Liquid dishwashing detergent composition

Abstract

This invention provides a liquid dishwashing detergent that further improves the drying speed of dishes after handwashing. [Solution] A quaternary acrylic copolymer and a surfactant system that enhances its effectiveness are incorporated into a liquid dishwashing detergent. The surfactant system comprises a. an anionic surfactant and b. an auxiliary surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

Description

Technical Field

[0001] The present invention relates to a liquid dishwashing detergent composition containing a quaternized acrylic copolymer and providing further improvement in the drying time of dishes after rinsing.

Background Art

[0002] Manual dishwashing is a time-consuming task that many people who perform it consider complete when they can put away the dishes. Therefore, quick drying of dishes after washing and rinsing is highly desirable. Drying is particularly affected by the hardness of the water, and when using water with a lower hardness, the sheeting of water from the dishes is reduced. As the popularity of household water softeners progresses, the need to improve sheeting and thus the drying rate still remains significant.

[0003] The use of quaternized acrylic copolymers to improve the drying rate is known. Such copolymers increase the drying rate by improving the sheeting of water from the dishes and improving the beading of water.

[0004] However, it has been found that the performance of such copolymers in liquid detergent compositions that do not contain alkoxylated alcohol nonionic surfactants is relatively poor, particularly under soft water conditions. Therefore, there remains a need to further improve the drying time after manual washing of dishes without the need to formulate using high levels of alkoxylated alcohol nonionic surfactants. [[ID=二十一]] [[ID=二十二]]

[0005] [[ID=二十三]] International Publication No. 201836864(A) relates to a hard surface treatment composition comprising a quaternary acrylic copolymer and an amphoteric modified polysaccharide, wherein the weight ratio of the quaternary acrylic copolymer to the amphoteric modified polysaccharide is 0.75:1 to 3:1, and the quaternary acrylic copolymer is different from the amphoteric modified polysaccharide. European Patent No. 3835399(A1) relates to a hard surface cleaning composition comprising a surfactant system, a first polymer, and a second polymer, wherein the first polymer is polyethyleneimine, and to the use of the composition for cleaning glass surfaces. U.S. Patent Application Publication No. 20030134770(A) relates to a liquid detergent composition comprising a polymer material which is a foam enhancer and foam volume expander, the composition having increased effectiveness in preventing the redeposition of grease during hand washing, the polymer material being suitable as a foam volume and foam durability enhancer, and comprising an effective amount of a polymer foam enhancer containing quaternary nitrogen-containing monomer units and / or zwitterionic monomer units. European Patent No. 3835399(A1) relates to a hard surface cleaning composition comprising a surfactant system, a first polymer, and a second polymer, the first polymer being polyethyleneimine. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 201836864(A) [Patent Document 2] European Patent No. 3835399(A1) [Patent Document 3] U.S. Patent Application Publication No. 20030134770(A) [Overview of the project] [Means for solving the problem]

[0007] The present invention relates to a liquid dishwashing detergent composition comprising a quaternary acrylic copolymer and a surfactant system in an amount of 5.0% to 50% by weight of the liquid dishwashing detergent composition, wherein the surfactant system comprises an anionic surfactant and an auxiliary surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, and the anionic surfactant and the auxiliary surfactant are present in a weight ratio of less than 1.5:1. [Modes for carrying out the invention]

[0008] In addition to quaternary acrylic copolymers, the liquid cleaning composition can be combined with a surfactant system, as described herein, to improve the drying speed of dishes after hand washing.

[0009] As used herein, articles such as "a" and "an" used in a patent claim are understood to mean one or more of the things being claimed or described.

[0010] As used herein, the term “contains” means that steps and components other than those specifically mentioned may be added. This term encompasses the terms “consisting of” and “consisting essentially of.” The compositions of the present invention may consist of, or be essentially composed of, the essential elements and limitations of the present invention as described herein, as well as any additional or optional components, elements, steps, or limitations as described herein.

[0011] As used herein, the term “tableware” includes, in non-limiting examples, cookware and tableware made from ceramics, porcelain, metal, glass, plastics (e.g., polyethylene, polypropylene, polystyrene, etc.) and wood.

[0012] As used herein, the terms “oils and fats” or “oil-based” mean that the substance contains, at least partially (i.e., at least 0.5% by weight of oils and fats 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.

[0013] The term "include / includes / including" means that it is non-restrictive.

[0014] As used herein, the term “particulate matter” means inorganic and, in particular, organic solid contaminant particles, in particular food particles, and, in non-limiting examples, ultrafine elemental carbon particles, calcined fat particles, and meat particles.

[0015] As used herein, the term “foaming profile” refers to the properties of a cleaning composition relating to the nature of the foam during the dishwashing process. The term “foaming profile” of a cleaning composition includes the dissolution and agitation of the cleaning composition in an aqueous cleaning solution, the initial foaming volume typically generated during manual agitation, and the retention of foam during the dishwashing process. Preferably, a dishwashing cleaning composition characterized by having a “good foaming profile” tends to have a large initial foaming volume and / or persistent foaming volume for a significant portion or all of the dishwashing process. This is important because consumers use the size of the foam as an indicator that sufficient cleaning composition has been added. Furthermore, consumers also use the persistence of foaming 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, low-foaming cleaning compositions tend to be replenished more frequently than necessary by consumers due to their low foaming level.

[0016] It will be 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.

[0017] Unless otherwise specifically stated, all proportions are based on the total weight of the composition, as is evident from the context. Unless otherwise specifically stated, all ratios are weight ratios, and all measurements are taken at 25°C unless otherwise specified.

[0018] Liquid cleaning compositions The cleaning composition is a liquid cleaning composition, preferably a liquid dishwashing cleaning composition, and is therefore in liquid form. The liquid cleaning composition is preferably an aqueous cleaning composition. Therefore, the composition may contain 50% to 85% by weight, preferably 50% to 75% by weight, of water in total.

[0019] The liquid cleaning composition has a pH greater than 6.0, or between 6.0 and 12.0, preferably between 7.0 and 11.0, and more preferably between 7.5 and 10.0, as measured as a 10% aqueous solution in desalinated water at 20°C.

[0020] The liquid cleaning composition of the present invention may be a Newtonian fluid or a non-Newtonian fluid, but is preferably a Newtonian fluid. Preferably, the composition 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 a combination thereof. The viscosity is measured at 20°C using a Brookfield RT viscometer with a spindle 31 adjusted to achieve a torque of 40% to 60%.

[0021] Quaternary acrylic copolymer The liquid dishwashing detergent contains a quaternized acrylic copolymer. As used herein, "copolymer" refers to a polymer containing at least two different monomer compositions. A quaternized polymer contains a quaternary ammonium group, which is a polyatomic ion with a positive charge of structure NR4+, where R is an alkyl group or an aryl group. Unlike ammonium ions (NH4+) and primary, secondary, or tertiary ammonium cations, quaternary ammonium cations are permanently charged regardless of the pH of their solutions.

[0022] The composition preferably contains from 0.01% to 3.0% by weight, preferably from 0.05% to 2.0% by weight, more preferably from 0.1% to 1.0% by weight of the quaternized acrylic copolymer, based on the weight of the composition.

[0023] The quaternized acrylic copolymer can have a weight average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC - MALLS) in the range of 5,000 to 500,000 Da, preferably 15,000 to 300,000 Da, even more preferably 25,000 to 75,000 Da.

[0024] The quaternized acrylic copolymer can be characterized by its cationic charge density. Cationic charge density is typically expressed as milliequivalents of charge per gram of compound (mEq / g). The hydrophobically modified cationic polyvinyl alcohol of the present disclosure can be characterized by a cationic charge density (or "CCD") in the range of 0.10 mEq / g to 4.0 mEq / g, preferably 1.0 mEq / g to 3.50 mEq / g, more preferably 1.75 mEq / g to 2.75 mEq / g.

[0025] Preferably, the different types of monomer units are randomly distributed throughout the quaternized acrylic copolymer.

[0026] The quaternary acrylic copolymer is preferably derived from cationic monomer units and ethylenically unsaturated monomer units.

[0027] The cationic monomer units can be selected from the following: CH2=CR1-Y-(CH2)n-N+R2R3R4X (a), During the ceremony, Each R1 is independently selected from hydrogen or methyl, preferably methyl. Each R2 is independently selected from C1-C4 alkyl (alkylene), preferably CH2CH=CH2 or methyl, more preferably methyl. Each R3 and R4 is independently selected from C1-C4 alkyl groups, preferably C1-C3 alkyl groups, and more preferably methyl groups. Each Y is independently selected from CO-NR5-(CH2)n, CO-O-(CH2)n, or (CH2)n, preferably CO-NR5-(CH2)n or (CH2)n, more preferably CO-NR5-(CH2)n, and is a linking group. During the ceremony, Each R5 is independently selected from hydrogen or methyl, preferably hydrogen. n is the average of 1 to 4, preferably 1 or 3, more preferably 3. X- is a suitable counterion, preferably a halide counterion, and more preferably Cl-.

[0028] The selection of linking group Y depends on the reaction scheme used to produce the quaternized acrylic copolymer. Preferably, all Y groups are the same. Preferably, all R5 groups are the same.

[0029] The cationic monomer units can be selected from the group consisting of acrylamidopropyl trimethylammonium chloride (APTAC), methacrylamidopropyl trimethylammonium chloride (MAPTAC), diallyl dimethyl ammonium chloride (DADMAC), acryloyloxyethyl trimethylammonium chloride (AETAC), methyloyloxyethyl trimethylammonium chloride (METAC), and mixtures thereof. Particularly preferred cationic monomers are (meth)acrylamidopropyl trimethylammonium chloride (APTAC or MAPTAC) or diallyl dimethyl ammonium chloride (DADMAC), with methacrylamidopropyl trimethylammonium chloride (MAPTAC) being the most preferred. When polymerizing DADMAC, two polymer structures are possible: an N-substituted piperidine structure or an N-substituted pyrrolidine structure. A pyrrolidine structure is preferred (see John, Wilson; et al. (2002), Synthesis and Use of PolyDADMAC for Water Purification).

[0030] Ethylene-unsaturated monomers can be selected from the group consisting of C3-C8 ethylenically unsaturated acids and / or their salts, C3-C8 hydroxyalkyl acrylates, and mixtures thereof. C3-C8 means that the ethylenically unsaturated acid and / or its salt, or the C3-C8 hydroxyalkyl acrylate, contains 3 to 8 carbon atoms.

[0031] Suitable C3-C8 ethylenically unsaturated acids and / or salts thereof include (meth)acrylic acid and mixtures thereof, with acrylic acid being preferred. Suitable salts include alkali metal and ammonium salts.

[0032] Suitable C3-C8 hydroxyalkyl acrylates can be selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate, with ethyl acrylate being the most preferred.

[0033] The quaternary acrylic copolymer may further contain additional monomers as polymerization monomers selected from the group consisting of ethyl acrylate, 2-acrylamido-2-methylpropane-sulfonic acid, N-isopropylamide, vinylpyrrolidone, and mixtures thereof, with ethyl acrylate and / or vinylpyrrolidone being preferred, and ethyl acrylate being particularly preferred.

[0034] The additional monomers are preferably present at a level of less than 20 mol%, preferably less than 15 mol%, and more preferably less than 10% of the total monomers present in the quaternized acrylic.

[0035] Quaternary acrylic copolymers may contain hydroxyethyl acrylate as an ethylenically unsaturated monomer and diallyldimethylammonium chloride (DADMAC) as a cationic monomer. Such quaternary acrylic copolymers may also contain vinylpyrrolidone as an additional monomer. An example of such a quaternary acrylic copolymer is sold by Solvay under the trademark name Mirapol® SURF-S FAST DRY.

[0036] More preferably, the quaternary acrylic copolymer may contain acrylate and / or ethyl acrylate as ethylenically unsaturated monomers, along with (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) as a cationic monomer. Such a quaternary acrylic copolymer may also contain ethyl acrylate as an additional monomer. Examples of such quaternary acrylic copolymers include those sold by BASF under the trademark name Polyquart®, with Polyquart 149A® being particularly preferred.

[0037] Surfactant-based The liquid cleaning composition contains, based on the total weight of the composition, 5.0% to 50% by weight, preferably 6.0% to 40% by weight, and most preferably 15% to 35% by weight of a surfactant system. The surfactant system includes an anionic surfactant and auxiliary surfactants selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

[0038] The anionic surfactant and auxiliary surfactant are present in a weight ratio of less than 1.5:1, preferably 0.5:1 to 1.5:1, and more preferably 0.8:1 to 1.2:1.

[0039] Anionic surfactants The surfactant system includes an anionic surfactant. The surfactant system may contain at least 35% by weight, preferably 35% to 65% by weight, and more preferably 40% to 60% by weight of anionic surfactant. Since such fatty acids hinder foam formation, the surfactant system preferably does not contain fatty acids or salts thereof.

[0040] Suitable anionic surfactants can be selected from the group consisting of alkyl sulfated surfactants, alkyl sulfonate surfactants, alkyl sulfosuccinate and dialkyl sulfosuccinate ester surfactants, and mixtures thereof.

[0041] The anionic surfactant may include at least 70% by weight, preferably at least 85% by weight, and more preferably 100% by weight of alkylsulfated anionic surfactant.

[0042] To provide a combination of improved grease removal and enhanced cleaning speed, the molar average alkyl chain length of the alkyl sulfated 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.

[0043] The alkyl chain of the alkyl sulfated anionic surfactant can 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 in the presence of particulate matter is not impaired.

[0044] The relative molar amounts of C13 and C12 alkyl chains in alkyl sulfated anionic surfactants can be derived from the carbon chain length distribution of the anionic surfactant. The carbon chain length distribution of the alkyl chains in alkyl sulfated anionic surfactants can be obtained from the technical data sheet of the supplier of the surfactant or the alkyl alcohol constituting it. Alternatively, the chain length distribution and average molecular weight of the aliphatic alcohol used to prepare alkyl sulfated anionic surfactants can also be determined by methods known in the art. Such methods include capillary gas chromatography with a flame ionization detector on 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 sulfated anionic surfactants must be hydrolyzed back to the corresponding alkyl alcohol and alkyl alkoxylated alcohol before analysis, for example, using hydrochloric acid.

[0045] Alkyl sulfated surfactants may be alkoxylated or not. If alkoxylated, alkyl sulfated anionic surfactants may have an average degree of alkoxylation of less than 3.5, preferably 0.3 to 2.0, 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 foaming persistence. If alkoxylated, ethoxylation is preferred.

[0046] The average degree of alkoxylation is the molar average of the degrees 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, moles of non-alkoxylated alkyl sulfate anionic surfactants are included.

[0047] 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, etc. 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.

[0048] A preferred alkylalkoxy sulfate is an alkylethoxysulfate.

[0049] Alkyl sulfated anionic surfactants may have a weight-average branching degree of at least 10%, preferably 20% to 60%, and more preferably 25% to 45%.

[0050] The alkyl sulfated anionic surfactant may 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 of the non-alkoxylated alkyl sulfated anionic surfactant and counting from the alkoxylated alkyl sulfate anionic surfactant from the alkoxylated group furthest from the sulfate group). More preferably, more than 75% by weight, and even more preferably more than 90% by weight of the total branched alkyl, consists of a C1-C5 alkyl moiety, preferably a C1-C2 alkyl moiety. When compositions of the present invention are formulated using alkyl sulfated anionic surfactants having the aforementioned degree of branching, improved stability at low temperatures has been observed. Such compositions require less solvent to achieve good physical stability at low temperatures. Therefore, the compositions may contain low concentrations of organic solvent, less than 5.0% by weight, based on the weight of the liquid cleaning composition, while still having improved low-temperature stability. More branching of the surfactant also leads to faster initial foam formation, but typically results in lower foam persistence. The weight-average branching described herein has been found to provide improved low-temperature stability, initial foam formation, and foam persistence.

[0051] 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.

[0052] 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 a flame ionization detector on 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 sulfated anionic surfactant.

[0053] Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, but sodium is preferred.

[0054] Suitable examples of commercially available alkyl sulfated anionic surfactants include those derived from alcohols sold by Shell under the trade name Neodol®, or by Sasol under the trade names Lial®, Isalchem®, and Safol®, or some of the natural alcohols produced by Procter & Gamble Chemicals. Based on the relative fractions of C13 and C12 in the starting alcohols obtained from the supplier's technical data sheet 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.

[0055] The performance of the final product, including its oil-cleaning, foaming, low-temperature stability, and viscosity, 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 the alkoxylated alkyl sulfate anionic surfactant.

[0056] While we do not wish to be constrained by theory, in the presence of ethoxylated alkyl sulfates, the amount of 1,4-dioxane by-products in the alkoxylated product, particularly the ethoxylated alkyl sulfate, can be reduced by strictly controlling the processing conditions and the composition of the raw materials during both the ethoxylation and sulfation steps. Based on recent technological advances, further reduction of 1,4-dioxane by-products 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 are widely described in the art. Alternatively, control of 1,4-dioxane levels 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.

[0057] 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, but C11-C13 alkylbenzene sulfonates are preferred. The above surfactants may 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).

[0058] 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 sulfated anionic surfactants.

[0059] auxiliary surfactants To improve the packing of the surfactant after dilution, and consequently improve foaming persistence, the surfactant system may include auxiliary surfactants. Auxiliary surfactants can be selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

[0060] The composition preferably contains 1.0% to 30% by weight, more preferably 5.0% to 25% by weight, and particularly 10% to 20% by weight of auxiliary surfactants of the cleaning composition.

[0061] The surfactant system of the cleaning composition of the present invention preferably contains an auxiliary surfactant of up to 65% by weight of the surfactant system, preferably 30% to 65% by weight, and more preferably 40% to 60% by weight.

[0062] The auxiliary surfactant is preferably an amphoteric surfactant, more preferably an amine oxide surfactant.

[0063] 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 (wherein R1 is a C8-18 alkyl group, and 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. Specific examples of linear amine oxide surfactants include linear C10-C18 alkyldimethylamine oxides and linear C8-C12 alkoxyethyl dihydroxyethylamine oxides.

[0064] Preferably, the amine oxide surfactant is selected from the group consisting of alkyldimethylamine oxide, alkylamidopropyldimethylamine oxide, and mixtures thereof. Alkyldimethylamine oxides such as C8-18 alkyldimethylamine oxide or C10-16 alkyldimethylamine oxide (such as cocodimethylamine oxide) 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.

[0065] Suitable alternative amine oxide surfactants include medium-branched amine oxide surfactants. As used herein, “medium-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, “symmetric” means that in at least 50% by weight, more preferably at least 75% to 100% by weight, of the branched amine oxide used herein, the |n1-n2| group consists of 5 or fewer carbon atoms, 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, the two portions are selected from C1-3 alkyl, and more preferably, both are selected as C1 alkyl.

[0066] 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) Based on the weight of the amine oxide, approximately 10% to approximately 45% by weight of a low-cut amine oxide of formula R1R2R3AO (wherein 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) The amine oxide may include 55% to 90% by weight of a midcut amine oxide of the formula R4R5R6AO (wherein R4 and R5 are independently selected from hydrogen, C1-C4 alkyl, or a mixture thereof, and R6 is selected from C12-C16 alkyl, or a mixture thereof).

[0067] In the low-cut amine oxides preferred for use herein, R3 is n-decyl, and preferably both R1 and R2 are methyl. In the mid-cut amine oxide of formula R4R5R6AO, preferably both R4 and R5 are methyl.

[0068] Preferably, the amine oxide comprises less than about 5% by weight, more preferably less than 3% by weight, of the amine oxide of formula R7R8R9AO (wherein R7 and R8 are selected from hydrogen, C1-C4 alkyl groups and mixtures thereof, and R9 is selected from C8 alkyl groups and mixtures thereof). Limiting the amount of the amine oxide of formula R7R8R9AO improves both physical stability and foaming persistence.

[0069] Suitable zwitterionic surfactants include betaine surfactants. Examples of such betaine surfactants include alkylbetaine, alkylamidebetaine, amideazolinium betaine, sulfobetaine (INCI sultaine), and phosphobetaine, which preferably satisfy formula (I). R1-[CO-X(CH2)n]x-N+(R2)(R3)-(CH2)m-[CH(OH)-CH2]yY- (In formula (I), 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. X is selected from the group consisting of NH, NR4 (wherein 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 hydroxyl such as hydroxyethyl, and mixtures thereof, preferably both R2 and R3 are methyl. m is an integer between 1 and 4, preferably an integer of 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 residue).

[0070] Preferred betaines are alkylbetaine of formula (Ia), alkylamidopropylbetaine of formula (Ib), sulfobetaine of formula (Ic), and amidesulfobetaine of formula (Id). R1-N+(CH3)2-CH2COO- (IIa) R1-CO-NH-(CH2)3-N+(CH3)2-CH2COO- (IIb) R1-N+(CH3)2-CH2CH(OH)CH2SO3- (IIc) R1-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).

[0071] 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, oleadopropyl 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 is particularly preferred.

[0072] Nonionic surfactants: The surfactant system may further contain less than 3.0% by weight of an alkoxylated alcohol nonionic surfactant of the composition. If present, the surfactant system preferably contains at least 0.5% by weight, preferably at least 1.0% by weight, and more preferably at least 2.0% by weight of the alkoxylated alcohol nonionic surfactant of the composition. Alternatively, the composition may contain more than 3.0% by weight, preferably 3.5% to 10% by weight, and more preferably 4.0% to 7.5% by weight of the alkoxylated alcohol nonionic surfactant of the liquid dishwashing detergent composition.

[0073] Anionic surfactants and alkoxylated alcohol nonionic surfactants may be present in a weight ratio of less than 10:1. Preferably, anionic surfactants and alkoxylated alcohol nonionic surfactants are present in a weight ratio of 0.8:1 to 6.0:1, more preferably 3.5:1 to 5.5:1.

[0074] The surfactant system of the liquid dishwashing detergent composition may contain at least 5% by weight, preferably 5% to 35% by weight, and more preferably 10% to 30% by weight of an alkoxylated alcohol nonionic surfactant.

[0075] Preferably, the alkoxylated alcohol nonionic surfactant is a linear or branched, preferably linear, primary or secondary alkylalkoxylated nonionic surfactant, preferably an alkylethoxylated nonionic surfactant, containing 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 alkylene oxide per mole of alcohol. The alkoxylated alcohol nonionic surfactant is preferably ethoxylated and / or propoxylated, more preferably ethoxylated.

[0076] The surfactant system may include further nonionic surfactants, such as alkyl polyglucoside nonionic surfactants.

[0077] The combination of alkyl polyglucosides with anionic surfactants, particularly alkyl sulfate anionic surfactants, has been found to improve polymerized oil removal, sustained foaming performance, reduced viscosity changes due to changes in surfactants and / or systems, and more sustained Newtonian rheology.

[0078] 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.

[0079] 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 the short-chain alkyl polyglucoside surfactant to the 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 a blend of short-chain alkyl polyglucoside surfactants and long-chain alkyl polyglucoside surfactants results in faster dissolution and improved initial foaming of the detergent solution in water, combined with improved foaming stability.

[0080] C8-C16 alkyl polyglucosides are commercially available from several suppliers (e.g., Simusol® surfactant from Seppic Corporation, and Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP / MB, and Glucopon® 650 EC / MB from BASF Corporation). Glucopon® 215UP is a preferred short-chain APG surfactant. Glucopon® 600CSUP is a preferred medium-to-long-chain APG surfactant.

[0081] If present, alkyl polyglucosides may be present in the surfactant system at a concentration of 0.5% to 20% by weight, preferably 0.75% to 15% by weight, more preferably 1% to 10% by weight, and most preferably 1% to 5% by weight of the surfactant composition. Alkyl polyglucoside nonionic surfactants typically exhibit higher foaming properties than other nonionic surfactants such as alkyl ethoxylated alcohols.

[0082] In other preferred compositions, alkyl polyglucosides are present at a level of less than 2.0% by weight, preferably less than 1.0% by weight, and more preferably less than 0.5% by weight of the composition.

[0083] In a more preferable composition, the composition does not contain any further nonionic surfactants.

[0084] Further ingredients: This composition may contain further components such as amphiphilic alkoxylated polyalkyleneimines, cyclic polyamines, triblock copolymers, hydrotropes, organic solvents, other auxiliary components as described herein, and mixtures thereof, selected from these.

[0085] Amphiphilic alkoxylated polyalkyleneimines: The compositions of the present invention may further contain 0.05% to 2% by weight, preferably 0.07% to 1% by weight, of an amphiphilic polymer in total weight of the composition. Suitable amphiphilic polymers may be selected from the group consisting of amphiphilic alkoxylated polyalkyleneimines and mixtures thereof. Amphiphilic alkoxylated polyalkyleneimine polymers have been found to reduce gel formation on hard surfaces being cleaned when their liquid composition is added directly to a cleaning tool (such as a sponge) before cleaning and then comes into contact with a heavily soiled surface, especially when the cleaning tool contains little to no water, for example, when using a pre-moistened sponge.

[0086] A preferred amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I):

[0087] [ka] (In the formula, the polyethyleneimine main chain has a weight-average molecular weight of 600, n in formula (I) is average 10, m in formula (I) is average 7, and R in formula (I) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen). The permanent degree of quaternization of formula (I) may be 0% to 22% of the nitrogen atoms of the polyethyleneimine backbone. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 10,000 to 15,000 Da.

[0088] More preferably, the amphiphilic alkoxylated polyethyleneimine polymer has the general structure of formula (I), wherein the polyethyleneimine skeleton has a weight-average molecular weight of 600 Da, n in formula (I) is average 24, m in formula (I) is average 16, and R in formula (I) is selected from hydrogen, C1-C4 alkyl, and mixtures thereof, preferably hydrogen. The permanent degree of quaternization of formula (I) may be 0% to 22% of the nitrogen atoms of the polyethyleneimine skeleton, preferably 0%. The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer is preferably 25,000 to 30,000, most preferably 28,000 Da.

[0089] Amphiphilic alkoxylated polyethyleneimine polymers can be prepared by the method described in detail in International Publication No. 2007 / 135645.

[0090] Alternatively, the composition may not contain an amphiphilic polymer.

[0091] Cyclic polyamines This 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 in total.

[0092] Cyclic polyamines have at least two primary amine functional groups. While the primary amines may 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 provide improved grease and oil cleaning performance.

[0093] 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. These particular cyclic polyamines, when combined with the surfactant system of the compositions of the present invention, have the function of improving the foaming and grease-cleaning profiles throughout the dishwashing process.

[0094] Suitable cyclic polyamines can be supplied by BASF under the trade name Baxxodur, with Baxxodur ECX-210 being particularly preferred.

[0095] A combination of cyclic polyamine and magnesium sulfate is particularly preferred. Therefore, the composition may further contain magnesium sulfate at a level 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.

[0096] Triblock copolymer The compositions of the present invention may contain triblock copolymers. The triblock copolymer may be present at a level of 1% to 20% by weight, preferably 3% to 15% by weight, and more preferably 5% to 12% by weight of the whole composition. A suitable triblock copolymer is an alkylene oxide triblock copolymer defined as a triblock copolymer having an alkylene oxide moiety according to formula (I): (EO)x(PO)y(EO)x, where EO represents ethylene oxide and x represents the number of EO units in each EO block. Each x can be independently 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 of x between the two EO blocks is at most 2 units, preferably at most 1 unit, and more preferably both x have the same number of units. PO represents propylene oxide and y represents the number of PO units in the PO block. Each of y can be set to an average of 28 to 60, preferably 30 to 55, and more preferably 30 to 48.

[0097] Preferably, the ratio of y to each x in the triblock copolymer is 3:1 to 2:1. The ratio of y to the average x of the two EO blocks in the triblock copolymer is preferably 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 case of 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).

[0098] 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 term “block copolymer” is synonymous with this definition of “block polymer.”

[0099] Triblock copolymers according to formula (I), having specific EO / PO / EO configurations and respective homopolymer lengths, have been found to enhance the sustained foaming performance and / or foam consistency throughout dilution in liquid dishwashing detergent compositions in the presence of oily stains.

[0100] Suitable EO-PO-EO triblock copolymers are commercially available, for example, from BASF as the Pluronic® PE series and from Dow Chemical Company as the Tergitol® L series. Particularly preferred triblock copolymers from BASF are sold under the trademark names Pluronic® PE6400 (approximately 2900 MW, approximately 40% by weight EO) and Pluronic® PE9400 (approximately 4600 MW, approximately 40% by weight EO). Particularly preferred triblock copolymers from Dow Chemical Company are sold under the trademark name Tergitol® L64 (approximately 2700 MW, approximately 40% by weight EO).

[0101] Preferred triblock copolymers readily biodegrade under aerobic conditions.

[0102] 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.

[0103] salt: 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.

[0104] Hydrotrope: The composition of the present invention may contain about 0.1% to about 10% by weight, preferably about 0.5% to about 10% by weight, or more preferably about 1% to about 10% by weight, of hydrotrope or a mixture thereof, preferably sodium cumenesulfonate, in the total composition.

[0105] Organic solvents: The composition may contain, based on the total weight of the composition, about 0.1% to about 10% by weight of an organic solvent, preferably about 0.5% to about 10% by weight, or more preferably about 1% to about 10% by weight. Suitable organic solvents include alcohols, glycols, glycol ethers, and mixtures thereof, preferably organic solvents selected from the group consisting of alcohols, glycols, and mixtures thereof. 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.

[0106] auxiliary ingredients This cleansing composition may optionally contain many 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, antibacterial 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, sodium carbonate, bicarbonates, sesquicarbonates, and other carbonates).

[0107] Packaged Products Dishwashing detergent compositions can be packaged in containers, typically plastic containers. Suitable containers include an orifice. 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.

[0108] The orifice may have an open 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).

[0109] 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.

[0110] 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 steps of supplying the composition of the present invention to a predetermined volume of water to form a washing solution, and immersing the tableware in the solution. The tableware is washed with the composition in the presence of water.

[0111] The dishes may be rinsed as desired. In this specification, “rinsing” means bringing the dishes, which have been cleaned by the process according to the present invention, into contact with a considerable amount of a suitable solvent, typically water. “Considerable amount” usually means about 1 to about 20 liters or under running water.

[0112] 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 detergent composition of the present invention diluted with water (for about 25 dishes to be processed), preferably in liquid form. The actual amount of cleaning composition used is at the user's discretion and typically depends on factors such as the specific product formulation of the cleaning composition, including the concentration of the active ingredients in the cleaning composition, the number of soiled 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 cleaning 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 diluted cleaning composition thus obtained, the soiled surfaces of the dishes are brought into contact with a cloth, sponge, or similar cleaning tool. The cloth, sponge, or similar cleaning tool may be immersed in a mixture of the cleaning composition and water before contact with the dishes, typically for a period ranging from about 1 to about 10 seconds, although the actual time will vary depending on the application and user. Contacting the cloth, sponge, or similar cleaning tool with the dishes involves simultaneously scrubbing the dishes.

[0113] Alternatively, the composition as herein may be applied to the dishes to be processed in its undiluted form. “In its undiluted form” means, as herein, that the composition is applied directly to the surface to be processed, or to a cleaning device or tool such as a brush, sponge, nonwoven or woven material, without any significant dilution by the user prior to application (immediately before). “In its undiluted form” also includes, for example, slight dilution due to the presence of water on the surface of the cleaning device, 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.

[0114] method: A) Determination of molecular weight by gel permeation chromatography: Gel permeation chromatography (GPC) with multi-angle light scattering (MALS) and refractive index (RI) detection (GPC-MALS / RI) is a well-known system for directly measuring the weight-average molecular weight Mw and number-average molecular weight Mn of polymers without the need for comparison with known reference standards.

[0115] The true number-average molecular weight Mn of a polymer can be obtained by GPC combined with light scattering detection and refractive index detection, provided that the sampled slices are sufficiently monodisperse with respect to molecular weight and composition, even when the composition, and therefore the refractive index increment, changes with the elution volume.

[0116] For example, the molecular weight distribution of a polymer can be measured using a liquid chromatography system such as an Agilent 1260 Infinity pump system with OpenLab Chemstation software (from Agilent Technology, Santa Clara, CA, USA), which includes two 7.8 mm inner diameter × 300 mm long ultrahydrogel linear columns (S / N 002C180181 VE077 and 005C180181 VE084) used in series, supplied by Waters Corporation (Milford, Mass., USA), as well as an ultrahydrogel guard column (6 mm inner diameter × 40 mm long, S / N 2016260401BE105, also supplied by Waters Corporation (Milford, Mass., USA)) operated at 40°C, which is placed between the injector and the analytical column to prevent any impurities and suspended solids from reaching the analytical column. Multi-angle light scattering (MALS) detector DAWN® and differential refractive index (RI) detector (Wyatt Technology (Santa Barbara, Calif., USA)) controlled by Wyatt Astra® software can be used for detection.

[0117] Because the analyte diffuses over a relatively narrow time window, a constant composition elution method can be used instead of a gradient elution method. Constant composition means that the mobile phase mixture remains consistent throughout the entire test time. Using a gradient implies that the composition of the eluent mixture changes during measurement, which affects analyte retention. When using a gradient method, the separation can be either accelerated or slowed.

[0118] 0.1 M sodium nitrate in water containing 0.02% sodium azide is used as the mobile phase. The sample is prepared by dissolving the polymer in the mobile phase at approximately 1.0 mg / ml and mixing the solution overnight at room temperature to ensure complete hydration of the polymer. The sample is then filtered into an LC autosampler vial using a 3 ml syringe through a 0.8 μm Versapor membrane filter (AP4189, supplied by PALL, Life Sciences, NY, USA). The sample is then pumped into the column at a flow rate of 1.0 mL / min.

[0119] The number-average molecular weight and weight-average molecular weight of the polymer are calculated from the dn / dc (derivative change in refractive index with concentration) measurements provided by the Astra detector software.

[0120] B) Water seating: The drying rate is related to the degree of water sheeting. The higher the water sheeting, the less water is retained on the wet article.

[0121] Water seating behavior is evaluated by washing a gray ceramic plate ("Dinera" plate, 26 cm diameter, supplied by IKEA) with a test composition of dishwashing detergent, and then scoring the amount of water seating observed on the plate when it is placed vertically on a drying rack. More specifically, A sponge (Scotch-Brite® Classic-schuurspons van cellulose - dimensions: 7cm x 10cm, supplied by 3M Belgium) is uniformly moistened with water equivalent to 0.36 mmol / l CaCO3 hardness at 25°C by saturating the sponge with water and then manually squeezing it until no further water can be squeezed out.

[0122] 1 ml of dishwashing composition is evenly distributed across the sponge. The sponge is then manually squeezed four times with full force over the ceramic dish using one hand to create lather, and then the dish is washed with 10 circular clockwise movements, covering the edges and center of the dish so that the entire dish is treated with lather.

[0123] Next, the dish is rinsed for 30 seconds under running water (water at 25°C with the same water hardness as before (equivalent to 0.36 mmol / l CaCO3)) at a sufficient flow rate to allow for complete removal of foam and complete coating with water. After that, the dish is placed vertically on a drying rack under standard room conditions (20+ / -1°C).

[0124] Next, the water flowing down the plate is visually evaluated, and a score from 0 to 100% is given depending on the amount of water that flows down the plate in the first 30 seconds, and thus leaves the plate's surface already dry. 0% corresponds to no water remaining on the entire plate, 50% indicates that half of the plate is covered with a film of water, and 100% indicates that no film of water is visible. [Examples]

[0125] The following compositions were prepared and their water-sheeting behavior was evaluated using the methods described herein. Rapid water-sheeting is an indicator of rapid drying after rinsing.

[0126] In the compositions shown in Table 1, Example 1 of the invention contained both an anionic surfactant and an auxiliary surfactant in a 1:1 weight ratio, in addition to the quaternary acrylic copolymer. Comparative Example A contained the same surfactant system but did not contain the quaternary acrylic copolymer. By comparing the water-feeding results of Example 1 with those of Example A, an improvement in water-feeding can be seen from the addition of the quaternary acrylic copolymer to a composition containing anionic surfactants and auxiliary surfactants in the desired ratio. In contrast, the water-feeding results of Comparative Examples B-D show that the water-feeding benefit is substantially reduced when the anionic surfactant to auxiliary surfactant ratio exceeds the desired range.

[0127] [Table 1] *Comparative Example A quaternized acrylic copolymer useful in this invention, sold under the trademark name 1Polyquart(registered trademark)149A and supplied by BASF.

[0128] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise indicated, 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." [1] A liquid dishwashing detergent composition comprising a quaternary acrylic copolymer, The aforementioned liquid dishwashing detergent composition contains a surfactant system comprising 5.0% to 50% by weight, a. Anionic surfactants, b. A surfactant system comprising an auxiliary surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, A composition in which the anionic surfactant and the auxiliary surfactant are present in a weight ratio of less than 1.5:1. [2] The composition according to [1], wherein the composition comprises 0.01% to 3.0% by weight, preferably 0.05% to 2.0% by weight, and more preferably 0.1% to 1.0% by weight of the quaternized acrylic copolymer. [3] The composition according to [1] or [2], wherein the quaternized acrylic copolymer has a weight-average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da, preferably 15,000 to 300,000 Da, and more preferably 25,000 to 75,000 Da. [4] The composition according to any one of [1] to [3], wherein the quaternized acrylic copolymer has an average cation charge density of 0.01 to 2.8, preferably 0.1 to 2.75, and more preferably 0.75 to 2.25 mEq / g. [5] The aforementioned quaternary acrylic copolymer a. A cationic monomer unit selected from the following: i.CH2=CR1-Y-N+R2R3R4X- (a) During the ceremony, Each R1 is independently selected from hydrogen or methyl, preferably methyl. Each R2 is independently selected from C1-C4 alkyl (alkylene), preferably CH2CH=CH2 or methyl, more preferably methyl. Each R3 and R4 is independently selected from C1-C4 alkyl groups, preferably C1-C3 alkyl groups, and more preferably methyl groups. Each Y is independently selected from CO-NR5-(CH2)n, CO-O-(CH2)n, or (CH2)n, preferably CO-NR5-(CH2)n or (CH2)n, more preferably CO-NR5-(CH2)n, and During the ceremony, Each R5 is independently selected from hydrogen or methyl, preferably hydrogen. n is the average of 1 to 4, preferably 1 or 3, and more preferably 3. X- is a cationic monomer unit, which is a suitable counterion, preferably a halide counterion, more preferably Cl-. b. A composition according to any one of [1] to [4], derived from an ethylenically unsaturated monomer unit. [6] The composition according to [5], wherein the cationic monomer unit is selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC), diallyldimethylammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium chloride (AETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), methyloyloxyethyltrimethylammonium chloride (METAC), and mixtures thereof, preferably (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC), more preferably methacrylamidopropyltrimethylammonium chloride (MAPTAC). [7] The composition according to [5] or [6], wherein the ethylenically unsaturated monomer unit is selected from the group consisting of C3-C8 ethylenically unsaturated acids and / or salts thereof, C3-C8 hydroxyalkyl acrylates, and mixtures thereof. [8] The composition according to [7], wherein the ethylenically unsaturated monomer unit comprises a C3-C8 ethylenically unsaturated acid and / or a salt thereof, and the C3-C8 ethylenically unsaturated acid and / or a salt thereof is selected from the group consisting of (meth)acrylic acid and / or a salt thereof, more preferably selected from acrylic acid and / or a salt thereof. [9] The composition according to [7] or [8], wherein the ethylenically unsaturated monomer unit comprises a C3-C8 alkyl acrylate selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate, and most preferably ethyl acrylate.

[10] The composition according to any one of [1] to [9], wherein the anionic surfactant and the auxiliary surfactant are present in a weight ratio of 0.5:1 to 1.5:1, preferably 0.8:1 to 1.2:1.

[11] The composition according to any one of [1] to

[10] , wherein the composition comprises the surfactant system in an amount of 6.0% to 40% by weight, preferably 15% to 35% by weight, of the entire composition.

[12] The composition according to any one of [1] to

[11] , wherein the surfactant system comprises at least 35% by weight, preferably 35% to 65% by weight, and more preferably 40% to 60% by weight of the anionic surfactant of the surfactant system.

[13] The composition according to any one of [1] to

[12] , wherein the anionic surfactant comprises at least 70% by weight, preferably at least 85% by weight, and more preferably 100% by weight of an alkyl sulfated anionic surfactant.

[14] The composition according to any one of [1] to

[13] , wherein the auxiliary surfactant comprises an amphoteric surfactant, preferably an amine oxide surfactant.

[15] The composition according to any one of [1] to

[14] , wherein the surfactant system comprises less than 10.0% by weight, preferably less than 5.0% by weight, of the surfactant system, and more preferably does not contain alkoxylated alcohol nonionic surfactant.

Claims

1. A liquid dishwashing detergent composition, The liquid dishwashing detergent composition contains 0.1% to 2.0% by weight of a quaternary acrylic copolymer, A surfactant system comprising 5.0% to 50% by weight of the aforementioned liquid dishwashing detergent composition, a. Anionic surfactants and b. A surfactant system comprising an auxiliary surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, The anionic surfactant and the auxiliary surfactant are present in a weight ratio of 0.5:1 to 1.5:

1. The aforementioned anionic surfactant is an alkyl sulfated anionic surfactant. A composition wherein the quaternary acrylic copolymer is derived from cationic monomer units and ethylenically unsaturated monomer units, and either (i) or (ii) is applicable. (i) The cationic monomer unit is selected from the group consisting of acrylamidopropyltrimethylammonium chloride (APTAC), acryloyloxyethyltrimethylammonium chloride (AETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), methyloyloxyethyltrimethylammonium chloride (METAC), and mixtures thereof, and the ethylenically unsaturated monomer unit is selected from the group consisting of (meth)acrylic acid or its salts and / or ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof. (ii) The cationic monomer unit is diallyldimethylammonium chloride (DADMAC), and the ethylenically unsaturated monomer unit is selected from the group consisting of ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof.

2. The composition according to claim 1, wherein the composition comprises 0.1% to 1.0% by weight of the quaternized acrylic copolymer.

3. The composition according to claim 1 or 2, wherein the quaternized acrylic copolymer has a weight-average molecular weight (Mw) measured by aqueous gel permeation chromatography (GPC) equipped with light scattering detection (SEC-MALLS) in the range of 5,000 to 500,000 Da.

4. The composition according to claim 1 or 2, wherein the quaternized acrylic copolymer has an average cation charge density of 0.01 to 2.8 mEq / g.

5. The composition according to claim 1 or 2, wherein the (i) above applies, and the cationic monomer unit is (meth)acrylamidopropyltrimethylammonium chloride (APTAC or MAPTAC).

6. The composition according to claim 5, wherein the cationic monomer unit is methacrylamidopropyltrimethylammonium chloride (MAPTAC).

7. The composition according to claim 1 or 2, to which the above (ii) applies.

8. The composition according to claim 1 or 2, wherein the ethylenically unsaturated monomer unit comprises ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, or a mixture thereof.

9. The composition according to claim 1 or 2, wherein the ethylenically unsaturated monomer unit comprises ethyl (meth)acrylate.

10. The composition according to claim 1 or 2, wherein the ethylenically unsaturated monomer unit comprises ethyl acrylate.

11. The composition according to claim 1 or 2, wherein the anionic surfactant and the auxiliary surfactant are present in a weight ratio of 0.8:1 to 1.2:

1.

12. The composition according to claim 1 or 2, wherein the composition comprises 6.0% to 40% by weight of the surfactant system in the total composition.

13. The composition according to claim 1 or 2, wherein the surfactant system comprises at least 35% by weight of an anionic surfactant of the surfactant system.

14. The composition according to claim 1 or 2, wherein the surfactant system comprises less than 10.0% by weight of the alkoxylated alcohol nonionic surfactant of the surfactant system.

15. The composition according to claim 1 or 2, wherein the auxiliary surfactant includes an amphoteric surfactant.

16. The composition according to claim 1 or 2, wherein the surfactant system comprises less than 5.0% by weight of the alkoxylated alcohol nonionic surfactant of the surfactant system.

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