Liquid detergent composition for hand washing dishes

Abstract

The present invention provides a dishwashing detergent composition that uses cleaning components that provide effective grease removal and persistent foaming in the presence of oily stains, while simultaneously exhibiting improved biodegradability. [Solution] A detergent composition having a surfactant system comprising an anionic surfactant and a diamine alkoxylate having a weight-average molecular weight (Mw) in the range of 1,200 to 3,200 g / mol and a propylene oxide content of 65% to 95% by weight relative to the total weight of the diamine alkoxylate.

Description

[Technical Field]

[0001] This invention relates to a liquid detergent composition for hand washing dishes. [Background technology]

[0002] Dishwashing detergents are widely used in homes to clean dishes, kitchenware, and cookware. These detergents typically contain a combination of surfactants, solvents, builders, and polymers to enhance grease removal and overall cleaning performance. However, many of the better-performing ingredients, particularly cleaning polymers, are either not biodegradable or are relatively slow-degrading.

[0003] There is a growing demand for more environmentally friendly dishwashing detergent compositions with improved biodegradability. After use, detergent compositions typically enter the household wastewater. While cleaning polymers improve the effectiveness of grease removal, many can take a long time to biodegrade in the wastewater.

[0004] Various attempts have been made to incorporate more biodegradable materials into detergent compositions. However, achieving a balance between improved biodegradability and effective cleaning, especially grease removal, remains a challenge.

[0005] Therefore, there is still a need for dishwashing detergent compositions that provide effective grease removal and sustained foaming properties in the presence of oily stains, while also utilizing cleaning ingredients with improved biodegradability.

[0006] Alvarez-Lorenzo et al. (Alvarez-Lorenzo, C. et al.; 2010; Front Biosci (Elite Ed); 1; 2(2); 424-40; doi: 10.2741 / e102) disclose alkoxylated diamines, namely the BASF Tetronic® series. These alkoxylates are X-type amphiphilic block copolymers formed by four arms of a poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block bonded to a central ethylenediamine moiety. In contrast to the alkoxylates used in the present invention, the disclosed polymers have a higher molecular weight (Mw) of at least 3600 g / mol or a propylene oxide content of less than 80% by weight relative to the total weight of the diamine alkoxylate. While the present invention relates to liquid detergent compositions for hand washing dishes, the polymers described by Alvarez-Lorenzo et al. are used to aid in drug delivery. Those skilled in the art would expect that Alvarez-Lorenzo's polymers having a molecular weight (Mw) exceeding 3200 g / mol are not significantly biodegradable, and that polymers having a propylene oxide content of less than 80% by weight relative to the total weight of the diamine alkoxylate do not exhibit significant cleaning performance. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Alvarez-Lorenzo et al. [Overview of the project] [Means for solving the problem]

[0008] The present invention relates to a liquid detergent composition for hand-washing dishes. The liquid detergent composition for hand-washing dishes comprises a surfactant system accounting for 5% to 50% by weight of the composition, the surfactant system being a surfactant system containing an anionic surfactant, and a diamine alkoxylate, wherein at least one of the NH-functional groups of the diamine is modified to form a polyalkylene oxide branch, each of at least one polyalkylene oxide branch contains ethylene oxide (EO) and propylene oxide (PO), the weight average molecular weight (Mw) of the diamine alkoxylate ranges from 1,200 g / mol to 3,200 g / mol, and the propylene oxide content is 65% to 95% by weight based on the total weight of the diamine alkoxylate.

Embodiments for Carrying out the Invention

[0009] As described herein, by formulating a liquid detergent composition for hand-washing dishes to contain a diamine alkoxylate, a composition is provided that has improved biodegradability, improved removal of oily stains, and improved foam persistence.

[0010] As used herein, and when used in the claims, the articles such as "a" and "an" are understood to mean one or more of what is claimed or described.

[0011] As used herein, the term "comprising" means that steps and components other than those specifically recited can be added. This term encompasses the terms "consisting of" and "consisting essentially of". The compositions of the present invention can include, consist of, and consist essentially of any of the essential elements and limitations of the invention described herein, as well as the additional or optional components, elements, steps, or limitations described herein.

[0012] As used herein, the term "tableware" includes, by way of non-limiting example, cooking utensils and tableware made from ceramic, porcelain, metal, glass, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.), and wood.

[0013] As used herein, the term "oil and fat" or "oily" means that a substance contains, at least in part (i.e., at least 0.5% by weight of oil and fat in the substance), saturated and unsaturated fats and oils, preferably oils and fats derived from animal raw materials such as beef, pork, and / or chicken.

[0014] The terms "include", "includes", and "including" are meant to be non-limiting.

[0015] As used herein, the term "particulate soil" means inorganic and especially organic solid soil particles, especially food particles, by way of non-limiting example, ultrafine particulate elemental carbon, fired oil and fat particles, and meat particles.

[0016] As used herein, the term “foaming profile” refers to the foaming properties of a composition during the dishwashing process. The “foaming profile” of a composition includes the dissolution and agitation of the composition in an aqueous cleaning solution, the initial foam volume typically generated during manual agitation, and the retention of foam during the dishwashing process. Preferably, a dishwashing composition characterized by having a “good foaming profile” tends to have high initial foam volume and / or foam volume persistence, particularly over a substantial portion or all of the dishwashing process. This is important because consumers use a lot of foam as an indicator that a sufficient amount of composition has been added. Furthermore, consumers also use persistence of foam volume, even towards the end of the dishwashing process, as an indicator that sufficient active cleaning components (e.g., surfactants) are present. Consumers typically refresh the cleaning solution when foaming decreases. Therefore, compositions with low foaming tend to be replaced more frequently than necessary by consumers due to their low foaming level.

[0017] "Easy rinsing" or "easy rinsing profile" means that foam generated during the main wash cycle can be rinsed away more quickly, and less water is used to eliminate foam from the main wash cycle. Eliminating foam more quickly is also desirable because it reduces the amount of time spent rinsing and the overall washing time. Reducing the amount of water used to eliminate foam is also desirable because it helps conserve water.

[0018] It is understood that the test methods disclosed in the Test Methods section of this application must be used to determine the values ​​of each parameter of the applicant's invention described herein and claimed.

[0019] Unless otherwise specified, all proportions are based on the total weight of the composition, as is evident from the context. Unless otherwise specified, all ratios are weight ratios, and all measurements are taken at 25°C.

[0020] Liquid detergent composition for hand washing dishes The composition is a liquid composition, specifically a liquid composition for hand washing dishes, and is therefore in liquid form. The liquid composition for hand washing dishes is preferably an aqueous composition. Therefore, the composition may contain 50% to 85% by weight, preferably 50% to 75% by weight, of water in the total composition.

[0021] The composition, when measured as a 10% desalted aqueous solution at 20°C, may have a pH of 6.0 or higher, or a pH of 6.0 to 12.0, preferably 7.0 to 11.0, and more preferably 7.5 to 10.0.

[0022] The compositions of the present invention typically have a lead time of 0.1 seconds. -1 ~100s -1 The composition may be Newtonian or non-Newtonian, preferably Newtonian, over the specified range of shear rates. Preferably, the composition, in the case of Newtonian, has a viscosity of 10 mPa·s to 10,000 mPa·s, preferably 100 mPa·s to 5,000 mPa·s, more preferably 300 mPa·s to 2,000 mPa·s, or most preferably 500 mPa·s to 1,500 mPa·s, or alternatively a combination thereof, over a typical range of shear rates, as measured according to the test methods described herein.

[0023] Diamine alkoxylate The liquid dishwashing detergent composition contains at least one diamine alkoxylate. For clarity, the term “diamine alkoxylate” refers herein to a compound derived from a diamine, which is called a “diamine core,” but does not necessarily have any unmodified amine group. The diamine alkoxylate may be present in the composition at a concentration of 0.05% to 5.0% by weight, more preferably 0.1% to 3.5% by weight, and most preferably 0.3% to 2.5% by weight.

[0024] In diamine alkoxylates, i. At least one of the NH-functional groups of the diamine is modified to form a polyalkylene oxide branch, ii. Each of at least one polyalkylene oxide branch comprises ethylene oxide (EO) and propylene oxide (PO), iii. The weight-average molecular weight (Mw) of the diamine alkoxylate is in the range of 1,200 g / mol to 3,200 g / mol. iv. The propylene oxide content is 65% to 95% by weight relative to the total weight of the diamine alkoxylate.

[0025] In the context of diamine alkoxylates used in this invention, the term "NH-functional group" is defined as follows: A primary amine group (-NH2) has two NH-functional groups, a secondary amine group has only one NH-functional group, and a tertiary amine group, as a result, does not have a reactive NH-functional group. Therefore, a diamine having two primary amine groups before modification has four NH-functional groups.

[0026] The diamine alkoxylates used in the present invention include a side chain, a (poly)alkylene oxide branch, directly bonded to the nitrogen atom of the NH-functional group of the diamine. The side chain is preferably composed of (only) ethylene oxide and propylene oxide. Typically, the side chain has an average of 6 to 20, preferably 7 to 13, AO units. The AO units used are usually evenly distributed across different branches, including moderate statistical variation. More detailed embodiments describing different chain lengths are provided below.

[0027] It should be noted that all such numbers are “average” numbers, meaning that such numbers refer to the average number of such units per NH-functional group calculated based on all NH-functional groups of the diamine alkoxylate.

[0028] The reaction yielding the compounds of the present invention is a statistical reaction, meaning that there is never just one chemically precisely defined compound. However, the diamine alkoxylates used in the present invention are always a mixture of slightly deviant structures, all originating from the same reaction within a single reaction space. These structural differences clearly arise from the fact that the reaction does not proceed in exactly the same way and at the same rate for all functional units, particularly because the chemical reactivity of the functional units, mainly the -NH groups, differs depending on their environment. This means that primary amine groups react differently to secondary amines, and the chemical environment of the groups can differ. This, overall, leads to the existence of slightly deviant structures. Therefore, it should be emphasized that the diamine alkoxylates used in the present invention as defined and described herein are not simply one compound, but always a mixture of slightly deviant compounds with a statistical distribution. Since the reactivity of these groups does not differ significantly, the deviations are relatively small. Thus, defining the diamine alkoxylates used in the present invention by prototype members is a viable method for defining the structure. Furthermore, defining the side chain composition by average number (including a variable defined in this embodiment and subsequent embodiments based on the number of NH-functional groups present in the diamine alkoxylate) is a useful way to define the overall composition of any mixture described herein as "diamine alkoxylate used in the present invention."

[0029] Therefore, unless otherwise indicated, the values, ranges, and ratios given herein for the number of NH-functional groups, weight-average molecular weight (Mw), and number-average molecular weight (Mn) relate to the average values ​​of heterogeneous mixtures of synthesized diamine alkoxylates, each containing slightly deviated chemical structures from the others, resulting from the preparation methods used. As is known in polymer science, polydispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is then a measure of homogeneity (heterogeneity) within a mixture of different types of “diamine alkoxylates”.

[0030] As used herein, the term “average number of AO(EO and / or PO) per polyalkylene oxide branch” refers to the calculated number of AO units that should be present in one polyalkylene 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 results in a mixture of slightly deviant compounds that form the basis of a statistical distribution. Thus, the “average number of AO per polyalkylene oxide branch” is calculated by dividing the total amount of moles of AO(EO+PO) used per mole of diamine by the number of NH-functional groups in the diamine.

[0031] With respect to diamines or diamine alkoxylates, the terms "essentially consisting of" or "consisting essentially of," as used interchangeably herein, mean that the compound may contain impurities or other types of compounds in amounts of up to 10 w / w%, 7.0 w / w%, 5.0 w / w%, 3.0 w / w%, 2.0 w / w%, 1.0 w / w%, 0.5 w / w%, or 0.1 w / w%.

[0032] It should be noted that the alkylene oxide used to prepare the compounds of the present invention may be derived from a fossil carbon source, a non-fossil carbon source, or a mixture 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 non-fossil carbon atoms. Those skilled in the art are well aware of commercially available alkylene oxide products made from non-fossil carbon sources (these products are often marketed as sustainable, renewable, or bio-based). For example, methods for preparing bio-based propylene oxide are known (see Abraham, DS, "Production of propylene oxide from propylene glycol," Master's Thesis University of Missouri-Columbia (2007) (page 75)).

[0033] Similarly, those skilled in the art recognize diamines based on non-fossil carbon atoms. In preferred diamine alkoxylates, at least 10%, at least 20%, at least 40%, at least 70%, at least 95%, or even 100% of the carbon atoms in the diamine are of non-fossil origin. For example, 1,4-diaminobutane (BDA) is widely produced on an industrial scale from renewable source materials (i.e., plants) by biotechnological processes (Li, Z. et al., 2018, J. Ind. Microbiol. Biotech., 45(2), pp. 123-139) or by microbiological pathways (Qian, Z. Get al., 2009, Biotech. Bioeng., 104(4), pp. 651-662).

[0034] Preferably, the propylene oxide content is 70% to 95% by weight, preferably 80% to 95% by weight, and more preferably 85% to 90% by weight, relative to the total weight of the diamine alkoxylate.

[0035] The diamine used to form the diamine alkoxylate (i.e., the diamine core) typically has two amine groups and may have one to four NH-functional groups. Preferably, the diamine has two primary amine groups (corresponding to four NH-functional groups). As used herein, the term “primary amine group” refers to the chemical group -NH2, where a dash indicates a bond to the rest of the amine. The diamine used to prepare the diamine alkoxylate of the present invention preferably had two of the above primary amine groups.

[0036] Each of the polyalkylene oxide branches of diamine alkoxylates, on average, a) at least one ethylene oxide unit (EO), and b) May contain or consist of at least five polypropylene oxide units (PO), preferably at least seven PO.

[0037] Each of the polyalkylene oxide branches of diamine alkoxylates, on average, a) Five or fewer EOs, preferably four or fewer EOs, preferably three or fewer EOs, preferably two or fewer EOs, and b) May include or consist of PO of 12 or less, preferably PO of 11 or less.

[0038] In a preferred embodiment, one alkylene oxide branch has an average molecular weight in the range of 300 g / mol to 1050 g / mol, preferably 350 g / mol to 750 g / mol.

[0039] Diamine alkoxylates having the above modifications may also be called "alkoxylated," "ethoxylated and propoxylated," and / or "modified."

[0040] Each of the polyalkylene oxide branches may contain blocks or random structures of ethylene oxide and propylene oxide, preferably a block structure, more preferably polyethylene oxide and polypropylene oxide blocks, and even more preferably the diamine is modified first with polypropylene oxide and then with polyethylene oxide blocks.

[0041] The (poly)alkylene oxide branch preferably has a block structure consisting of a (poly)PO block and a (poly)EO block, where the (poly)PO block reacts with the -NH2 group of the diamine. Alternatively, the polyalkylene oxide branch has a block structure consisting of a (poly)EO block and a (poly)PO block, where the (poly)EO block reacts with the -NH2 group of the diamine.

[0042] Those skilled in the art will understand that diamines may be alkoxylated with alkoxylates other than ethylene oxide or propoxylen oxide. In this context, butylene oxide is an example. Furthermore, those skilled in the art are also well aware of useful modifications of the alkoxy chain, such as modifications with lactones or hydroxycarboxylic acids described in International Publication No. 2021165468(A). More preferably, the diamine alkoxylate comprises alkoxylates selected from the group consisting of PO and EO.

[0043] The polyalkylene oxide branch may consist of ethylene oxide and propylene oxide. The polyalkylene oxide branch preferably ends with an -OH group, but may alternatively be capped with, for example, a C1-C20 alkyl group, preferably a C1-C6 alkyl group, more preferably a C1 alkyl group.

[0044] As used herein, the term "polyalkylene oxide branched" refers to a substructure of the compound of the present invention that includes, essentially consists of, or comprises multiple AO units, i.e., EO units and PO units.

[0045] In the diamine alkoxylate used in the present invention, at least three NH-functional groups, preferably all NH-functional groups, are modified with alkylene oxide (AO) units.

[0046] All polyalkylene oxide branches bonded to the NH-functional group of a diamine may have the same structure in the sense that the number of EO units and PO units per polyalkylene oxide branch is the same, or alternatively, the (poly)alkylene oxide branch structures may differ slightly.

[0047] While we do not wish to be bound by the following explanation, there is a basis for explaining the resulting structure of the diamine alkoxylates. The fact that the reaction in question, which is necessarily used to prepare these structural orders of the side chains and therefore to prepare the compounds of the present invention, is a highly reactive species of reaction that, under appropriate conditions, can yield nearly 100% if not 100%, nearly complete, and even "essentially complete" transformations, means that the statistical deviation of the composition of the mixture of "diamine alkoxylates" is not very high, and this means that the structural orders of the side chains do not deviate much. Therefore, the existence of such deviations is generally accepted as a reliable assumption that can be proven in principle by advanced, and therefore time-consuming and expensive, analytical means (such as multidimensional NMR analysis). Therefore, it is clear that a "specific diamine alkoxylate" is not "just one chemical compound with a clearly defined chemical structure," but rather a) consists of a mixture of slightly different compounds, b) the differences present in such slight deviations may already be present in the structure of the compounds constituting the "(unmodified) diamine" used in further modification steps, c) slight deviations in the structural order of the side chains may be added by d) multi-step reactions, e) due to variations in the chemical reactivity of the -NH2 group, and f) due to slight heterogeneity that occurs in commercial-scale processes. All of these factors a) to f), which are merely a few important ones, result in a "specific diamine alkoxylate" being not one specific chemical compound, but in fact a mixture of slightly different compounds with very similar chemical structures overall. Thus, such structures are best described by the average number of variables and the percentage of the amount of dominant structural order.

[0048] The weight-average molecular weight (Mw) of the diamine alkoxylate may be in the range of 1,500 g / mol to 3,000 g / mol, preferably in the range of 2,000 g / mol to 2,900 g / mol, and more preferably in the range of 2,500 g / mol to 2,800 g / mol.

[0049] The diamine used to produce the diamine alkoxylate may have a molecular weight in the range of 50 g / mol to 1500 g / mol, preferably 60 g / mol to 1000 g / mol, and more preferably 60 g / mol to 200 g / mol. Suitable diamines can be selected from the group consisting of 1,2-diaminoethane (EDA), 1,3-diaminopropane, 2,2-dimethyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, cyclohexyl-diamine, and methylcyclohexyl-diamine.

[0050] The diamine alkoxylate preferably exhibits at least 20%, preferably at least 40%, or more preferably at least 60% biodegradability after 56 days, preferably after 28 days, according to standard OECD 301F.

[0051] Diamine alkoxylates may include secondary amines derived from a primary amine group of a diamine modified with only a single polyalkylene oxide branch. As used herein, a secondary amine means an amine in which the nitrogen atom is bonded to two carbon atoms and one hydrogen atom. On the other hand, the compounds of the present invention may include a tertiary amine group derived from the reacted secondary amine group of the diamine and reacting with an additional polyalkylene oxide branch. Alternatively, preferably, the compounds of the present invention may include a tertiary amine group derived from a primary amine group of a diamine that is alkoxylated with a single or small amount of alkoxyl units and then reacts with an alkylene oxide monomer to obtain two polyalkylene oxide branches. As described above, in preferred embodiments, all (four) NH-functional groups are modified with alkylene oxide (AO) units, i.e., ethylene oxide (EO) units and propylene oxide (PO) units, meaning that these compounds contain only tertiary amine groups.

[0052] The amount of secondary amine groups in a diamine alkoxylate can be measured by methods known to those skilled in the art, such as NMR spectroscopy, for example, 13C NMR spectroscopy and / or 1H NMR spectroscopy.

[0053] Suitable diamine alkoxylates can be prepared by a process in which a diamine having at least two, preferably two, primary amine groups is reacted with (i) at least 20 propylene oxide molecules and (ii) at least 4 ethylene oxide molecules to obtain each diamine alkoxylate.

[0054] Diamines can be reacted with (i) 3 to 32, 4 to 16, or 4 to 9 ethylene oxide molecules and (ii) 16 to 50, 18 to 48, or 20 to 45 propylene oxide molecules to obtain each diamine alkoxylate.

[0055] The diamine is preferably selected from the group consisting of 1,2-diaminoethane (EDA), 1,3-diaminopropane, 2,2-dimethyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, cyclohexyl-diamine, and methylcyclohexyl-diamine.

[0056] The conversion rate of the reaction step may be monitored, and in a preferred embodiment, the conversion rate of this step is at least 95%, preferably at least 99%, and more preferably at least 99.5%. All other structural orders of the side chains defined above, as well as undefined structures resulting from uncontrollable parameters, are carried out in this defined manner, and the statistical mean yields the defined structural orders that are directly derived from the manner in which such reactions are carried out.

[0057] The conversion rate of the reaction can be determined by methods known to those skilled in the art, for example, by NMR spectroscopy such as 13C-NMR spectroscopy and / or 1H-NMR spectroscopy.

[0058] Preferred reaction conditions, such as catalysts, temperature, duration, and purification, for generating side chain units of diamine alkoxylates can be obtained from the disclosures of European Patent Application Publication No. 3298120(A), Japanese Patent Publication No. 2022056680(A), and U.S. Patent No. 7468348(B).

[0059] Alkoxylation can be carried out in the presence of at least one catalyst. In this step reaction of the alkoxylation process, the catalyst is preferably a basic catalyst. Examples of suitable catalysts are alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; alkali metal alkoxides, particularly sodium and potassium C1-C4 alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; alkali metal and alkaline earth metal hydrides such as sodium hydride and calcium hydride; and alkali metal carbonates such as sodium carbonate and potassium carbonate. Alkali metal hydroxides and alkali metal alkoxides are preferred, with potassium hydroxide and sodium hydroxide being particularly preferred. The typical amount of base used is 0.05% to 10% by weight, particularly 0.05% to 2% by weight, of the final product, based on the total amount of diamine and alkylene oxide.

[0060] Diamine alkoxylates are produced in the following process steps: a) Purification using standard means such as steam distillation, thermal distillation, vacuum evaporation, including removal of all solvents and dialysis, and / or b) Further drying using standard drying methods such as spray drying, drum drying, paddle drying, and vacuum drying, including flocculation methods such as fluidized bed drying. A purified solution, a purified liquid, a solid compound, or a purified solid compound can be obtained.

[0061] If, after the reaction yielding the diamine alkoxylate used in the present invention, an undesirable amount of residual extract (diamine and / or alkylene oxide) is present, the resulting product mixture containing the diamine alkoxylate may be further purified by standard means to reduce the amount of residual extract, reduce the amount of any by-products, reduce the amount of solvent used (i.e., concentrate it), or replace the solvent with another solvent. Such processes are known to those skilled in the art.

[0062] Preferably, any undesirable amount of residual unreacted extract is removed, preferably by a distillation process, more preferably by a thermal distillation process, which may further include the application of reduced pressure to increase the rate and / or effectiveness of removal.

[0063] In a preferred embodiment, only the additional process step a) is used.

[0064] With respect to diamine cores, the terms "essentially having" or "having essentially" as used interchangeably herein mean that the diamine core may contain impurities or other types of amines in amounts of up to 10 w / w%, 7 w / w%, 5 w / w%, 3 w / w%, 2 w / w%, 1 w / w%, 0.5 w / w%, or 0.1 w / w%.

[0065] Surfactant-based The liquid composition contains a surfactant system in an amount of 5.0% to 50% by weight, preferably 6.0% to 40% by weight, and most preferably 15% to 35% by weight of the total composition.

[0066] Anionic surfactants The surfactant system includes an anionic surfactant. The surfactant system may contain at least 40% by weight, preferably 50% to 90% by weight, and more preferably 65% ​​to 85% by weight of anionic surfactant. Since fatty acids hinder foam formation, the surfactant system preferably does not contain fatty acids or their salts.

[0067] Suitable anionic surfactants can be selected from the group consisting of alkyl sulfate surfactants, alkyl alkoxy sulfate surfactants, alkyl sulfonate surfactants, alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants, and mixtures thereof.

[0068] The anionic surfactant may include at least 70% by weight, preferably at least 85% by weight, more preferably 100% by weight of an alkyl sulfate anionic surfactant, an alkyl alkoxy sulfate anionic surfactant, or a mixture thereof.

[0069] To provide a combination of improved grease removal and enhanced cleaning speed, the molar-average alkyl chain length of the alkyl sulfate anionic surfactant or alkyl alkoxy sulfate anionic surfactant may be 8 to 18 carbon atoms, preferably 10 to 14, more preferably 12 to 14, and most preferably 12 to 13 carbon atoms.

[0070] The alkyl chain of an alkyl sulfate anionic surfactant or alkyl alkoxy sulfate anionic surfactant may have a mole fraction of C12 and C13 chains of at least 50%, preferably at least 65%, more preferably at least 80%, and most preferably at least 90%. When the C13 / C12 molar ratio of the alkyl chain is at least 57 / 43, preferably 60 / 40 to 90 / 10, more preferably 60 / 40 to 80 / 20, and most preferably 60 / 40 to 70 / 30, foam persistence is particularly improved, especially in the presence of oily contaminants, while foam persistence is not impaired in the presence of particulate matter.

[0071] The relative molar amounts of C13 alkyl chains and C12 alkyl chains in alkyl sulfate anionic surfactants or alkyl alkoxy sulfate anionic surfactants can be derived from the carbon chain length distribution of the surfactant. The carbon chain length distribution of the alkyl chains in alkyl sulfate surfactants and alkyl alkoxy sulfate surfactants can be obtained from the technical data sheets of the suppliers of the surfactant or the alkyl alcohols that constitute it. Alternatively, the chain length distribution and average molecular weight of the aliphatic alcohols used to prepare alkyl sulfate anionic surfactants or alkyl alkoxy sulfate anionic surfactants can also be determined by methods known in the art. Such methods include capillary gas chromatography with flame ionization detection in a medium-polarity capillary column using hexane as the solvent. The chain length distribution is based on the starting alcohol and the alkoxylated alcohol. Therefore, alkyl sulfate anionic surfactants must be hydrolyzed back to the corresponding alkyl alcohol and alkyl alkoxylated alcohol, for example, using hydrochloric acid, before analysis.

[0072] Alkylalkoxysulfate surfactants may have an average degree of alkoxylation of less than 3.5, preferably less than 2.0, and more preferably 1.0 or less. Alternatively, alkylalkoxysulfate surfactants may have an average degree of alkoxylation of less than 3.5, preferably 0.3 to 2.0, and more preferably 0.5 to 0.9, in order to improve the physical stability of the composition of the present invention at low temperatures and improve foam persistence. When alkoxylation is performed, ethoxylation is preferred.

[0073] The average degree of alkoxylation is the molar average degree of alkoxylation of all alkyl sulfate anionic surfactants (i.e., the molar average degree of alkoxylation). Therefore, when calculating the molar average degree of alkoxylation, the number of moles of non-alkoxylated sulfate anionic surfactants is included. Molar average degree of alkoxylation = (x1* Degree of alkoxylation of surfactant 1 +x2 * Degree of alkoxylation of surfactant 2 + ...) / (x1 + x2 + ...) In the formula, x1, x2, ... are the number of moles of each alkyl (or alkoxy) sulfate anionic surfactant in the mixture, and the degree of alkoxylation is the number of alkoxy groups in each alkyl sulfate anionic surfactant.

[0074] A preferred alkylalkoxy sulfate is an alkylethoxysulfate.

[0075] Alkyl sulfate anionic surfactants and alkyl alkoxy sulfate anionic surfactants may have a weight-average branching degree of at least 10%, preferably 20% to 60%, and more preferably 25% to 45%. Alternatively, alkyl sulfate anionic surfactants and alkyl alkoxy sulfate anionic surfactants may have a weight-average branching degree of less than 10%, and preferably, alkyl sulfate anionic surfactants and alkyl alkoxy sulfate anionic surfactants are non-branched.

[0076] Alkyl sulfate anionic surfactants and alkyl alkoxy sulfate anionic surfactants can contain at least 5% by weight, preferably at least 10% by weight, and most preferably at least 25% by weight of branching at the C2 position (measured by counting carbon atoms from the sulfate group for non-alkoxylated alkyl sulfate anionic surfactants and from the alkoxy group furthest from the sulfate group for alkoxylated alkyl sulfate anionic surfactants). More preferably, more than 75% by weight, and even more preferably more than 90% by weight of the total branched alkyl content consists of a C1-C5 alkyl moiety, preferably a C1-C2 alkyl moiety. It has been found that low-temperature stability is improved by formulating the compositions of the present invention using alkyl sulfate surfactants or alkyl alkoxy sulfate surfactants having the above degree of branching. Such compositions require less solvent to achieve good physical stability at low temperatures. Therefore, the compositions can contain lower concentrations of organic solvents, such as less than 5.0% by weight of the liquid composition, while still having improved low-temperature stability. Furthermore, while a higher degree of branching in the surfactant leads to faster initial foam formation, it typically results in lower foam persistence. The weight-average branching described herein has been found to result in improved low-temperature stability, initial foam formation, and foam persistence.

[0077] The weight-average branching degree of anionic surfactant mixtures can be calculated using the following formula. Weight-average branching degree (%) = [(x1 * Weight % of branched-chain alcohol 1 in alcohol 1 + x2 * (Weight of branched-chain alcohol 2 in alcohol 2 % + ....) / (x1 + x2 + ....)] * 100 In the formula, x1, x2, ... are the weights (grams) of each alcohol in the total alcohol mixture of alcohols used as starting materials before (alkoxylation and) sulfation to produce alkyl (alkoxy) sulfate anionic surfactants. The weight-average degree of branching calculation includes the weight of the alkyl alcohols used to form the unbranched alkyl sulfate anionic surfactant.

[0078] The weight-average degree of branching and branching distribution can usually be obtained from the technical data sheet of the surfactant or the alkyl alcohol constituting it. Alternatively, branching can also be determined through analytical methods known in the art, including capillary gas chromatography with flame ionization detection in a medium-polarity capillary column using hexane as the solvent. The weight-average degree of branching and branching distribution are based on the starting alcohol used to produce the alkyl sulfate anionic surfactant.

[0079] Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, but sodium is preferred.

[0080] Suitable examples of commercially available alkyl sulfate anionic surfactants include those derived from alcohols sold by Shell under the trademark Neodol®, or by Sasol under the trademarks Lial®, Isalchem®, and Safol®, or some of the natural alcohols manufactured by Procter & Gamble Chemicals. Based on the relative fractions of C13 and C12 in the starting alcohols obtained from technical data sheets from suppliers or from analysis using methods known in the art, alcohols can be blended to achieve the desired mole fractions of C12 and C13 chains and the desired C13 / C12 ratio.

[0081] The performance characteristics, including oil and grease cleaning, foaming, low-temperature stability, and viscosity of the final product, can be influenced by the width of the alkoxylation distribution of the alkoxylated alkyl sulfate anionic surfactant. The alkoxylation distribution, including its width, can be altered through the selection of catalysts and process conditions when preparing alkoxylated alkyl sulfate anionic surfactants.

[0082] While not wishing to be constrained by theory, in the presence of ethoxylated alkyl sulfates, the amount of 1,4-dioxane byproducts in alkoxylation, particularly ethoxylated alkyl sulfates, can be reduced by strictly controlling the processing conditions and raw material composition during both the ethoxylation and sulfation steps. Based on recent technological advances, further reduction of 1,4-dioxane byproducts can be achieved by subsequent stripping, distillation, solvent evaporation, centrifugation, microwave irradiation, molecular sieving, or catalytic or enzymatic decomposition steps. Processes for controlling the 1,4-dioxane content in alkoxylated / ethoxylated alkyl sulfates have been widely described in the art. Alternatively, control of the 1,4-dioxane concentration in detergent formulations by adding 1,4-dioxane inhibitors such as 5,6-dihydro-3-(4-morpholinyl)-1-[4-(2-oxo-1-piperidinyl)-phenyl]-2-(1-H)-pyridone, a mixture of 3-alpha-hydroxy-7-oxo stereoisomers of cholanaic acid, 3-(N-methylamino)-L-alanine, and mixtures thereof to formulations containing 1,4-dioxane has also been described in the art.

[0083] Suitable anionic alkyl sulfonate or sulfonic acid surfactants for use herein include alkylbenzene sulfonates, alkyl ester sulfonates, primary and secondary alkanesulfonates (such as paraffin sulfonates), alpha or internal olefin sulfonates, alkyl sulfonated (poly)carboxylic acids, and mixtures thereof, in acid and salt forms. Suitable anionic sulfonate or sulfonic acid surfactants include C5-C20 alkylbenzene sulfonates, more preferably C10-C16 alkylbenzene sulfonates, more preferably C11-C13 alkylbenzene sulfonates, C5-C20 alkyl ester sulfonates, particularly C5-C20 methyl ester sulfonates, C6-C22 primary or secondary alkanesulfonates, C5-C20 sulfonated (poly)carboxylic acids, and any mixtures thereof, with C11-C13 alkylbenzene sulfonates being preferred. The above surfactants can vary widely in their 2-phenyl isomer content. Compared to the sulfonation of alpha-olefins, the sulfonation of internal olefins can occur at any position because the double bond is randomly positioned. This allows for various twin-tail branched structures, with the hydrophilic sulfonate and hydroxyl group of IOS located in the center of the alkyl chain. Examples of alkanesulfonates include paraffin sulfonates and other secondary alkanesulfonates (such as Hostapur SAS60 from Clariant).

[0084] Alkyl sulfosuccinates and dialkyl sulfosuccinate esters are organic compounds having the formula MO3SCH(CO2R')CH2CO2R, where R and R' can be H or alkyl groups, and M is a counterion such as sodium (Na). Alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants may be alkoxylated or non-alkoxylated, preferably non-alkoxylated. This surfactant system may contain further anionic surfactants. However, the composition preferably contains less than 30% by weight, preferably less than 15% by weight, and more preferably less than 10% by weight of the surfactant system as further anionic surfactants. Most preferably, the surfactant system does not contain further anionic surfactants, preferably anionic surfactants other than alkyl sulfate anionic surfactants.

[0085] auxiliary surfactants To improve surfactant filling after dilution and therefore foam persistence, the surfactant system may include auxiliary surfactants selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

[0086] The weight ratio of the anionic surfactant to the auxiliary surfactant may be 1:1 to 8:1, preferably 2:1 to 5:1, and more preferably 2.5:1 to 4:1.

[0087] The composition preferably contains 0.1% to 20% by weight, more preferably 0.5% to 15% by weight, and especially 2% to 10% by weight of auxiliary surfactants of the cleaning composition.

[0088] The surfactant system of the cleaning composition of the present invention preferably contains an auxiliary surfactant of up to 50% by weight of the surfactant system, preferably 10% to 40% by weight, and more preferably 15% to 35% by weight.

[0089] The auxiliary surfactant is preferably an amphoteric surfactant, more preferably an amine oxide surfactant.

[0090] Amine oxide surfactants may be linear or branched, but linear is preferred. Preferred linear amine oxides are typically water-soluble and characterized by the formula R1-N(R2)(R3)O. R1 is a C8-18 alkyl group, preferably a linear alkyl chain, more preferably derived from a natural renewable source such as coconut or palm kernel, with coconut being particularly preferred. The R2 and R3 portions are selected from the group consisting of C1-3 alkyl groups, C1-3 hydroxyalkyl groups, and mixtures thereof. For example, R2 and R3 can be selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl, and mixtures thereof, but it is preferable that one or both of R2 and R3 are methyl. Examples of linear amine oxide surfactants include linear C10-C18 alkyldimethylamine oxides and linear C8-C12 alkoxyethyl dihydroxyethylamine oxides.

[0091] Preferably, the amine oxide surfactant is selected from the group consisting of alkyldimethylamine oxide, alkylamidopropyldimethylamine oxide, and mixtures thereof.

[0092] Alkyldimethylamine oxides such as C8-18 alkyldimethylamine oxide or C10-16 alkyldimethylamine oxide (cocodimethylamine oxide, etc.) are particularly preferred. Suitable alkyldimethylamine oxides include C10 alkyldimethylamine oxide surfactants, C10-12 alkyldimethylamine oxide surfactants, C12-C14 alkyldimethylamine oxide surfactants, and mixtures thereof. C12-C14 alkyldimethylamine oxide is particularly preferred.

[0093] A suitable alternative amine oxide surfactant is a moderately branched amine oxide surfactant. As used herein, “moderately branched” means that the amine oxide has one alkyl moiety having n1 carbon atoms, and one alkyl branch in the alkyl moiety has n2 carbon atoms. The alkyl branch is located from the nitrogen to the alpha carbon on the alkyl moiety. This type of branching of amine oxide is also known in the art as internal amine oxide. The sum of n1 and n2 may be 10 to 24, preferably 12 to 20, and more preferably 10 to 16 carbon atoms. The number of carbon atoms in one alkyl moiety (n1) is preferably the same as or similar to the number of carbon atoms in one alkyl branch (n2), so that the alkyl moiety and its alkyl branch are symmetrical. As used herein, “symmetrical” means that in at least 50% by weight, more preferably at least 75% to 100% by weight of the moderately branched amine oxide used herein, |n1-n2| has 5 or fewer, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two portions independently selected from C1-3 alkyl, C1-3 hydroxyalkyl, or polyethylene oxide groups containing an average of about 1 to about 3 ethylene oxide groups. Preferably, these two portions are selected from C1-3 alkyl, and more preferably, both are selected as C1 alkyl.

[0094] Alternatively, the amine oxide surfactant may be a mixture of amine oxides, including a mixture of low-cut amine oxides and mid-cut amine oxides. Therefore, the amine oxides in the composition of the present invention are a) A low-cut amine oxide of formula R1R2R3AO in an amount of approximately 10% to approximately 45% by weight of amine oxide, where R1 and R2 are independently selected from hydrogen, C1-C4 alkyl, or mixtures thereof, and R3 is selected from C10 alkyl and mixtures thereof. b) 55% to 90% by weight of an amine oxide, a mid-cut amine oxide of the formula R4R5R6AO, wherein R4 and R5 are independently selected from hydrogen, C1-C4 alkyl, or mixtures thereof, and R6 is selected from C12-C16 alkyl or mixtures thereof, can be included.

[0095] In the low-cut amine oxide preferably used herein, R3 is n-decyl, and preferably both R1 and R2 are methyl. In the mid-cut amine oxide of the formula R4R5R6AO, preferably both R4 and R5 are methyl.

[0096] Preferably, the amine oxide contains less than about 5% by weight, more preferably less than 3% by weight, of an amine oxide of the formula R7R8R9AO, wherein R7 and R8 are selected from hydrogen, C1-C4 alkyl, and mixtures thereof, and R9 is selected from C8 alkyl and mixtures thereof. By limiting the amount of the amine oxide of the formula R7R8R9AO, both physical stability and foam persistence are improved.

[0097] Suitable zwitterionic surfactants include betaine surfactants. Such betaine surfactants include alkyl betaines, alkyl amide betaines, amido azolinium betaines, sulfobetaines (INCI sultaines), phosphobetaines, and mixtures thereof, and preferably satisfy the following formula (I). R 1 -[CO-X(CH2) n x -N + (R 2 )(R3)-(CH2) m -[CH(OH)-CH2] y -Y - <0​​​R1 is selected from the group consisting of saturated or unsaturated C6-22 alkyl residues, preferably C8-18 alkyl residues, more preferably saturated C10-16 alkyl residues, and most preferably saturated C12-14 alkyl residues. R1 is preferably a linear alkyl chain and preferably derived from a natural renewable source such as coconut or palm kernel, preferably coconut. X is selected from the group consisting of NH, NR4 (where R4 is a C1-4 alkyl residue), O, and S. n is an integer between 1 and 10, preferably between 2 and 5, more preferably between 3. x is 0 or 1, preferably 1. R2 and R3 are independently selected from the group consisting of C1-4 alkyl residues, substituted hydroxyls such as hydroxyethyl, and mixtures thereof, preferably both R2 and R3 are methyl. m is an integer between 1 and 4, preferably 1, 2, or 3. y is either 0 or 1. Y is selected from the group consisting of COO, SO3, OPO(OR5)O, or P(O)(OR5)O (wherein R5 is H or C1-4 alkyl residues).

[0098] Preferred betaines are alkylbetaine of formula (Ia), alkylamidopropylbetaine of formula (Ib), sulfobetaine of formula (Ic), and amidesulfobetaine of formula (Id). R 1 -N + (CH3)2-CH2COO - (IIa) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2COO - (IIb) R 1 -N + (CH3)2-CH2CH(OH)CH2SO3 - (IIc) R 1 -CO-NH-(CH2)3-N + (CH3)2-CH2CH(OH)CH2SO3 - (IId) In the formula, R1 has the same meaning as in formula (I). Particularly preferred are the carbobetaines of formulas (Ia) and (Ib) [i.e., in formula (I), Y- is COO-], and more preferred is the alkylamide betaine of formula (Ib).

[0099] Preferred betaines can be selected from the group consisting of capryl / capramidopropyl betaine, cetyl betaine, cetylamidopropyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocobetaine, decyl betaine, decylamidopropyl betaine, hydrogenated taro betaine / amidopropyl betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, myristylamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleyl betaine, palmamidopropyl betaine, palmitoamidopropyl betaine, palm kernelamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, taroamidopropyl betaine, taro betaine, undecylenamidopropyl betaine, undecyl betaine, and mixtures thereof, or [named according to INCI]. Preferred betaines are selected from the group consisting of cocamidopropyl betaine, cocobetaine, lauramidopropyl betaine, lauryl betaine, myristylamidopropyl betaine, myristyl betaine, and mixtures thereof. Cocamidopropyl betaine and / or laurylamidopropyl betaine are particularly preferred.

[0100] Nonionic surfactants This surfactant system may further contain a nonionic surfactant. Suitable nonionic surfactants include alkoxylated alcohol nonionic surfactants, alkyl polyglucoside nonionic surfactants, and mixtures thereof, with alkoxylated alcohol nonionic surfactants being preferred.

[0101] Alkoxylated alcohol nonionic surfactant The surfactant system of the composition of the present invention may, if present, contain 0.1% to 10% by weight, preferably 2.0% to 9.0% by weight, and more preferably 4.0% to 8.0% by weight of an alkoxylated alcohol nonionic surfactant of the detergent composition.

[0102] Preferably, the alkoxylated alcohol nonionic surfactant is a linear or branched primary or secondary alkylalkoxylated nonionic surfactant, preferably an alkylethoxylated nonionic surfactant, which preferably contains an average of 9 to 15 carbon atoms, preferably 10 to 14 carbon atoms, and an average of 5 to 12, preferably 6 to 10, most preferably 7 to 8 units of ethylene oxide per mole of alcohol.

[0103] Alkyl polyglucoside nonionic surfactant Alkyl polyglucosides, if present, can be found in the surfactant system at a concentration of 0.1% to 10% by weight, preferably 2.0% to 9.0% by weight, and more preferably 4.0% to 8.0% by weight of the detergent composition. Alkyl polyglucoside nonionic surfactants typically produce more foam than other nonionic surfactants such as alkyl ethoxylated alcohols.

[0104] The combination of alkyl polyglucosides with anionic surfactants, particularly alkyl sulfate anionic surfactants, has been found to improve polymerized oil removal, foam retention, viscosity changes due to changes in surfactants and / or systems, and more sustainable Newtonian rheology.

[0105] Alkyl polyglucoside surfactants can be selected from C6-C18 alkyl polyglucoside surfactants. Alkyl polyglucoside surfactants can have a number average degree of polymerization of 0.1-3.0, preferably 1.0-2.0, and more preferably 1.2-1.6. Alkyl polyglucoside surfactants can include blends of short-chain alkyl polyglucoside surfactants having alkyl chains containing 10 or fewer carbon atoms and medium- to long-chain alkyl polyglucoside surfactants having alkyl chains containing more than 10 to 18 carbon atoms, preferably 12-14 carbon atoms.

[0106] Short-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C8-C10, medium-to-long-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C10-C18, while medium-chain alkyl polyglucoside surfactants have a monomodal chain length distribution of C12-C14. In contrast, C8-C18 alkyl polyglucoside surfactants typically have a monomodal distribution of alkyl chains of C8-C18, such as C8-C16. Therefore, combinations of short-chain alkyl polyglucoside surfactants with medium-to-long-chain or medium-chain alkyl polyglucoside surfactants have a broader chain length distribution, or even a bimodal distribution, than unblended C8-C18 alkyl polyglucoside surfactants. Preferably, the weight ratio of short-chain alkyl polyglucoside surfactant to long-chain alkyl polyglucoside surfactant is 1:1 to 10:1, preferably 1.5:1 to 5:1, and more preferably 2:1 to 4:1. Such blends of short-chain alkyl polyglucoside surfactants and long-chain alkyl polyglucoside surfactants have been found to result in faster dissolution and improved initial foaming of the detergent aqueous solution, combined with improved foam stability.

[0107] C8-C16 alkyl polyglycosides are commercially available from several suppliers (e.g., Seppic's Simusol® surfactant, and BASF's Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP / MB, and Glucopon® 650 EC / MB). Glucopon® 215UP is a preferred short-chain APG surfactant. Glucopon® 600CSUP is a preferred medium-to-long-chain APG surfactant.

[0108] In a preferred composition, the surfactant system may include an alkyl sulfate anionic surfactant having an average degree of branching of less than 10% and an alkyl polyglucoside nonionic surfactant.

[0109] divalent salt The composition is preferably a divalent metal salt, preferably a salt of calcium or magnesium (Ca 2+ Salt or Mg 2+ Contains salts. Suitable divalent salts include magnesium and / or calcium chloride salts, sulfates, carbonates, bicarbonates, linear alkylbenzene sulfons, and mixtures thereof, with magnesium salts being particularly preferred. Magnesium chloride salts, sulfates, linear alkylbenzene sulfons, and mixtures thereof are particularly preferred, magnesium chloride salts, sulfates, and mixtures thereof are even more particularly preferred, and magnesium chloride is most preferred.

[0110] When calcium salts are present, magnesium ions and calcium ions are preferably present in a molar ratio of 1:1 or higher, preferably 1.5:1 or higher, and preferably 2:1 or higher.

[0111] Compositions of the present invention further containing such divalent salts have been found to not only improve cleaning power but also reduce the slipperiness of tableware after washing with such compositions. It is believed that residual anionic surfactants remain somewhat on the tableware, and the presence of divalent ions reduces electrostatic interactions between residual anionic surfactants, thereby improving cleaning power and reducing slipperiness, especially when the tableware is washed with soft water having a hardness of less than 1.25 mmol / L of calcium equivalent.

[0112] The divalent salt is preferably water-soluble. As used herein, the term "water-soluble" refers to a compound that can dissolve in water at a concentration of more than 1.0% by weight in distilled water at 21°C.

[0113] Further ingredients The composition may include further components, such as triblock copolymers, hydrotropes, organic solvents, other auxiliary components such as those described herein, and mixtures thereof, selected from among them.

[0114] Triblock copolymer The composition of the present invention may contain a triblock copolymer. The triblock copolymer may be present in a concentration of 1% to 20% by weight, preferably 3% to 15% by weight, and more preferably 5% to 12% by weight of the total composition. A suitable triblock copolymer is given by formula (I):(EO) x (PO) y (EO) xThe alkylene oxide triblock copolymer is defined as a triblock copolymer having an alkylene oxide moiety, wherein EO represents ethylene oxide, and each x represents the number of EO units in the EO block. Each x can independently be 5 to 50 on average, preferably 10 to 40, and more preferably 10 to 30. Preferably, x is the same for both EO blocks, where “same” means that the difference in x between the two EO blocks is at most 2 units, preferably at most 1 unit, and more preferably both x are the same number of units. PO represents propylene oxide, and y represents the number of PO units in the PO block. Each y can be 28 to 60 on average, preferably 30 to 55, and more preferably 30 to 48.

[0115] Preferably, the ratio of y to each x in the triblock copolymer is 3:1 to 2:1. Preferably, the ratio of y to the average x of the two EO blocks in the triblock copolymer is 3:1 to 2:1. Preferably, the triblock copolymer has an average weight percentage of all EO that is 30% to 50% by weight of the triblock copolymer. Preferably, the triblock copolymer has an average weight percentage of all PO that is 50% to 70% by weight of the triblock copolymer. It is understood that the average total weight percentage of EO and PO in the triblock copolymer is 100%. The triblock copolymer can have an average molecular weight of 2060 to 7880, preferably 2620 to 6710, more preferably 2620 to 5430, and most preferably 2800 to 4700. The average molecular weight is determined using 1H NMR spectroscopy (see Thermo Scientific Application Note No. AN52907).

[0116] A triblock copolymer has a basic structure ABA, where A and B are different homopolymer and / or monomer units. In this case, A is ethylene oxide (EO) and B is propylene oxide (PO). Those skilled in the art will recognize that the phrase “block copolymer” is synonymous with this definition of “block polymer.”

[0117] Triblock copolymers according to formula (I), having specific EO / PO / EO configurations and respective homopolymer lengths, have been found to enhance the foam retention performance and / or foam consistency throughout dilution in dishwashing liquid detergent compositions in the presence of oily stains.

[0118] Suitable EO-PO-EO triblock copolymers are commercially available from BASF, such as the Pluronic® PE series, and from Dow Chemical, such as the Tergitol® L series. BASF's particularly preferred triblock copolymers are sold under the trademark names Pluronic® PE6400 (approximately 2900 MW, approximately 40% by weight EO) and Pluronic® PE 9400 (approximately 4600 MW, approximately 40% by weight EO). Dow Chemical's particularly preferred triblock copolymer is sold under the trademark name Tergitol® L64 (approximately 2700 MW, approximately 40% by weight EO).

[0119] Preferred triblock copolymers readily biodegrade under aerobic conditions.

[0120] Cyclic polyamines The composition may contain a cyclic polyamine having an amine functional group that aids in cleaning. The composition of the present invention preferably contains 0.1% to 3% by weight, more preferably 0.2% to 2% by weight, and particularly 0.5% to 1% by weight of a cyclic polyamine.

[0121] Cyclic polyamines have at least two primary amine functional groups. While primary amines can be located at any position within the cyclic amine, it has been found that better performance is obtained when the primary amines are located at positions 1 and 3, from the viewpoint of grease and oil cleaning. It has also been found that cyclic amines in which one substituent is -CH3 and the rest are H atoms result in improved grease and oil cleaning performance.

[0122] Therefore, the most preferred cyclic polyamines for use in the cleaning compositions of the present invention are cyclic polyamines selected from the group consisting of 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, and mixtures thereof. When these particular cyclic polyamines are formulated with the surfactant system of the compositions of the present invention, they function to improve the foam and grease-cleaning profile throughout the dishwashing process.

[0123] Suitable cyclic polyamines can be supplied by BASF under the trademark name Baxxodur, with Baxxodur ECX-210 being particularly preferred.

[0124] A combination of cyclic polyamine and magnesium sulfate is particularly preferred. Therefore, the composition may further contain magnesium sulfate at a concentration of 0.001% to 2.0% by weight, preferably 0.005% to 1.0% by weight, and more preferably 0.01% to 0.5% by weight of the composition.

[0125] Salts, hydrotropes, organic solvents The compositions of the present invention may further comprise at least one active substance selected from the group consisting of i) salts, ii) hydrotropes, iii) organic solvents, and mixtures thereof.

[0126] The compositions of the present invention may contain, more preferably, about 0.05% to about 2% by weight, preferably about 0.1% to about 1.5% by weight, or more preferably about 0.5% to about 1% by weight of a salt, preferably a monovalent or divalent inorganic salt, or a mixture thereof, more preferably a salt selected from sodium chloride, sodium sulfate, and mixtures thereof. Sodium chloride is most preferred.

[0127] The composition of the present invention may contain about 0.1% to about 10% by weight of hydrotopes or mixtures thereof, preferably sodium cumenesulfonate, in an amount of about 0.1% to about 10% by weight of the whole composition, or preferably about 0.5% to about 10% by weight, or more preferably about 1% to about 10% by weight.

[0128] The composition may contain an organic solvent in an amount of about 0.1% to about 10% by weight of the total composition, preferably about 0.5% to about 10% by weight, or more preferably about 1% to about 10% by weight. Suitable organic solvents include those selected from the group consisting of alcohols, glycols, glycol ethers, and mixtures thereof, with alcohols, glycols, and mixtures thereof being preferred. Ethanol is a preferred alcohol. Polyalkylene glycols, particularly polypropylene glycols, are preferred glycols, with polypropylene glycols having a weight-average molecular weight of 750 Da to 1,400 Da being particularly preferred.

[0129] auxiliary ingredients The composition may optionally contain a number of other auxiliary components such as builders (preferably citrates), chelating agents, conditioning polymers, other cleansing polymers, surface modifying polymers, structuring agents, emollients, wetting agents, skin rejuvenating active substances, enzymes, carboxylic acids, scrub particles, fragrances, odor suppressants, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such as alkaline earth metals like Ca / Mg ions, antimicrobial agents, preservatives, viscosity modifiers (e.g., salts such as NaCl and other monovalent, divalent, and trivalent salts), and pH adjusters and buffering means (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, and carbonates such as sodium carbonate, bicarbonates, and sesquicarbonates).

[0130] Packaged Products The dishwashing detergent composition for hand washing can be packaged in a container, typically a plastic container. A suitable container includes an orifice. Suitable containers include conventional upright dispensers where the orifice is located at the top of the container, and inverted / bottom dispensers where the orifice is located at the bottom of the container. In the case of inverted / bottom dispensers, the orifice may be capped and / or equipped with a slit valve, as described in U.S. Patent No. 10,611,531. Typically, the container has a cap, and the orifice is typically located on the cap. The cap may have a spout, and the orifice is located at the outlet of the spout. The spout may have a length of 0.5 mm to 10 mm.

[0131] The orifice may have an opening cross-sectional area of ​​3 mm² to 20 mm², preferably 3.8 mm² to 12 mm², more preferably 5 mm² to 10 mm² at the outlet, and the container further comprises the composition according to the present invention. The cross-sectional area is measured perpendicular to the liquid outlet from the container (i.e., perpendicular to the liquid flow during distribution).

[0132] The container can typically contain a liquid dishwashing detergent composition in a volume of 200 mL to 5,000 mL, preferably 350 mL to 2,000 mL, and more preferably 400 mL to 1,000 mL.

[0133] Cleaning method The present invention further relates to a method for manually washing tableware with the composition of the present invention. This method includes the step of bringing the tableware into contact with the composition according to the present invention.

[0134] A preferred method may include the steps of supplying the composition of the present invention to a predetermined amount of water to form a washing solution, and immersing the tableware in the solution, in order to bring the tableware into contact with the composition of the present invention. The tableware is then washed with the composition in the presence of water.

[0135] The dishes can be rinsed. In this specification, “rinsing” means bringing the dishes, which have been cleaned by the process according to the present invention, into contact with a substantial amount of a suitable solvent, typically water. “Substantial amount” usually means about 1 to about 20 liters or under running water.

[0136] The compositions described herein may be applied in their diluted form. Soiled dishes are brought into contact with an effective amount, typically about 0.5 mL to about 20 mL, preferably about 3 mL to about 10 mL, of the composition of the present invention diluted with water (for about 25 dishes to be processed), preferably in liquid form. The actual amount of composition used depends on the user's judgment and typically depends on factors such as the specific product formulation of the composition, including the concentration of the active ingredient in the composition, the number of dishes to be cleaned, and the degree of soiling of the dishes. Generally, about 0.01 mL to about 150 mL, preferably about 3 mL to about 40 mL, of the composition of the present invention is combined with about 2,000 mL to about 20,000 mL, more typically about 5,000 mL to about 15,000 mL, of water in a sink. After immersing the soiled dishes in the sink containing the thus diluted composition, the soiled surfaces of the dishes are brought into contact with a cloth, sponge, or similar cleaning tool. Cloth, sponge, or similar cleaning tool may be immersed in a mixture of the composition and water before contact with the dishes, and is typically in contact with the dishes for a time ranging from about 1 to about 10 seconds, although the actual time will vary depending on the application and user. Contact of the cloth, sponge, or similar cleaning tool with the dishes simultaneously involves scrubbing the dishes.

[0137] Alternatively, the composition in its undiluted form may be applied to the tableware to be processed. “In its undiluted form” means, as used herein, that the composition is applied directly to the surface to be processed, or to cleaning supplies or tools such as brushes, sponges, nonwoven or woven materials, without being significantly diluted by the user before application (immediately beforehand). “In its undiluted form” also includes slight dilution, for example, due to the presence of water on the cleaning supplies or the addition of water by the consumer to remove any remaining amount of the composition from the bottle. Therefore, the composition in its undiluted form includes a mixture of the composition and water in a ratio ranging from 50:50 to 100:0, preferably 70:30 to 100:0, more preferably 80:20 to 100:0, and even more preferably 90:10 to 100:0, depending on the user’s habits and cleaning operations.

[0138] Test method polymer biodegradability The biodegradability of wastewater was tested three times using the OECD 301F manometric respirometry method. OECD 301F is an aerobic test that measures the biodegradation of a sample by measuring the amount of oxygen consumed. A predetermined amount of culture medium to be measured is mixed with a test substance at a nominal carbon source of 100 mg / L, along with an inoculant (30 mg / L, buoyant sludge collected from the Mannheim wastewater treatment plant). This mixture is stirred in a sealed flask at a constant temperature (20°C or 25°C) for 28 days or 56 days, respectively. Oxygen consumption is determined by measuring the pressure change in the apparatus using OxiTop® C (Xylem 35 Analytics Germany Sales GmbH&Co KG). The generated carbon dioxide is absorbed by a sodium hydroxide solution. A nitrification inhibitor is added to the flask to prevent oxygen consumption by nitrification. The amount of oxygen taken up by the microbial community during the biodegradation of the test substance (corrected for and performed in parallel with oxygen uptake by the blank inoculum) is expressed as a percentage of ThOD (theoretical oxygen demand measured by elemental analysis of the compound). Positive control glucose / glucosamine is run through each cabinet together with the test sample.

[0139] Diamine alkoxylate Molecular Weight, PO%, EO%, Diamine Core% Those skilled in the art know how to determine / measure the weight-average molecular weight (Mw) of each material. This can be done, for example, by using size exclusion chromatography (such as GPC, or in combination with light scattering), by mass spectrometry, by mass photometric measurement, or by calculation from the molar ratio of the starting materials used.

[0140] Preferably, the Mw value is determined by the following method: OECD TG 118 (1996), which specifically 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, at https: / / doi.org / 10.1787 / 9789264069848-en.

[0141] The molecular weight of the starting material may be determined as described above. The molecular weight of the diamine alkoxylate can be determined 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) at 50°C for 1 hour. All sample solutions were filtered using Chromafil Xtra PTFE (filtered at 0.20 μm 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, the Agilent system includes a differential refractive index (DRI) and a variable ultraviolet (UVW) detector 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 a PSS SDV Guard (7.5 × 50 mm) column and three SDV columns (1000A, 100000A, and 1000000A, all 7.5 × 300 mm) was arranged in series at 60°C. THF + 0.035 mol / L diethanolamine was used as the eluent at a flow rate of 1 mL / min. 100 μL of each sample solution was injected. Calibration was obtained using a polyalkoxylene oxide (a mixture of EO and PO) standard (Agilent) with a narrow molar mass distribution having a molar mass range of M=160 to M=1.378.000 g / mol. Molar masses outside this range were extrapolated.

[0142] "Mw" is the weight-average molecular weight, and "Mn" is the number-average molecular weight. The respective values ​​of Mw and / or Mn can be determined as described in the experimental section below.

[0143] The molar mass distribution Mw / Mn obtained by GPC is equal to the polydispersity index (PDI), which is unitless [g / mol / g / mol].

[0144] For the diamine alkoxylates described herein, the molecular weight (MW) can also be calculated from the molar ratio of the starting materials used. Typically, the molecular weight (MW) of an alkoxylated polymer can be calculated using the following formula: MW = of diamine alkoxylates Total MW of diamine + total MW of PO + total MW of EO + total MW of other monomers (if any)

[0145] The weight percentages of PO, EO, or diamine in an alkoxylated polymer can be calculated according to the same principle.

[0146] It will be apparent to those skilled in the art that, for the alkoxylated polymer of the present invention, the measured molecular weight and the calculated molecular weight obtained by GPC, mass spectrometry, or mass photometric measurement are consistent in the sense that the measured molecular weight does not change significantly.

[0147] Foam persistence index in the presence of oily dirt The foam retention performance in the presence of oily dirt was evaluated using the following method. The purpose of the foam persistence index test is to compare the time-dependent development of foam volume generated for different test formulations at specified water hardness, solution temperature, and formulation concentration while under the influence of periodic fouling injection. The data are compared and expressed as a foam persistence index relative to a reference composition (the reference composition has a foam persistence index of 100). The procedure is as follows: 1) Dispense a specified amount of the test composition corresponding to the target composition concentration (0.12 wt%) into a sink filled with water at a constant pressure of 4 bar until it reaches 4 L (using water with a hardness of 1.25 mmol / LCa equivalent (7 dH) at 42°C) using a plastic pipette at a flow rate of 0.67 mL / second, at a height of 37 cm above the bottom surface of the sink (dimensions: diameter 300 mm and height 288 mm). 2) Initial foam volume generated (measured as average foam height × sink surface area, cm²) 3 The value (represented by ) is recorded immediately after filling is complete. 3) Immediately pour a fixed amount (6 mL) of the dirt into the center of the sink. 4) The resulting solution is mixed using a metal blade (10 cm x 5 cm) positioned in the center of the sink at a 45-degree angle at the gas-liquid interface, rotating 20 times at 85 RPM. 5) Record another measurement of the total foam volume immediately after the blade rotation ends. 6) The total foam volume measured was 400 cm³ 3 Repeat steps 3-5 until the minimum level is reached. 400cm 3 The amount of dirt added required to reach that level is considered to be the foam persistence of the test composition. 7) Each test composition is tested four times under the same test conditions (i.e., water temperature, composition concentration, water hardness, and type of dirt). 8) The average foam persistence is calculated by taking the average of four trials performed for each sample. 9) The foam persistence index is calculated by comparing the average persistence of the test composition sample with that of the reference composition sample. The calculation is as follows:

[0148]

number

[0149] A stain composition is produced by a standard mixture of the components listed in Table 1.

[0150] [Table 1]

[0151] Viscosity measurement Viscosity is measured using a controlled stress rheometer (such as Thermo Scientific's HAAKE MARS or equivalent) with a 60 mm 1° cone and a 52 micrometer gap size at 20°C. After temperature equilibrium for 2 minutes, the sample is subjected to 10s-1 The mixture is sheared for 30 seconds at a shear rate. The reported viscosity of the liquid dishwashing detergent composition is the average shear stress applied at 20°C for 15 to 30 seconds of shearing. -1 It is defined as the result of dividing by the shear rate.

[0152] pH Unless otherwise specified, pH is measured as a 10% by weight desalinated aqueous solution at 20°C. [Examples]

[0153] The diamine alkoxylates of the present invention were prepared as follows. 1,2-ethylenediamine (IE5) propoxylated with 40 moles of propylene oxide and ethoxylated with 8 moles of ethylene oxide. Propoxylation of diamines In a 2 L autoclave, 102.3 g of 1,2-ethylenediamine (Quadrol® L, BASF SE) propoxylated with 4 molars of propylene oxide and 1.7 g of potassium tert. butoxide were added, and the mixture was heated to 140°C. The container was purged three times with nitrogen. 731.8 g of propylene oxide was added continuously within 10 hours. To complete the reaction, the mixture was further reacted at 140°C for another 10 hours. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum (10 mbar) at 90°C for 2 hours. 825.0 g of pale orange oil was obtained (hydroxyl value 103.3 mg KOH / g, amine value 52.3 mg KOH / g).

[0154] Ethoxylation of propoxylated diamines In a 2 L autoclave, 361.9 g of pre-formed propoxylated diamine (1,2-ethylenediamine propoxylated with 40 mol of propylene oxide) was heated to 130°C, and the container was purged three times with nitrogen. 53.1 g of ethylene oxide was continuously added within 0.5 hours. To complete the reaction, the mixture was further reacted at 130°C for 5 hours. The reaction mixture was stripped with nitrogen, and volatile compounds were removed under vacuum (10 mbar) at 90°C for 2 hours. 412.0 g of pale orange oil was obtained (hydroxyl value 88.3 mg KOH / g, amine value 46.9 mg KOH / g).

[0155] IE1, IE3, CE A, and CE B were prepared in the same manner. IE2 was prepared similarly, except that propylene oxide and ethylene oxide were added together with tert. butoxide and the reaction was carried out at a temperature of 140°C. IE4 was prepared by first reacting 1,2-ethylenediamine with ethylene oxide until an average of 1EO per NH was achieved, and then ethoxylation before propoxylation as described above.

[0156] The structure is summarized in Table 1.

[0157] [Table 2] a wt% propylene oxide content relative to the total weight of diamine alkoxylates b Weight % ethylene oxide content relative to the total weight of diamine alkoxylates c Molecular weight calculated based on the molar ratio of the starting materials

[0158] The following liquid compositions for hand-washing dishes were prepared by simple mixing. Each example contained the same concentration of surfactant and the same ratio of anionic surfactant and auxiliary surfactant.

[0159] Examples 1 to 4 of the present invention contained 2% by weight of the diamine alkoxylate used in the present invention. In contrast, Comparative Examples A and B contained diamine alkoxylates (CE A and CE B, respectively) with a lower propylene oxide content than required by the present invention. Comparative Example C did not contain diamine alkoxylate and was used as a baseline for evaluating foam persistence (index 100).

[0160] [Table 3] * comparison + After 26 or 28 days, follow the instructions provided herein. ++ Exponential vs. Comparative Example C 1 Branching rate: 42.06%

[0161] Experimental results show that the diamine alkoxylates used in the present invention are more readily biodegradable and simultaneously improve foam life under oily conditions (Examples 1 to 4 of the present invention). Biodegradability has been shown to be further improved by using diamine alkoxylates containing 7 to 11 PO molecules per alkoxylate branch and / or having a weight-average molecular weight (Mw) in the range of 2,000 to 2,900 g / mol, more preferably 2,500 to 2,800 g / mol (see Examples IE2, IE4, and IE5 in Table 1).

[0162] In contrast, the diamine alkoxylate used in Comparative Example A had a lower weight-average molecular weight than the diamine alkoxylate used in the present invention, while the diamine alkoxylate used in Comparative Example B had a lower propylene oxide content than the diamine alkoxylate used in the present invention. In both cases, the resulting diamine alkoxylates exhibited substantially reduced biodegradability. Furthermore, as can be seen from Comparative Example A, a decrease in the molecular weight of the diamine alkoxylate also substantially reduced the foam life in the presence of oily contaminants.

[0163] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise specified, each such dimension is intended to mean both the listed value and the functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."

Claims

1. A liquid detergent composition for hand washing dishes, a) A surfactant system comprising 5% to 50% by weight of the composition, wherein the surfactant system includes an anionic surfactant, b) Diamine alkoxylate, i. At least one of the NH-functional groups of the diamine is modified to form a polyalkylene oxide branch, ii. Each of the at least one polyalkylene oxide branch comprises ethylene oxide (EO) and propylene oxide (PO), iii. The weight-average molecular weight (Mw) of the diamine alkoxylate is in the range of 1,200 g / mol to 3,200 g / mol. iv. A liquid dishwashing detergent composition comprising a diamine alkoxylate in which the propylene oxide content is 65% to 95% by weight relative to the total weight of the diamine alkoxylate.

2. The composition according to claim 1, wherein the diamine used to form the diamine alkoxylate has two primary amine groups.

3. Each of the aforementioned polyalkylene oxide branches, on average, a) at least one ethylene oxide unit (EO), and b) The composition according to claim 1 or 2, comprising or comprising at least five polypropylene oxide units (PO), preferably at least seven PO.

4. Each of the aforementioned polyalkylene oxide branches, on average, a) Five or fewer EOs, preferably four or fewer EOs, preferably three or fewer EOs, preferably two or fewer EOs, and b) The composition according to any one of claims 1 to 3, comprising or consisting of 12 or less PO, preferably 11 or less PO.

5. The composition according to any one of claims 1 to 4, wherein the propylene oxide content is 70% to 95% by weight, preferably 80% to 95% by weight, relative to the total weight of the diamine alkoxylate.

6. The composition according to any one of claims 1 to 5, wherein the diamine used to form the diamine alkoxylate has a molecular weight (Mw) in the range of 50 g / mol to 1500 g / mol, preferably 60 g / mol to 1000 g / mol, and more preferably 60 g / mol to 200 g / mol.

7. The composition according to any one of claims 1 to 6, wherein the weight-average molecular weight (Mw) of the diamine alkoxylate is in the range of 1,500 g / mol to 3,000 g / mol, preferably in the range of 2,000 g / mol to 2,900 g / mol, and more preferably in the range of 2,500 g / mol to 2,800 g / mol.

8. The composition according to any one of claims 1 to 7, wherein the diaminediamine used to form the diamine alkoxylate is selected from the group consisting of 1,2-diaminoethane (EDA), 1,3-diaminopropane, 2,2-dimethyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, cyclohexyl-diamine, and methylcyclohexyl-diamine.

9. The composition according to any one of claims 1 to 8, wherein each of the polyalkylene oxide branches comprises blocks or random structures of ethylene oxide and propylene oxide, preferably comprising block structures, more preferably comprising blocks of polyethylene oxide and polypropylene oxide, and even more preferably the diamine is modified first with the polypropylene oxide and then with the polyethylene oxide blocks.

10. The composition according to any one of claims 1 to 9, wherein the diamine alkoxylate is present in the composition at a concentration of 0.05% to 5.0% by weight, preferably 0.1% to 3.5% by weight, and more preferably 0.3% to 2.5% by weight.

11. The liquid dishwashing detergent composition according to any one of claims 1 to 10, wherein the composition comprises 6.0% to 40% by weight, preferably 15% to 35% by weight, of the surfactant system in the detergent composition.

12. The surfactant system comprises at least 40% by weight, preferably 50% to 90% by weight, and more preferably 65% ​​to 85% by weight of the anionic surfactant, Preferably, the anionic surfactant comprises at least 70% by weight, preferably at least 85% by weight, more preferably 100% by weight of an alkyl sulfated anionic surfactant, and preferably, the alkyl sulfated anionic surfactant has a number-average alkyl chain length of 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, more preferably 12 to 14 carbon atoms, and even more preferably 12 to 13 carbon atoms, according to any one of claims 1 to 11.

13. The liquid dishwashing detergent composition according to claim 12, wherein the alkyl sulfated anionic surfactant has an average degree of alkoxylation of less than 3.5, preferably less than 2.0, and more preferably 1.0 or less.

14. The liquid dishwashing detergent composition according to claim 12 or 13, wherein the anionic surfactant comprises a branched anionic surfactant, and more preferably the anionic surfactant has a weight-average branching degree of at least 10%, preferably 20% to 60%, and more preferably 25% to 45%.

15. The composition further comprises an amphoteric surfactant, a zwitterionic surfactant, and an auxiliary surfactant selected from mixtures thereof, preferably the anionic surfactant and the amphoteric auxiliary surfactant are present in a weight ratio of 1:1 to 8:1, more preferably 2:1 to 5:1, and most preferably 2.5:1 to 4:

1. Preferably, the auxiliary surfactant comprises an amphoteric surfactant, and the amphoteric surfactant comprises an amine oxide amphoteric auxiliary surfactant, and more preferably, the amine oxide amphoteric auxiliary surfactant is selected from the group consisting of alkyldimethylamine oxide, alkylamidopropyldimethylamine oxide, and mixtures thereof, the liquid dishwashing detergent composition according to any one of claims 1 to 14.

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