / or liquid dishwashing detergent formulations.

15. Laundry detergents, cleaning compositions, fabric care and home care products, cosmetic formulations, crude oil emulsion disruptors, pigment dispersions for inkjet inks, formulations for electroplating, cement-based compositions and / or dispersants for pesticide formulations, preferably laundry detergents, cleaning compositions and / or fabric care and home care products comprising at least one propoxylated polyol as described in any one of claims 1 to 10.

16. A laundry detergent, cleaning composition, fabric care or home care product according to claim 15, (a) An antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dicolo-2-hydroxydiphenyl ether, preferably comprising 2-phenoxyethanol in the range of 2 ppm to 5% by weight of the composition, more preferably comprising 0.1 to 2% phenoxyethanol, or preferably comprising 4,4'-dicolo-2-hydroxydiphenyl ether, each in a concentration of 0.001 to 3% by weight, more preferably 0.002 to 1% by weight, and even more preferably 0.01 to 0.6% by weight of the composition, (b) Laundry detergent, cleaning composition, fabric care or home care product according to claim 15, further comprising: (b) lipase, hydrolase, amylase, DNase, protease, cellulase, hemicellulase, phospholipase, esterase, mannanase, xylanase, dispersin, oxidoreductase, cutinase, pectinate lyase, pectinase, lactase, and peroxidase, and preferably one or more enzymes selected from a list consisting of at least two combinations of the above types, preferably at least one enzyme selected from combinations of at least two types, more preferably at least one enzyme selected from proteases.

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